Widom Larsen Superconducting Hydrides and Directed Speculation

Things I do late at night when sleep evades…

It was about 1 A.M. and “laying in bed eyes wide open” time. So I reached over and grabbed the tablet. “Maybe reading some physics can put me to sleep”… I started checking the recent “news” on the E-Cat and LENR. Not much. Same story. Claims it is working, in production. But at only one secret site and nobody gets a tour or proof until the “test” is over at the end of 2015. Or maybe in 2016. Sigh.

I then wandered off to have a look again at the Widom Larsen theory. It is intriguing, but a bit dense. Mostly because it uses physics concepts that were developed after I took physics and that are new and alien to me. Things like “heavy electrons” and “plasmon polaritons” and similar things. OK, I’ll skip the details as I don’t want YOU to all go to sleep… but the basic idea of a ‘heavy electron’ is that in some atom orbital states the electron acts like it has a higher mass, and the basic idea of the plasmon and polariton is that clusters of electromagnetic wave energy can flow along the surface of a metal (if inside the metal face, it is a plasmon, outside the metal / dialectric interface it is a polariton).

In any case, the W-L theory says a blob of this energy is important in making a ‘heavy electron’ that then whacks into a proton (hydrogen ex-electron) and makes a ultra slow neutron; which can then drift into a convenient metal nucleus and cause transmutation and energy release.

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

That lead me to a bunch of pages about the various ways to get those SPPs to form. (Surface Plasmon Polariton). You can do it with electricity, or with light, mostly. Light doesn’t directly couple into the metal (for some odd exclusion property reason that I didn’t care enough to follow down that rat hole…) and typically takes a prism or surface grating (i.e. roughness of just the right size). This, then leads to the speculation that the difficulty of replication for things like Pons & F. and the various “works sometimes” issues could easily be related to what the ambient EM leakage in the lab might be and / or what the surface roughness was like on any given metal.

Who had Wi-Fi in their lab, or who was in the line of sight of a local airport radar (or even just a favorite radar speed trap) could change the degree of formation of such SPP critters. Heck, even the kind of lighting. Incandescent makes mostly IR, that can induce them. Fluorescent has more UV and even some soft X-rays. As some devices claim to be using what looks like microwaves (or similar range electric currents) to stimulate their “magic dust”, there is some reason to think that the ambient level of such fields could explain variation in results.

The SPPs seem to be longer lived in things that conduct well (being basically an electrical flow). From that wiki:

“An SPP will propagate along the interface until its energy is lost either to absorption in the metal or scattering into other directions (such as into free space).”

Which implies that in addition to worry about how to get the suckers to form (surface grating / roughness, light bombardment, EM field application, or high frequency current flows) one might expect materials that “conduct well” to have them hang around longer, and thus do more…

Then, as is often the case, the “directed speculation” leap happens. The question comes from nowhere. It just is. Suddenly. “Would superconductors work better?”… that then directs into “Is there a metal hydride that is a superconductor?”. The answer? Well, yes. Pd and Pd-Ni alloy form superconducting hydrides. Golly, what a “coincidence”…

http://onlinelibrary.wiley.com/doi/10.1002/pssa.2210110253/citedby

Short Note

Superconductivity in the palladium-hydrogen and palladium-nickel-hydrogen systems
T. Skoskiewicz†

Article first published online: 17 FEB 2006
DOI: 10.1002/pssa.2210110253
Copyright © 1972 WILEY-VCH Verlag GmbH & Co. KGaA

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

Superconductivity

PdHx is a superconductor with a transition temperature Tc of about 9 K for x=1. (Pure palladium is not superconducting). Drops in resistivity vs. temperature curves were observed at higher temperatures (up to 273 K) in hydrogen-rich (x ~ 1), nonstoichiometric palladium hydride and interpreted as superconducting transitions. These results have been questioned and have not been confirmed thus far.

Hmmm….

Then this patent gives some ideas on how to get that material forming more easily via surface treatments. Might this shorten the “loading time” of LENR electrodes? Might the degree of surface oxidation or presence of some kinds of contaminants (like “metal, metal oxide, ceramic, or polymer”) explain some of the variations in loading? Perhaps the more folks tried to make things pure and clean, the worse their results?

https://encrypted.google.com/patents/US7033568

High Tc palladium hydride superconductor
US 7033568 B2

ABSTRACT

A palladium hydride superconductor, PdyHx where yHx is 1Hx, 2Hx, or 3Hx, having a critical temperature Tc≧11K and stoichiometric ratio x≧1. The critical temperature is proportional to a power of the stoichiometric ratio, which is stable over periods exceeding 24 hours, temperature variations from 4K to 400K, and pressures down to 1 mbar. The palladium hydride is coated with a stabilizing material such as a metal, metal oxide, ceramic, or polymer that can bond to palladium. It can be made by electrochemically loading a palladium lattice with isotopic hydrogen in an electrolytic solution, by allowing isotopic hydrogen to diffuse into a palladium thin film in a pressure chamber, or by injecting isotopic hydrogen into a palladium thin film in a vacuum chamber. The stabilizing material can be electrochemically bonded to the surface of the palladium hydride, or deposited using chemical vapor deposition or molecular beam epitaxy.

There are interesting hints that other folks have come near to noticing this ‘connection’ between superconductor materials and LENR, but they seem more “in passing” than central to their thinking. For example:

hhttp://www.infinite-energy.com/iemagazine/issue105/LENRatWilliamsburg.html

To study cluster creation, Miley has used thin Pd plates with Pd oxide layers on the surfaces. Repeated electrolytic loading and deloading was performed to create dislocation loops at the interfaces and near surface. The numbers of clusters and their density were studied using temperature controlled desorption and EM SQUID measurements. The SQUID measurement showed the cluster material was what amounted to a Class 2 superconductor, demonstrating near metallic density. More recently, Miley’s group has used a Petawatt laser to drive MeV deuterium beams out of foils containing deuterium clusters.

Miley said he was inspired to extend these thin film methods to nanoparticles when Rossi announced his gas loaded hydrogen-nickel nanoparticle power units. Nano materials have more surface area, thus have good ability to form abundant clusters. Clusters mainly form in pores close to the surface. To study this he worked on four different types of alloys—two that were Ni rich allow for hydrogen loading and two Pd rich alloys for D2 loading. To date he has mainly concentrated on D-Pd. Palladium is expensive, but he is studying ways to recycle palladium from “used” nanoparticles. He said that if they run six months or more before replacement, and recycling is used, the economics may not be so crucial.

So why not just make a batch of superconductor directly, instead of discovering it in “patches” and “clusters”? Might that not work better?

In looking for Ni based superconductors, there are several compounds that pop up. This, to me, implies that impure Ni would be more reactive as it would be more likely to have such “accidental superconductor” zones. Again, using overly pure material might “cause issues” in replication. Again, Hmmm…

One interesting example is ZrNi2Ga. If your nickel has some contaminant zirconium and gallium in it, well…

http://www.researchgate.net/publication/242372867_Ni-based_superconductor_Heusler_compound_ZrNi2Ga

ABSTRACT This work reports on the Heusler superconductor ZrNi2Ga . Compared to other nickel-based superconductors with Heusler structure, ZrNi2Ga exhibits a relatively high superconducting transition temperature of Tc=2.9K and an upper critical field of mu0Hc2=1.5T . Electronic structure calculations show that this relatively high Tc is caused by a Van Hove singularity, which leads to an enhanced density of states at the Fermi energy N(gammaF) . The Van Hove singularity originates from a higher-order valence instability at the L point in the electronic structure. The enhanced N(gammaF) was confirmed by specific-heat and susceptibility measurements. Although many Heusler compounds are ferromagnetic, our measurements of ZrNi2Ga indicate a paramagnetic state above Tc and could not reveal any traces of magnetic order down to temperatures of at least 0.35 K. We investigated in detail the superconducting state with specific-heat, magnetization, and resistivity measurements. The resulting data show the typical behavior of a conventional weakly coupled BCS ( s -wave) superconductor.

So then the question becomes, what about Nickel Hydride systems? When do you get H into Ni anyway?

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

Hydrogen atoms bond strongly with a nickel surface, with hydrogen molecules disassociating in order to do so.

Disassociation of dihydrogen requires enough energy to cross a barrier. On a Ni(111) crystal surface the barrier is 46 kJ/mol, whereas on Ni(100) the barrier is 52 kJ/mol. The Ni(110) crystal plane surface has the lowest activation energy to break the hydrogen molecule at 36 kJ/mol. The surface layer of hydrogen on nickel can be released by heating. Ni(111) lost hydrogen between 320 and 380 K. Ni(100) lost hydrogen between 220 and 360 K. Ni(110) crystal surfaces lost hydrogen between 230 and 430 K.

In order to dissolve inside the nickel, hydrogen must migrate from on the surface through the face of a nickel crystal. This does not take place in a vacuum, but can take place when the hydrogen coated nickel surface is impacted by other molecules. The molecules do not have to be hydrogen, but they appear to work like hammers punching the hydrogen atoms through the nickel surface to the subsurface. An activation energy of 100 kJ/mol is required to penetrate the surface.

So you need it cold enough to have the gas bond to the surface, but hot enough to provide energy to disassociate the H2. The exact isotope determines some of the temperature limits, and having a heavy gas in the mix might help. Shades of Xenon and the Pap Engine… Wonder if he had Ni inside the piston / cylinder / igniter systems anywhere…

Then, using high pressure gas, or having H electrolytically delivered, can get high loading:

High pressure phases

A true crystallographically distinct phase of nickel hydride can be produced with high pressure hydrogen gas at 600 MPa. Alternatively it can be produced electrolytically. The crystal form is face centred cubic or β-nickel hydride. Hydrogen to nickel atomic ratios are up to one, with hydrogen occupying an octahedral site. The density of the β-hydride is 7.74 g/cm3. It is coloured grey. At a current density of 1 Amp per square decimeter, in 0.5 mol/liter of sulfuric acid and thiourea a surface layer of nickel will be converted to nickel hydride. This surface is replete with cracks up to milimeters long. The direction of cracking is in the {001} plane of the original nickel crystals. The lattice constant of nickel hydride is 3.731 Å, which is 5.7% more than that of nickel.

The near-stoichiometric NiH is unstable and loses hydrogen at pressures below 340 MPa.

Gak! MPa… I hate those dinky non-intuitive units…made worse with gigantic non-intuitive prefixes… A bar is more rational… It’s about 1 atmosphere. It is also 100,000 Pa. So our 10^6 Pa becomes 10 x bar. OK, it’s about 10 x 14.5 x 340 = 43,500 PSI if I’ve not screwed up the conversion… So not very stable all on it’s own, and takes a lot of pressure to get it done. Thus, I would speculate, the “magic dust” powders. More surface area for absorption, and more potential for admixtures that help stabilize the hydride. Perhaps even lowering the pressure needed to get it loaded to something like a few hundred pounds. That’s the avenue I’d follow for making “magic dust”. And once again, too much emphasis on “purity” could remove the “contaminants” that make the process function…

But what about Nickel alloys and especially with hydrogen in them?

https://encrypted.google.com/patents/US4043809

High temperature superconductors and method

US 4043809 A

ABSTRACT

This invention comprises a superconductive compound having the formula:
Ni1-x Mx Zy
wherein M is a metal which will destroy the magnetic character of nickel (preferably copper, silver or gold); Z is hydrogen or deuterium; x is 0.1 to 0.9; and y, correspondingly, 0.9 to 0.1, and method of conducting electric current with no resistance at relatively high temperature of T>1° K comprising a conductor consisting essentially of the superconducting compound noted above.

Note, especially, the use of Copper. Since one of the products of stuffing a Neutron (n) into a Nickle (Ni) is a Copper (Cu) then it makes sense that you would be slowly making more of this Ni Cu alloy over time. Now if you have a tiny contamination of Cu to start with, you have an initial active site, and as more Cu builds up, you get more activity. Might this explain the tendency for some test cells to need a long waiting time before they stared to “work” enough to detect anything? Might is also explain why folks using ultra pure Ni might get no results, while the guys doing it in the garage had better results? Hmmmm…..

In Conclusion

To me, this directed speculation seems to have reached an interesting and perhaps useful point. Searching the superconductor space for materials that can be loaded with hydrogen ought to be a productive exercise. Directly making a NiCuH alloy as in that patent ought to make a very good test material. Assuring that your Ni has at least a little Cu in it for any cell likely will help things get started. Once cell material gets “used up”, simply removing some of the copper (or adding a lot more Ni) will likely let it “go” again.

There is also the implication that many of the more exotic superconductor materials might have promise. That makes the field of inquiry much larger than just Pd and Ni (and potentially reduces the cost too). Again, from that last patent link:

The search for superconductors with higher transition temperatures has led to the discovery of various compounds with Tc ≅ 20° K. Some examples are Nb3 Ge, Nb3 Sn, PdH, PdD, and PdCuH. The highest Tc material discovered so far is Nb3 Ge with Tc = 23.2° K. As such, costly refrigeration methods must also be employed to use these compounds as superconducting wires. Also, many of the presently available high temperature superconductors such as Nb3 Ge with Tc = 23° K, are difficult to manufacture and contain relatively expensive ingredients.

It should be noted that some substances are not superconducting at all. This group of materials includes the elements Cu, Ni, Pd and compounds such as NiH.

Again we see a bit of clue that perhaps some copper contamination in your Pd wire might help it go… and that pure NiH might not work so well. Also a PdCuH alloy might work better…

So if this bit of speculation is valid, then the literature of superconductors can be leveraged, as can all the people working on superconductors and all the money already poured into them. It would also let you have a quick test for the probability that a given material might work well in a cell; just dunk it in some liquid He and see if it superconducts… For example, here’s a patent for hydriding a Uranium Zirconium alloy:

https://encrypted.google.com/patents/US3776508

Now you might have no idea if that would be usable in a LENR cell. But I’d speculate that shoving neutrons into U ought to cause something to happen! ;-) and you might not want to try making a cell with radioactive materials just to ‘find out’. Perhaps just putting a chunk in the deep freeze and testing conductivity would be a bit quicker and safer…

Zirconium hydride is an excellent moderating material for a nuclear reactor core, particularly where cores of small diameter or high power density are required. Hydrogen has the greatest neutron slowing down ability of any element, and combined with zirconium, a structural metal of relatively low thermal neutron absorption cross section, the hydrogen is in a relatively stable, high density form adapted for high temperature utilization.

So perhaps some kind of NiZrH or NiCuZrH might also make a useful material. And if the “dunk test” gets you quick clue on what will fail, many things can be tested in hours rather than months. It also gives a quick “search method” to find potential candidates, such as:

http://www.sciencedirect.com/science/article/pii/0038109881910644

Superconductivity in zirconium-nickel glasses

E. Babić, R. Ristić, M. Miljak

Institute of Physics of the University, Zagreb, Yugoslavia
M.G. Scott, G. Gregan
School of Engineering & Applied Sciences, University of Sussex, Brighton, England

Abstract
The superconducting transition temperatures (Tc) and magnetic susceptibilities of amorphous Zr100−xNix alloys have been measured. Tc decreases linearly with increasing x. The results are compared to those for amorphous ZrPd and ZrCu alloys and discussed in terms of changes in the electron to atom ratio on alloying.

So ZrPd and ZrCu alloys, along with ZrNi alloys all can superconduct. Add some H and see what happens…

It’s now approaching 4 A.M., and I’m thinking maybe it’s time to try sleeping again. Then again, not sleeping tends to result in things like this… so maybe I ought to not sleep more often. ;-)

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