Ultrasonic Fuel Treatment As A Gateway To Nickel/Hydrogen LENR

Ultrasonic Fuel Treatment As A Gateway To Nickel/Hydrogen LENR

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DISCUSSION DOCUMENT

Hank Mills and Alan Smith (www.lookingforheat.com) OCTOBER 2016

“There are very few human beings who receive the truth, complete and staggering, by instant illumination. Most of them acquire it fragment by fragment, on a small scale, by successive developments, cellularly, like a laborious mosaic. Anais Nin”

Abstract: In this discussion paper we describe a proposed method of preparing nickel powder for use in ‘dogbone’ or ‘Model T’ nickel-lithium-hydrogen reactors. This method, while not new, has seemingly been overlooked by many LENR researchers and replicators. The use of ultrasonic cleaning of nickel as a slurry in an alkane solvent (n-hexane), magnetic separation of pure nickel from oxide fragments and subsequent measures to limit the reformation of oxides and promote the absorption of hydrogen are described in detail. Links to published research papers on sonication of nickel powders and the subsequent stimulating effect on catalytic activity are appended.

IMPORTANT:-  Replicators should be aware that this is a time-consuming process demanding care, thought, and a fair degree of technical skill in setting up and handling the required equipment.

Purpose: To induce more reliably nuclear-based exothermic reactions in LENR experimental systems by utilizing meticulous cleaning methods, including the use of ultrasound and other processes, for example vacuum degassing under heat, to enhance the catalytic properties and hydrogen interaction potential of nickel.

Hypothesis: The use of the ultrasonic cleaning method described promotes  removal of the stubborn oxide layer from nickel powder. This removal is affected by two different mechanisms. Firstly, but high-speed collisions between particles, and secondly by the action of cavitation/collapse jets striking the particle surface. The deleterious effects of such oxide films on the interaction between nickel and hydrogen have been widely discussed in the literature of catalysis. The suggested cleaning process improves hydrogen absorption, thus facilitating low energy nuclear reactions inside the reactor.  Preliminary baking actually promotes oxidation- it is part of our hypothesis that first creating and then stripping off the oxides is an important part of the ‘activation’ process.

Desired Outcomes: Improved success rates of anomalous heat production, and XS heat outputs possibly as good as those achieved by other replicators, hopefully comparable to the most successful tests of the Rossi Effect performed by third party replicators including “heat after death” (persistent heat production with zero input.)

Materials and Equipment

1) We are proposing to test our hypothesis using ‘Gem Grade’ 20uM Nickel Powder from Archer UK. This was chosen for its low declared level of impurities, and because the stated particle size is a good starting point. We hope this reduces the chance that contaminants or impurities are present in the Nickel powder that act as “catalyst poisons.”

2) Alfa Aesar 97% LiAlH4 – Chosen for its claimed high hydrogen content and small particle size of around 10 microns vs. the much larger particle size for other brands (e.g. Sigma-Aldrich 50 -150 microns). This small size helps to improve surface area and thus maximize hydrogen release at the lowest temperatures possible.

3) Looking for Heat ‘Model-T’ Unit. We are considering using 2 Model T’s , with all 4 heaters coupled in series and ports calibrated to achieve equal temperatures with empty ‘control’ tubes.

4) Packard 7525 High Purity Hydrogen Generator. (99.999% pure H2 @ 300ml minute at 1 Bar, max delivery pressure 6 Bar). Other types are available.

5) Ultrasonic Transducer (28khz & 100w). Ex Ebay

6) Anhydrous Hexane (Assay: >98% Molecular Formula: CH3(CH2)4CH3:Molecular Weight: 86.18:Boiling Point: 69 deg C supplied by APC Pure Ltd UK.

7) Vacuum Pump. Single stage oil-filled ¼ Hp:- theoretically good down to 0.5Pa. If a two stage pump becomes available, it will be used instead.

8) Glove Box/Bag – Hydrogen or Argon filled.

9) Fume hood or very good workplace air extraction (Optional but very desirable due to releases of hydrogen gas and n-hexane vapor.) See safety notes on n-hexane below.

10) Electric hotplate..

11) High-Temperature Furnace.

 

Brief Hazard Notes for N-Hexane (CAS : 110-54-3)

Affects: Nervous and reproductive systems.
Cancer classification: None known. 
Chemical classification: Volatile hydrocarbon. 

Summary:  Pure n-Hexane is a colourless liquid with a slightly disagreeable odor. It is highly flammable, and its vapour can be explosive.  A major use for n-Hexane is to extract vegetable oils from crops and it is found in gasoline,  cleaning materials and solvent-based glues.

 

Nickel Powder Treatment Protocol

NOTE – Carefully clean all equipment before use, wash and rinse in de-ionised water where necessary and bake (to minimise surface contaminants) at 200C for 1 hour.

high-temp-annealing

2.Ultrasound Oxide Removal – Into a glass vacuum flask (100ml Buchner type) place 5 grams of nickel powder and 21ml of n-hexane. Stir briefly to create a slurry. Position in an ice bath attached to the ultrasonic generator horn. The purpose of the ice bath is to keep the nickel slurry temperature below 25C to prevent any chance of an unwanted ‘bulk reaction’ between nickel and n-hexane during the sonication treatment. Connect vacuum pump via a ‘T Valve’ line or, if available, a Perkin triangle assembly (see photograph) and start evacuating the flask. IMPORTANT: The boiling point of n-hexane (75C approx.) means that it boils at even lower temperature under vacuum. This means that both the flask temperature and the vacuum level must be controlled and (at this stage) vacuum applied intermittently. Maintain ultrasound treatment of for five hours or longer.

 

perkin-triangle

 

3. Magnetic Separation of Nickel and Oxides. Check the flask contents regularly to ensure that there is sufficient n-hexane to keep the slurry mobile. If required the spare line on the Perkin system or T-valve can be used (cautiously!) with the vacuum pump isolated to suck more n-hexane into the flask.  When the ultrasound treatment is done, use a strong permanent magnet to separate ferromagnetic nickel particles from the slurry, leaving the non-magnetic nickel oxide fragments suspended in the hexane. Wash the nickel three times with around 25 ml of hexane, to remove the maximum amount of oxide particles. Use manual agitation and the magnetic separation method each time.

 

magnetic-separation-nickel

 

NOTE. The magnetic separation method described in 3 above, and all subsequent stages of this process preferably require keeping the ‘washed and naked ‘ oxide free nickel particles away from contact with air – since the literature suggests that  clean micro-nickel re-oxidises very rapidly  If a glove box filled with hydrogen (careful!) or argon is available this might be used with some advantage.

However, one of the authors discussed this re-oxidation problem at length with a very senior and experienced analytical chemist who was firmly of the opinion that since at all times in stage 3, and at the start of stage 4 (below) the nickel is confined in a flask in the presence of a large amount of n-hexane, and under a blanket of hexane vapor it is to a large extent protected from oxidation by the atmosphere. But he stressed the need to ‘be quick and be careful’, whenever the powder is exposed to air. A moment’s carelessness could ruin a whole day’s work.  

 

4. Hot De-gassing– Transfer the Buchner flask with the nickel powder still wet with Hexane from the ultrasound device onto a hotplate, switch on vacuum pump and pump down to as low a pressure as possible. When this is done, turn on the hotplate and slowly heat the flask and contents up to 200C maximum. The combination of heat and vacuum will remove all the now unwanted components of the system eg. hexane, air, water vapor etc. Keeping the temperature at or below 200C helps to avoid sintering the oxide free nickel which can occur even at low temperature. Continue heating for at least six hours with the vacuum pump (if not continuously rated) working on a 50% duty cycle. A pump rated for continuous use may be run for twelve hours or longer.  There seems to be little limit on how long this phase  of fuel preparation can be maintained.

5. Hydrogenation Phase. Using a ‘T’ valve system, or your Perkin Triangle introduce hydrogen into the flask. You can use the valve system and the vacuum pump to flush the system with hydrogen for a few moments, then close the appropriate valves and let the hydrogen pressure rise to 2 Bar.

NOTE. 2 Bar, or the highest pressure below this your system can safely handle.  Using silicone rubber bungs means that in our case we will only take the pressure up to 1.5 Bar.

 Maintain system temperature up to 200C over a one hour time period, introducing more hydrogen generator to maintain your desired pressure to compensate for pressure reduction as the nickel absorbs hydrogen. Maintaining positive hydrogen pressure also prevents atmospheric oxygen from entering the flask.

 Continue this  process for up to 6 hours. It is a beneficial side effect of this hydrogenation phase that it also tends to reduce residual oxides on the nickel to some (unknown) extent. Normally,  the reduction of nickel oxides with hydrogen requires temperatures of 625C or more. However, due to the nickel being in the form of powder and already cleaned of oxides by the ultrasound process – which promotes sintering — a lower temperature must be utilized to avoid sintering and reduction of surface area and potentially of LENR- catalytic activity. Clean nickel has been reported to sinter at temperatures of 310C or lower according to Bob Higgins of the MFMP. The temperature of 200C has been chosen in the hope that no sintering whatsoever will take place.

 

buchner-vacuum-flasks

6. Collection/Storage – Allow flask to cool and remove hydrogen line in a manner that prevents exposure of the contents to air. Place flask into hydrogen (or Argon) glove box and transfer contents into appropriate hydrogen filled bag/bottle within another hydrogen filled container.  Vacuum seal packaging if possible.

DISCUSSION POINTS

1 – There is discussion about using iron oxide or alumina powder mixed in with the fuel during all stages of processing to separate the nickel powder to prevent sintering. Although this may be effective, none of the most successful replicators – N. Stepanov, Songsheng, Parkhomov – have utilized such a method.  Instead, we have decided to use a low temperature approach to prevent sintering.  This may reduce the rate of oxide reduction which accelerates dramatically at higher temperatures in the presence of hydrogen. Also, the lower temperature will reduce the quantity of hydrogen absorbed into the nickel lattice. But if we attempted high temperature pre-loading of hydrogen, we could risk sintering or LENR processes taking place before the test begins.

2 – The ultrasonic irradiation process may do more than clean the surface of nickel and copper of oxides. A thin layer of carbon has been found on the surface of both ultrasonically irradiated nickel and copper. It is speculated that the carbon may come from the carbon in the solvent being thermo-chemically cracked when two particles in the solvent collide at high speed producing temperatures of thousands of degrees at the contact point. Interestingly, one production method of graphene is to ultrasonically irradiate carbon that has been deposited onto a nickel surface. There is speculation that broken, imperfect sheets of graphene and similar arrangements of carbon atoms may be produced on the surface of ultrasonically irradiated nickel. The extremely high levels of catalytic activity after ultrasonic irradiation may be too high to be explained by only the removal of the oxide layer.

3 – Acids are also often used to remove oxide layers from nickel powder.  One example of a commonly used chemical is hydrochloric acid. However, the chlorine in HCL points the catalytic ability of nickel to adsorb hydrogen – the first process in hydrogen absorption. This is because chlorine is an electronegative element. For this reason and the fact we do not wish to contaminate the fuel with a multitude of different chemical elements, we are forgoing the use of chemical dissolution of the oxide layer.  Coming next, the experimental stage.

 

REFERENCES ON NICKEL POWDER CATALYST IMPROVEMENT TECHNIQUES

 

1. ABSTRACT: Treatment of nickel powder slurry in decane with 20 kilohertz high intensity ultrasound at 50 watts per cc. of slurry at a temperature of 293K. Starting with a particle size of 160um, sonication resulted in a particle size of approximately 80um, reduction in the thickness of the surface oxide layer and a massive increase in the catalytic properties of nickel. Improved catalyst performance (to similar levels as Raney nickel) was primarily due to the decrease in oxide level

Papers by the Suslick Research Group, University of Illinois.

(1A) http://www.scs.illinois.edu/suslick/sonochemistry.html

Heterogeneous Sonocatalysis with Nickel Powder. Kenneth S. Suslick* and Dominick J.Casadonte

(1B) http://scs.illinois.edu/suslick/documents/jacs873459.pdf

Sonocatalysis. Kenneth S. Suslick and Sara E. Skrabalak

(1C) http://www.scs.illinois.edu/suslick/documents/sonocatalysis.pdf

(1D) http://www.scs.illinois.edu/suslick/documents/science901439.pdf

The Effects of Ultrasound on Nickel and Copper Powders: Suslick, Casadonte And Doktycz. School of Chemical Sciences, University of Illinois.

(1E) http://www.scs.illinois.edu/suslick/documents/solidstateionics.1989.pdf

The Chemical Effects of Ultra Sound

(1F) http://www.scs.illinois.edu/suslick/documents/sciamer8980.pdf

(1G) http://www.scs.illinois.edu/suslick/documents/ultrasonsonochem.2014.1908.pdf

 

Ultrasonic Irradiation Of Copper Powder

ABSTRACT: Interparticle collisions still occur and surface morphology and chemical reactivity can be affected, but particle agglomeration will not occur, for example, as with 160um diameter Ni. In sufficiently viscous liquids the velocity of inter-particle collisions will probably be diminished. However we observed similar inter-particle collision in various synthetically useful liquids including several alkanes (n-octane through n-tetradecane), dimethylformamide, and dioxane. Further work is in progress.

(1H) http://www.scs.illinois.edu/suslick/documents/chemmater.1989.pdf

 

PARTICLE MORPHOLOGY STUDIES

2. ABSTRACT: Electron micro-photographs taken ‘before and after’ sonication.

The Effect Of Ultrasound Irradiation On The Morphology Of Ni Powder Synthesized By Electrodeposition Authors: Mahdiyar HOOBAKHT , Alireza ZAKERI, Alireza SHAHIDI

(2A) http://www.ultrasonic.co.ir/files/Ni%20powder.pdf

Larger Image of Smoothed Nickel Particles

(2B) http://chempedia.info/pics/4121/

Chemical Modification of Chemisorptive and Catalytic Properties of Nickel

(Chlorine, a common contaminant in LiAlH4, poisons the ability of nickel to adsorb hydrogen due to being electronegative. Other electro-negative elements also poison the nickel. Potassium, found in Rossi’s early fuel, enhances adsorption due to being electropositive. Lithium is not discussed in this paper, but since it is electropositive, it may help hydrogen adsorption. NOTE: Adsorption (attachment to surfaces) is the first process which takes place before hydrogen absorption can happen.

Chemical Modification of Chemisorptive and Catalytic Properties of Nickel

http://www.chem.tamu.edu/rgroup/goodman/pdf%20files/40_appl%20ss-19-84-1.pdf

Books.Google.Com

 

 Nickel vapors were allowed to react with three different solvents (hexane, toluene, and THF) to give very reactive metal slurries having high surface areas. Furthermore, these metal-solvent complexes can react with triethylphosphite to afford nickel clusters. Interestingly, metal slurries can be deposited on supports such as alumina, silica, molecular sieves, or activated carbon. Additionally the metal particles formed from metal slurries on warming can surve as active catalysts. Nickel-hexane powders are more active hydrogenation catalysts than Raney nickel. In contrast, Ni-THF powder is a poor and unreacted hydrogenation catalyst, but it is efficient for alkene disproportionation.

Books.Google.Com

 

New catalysts made by mixing metal vapour with solvents

A new method, using solvents, for making tiny metal particles has been invented by scientists working wat the University of North Dakota. They may have created a new class of industrial catalysts.

K.J Klabunde, H. F. Efner, T. O. Murdock and R. Ropple have recently been experimenting with the technique of vacuum deposition. In this technique materials are vaporised, then deposited onto a cold finger usually a quartz probe kept at negative 196C. They began a project where a metal and a solvent were deposited at the same time. When they co-deposited nickel with the solvent hexane, toluene, and textrahydrofuran, they managed to produce nickel powders with extremely interesting properties (Journal of the American Chemical Society, vol. 98, p1021).

Nickel powders of a tiny particle size were produced in a series of stages. Briefly, when the metal atoms and solvent molecules are co-deposited, a weak complex forms between them. Warming slightly allows the metal to dissolve, especially if the solvent is in large excess (more than 30 parts to 1). The solutions produced contain metal atoms. Warming again causes the metal atoms to coalesce to form particles, their size and shape dependeint on the solvent used. Excess solvent can be evaporated to leave a finely-divided metal powder. When hexane is used as the solvent, a black complex forms. This ultimately gives a powder which is an extremely active hydrogenation catalyst for compounds like benzene and norbornene. It has proved to be more active than Raney nickel which is presently used widely in the chemical industry. The yellow nickel-tetrahydrofuran complex forms a very finely divided powder comprised of very finely divided powder comprised tiny spheres with particle sizes of 0-5 to 1-5um, which also compares favorably to Raney nickel.

 

Books.Google.Com

 

TO FOLLOW- PART 2 – EXPERIMENTS PERFORMED USING SONICATED NICKEL…

 

 

 

  • Hank Mills

    Hello Bob,

    In at least one paper, I’ve read that the bubble produced by 20khz ultrasound is approximately 160 microns in diameter — in decane. The use of hexane should increase the power of the cavitating bubbles, because it has a lower vapor pressure. However, I’m not sure of the size bubbles that will result from using hexane. Are you proposing that the bubbles will match the wavelength of the ultrasound in hexane? If the cavitating bubbles are larger, that would be a good thing. The larger the bubble the more kinetic energy is imparted to the nickel.

    My thinking is that total hydrogen absorption is the key here. This can probably be performed in a number of ways.

    – Doping the fuel mix with reverse spillover catalysts such as copper, palladium, platinum, etc.
    – Using powder with a very high surface area.
    – Using very clean nickel totally free of oxides on the surface and gaseous contaminants on the inside.
    – Using electropositive hydrogenation promotors such as lithium or potassium rather than poisons such as chlorine (that typically make up 1% of LiAlH4).

    Performing one of the above may make up for another. For example, the high surface area of carbonyl nickel may make up for the lack of a spillover catalyst and/or oxides that remain on the surface. If you have a very high surface area, even if only a smaller percentage of the surface is clean you could still have the same hydrogen absorption.

    Since some individuals have produced very good results with nickel in the form of bars or wire with a low surface area, I don’t think having a super high surface area is critical if you still get the hydrogen into the lattice. My thinking is that 20 micron particles completely clean should have an adequate surface area if we can boost the loading high enough.

  • Well, interesting experiment. It is not clear that the motivations are all in sync. The paper cited for use of the ultrasound was about electrolytic prep of Ni nanoparticles. In such systems, the ultrasound may provide both activation energy and relief of bubbles. In their case, it reduced particle size from 50nm to 20nm. In hexane, the 28 kHz ultrasound wavelength will be about 43,000 microns. Your planned particles are large for the LENR purpose at 20 microns, but this is still 2000x smaller than the wavelength of the ultrasound. The only expected effect is to give your particles a good mechanical cleaning.

    The old gold mining addage is, “If you want to find gold, look where gold has been found before.” Most of the Ni-H experiments using Ni powder that have shown XH have used Mond process powder with 2-6 micron diameter spiky morphology particles. Rossi has historically used Vale T255. Evidence for T255 shows in the SEMs of the fuel powder in the Lugano report. My personal opinion is that purity is less important than proper high surface area morphology for the Ni particles.

    I agree that proper pre-treatment of the Ni is valuable. Exactly what the best prep comprises is still open for debate. Note that when the Ni does sinter, it sinters first into a highly porous body where connection only occurs where the particles touch and leaves a lot of the particle surface morphology intact. The heat treatment at higher temperatures (higher than 200C) in a vacuum or in inert atmosphere is probably desirable because the higher temperatures may be more useful in diffusion of the contaminants. If the Ni particles sinter, you can break the chunks apart into manageable particles with a mortar and pestle. You can also prevent some of the sintering by mixing the Ni with an inert compound such as alumina powder and then magnetically separating after heat treatment.

    Note that surface oxidation of Ni occurs readily, but the Ni oxide is weak and easily removed in-situ when H2 is present at elevated temperature (120C+). The heating in H2 and evacuation in the final reactor will readily strip the surface oxides from the Ni. You must also do this (vacuum, reduce) to remove the oxygen from the hydroxides that have formed on the LAH. Pre-treatment is not a substitute for in-situ reduction – both are probably necessary.

    • Alan Smith

      Thank you for your observations Bob. We have T255 in stock, so not a big jump. As for synching our motivations, the protocol we chose to describe is the result of reading many papers- but we really will take your comments on board and consider how to incorporate them. No point in posting a discussion paper and then refusing to discuss!

  • Simon Derricutt

    A great explanation of both what is done and the reasons for choosing that method. I hope it succeeds as planned.