Posts by kirkshanahan

    My point was that it isn't safe to extrapolate a statistical fit very far. The cubic fit gives the inflection point as you noted which I think your system isn't going to show. Therefore trying to use the cal curve at any temperature in excess of say 10% over your maximum value in the cal data set introduces a 'modeling error' of unknown magnitude. The only way to know what that is is to calibrate at higher input powers, which you unfortunately can't do due to equipment limitations. But this error means that in general one should run the experiment to keep the final temp in the calibrated range. IOW, a COP of 2 due to some 'excess heat' would mean the input should be no higher than half of your calibration range.


    I have to wonder how many people doing the Mizuno (and other) experiment(s) do that...

    @Wyt Your questions have already been answered before your post. As usual, you don't read, just like 95% of those here.


    I wrote:

    Re.: “anyrecombination reactions would persist only for a brief timescale until all theavailable oxygen is used up - certainly not over periods of days or weeks.”


    Examine Figure 6 in the Takehashi report. There are two things going on in the apparentexcess heat curve, a peaking reaction that seems to peak in about 2 hrs. andlast for ~6 hrs plus a baseline shift. Idon’t consider a 6 hr. long reaction unusual for this kind of chemistry, especiallyif you fold in calorimeter response time to make sure part of that is not justslow response. The baseline shift is apotentially separate issue involving calibration issues, electrical noise,and/or many other things. (Ask Dr.Storms about why he repeated the 10 runs I reanalyzed in my 2002 paper. I used the Feb. 2000 data, the first postedset was from January 2000.) Trying to claim a baseline shift indicatesreal excess heat is a stretch without demonstrating control over it. They haven’t done enough to do that at thistime.


    To summarize, I suspect the reduction reaction lasts a very few hours at most. I also suspect a baseline shift, whose origin is unknown.



    [email protected] as your previous post shows zirconia itself dissociated hydrogen molecules to atomic form so as I said the same energy release would occur from water formation with or without the PdNi or CuNi being present. Which makes the control valid, no?


    You are referring to the paper refs I posted I assume. Substoichiometric ZrO2 has free metal atoms exposed, thus they function like any other metal atom, so you get some dissociation. The question is: Is there enough of these sites in the zirconias used by T, et al, during calibration to register a heat signal in his calorimeter. Since they fail to acknowledge that such things can happen anyway, I doubt we can answer that question from his work. Perhaps with full data disclosure, like Ed Storms did in 2000.


    You discount the difference between having the oxidized alloys present. I do not. It is a major difference, fully capable of producing heat bursts in a few hour window, especially if the calibration is wrong. You continue to assume no calorimetric error exists (as per every other 'true believer' on this forum). My experience so far in this field is that is typically all there is.


    RB's comments are ignores as usual.


    Wyt and Dr R are unlikely to agree, so I am done here now, even if a newbie replies.

    Dr Richard wrote:


    "......the control experiment of zirconia beads alone shows no excess heat - if water is forming from recombination of H or D with oxide - sourced oxygen the same amount of energy due to this source would occur in both test and control conditions. Secondly, any recombination reactions would persist only for a brief timescale until all the available oxygen is used up - certainly not over periods of days or weeks. The progressive increase in excess power with recalcining also suggests there is an optimal configuration of nanoparticles which enhances fusion reactions, something which would not be observed if it were due to a simple exothermic chemical reaction. Then there is also a very recent Google patent on electron clusters using a very similar nanostructural setup with Thz stimulation (a fancy name for heat) which would support Takahashi's work, the theory being that electron clustering between protons lowers the Coulomb barrier and so raises the probability of fusion etc. Or maybe H* is involved too in forming quasi - neutrons which removes the barrier. Well if it's good enough for Google after their negative Nature paper then these positive results from Japan should not be rejected out of hand by being overly skeptic."


    Since you haven’t replied before I will come back to respond to you. You obviously haven’t read what I wrote. I wrote:

    “Some people may think that having a large mass of zirconia beads is good for avoiding this, but the reverse is true. Atomized hydrogen is highly diffusive and reactive. If there is an atomization source, such as metal surfaces or particles present, atomized hydrogen will be formed and diffuse to all of the zirconia in the reactor.”


    So, if an atomizing metal surface is not present (with significant physical contact to the beads), the reduction to water will likewise not happen and there will be no heat signal that can be misinterpreted.


    Note that this is the premise behind this that I wrote:

    “Your presumption is that the calorimetry is correct. Why do you presume that? They ‘calibrate’ with a significantly different system, zirconia only, vs. the experimental runs of zirconia + oxidized metal alloy. “


    Re.: “any recombination reactions would persist only for a brief timescale until all the available oxygen is used up - certainly not over periods of days or weeks.”


    Examine Figure 6 in the Takehashi report. There are two things going on in the apparent excess heat curve, a peaking reaction that seems to peak in about 2 hrs. and last for ~6 hrs plus a baseline shift. I don’t consider a 6 hr. long reaction unusual for this kind of chemistry, especially if you fold in calorimeter response time to make sure part of that is not just slow response. The baseline shift is a potentially separate issue involving calibration issues, electrical noise, and/or many other things. (Ask Dr. Storms about why he repeated the 10 runs I reanalyzed in my 2002 paper. I used the Feb. 2000 data, the first posted set was from January 2000.) Trying to claim a baseline shift indicates real excess heat is a stretch without demonstrating control over it. They haven’t done enough to do that at this time.


    “The progressive increase in excess power with recalcining also suggests there is an optimal configuration of nanoparticles which enhances fusion reactions, something which would not be observed if it were due to a simple exothermic chemical reaction.”


    Agreed, except for the word ‘fusion’. Delete it, add 'apparent', and this is correct.

    “The progressive increase in apparent excess power with recalcining also suggests there is an optimal configuration of nanoparticles which enhances reactions, something which would not be observed if it were due to a simple exothermic chemical reaction.”


    The reported observations may well indicate that a conditioning of the material occurs, which is not expected or unexpected.


    I haven’t look at the patent you reference, but I doubt it is real. Do they indicate how they exclude mundane chemical reactions and the implications that might arise from them? If not, they are ‘doing it’ as well, I.e., not investigating mundane alternatives adequately.


    “these positive results from Japan should not be rejected out of hand by being overly skeptic.”


    I don’t reject them, I attribute them to normal, everyday chemistry.

    I find I need to correct a mistake I made in my last post. I wrote:


    “As can be seen from the results in the tables presented in the paper referenced at the start of this thread, the yield decreases with each cycle and is restored by recalcining.”


    I was working from memory, always a bad thing to do, and that is not the trend displayed. However, what is actually presented is misleading. Takehashi, et, al, present tabular data for Wex (max) and also list the RTD4 max T, and as one can see the T’s are different between the first run after air oxidation and the subsequent runs. So clearly, the full curve shape needs to be considered, i.e. the integrated area and what should be compared is not the peak maximum but the peak area. IOW Tables 1 and 2 are not reliable indicators of what was going on.


    Curbina wrote:


    So, about your answer:


    I understand what you say is that the whole excess heat does not come from the hypotethic hidden well of water claimed by Ascoli, but comes from the reaction between the oxygen (that at those pressures can only come from a greatly underestimated, hidden pool that stubbornly scapes all the experimentators attempts of removing it from the experimental material), in the form of highly resistant oxydes in the powder, that once the hydrogen and/or deuterium is injected, comes out of its hiding and creates the plain ordinary heat excess, but somehow manages to get back to its hiding place in the metal as oxydes and repeat the cycle indefinitely, creating a lot of excess energy for several days.


    That is some miracolous oxygen, don't you think?

    ---


    I didn’t think Ascoli ‘invented’ a ‘hidden well of water’. I thought he computed how much water could be formed if the observed weight gain during calcining were O and covered to H2O. As I noted in the last post, that is what I am saying can happen. But perhaps I got that wrong. I entered the fray again because people here are using ridicule to deal with Ascoli’s comments, which a) is rude, and b) is useless scientifically.


    Your presumption is that the calorimetry is correct. Why do you presume that? They ‘calibrate’ with a significantly different system, zirconia only, vs. the experimental runs of zirconia + oxidized metal alloy. Haven’t you learned from my analyses of Storms’ Pt experiments and F&P’s calorimetric method that ignoring reality usually bites you? I detailed in the comment on Takehashi’s 2009 Phys. Lett. A paper (Appendix B of my whitepaper) why his results were suspect at that time, but he and his coworkers have completely ignored that and proceeded ‘as usual’. I simply expect that a careful consideration of ‘mundane’ everyday chemistry in this system will explain the observed thermal characteristics. But I admit I haven’t done that for the recent paper, nor am I likely to, until such time as the authors decide to consider all the real chemistry instead of just the parts and pieces they like. However, your use of ridicule and ignoring real chemistry doesn’t prove your points at all.


    I will be exiting the fray once more…

    Jed wrote:


    Two questions arise:


    1. After baking for 180 hours in an electric oven, in ambient air, at 450 deg, the powder is then baked in a vacuum at 450 deg C for several days. Why doesn't this remove the oxygen?


    2. When you heat the powder up to 300 deg C in hydrogen, why does the pressure gradually fall? (As described in the paper.)


    Takahashi and others have said many times they take these steps ensure there is no contamination in the powder, and that the powder will absorb gas. You are saying this method does not work. They have failed to remove the oxygen, which is known to contaminate and prevent the cold fusion reaction. So, if their method does not work, what do you recommend they do instead? (Side question: And do you really think you know more chemistry than the authors of these papers? Yes, of course you do!)

    -------


    Re: 1. Baking for 180 hrs in air at 450C reacts atmospheric oxygen with the substoiciometric ZrOx, bring it back closer to the theoretical ZrO2 composition. To decompose that oxide under vacuum will require considerably higher temperatures. However, placing hydrogen oven the material, if an atomizing substance like metal particles or surfaces is present, will allow the occurrence of a different sequence of chemical reactions involving formation of various types of surface hydroxyl moieties, which can then further react to form water. These reactions will release heat as they are spontaneous. As can be seen from the results in the tables presented in the paper referenced at the start of this thread, the yield decreases with each cycle and is restored by recalcining. This behavior is reminiscent of the systematic behavior I noted in Ed Storms Pt anode/Pt cathode experiments in my 2002 paper.


    The formed water may or may not be released from the surface depending on conditions. However at the usual reaction temperatures most of it would come off.

    Some people may think that having a large mass of zirconia beads is good for avoiding this, but the reverse is true. Atomized hydrogen is highly diffusive and reactive. If there is an atomization source, such as metal surfaces or particles present, atomized hydrogen will be formed and diffuse to all of the zirconia in the reactor.


    Curbina asked where the hydrogen comes from. The answer is from Takehasi, when he adds it. (P.S. Your sarcastic tone is an example of why I don't participate here much anymore.)


    RB cited a DFT calculation as to the energetics of the situation. In doing so he misinterprets how those results apply here. Those authors computed cases for a flat surface and nanoparticles. The flat surface calculation would be representative, insofar as it is accurate, to the bulk of the zirconia. We are not talking about fully metallizing the Zr in the ZrO2. That as shown in the calculation is extremely difficult to do in the fashion simulated. What we are talking about could be termed ‘defect ZrOx’, and it represents some unspecified low fraction of the total Zr oxide. (One could potentially calculate the amount by comparing the O2 uptake by weight gain measurements to the total mass of ZrOx, which is essentially what Ascoli did to calculate amount of water formation.) The NP (nanoparticle) results are more appropriate to compare to the defect-site ZrOx. As the Italian authors write: “on zirconia NPs, characterized by the presence of low coordinated ions [i.e., defects], water desorption becomes accessible such that even at temperatures close to 450 K [that’s 177C] the reaction becomes exergonic [i.e. gives up heat]”


    Re. 2: If one understands the mechanisms described above, the answer is most likely because a.) some hydrogen remains in the solid as hydroxyl species, and b) esp in the Pd-containing case, some hydrogen remains in the Pd, this is less applicable with the CNZ case. However, to actually come up with a definitive explanation, a lot more data is needed, especially concerning the gas phase composition and some idea of what was happening to the bulk solids.


    In the end the ‘PNZ’-type work fails to provide adequate information to understand what is going on chemically, and then attributes apparent excess heat to speculative nuclear reactions. Further, even though there are clear examples of the need to evaluate error levels quantitatively now, this is also not done.


    Re: “So, if their method does not work, what do you recommend they do instead?”


    I recommend they take all relevant factors into account in their data analysis. Given the materials they are working with there is little they can do to avoid this oxidation-reduction cycle.

    Bruce__H wrote:

    Ascoli65 has introduced a rational point regarding the interpretation of the Takahashi et al results


    Jed Rothwell replied:


    As Alan Smith pointed out, this is not rational. It is not possible to calcinate powder in for 180 hours in an electric oven, in ambient air, at 450 deg C, and still have it be "very wet."


    Bruce__H wrote:

    Entertaining a hypothesis is not lying. You guys need to grow up.


    Jed Rothwell replied:


    I would not call that a hypothesis. It is so far beyond what is possible, I have to conclude that either Ascoli did not read the paper, or he is trolling us.


    Or do you seriously think that powder that has been left in ambient air at 450 deg C for 180 hours might be wet? Do you find that plausible? Is that what you consider a viable hypothesis, worth discussing here?

    ------------------------------------------------------------------



    This demonstrates Jed’s (and Alan’s) lack of scientific background in the materials under question (as well as Takehashi, et al). Jed and Alan are partially correct in that heating ZrOx at 450C for an extended period in air will drive off water. However, it also causes full oxidation to ZrO2. Then, when the material is exposed to H2, it immediately forms surface hydroxyls, which then further react with H atoms on the surface to form water, which desorbs. Ascoli’s calculation based on weight gain is likely correct as the weight gained was obviously removable to begin with, and will be removed again, as water.


    For a full discussion of this type of chemistry, see R. Prins, “Hydrogen Spillover, Facts and Fiction”, Chemical Reviews, 112, (2012) 2714-2738. ZrOx materials are explicitly discussed.


    Also note that in my whitepaper in the Appendix I have a manuscript that was submitted to Phys. Lett. A commenting on A. Kitamura, T. Nohmi, Y. Sasaki, A. Taniike, A. Tahahaski, R. Seto, Y. Fujita, Phys. Lett. A 373 (2009) 3109, wherein I bring out this point. Specifically, I wrote:


    “A significant complicating factor with metal oxides is the observation that absorbed hydrogen can migrate onto the oxide, ZrO2 in this case, to form surface hydroxylated material, i.e. ZrO2Hx, where x in indeterminate and difficult to control, in a process typically known as spillover. Kitamura rejects this possibility but without specifying why. PdO/ZrO2 has been specifically studied in this regard and spillover noted9. “


    where ref 9 is L. F. Chen, J. A. Wang, M. A. Valenzuela, X. Bokhimi, D. R. Acosta, O. Novaro, J. Alloy and Cmpds. 417 (2006) 220


    Note that the hydrogen migrating onto the oxide is atomic in nature, and is formed by H2 absorbtion and disassociation on metal particulates/surfaces. Takehashi’s control experiments will not show this effect since he excludes any metal particulate material.

    One last post…

    To Team Google:


    Perhaps the most controlled cold fusion experiment I ever saw in my 24 years of following the field is that described by Edmund Storms in his ICCF8 presentation and reanalyzed by myself in my 2002 publication. That was a Fleischmann and Pons electrolysis cell equipped with platinum (Pt) anode and cathode. In 20 voltage sweeps from 0V up to the max reached and back down, Ed obtained apparent excess heat curves that showed a highly systematic behavior. He used a closed cell (i.e. with recombiner) and a mass flow calorimeter that captured ~98.4% of the power input. He did have to somehow get the Pt activated, as usual in F&P CF experiments, and it did deactivate, usually within 3 cycles, although there was at least one case where that went to 4, but he could reactivate the cathode by an apparent anodic strip, recovering the maximum excess heat signal on the immediately following cycle. Unfortunately, I do not know how he activated it initially. I suggest you ask him.


    Of course, the CF legend lore is that Pt is inactive, but a quick look at Ed’s results disproves this. It also disproves the idea that ‘high loading’ is required to get the FPE. Pt has never shown any hydriding activity, even at Gigapascals of pressure in diamond anvil experiments. Thus the effect is clearly a surface effect. However, in 2017 Melvin Miles communicated with me on a possible publication, and in those emails he noted that he and Fleischmann were sitting together at ICCF8 when Ed presented his work, and “immediately” knew Ed was wrong. Of course, that is just predetermining the experiments outcome and not real science. Pt definitely showed the FPE, and since the system is simpler in principle than a Pd cathode, it should be an ideal test vehicle. Talk to Ed to get details.


    Good luck.

    Yeah so, this has reached the point of diminished returns. I'm gone, I hope permanently this time. Scientists who have actual questions will know how to reach me. If any of the rest of you do, I know how to use the 'D' key. Bye.

    JR: Yes. If these claims were true, and they became generally known, Shanahan would win a Nobel prize. I am not exaggerating.


    KS: Yes you are. One doesn’t win Nobel prizes by pointing out others’ mistakes. This is pure Jedism.


    JR: I cannot imagine a professional scientist who sincerely believed he had made such an important discovery doing nothing to bring it to the attention of the wider scientific community for decades.


    KS: Jed demonstrating his lack of understanding again. Finding the systematic effect in Ed’s data was an interesting scientific discovery, but in the end will be of interest to about 3 people across the planet IMO. The rest is more Jedism.


    JR: I also cannot imagine that such fundamental laws and techniques, that have been so widely used, are wrong.


    KS: More Jed misunderstanding. The specific details of this situation (F&P-type cell electrolysis/calorimetry) are what causes the problem, not the basic method itself. Although it is true that one of the earliest criticisms (not mine!) of F&P’s work was the use of single-point temp measurement. That can be afflicted with hot or cold spot problems. That in turn is fixed by using more thermocouples (or whatever), up to the level of a fully-integrating calorimeter like the good Seebeck and mass flow ones used by Storms and McK for example. However, that just reduces the magnitude of the problem, it doesn’t fully remove it. And thus the need to quantitatively evaluate things. In Ed’s 98.4% calorimeter, the error is on the order of a watt. Ed thought it was on the order of 80 mW.


    JR: When someone claims he has found a problem with "practically every known analytical chemistry method," that sounds to me like an out-of-control ego, or an Einstein wannabe.


    KS: That would sound that way because you refuse to understand what I am saying. 99.998+% of analytical methods (all types) use calibration. That means an equation to convert the measured quantity for the inherent inaccuracy of the technique, whatever that may be. Get the coefficients of the equation wrong, your computed answer is wrong. It’s as simple and as understandable, by those who want to, as that.


    JR: One of these people who thinks Relativity is wrong and he alone knows the answer.


    KS: Jedism. Or maybe he thinks he’s psychic.


    JR: I think the chances that there is a measurable, significant problem with "every known analytical chemistry method" is astronomically small.


    KS: This is an example of Jed’s use of misdirection. Taken by itself, his statement is correct. However, his use of it is to imply in the case of F&P calorimetry, there also is no problem. But the fact is that for any method, one has to prove that by quantitatively evaluating error.


    JR: Of course there are problems. As you go to finer and finer measurements, and more decimal places, you will find more complex laws of physics apply, until you get to something like quantum theory (I suppose).


    KS: Amusing. Jed almost has it right, but not really. All ‘laws of physics’ apply all the time. The problem is in what proportion. One determines that by quantitative error evaluation. And yes, the Heisenberg Uncertainty Principle limits how small you can go. But the experiment that is limited by that is rare, almost to the point of non-existence. Most are well above that limit, where deterministic thinking is still useful. (deterministic thinking == quantitative error evaluation)


    JR: The general laws in a chemistry textbook are nearly all approximations that do not take into account every known aspect of physics.


    KS: Exactly, which is why you have to evaluate your error to see if you need to add in more terms or tweak them up, as in the case of F&P calorimetry where there are no terms in the energy balance equation for entrainment and evaporation. Which is why Szpak, et al, in their 2004 paper that I commented on in 2005, find an excess of water exiting the cell.

    but the preference of it instead of continuing pursuing the anomaly to see if it exists or not.


    I don't recall Byrnes saying anything about not pursuing something. Got a quote on that?


    I think the whole point is that when you have a mundane explanation of an anomaly, it is bad science to ignore and/or denigrate that explanation without serious, rational, and reasonable consideration. That has not happened at all regarding (a) CCS/ATER, (b) contaminant concentration, and (c) mechanical damage as the source of CR39 pits (with possibly more that can be added to the list).

    Well, I spent some minutes reading and my impression is that the confusion with hot fusion as Stormshas pointed out, reigns.


    Considering I read the whole thing and didn't see any confusion at all leads me to believe you read with pre-determined conclusions in mind. How about some examples of this 'confusion'?


    Every scientist or engineer doing research has to analyze the experimental design thoroughly for potential sources of error and either weed out or control them. This is basic of experimental design. No surprises there and no one would disagree.


    But blanket dismissing the whole body of LENR research because of a perceived “rational explanation” is preferred as plausible (but not demonstrated), is a show of bias.


    So we agree on error analysis and control. So why do you think LENR researchers never document any of this, especially after they have been repeatedly challenged on this issue?


    I don't think Byrnes 'dismisses' LENR research. He just does the normal thing, and opts for conventional wisdom regarding anomalies, especially given there are viable mundane explanation of such (even though you detest them).

    Actually, that particular experiment has been done many times,


    Actually it has not. Your understanding of what I suggest is, as usual, incorrect. In fact, I pointed out in my first paper that Ed got differences in calibration constants when he calibrated with the joule heater vs. when he calibrated with electrolysis. However, both cases used an inactive electrode, so the variance was about what you'd expect for the residual noise after removing the systematic effect I described. But, no one has ever tried less than 100% recombination at the recombination catalyst, probably because (a) they didn't think it would be a problem, and (b) it would be extremely difficult if not impossible to experimentally do that (any setup that potentially could do that would probably be so far from the original as to be worthless). So no, no one has ever tested my thesis.