ENERGY SCIENCE ESSAY NO. 5: CONTINUATION
‘WARM SUPERCONDUCTIVITY'(CONTINUATION)
Copyright, Harold Aspden, 1997
THE PEROVSKITE COMPOSITION
It is noted that some of the substances listed in TABLE II are of perovskite composition and that it is of record in the science literature (Jonker and Van Staten, Physica, v. 16, pp. 337 and 599, 1950) that compounds of the form (La1-xAx)MnO3 have a perovskite composition centred around the lanthanum atom or its substitute denoted by the symbol A, which here represents calcium, strontium or barium. It was reported that this substance had good electrical conductivity for values of x between 0.2 and 0.4 and that in this range the substances were also ferromagnetic.
Note that the manganese atoms form a simple cubic structure and that Mn stands next to Fe, Ni and Co in the periodic table of elements. The latter are ferromagnetic.
What is of interest here is that this particular substance comes close in composition to the first amongst the list of 11 in TABLE II above. Important also is the fact that manganese has a 100% abundant isotopic form of atomic mass number 55.
The compounds covered by this generic formula can be made up in what, hopefully, might be very close to a homogeneous mass-distributed system. This is provided calcium is selected as the substitute variable. Calcium 40 is a 97% dominant isotopic form, which means that a fairly definite mass value applies whether the particular atom has the calcium or lanthanum composition. For the lanthanum-centred structure the unit mass number is 242 and for calcium-centred structure it is 143. Assuming that the aim is to have a molecular grouping which is a multiple of 102, one needs to imagine the molecules responding in clusters of 5. Thus 5 calcium centred molecules has a total mass of 715 units which is 7 times 102.14. In fact, since the calcium and the manganese isotopes have actual masses slightly below the integer values, the combination of 5 such molecules gives a result even closer to the 102 norm.
The latter condition takes the substance outside the bounds of the 40% A-component of the generic formula specified by Jonker and Van Staten and one is therefore left to wonder whether the simple calcium trioxymanganate would be a conductor. Since the 0% A-component version lanthanum trioxymanganate is included in the above reference list of 39 but is stated only to be a semiconductor, one must, however, assume that the 20% to 40% range specified is a constraining condition.
It is possibly of significance that a cluster of 5 molecules is needed to establish the dynamic matching under discussion. Given such a cluster one can see how one or two molecules in the 5 can have the calcium-centred form. The different cluster versions have, respectively, masses that are 11 units of 101 and 10 units of 101.2. This might suggest that, in spreading its action over several molecules, the supergraviton has an effective mass value that is closer to 101 atomic units than to 102 such units.
WARM SUPERCONDUCTIVITY
In proceeding from this point, the reader should take note of the fact that the evidence discussed above all dates from data of record before 1984, which is before the Nobel prizewinning breakthrough on ‘warm superconductivity’ was reported. This is a reference to the discovery of perovskite properties of superconductivity at temperatures exceeding that of liquid nitrogen.
There were several compositions that then became the centre of interest, one of which is amongst the above list of 11. This is La2CuO4 which has a molecular weight of 405.35 units on the C-12 scale. Note that this is very nearly 4 times 101. Another high Tc superconductor reported was Sr2CuO4 which has a molecular weight of 302.78 which is very nearly 3 times 101. Note that one gives a value marginally above 101 and the other a value marginally below 101 and that the discrepancy is a very small fraction of one per cent in each case.
This again urges one to the conclusion that there is something special about the quantum of 101 mass units and that, for these molecular clusters involving many atoms, we mean 101 and not 100 or 102.
As an aside here, however, one must conjure a picture of a group of atoms forming molecules which, in turn, form groups or clusters which tend to have their own dedicated supergraviton system, with the supergraviton form jumping around to spread its favours amongst all the group components in acting as a dynamic balancing agent. Perhaps, if the supergravitons have only to range over a few atoms in a metal crystal (as for the U238 situation), their effective mass is higher at the 102 value. If they have to share their effects in ranging over 7 atoms, as in the two superconductor substances just mentioned, or 25 atoms, as in the manganese perovskite, then some of their reacting capacity is wasted in a component of disordered motion in migrating over the necessary range. They would then lose some effectiveness and this could be why the 101 value comes into evidence in these substances.
EVEN MORE EMPIRICAL DATA
The reader may think that the emphasis being placed on the optimum mass number of 102 is just a ‘play on numbers’ that has no physical meaning. It is tempting to suggest that if what I am saying is true one should be able to contrive the artificial creation of molecules from isotopes which fit the mass match condition and thereby produce new superconductors. Hopefully this could take us into the realm of the warm superconductor at ambient temperatures.
Well, the author here admits that the idea did present itself so strongly that patent protection was sought for this very proposition, though the U.S. Patent Examiner was not amenable to the granting of a patent in the absence of a proven and demonstrable showing of the working invention. The U.K. Patent Office was more obliging and GB Patent No. 2,210,870 dating from an application filed on October 12, 1987 was duly granted on this subject.
In the event, however, the author later came to realize that the workers in this new and specialist field tend to be intent on developing their own ideas. They do not listen to theories offered by intruders. In the absence of demonstrable proof of a working invention, the commercial value of the patent, which was a mere speculative venture, is therefore minimal. Also, it was only after that patent was granted, that the research by Jonker and Van Santen at the Philips Eindhoven-Netherlands Laboratories reported above and dating from as long ago as 1950 came to the author’s attention. As explained above, it concerns perovskites having compositions which could be deemed relevant to the territory covered by the author’s patent. On the other hand, that 1950 research presumably did not probe the high conductivity phenomenon discovery with superconductivity and the magical 102 atomic mass number in mind. An extension of that research on manganese compounds could well be warranted.
To add just a little to show that we are not here talking about mere numbers, but rather something physical, it is interesting to consider how the properties of a superconductor can be affected by very slight adjustment of the molecular mass. The way this can be done experimentally is to consider metals which form hydrides by absorbing hydrogen or deuterium.
An extensive review of research on this very subject appeared in 1978 in a report by Stritzker and Wuhl [Sadly, in the lapse of time, some five years, between writing this text in a draft form and preparing it for these Web pages, I have lost the specific reference data.]. On page 246 et seq of the referenced text they explain how for some substances the addition of H or D causes the critical superconductor temperature to increase whereas for other substances the addition causes a critical temperature decrease.
The standard argument adopted to explain these effects is that impurities can influence superconductivity, but that really is a vague design criterion if one seeks to fabricate the perfect superconductor.
The data discussed includes mention of the effect of adding H to niobium alloys. These were chosen because Nb was the superconducting element with the highest Tc value of 9.2 K. The alloys investigated were Nb-Pd, Nb-Pd-Mo, Nb-Pd-W and Nb-Ru.
Now, before we consider the findings, note the atomic weights involved. These are Nb=92.91, Pd=106.4, Mo=95.94, W=183.85 and Ru=101.07.
Taking a pairing of an atom of Nb and Pd the combined mass number is 199.31, very slightly below twice the value we said was optimum. Therefore, if we add one or two atoms of H or D we should bring the relevant mass quantity closer to the optimum dynamic condition and should increase Tc.
Taking Nb-Pd-Mo we can see also that the Pd and Mo atoms might pair together to give a mass number of 202.34. Simply add two H or one D atom to this pair to form what is effectively a hydride molecule and the optimum match at twice 102 is expected for these components of the alloy. Tc should be increased for this alloy when absorbing hydrogen.
Taking Nb-Pd-W much depends upon the amount of Pd in the alloy but if W were to combine with two Pd atoms to give a combined mass number of 396.65 we would again need to add just a few hydrogen atoms to bring this closer to being a multiple of the 101 or 102 quantity which our analysis says should increase Tc.
Finally, Nb-Ru is interesting because we know that Nb as a non-alloyed element has the Tc value of 9.2 K. If we add one atom of Ru of mass number 101.07 plus one hydrogen atom as well, we are adding the optimum 102 mass value. The value of Tc must therefore increase.
For these reasons, all four alloys should show improved superconductor performance when hydrogen is added. In the event, quoting the source text:
Nb based alloys were chosen because Nb is the superconductive element with the highest Tc (9.2 K) and dissolves large amounts of H. The transition temperatures of the alloys investigated varied between 0.4 and 3 K. A remarkable Tc increase of about 2 to 4 K is observed in these alloys after addition of H.
If the reader thinks that this comes about merely from the addition of hydrogen and has nothing to do with the 102 mass resonance, then let the following further evidence from the Stritzker and Wuhl review come under consideration.
They refer to the alloy HfV2 which has a Tc value of 9.7 K and point out that when the composition became HfV2H the value of Tc dropped to 4.9 K, but further, when deuterium was added instead of hydrogen to bring the composition to HfV2D the value of Tc became 2.8 K.
Now, looking solely at the pair formed by the two vanadium atoms, which incidentally has a 99.76% isotope of mass number 51, these have a combined mass number of 102, which is the value we are prescribing for near resonance and good superconductivity. If we now add a single H atom, the mass value moves away from optimum and so Tc should decrease. If, instead, we add a single D atom, then Tc should decrease even further. This is exactly what is reported.
Quite clearly, we are not dealing here with something that is merely fortuitous ‘number play’.
To confirm what is said even further, consider the simple metal elements vanadium, niobium and tantalum and add hydrogen. The reported review notes that vanadium has a Tc value of 5.3 K. As just observed above we recognize that two V atoms have a combined mass number 102. Similarly Nb has a Tc value of 9.2 K and 11 Nb atoms have a combined mass number of 10x(102.20). Tantalum has a 99.99% isotopic form of mass number 181 and 5 Ta atoms therefore have a combined mass number of 9x(100.56). Its Tc value is rather lower at 4.4 K.
Now read further from the quoted review article:
Satterwaite and Peterson searched in vain for superconductivity above 1.2 K in the compounds VH2, NbH2 and TaH.
Evidently the added hydrogen took the first two metal hydrides off their resonant mass values, but in the case of tantalum, here, admittedly, we do see a departure from the theme we are advancing. Is it speculation, however, to wonder whether the dynamic resonance adapts to a larger cluster of atoms if there is a closer fit to the 102 condition for a somewhat larger grouping? Thus, for tantalum, it is noted that the 181 mass number really corresponds to 180.948 atomic mass units and 13 such units combine as a mass of 23x(102.27). In this circumstance it becomes understandable why the addition of hydrogen does reduce the Tc value of TaH so markedly.
Following this theme one can now examine the corresponding effect of varying the composition of a warm superconductor perovskite by addition of oxygen.
F. Devaux, A. Manthiram and J. B. Goodenough (Physical Review B, 41, 8723-8732 [1990] have presented data showing the progressive increase of Tc from zero to near 100K as x changes from 0.4 to 1.0 in YBa2Cu3O6+x and the progressive decrease of Tc from near 100K to zero as y changes from 0.1 to 0.4 in Nd1+yBa2-yCu3O6+x, where x=0.94+0.5y.
These two results provide a way of testing the ‘102-theory’ and determining its the optimum resonance mass and the width of the resonance.
For the Y-based composition we find that with Y=88.90, Ba=137.34, Cu=63.54 and O=16.00, the molecular unit has a mass number 650.2+16x. Therefore we expect two such molecules to define a resonant group, making the mass 1300.4+32x units dynamically reacting with 13 supergravitons.
The authors state that the value of Tc is at a plateau maximum when x is between 0.90 and 0.98, which implies a supergraviton mass having a value between 102.246 and 102.443. When x is 0.4 Tc is zero so a lower limit on the graviton mass is 101.015, which is a little just over 1% below the resonant condition.
For the Nd-based composition, we see that Nd=144.24 replaces Y=88.9, meaning that, when y=0, which is when x=0.94, we have an extra mass quantity of 55.34 to add to the 650.2+16x value above. In this case the result of 720.58 represents a molecule which stands alone as a resonant unit interacting with 7 supergravitons. With y=0 to y=0.1, the value of Tc is at its plateau and this corresponds to a superconductivity induced by partial resonance at a supergraviton value between 102.94 and 102.89, which seems high from our foregoing analysis. However, as y in increases to 0.4, taking x up to 0.96, this adds 0.32 in oxygen mass and 2.76 in Nd-Ba mass to the y = 0 value, making the loss of superconductivity occur for a system of mass 7(103.38), which is 723.66. The mass quantity of 103.38 fixes an upper limit on the bounds of the supergraviton resonance.
From this one can see that the evidence points to a resonant effect centred on a supergraviton state having 102.3 atomic mass
units, with 1% either way, for the small molecular cluster being enough to destroy resonance and so the superconductive state.
Note that it was suggested earlier that if many individual atomic structures were sharing in the group reaction, the effective mass value could be effectively reduced to 101. However, where one or two molecules constitute a dynamically reacting group, the supergraviton value of about 102 is governing. Where three individual atoms, as with U238, form a group, the 102 value holds.
It is submitted that very strong evidence has been presented to show that something special affecting superconductivity centres on a mass quantum of 102 atomic mass units.
A full explanation of how this can be justified in terms of physical theory is, as already mentioned, of reference elsewhere [1989a].
However, to end this empirical account of the 102 phenomenon, let us just bring the endeavour up to date by noting that the author is writing this text in July 1992 and referring to the review given in the July 1992 issue of Physics World. On page 37 under the title ‘Superconductors’ Ken-Ichi Sato describes a substance identified as 2223-BSCCO which has a Tc value of 110 K and a composition (Bi,Pb)2Sr2Ca2Cu3O10.
Inevitably, the author applies the ‘102 test’ to find the following:-
Pb:207.19 2xPb:414.38 Bi:208.98 2xBi:417.96 Sr: 87.62 2xSr:175.24 2xSr:175.24 Ca: 40.08 2xCa: 80.16 2xCa: 80.16 Cu: 63.54 3xCu:190.62 3xCu:190.62 O: 16.00 10xO:160.00 10xO:160.00 (SUM): 1020.40 1023.98
Quite clearly, there are 10 dynamic reacting supergraviton mass quanta involved but a single molecular compsition, and, depending upon the relative composition content of lead and bismuth the mass quantum indicated ranges from 102.04 atomic mass units to 102.39 atomic mass units.
Compare this with the findings deduced above from the 1978 review of superconductive hydride compositions.
CONCLUSIONS
What has been attempted in this Essay is an explanation of the phenomenon of superconductivity in a way which leads us to a reacting mass quantum in the vacuum field. It would be foolish to ignore the very strong evidence which the above empirical argument provides. There is a strong case for suspecting that the supergraviton, which is the name we assign to the reacting mass quantum, has a mass value of the order of 102 atomic mass units, which might in some cases reduce to 101 units in certain large molecular systems.
More important, from an energy science viewpoint, is the guidance which the above research should offer in helping researchers to find superconductive substances which have even higher critical temperatures. Such research should focus on the need for that homogeneity of mass distribution which can interact efficiently with that supergraviton mass quantum.
The chemistry of warm superconductivity can, it seems, help to tell us something about the reaction properties of the vacuum field, which is the primary topic of the author’s work.
Nothing has been said about the BCS theory of superconductivity but that is understandable, having regard to the fact that the author’s theoretical objective has been to connect this remarkable phenomenon with the quantum features of gravitation. It is the author’s thesis that the ability of electricity to flow as current, meaning transported electrical charge, by travelling through material substances without apparently encountering resistance depends simply upon a dynamic balance and reaction processes inherent to the vacuum field. This is the realm which governs not only the action of gravitation (hence our choice of the name ‘graviton’ above) but the quantum of action we know as Planck’s constant, which is a universal regulator sourced in the vacuum field.
From an energy science point of view the graviton is a catalyst which assists in the thermodynamic actions between a flow of electrons and the quasi-rigid crystalline structure, not only of matter but also that of the aether. Superconductivity is a clear manifestation of the ability of the vacuum medium to assert action which causes a reversal of the degenerative process we associate with the second law of thermodynamics.
FOOTNOTE
Warm superconductivity was a topic that hit the media headlines in 1987. At that time superconductivity was, so far as this author was concerned, a low temperature phenomenon with little future except as applied to the magnetizing coils of powerful electromagnets. One application which had, however, been a subject of some personal attention was the possibility of building superconductive field windings into the alternators used in association with turbine prime movers to generate electrical power. To operate such machines with their innermost core system cooled to liquid helium or liquid hydrogen temperatures has its problems.
The author had, by association with co-inventor Frank Mumford of Southampton University in England, before he joined GEC’s Engineering Research Centre at Stafford, contributed to the idea of a new form of electrical generator which has its main field windings on the stator structure. This became the subject of granted U.K. Patent No. 2,183,102. The need to convey current across brushgear and sliprings to feed a powerful magnetic field set up by a superconductive circuit was thereby avoided. The patent application was filed before the news of the breakthrough discovery of perovskites which are superconductive at liquid nitrogen temperature 77K. This was seen as a step which could benefit the ‘Inside-out’ design of the machine we had patented. It had special promise, because whereas the new superconductors were of a brittle composition in comparison with metals and alloys, this weakness as a design property is less important for applications in a stator structure compared with use in a high speed rotor.
A curious circumstance was drawn to the author’s attention at the time ‘warm superconductivity’ was ‘hot news’. This was in respect of a substance that was said to be superconductive at room temperature and had led to the grant of a U.S. Patent. (Again, sadly, the author has misplaced the reference data and so cannot quote it in these Web pages.) This described the invention as comprising a series of very thin bismuth filaments embedded in a matrix composition.
Bismuth has an atomic mass number of 209 and so it is not a good candidate for the multiple-of-102 classification explored above. One may, however, wonder whether something akin to the molecular mass number effect in the perovskites could develop by surface oxidation along these bismuth filaments. For example, bismuth oxide Bi2O3 has an molecular atomic mass number of 466 and two such molecules form a group that is slightly greater than 9 times 102. The difference is too great to meet the criteria suggested above, but maybe the constraints enforced by the filamentary path feature can relax the criteria just a little. Also, one should keep in mind that what a physicist regards as ‘superconductive’ need not necessarily be essential in fabricating some types of electrical power equipment. If loss is the primary criterion, the a superconductor having sporadic but short-lived interludes of normal conductivity can still have scope for commercial application.
When one considers electrical conductivity in very thin films or wires, where the thickness is less than the mean free path of the charge carriers, it could well be that a very substantial enhancement occurs over the bulk conductivity. Perhaps the constraint of guiding the electron motion to be in-line with the flow path so far as possible, with less chance of random divergence by collision, can regiment the energy exchanges so that ohmic losses actually fall below the cooling effect resulting from collisions which cause the slowing down of the counter moving opposite-polarity ionic lattice structure.
If the claim to have achieved room temperature superconductivity in bismuth filaments is unwarranted, then our speculation here on that topic serves little purpose. However, as already stated, one needs to be cautious about what is meant by ‘superconductivity’. It has come to mean zero resistivity, but from a technological viewpoint a very substantial reduction of resistivity well below that of a normal metal for the same temperature may well suffice as a ‘superconductive’ condition.
According to ‘Superconductor Week’ Vol. 6, No. 26 for August 24, 1992, there is now a school of thought which argues that there are ‘radical differences’ when comparing certain characteristics of high Tc and low Tc compounds. The alternative argument is that both are similar and that the phenomena are explicable in terms of conventional BCS pairing via electron-phonon interaction and a special Fermi surface feature called the “van Hove singularity (vHs)”. However, the developing opinion is that one needs to pay attention to the fact that a magnetic field applied to a high Tc superconductor develops a gradual electron-pairing because of the strong thermal fluctuations. For a low Tc superconductor excess magnetic field leads to an abrupt step function in the resistivity transition.
This suggests that there is still much to learn about the effects of a magnetic field upon electrical current flow through conductors and the thermodynamic interactions associated with those effects, particularly in thin films and filaments. Hopefully, the vast amount of effort going into research on superconductivity research will bring its reward, but a different aspect of electrical conductivity began to capture this author’s attention early in 1988.
The author’s research had been attentive to experimental anomalies in electrodynamics and the underlying theory where current is carried not just by electrons, but also by heavy ions, as in plasma discharges using cold cathodes. The current breaks up into filaments when such discharges reach certain critical levels of current. The author had long thought that here was a process where the discharge involved avalanche process of an in-line organized filamentary flow of charge carriers, one behind the other, in short transitory bursts. Transiently, this means that current flows without collision and so without loss, for those momentary periods before the filament collapses and a new one is regenerated to sustain the discharge.
The latter was deemed by this author to occur also in bulk metal, and the only pointers, it seemed, to such a phenomenon were the implications to be drawn from certain electrodynamic force anomalies in the cold cathode arc discharges, a phenomenon which had ceased to command interest in mainstream physics.
This situation, so far as this author was concerned, changed in a dramatic way in 1988, when it came to attention that something unusual could happen to the thermoelectric EMF generated by the Seebeck Effect in a thermocouple subjected to a magnetic field. Tests to verify this were performed by John Scott Strachan, a research scientist in Edinburgh, Scotland and it was realized that this could imply that oscillations were occurring in the current flow across the bimetallic junctions. Here was a clue to that suspected filamentary surge process in current conduction through metals.
The consequence of this was a first meeting between the author and Strachan on the occasion of a conference held in Canada in July 1988. Peripheral to that event, and before leaving Canada to return home, a plan for building a test device for converting heat into energy, incorporating a magnetic and thermoelectric structure, was agreed.
This venture promises the means for the conversion of heat to electrical energy and vice versa at a level of efficiency which surpasses prior art techniques by an enormous margin of performance.
That project can be linked in a way with the subject of this Essay by reference to the filamentary flow of electrons through ‘superconductive’ channels. One has only to consider a concentrated flow of filamentary current across a Peltier cooled junction interface between two metals. It is then realized that cooling at a spot in the junction interface will enhance the conductivity and possibly cause the regenerated current filaments to take the path of least resistance, always through that same spot. The result is that the conventional thermocouple chokes itself by reducing the effective temperature at the Peltier cooled interface to a value far below that of the external heat input. The spot temperature falls and could go down to the superconductity threshold Tc, were it not for the fact that the Peltier current flow would cease if the temperature fell to that of the Peltier heated junction interface. This action devastates the efficiency of the conventional bimetallic thermocouple.
Since the above Essay was written, in 1992, that thermoelectric project ran into problems, owing to what this author now regards as a progressive magnetic saturation of the device in a curious manner connected with the start-up and switch-off heat cycle arising from repeated demonstrations. In 1997 the topic became the subject of Energy Science Report No. 3 of record in these Web pages.
