international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

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journal homepage: www.elsevier.com/locate/he

The role of superabundant vacancy delta to delta

prime transformation in stopping Fleischmann-
Pons heat effect in palladium-deuterium

M.R. Staker a,b,*

a
Department of Engineering, Loyola University Maryland, 4501 North Charles St, Baltimore, MD, 21210, USA
b
American Patent Institute, 2817 Wesleyan Drive, Churchville, MD, 21028, USA

highlights graphical abstract

The revised phase diagram of the

Palladium - Deuterium system is
employed.

Delta phase of the Super Abundant
Vacancy phases (SAV) is key.

Phase transformation stops excess
heat in a Low Energy Nuclear
Reaction.

Measurement of delta to delta
prime phase transition is made by
calorimetry.

A quench heat treatment initiates
delta to delta prime phase
transition.

article info abstract

Article history: A calorimeter, designed for electrolysis of Pd in heavy water, capable of measuring heat
Received 15 November 2022 and power output with a precision of ± 0.5%, was used to determine changes in output
Received in revised form during a compulsory quick-drop in temperature. The change in temperature was forced on
24 December 2022 the electrolysis cell while it was producing nuclear energy at excess power levels of 240 W/
Accepted 1 January 2023 cm3 and after producing a continuous excess heat amount of 150 MJ/cm3 (14 000 eV/atom
Available online xxx of Pd). The temperature change (from 82.5  C to ~0  C) resulted in a total loss of excess
power (nuclear power) and indicates the regions of the microstructure that were ordered
Keywords: superabundant vacancy (SAV) phase transformed from d to the ordered superabundant
Cold fusion vacancy phase d0 . The d phase is responsible for producing excess heat and power while the
Low energy nuclear reactions (LENR) d0 phase produces no excess heat or power. Deuterium in the d phase occupies the octa-
Fleischmann-pons heat effect hedral sites but occupies the tetrahedral sites in the d0 phase. In either case, d and d0 are
Nuclear active environment (NAE) minor phases with volume fractions in the two-phase microstructure of approximately

* Corresponding author.
E-mail address: [email protected].
https://doi.org/10.1016/j.ijhydene.2023.01.001
0360-3199/© 2023 The Author(s). Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC. This is an open access article under the CC BY-NC-
ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article as: Staker MR, The role of superabundant vacancy delta to delta prime transformation in stopping Fleischmann-
Pons heat effect in palladium-deuterium, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.01.001
2 international journal of hydrogen energy xxx (xxxx) xxx

Palladium-deuterium phase 0.03 and 5.0 percent for d and d0 , respectively. This evidence of termination of excess power
diagram supports previous indications in the literature of such a transformation.
Phase transition controls nuclear © 2023 The Author(s). Published by Elsevier Ltd on behalf of Hydrogen Energy Publications
energy LLC. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

octahedral to tetrahedral sites (or vice versa) while the or-

Introduction dered SC shell remains otherwise essentially unchained
except for the increased negative charge on the VAC [12] (see
Both delta and delta prime (d and d0 ) phases in palladium (Pd) next section).
deuteride (D) are ordered superabundant vacancy (SAV) pha- Pitt and Gray [39] and Ferguson et al. [40] have measured
ses with compositions and structures of Pd3Vac1Dx [1e16] the hydrogen (or deuterium) in Pd-D (or PdeH) in octahedral
where x is 4e8, depending on the D activity. This structure, sites near room temperature, with a shift to tetrahedral sites
originally face centered cubic (FCC), becomes simple cubic (SC) at lower temperature. It has been suggested [12e15] that
with the introduction of ample D or hydrogen (H) and an active excess heat (more heat produced than is put in by electrolysis)
source of vacancies (VAC). In this ordered state, VAC occupy during Low Energy Nuclear Reactions (LENR), or Lattice
the eight corners while Pd occupies the six face-centered po- Assisted Nuclear Reactions (LANR), in Pd-D occurs when
sitions of the original FCC unit cell [13]. Delta and delta prime deuterium occupies octahedral interstitial sites (d) rather than
phases result from hydrogen-induced vacancy formation tetrahedral sites (d0 ). Further, changes in resistivity [13,14]
[1,4a,15-36] at high temperature and pressure or at ambient strongly suggested spontaneous transformations of some
conditions: it has been proposed that VAC are produced dur- d phase to d' (or new d0 formation) during excess heat. Since the
ing room temperature electrolysis by a dislocation mecha- proposed new phase diagram for Pd-D (shown in Fig. 1) shows
nism involving dragging edge jogs connected between screw d phase is present near room temperature and higher, while
dislocations, followed by VAC relocation (attracted to Dþ d0 phase is present at lower temperatures, it is instructive to
during electromigration) to the corners of the original FCC unit see if the production of excess (nuclear) power and heat (or
cell [13]. These SAV unit cells are only possible because of the termination thereof) would correlate to this transition in
long range order that develops when the atom fraction of VAC temperature (lowering) and the accompanying phase change.
becomes about 33% with a reduction in free energy due to long Much has be learned about the conditions necessary to start
range order. VAC distributed at random unit cell positions [15] the Fleischmann-Pons heat effect in Pd-D (i.e. LENR or
(including both corners and face-centered) have higher free LANR), but more can also be learned about the mechanism
energy than when the VAC become ordered (occupying only from implementing conditions to stop the Fleischmann-Pons
the unit cell corner positions). SAV d or d0 would not be heat effect.
possible if there was no long range order, even if the atomic
fraction were 33%. Screw dislocation intersections during
plastic deformation form these edge jogs, and strings of VAC Materials and experimental methods
are created in the wake of these moving edge jogs because
their Burgers vectors are perpendicular to motion [13,15,36- Complete experimental details of the calorimeter are in
38a]. Thus, plastic deformation is essential in creating SAV Ref. [13], however Pd/D2O (active) and Pt/H2O (control) elec-
phases at room temperature and is provided by using cold trolytic cells, for electrolysis of Pd in heavy water with 0.5 M
worked Pd and enhanced further initially (at the start of LiOD are shown in Fig. 2. The present research uses the same
electrolysis) by multiple loadings and unloadings of D by methods and materials of previous papers [13e15] including
reversing electrolysis polarity multiple times, causing multi- calibrations before and after the experiment. In these prior
ple trips through the alpha (a) plus beta (b) miscibility gap and publications [13e15], it was shown that excess power (nuclear)
the associated plastic deformation [13]. This mechanism persisted continuously for 46 days at levels from 20 to 240
provides for the formation of SAV phases near room temper- Watts/cm3 and these power levels integrated to excess heat
ature in spite of VAC diffusion being too slow. Each stint of amounting to 150 MJ/cm3 (14 000 eV/atom of Pd). After the
unloading and reloading D preserves most of the previously electrolysis was run for 46 days, the excess power was at a level
created VAC, allowing the VAC concentration to ratchet up of 240 Watts/cm3 and a temperature of 82.5  C. The calorimeter
with each trip through the miscibility gap [15]. A quantitative box was quickly opened, and a pre-prepared 8 L bucket of ice-
estimate [14] of the volume fraction of VAC needed for d phase water mixture at approximately 0  C was placed under the Pd/
(or even d0 ) by this mechanism, shows diffusion of vacancies D2O cell and quickly raised, surrounding and immersing the
from the surface or from grain boundaries is not required in cell to just below the Teflon stops. The monitored (measured)
order to form these phases at room temperature (Appendix B temperature in the cell quickly approached 0  C. After thermal
of Ref. [13]). In addition, Fukai [4a] reveals that: “this structure equilibrium was achieved (just above 0  C), the bucket was held
[M3VacH4], once formed under high pH, T [pressure, temper- in place for a further 15 min; then the bucket was removed and
ature] conditions, remains stable after recovery to ambient the continually operating cell was allowed to return to its
conditions.” Here M is a variety of metals [13]. The subject of operating temperature prior to emersion. This, however, was
this research is the shifting of H or D in M3VacD4 from not the same temperature of 82.5  C (with excess power), but

Please cite this article as: Staker MR, The role of superabundant vacancy delta to delta prime transformation in stopping Fleischmann-
Pons heat effect in palladium-deuterium, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.01.001
 international journal of hydrogen energy xxx (xxxx) xxx 3

Fig. 1 e Equilibrium Phase Diagram for Hydrogen e Palladium [13e15] with SAV delta phase from 1.14 to >1.4 D/Pd ratio. In
the two-phase field (g þ d), the D/Pd ratio ranges from 1.14 to 1.24. Delta and Delta prime are stoichiometric at 1.33, but
range from 1.24 to 1.42 (d) or 2.66 (d′).

rather the calibrated temperature without excess power for that previously assessed [14] volume fractions of 0.03 and 5.0
input power level. Then a calibration check was run, confirm- percent for d and d0 , respectively. It is suggested that this heat
ing that the cell had returned to its calibration level of input treatment results in a shift of the deuterons from the octa-
power and delta temperature, DT (difference between cell hedral sites to the tetrahedral sites, corresponding to the d to
interior and surrounding air temperature inside the box of the d0 phase transformation (Figs. 1 and 3), supportive of a pre-
calorimeter). The cell temperature and input powers were diction [14] from the literature:
monitored for another 30 days.
“It has been understood that d phase, with interstitial oc-
cupancy at octahedral sites, is more probable than d0 phase
Results and discussion with interstitial occupancy at tetrahedral sites near room
temperature. This is possibly true for the lower D/Pd ratios
During the 30 days after emersion (quench), the monitored (rx). However at high rx, this research [14], along with other
cell did not produce any further excess power or heat. It research [29,32,34,39e41], suggests the reverse (tetrahedral
stayed on the calibration curve of delta temperature (DT), more likely) since the volume fraction of d0 (5.0%) is much
absent excess power, vs input power. This can be seen from higher than the volume fraction of d (.03%). Isaeva et al. [29]
Table 1. This also verified that there was no shift in the cali- has indicated the phase change to tetrahedral site occu-
bration of the cell during the 76 days of operation. pancy is a change with more order than that of octahedral
These results reveal that a sudden forced lowering of the site occupancy: tetrahedral site is favored by having more
temperature of the Pd-D cathode by about 82  C stopped order.”
excess power and heat (nuclear power and heat), even though
it was still under electrolysis and still loaded with high In this shift, the distance from the center of the deuteron to
fugacity D. Resistivity measurements, using the same meth- the center of the VAC changes from ao/2 (in d) to ao$√3/4 (i.e.
odology previously reported in prior papers [13e15] of the 0.433$ao in d0 ) where ao is the lattice parameter (see Fig. 3). Not
experimental correlation between measured resistance and all tetrahedral sites would be filled in the initial transition
D/Pd ratio, indicated the Pd cathode remained loaded to the without additional deuterons moving in. In d there are 6
same activity level (approximate average bulk D/Pd ratio of nearest neighbor deuterons (to the VAC) which are each
0.93) as that prior to emersion. As will be seen below, this shared by two VAC (one on either side of the deuteron) giving
produced a violation of the conditions necessary for achieving an effective nearest neighbor count of 3 deuterons per VAC (1
the Fleischmann-Pons heat effect [15]. deuteron at ½, ½, ½ is surrounded by only Pd atoms, see Fig. 3).
Delta and delta prime are minor SAV micro-constituents in But in d0 , the VAC has 4 unshared nearest neighbor deuterons
a two-phase microstructure in the Pd-D cathode with per VAC (without additional deuterons moving in, or

Please cite this article as: Staker MR, The role of superabundant vacancy delta to delta prime transformation in stopping Fleischmann-
Pons heat effect in palladium-deuterium, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.01.001
4 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 2 e Electrolytic cells of four nested (not shown) Pyrex test tubes [13] with Pd or Pt cathodes and Pt anodes, sealed with
Teflon tops (not shown). Cells are in series on one “current controlled” power supply (P. S.). Independent electromigration
currents from P. S.‘s for each cell were operated in “current control” mode. The left cell (Pd cathode) has 18 ml of 0.5 M LiOD
and the right cell has 18 ml of 0.5 M LiOH, from Refs. [13e15].

potentially 8, if additional deuterons move in to fill all the Mixed amounts of tetrahedral and octahedral occupancy
tetrahedral sites), at a closer distance, creating a more nega- have been previously observed [39,40]. Remarkably, density
tive charge [12] on the VAC (to balance local charge from the functional theory (DFT) calculations for PdH at rx ¼ 1.0 b y
deuterons). It is suggested that this negative charge on the Setayandeha et al. [42] found mixed octahedral and tetrahe-
VAC, which is supplied by a slight localization of the con- dral occupancy was the only result that would bring the par-
duction band electrons, also serves to lower the free energy tial atomic volume of hydrogen vH into agreement with
state of the system since binding between VAC and Dþs is experiment, indicating PdH must contain 15e20% tetrahedral
stronger due to a shorter distance and the higher numbers of H with the remaining H in octahedral sites. Akiba [43] used the
Dþs per VAC. Rietveld analysis to show that 30% of D atoms are in

Table 1 e Experimental conditions (ambient temperature ¼ 23  C).

State D/Pd ratio Temperature Condition of Result (Excess heat Reference
of Cell (oC) Pd-D Cathode and power?)
prior to quench 0.93 82.5 b þ 0.03% d þ 5.00% d0 excess heat þ 240 W/cm3 ex. Power this work,13,14
at quench 0.93 dropping transitioning transitioning this work
0e15 min after quench 0.93 ~0 b þ 5.03% d0 no excess power this work,14
After 15 min 0.93 rising b þ 5.03% d0 no excess power this work,14
during 30 d after quench 0.93 42 to 45 b þ 5.03% d0 no excess power this work,14
calibration 0.93 45 b þ 5.03% d0 on calibration this work,14

Please cite this article as: Staker MR, The role of superabundant vacancy delta to delta prime transformation in stopping Fleischmann-
Pons heat effect in palladium-deuterium, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.01.001
 international journal of hydrogen energy xxx (xxxx) xxx 5

Fig. 3 e The transformation of d phase, with Dþ at octahedral sites, to d′ phase, with Dþ at tetrahedral sites. The octahedral
interstitial site, defined, in the FCC unit cell, by an octahedron of 8 faces each face bounded by 3 close-packed directions. At
the left, one is visible at d phase center, but midpoints of FCC edges are equivalent FCC octahedral positions and become
VAC tube locations in SAV for resonance vibrations (excess heat). The tetrahedral interstitial site, defined, in the original
FCC unit cell, by a regular tetrahedron of 4 faces each bounded by 3 close-packed directions, visible in d′ phase at ¼, ¼, ¼ of
the lattice parameter (FCC edges). Unit cell face diagonals are also close-packed directions and each tetrahedron includes 3
half-diagonals. These tetrahedral interstitial sites are not in the VAC tube and therefore do not enable resonance vibrations
(excess heat).

tetrahedral sites while 70% are in octahedral sites. Several “… most important implication in the physics of SAV is that
other researchers using Pd and its alloys with gold (Au) also the most stable structure of all M  H alloys is in fact the
found partial occupancy of tetrahedral sites by D. Also, by defect structure containing a large number of M-atom va-
quickly quenching PdD, formed by loading with deuterium at cancies. All M  H alloys should tend to assume such defect
elevated temperature, Syed et al. [44] measured a noteworthy structures, ordered or disordered depending on the tem-
increase in the temperature of superconductivity Tc to about perature, as long as the kinetics allows. In practice, however,
60 kelvin. This assents to previous results [14] showing that a MeH alloys are in most cases prepared under conditions where
partial d to d0 transformation spontaneously occurred (or at M-atom vacancies cannot be introduced. Thus it can be said
least more d0 formed in addition to the existing combination of that most (all) phase diagrams of M  H systems reported
d þ d0 ) during the production of excess heat; and it was to date are metastable ones. These metastable diagrams
concluded that the d0 portion (phase) had very low resistivity. are certainly useful as such, but the recognition that they
This low resistivity suggested [45] a possible link between are metastable ones is of basic importance. The real equi-
LENR, SAV and superconductivity. Complementarily, Mayer librium phase diagrams including M-atom(s) vacancies
[46] has proposed that LENR is initiated in a phase-transition have not been obtained so far.” [emphasis added]
yielding a fraction of the electrons as superconducting elec-
trons via Cooper pairs, which then start a deuteron-driven Tetrahedral site occupancy has more order and lower free
chain of nuclear reactions. energy [32]. Increasing temperature and coaxing deuterons
However, once transformation has proceeded completely to back into octahedral sites, agrees with (and explains) reported
d0 , this SAV phase in Pd-D is now in a lower free energy state as [47e52] “positive feedback” (an increase in temperature pro-
can be seen from the stronger bond as explained above and duces more excess power which increases the temperature
also supported by Bukonte et al. [32] and will need additional further and so on). But, if all previously available VAC (origi-
activation energy to force the deuterons back into the octa- nally scattered throughout the b-phase) become locked in the
hedral sites (d phase). Occupation of either octahedral or d0 phase, it would be necessary to create more VAC in order to
tetrahedral (with temperature dependence) and a high VAC form any new d phase near room temperature. A total shift of
concentration is consistent with the astute recognition and all d to d0 would produce violations of rules number 1 and 4 of
statement of Fukai [4b]: the essential criteria for achieving the Fleischman-Pons heat

Please cite this article as: Staker MR, The role of superabundant vacancy delta to delta prime transformation in stopping Fleischmann-
Pons heat effect in palladium-deuterium, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.01.001
6 international journal of hydrogen energy xxx (xxxx) xxx

effect [15]: (1) a highly available VAC concentration and (4) ex- vibration frequency of 5.7 THz [12]. The Dþ ions vibrate inside
istence of d phase; and thus make excess heat implausible. these (green) tubes. These resonances have amplitudes
Creating new VAC near room temperature requires new plastic exceeding unit cell dimensions (Fig. 4) and high velocities [12]
deformation (since diffusion is too slow). A way to introduce raising the likelihood of nuclear interactions. These displace-
added plastic deformation would be by multiple reversals of ments also produce phonons from a quantum mechanical
polarity of the electrolysis (unload D anodically followed by perspective. However, this is not possible if there are no deu-
cathodically reloading), thus transitioning the a þ b miscibility terons (Fig. 3 and Fig, 4 insert) in the d0 tubes (referred to as
gap multiple times, as was done at the beginning of this vacancy channels [12], lattice tubes [13] or empty undulating
experiment [13e15]. In addition, the crystallography of the diameter tubes [14]). Inability to revert back to d phase is an
d0 phase with the deuterons at tetrahedral sites does not allow example of sluggish kinetics (for the production of VAC) which
for resonance conditions that allow large vibrations of the bars achievement of phase diagram equilibrium conditions for
deuterons and a nuclear active environment necessary for the d. A classic example of meta-stability is as-quenched
production of excess heat and power [12,15]. A review of con- martensite (with trapped interstitial carbon) where kinetics
ditions was recently published [53]. The green tubes running prevent the achievement of equilibrium phases of ferrite and
along all 12 edges of the unit cell (Figs. 3 and 4) are the locations free carbon (graphite). Apparently, heating a SAV phase pro-
of deuteron longitudinal vibrations (arrows) and resonance motes D-jumps from tetrahedral to octahedral sites and pro-
during excess heat in d. These VAC tubes are empty tubes duction of excess heat, while cooling a SAV phase promotes D-
except for strings of deuterons with spacing equal to the lattice jumps to tetrahedral sites and absence of excess heat.
parameter and are a result of the unique lattice geometry of From the phase diagram (Fig. 1), the production of d phase
SAV d phase shown in Fig. 3 Of Ref. [12] where both lattices of requires, at least a local D/Pd ratio, rx, of 1.14 (see the lever rule
beta (b) deuteride of PdeD and d of Pd3VacD4 line up in the [100], in Fig. 3 of Ref. [15]), and available VAC. If rx < 1.14, locally and
[010] and [001] directions. The vacancy channel (green tube) is globally, or VAC content is too low (and cannot be introduced),
shown with a varying diameter of between 0.414 and 1.0 of that SAV d-phases will not form, barring excess heat. In gas loading
of the Pd atom diameter (2.75 £ 1010 m). The Pd atoms at the (without electrolysis and electromigration), or even if done via
end of each tube (from b deuteride) supply the driving force for electrolysis, but with only minor electromigration [14], where
the resonance condition from the force available through bulk loading reaches merely rx ~1.0, SAV d-phase would not
Hooke's law (see Ref. [12]). The driving force comes from the form because (at least) the local rx (enhanced by electro-
normal thermal vibration of the Pd atom at its own natural migration) needs to be  1.14 [15,38b]. If VAC concentration is

Fig. 4 e Amplitude of vibrations of seven deuterons of SAV (d phase) due to Pd end atom at various frequencies, after Staker
[12,15]. The first peak (m ¼ 1, where m is mode number as defined in Ref. [12]) at 5.693 THz (approximate midpoint of half
width) matches thermal vibration frequency of Pd (5.70 THz). If peak widths are taken into account, other peaks (2 ≤m ≤ 7)
also match calculated resonance frequencies; but as m increases the peak widths overlap. Insert is the geometry of the
vacancy tubes in d in which the deuterons vibrate.

Please cite this article as: Staker MR, The role of superabundant vacancy delta to delta prime transformation in stopping Fleischmann-
Pons heat effect in palladium-deuterium, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.01.001
 international journal of hydrogen energy xxx (xxxx) xxx 7

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Declaration of competing interest measurements, in conjunction with an emended and more
complete phase diagram of the Palladium - isotopic
The author declares that he has no known competing finan- Hydrogen system. J. Condensed Matter Nucl. Sci.
2019;29:129e68. https://www.lenr-canr.org/acrobat/
cial interests or personal relationships that could have
StakerMRpreprintco.pdf.
appeared to influence the work reported in this paper. [14] Staker MR. Estimating volume fractions of superabundant
vacancy phases and their potential roles in low energy
nuclear reactions and high conductivity in the
Acknowledgements Palladiumeisotopic Hydrogen system. Mater Sci Eng B
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Pons heat effect in palladium-deuterium, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.01.001
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Please cite this article as: Staker MR, The role of superabundant vacancy delta to delta prime transformation in stopping Fleischmann-
Pons heat effect in palladium-deuterium, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2023.01.001