ArticlePDF Available

Search for Evidence of Nuclear Transmutations in the CETI RIFEX Kit

Authors:
  • Institute for Advanced Studies at Austin

Abstract and Figures

A series of experiments has been performed with the CETI RIFEX kit. In each experiment an electrolytic cell with a cathode composed of metal-coated plastic beads was operated for two weeks. The cathode beads were then analyzed by x-ray fluorescence for evidence of nuclear transmutations. Several elements were observed to appear in the reacted beads. Analyses of the electrolyte and other components of the system in contact with the electrolyte are not conclusive but suggest to us that these elements were present in the system initially.
Content may be subject to copyright.
1
Search for Evidence of Nuclear Transmutations in the
CETI RIFEX Kit
Scott Little and H. E. Puthoff, Ph.D., EarthTech International, Inc
4030 Braker Lane West, Austin, TX 78759
Abstract
A series of experiments has been performed with the CETI RIFEX kit. In each
experiment an electrolytic cell with a cathode composed of metal-coated plastic beads
was operated for two weeks. The cathode beads were then analyzed by x-ray
fluorescence for evidence of nuclear transmutations. Several elements were observed to
appear in the reacted beads. Analyses of the electrolyte and other components of the
system in contact with the electrolyte are not conclusive but suggest to us that these
elements were present in the system initially.
Introduction
RIFEX stands for Reaction In a Film Excited compleX. Clean Energy Technologies, Inc
(CETI) made the RIFEX kit available in late 1996 to provide "the opportunity to examine
and conduct research on CETI's Patterson Power Cell which has received several U.S.
Patents and has been acclaimed as the first device to reliably demonstrate chemically
assisted nuclear reactions."
1
Most of the evidence for these nuclear reactions comes from
the work of Dr. George Miley at the University of Illinois.
2,3
The RIFEX kit consists mainly of a special electrolysis cell that is very similar to the cell
described in patents
4
by Dr. James A. Patterson of CETI. The cathode in this cell is
composed of a bed of plastic beads that have been coated with a thin layer of metal. It is
in this thin metal coating that the nuclear reactions are reported to occur.
During operation of the cell, 86 ml of Li
2
SO
4
electrolyte is circulated slowly through the
cell by an external pump. Electrolysis is conducted at a 20 mA and the electrolyte is
maintained at about 70°C by an in-line heater located in the electrolyte circuit just before
the cell.
A typical run lasts for two weeks. The beads are then removed from the cell and analyzed
for evidence of nuclear reactions (e.g., new elements, unusual isotopic ratios).
Due to the electrolysis, many cations that are present in the electrolyte will be deposited
on the cathode beads. Therefore it is important that all possible sources for these
elements be ruled out before concluding that they have been created in the film by a
nuclear reaction. To this end, the RIFEX kit is primarily constructed of non-metallic
components.
Our primary goal in this investigation was confirmation of Dr. Miley's reports that new
elements were being created in the bead coatings. With large excess power ratios being
2
reported by CETI for cells with similar beads, Dr. Miley's results appeared to fit perfectly
with the hypothesis that nuclear reactions were occurring in the cell.
To look for these elements we employed x-ray fluorescence (XRF) which is a non-
destructive elemental analysis technique that provides excellent specimen versatility.
Liquids, solids, powders, beads and odd shapes can all be accommodated with relative
ease. Importantly, we happen to have a great deal of experience with XRF analysis
consisting of 20+ years designing, building, and supporting a wide variety of industrial
XRF analyzer systems.
5
This work involved countless application studies wherein XRF
results were compared with other analytical techniques. An incredible variety of errors
were encountered in these application studies, and the experience of finding and
correcting them has been of great value to the present investigation.
We decided to limit our investigation to elements whose x-ray emission lines fall in a
region (4-14 keV) where analytical conditions are favorable and quantification of results
is relatively straightforward. This region includes 56 elements in two groups: Sc-Sr (K x-
rays) and Cs-U (L x-rays). Possibly important elements missing from this region include:
Li, Al, Si, Zr, Pd, Ag, & Cd. Seven of the nine elements Miley referred to as "NAA
elements"
2
are included in these two groups. NAA stands for Neutron Activation
Analysis. Miley's NAA elements are Mg, Al, V, Fe, Co, Ni, Cu, Zn, & Ag. Our analysis
misses only Mg, Al, & Ag.
Over most of our analytical range, the x-rays are sufficiently energetic to penetrate
through several layers of the styrene beads used in this study. This enabled us to analyze
the 1 cc of beads typically involved in a run all at once and obtain a single result that
represented the average composition of the beads.
XRF does not distinguish between the different isotopes of an element. It is sensitive
only to total elemental concentrations. In some respects this can be considered beneficial
for an initial investigation because it eliminates a complex set of variables from the
analytical puzzle. If we can first confirm that new elements are indeed being created then
additional studies to investigate isotopic distributions are certainly warranted.
A secondary goal in this investigation was confirmation of the excess heat measurements
made by Miley and Cravens on similar beads undergoing electrolysis. This work is
covered in a separate paper.
6
3
Initial Preparations and Description of Apparatus
We received our RIFEX kit in December 1996 immediately after attending a training
session hosted by Dr. Miley on the University of Illinois campus. The session provided
basic instructions on the experiment protocol and a review of Dr. Miley's findings.
There were 3 different kinds of beads
included in the kit. All of them were
based on the same 1 mm diameter
(nominal) polystyrene beads but the
coatings were (1) 0.2 micron Pd, (2)
0.2 micron Pd and 0.2 micron Ni, and
(3) 800 Angstrom (0.08 micron) Ni.
The first two were made by CETI
using their patented electroplating
process. The third type was made in
Miley's lab by sputtering Ni onto bare
polystyrene beads. At the training
session Miley suggested that we focus
our transmutation investigation on the
Ni beads because most of his results at
that time had been obtained on similar
beads.
The kit contained two cells. A twice-
scale section view of the assembled
cell is shown in Figure 1. The cell
consists of a tubular body with two
endplugs. Each endplug has a Pt lead
wire that passes through a seal and
then is crimped onto a perforated Ti
plate that serves in the upper case as
the anode and in the lower case as a
contact for the beads which form the
cathode in this cell. The bead bed sits
in direct contact with the cathode
endplug. On top of the bead bed are
two nylon screens that prevent the
beads from escaping. An O-ring sits
on top of the screens to space the
anode endplug away from the screens.
As shown in the drawing the endplugs are sealed to the cell body with O-rings and have a
1/8 NPT female thread that accepts a male run tee fitting. This tee fitting (not shown)
provides an electrolyte passage and a port for the temperature probe.
FLOW
BEADS
NYLON
SCREENS
O-RING
(BUNA)
ANODE (Ti)
CATHODE
CONTACT
(Ti)
LEAD WIRE
(0.020" DIA Pt)
WIRE SEAL
(EPOXY, LATER
CHANGED TO
BUNA)
1/8 NPT
CELL
BODY
(NYLON)
END
PLUG
(NYLON)
SCALE: 2X
Figure 1
4
The kit also contained an electrolyte reservoir made of acrylic plastic, additional plastic
fittings, 1/4" OD Teflon tubing, a Gelman 47mm in-line polycarbonate filter holder with
cellulose acetate filters, reagent grade Li
2
SO
4
, a plastic stand to hold the cell and
reservoir, and an insulated test chamber. Also included was a detailed written protocol
for the experiment. The kit did not include the electrolyte pump, in-line electrolyte
heater, electrolysis power supply, temperature sensors, meters, or data recording
equipment.
Schematic of Electrolyte Circuit:
Electrolyte Pump: We purchased the recommended pump (model RHOCKC) and flow
controller (model V200) from Fluid Metering Inc. This pump has a ceramic piston and
cylinder that contact the fluid. The flow controller serves to run the pump motor at a
precisely regulated, selectable speed. We constructed a stand to support the pump in one
of the manufacturer's recommended orientations (45° angle downward as shown).
Electrolyte Heater: We designed and constructed our own in-line electrolyte heater.
The first version of this heater was a stirred oil-bath into which a seamless coil of Teflon
tubing was immersed. The aluminum bath vessel was heated with a wrap-around heating
element controlled by an Omega CN76000 that sensed bath temperature via a K
thermocouple immersed in the bath. This system worked very well as an in-line heater
during initial qualification tests of the circulation system. However it became apparent
during these tests that it would be very difficult to guarantee that traces of oil would not
INLET
TEMPERATURE
PROBE HEATER
FILTER
PUMP
ELECTROLYTE RESERVOIR
GAS VENT
OUTLET TEMPERATURE PROBE
CELL
TEST
CHAMBER
MALE RUN TEE (2)
Figure 2
5
contaminate the interior of the circulation system during routine handling and
disassembly of the various components.
The oil-bath was abandoned and a second in-line heater was designed and constructed.
Great care was taken to ensure that the electrolyte system was not contaminated with oil
during the removal of the first heater. The new heater consisted simply of two
rectangular Al blocks with half-round grooves on one side that were bolted together
around a 19 cm long section of the Teflon tubing like a stockade clamp. A 50 W strip
heater was attached to one of the Al blocks and the K thermocouple was secured to the
other. The whole assembly was placed in a Styrofoam box to minimize heat losses.
During operation the Omega controller maintained the Al block assembly at an
empirically determined temperature of 115°C. This was sufficient to warm the
electrolyte to 70°C during its 15 sec residence within the heater (the inside diameter of
the Teflon tubing is 4.8 mm so, at the nominal electrolyte flow rate of 14.3 ml/min, the
fluid velocity is 1.3 cm/sec).
Test Chamber: The test chamber (a modified ice chest) supplied with the RIFEX kit was
designed so that the cell and reservoir had to first be placed down into the relatively tight
interior of the chamber and then the tubing connections made up. This proved to be
virtually impossible for our hands so a new chamber was constructed from a larger ice
chest. The lid of the new ice chest was inverted and mounted on elevated supports to
provide access to the underside. The cell and reservoir assembly was then installed on
top of the inverted lid and all the necessary tubes and wires were led down and out
through small holes drilled in the lid. This arrangement provided easy access to the cell
for servicing. Inverting the unmodified lower portion of the ice chest and setting it down
over the cell onto the lid easily closed the new chamber. Photographs of this
experimental setup can be viewed on our web page.
7
Power Supply: We used a Kepco Model PAT 21-1 wired for constant-current operation
(regulation stability <0.1%). This supply is capable of a maximum of 1 ampere and has a
ceiling of about 42 volts in constant-current mode.
Data Recording and Temperature Measurement: To monitor the runs we used a
Keithley Model 2000 DVM with a 10-channel scanner card interfaced to an IBM-
compatible PC running a custom data acquisition program. The following parameters
were measured every 20 seconds, plotted on screen and logged to disk:
1. inlet electrolyte temperature
2. outlet electrolyte temperature
3. cell voltage
4. cell current
5. room air temperature
6. temperature of the in-line heater block.
All temperatures were measured with BetaTHERM precision 0.2°C interchangeable
thermistors. These thermistors were simply connected directly to the inputs of the
6
Keithley, which read their resistance and reported it to the computer, which calculated the
corresponding temperature using the Steinhart-Hart equation (with coefficients supplied
by BetaTHERM). We have compared these thermistors to precision 0.1°C glass
thermometers on numerous occasions in our lab and they always agree within 0.2°C.
Li
2
SO
4
: 16 g of Li
2
SO
4
was supplied with the RIFEX kit. To provide sufficient material
for several experiments and the necessary analytical work, we purchased an additional 50
g of the same grade (product number 20365-3) from Aldrich Chemical Co. Fortunately
our Li
2
SO
4
came from the same Aldrich lot (lot number 06207MF) as the material
supplied with the kit. We blended all the Li
2
SO
4
together thoroughly before starting the
experiments.
Leaks: During qualification tests we had a number of problems with leaks in the original
RIFEX kit design. The plastic pipe thread (1/8 NPT) connection between the male run
tee fitting and the machined nylon cell endplugs was the biggest problem. Expansion and
contraction of the plastic during cycling from ambient to 70°C always seemed to loosen
that connection to the verge of leaking. Eventually, as noted later, we modified those
connections to use O-ring seals. We also had problems with the wire seals that were
originally made with epoxy. We eventually replaced them with custom-made elastomer
seals.
Initial Analytical Investigations: Before performing any experimental runs with the
RIFEX kit we performed semi-quantitative XRF analysis on several of the components.
The XRF spectrometer employed for this investigation was a Model EX-6000
manufactured by Jordan Valley Applied Research. This is a high-performance Si(Li)
detector laboratory XRF system with both direct-filtered and secondary-target excitation
capabilities. We were very fortunate to have free unlimited access to this instrument for
this study. Detailed XRF analyses can be quite expensive at a commercial laboratory.
To perform an XRF analysis the sample must be placed in the spectrometer so that its
surface is located where the x-ray beam will strike it and where the resulting scattered
and fluorescent radiation will enter the detector. Powders and liquids are usually placed
in special XRF cups with thin-film bottoms (typically 6 micron thick polypropylene) that
allow the x-rays to enter and leave the cup without significant absorption. Large solid
samples such as fittings, machined pieces, etc. must be supported over the spectrometer
aperture so that at least some portion of the sample is in the correct location.
The analysis is performed by illuminating the sample surface with energetic x-rays and
detecting the fluorescent and scattered x-rays that are emitted. In the EX-6000 the
illuminating radiation is generated by an x-ray tube. The tube voltage is adjusted so that
the radiation is sufficiently energetic to excite the desired electron shells in the selected
analytes. The tube current is adjusted to provide the desired total x-ray intensity at the
detector (several thousand x-rays per second). In the EX-6000, filters are available to
alter the spectral distribution of the tube radiation. These are generally used to "harden"
the tube spectrum, eliminating most of the lower energy radiation which, if not filtered
7
out, interferes directly with the x-rays of interest from the sample. The EX-6000 also has
a secondary-target capability in which the tube radiation is directed at a selected pure-
element target and then the K x-rays emitted by the target are directed at the sample for
the analysis. This feature provides almost monochromatic excitation and yields the best
detection limits for a selected range of elements because the excitation efficiency is high
and the low-energy background from the x-ray tube is virtually eliminated.
The detector must have sufficient energy resolution to separate the various x-rays from
the sample so that the constituents can be accurately identified and quantified. The Si(Li)
detector used in the JVAR EX-6000 operates at liquid nitrogen temperatures and achieves
an energy resolution of ~150 eV (FWHM for the 6 keV line from
55
Fe). This resolution
is quite sufficient for most XRF analytical purposes. Note: x-ray energy is inversely
related to x-ray wavelength by E = hc/λ.
The detector counts individual x-rays and together with the supporting electronics infers
the energy of each detected x-ray from the pulse height. The measured energy is used to
address the corresponding channel in a 2048-channel analyzer and the count therein is
incremented. As the analysis proceeds, each detected x-ray increments one of these
channels and thus the spectrum of x-rays from the sample is recorded.
As emission spectra go, x-ray spectra are particularly simple to interpret. For the
purposes at hand the K x-ray signature of an element is a doublet (two closely-spaced
lines). The lower energy line, called the K
α
, is about 6 times more intense that the higher
energy line, the K
β
. The L x-ray signature of an element is a little more complex. There
are three main groups of L lines, the L
α
, L
β
, and L
γ
(in order of increasing energy). Each
of these groups contains two or more lines but usually the L x-ray signature appears as a
simple triplet. As emitted by typical samples the L
α
and L
β
are about the same intensity
and the Lγ is about 1/6 of that intensity. The K and L series of x-ray lines overlap but
within each series the lines increase monotonically in energy with increasing atomic
number. This and the characteristic doublet/triplet appearance makes identification of
elements by their x-ray signature easy and quite reliable. Sometimes there are overlaps
which must be untangled but x-ray spectra are far simpler and less cluttered than optical
emission spectra for example. A table giving the energies of the x-ray lines for all the
elements can be found in the CRC Handbook of Chemistry and Physics.
In the x-ray spectrum collected during an XRF analysis, the intensity of a given element's
x-rays is directly related to the concentration of that element in the sample. This fact
permits easy semi-quantitative interpretation of x-ray spectra. A big peak means there is
lots of that element present, a little peak means a small concentration, and no peak means
that the element's concentration is below the detection limit. Detection limits vary
considerably but are often in the 1-50 ppm range.
The first thing we looked at with XRF was the dark gray epoxy used to hold the
electrodes into the cell endplugs. This epoxy was in direct contact with the electrolyte in
the cell. The x-ray spectrum from the epoxy is shown in Figure 3. The horizontal axis is
x-ray energy ranging from 0 to 40 keV. The vertical axis is the intensity of the x-rays.
8
Fi
g
ure 3
The most familiar lines are the K
x-ray doublet from Fe at about 6
keV. The label "Fe" appears near
the top of the Fe K
α
and the
smaller Fe K
β
immediately to the
right is not labeled. To the left of
the Fe peaks are those of Ca and
Ti (small). To the right of the Fe
peaks we see the K x-ray
signature of Sr (again the K
β
is
not labeled). Further to the right
we come to a mess of lines and a big hump that comprise the scattered radiation from the
x-ray tube, which has a Rh anode. The tube emits a spectral continuum (bremsstrahlung)
with the Rh lines superimposed. These x-rays scatter both elastically (no energy loss)
and inelastically (with some energy loss) from the sample which splits each Rh line into
two. At the far right we see the K x-ray signature of Ba (excited by the high-energy tail
of the bremsstrahlung). Both the K
α
and K
β
are labeled and, at these high energies, you
can see the K
β
resolved into the K
β1
and K
β2
. The "VFS: 4000" label tells how many
counts it takes to reach full vertical scale.
We contacted CETI about the epoxy and learned that it is a type known as J-B WELD.
We contacted the J-B WELD Company and they provided the following concentrations
for the inorganic constituents of J-B WELD epoxy:
35-40% CaCO
3
17-20% BaSO
4
1-3% TiO
2
1-3% magnesium silicate
8-10% Fe (iron powder) 1-3% SiO
2
Comparing these concentrations to the peak heights in Figure 3 we can see that the XRF
sensitivity varies significantly from element to element. For example, the Ca peak is
smaller than the Fe peak yet the elemental Ca concentration is about equal to the Fe
concentration. This is due to Fe being more efficiently excited than Ca in this analysis
and Fe x-rays being less heavily absorbed in the sample matrix than Ca x-rays. Consider
the Sr peak. Sr is so efficiently excited in this analysis that the Sr concentration is
probably less than 1% of the Ca concentration. In fact, it is likely that the Sr is simply a
trace constituent of the CaCO
3
filler material. Despite these difficulties, the x-ray
spectrum provides a quick easy way to examine the elemental content of a wide variety
of materials.
We discussed the epoxy as a potential source of contamination with CETI and then
decided to proceed on the first run using these endplugs because the epoxy prevented
disassembly of the endplugs and no other endplugs were immediately available.
9
Next we disassembled the FMI
pump head and used XRF to look
at the ceramic piston (3/16"
diameter, 1" long); one of the
few components in the
electrolyte circulation system
that was not plastic. As indicated
in Figure 4, we observed only
low levels of Fe and Zr in this
ceramic. Because of the size and
shape of the piston it could not
be presented properly to the
spectrometer. We could
therefore only estimate the concentrations of these elements: a few tenths of a percent Fe
and a few hundredths of a percent Zr (again the analysis is much more sensitive to Zr
than to Fe).
We also looked at the fresh Ni
beads before starting the run. In
Figure 5, you can see the expected
prominent Ni peak (both the K
α
and K
β
lines are visible and
labeled) and a small Fe peak which
indicates that the Fe/Ni ratio of the
fresh coating is about 0.1. We
discussed this result with Mike
Williams who made these beads in
Miley's lab and he could provide
no explanation for the source of
this Fe. He said the sputtering
target was very pure Ni with only 20 ppm Fe in it. He further related that the Auger
specialist at the University of Illinois said there was no sign of Fe peaks in the surface
surveys performed on similar beads during Miley's investigations. Interestingly, the
NAA results on fresh Ni beads presented by Miley
2
in Table 4a show an Fe/Ni ratio of
0.12, essentially the same as we
observed.
We resolved this mystery by
examining the uncoated beads
supplied with the RIFEX kit.
The spectra in Figure 6 show
the uncoated beads in solid gray
and the Ni beads as a solid
black line. Note that the Fe
peaks overlap perfectly
Figure 4
Figure 6
Figure 5
10
indicating that the Fe content of both beads is the same. The Fe is not in the coating but
in the bead. XRF (and NAA) can see right through these thin Ni coatings but Auger
electron spectroscopy cannot. Interestingly, the uncoated beads also have a noticeable Ni
peak and a low-intensity Zn peak that does not appear in the Ni coated beads, which were
unsulfonated. The uncoated beads had been sulfonated by CETI. Perhaps the Ni and Zn
were picked up in that process.
Run 1
We started preparations for Run 1 by washing all components of the cell with Alconox
detergent and rinsing with DI water (we used DI water for all our RIFEX procedures and
will refer to it simply as water from here on). Wearing undusted latex finger cots (used
for all cell assembly procedures hereafter) and following the steps in the protocol we
assembled the cell with a 1 cc charge of the Ni-coated beads. First the cathode endplug
was inserted halfway into the cylindrical cell body. This assembly was held upright and
the beads poured into the cell body and settled into a close-packed flat-topped bed by
flooding them with water and tapping the side of the cell. The water was drained from
the cell and two discs of nylon screen (a 200 micron mesh followed by a 500 micron
mesh) were placed on top of the bead bed. Next an O-ring that fits snugly inside the cell
body was pushed down into contact with the nylon screens. Finally the anode endplug
was inserted into the cell body without twisting until it contacted the O-ring.
The cell assembly was placed between two plastic compression plates that engage
shoulders on the protruding endplugs. Four bolts connect the two compression plates and
were tightened until a 15-30 pound compressive force was achieved. This force is
transmitted by the endplugs directly to the cell contents.
After assembling the cell and installing it in the electrolyte circuit, we cleaned the circuit
by circulating a 5% NH
4
OH solution for 30 minutes. We rinsed the circuit with DI water
until the pH of the water exiting the system was below 7.1.
We emptied the electrolyte circuit as well as possible, leaving perhaps 5ml of water
behind, and filled the reservoir with 86 ml of 0.5M Li
2
SO
4
solution. This solution was
circulated at 14.3 ml/min for the remainder of the run.
We started the run at about 1400 hours on 23JAN97 by applying a constant current of
0.020 amps to the cell. This current was maintained for the remainder of the run. The
electrolyte heater was off at this time and the electrolyte temperature was about 25°C.
After a 3 hour loading period during which the cell voltage rose from 3.9 volts to about
4.5 volts, the electrolyte heater was turned on. After two more hours, the electrolyte
temperature stabilized at about 70°C. This temperature was maintained for the remainder
of the run. The elevated electrolyte temperature lowered the cell voltage to about 4.0
volts.
11
Throughout the run we added DI water to the reservoir periodically to make up for
electrolysis and evaporative losses. The former was only about 0.2 ml/day but the latter
was 5-10 ml/day. These additions were very carefully made with a clean plastic syringe
and a length of small-bore Teflon tubing leading into the reservoir.
On 27JAN97 a gradual seepage was observed at the 1/8 NPT connection to the bottom
endplug.
On 31JAN97 a small wet spot was observed under the cell. The loss of Li
2
SO
4
was
negligible.
On 1FEB97 the leak had increased to the point where action was required. We
interrupted the electrolysis power and quickly drained the cell, disconnected the lower
electrolyte line, tightened the lower tee fitting one full turn, reconnected the line, resumed
circulation and restored electrolysis power within 13 minutes of interrupting it.
For some reason this procedure made the cell voltage jump to about 5.2 volts. After
consultation with CETI, we tightened the axial clamp bolts one full turn but that did not
change the voltage. It remained at about 5.2 volts for the remainder of the run.
On 9FEB97 we ended the run. Total duration under electrolysis power at 70°C was
about 400 hours. We drained the circuit and collected the used electrolyte. Upon
disassembly of the cell we discovered that the beads were significantly altered in
appearance. Virtually all of the original metallic sheen was gone. Some of the beads
looked totally clear, most were a light brown color. Most of the other components in
contact with the electrolyte including the nylon screens, the anode, and the plastic fittings
throughout the electrolyte circuit were noticeably brown in color.
We recovered the beads, washed them in water thoroughly and dried them gently. With
clean, dry, reacted beads in hand we proceeded directly to the XRF spectrometer and
collected the spectrum shown in Figure 7.
Fresh Beads
Reacted Beads
Fi
g
ure 7
12
The reacted bead spectrum is solid gray and the fresh bead spectrum is overlaid as a black
line for comparison. The horizontal scale is 4-14 keV. Examining these spectra we see
first that the reacted beads have significantly more Fe and less Ni than the fresh beads.
Also, the reacted beads have high levels of Zn & Pt (note the characteristic L x-ray
signature of Pt) and a lower level of Pb, none of which were noticeable in the fresh beads.
For all practical purposes, no other elements in this region were detected. Roughly, the
"visual" detection limit for these elements is 30 ppm or 0.01 microgram/bead, which is
equivalent to about 15 micrograms in the entire 1cc bead bed. This is the concentration
required to make a noticeable peak in the spectrum. For reference the Ni concentration in
the fresh beads is about 1700 ppm or 0.6 micrograms/bead. We will quantify these
results in detail later but for this semi-quantitative discussion you can assume that the
XRF sensitivity for all the elements in this region is the same.
Notable elements absent from our reacted bead spectrum include Cr and Cu. Miley
reported
8
finding 1840 ppm Cu in similar reacted beads. Such a concentration in our
beads would have produced a very large peak higher than the Ni peak in the fresh beads.
He also reported 1126 ppm Cr, which would have produced a half-scale peak in our
spectrum above. Miley did report finding Fe, Zn, & Pb in his early work
2
and later he
reported
3
finding Pt in the reacted beads.
Actually, we were heartened by these findings. At least we had found some new elements
in our beads and some of the same ones that Miley reported.
We next set out to examine the various components of the electrolyte circuit for possible
sources of the new elements in our reacted beads: Fe, Zn, Pt, & Pb.
There was an obvious potential source for the Pt. Each endplug had a Pt lead wire
running in through a wire seal and leading up to the Ti electrodes where it was crimped
through a pair of closely spaced holes in the electrode. It did not seem likely that such a
small exposed area of Pt could be responsible for the large Pt peaks observed in the
reacted bead but we resolved to eliminate the Pt from the cell anyway.
We noticed that many of the plastic fittings in the circuit were rather brown in color after
the run. In particular, the little nylon inserts that keep the Teflon tubing from collapsing
in the compression fittings were quite brown in color. We examined these brown parts
with XRF and observed a significant Pt signal and nothing else. Apparently the Pt was
circulating throughout the system and depositing on these fittings as well as the beads.
The lot analysis supplied by Aldrich Chemical Co for the Li
2
SO
4
included only one of
our elements of interest: Zn. They listed its concentration as 4 ppm. A rough estimate of
the Zn concentration we observed in the reacted beads indicated that the entire bead bed
contained about 100 micrograms of Zn. At 4 ppm Zn, the 86ml of 0.5M Li
2
SO
4
electrolyte used in the experiment would contain only 19 micrograms of Zn. Clearly
there was additional Zn coming from another source.
13
The male run tees used to connect to the cell were white and opaque compared to the
rather translucent fittings used elsewhere in the circuit. We therefore suspected that these
fittings contained some kind of filler material. One of these fittings was presented to the
XRF spectrometer and we found measurable levels of Al, Si, Ca, Ti, Fe, & Zn (we
adjusted the spectrometer to look at lighter elements for this analysis). A rough estimate
of the concentrations of these elements was obtained via standardless fundamental
parameters:
9
3100 ppm Al, 14200 ppm Si, 360 ppm S, 10800 ppm Ca, 3600 ppm Ti, 170
ppm Fe, 90 ppm Zn, & 110 ppm Sr. We cut open one of the used fittings and flattened it
out so the interior surface, which had been exposed to the circulating electrolyte, could be
presented to the XRF analyzer. We did the same for a new fitting and compared the two
surfaces. There were no striking differences in the two spectra but, due to the high x-ray
transmission of polypropylene, a depletion of the fillers in the surface of the used sample
might not cause a noticeable reduction in the peak heights. Still it seemed unlikely that
the low concentrations of Fe and Zn in these fittings could be the cause of the Fe and Zn
observed in the reacted beads.
We looked at the polycarbonate body of the filter holder. It was very clean.
The filter holder had a black plastic support grate in it. We examined this grate via XRF
and observed only very low levels (few ppm) of S and Fe.
We looked at the used Ti anode and found it to be pretty clean. There were no Zn, Fe, or
Pb peaks visible.
We looked at the nylon cell body and the nylon part of the endplugs. They were both
very clean.
We looked at the Teflon tubing used in the electrolyte circuit. It was very clean.
We finally got around to looking
at the buna spacer O-ring that
was inside the cell...what a
strong Zn signal! The spectra in
Figure 8 show the comparison
between the O-ring (solid gray)
and the fresh Ni beads (black
line) under the same XRF
excitation conditions. We spoke
to Dennis Coz of the Akron
Rubber Development Group and
he informed us that many rubber
formulations including buna
have 2-5 pph (parts per hundred) of ZnO to help activate the curing process. He further
informed us that Viton rubber would probably be free of Zn.
Figure 8
14
This discovery stimulated us to examine the orange silicone O-ring in the filter holder.
As might be expected from the color, we observed a small Fe peak in its spectrum,
probably less than 1% Fe.
Armed with potential explanations for the Pt, Zn & Fe (but not the Pb) we set out to
perform Run 2.
Run 2
In response to our concerns about the JB-WELD epoxy, CETI provided a new cell with a
new endplug design that contained no epoxy at all. The new Ti electrode was a neatly
machined disc that fit into a shallow recess in the face of the endplug.
We were determined to eliminate the Pt lead wires for Run 2. Having some skill at TIG
welding we proposed to CETI that we change the lead wires from Pt to Ti and weld them
to the electrodes to create an all-Ti design. CETI approved of this plan
10
so we ordered
some Ti wire and began to practice the extremely delicate process of fusing a 0.5 mm
diameter Ti wire to a 0.25mm thick Ti sheet. We rapidly discovered that our welding
machine was much too coarse for the job. At its minimum current setting (about 10
amps) the Ti sheet melted away at an uncontrollable rate. Through the cooperation of the
local Miller representative, we located a Miller Synchrowave 350 that can go down to 2
amperes of welding current. We made arrangements to borrow some time on the 350
from its owner and, with a bit of luck, managed to make two very satisfactory welds. We
had the all-Ti electrode assemblies.
We also replaced nearly every O-ring in the electrolyte circuit with a Viton O-ring. We
had to purchase several sizes of Viton O-rings for this purpose. Using standardless
fundamental parameters again we found the following elemental concentrations (in ppm)
in them.
Table 1: XRF Analysis of Viton O-rings
Size Ba Sr Ca
15 mm x 2 mm 7000 170 1500
-010 2400 57 7600
-115 1100 45 7300
-003 6000 200 16000
Clearly these O-rings were made from different Viton formulations but at least none of
them had any Zn.
Somehow we forgot to replace the orange silicone O-ring in the filter holder.
We replaced the white male run tee fittings and all the fittings and inserts that were
colored brown from the first run with new translucent polypropylene fittings that looked
very clean on XRF. We modified the new male run tee fittings to provide an O-ring seal,
which eliminated leakage in the pipe threads.
15
Using a fresh 1 cc charge of Ni beads and our all-Ti electrode assemblies we assembled
the cell exactly as before. We installed the assembled cell in the circuit and performed
the same cleaning and flushing procedure as before, strictly following the RIFEX
protocol.
We filled the reservoir with 86 ml of fresh 0.5M Li
2
SO
4
solution (same batch used in Run
1) and started circulation at 14.3 ml/min.
With the system at ambient temperature we applied the 20 mA electrolysis power and
observed the cell voltage. It started at 9 volts and climbed in seconds to 20 volts! It was
still climbing when we decided to turn off the power a few minutes later. In disbelief we
connected a voltmeter across the cell to check our data acquisition system. When we
restored power the voltmeter confirmed a cell voltage of 20 volts and climbing! To make
sure the problem wasn't due to a pocket of air in the cell, we briefly circulated the
electrolyte at 80 ml/min. The voltage continued to climb past 25 volts. We shut down
everything. It was becoming apparent that something was dreadfully wrong with this cell,
and it probably involved the all-Ti electrodes.
We set up a simple experiment on the bench with two Ti wires dipped down into a small
beaker full of 0.5M Li
2
SO
4
solution. When we connected our constant current supply to
this test cell, we observed the same behavior. At first the voltage was relatively low and
we got the usual bubbling at each electrode. However, in less than a minute, the voltage
climbed up to the power supply's limit (42 volts) and the bubbling essentially stopped.
We inserted an ammeter in the circuit and discovered that the cell had become non-
conductive. Even at 42 volts only a couple of milliamps were flowing through the cell.
We made only one change in this little experiment and the answer to our quandary
became apparent. We replaced the Ti anode wire with a Pt wire of similar dimensions
and the voltage immediately fell to about 4 volts and stayed there while both electrodes
bubbled furiously.
Conclusion: Ti does not work as an anode. As it turns out, bare Ti does not work as an
anode. John Healy of Heraeus Englehard Electrochemistry Corp. informed us that Ti is
commonly used as an anode in industrial electrolytic processes but it is always coated
with a precious metal oxide such as iridium oxide or ruthenium oxide. Actually he said
that the coating is the real anode. The Ti just serves as a corrosion-resistant electrically-
conductive support for the coating. When we described our problem to him he said that
bare Ti would rapidly form an oxide coating under anodic conditions and would become
completely insulated from the electrolyte under almost all conditions (the only exception
being strong fluorine-based electrolytes which would dissolve the titanium oxide). This
behavior is apparently what makes Ti the material of choice for the racks that hold
aluminum parts during anodizing.
16
It was now clear to us that the Ti disc was an inactive part of the original anode. All the
electrolysis current was apparently being conducted to the electrolyte through the small
exposed surface of the Pt lead wire.
We related all this to CETI and, frankly, the information was not well received. They
maintained that bare Ti would function properly as an anode in the RIFEX cell and
instructed us to return to the original anode design. Reluctantly, we complied.
We disassembled the cell, taking care to collect all the beads. To our surprise we
discovered that the Ni coatings were totally gone. We had only exposed these beads to a
few milliamps of electrolysis current for less than 5 minutes during our discovery of the
Ti anode problem. After that they sat in the cell immersed in Li
2
SO
4
solution for a few
days while we investigated the anode problem. We shipped the damaged beads back to
CETI and they replaced them with new ones.
We removed the welded Ti wire from the Ti anode disc and crimped a Pt lead wire
through the holes provided just like the original anode was constructed. This time
however, the holes were considerably closer to the outside edge of the Ti sheet than
before.
Using a fresh 1 cc charge of Ni beads, the new anode assembly, and the all-Ti cathode
assembly we assembled the cell exactly as before. We installed the assembled cell in the
circuit and performed the same cleaning and flushing procedure as before.
We filled the reservoir with 86 ml of fresh 0.5M Li
2
SO
4
solution (same batch used in Run
1) and started circulation at 14.3 ml/min.
With the system at ambient temperature we applied the 20 mA electrolysis power and
observed the cell voltage. It started at 5 volts and climbed steadily over a few minutes to
about 7 volts. Something was still wrong! It occurred to us that the new location of the
Pt lead wire, closer to the outside of the disc, was probably somewhat underneath the
spacer O-ring in the cell. Further, when the axial clamping force was applied to the cell it
was likely that the O-ring would flatten and cover even more of the small loop of Pt wire.
Anxious to get Run 2 underway and convinced that we understood the problem we threw
caution to the winds and took matters into our own hands. We drained the cell and
carefully removed the anode endplug without disturbing the O-ring, nylon screens, and
bead bed. We uncrimped the Pt wire from the Ti disc and pulled about 2cm of it through
the hole in the disc. Fortunately there was sufficient excess outside the cell to allow this
and our elastomer wire seal also permitted this sliding to occur. We then fashioned this
length into a circular loop about 0.6cm in diameter, bent the wire sharply where it came
through the disc, and arranged the loop to lie flat and centered against the Ti disc. Thus
we had fashioned a simple Pt anode of substantial area.
We carefully reassembled the cell and restored circulation of the electrolyte at 14.3
ml/min. With the system at ambient temperature we again applied the 20 mA electrolysis
17
power and observed the cell voltage. It started at 3.32 volts and climbed steadily over a
one-hour period to 3.44 volts. The anode problem was solved! It was 1900 hours on
13MAR97 so we left the system running at ambient temperature overnight.
By the next morning the voltage was up to 3.51. We enabled the electrolyte heater at
0900 on 14MAR97. After reaching the operating temperature of 70°C, the cell voltage
had dropped to ~2.9 volts where it remained for the rest of the run.
There were no leaks encountered on this run. As before we added 5-10 ml of water every
day to make up for evaporative and electrolysis losses.
We ended Run 2 at 1400 on 27MAR97. Total duration under electrolysis power at 70°C
was about 315 hours. We drained the circuit and collected the used electrolyte. Upon
disassembly of the cell we discovered that the beads were much less altered in
appearance than the Run 1 beads. Most of the Run 2 beads still had a metallic
appearance. Some were completely clear. Unlike Run 1, there was little or no brown
coloration present.
We recovered the beads, washed them in water thoroughly, dried them gently, and
proceeded directly to the XRF spectrometer and collected the spectrum shown in Figure
9.
Figure 9
The Run 2 beads are shown in solid gray. The Run 1 beads are shown as a black line for
comparison. As the peak heights indicate, the Run 2 beads have less Fe, more Ni, less
Zn, more Pt, and more Pb than the Run 1 beads.
We were surprised to see the increase in Pt. We expected the increased Pt anode area in
Run 2 to reduce the amount of Pt dissolved in the electrolyte because it greatly reduced
the anode current density. On the other hand it greatly increased the anode area. We are
not experts in electrochemistry so it is distinctly possible that this result is not unusual.
18
The level of Zn in the Run 2 beads is about half of that in the Run 1 beads. This
reduction fits with the removal of the buna O-rings but we were apparently still getting
Zn from another source.
Figure 10 compares the Run 2 beads (solid gray) to the fresh Ni beads (black line):
Figure 10
As you can see, the Fe peak in the Run 2 beads is only slightly higher than the Fe peak in
the fresh beads. Possibly the Fe is coming from a specific source that was being depleted
from run to run. In comparing these two spectra there is an apparent anomaly in the Ni
K
α
/K
β
ratio. This is caused by a minor Pt L x-ray called the L
l
(Ell-ell) which falls right
on top of the Ni K
β
, making it look anomalously large in the Run 2 bead spectrum.
It was difficult to draw any firm conclusions from Run 2. We saw the same elements that
Run 1 produced but in different amounts. As mentioned above, the beads looked quite
different so it was apparent that the reaction had proceeded differently in Run 2. This
alone could be responsible for most of the concentration differences. Perhaps the reason
for these differences was simply the fact that Run 2 lasted only 315 hours whereas Run 1
had lasted 400 hours.
We decided to move on to Run 3. Again we were determined to eliminate Pt from the
cell but, this time, we did not have CETI's support. In fact, they had cautioned during the
Ti anode discussions that changing the anode in the cell might alter the reactions we were
investigating significantly. We were naturally concerned about this possibility but
decided that we had to take the risk.
19
Run 3
We purchased some Pd wire and fabricated a Pd anode very similar to the Pt loop anode
used in Run 2. We selected Pd because it is chemically similar to Pt and its x-ray lines
are very distinct from those of Pt.
Using a fresh 1 cc charge of Ni beads and the new Pd anode assembly we assembled the
cell exactly as before. We installed the assembled cell in the circuit and performed the
same cleaning and flushing procedure as before, strictly following the RIFEX protocol.
We filled the reservoir with 86 ml of fresh 0.5M Li
2
SO
4
solution (new batch) and started
circulation at 14.3 ml/min.
With the system at ambient temperature we applied the 20 mA electrolysis power and
observed the cell voltage. It started at 2.92 volts and climbed steadily over the next hour
to 3.2 volts. It appeared that Pd was working properly as an anode.
At 1800 hours on 2APR97 we enabled the electrolyte heater (right after the one-hour
loading period).
As before we added 5-10 ml of water every day during the run to make up for
evaporative and electrolysis losses.
We ended the run at 2200 hours on 16APR97. Total duration under electrolysis power at
70°C was about 314 hours. We drained the circuit and collected the used electrolyte.
Upon disassembly of the cell we discovered that the beads were very similar in
appearance to the Run 2 beads. Some of them were clear and had apparently lost their
coatings but most of them retained a metallic appearance.
We recovered the beads, washed them in water thoroughly, dried them gently, and
proceeded to the XRF spectrometer and collected the spectrum shown in Figure 11.
Figure 11
20
The Run 3 beads are shown in solid gray. The Run 2 beads are shown as a black line for
comparison. The most obvious difference is the dramatic reduction in Pt content.
Eliminating the Pt from the cell had virtually eliminated the Pt from the reacted beads.
The small level of Pt that does show up in the Run 3 beads is likely to be from Pt that was
deposited throughout the electrolyte circuit during the earlier runs when Pt was
presumably present at high levels in the electrolyte. These Pt deposits could have been
dissolved and transported to the beads in Run 3.
Note that the Zn content of the Run 3 beads is somewhat lower than that of the Run 2
beads. We speculate that this reduction is due to a gradual purging of Zn from the
electrolyte circuit since Run 1 when Zn levels were high due to the buna O-rings.
Figure 12 shows a different portion of the x-ray spectrum where the K x-rays of Pd lie.
Figure 12
The Run 3 beads are shown in solid gray. The Run 2 beads are shown as a black line for
comparison. The huge peak in the center is radiation emitted by the x-ray tube. Note the
Pd x-ray peak in the Run 3 beads. The sensitivity for Pd is not very good under these
conditions. It could easily be the case that this little peak represents as much or more Pd
as the Pt found in the Run 2 beads.
This comparison essentially proves that some of the anode material was deposited on the
beads in both cases. This should not be surprising even for relatively inert metals such as
Pt. The electrolysis action exposes the anode metal to atomic oxygen, which is very
reactive. Although resistant to oxidation, Pt and Pd are not absolutely immune.
Once dissolved, the electrolysis action tends to plate the anode metal onto the cathode.
21
Figure 13 compares the Run 3 beads (solid gray) to fresh Ni beads (black line).
Figure 13
Despite CETI's cautions we were satisfied that the Pt was coming from the Pt lead wires
used in the earlier runs. We found it impossible to entertain the hypothesis that Pt was
being produced by transmutation in the cell only when Pt lead wires were used.
We had also greatly reduced the Zn by eliminating the buna O-rings. The remaining
anomalies were the Pb, the remaining Zn, and the slight increase in Fe content. The
reduction in Ni content is not surprising as some of the reacted beads are clear and have
obviously lost their coatings.
Quantification of XRF results
The traditional method of quantifying XRF results is to calibrate the spectrometer's
response with known standards. In a case like this where the sample form is unusual
(relatively large metal-coated plastic beads) it is very important to have a known standard
that is similar in form to the unknown samples. The obvious candidate for this known
standard was the fresh Ni beads. Unfortunately, we discovered that there is considerable
uncertainty in their Ni content.
The beads were identified as "Microspheres - 800 Angstroms Ni" in the RIFEX kit.
Miley told us, however, that these beads were essentially identical to the ones he had
used in his research. In both of his papers
2, 3
he gives the Ni coating thickness as 650 A.
Unfortunately, the RIFEX Ni beads have never been analyzed by NAA but Miley was
able to give us NAA results for the 4 previous batches of similar beads. The results are
shown in Table 2 below:
22
Table 2: Miley's NAA Ni results on beads similar to the RIFEX beads
Batch # ppm Ni
n60 1821
60 1729.5
60(4) 1635
76 1784
Since the RIFEX beads were produced by the same process as these four batches we
elected to average these concentrations and assign the tentative value of 1743 ppm Ni to
the RIFEX beads.
To convert this bulk concentration value into a Ni coating thickness we needed to know
the average diameter of the beads. We measured 100 beads with Brown & Sharpe dial
calipers (accurate to 0.02 mm) and found the size distribution depicted in Figure 14.
The mean diameter (for surface area and volume calculations) was found to be 0.863 mm
(Miley gives
2
the bead diameter as 1.06 mm). Assuming the specific gravity of the beads
was 1.05 (polystyrene), we calculated the average mass of a bead to be 353 micrograms
(Miley gives
2
609 micrograms). If our average bead wa 1743 ppm Ni, the mass of Ni
present would be 0.615 micrograms. If that much Ni was spread uniformly over the
surface of a 0.863 mm diameter sphere, the thickness would be only 296 A.
This uncertainty (296-800 A) in the Ni coating thickness prevented us from using the
fresh Ni beads as a calibration standard. We therefore resorted to a standardless
fundamental parameters
9
(SFP) calibration for these beads. We made the assumption that
the bead matrix was styrene and we corrected for the fact that 1 cc of beads in an 18mm
sample cup did not constitute an infinitely thick sample for the x-rays. Fortunately we
had available some pure Ni balls about the same size as the RIFEX beads and these were
used to establish the sensitivity of the XRF spectrometer to Ni and to automatically
correct for any geometry effects from the relatively large spherical shapes. The result of
Figure 14
23
this calibration (details available upon request
11
) was an XRF analysis of 1594 ppm Ni.
This was reasonably close (only 9% low) to the average value of Miley's NAA Ni results.
Based upon a general confidence in NAA results derived from previous experiences and
a past history of modest successes with SFP, we decided to simply accept our SFP
calibration results for all the elements of interest. The results are presented in Tables 3
and 4.
Table 3: XRF Results (ppm)
Sample ID Fe Ni Zn Pt Pb
Fresh 196 ±14 1594 ±20 1 ±3 2 ±4 2 ±2
Run1 623 ±20 430 ±11 184 ±6 539 ±11 31 ±4
Run 2 377 ±16 755 ±14 67 ±4 1438 ±17 72 ±5
Run 3 337 ±16 958 ±15 37 ±3 36 ±5 68 ±4
Table 4: XRF Results (total micrograms in bead bed)
Sample ID Fe Ni Zn Pt Pb
Fresh 130 ±9 1062 ±13 1 ±2 1 ±2 1 ±2
Run1 415 ±13 286 ±7 122 ±4 359 ±8 20 ±2
Run 2 251 ±11 503 ±9 45 ±3 958 ±11 48 ±3
Run 3 225 ±10 638 ±10 25 ±2 24 ±3 46 ±3
The values in Table 4 were calculated from those in Table 3 using a bead bed weight of
0.67 g (measured on fresh beads). The analytical conditions used for these analyses
were 40 kV anode voltage, 4 mA emission current, Mo secondary target, and a 400
second measurement time.
The stated error limits are 2-sigma counting statistics and represent only the calculated
statistical precision of these measurements. The accuracy is likely to be much worse.
Past experiences with SFP calibrations have produced results that are almost always
within ±50% of the actual value and usually within ±20%.
Tentative Conclusions
Patterns in the XRF results suggest that the electrolyte circuit can become contaminated
with an element during one run and then deliver that element to the beads in subsequent
runs. Look at the Zn concentrations, for example. In Run 1, the system was probably
contaminated with Zn from the buna O-rings and 122 micrograms of Zn were collected
on the beads. In Run 2, with the buna O-rings removed, we got 45 micrograms of Zn and
then in Run 3 we got 25 micrograms of Zn, as if the Zn was slowly being purged from the
circuit.
Also consider the Pt results. In Run 1 and Run 2 the system was probably contaminated
with Pt from the Pt anode. In Run 3, with the Pt removed from the system we see a much
24
smaller but still measurable quantity of Pt in the reacted beads, almost certainly due to Pt
contamination of the circuit.
With this perspective we decided to focus our attention on the remaining anomalies in the
results from Run 3, i.e. where did the Fe, Zn, and Pb come from?
Analysis of the Electrolyte
We decided to have the fresh Li
2
SO
4
analyzed for Fe, Zn and Pb. We sent samples of our
well-blended Li
2
SO
4
stock to Galbraith Laboratories
12
and General Engineering
Laboratories.
13
The results are presented in Table 5.
Table 5: Laboratory analysis of the Li
2
SO
4
(in ppm)
Lab Fe Zn Pb
Galbraith <0.9 9 5
General Engineering 2.9 51 9
Aldrich lot analysis - 4 -
The agreement among these results is, in our experience, fairly typical of such low-level
analyses with the exception of the General Engineering Zn result. We asked them to
repeat the Zn analysis on a fresh split of the Li
2
SO
4
and their second result was 31 ppm
Zn…not a lot better. A possible cause for their apparent error is the unusual sample
matrix (i.e. pure Li
2
SO
4
).
Using these results we calculated the mass of each element present in the RIFEX
electrolyte circuit (i.e. the mass of each element in 86 ml of a 0.5M solution of this
Li
2
SO
4
). The results, along with the increase in mass observed for each of these elements
in the Run 3 reacted beads are presented in Table 6.
Table 6: Total micrograms of element in fresh electrolyte and observed increase in
element in the reacted beads
Fe Zn Pb
Galbraith <4 43 24
General Engineering 14 147
*
43
Aldrich lot analysis - 19 -
Run 3 reacted beads 95 24 45
*
based upon their second analysis
Except for the Fe it was now apparent that the Li
2
SO
4
contained sufficient quantities of
these elements to explain their appearance in the reacted beads. There was only one thing
left to do: analyze the used electrolyte to see if it had been depleted of these elements.
We slowly evaporated (at 70°C) some of the Run 3 electrolyte to dryness and sent a
measured sample to Galbraith Labs for analysis. We corrected the results they got for the
fact that the used Li
2
SO
4
was actually Li
2
SO
4
·H
2
O whereas the new Li
2
SO
4
was
25
anhydrous. The corrected results are presented in Table 7 along with their original results
on the new Li
2
SO
4
for comparison.
Table 7: Galbraith Labs Analysis of New and Used Li
2
SO
4
(in ppm)
Sample Fe Zn Pb
New Li
2
SO
4
<0.9 9 5
Li
2
SO
4
from Run 3 1.4 6 <1
Both Pb and Zn had indeed been depleted. In the case of Zn, the observed depletion
would provide 14 micrograms to deposit on the beads, somewhat less than the 24
micrograms found in the Run 3 beads. In the case of Pb, the observed depletion would
provide 19-24 micrograms, again somewhat less than the 45 micrograms of Pb found in
the Run 3 beads.
Interestingly the Fe content of the electrolyte appeared to increase slightly due to usage as
if there was still a source of Fe in the system.
Discussion
Despite a large investment in time and money, this study is not exhaustive. We performed
only three runs with our RIFEX kit. We followed the protocol provided by CETI to the
best of our ability but difficulties with the apparatus forced us to make a few changes on
each run. As a result each of the three runs behaved noticeably differently.
The Ni coating on the beads was heavily attacked in each of our runs (see Table 4). In
contrast, Miley's run with similar beads (his run #8) appears to have produced Ni. Table
4a in reference 2 indicates that his beads doubled in Ni content during the run. We
cannot explain this difference. Primarily interested in new elements on the beads, we
made no effort to track the Ni lost from our beads.
We employed only elemental analysis (not isotopic analysis) in our study and we limited
our investigation to a few prominent elements that appeared in the reacted beads. The
laboratories we employed for analysis of the electrolyte were expensive and incredibly
slow. We were disappointed, but not surprised, by the lack of agreement between these
laboratories on the same samples.
The small volume of material produced by these runs significantly limits the depth to
which the analytical investigation may be carried. For example, it took almost all of the
electrolyte from Run 3 just to obtain the few laboratory analyses presented above.
We did obtain results from our investigation. However, we can only speculate as to their
significance.
26
Speculation
We are convinced by the dramatic reduction in Pt in Run 3 (which used a Pd anode) that
the Pt observed in the Run 1 and Run 2 beads came from the Pt anodes used in those
runs. We spoke to several electrochemists about this issue and the general consensus was
that Pt does indeed oxidize under anodic conditions but more slowly than any other
metal.
For Pb and Zn, the analyses of the new and used electrolyte strongly suggest to us that the
appearance of these elements in the reacted beads is due to a simple electrodeposition
process. The observed depletion of these two elements falls about a factor of 2 short of
matching their concentration in the reacted beads but this difference is not likely to be
significant. In the case of Zn, the data in Table 4 indicates that we could still be collecting
Zn that was introduced into the circuit in Run 1. If only 10 of the 24 micrograms of Zn
found in the Run 3 beads came from residual Zn in the circuit, the electrolyte depletion
would explain the balance. In the case of Pb, perhaps Galbraith's analysis of the new
Li
2
SO
4
was low by a factor of 2. General Engineering Labs reported almost twice as
much Pb in the new Li
2
SO
4
as Galbraith. Finally we must consider the possibility of
errors in our XRF results.
The Fe content of the reacted beads is a bit more mysterious. All the electrolyte analyses
agree that it is not coming from the Li
2
SO
4
. The iron powder in the JB-WELD epoxy
clearly contaminated the system during Run 1 but the data in Table 4 suggests that the Fe
content of the reacted beads would level off at about 200 ppm if more runs were
performed. Since the uncoated beads contain 130 ppm Fe, this leaves about 70 ppm (47
micrograms in the bead bed) of Fe that somehow appears in the reacted beads. Possible
identified sources for this iron include residual Fe deposited in the circuit during Run 1,
the red silicone O-ring in the filter holder, and the ceramic piston and cylinder in the
electrolyte pump.
We believe that these elements appear in the reacted beads as a result of electrodeposition
of cations in the electrolyte that were either present initially or were dissolved from
various sources in the electrolyte circuit. However, our quantification of these elements
and their potential sources does not balance precisely. In our opinion the possible
explanations for this discrepancy in quantification should be prioritized as follows:
1. Errors in the laboratory analysis of the fresh and used electrolyte
2. Errors in the XRF analysis of the reacted beads
3. Residual contamination of the electrolyte circuit from Run 1
4. Known sources of contamination within the electrolyte circuit (in the case of Fe)
5. As yet unidentified sources of contamination within the electrolyte circuit
6. Creation of these elements by nuclear transmutations in the cell
We do not lightly place nuclear transmutations last in this list. At the outset of this study,
we were encouraged by reports of large excess heat from cells with similar beads.
Indeed, Miley reported
3
observing low levels of excess heat (~0.5 watt) from beads
27
virtually identical to those in the RIFEX kit. The existence of a strong excess heat
phenomenon, exceeding all possible stored chemical energy limits, essentially demanded
that nuclear reactions were involved.
One must consider the possibility that the excess heat measurements were in error.
If there were no excess heat, essentially all incentive to search for evidence of nuclear
reactions would disappear. Further, we would no longer be tempted to interpret relatively
minor discrepancies in the analysis of the cell components as such evidence.
Our own calorimetric measurements on the beads in the RIFEX kit
6
show no evidence of
excess heat. This is at odds with Dr. Miley's experimental results
3
but consistent with the
possibility that there are no nuclear reactions occurring in the RIFEX kit.
Acknowledgements
We would like to thank Dr. George Miley and Mike Williams of the University of Illinois
for discussions. We are also indebted to Dr. Dennis Cravens and Maria Okuniewski of
CETI for their patience and guidance with the RIFEX protocol.
We would like to thank Dr. Peter F. Berry of TN Technologies, Inc., Round Rock TX, for
his invaluable assistance with the standardless fundmental parameters XRF calibration.
We would also like to thank Rick Comtois and Dr. Robert Tisdale of Jordan Valley
Applied Research, Inc. Austin TX, for making the EX-6000 XRF system available for
this study.
Finally, we gratefully acknowledge partial support of this work by the Fetzer Institute,
Kalamazoo, MI.
28
Epilogue
SIMS Analysis of the Run 3 Beads
After reviewing a draft of our report, Dr. Miley offered to perform SIMS (Secondary Ion
Mass Spectroscopy) analysis on the Run 3 beads. We submitted the entire lot (~1 cm3)
to him for analysis and encouraged him to measure several spots on several beads to
obtain a representative result.
Miley's SIMS lab performed 4 separate analyses on the Run 3 beads and averaged the
results
14
.
Figure E1 shows a comparison between the elemental concentrations found in our Run 3
beads (solid black circles) and those found in 7 of the runs that Miley has included in his
reports
2,3
(various symbols according to the legend). The graph is a plot of production
rate vs mass number.
It is immediately apparent that there is a substantial similarity between these results. The
SIMS detected scores of elements in our Run 3 beads at levels similar to those found in
Miley's runs!
Fi
g
ure E1
29
To evaluate the SIMS results properly, we need to quantify the relationship between
production rate and weight concentration in the reacted beads. The production rate is
stated in atoms/sec per cubic centimeter of coating and can be calculated as follows:
tVA NmC
R
A
=
where
R = production rate
C = change in weight concentration of an element in the reacted beads
m = mass of a bead
N
A
= Avogadro's number
A = atomic weight of the element
V = volume of the bead coating
t = duration of the run (~300 hours)
In applying this relationship we are faced with an unresolved factor-of-two uncertainty.
Miley's standard bead is 1.05 mm in diameter, weighs 606 micrograms, and has a 650Å
thick coating. Our measurements of the actual RIFEX beads indicate a 0.86 mm
diameter, a weight of 353 micrograms, and a 296Å coating. Fortunately, a factor-of-two
uncertainty is not very important here. We are considering a range of production rates
that covers 10 orders of magnitude from 10
7
to 10
17
atoms/sec-cc.
Of primary interest is the production rate that corresponds to the minimum detectable
amount of an element in the reacted beads. Using our XRF methods, the detection limit
approaches 10 ppm under favorable conditions. Taking the element V for example, 10
ppm in the reacted beads (assuming the fresh beads contained no V) corresponds to a
production rate of about 4x10
14
atoms/sec-cc. This is quite a large value, near the top of
the observed SIMS production rates.
Does this mean that XRF is relatively insensitive? For comparison let's look at the
various methods employed to analyze the electrolyte. In our case we submitted the dry
Li
2
SO
4
to the laboratory so they could control the sample preparation as needed to
achieve the best possible detection limit. Galbraith Labs balked at our request to achieve
0.1 ppm accuracy in the analysis of Fe, Zn & Pb in Li
2
SO
4
. They estimated an accuracy
of 0.5 ppm and they reported the results rounded to the nearest ppm. It is therefore
reasonable to assume that their detection limit is about 1 ppm for such elements in
Li
2
SO
4
. Our RIFEX runs used 4.5 g of Li
2
SO
4.
At a concentration of 1 ppm, there would
be 4.5 micrograms of that element in the fresh electrolyte. If all of that element were
deposited on the beads during the run, the resulting concentration in the reacted beads
would be 7 ppm…very close to the XRF detection limit.
What about direct analysis of the electrolyte? Here is an ICP-MS analysis performed by
CETI on a 0.5M solution of the RIFEX Li
2
SO
4
(data received via email from Maria
Okuniewski on 12MAR97):
30
Element Mass Concentration (µg/L)
Mg 25 <1000
Ca 44 <5000
Ti 49 617
V 51 <250
Cr 52 <150
Mn 55 <10
Fe 57 <1250
Co 59 <50
Ni 60 <20
Ni 62 <150
Cu 63 <400
Cu 65 <400
Zn 68 <500
Ge 73 <100
Se 82 <250
Zr 90 188.9
Zr 91 182.2
Nb 93 <100
Mo 97 <50
Ru 101 <100
Pd 102 105.2
Pd 104 <100
Pd 105 <100
Ag 107 <10
Ag 109 <10
Cd 114 <150
Sn 117 <50
Sn 118 <50
Sn 119 <50
Sn 120 <50
Yb 171 <100
Yb 172 <100
Yb 173 <100
Hf 177 <100
Hf 178 <100
Hf 179 <100
A report of "<50" tells us that the detection limit is 50 µg/L. There are a few elements
with detection limits better than 50 µg/L and many that are worse. Taking 50 µg/L as a
typical detection limit, we can convert that into a total of 4.3 micrograms in the 86 ml of
electrolyte used in our RIFEX runs. If all of that were deposited on the beads the
resulting concentration would be about 6 ppm, again close to the XRF detection limit of
10 ppm.
31
So all these analytical methods, except SIMS, have roughly equivalent detection limits.
Using the production rate formula we can plot a line on the SIMS data from our Run 3
beads that represents the approximate detection limit of the other analytical methods.
(The line has been labeled "1 ppm" because it represents that concentration in the dry
Li
2
SO
4
).
Most of the SIMS results are below the line! SIMS is a very sensitive analytical
technique but, in this case, the effective sensitivity is greatly enhanced. The SIMS
directly analyzes the thin bead coating upon which contaminants from the entire volume
of electrolyte tend to be deposited by the electrolysis. In essence, the RIFEX experiment
serves as a preconcentration step for SIMS analysis of trace elements in the electrolyte.
This realization has an enormous impact on the matter at hand:
Every SIMS element that sits below the 1 ppm line could possibly be
coming from an undetectable trace contaminant in the electrolyte.
For the purposes at hand, we will therefore ignore all of the SIMS results that are below
the 1 ppm line. We simply do not have the means to prove that those elements were not
present in the electrolyte at the start of the run. Even if we employed analytical methods
Figure E2
32
with 10x better sensitivity only a handful of additional elements would be included. The
majority of the SIMS results are several orders of magnitude below the 1 ppm line.
What about the elements that are above the 1 ppm line? Several of them (Fe, Zn, Pb, Pt,
& Pd) were detected in our analytical work and have been traced to identifiable sources
within the RIFEX circuit. Some of them (C, S, Zr, & Cd) are not in our XRF analytical
range. The remainder (Ti, As, & Hg) warrant some discussion. The total SIMS Ti result
is equivalent to 213 ppm Ti in the Run 3 beads. Our XRF results showed little or no Ti
and our detection limit for Ti is probably ~30 ppm. We cannot resolve this Ti
discrepancy. Regarding As, the SIMS may well be correct. The SIMS result works out
to 28 ppm As. Such an As peak could be hiding beneath the Pb L
α
peak from the 68 ppm
Pb; it's a classic XRF interference.
The Hg is an interesting case. The point labeled Hg in Figure E2 is
204
Hg. There were
only 2 counts in that channel in the SIMS raw data…and there were zero counts in the
channels for
196
Hg,
198
Hg,
199
Hg,
200
Hg,
201
Hg, &
202
Hg which comprise the other 70% of
the naturally occurring Hg isotopes. Should we conclude that the run produced a small
amount of
204
Hg and none of the other Hg isotopes?…or should we suspect that noise or
some other instrumental error is responsible for those 2 counts?
Discussion
As far as we are concerned, Miley's SIMS analysis of our Run 3 beads does not change
the conclusions and speculations presented earlier in the main report.
In our opinion further investigation into the possibility of nuclear reactions in the RIFEX
kit should be contingent upon confirmation of the excess heat phenomenon. At this time,
we have concluded our search for excess heat in the RIFEX kit with negative results
6
.
However, we stand ready to test new beads for excess heat if/when they become
available. If we can confirm the excess heat phenomenon, we will eagerly reopen our
search for evidence of nuclear reactions.
1
RIFEX kit sales brochure, Clean Energy Technologies, Inc. 1996
2
Miley, George H. & James A. Patterson. 1996a. Nuclear transmutations in thin-film nickel coatings
undergoing electrolysis. Second International Conference in Low-Energy Nuclear Reaction. Texas A&M,
College Station, Texas. (September 13-14).
3
Miley, George H., G. Narne, M. J. Williams, J. A. Patterson, J. Nix, D. Cravens, and H. Hora. 1996b.
Quantitative observation of transmutation products occurring in thin-film coated microspheres during
electrolysis. Proceedings of the ICCF-6. Hokkaido Japan. (October 14-17).
4
U.S. Patent 5,372,688, James A. Patterson, Inventor, "System For Electrolysis of Liquid Electrolyte"
5
Scott Little was General Manager of ASOMA Instruments, Inc. Austin TX from 1979 to 1990 and
Manager of Analytical Instrument Development at TN Technologies, Inc, Round Rock, TX from 1990 to
1993.
33
6
Little, Scott & H. E. Puthoff, "Calorimetric Study of Pd/Ni Beads from the CETI RIFEX Kit". Available
upon request. Contact little@eden.com.
7
http://www.eden.com/~little/rifex1.jpg and http://www.eden.com/~little/rifex2.jpg
8
Table 4a of ref 2
9
Standardless fundamental parameters is an XRF calibration method wherein the analyte concentrations
are calculated from the measured x-ray line intensities and the known values of fluorescent yields,
photoelectric cross sections, mass attenuation coefficients, and densities of the elements observed in the
sample. Usually some approximations must be made for the light elements in the sample that cannot
practically be measured via XRF (e.g. Z<11).
10
Telephone conversation with Dr. Patterson on 18FEB97
11
A Mathcad 6.0 worksheet containing the calculations behind our XRF results is available upon request.
Contact little@eden.com.
12
Galbraith Laboratories, Inc. 2323 Sycamore Drive, Knoxville TN 37950-1610
13
General Engineering Laboratories, 2040 Savage Road, Charleston SC 29417
14
Raw SIMS data available upon request from EarthTech. Contact little@eden.com
... In a previous study [4], we found that (i) the transmutation data of three independent experiments (Miley et al., [5][6][7], Mizuno et al. [8,9], Little and Puthoff [10]) show a similar pattern and (ii) this pattern correlates with a modelbased prediction of Widom and Larsen (WL) [11] Both correlations were statistically significant. ...
Article
Full-text available
Nuclear transmutations are reported in many low-energy nuclear reaction (LENR) experiments. We showed in a previous study (Scholkmann and Nagel, J. Condensed Matter Nucl. Sci. 13 (2014) 485–494) that (i) the transmutation data of three independent experiments have a similar pattern and (ii) this pattern correlates with a model-based on the prediction of Widom and Larsen (WL). In the present study, we extended our analysis and investigated whether the abundance of elements in Earth's crust is correlated with either (i) the WL-prediction, or (ii) the three LENR transmutation data sets. The first analysis revealed that there is no statistically significant correlation between these variables. The second analysis showed a significant correlation, but the correlation only reflects the trend of the data and not the peak-like pattern. This result strengthens the interpretation that the observed peak-like pattern in the transmutation data sets does not originate from contamination. Further implications of our study are discussed and a recommendation is given for future transmutation experiments.
ResearchGate has not been able to resolve any references for this publication.