NRL Co-Deposition Project Notebook
4/25/2009 10:48:00 AM
Task 1 Completion Report
Principal Investigator, Dennis Letts
October 31, 2008
Task 1: Experimental Design.
Develop an electrolytic system for co-deposition of Pd and D. Design a calorimeter that can measure excess
heat (power) with a maximum error of 3% of cell input power. The calorimeter should be easily duplicated
using off-the-shelf components. The calorimeter must accommodate external stimulation using electric fields,
magnetic fields, laser light, infrared and radio waves as potential triggers of the FPE. The electrolytic system
will be closed, using a platinum catalyst for recombination of evolved gases.
Letts proposes to construct a calorimeter using a copper box 120 mm x 120 mm x 180 mm fabricated with .02”
copper sheet commonly available. The box is to be made by brake-bending copper sheet with the final closing seams
TIG welded. The copper box is to have a square copper base 120mm x 120mm x 12.7mm to support the cell. The
copper box will also provide for two 14 mm diameter holes drilled in the back of the base for wire pass-throughs.
The base will also support two copper plate/magnet holders with 40mm x 40mm copper plates or 2” x 2” permanent
magnets. It is anticipated that the box will be composed of a top part that will fit inside a bottom part. The base will
fit inside the bottom part of the box and be epoxied in place with thermally conductive epoxy. A four- inch brushless
DC fan will be epoxied to the inside top of the box to stir the air vigorously. Thermoelectric devices (peltiers) will
be epoxied to the exterior of the box with thermally conductive epoxy. The box will be placed inside an Avanti
temperature controlled box with stirred air and held at 25 +/- .03 C. The peltiers will be connected in series and their
collective voltage read by a datalogger. The peltiers will produce a reproducible voltage when operated with a
specific temperature differential between the hot (interior) side facing the cell and the cooler (exterior) side.
Thermistors will be placed around the copper box exterior to provide temperature control of the Avanti. Shop
drawings were made for the copper box and a plastic full-scale model was constructed to test for clearances and
laser beam access to the cathode. See the following figures.
Figure 1 - Oblique View of Standard Cell Inside the Lower Section
Figure 1 shows the lower portion of the plastic model box with my standard electrolytic cell. Twin lasers are shown
irradiating the cathode through two laser ports. The white squares are meant to simulate the size and shape of 30 mm
square peltiers, commonly available. Inside the lower portion of the box four 3/8 inch dowel rods are visible
supporting two 40mm x 40mm squares of copper plate that will provide a DC/AC electric field for cathode
stimulation. The dowel rods will also serve as magnet holders when required. A copper coil can also be wrapped
around the cell for RF stimulation. Two 14 mm diameter holes directly behind the cell will serve as wire access
ports for instrumentation, DC/AC and RF stimulation. The wires will be epoxied in the pass-through holes with
thermally conductive epoxy. The laser access ports will be covered with glass. The gas vent tube shown in the photo
will also be fed through the access ports behind the cell.
Figure 2 - Oblique View of Transparent Plastic Top
Figure 2 shows the addition of a plastic lid to show how the cell will fit in the finished copper box. When a four inch
fan is added to the inside top of the lid, there will be 31.3 mm of head space. Close but adequate if the cell leads are
designed to turn 90 degrees as does the electrode to the right in figure 2. The cell will probably be placed on very
small spacers so that air will circulate under the cell during operation, which will reduce the headspace by about 1
mm.
Figure 3 - Front View of Plastic Model
Figure 3 shows the complete plastic model box with the front panel covered in simulated 30 mm square peltiers. The
top portion of the box was spray painted with a copper color to suggest the intended material to be used in the final
design. Of course, each peltier will have a set of electrical leads and suggests that using jumbo peltiers would be
helpful. 50mm and 62 mm peltiers are commonly available and would lend themselves well to this application. A
few 30 mm peltiers will be required because annular peltiers have not been found in the jumbo size - 26 mm and 30
mm peltiers are manufactured with a hole in the center. It is anticipated that the laser wavelength can be measured
by reflection at the laser ports.
Figure 4 - Top View
Figure 4 shows a top view of the 120 mm x 120 mm x 12.7 mm square base. The base fits snugly inside the bottom
part of the copper box, which is to be slightly larger than 120 mm x 120 mm. The 12.7 mm thick copper base will
provide mechanical strength and rigidity to accommodate the wire pass-throughs and the copper plate/magnet
holders. The exterior bottom of the copper base will also be covered with peltier devices to sense the flow of heat
from the cell through the copper base out to the temperature controlled environment. Ambient temperature control
will be critical to the overall precision of the calorimeter. The Avanti has a seven year history of controlling the
ambient environment to within +/- .03 C [1]. While it's difficult to predict the actual performance of the calorimeter
until it is built, this calorimeter design is based partly on that used by Storms [2]. It is anticipated that this
calorimeter will have a precision of approximately +/- 50 mW on input power of 10 Watts. This will exceed the 3%
precision requirement of task 1. Other shop drawings follow.
Figure 5 - Front View of Lower Section and Cell
Figure 5 shows the cell sitting in the lower portion of the calorimeter. The 12.7 mm base is shown in cross section
supporting the cell. The copper plate/magnet holders are not shown in this view. The 14 mm diameter laser ports
provide access for irradiating the cathode. The laser ports will be covered with at least one pane of thin glass. The
width and depth of the lower portion of the box will probably be 120.25 mm to provide clearance for the top of the
copper box to be inserted into the lower portion of the box. The idea is that all heat flow from the cell will encounter
a peltier attached to the outside of the copper box. All of the copper box surface area will be covered by peltier
devices capable of generating a substantial voltage in response to a temperature difference across the calorimeter
walls. This voltage will be calibrated against cell input power to create a regression equation for use when testing
cells that might produce excess power. The calibration procedure is well known and described by Storms [2].
Figure 6 - Front View Assembled
Figure 6 shows a front view of the entire calorimeter with fan and cell dimensions marked. As currently designed ,
the cell will fit in the calorimeter with a head space clearance of 31.3 mm. It is possible that a fan with a smaller
profile can be located, which will provide additional head space clearance. The clearance now available is deemed to
be acceptable. The top and bottom sections of the calorimeter will be joined thermally by a 6 mm overlap of copperto-copper. This should provide good thermal coupling to the peltiers located near the joining seam.
b. Define the cathode and anode materials. Letts will test a minimum of 8 electrolytic cells for the codeposition project.
Cell 1 - The anode will be .5 mm diameter platinum wire, .999 purity, 10 mm diameter with 5 turns over 10 mm
length. The cathode will be 6 mm x 8mm x .6mm copper substrate, co-deposited with palladium and deuterium.
Cell 2 - The anode will be .5 mm diameter platinum wire, .999 purity, 10 mm diameter with 5 turns over 10 mm
length. The cathode will be 6 mm x 8 mm x .6 mm copper substrate, plated with 24kt gold , co-deposited with
palladium and deuterium.
Cell 3 - The anode will be .5 mm diameter platinum wire, .999 purity, 10 mm diameter with 5 turns over 10 mm
length. The cathode will be 6 mm x 8mm x .6mm copper substrate, co-deposited with titanium and deuterium.
Cell 4 - The anode will be .5 mm diameter platinum wire, .999 purity, 10 mm diameter with 5 turns over 10 mm
length. The cathode will be 6 mm x 8 mm x .6 mm copper substrate, plated with 24kt gold , co-deposited with
scandium and deuterium.
Cell 5 - The anode will be .5 mm diameter platinum wire, .999 purity, 10 mm diameter with 5 turns over 10 mm
length. The cathode will be 6mm x 8mm x .20 mm palladium bulk loaded with deuterium; gold will be plated over
the cathode after loading with deuterium for 120 hours .
Cell 6 - The anode will be .5 mm diameter platinum wire, .999 purity, 10 mm diameter with 5 turns over 10 mm
length. The cathode will be 6mm x 8mm x .20 mm palladium bulk loaded with deuterium; gold will be plated over
the cathode after loading with deuterium for 120 hours .
Cell 7 - The anode will be .5 mm diameter platinum wire, .999 purity, 10 mm diameter with 5 turns over 10 mm
length. The cathode material will be determined by the results obtained from cells 1 through 6. This cell will be
taken to NRL for demonstration.
Cell 8 - The anode will be .5 mm diameter platinum wire, .999 purity, 10 mm diameter with 5 turns over 10 mm
length. The cathode material will be determined by the results obtained from cells 1 through 6. This cell will be
taken to NRL for demonstration.
c. Define the chemistry of the electrolyte.
Cell 1 - The electrolyte composition will follow that used by Szpak et al, .025 M PdCl2 + .3 M LiCl in 100 g D2O.
Cell 2 - The electrolyte composition will follow that used by Szpak et al, .025 M PdCl 2 + .3 M LiCl in 100 g D2O.
Cell 3 - The electrolyte composition will be .025 M TiCl4 +.3 M LiCl in 100 g D2O.
Cell 4 -The electrolyte composition will be .025 M ScCl3 + .3 M LiCl in 100 g D2O.
Cell 5 - Electrolyte composition will be .5M LiOD in 100 g D2O.
Cell 6 - Electrolyte composition will be .5M LiOD in 100 g D2O.
Cell 7 - Electrolyte composition will be determined by the results obtained from cells 1 through 6. This cell will be
taken to NRL for demonstration.
Cell 8 - Electrolyte composition will be determined by the results obtained from cells 1 through 6. This cell will be
taken to NRL for demonstration.
Note that if excess power is produced in cells 1 or 2, then Letts may elect to continue with the Pd-D co-deposition
methods of Szpak et al for all 8 cells. If the Szpak method does not produce excess power in cells 1 or 2, then Letts
will follow the protocol outlined in parts b and c above.
d. Define the geometry configuration of the cathode and anode.
All cells will be the standard electrolytic cell used by Letts since 1995. The cell is a Kimax 200 ml glass vessel, No.
14020. The lid is custom-machined Teflon with 7 pass-throughs, o-ring sealed. The lid has a second groove to hold
the recombiner pellets from Alfa-Aesar. The system is closed with orphaned gas vented through a 5 mm glass tube
connected to a flexible tube. The cathodes will be centered inside a 10 mm diameter platinum anode spiral. Two
photos follow.
Figure 7 - Side View of Standard Cell
Figure 8 - Top View of Standard Cell Teflon Lid
Figure 7 shows the Kimax 14020 cell which is 104 mm tall and 57 mm in diameter. The lid adds 7 mm to the height
of the glass body for an overall height of 111 mm. Figure 7 shows the geometry of the anode and cathode.
Figure 8 shows the Teflon lid which is 70 mm wide at its top and has 7 pass-throughs that are o-ring sealed. The
pass-throughs accommodate 5 mm glass tubing. The pass-throughs will be utilized as follows:
#1
Cathode (center)
#2
Anode
#3
T1
#4
T2
#5
On-board 10 Ohm resistance heater
#6
Vent tube
#7
Spare pass-through; will be used to accommodate a second anode when plating gold in-situ is required.
e. Define suitable controls to rule out the null result.
A control cell will be fabricated. It will be identical in all respects to the cells under test. The anode will be .5 mm
diameter platinum wire, .999 purity, 10 mm diameter with 5 turns over 10 mm length. The cathode will be 6 mm x 8
mm x .25 mm platinum foil.
The electrolyte composition will be H2SO4 mixed to a concentration in 100 g of H2O to produce a cell resistance of
9-10 Ohms. The calorimeter will be calibrated using this cell and a post-run calibration will be performed after any
run that produces apparent excess power. Recall that a 10 Ohm resistance heater will also be in each cell so that an
on-the-fly calibration check can be made without interrupting the experiment. The calorimeter will be calibrated
using both resistance and electrochemical heat sources and any sensitivity to the type of heat source used will be
characterized prior to testing.
f. Make an estimate of cost for one or more electrolytic systems.
The system is comprised of cell body, lid, o-ring seal, recombiner pellets, 100 g of D2O, salts or co-depositional
additives , anode, cathode , one resistance heat source, two temperature probes and the calorimeter.
Cell:
Item
Cell Body, Kimax 14020-200
Lid, Teflon custom made1
O-ring/glass electrodes
Recombiner pellets #89106
D2O, 100 g #151882-100g
Salts, additives2
Anode Pt wire3 43288 (25 cm)
Cathode, Pd4 #11917
Resistance Heat Source
Temperature probes (2) #44033
Vendor
Colonial Scientific
United States Plastic Corp.
Austin Seal/Richland Glass
Alfa Aesar
Aldrich
Aldrich
Alfa Aesar
Alfa Aesar
George Luce, Austin, TX
Omega
Total
Cost
$ 5.00
$100.00
$ 1.00
$ 10.00
$ 75.00
$ 25.00
$146.00
$ 25.00
$ 25.00
$ 50.00
$462.00
1. Raw stock is estimated at $40 and machining cost is estimated at $60 for a total of $100.
2. Salts and additives are estimated based on a total cost of $250 for various chemicals; approximately 10% of the
material used on a single cell.
3. Letts plans to use 1/16 " copper rod sealed inside glass tubing for hook-up wire. Platinum wire will only be used
when in contact with electrolyte, saving significant platinum cost.
4. Bulk Palladium will be used only for cells 5 and 6. Cells 1-4 will be co-deposited using salts & additives.
Calorimeter:
Item
Copper Plate and Base
Vendor
Online Metals.com
Cost
$ 150.00
fabrication/machining
Peltiers
4 inch brushless DC fan
Avanti #EWC16B
Thermistors (6) #44033
Resistance heater for Avanti
6 Brushless DC fans for Avanti
Custom Sheet Metal (Austin)
Heibi Ltd (China)
Fry's Electronics
Target
Omega
United Nuclear-Nichrome wire
Fry's electronics
Total
$1,200.00
$ 500.00
$ 20.00
$ 150.00
$ 150.00
$ 20.00
$ 120.00
$2,310.00
Combined materials cost for co-deposition project:
8 Cells @ $462
Calorimeter
Sub-total
Temperature Controlled Box (Avanti)
Avanti components
Total
$3,696.00
$2,310.00
$6,006.00
$ 150.00
$ 290.00
$6,446.00
Project Summary:
Item
Cells, calorimeter, Avanti & components
Labor
Contracting fees
Travel to NRL for 5 days (plus equip. shipping)
Total project cost
Cost
$ 6,446.00
$ 9,000.00
$ 2,000.00
$ 2,554.00
$20,000.00
References
[1] Letts, D, Cravens, D., Hagelstein, P.,
Thermal Changes in Palladium Deuteride Induced by Laser Beat
Frequencies. American Chemical Society Symposium Series, Low Energy Nuclear Reactions Sourcebook, Oxford
University Press, August, 2008; Jan Marwan, Steven Krivit, editors.
[2] Storms, Edmund, Anomalous Heat Produced by Electrolysis of Palladium using a Heavy-Water Electrolyte.
Submitted to Thermochimica Acta, May 2006.
Task 2
4/25/2009 10:48:00 AM
April 9, 2009
Funds for task 1 completion arrived and task 2 work began. Checked with vendors for parts availability and lead
time. The effects of a global economic collapse were detected - parts and equipment that used to be "off-the-shelf"
are not available without a substantial lead time.
April 14, 2009
1.
Ordered Stanford Research 5kV power supply to produce high E fields for use during co-deposition.
2.
Ordered required peltier devices from vendors (see vendors section below for complete information).
3.
Completed shop drawing for the Seebeck Cell (see the shop drawings section below);this drawing indicates that
twelve 50 x 50 mm peltier devices, three 15 x 30 mm peltier devices , two 15 x 23 mm peltier devices and nine
15 x 15 mm devices with a 7.2 mm hole in the center will be required. Five lid pass-throughs are anticipated,
not nine.
Note that the two views shown in the shop drawing are for a cell height that provides for head space and one that
does not. The head space decision will depend on how the pass-throughs are handled. If Aerogel is needed to
prevent heat loss through the top, then head space will be required. This will be driven by the availability of
thermoelectric devices with small holes in their centers. Ordered all thermoelectric devices; so far, I've been lucky everything was in stock.
April 16, 2009
Located and purchased two small immersion heaters, small diameter epoxy dispensing syringe and heat shrink
tubing. Ordered chemistry labware required for the co-dep experiments.
April 17-22
Upgraded lab computer and wireless modem to operate on "N" band instead of "G". This has increased internet
speed and reliability. Set up a website with the domain name lettslab.org. Will spend the next few days finalizing
web site design to provide an internet viewable lab notebook for use by NRL during the co-deposition experiments.
As of 4-22-09 about one third of the supplies needed for the experiments have been received. I expect all supplies to
be delivered by approximately April 30.
April 23-24
Received more materials and chemicals; worked on web site design and content selection.
Task 3
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Task 4
4/25/2009 10:48:00 AM
NRL Calorimeter Shop Drawings
4/25/2009 10:48:00 AM
Drawing 1 shows the top view of the ½ inch thick copper base; shown are the outline of the cell, left and right
parallel plate/magnet holders and two wire access ports.
Drawing 2 shows the cell sitting in the lower part of the calorimeter; two laser ports are shown providing access for
laser stimulation of the cathode. The ½ inch copper base is also shown in cross section. The calorimeter shop
drawings are shown in millimeters because the peltier devices are usually manufactured with this scale.
Drawing 3 shows the full view of the calorimeter, including the 4 inch fan epoxied to the inside of the calorimeter
top and the ½ inch copper base. Note the 6 mm overlap provided where the top and bottom sections of the
calorimeter join. The copper overlap is provided to transfer heat more efficiently to the peltier devices located at the
union of the two sections.
The 6 mm overlap will be provided in one of two ways: (1) the lower section will be made slightly larger than the
top section so the top section will contact slide inside the lower section. (2) The two sections will butt together and a
6 mm copper strip will be welded to the upper section, providing a thermal barrier across the joining seam. The
method used will be determined during the fabrication phase, as recommended by the sheet metal specialist at
Custom Sheet Metal of Austin, Texas.
April 09, 2009 - New NRL calorimeter design
Drafted Seebeck cell shop drawings. This calorimeter design may be more effective than the design shown above.
Drawings are shown below.
The Seebeck cell is a custom-made quartz glass cell 43.8 mm square and 143.8 mm tall. A square Teflon lid is
provided with o-ring seals. The square design allows direct attachment of peltier devices to the outside surfaces of
the cell. The peltier devices are of three sizes. Twelve peltier devices will be 50 x 50 x 3.1 mm; three devices will be
15 x 30 x 3.1 mm and two devices will be 15 x 23 x 3.1 mm. The peltier devices will be thermally connected to the
cell by use of thermally conductive double-sided tape. This will permit easy removal of the peltier devices. When
laser access is required, a solid 50 x 50 mm device can be replaced with 5 devices as shown in the drawing above.
This will provide a 5 x 43.8 mm slit for laser access and for cathode viewing. A wider slit can be provided by using
all devices that are 15 x 23 mm. Slit would then be 12 x 43.8 mm. When laser access is not required, a solid 50 x 50
mm device can be used.
Fabrication Process
4/25/2009 10:48:00 AM
Vendors
4/25/2009 10:48:00 AM
o
Vendors for this project:
1.
http://www.alltest.us, 5 kV Stanford Research power supply
2.
http://www.shop.customthermoelectric.com , Thermoelectric devices
3.
http://www.lairdtech.com, thermoelectric devices with hole in center (Monai Huston) Part No SH 1.0-2308L, 150 pieces in stock at $18. Devices for pass-throughs.
4.
http://www.watlow.com, small immersion heater, custom made $32 (1/8 x 1.5 "), Jim Ebbert, 314-628-4917;
Southwest Heaters 214-340-7500 (Buy through Southwest Heater and Control. Watlow (Jim Ebbert) is the
manufacturer, part no. is C1J-9415.
5.
http://www.united nuclear.com , chemistry labware, beakers, test tubes
6.
http://www.hebeiltd.com.cn , thermoelectric modules (China)
7.
http://www.digikey.com , 2252 ohm thermistors
8.
http://www.ellsworth.com , epoxy dispensing syringe
9.
http://www.midwayusa.com , desiccant for glove box
10. http://www.sigmaaldrich.com , chemicals for co-deposition experiments
11. http://www.alfa.com , Platinum wire
Final Report
4/25/2009 10:48:00 AM