ICCF-15
Evaluation of the Claim of Transmutation of Cesium to Praseodymium with the Mitsubishi Heavy Industries (MHI)
Structure – Part 1
Kenneth Grabowski, David Kidwell, Catalina Cetina, and Carmine Carosella
Naval Research LaboratoryWashington, DC 20375
ICCF-15
Summary of MHI Claims By permeating Deuterium though a Pd complex foil,
various elemental transmutations can be made to happen– Reported transmutations:
• 88Sr 96Mo Addition of 4D• 133Cs 141Pr Addition of 4D• 137Ba 149Sm Addition of 6D
(70°C)
Elemental Analysis of Pd Complexes: Effects of D2 Gas PermeationY. Iwamura , M. Sakano and T. ItohJpn. J. Appl. Phys. Vol. 41 (2002) pp. 4642–4650
ICCF-15
Pd complex used
Cross section TEM of Pd Complex,Y. IWAMURA, et al., Proc. ICCF-10, Cambridge MA 2003
25 mm x 25 mm
Thin Cs seed layer on surface
40 nm - Pd Cap Layer100 nm total - 5 x (2 nm CaO / 18 nm Pd)
100 µm - Bulk Pd
QuickTime™ and aTIFF (Uncompressed) decompressor
are needed to see this picture.
ICCF-15
Apparent transmutation of Cs into Probserved by XPS
1x1015 Pr = 235 ng
Elemental Analysis of Pd Complexes: Effects of D2 Gas PermeationY. Iwamura , M. Sakano and T. ItohJpn. J. Appl. Phys. Vol. 41 (2002) pp. 4642–4650
ICCF-15
NRL Research Effort
Collaborated with MHI to verify Pr present on their permeated samples– Initially with Accelerator Mass Spectrometry– Eventually with ICP-MS– NRL convinced Pr was present on some samples
NRL attempted to independently reproduce result– Modified XPS instrument to enable permeation of Pd sample– Built 5-sample chamber with line-of-site view of sample– Developed Pd-complex fabrication capability– Pd complex structures would not permeate sufficient D– Unsuccessful at producing Pr
Therefore, performed joint research with MHI
ICCF-15
Modified XPS and 5-Sample Chambers
Modified Sample Stage to Accept Reaction Cell
ICCF-15
Experimental Plan for Joint Research with MHI
Bulk analysis of Pd– Key decision point– Sufficient Pr to explain MHI result? – NO! < 10 ppb/wt, i.e., < 7 ng total
Sample production at MHI NRL observers at MHI Analysis at MHI and NRL
ICCF-15
NRL Analysis (Pr in components)
Group Cs solution Pd foil Comment
1 of 1 4 of 2 Executed of Planned MHI 106 (< 0.6 ng/cm2) GDMS by NRL MHI 107 (<0.6 ng/cm2) GDMS by NRL < 8 pg per 20 mL MHI 106 (42 pg/cm2) Bulk ICP-MS by NRL MHI 107 (53 pg/cm2) Bulk ICP-MS by NRL MHI 157 (<3 pg/cm2) Surface ICP-MS by NRL
MHI components
MHI 158 (<3 pg/cm2) Surface ICP-MS by NRL Cs Complex,
Non-Permeated Blank
Non-Cs Complex, Permeated
Blank
Cs Complex, Permeated Comment
0 of 3 0 of 3 3 of 3 Executed of Planned MHI 113 (<4 pg/cm2) Surface ICP-MS by NRL MHI 113 (36 pg/cm2) Bulk ICP-MS by NRL MHI 119 (10 pg/cm2) Surface ICP-MS by NRL MHI 119 (30 pg/cm2) Bulk ICP-MS by NRL MHI 124 (<3 pg/cm2) Surface ICP-MS by NRL
Chisai
MHI 124 (42 pg/cm2) Bulk ICP-MS by NRL
ICCF-15
Observer’s Tasks
Monitor all production steps of selected samples– Starting materials and their cleaning– Annealing foils– Etching foils– Deposition of multilayer film– Deposition of Cs– Permeation processing– Storing and shipping
ICCF-15
Observer’s Tasks (2)
Record observations without disrupting tasks– Video recording of key steps– Audio recording of instructions– Notations of events
Review observations– Amongst NRL staff – With MHI staff, using translator for key discussions
Report back to US– Frequently, digitally and verbally– In summary documentation
ICCF-15
Foil - Analysis Layout(typical)
ICP-MS @MHI
TEAMS @ NRL
ICP MS @ NRL
Note: Lower 2/3 Sent to NRL for Analysis
X
Reserved
Cs D2
ICCF-15
Foil Specimens Planned
No Bulk RedistributionNot From D2
Initial Structure Free of Pr
Pr ProductionPr Not in Pd FoilDemonstrates:
6662Total
333ChisaiChamber
333XPS Chamber
Non-Cs Complex, Permeated
Cs Complex, Non-Permeated
Cs Complex, Permeated
Pd Foil, as Manufactured
Sample Cs blank Perm. blank
ICCF-15
MHI samples & MHI analysis
* Data listed from Takasago/Toray facilities
Group Cs Complex,
Non-Permeated Blank
Non-Cs Complex, Permeated
Blank
Cs Complex, Permeated Comment
3 of 3 3 of 3 3 of 3 Executed of Planned
MHI 127 (0 ng/cm2) MHI 123 (0 ng/cm2) MHI 118 (13.4/20 ng/cm 2) Surface ICP-MS by MHI
MHI139 (0 ng/cm2) MHI 135 (0 ng/cm2) MHI 131 (7.8/9.2 ng/cm 2) Surface ICP-MS by MHI XPS
MHI 151 (0 ng/cm2) MHI 147 (0 ng/cm2) MHI 143 (13/26 ng/cm 2) Surface ICP-MS by MHI
1 of 3 1 of 3 4 of 3 Executed of Planned
MHI 101 (0 ng/cm2) MHI 109 (0 ng/cm2) MHI 103 (0 ng/cm2) Surface ICP-MS by MHI
MHI 113 (0 ng/cm2) Surface ICP-MS by MHI
MHI 119 (0 ng/cm2) Surface ICP-MS by MHI
MHI 124 (0 ng/cm2) Surface ICP-MS by MHI
Chisai
Unknown Problem On Hold
Total 4 of 6 4 of 6 7 of 6 Executed of Planned
SampleCs blank Perm. blank
ICCF-15
Evaluation of the Claim of Transmutation of Cesium to Praseodymium with the MHI
Structure – Part 2
David Kidwell, Kenneth Grabowski, Catalina Cetina, and Carmine Carosella
Naval Research LaboratoryWashington, DC 20375
(202)[email protected]
ICCF-15
Summary of MHI Claims By permeating Deuterium though a complicated layer
various elemental transmutations can be made to happen– Reported transmutations:
• 88Sr 96Mo Addition of 4D• 133Cs 141Pr Addition of 4D• 137Ba 149Sm Addition of 6D
From: C. Carosella - Visual Observations of MHI and NRL
Samples
Cross section of Pd complex (Pd/CaO/Pd) observed by TEM.From: Iwamura, Y., et al. Low Energy Nuclear Transmutation In Condensed Matter
Induced By D2 Gas Permeation Through Pd Complexes: Correlation Between Deuterium FluxAnd Nuclear Products. in Tenth International Conference on Cold Fusion. 2003.
ICCF-15
Rare Earths in the EnvironmentRare earths are not so rare
Hair REs Only
0
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0.016
0.018
DAK 2-12-97 DAK 9-7-98 DAK 4-17-02 DAK 8-7-04
La139(MR)Ce140(MR)Pr141(MR)Nd143(MR)Nd145(MR)Nd146(MR)Sm147(MR)Sm149(MR)
Currency REs
0
2
4
6
8
10
12
$20 bill 1:10 dilution all REs Norm al scan
ng/m
L
La139(MR)
Ce140(MR)
Pr141(MR)Nd143(MR)
Nd145(MR)
Nd146(MR)Sm 147(MR)
Sm 149(MR)
Comparison of RE ratios of Pd bulk with a flint
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
La139(MR) Ce140(MR) Pr141(MR) Nd143(MR) Nd145(MR) Nd146(MR)
Flint124.2 bulk113.2 Bulk119.2 Bulk
Environmental sources of Pr– Flints – “Misch Metal”– Specialty glazes on ceramics– Phosphors in CRTs (tends to be with other REs)
ICCF-15
Molecular Interferences or Misch Metal Contamination?
No!
Reanalysis of MHI118 for mass 137-181
0
20000
40000
60000
80000
100000
120000
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
PdAr
Pr
PrO
W=>
?
Ba and XeH
Two different ICP-MS instruments
ICCF-15
Raw ICP-MS Curves for MHI-006-boxSpectra shown at various resolutions
Low - file#Oct20d15LR
High -file#Oct20d15HR
Medium - file#Oct20d15MR
0
50000
100000
150000
200000
250000
300000
350000
400000
140.5 140.6 140.7 140.8 140.9 141 141.1 141.2 141.3 141.4 141.5
Pr = 140.907Pd105-Ar36 = 140.87263028Pd106-Cl35 = 140.87233571Pd104-Cl37 = 140.8699376
140.9
m/Δm = 500
0
5000
10000
15000
20000
25000
30000
35000
40000
140.85 140.87 140.89 140.91 140.93 140.95 140.97 140.99
140.87
Pr = 140.907Pd105-Ar36 = 140.87263028Pd106-Cl35 = 140.87233571Pd104-Cl37 = 140.8699376
140.9135
m/Δm = 7,400
Pr-141
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
140.84 140.86 140.88 140.9 140.92 140.94 140.96 140.98 141
140.87
Pr = 140.907Pd105-Ar36 = 140.87263028Pd106-Cl35 = 140.87233571Pd104-Cl37 = 140.8699376
140.9135
m/Δm = 16,800
Masses not perfect due to magnet drift
ICCF-15
Cross Validation of Pr Levels 15 extracts & 6 blanks were sent from MHI 18 Confirmed negative for Pr – LOD <0.045 ng/cm
– Includes 6 controls with the three positives (three sets of three)– One set from baby chamber – all negative
• Included a fully permeated sample
5.54%
-1.50%
5.00%
% Difference
9.29.1MHI131
2425MHI143
1920MHI118
NRLconcentration
ng/cm2
Toray concentration
ng/cm2
Sample
ICCF-15
0
10
20
30
40
50
60
70
80
90
100
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
MHI118.2 1:5MHI127.2 1:5MHI123.2 1:5MHI131.2 1:5MHI135.2 1:5MHI139.2 1:5MHI143.2 1:5MHI147.2 1:5MHI151.2 1:5
BaO/BaOHPdAr
Ba
Pr
Cs
Xe and PdAr Contribution SubtractedNormalized
More Detailed Scan of the Nine SamplesExtracted at MHI – Analyzed at NRL
Note clean RE levels and high Cs levels
ICCF-15
Concentration on Surface from BulkNo!
Levels too low to account for Pr in permeated samples– Methodology discussed at ICCF-14
0.0360.114MHI113.2
0.0420.121MHI124.2
0.0300.108MHI119.2
Pr (ng/cm2)Blank
subtracted
Pr (ng/cm2)Raw
Sample
From UM 9-25-05
ICCF-15
Foil - Analysis Layout(typical)
ICP-MS @MHI
TEAMS @ NRL
ICP MS @ NRL
Note: Lower 2/3 Sent to NRL for Analysis
X
Reserved
ICCF-15
Big Issue – Could not find Pr at NRL on our part of the foils!
ICCF-15
Example Showing That NRL Could HaveObserved Pr, If Present
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
0 10 20 30 40 50 60 70
Etching Time in Minutes
Tota
l Pd
Rem
oved
(ug)
SP8-8 extracted 2 times-ASP8-13 extracted 2 times-AMHI147.2.2 All remaining piece-AMHI143.2.2 All remaining piece-AMHI151.2.2 All remaining piece-A
Addition of HCl Catalyst
Controlled etching done on all samples– Discussed at ICCF-14
8 aliquotes taken and bulk analysis done– >100 samples + banks + controls
No Pr found
ICCF-15
Example Showing That NRL Could HaveObserved Pr, If Present
One series spiked with equivalent of 170 pg/cm2 Pr (~100x lower than expected)
Raw Pr Levels from MR
020406080
100120140160180
SP8-8 -ESP8-13 -E
MHI147 .2.2 -EMHI143 .2.2 -EMHI151 .2.2 -E
SK228 7-13-06-E
MHI123 .2.2 -EMHI118 .2.2 -EMHI127 .2.2 -E
SK229 7-19-06-E
MHI135 .2.2 -EMHI131 .2.2 -EMHI139 .2.2 -E
5% NA B lank #3 10-02-06
5% NA B lank #3 10-02-06 spiked with 5 pg P
SP8-8 -E Spike
d 5 pg P
SP8-13 -E Spike
d 5 pg P
MHI147 .2.2 -E Sp ike
d 5 pg P
MHI143 .2.2 -E Sp ike
d 5 pg P
MHI151 .2.2 -E Sp ike
d 5 pg P
SK228 7-13-06-E Spiked 5 pg P
MHI123 .2.2 -E Sp ike
d 5 pg P
MHI118 .2.2 -E Sp ike
d 5 pg P
MHI127 .2.2 -E Sp ike
d 5 pg P
SK229 7-19-06-E Spiked 5 pg P
MHI135 .2.2 -E Sp ike
d 5 pg P
MHI131 .2.2 -E Sp ike
d 5 pg P
MHI139 .2.2 -E Sp ike
d 5 pg P
ICCF-15
Possible Explanationsfor failure to find Pr
Wrong part of foil– Systematic issues – statistically improbable
Pr migrates into the interior – bulk analysis should find it!– Have done bulk analysis on MHI118 and essentially negative
Pr lost in transit or handling– Film unstable – Pr should be in boxes – checked and no
Pd catalyzes reverse nuclear reaction with time?– Real stretch of science
Pr not there – we clearly have the required sensitivity and specificity
ICCF-15
Months worth of work (frustration) later… Not etching enough Pd foil
– Loss of deuterium with time causes lower Pd etching Traveled to MHI to observe process and extract a freshly
prepared sample– Participated in extraction using their equipment on a fresh
sample– Take split sample extracts
Samples extracted at MHI in the presence of NRL personnel were negative at NRL and negative with a commercial laboratory in Japan
On whim, do environmental survey
ICCF-15
Results from Environmental SurveySummary of Pr from RE wipe scans
0
2000000
4000000
6000000
8000000
10000000
12000000
14000000
16000000
Vent C
over
#2
Hood in
side #
1
Hood I
nside #
2
Desk S
urface
- 3rd
floor
Inside
chem
lab -
3rd f
loor
Floor an
d top of
chem
lab
Prep be
nch -
clea
n roo
m
7-10-0
6 aceto
ne for ri
nsing -
after
rinse
Near b
alance
#1
Inside B
alance
#1
Hood s
ide and le
g
Inside
sputte
r cha
mber aft
e r sputt
ering
Copper
holde
r for X
PS chambe
r
Inside
XPS ch
amber
Near B
alanc
e #2
Vent lo
uvers
#1
Supply
air lo
uvers
#1
Sample
holder
for spu
tter c
hamber a
fter u
se
XPS cham
ber
Dust n
ear fl
oor m
ats
Supply
air #
2
Storage box
for e
lemen
ts
Top of
stora
ge ca
bnet
#2
Cabne
t abo
ve ac
id ca
bnet
Bot tom
cabn
et
Acid ca
bnet c
orros
ion
Genera
l dust
on top
of el
ectro
nics
Electro
chem
ical c
ell
Wipe in
side sp
uttere
r befo
re sp
utterin
g#1
Wipe in
side s
puttere
r befo
re sp
utterin
g#2
Electro
chem
ical h
older
Backin
g in X
PS chambe
r
Inside
balanc
e wipe #
2Ent r
y floo
rWaste
box
Storage ca
bnet
Floor b
y sto rag
e cab
net
Raw
Cou
nts
ICCF-15
Excess 137Ba and Thulium Found in SamplesOrigin??
Reanalysis of MHI118 for mass 137-181
0
20000
40000
60000
80000
100000
120000
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
PdAr
Pr
PrO
W=>
?
Ba and XeH
0
10
20
30
40
50
60
70
80
90
10013
7
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
m/z
MHI118.2 1:5MHI123.2 1:5MHI127.2 1:5MHI131.2 1:5MHI135.2 1:5MHI139.2 1:5MHI143.2 1:5MHI147.2 1:5MHI151.2 1:5
BaO/BaOH
Xe and PdAr Contribution Subtracted
x20
ICCF-15
Results from Environmental SurveySummary of Tm from RE wipe scans
0
500000
1000000
1500000
2000000
2500000
3000000
3500000
Vent C
over
#2
Hood in
side #
1
Hood In
side #
2
Desk S
urface
- 3rd
floor
Inside
chem
lab -
3rd f
loor
Floor a
nd to
p of c
hem la
b
Prep benc
h - cl
ean r
oom
7-10-0
6 ace
tone f
or rinsin
g - af
ter rin
se
Near ba
lance
#1
Inside B
alance
#1
Hood s
ide and
leg
Inside sp
utter
cham
ber a
fter s
putte
ring
Coppe
r hold
er for
XPS chambe
r
Inside
XPS ch
amber
Near Bala
nce #
2
Vent lo
uvers
#1
Supply
air lo
uvers
#1
Sample
holder
for spu
tter c
hambe
r afte
r use
XPS cham
ber
Dust n
ear fl
oor m
ats
Supply
air #
2
Storage bo
x for
e lemen
ts
Top of
stora
ge ca
bnet #
2
Cabinet
abov
e acid
cabine
t
Bot tom
cabin
et
Acid ca
bnet c
orros
ion
Genera
l dust
on to
p of e
lectro
nics
Electro
chem
ical c
ell
Wipe in
side s
puttere
r befo
re sp
utterin
g#1
Wipe in
side sp
uttere
r befo
re sp
utterin
g#2
Electro
chemica
l hold
er
Backin
g in XPS ch
amber
Inside
balanc
e wipe #
2Entry
floo r
Waste bo
x
Sto rage ca
binet
Floor b
y sto rag
e cabin
et
Raw
Cou
nts
ICCF-15
Trace Elements in Samples
0.001Blank
0.008SubstantialMHI139.2.2 -E
0.199SubstantialMHI131.2.2 -E
0.006NoMHI135.2.2 -E
0.003NoSK229 7-19-06-E
0.029SubstantialMHI127.2.2 -E
0.082SubstantialMHI118.2.2 -E
0.006NoMHI123.2.2 -E
0.004NoSK228 7-13-06-E
0.016SlightMHI151.2.2 -E
0.150SubstantialMHI143.2.2 -E
0.004NoMHI147.2.2 -E
0.002NoSP8-13 -E
0.005NoSP8-8 -E
Total amount of Tm found (LR mode)
Excess Ba137
presentSample
Highlighted lines are the positive samples
ICCF-15
SpeculationExplanations of Results
Two types of contamination occur: ICP-MS
– Extraction at MHI – contaminates the solutions• MHI extracts show Pr but NRL extracts do not• Individual doing extraction left MHI
–“Lucky” tweezers??• Last samples prepared and extracted in presence of NRL personnel are blank
in situ measurements - XRF/XPS – increase with permeation in a highly localized area – Contamination from dust in balance – contaminates the interior of the multi-layer
structure with small particles of Pr• Blank runs not sensitive enough to see buried Pr
–Under surface and localized• Pr migrates to surface under influence of the Deuterium flux
–Spreads as migrates• Looks like production of Pr!
ICCF-15
SpeculationScenario for how this contamination could have occurred
– MHI tried other elements, believed to see 133Cs 141Pr by in situ XPS• Cu can be confused for Pr• Needed standard of Pr – made one up in the laboratory to confirm XPS or ICP-MS analysis
• From that time forward, actually was looking at Pr but from whatsource?
–In initial XPS results, believed to see Sr Mo.• Secondary Ion Mass Spectrometry appeared to confirm 88Sr 96Mo• Observing other transmutations appears to strengthen each observation
–How strong was the evidence?
ICCF-15
Be Wary of Cluster IonsSecondary Ion Mass Spectrometry (SIMS)
Example: was 96Mo due to a cluster ion?
0.00E+00
1.00E+02
2.00E+02
3.00E+02
4.00E+02
5.00E+02
6.00E+02
7.00E+02
8.00E+02
9.00E+02
1.00E+03
80 85 90 95 100 105 110 115 120
Excess Mo96?
0
10
20
30
40
50
60
70
80
90
100
0
10
20
30
40
50
60
70
80
90
10 0
92 9 3 94 95 9 6 9 7 98 99 1 00
Mo
ICCF-15
Be Wary of Cluster IonsSecondary Ion Mass Spectrometry (SIMS)
Example: was 96Mo due to a cluster ion?
Observe Pd+40 (likely Ca), why not 56Fe+40Ca mass 96
0.00E+00
1.00E+02
2.00E+02
3.00E+02
4.00E+02
5.00E+02
6.00E+02
7.00E+02
8.00E+02
9.00E+02
1.00E+03
80 85 90 95 100 105 110 115 120
Excess Mo96?
0
10
20
30
40
50
60
70
80
90
100
0
10
20
30
40
50
60
70
80
90
10 0
92 9 3 94 95 9 6 9 7 98 99 1 00
Mo
0.00E+00
5.00E+02
1.00E+03
1.50E+03
2.00E+03
2.50E+03
3.00E+03
3.50E+03
4.00E+03
4.50E+03
5.00E+03
50 70 90 110 130 150 170
PdCaFe56
Pd
Excess Mo96?
0
10
20
30
40
50
60
70
80
90
100
0
10
20
30
40
50
60
70
80
90
100
94 95 96 97 98 99 100 101 102 103 104 105 106
FeCa
ICCF-15
Conclusions The complex, multi-layer MHI structure was claimed to
transmute elements Praseodymium is in the samples extracted by MHI at
MHI– Analyzed by ICP-MS by NRL and a commercial laboratory
with good agreement in results– Praseodymium in positive samples but not in controls– Praseodymium not in bulk palladium– Praseodymium signature not consistent with typical
contamination from misch metal from the environment
ICCF-15
Conclusions Praseodymium could NOT be extracted at NRL by NRL from
split portions of the samples Environmental surveys at MHI by NRL and MHI found
Praseodymium in key areas of laboratory 137Ba and Thulium also found on positive samples and in
laboratory at MHI– Not on historic samples prior to this study– Both handled previously to this study– Found in key areas of laboratory
Presence of Praseodymium may have other explanations than transmutation of Cs
“We are to admit no more causes of natural things than such as are both true and sufficient to explain their appearances.”- Isaac Newton
ICCF-15
AcknowledgementsFunding from DARPA is gratefully acknowledged. The insights provided by Graham Hubler, Michael Melich, Rodney Johnson, Alexander Ehrlich, and David Knies were very helpful. This work could not have been accomplished without the gracious help of Yasuhiro Iwamura, Takehiko Itoh, and Mitsuru Sakano.
Disclaimer: the views, opinions, and/or findings contained in this presentation are those of the presenter and should not be interpreted as representing the official views or policies, either expressed or implied, of the Defense Advanced Research Projects Agency or the Department of Defense.
Approved for Public Release,Distribution Unlimited (DARPA DISTAR 14224, 09/09/09)
NRL Release number - 09-1226-3241
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