evaluation of the claim of transmutation of cesium to...

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


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


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



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

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151

152

153

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155

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157

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159

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161

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165

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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

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137

138

139

140

141

142

143

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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


d 5 pg P


d 5 pg P

SK228 7-13-06-E Spiked 5 pg P


d 5 pg P


d 5 pg P


d 5 pg P

SK229 7-19-06-E Spiked 5 pg P


d 5 pg P


d 5 pg P


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

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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

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149

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151

152

153

154

155

156

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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


0.006NoMHI135.2.2 -E

0.003NoSK229 7-19-06-E



0.006NoMHI123.2.2 -E

0.004NoSK228 7-13-06-E

0.016SlightMHI151.2.2 -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

evaluation of the claim of transmutation of cesium to...

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