Deuterium Permeation Induced Transmutation Experiments ...newenergytimes.com/v2/conferences/2014/MIT/Iwamura-MIT-2014.pdf · Deuterium Permeation Induced Transmutation Experiments

© 2014 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved.

Deuterium Permeation Induced

Transmutation Experiments using

Nano-Structured Pd/CaO/Pd Multilayer

Thin Film

Y.Iwamura, S.Tsuruga and T.Itoh

Advanced Technology Research Center,

Mitsubishi Heavy Industries, ltd., Japan

2014 CF/LANR（Cold Fusion/Lattice Assisted Nuclear Reactions） Colloquium at MIT,

March.21-23, 2014, Massachusetts Institute of Technology, Cambridge, MA, USA

TECHNOLOGY & INNOVATION HEADQUARTERS

Contents

1© 2014 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved.

1. Introduction

3. Preliminary Results on Consecutive

Transmutation Experiments

2. Results of Batch Process Experiments

4. Replication Experiments by Toyota Central

Research and Development Laboratories

2-1. Transmuted Products Analyzed by

ICP-MS, SIMS and XPS

2-2. Observation of g-ray peaks


2

1. Introduction



Features of Our Method

3

D2 gas permeation through nano-structured Pd complex

真空

重陽子透過

CaOCaO 2nm

D Flux

Vacuum

D2 gas

D Permeation

Cs,Ba, etc.

Pd nano-sized multilayer film

Pd 20nm

Surface

CaO 2nm

Pd 40nm



Reactions observed in the case of Gas Permeation

SmBad

150

62

)3(6138

56

4

SmBad

149

62

)3(6137

56

Pr141

59

)2(4133

55

d

Cs

MoSrd

96

42

)2(488

38

1)Alkali metals; Electron Emitter

2)2d, 4d, 6d; capture reactions

TiCad

48

22

)(244

20

OsWd

188

76

)(2184

74

PtWd

190

78

)2(4182

74



Progress in Permeation Experiments

© 2014 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved. 5

～2010

Gas

Permeation

;Basic

Research

2011～2012

Increase of Products

for Future Application

2013～Consecutive Processing

Batch Processing Addition of fixed

quantity of Cs

Consecutive Processing

Aiming

Consecutive

Transmutation

of Cs

Pump

Cs Solution

D

Reaction cell

Pd/CaO/Pd


6

2. Results of Batch Process Experiments


2-1. Transmuted Products Analyzed by

ICP-MS, SIMS and XPS


7

Pr Dependence on D2 gas pressure

0

10

20

30

40

50

0 20 40 60 80 100

230kPa

赤：高圧

青：低圧

0

10

20

30

40

50

0 20 40 60 80 100

５０℃低圧

５０℃高圧

６０℃低圧

60℃高圧

70℃低圧

70℃高圧

80℃低圧

80℃高圧

90℃低圧

90℃高圧

５０℃低圧

５０℃高圧

６０℃低圧

60℃高圧

70℃低圧

70℃高圧

80℃低圧

80℃高圧

90℃低圧

90℃高圧

50℃ LP

50℃ HP

60℃ LP

60℃ HP

70℃ LP

70℃ HP

80℃ LP

80℃ HP

90℃ LP

90℃ HP

120～130kPa180～230 kPa

LP： 120～130kPaHP： 180～

230kPa

Red: High Pressure

Blue:

Low Pressure

Pr141

59

133

55 Cs

Conversion Rate(%)

Am

ou

nt

of

Pr

(ng/c

m2)

Pressure Pr



Gas vs. Electrochemical Permeation

8

Gas Permeation Electrochemical Permeation



9

Experimental Apparatus aiming Increase of D Density



10

SIMS Analysis; E006 Wide Spectra

Mass Number

E-006 center

E-006 corner

No Implantation

No Implantation: Corner

100 120 140 160 180 20010

2

103

104

105

106

SIM

S C

ou

nts

Increase around mass140

Decrease of 133Cs

Pd multilayer film

Center

Corner

D permeated



11

SIMS Analysis; E006

139La?

140Ce?

141Pr

142Ce?

130 135 140 145 150

20000

40000

60000

80000

100000 E-006 center

E-006 corner

No Implantation

No Implantation: Corner

SIM

S C

ounts

Mass Number

Pd multilayer film

Center

Corner

D permeated



12

ICP-MS Analysis; E006

SIMS (point) and ICP-MS (all surface) gave similar results

130 135 140 145 150

2000

4000

6000

8000

10000

Cs Implantation; E006

No Implantation

Co

un

ts

Mass Number

139La?

140Ce?141Pr

142Ce?

Different Tendency from D2 gas permeation © 2014 MITSUBISHI HEAVY INDUSTRIES, LTD. All Rights Reserved.


Confirmation of the products by XPS

13

930 940 950 960

18400

18800

19200

19600

20000 E6 permeated

Counts

(E6)

Energy(eV)

Pr 3d5/2

Pr 3d3/2

CuF2 2p3/2

CuF2 2p1/2Pr confirmed by XPS



14

2-2. Observation of g-ray peaks



15

Introduce a Gamma-ray Detector

Ge Detector for g-

ray measurement

Reactor Cell

Pb Shield



16

Example of Gamma-Ray Detection; E16

Cs ion implanted

1×1016/cm2 20kV

D Permeation

rate is

proportional to

this pressure

0 2 4 6 8 10 12

3

4

5

Ap

pli

ed

Vo

ltag

e(V

)

Period 1 Period 2 Period 3 Background

10days

Pd/Y2O3/Pd multilayer film

0.5MCsNO3-D2O Solution

Cs

Y2O3



17

Gamma-ray Measurement (period 1 )

Live time = 233,425sec

Gam

ma-

ray C

ount

Rat

e (c

ps)

Energy (keV)

~609.5keV

-0.005

0.000

0.005

0.010

600 610 620 630 640 650

E16 period1

s



18


Live time=574,586sec

Gam

ma-

ray

Count

Rat

e (c

ps)

Energy (keV)

E16 period2

~511.5keV;

Annihilation peak?

500 520 540 560 580

-0.004

-0.002

0.000

0.002

0.004



19


Live time=71,826sec

500 520 540 560 580-0.004

-0.002

0.00

0

0.002

0.004

Gam

ma-

ray

Count

Rat

e (c

ps)

Energy (keV)

~511.5keV;

Annihilation peak?

E16 period3



20

E16 Gamma-ray Measurement Summary

Time Gamma-ray

Period 1 609.5keV gamma-ray detected

No 511keV detected


No 609.5keV detected


No 609.5keV detected



Pr detected by XPS from the center of E16 sample


930 940 950 96026000

27000

28000

29000

30000

31000

32000

33000

Energy(eV)

Counts

(E16)

E16 permeated

35000

36000

37000

38000

39000

40000

41000

Counts(N

o p

ermeatio

n)

No permeation

Pr 3d5/2Pr 3d3/2




E28

Pd/CaO/Pd multilayer film

0.1MCsNO3-D2O Solution

Period 1 BackgroundPeriod 2 21days

CaO


1445keV

E28 ;1200-1600keV

1200 1250 1300 1350 1400 1450 1500 1550 1600

1E-3

0.01

0.1

E28

E28A

BFB15

Y A

xis

Tit

le

X Axis TitleEnergy(keV)

Em

issio

n R

ate

(cp

s)

Period 1

Period 2

Background

Clear g–ray peak

at 1445keV40K peak


1745keV

E28 ;1700-1850keV

1700 1750 1800 1850 1900

1E-4

1E-3

0.01

0.1

E28

E28A

BFB15

Y A

xis

Tit

le

X Axis TitleEnergy(keV)

Em

issio

n R

ate

(cp

s)

Period 1

Period 2

Background


Discussion on emitted g-ray during E28 period1

Unstable nuclei that emit g-ray ranging from 1444.5 to 1445.5keV

Energy(keV) cps

1445 3.50E-03

1109 1.00E-03

1745 3.00E-04

507.4 5.00E-04

578.9 1.00E-04

605 5.00E-04

Detected g-ray energy

We have not succeed to find a nucleus fit for the observed g-ray energies.

・g-rays from unstable nuclei

・g-rays from excited nuclei

・Thermal neutron capture g-rays

Observed g-rays seems to be attributed to minor short lived nuclei.


26

3. Preliminary Results on Consecutive

Transmutation Experiments



Batch vs. Consecutive Processing


Batch Consecutive

Pump

Cs Solution

D

Reaction cell

Pd/CaO/Pd

Addition of fixed quantity of Cs Circulation of Electrolyte


Cooling Pd Surface by Circulation of Electrolyte


Temperature(C)

Deu

teriu

m D

ensi

ty [

D/P

d]

T D/Pd

Cooling is important!

Circulation of Electrolyte


Experimental Setups for Consecutive Transmutation


Pump

Reservoir

Reaction Cell

N2 Flow meter

Evacuation

Electrolyte

N2 for Purge

Pd/CaO/Pd

（Cathode）

Pt

（Anode）

All Contact Surfaces with Electrolyte are made of Teflon to Avoid Contamination.

0.1M CsNO3

200mL


Reaction rates; Batch vs. Consecutive Processing


0 0.05 0.10 0.15 0.20 0.25

Current Density(mA/cm2)

Rea

ctio

n R

ate

[μg

/cm

2/w

eek

]

10

1

0.1

0.01

Batch Processing

Consecutive processing


Products; Batch vs. Consecutive Processing


Pd/CaO/Pd Thin Film 0.1M CsNO3 Solution

BatchConsecutive

BatchConsecutive

La

CePr

La

[g/cm2] [g/solution]

Ce Pr

0

2.0E-7

1.0E-7

1.5E-7

5.0E-8

0.0E+0

2.0E-7

1.0E-7

1.5E-7

5.0E-8

0.0E+0

Batch : Products

Consecutive : Products

On the Pd Thin Film

In Solution


32

4. Replication Experiments by Toyota

Central Research and Development

Laboratories, Inc.



33

Toyota Paper

T.Hioki et.al, Jpn. J. Appl. Phys. 52(2013) 107301


34

Experimental Setup

T. Hioki et.al, Jpn. J. Appl. Phys. 52(2013) 107301


35

Results

T. Hioki et.al, Jpn. J. Appl. Phys. 52(2013) 107301

Pr

2.5X1012/cm2

Cs/Pd/CaO/

Pd with D

permeation


36

Concluding Remarks

Deuterium Permeation Induced Transmutation Reaction

have been observed in the Pd complexes, which are

composed of Pd and CaO thin film and Pd substrate.

1.

2. Electrochemical permeation aiming the increase the local

deuteron density near the surface of Pd made increase

transmuted products.

Statistically significant g-rays which have clear energy

spectra were detected. At present, we have limited examples.

Further study is necessary.

3.

Preliminary consecutive transmutation experiments gave us

higher reaction rates than batch processing up to now.

Much products were recovered in the solution.


4.

Toyota R&D Lab successfully reproduced permeation

induced transmutation of Cs into Pr. 5.


37

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Deuterium Permeation Induced Transmutation Experiments ...newenergytimes.com/v2/conferences/2014/MIT/Iwamura-MIT-2014.pdf · Deuterium Permeation Induced Transmutation Experiments