Progress on Transmutation Experiments induced by D 2 gas permeation

12th International Workshop on Anomalies in Hydrogen Loaded Metals Progress on Transmutation Experiments induced by D 2 gas permeation T.Itoh 1,2, J. Kasagi 1, Y.Iwamura 1, S.Tsuruga 3 1 Condensed Matter Nuclear Reaction Division, Research Center for Electron Photon Science, Tohoku University, Sendai 982-0826, Japan 2 CLEAN PLANET Inc., Tokyo 105-0022, Japan 3 Research & Innovation Center, Mitsubishi Heavy Industries, Ltd., Yokohama 236-8515, Japan 1

Cs Pr Transmutation MHI Experiments 133 55 Cs 141 59 Pr J. J. App. Phys. 41(2002)4642 2

No Cs, only Multilayer No Cs, No Multilayer Replicated experiment of Toyota lab Cs implanted Multilayer D 2 permeation Hioki et al. JJAP 52 (2013) 107301 3

Object Successive various measurements showed existencs of 141 Pr XPS, ICP-MS, Tof-SIMS, In-situ XRF at SPring8 There is a criticism that the mass of the nucleus was not identified, since the employed mass spectrometry, such as ICP- MS, cannot exclude possibilities of chemical compound objects. Direct assignment of the nucleus (141Pr) by using nuclear physics approach is highly demanded. Therefore, we employed the Rutherford Backscattering Spectroscopy (RBS) to identify 141 Pr for direct nuclear mass assignment. 4

Rutherford Backward Scattering RBS Scattered by Nucleus; Mass determined by kinematics Advantage for large A and Z Surface Elements Pd base dy ρ7007+7008 TNb(ds/dW)(x) dx = ρtnb(ds/dw)(e) (de/dx)-1de 1.E+04 40Ar, 128MeV dy1/de 1.E+03 dy1/dy2 ~ (ρ1/ρ2) (Z1/Z2)2 1.E+02 X dy2/de 1.E+01 x Example: Compare W on surface / Pd Pd density 6.8 1022 atoms/cm3 (ZPｄ/ZW)2 = (46/74)2 = 0.386 W is more sensitive than Pd by 2.6 times 1.E+00 650 850 1050 1250 1450 Distributed near surface W density 5.4 1020 atoms/cm3 5

Expected RBS Spectrum by irradiation 128-MeV 40 Ar Count [count/100kev] (1) Pt impurity in thick Pd :100 ppm (2) 133 Cs:uniformly distributed in 0-20 nm depth; 200ng/cm2 (3) 141 Pr: uniformly distributed in 0-10 nm depth; 60 ng/cm 2 30 ng/cm 2 15 ng/cm 2 10 6 10 5 10 4 10 3 10 2 60 ng/cm 2 30 ng/cm 2 15 ng/cm 2 10 1 0 10 20 30 40 50 60 Energy (MeV) 6

Cs transmutation sample by D 2 gas Permeation Washing a Pd Sample with Acetone 900 10H Annealing under Vacuum Condition Washing the Sample with Aqua Regia D 2 Fabrication Pd-CaO Multilayer using Ion Beam Spattering Cs Deposition D2 Gas permeation Sample for RBS was provided by MHI 7

Cyclotron Radioisotpe Center, Tohoku University ECR ion source + 930 AVF Cyclotron Large Scattering chamber 8

Geometric Arrangement of Beam, Target and detector Detector(Si) 128MeV 40 Ar 7+ Beam: 40 Ar 7+ 128MeV ~ 1 particle na Target Si detector: 300 m in thickness 300 mm 2 x3, 450 mm 2 x2 = 165 total = 0.083 sr Several-hour measurement for a sample to identify Pr of 10 ng/cm 2 9

Sensitivity of Pr identification RBS spectrum Pr-implanted Pd/CaO foil Pr Implanted:23.4 ng/cm 2 Measured:18.9±4.8 ng/cm 2 Reproduced well!! Pt BG: ~ 95 ppm of Pd By measuring several hours,10 ng/cm 2 -Pr can be detected with the confidence level of 99% (or statitical significance of 2.6σ). *test peace was provided by Toyota Central Research and Development Laboratories 10

Sample Target ZnSe Au Am test peace Pr Implantation 10 14 Pr:23.4ng/cm 2 Au(10nm)/Si FG sample(sk137) Cs:134ng/cm 2 Pr:74ng/cm 2 Pd Au FG sample(sk132) Cs: 94.6 ng/cm 2 Pr: 51 ng/cm 2 Ref Sample (Cs Dope, No D 2 Permeation) Ref Sample (Only Multilayer) test peace Cs Implantation Pt FG sample(sk130) Cs: 57.7 ng/cm 2 Pr: 50.8 ng/cm 2 11

Count [count/100kev] RBS spectrum:with D 2 gas permeation Summed spectrum of foreground samples 10 6 10 5 10 4 Thick Pd 141 Pr nat W A=192 W Pt?? 10 3 133 Cs 10 2 10 ~1/5000 100 ppm Pt 1 0 10 20 30 40 50 60 Energy (MeV) BG: mainly Pt impurity in thick Pd ~100 ppm BG determine a detection limit. 133 Cs:distributed 0-80 nm in depth nat W: distributed 0-80 nm in depth contamination of W(182,183,184,186) of multilayer (1) A tiny peak at A=141 ( 141 Pr) 141 Pr exists on the surface. not observed for without D 2 consistent with MHI report 12

Count [count/100kev] RBS spectrum:with D 2 gas permeation Summed spectrum of foreground samples 10 6 10 5 10 4 Thick Pd (1) 141 Pr nat W A=192 W Pt?? 10 3 133 Cs 10 2 10 ~1/5000 100 ppm Pt 1 0 10 20 30 40 50 60 Energy (MeV) BG: mainly Pt impurity in thick Pd ~100 ppm BG determine a detection limit. 133 Cs:distributed 0-80 nm in depth nat W: distributed 0-80 nm in depth contamination of W(182,183,184,186) of multilayer (1) A tiny peak at A=141 ( 141 Pr) 141 Pr exists on the surface. not observed for without D 2 consistent with MHI report 13

Count [count/200kev] Count [count/100kev] Count [count/200kev] RBS spectrum with D 2 gas permeation: Cs, Pr detection Sample name:sk132 40 30 20 Sample Name:SK132 Exp. Pt (BG) fit 10 4 Pd 10 10 3 10 2 Cs Pr 0 30 32 34 36 38 40 42 44 46 48 50 Energy [MeV] 40 Sample Name:SK130 10 1 Pt 30 20 Exp. Pt (BG) fit Pt(BG) 10-1 0 10 20 30 40 50 60 Energy (MeV) 10 0 30 32 34 36 38 40 42 44 46 48 50 Energy [MeV] 14

Pr amount comparison of ICP-MS and RBS Sample Name Analytical method Cs(ng/cm 2) Pr(ng/cm 2 ) SK130 ICP-MS 57.7 50.8 RBS 94.1±10.9 < 6 SK132 ICP-MS 94.6 51 RBS 37.8±5.9 < 5.1±2.6 SK137 ICP-MS 134 74 RBS 19.7±7.8 < 11 Pr test Sample Pr Implanted 23.4 RBS 19±5 Comparing between the results of ICP-Ms and RBS, quantitative agreement is not good. Y(RBS)/Y(ICP) = 0.15 ~ 1.63 for 133 Cs < 0.15 for 141 Pr Measurement points of ICP-MS and RBS are different? may be due to the local distribution of 141 Pr 15

Counts Non-uniform distribution of Pr (XRF @ SPring- 8) XRF study shows: Existing probability of Pr strongly depends on location Average value of Pr in 13-4 4.4 10 13 atoms/cm 2 100 micron beam;sp-24, 13-4 X Y 1 2 3 4 5 6 1 2 3 4 5 6 100μ m Much Pr detection Pr detection No Pr 13-4 1200 1000 100μ m 800 600 400 Point 4-4 (Much Pr detection) Point 3-4(Pr detection) Point 6-4(No Pr) Pr 4X1014 /cm 2 1X10 14 /cm 2 Cs 200 0 3.5 4 4.5 5 5.5 Energy(keV) Y. Iwamura et al., Condensed Matter Nuclear Science, World Scientific, New Jersey, p.178, 2006. 16

Count [count/100kev] RBS spectrum:with D 2 gas permeation Summed spectrum of foreground samples 10 6 10 5 10 4 Thick Pd (2) 141 Pr nat W A=192 W Pt?? 10 3 133 Cs 10 2 10 ~1/5000 100 ppm Pt 1 0 10 20 30 40 50 60 Energy (MeV) BG: mainly Pt impurity in thick Pd ~100 ppm BG determine a detection limit. 133 Cs:distributed 0-80 nm in depth nat W: distributed 0-80 nm in depth contamination of W(182,183,184,186) of multilayer (1) A tiny peak at A=141 ( 141 Pr) 141 Pr exists on the surface. not observed for without D 2 consistent with MHI report 17

W & Pt in Pd-CaO Multilayer Ion beam Sputtering Apparatus W Filament Pd Substrate Pd(multilayer&Substrate) contain Pt about 100ppm Pd-CaO multilayer contain W from ion source Ar Ion (1kV15 20mA) CaO(2nm) CaO(2nm) CaO(2nm) CaO(2nm) CaO(2nm) Pd(40nm) Pd(20nm) Pd(20nm) Pd(20nm) Pd(20nm) Target (Pd,CaO) Pd 100μm 18

Count [count/100kev] RBS spectrum:with D 2 gas permeation Summed spectrum of foreground samples 10 6 10 5 10 4 Thick Pd 141 Pr nat W A=192 W Pt?? 10 3 133 Cs 10 2 10 ~1/5000 100 ppm Pt 1 0 10 20 30 40 50 60 Energy (MeV) BG: mainly Pt impurity in thick Pd ~100 ppm BG determine a detection limit. 133 Cs:distributed 0-80 nm in depth nat W: distributed 0-80 nm in depth contamination of W(182,183,184,186) of multilayer (1) A tiny peak at A=141 ( 141 Pr) 141 Pr exists on the surface. not observed for without D 2 consistent with MHI report 19

RBS spectrum Pd multi-layer without Cs dope & D 2 permeation Count [count/100kev] Samle name: M115 Pd-CaOMultilayer 600 400 contamination from filament of ion source 200 0 46 48 50 52 54 56 58 60 Energy [MeV] 20

RBS spectrum Cs Doped multilayer without D 2 permeation Count [count/100kev] 60 Samle name: S55B Cs Pd-CaO Multilayer 40 W 20 Pt(impurity of Pd) 0 46 48 50 52 54 56 58 60 Energy [MeV] 21

RBS spectrum Cs Doped multilayer after D2 permeation Count [count/100kev] 80 Samle name: SK130 Cs Pd-CaO Multilayer 60 40 20 W D 2 Permeation Mass 192 0 Pt 46 48 50 52 54 56 58 60 Energy [MeV] 22

RBS spectrum Cs Doped multilayer after D 2 permeation Count [count/100kev] 400 Samle name: SK132 Cs Pd-CaOMultilayer 300 200 100 W D 2 Permeation Mass 192 0 46 48 50 52 54 56 58 60 Energy [MeV] 23

Count [count/100kev] Count [count/100kev] What is a peak A=192 Os? Ir?, Pt? Count [count/100kev] 40 20 Samle name: SK130 W? Sample W(ng/cm 2 ) A~192 (ng/cm 2 ) SK130 346±14 91.7±7.4 Sk132 697±13 90.8±5.0 Sk137 911±20 104±7 0 46 48 50 52 54 56 58 60 Energy [MeV] 40 30 20 Pt (Natural) Ir(Natural) Os(Natural) 20 10 Ir(Natural) W(Natural)+4d:Transmutation 10 0 50 51 52 53 54 55 56 57 58 59 Energy [MeV] 0 50 52 54 56 58 Energy [MeV] Ir natural : 191 Ir (37%) 193 Ir(63%) 24

Conclusion 1.We performed Rutherford Backscattering Spectroscopy (RBS) to identify 141 Pr for direct nuclear mass assignment. 2. For FG samples, we could identify the 141 Pr events as well as 133 Cs, although the statistics is not enough. A comparison of the results between ICP-Ms and RBS shows that a quantitative agreement is not good. Y(RBS)/Y(ICP) = 0.15 ~ 1.63 for 133 Cs < 0.15 for 141 Pr Measurement points of ICP-MS and RBS are different? may be due to the local distribution of 141 Pr 3. A broad peak indicating the existence of a nuclide with mass number around 192 was observed. There is a possibility that the impurity W in Pd/CaO multi-layer complex was transmuted 25

Acknowledge RBS measurement was partially supported by IMPACT Program of Council for Science, Technology and Innovation in 2015. Program name is Reduction and Resource Recycle of High Level Radioactive Wastes with Nuclear Transmutation. The authors would like to thank Mr. Ryo Tajima, Dr.Yuki Honda, and Prof. Hidetoshi Kikunaga for their corporations on RBS analysis, Research Center for Electron Photon Science, Tohoku University and Mr. Hideki Yoshino and Mr. Masanao Hattori for their supports. 26

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W+4d 183 W(19%) + 4d 191 Pt (τ 1/2 = 2.8 d) 28