Pd Complex. Pd complex containing CaO. Thin Pd Film : 400A. CaO and Pd Layers :1000A. Bulk Pd : 0.1mm

Transcription

1 Pd Complex Pd complex containing CaO Thin Pd Film : 400A CaO and Pd Layers :1000A 25mm 25mm Bulk Pd : 0.1mm

2 Transmutation of Cs into Pr 133 Cs 55 Atomic N. +4 Mass N Pr 59

3 Transmutation of Sr into Mo 88 Sr 38 Atomic N. +4 Mass N Mo 42

4 Transmutation of Ba into Sm 137,138 Ba 56 Atomic N. +6 Mass N Alpha 149,150 Sm 62

5 Isotopic Anomaly of the Detected Mo Ion intensity (cps) Mo Natural Abundance Mass number Ion intensity (cps) Sr/Pd/CaO/Pd # Mass number Ion intensity (cps) Sr/Pd/CaO/Pd # Mass number Ion intensity (cps) Sr/Pd/CaO/Pd # Mass number

6 Evaluation of D 2 Gas Flow Rate D 2 D 2 試料 P C001 Flow Rate Calibration Unit C007 C002 C003 Mass Flow Controller for D 2 gas C007 TMP TMP C006 C002 C006 C002 DN 2 DP DP D 2 By-pass Line D 2 Pressure Measurement

7 Identification of Pr by TOF-SIMS(2) No D 2 Gas Permeation Cs Pd Pd CaO TOF-SIMS device (TRIFT TM Ⅱ;ULVAC-PHI)

8 Cs 添加 Pd 多層膜重水素透過後 Cs D Counts(cps) Pr 10ppb 14ng/cm 2 Pd Pd CaO Pr を検出 定量 141 Mass Number

9 Transmutation of Tm into Ta 173 Tm 69 Atomic N. +4 Mass N Ta 73

10 Element Addition (1: Electrolyte Addition) Pd Complex 1V Pd Complex Pt Cs or Sr 1mM CsNO 3 /D 2 O solution or 1mM Sr(OD) 2 /D 2 O solution Pd Complex

11 Element Addition (2: Ion Implantation) Pd Complex Cs Ion implantation Cs + Cs (18kV,1.0E15 ions/cm2) Pd Complex Pd Complex

12 Identification of Pr by XANES XANES(X-ray Absorption Near Edge Structure) Pr-L III Edge absorption 6 absorbance(a.u.) X-ray energy(kev) BL-9A Line, KEK, Tsukuba, Japan

13 Identification of Pr by ICP-MS Cs D Counts(cps) Pr 10ppb 14ng/cm 2 Pd Pd CaO Quantitative Analysis 141 Mass Number

14 Preparation of the Pd Complex Washing a Palladium Sample with Acetone 900 C 10H Annealing under Vacuum -7 Condition (< 10 Torr) Washing the Sample with Aqua Regia (100sec) 5 times Alternatingly Sputtering of CaO(20A ) and Pd(180A ) Ion Beam Sputtering of Pd only (400A ) Pd 400A Pd 0.1mm 25mm 25mm CaO/Pd 1000A

15 Procedure of an Experiment Element A Detected Elements by XPS D 2 Pressure Element B Sample Preparation Set the sample Heat up the sample 0 Time 760 Torr 760 Torr 10-8 Torr 10-8 Torr 10-8 Torr 0 D 2 gas Permeation Evacuation Time D 2 gas Permeation Evacuation XPS Pd D D 2 Gas Evacuation

16 Transmutation of Sr into Mo 88 Sr 38 Atomic N. +4 Mass N Mo 42

17 Excess Energy and Q-value Cs d Pr+ ( γ, phonon, e 59?) Q 50. 5MeV EXH = 800J Experimental results 14 Pr 10 atoms reaction time 100h P 2. 2mW EXH Undetectable in our experimental setup

18 Depth Profile of Cs and Pr : Ion Implantation 100A 変換試験前 Cs before Cs Pr Cs MHI001 変換試験後 Cs SK84 変換試験前 Before After P r M H I 変換試験後 P r SK 8 4 Counts(arv.unit) Cs after Pr after 0 Pr before Sputtering time(sec)

19 Surface Distribution of Cs and Pr : Ion Implantation Sample:Cs + Ion Implantation Analysis:Tof-SIMS(ULVAC fai) Cs Pr before 100μm after 100μm

20 Depth Profile of Cs and Pr : Electrolyte Addition 100A Counts(arv.unit) 変換試験前 Pr after Cs Pr Cs 未分析 変換試験後 Cs SK79 変換試験前 Before After P r 未分析 変換試験後 P r SK Cs after Sputtering time(sec)

21 Ultra Low Energy Beam Model D Permeation(D Flux) Ultra low D beam R = Cs σ N φ 3 R : reaction rate(event/cm /sec) 2 σ : cross section(cm ) N Cs : Number of 2 φ : Deuteron beam flux(1/cm /sec) Cs (1/cm 3 ) Given Cs; N D flux;φ Cs η = ( R N ) ( ) Cs dt = σ φ dt = σ t φ t t dt f FL Texp / S / φ dt t FL : Flow rate(sccm) T exp : Reaction Time(sec) 2 S : Permeation surface area(cm ) η FL Agree with the experimental results

22 Rough Estimation of the Cross Section η = σ f FL T / S exp = σ FL / = σ [ cm ] FL[ sccm] 3 10 [ 1/ cm / sccm] Experiment al results 0.3 = σ 3 10 σ [ ] 2 cm = 1[ barn] 23 cf. σ = c 27.2barn : 133 Cs for thermal neutron

23 Separation of the Products and Contaminants(1) 1.Rare Earth Element : Pr a) D 2 gas :The purity > 99.6% most of the impurity is H 2 ~0.4% N 2, D 2 O, O 2, CO 2, CO, HC<10 ppm b) A Pd complex deposited with Cs Pr < detection limit (0.01 ppt) by ICP-Mass If all of the Pr at 0.01ppt distributed in the Pd test piece gathered in the analyzed area, Max contamination Pr~0.1ng Less than the detected Pr(10ng~100ng)! D? Pd Complex? Pr Pr Pr (0.1 mm, 0.7 g)

24 Separation of the Products and Contaminants(2) 2. Anomalous Isotopic Composition: Mo Isotope ratio (%) Detected Mo Mass number Isotope ratio (%) Natural Mo Mass number Detection of Pr and Mo cannot be explain by contamination. Pr and Mo are the products of nuclear transmutation reactions.

25 Surface Distribution of Cs and Pr : Electrolyte Addition Sample:Cs is added using electrochemical method Analysis:Tof-SIMS(ULVAC fai) Cs Pr 100μm 100μm

26 Results from the depth profile and the surface distribution analyses Transmutation occurs in the thin surface region up to 100 angstrom. Correlated with D/Pd? Important to surface analysis The surface distribution of Pr basically seems to be uniform. There is no correlation between Pr and grain boundaries. However, in the case of electrolyte addition, slight non uniformity of Pr was found. Migration of Pr? Due to non uniformity of Cs addition?

27 実験装置概観 静電アナライザー 静電アナライザー 導入重水素ガス X 線銃 P D 2 D 2 試料 X 線銃 反応容器 TMP B-A TMP 試料ステージ D 2 透過重水素ガス 排気

28 試料ステージ概観 TC ヒーター

29 重水素ガスの透過経路 Analyzed region by XPS D 2 gas Pd Complex Test Piece Chamber Wall

30 Identification of Pr by TOF-SIMS(2) No D 2 Gas Permeation Cs D Pd Pd CaO TOF-SIMS device (TRIFT TM Ⅱ;ULVAC-PHI)

31 Quantitative Analysis of Pr by ICP-MS Step1:Solve the surface of the Pd Complex by nitric acid (The nitric acid is Ultra high purity; impurity Ni,Pb~50ppt Step2:Quantitative Analysis of the solution by ICP-MS ICP-MS(Inductively Coupled Plasma Mass Spectrometry) High Sensitivity: Detection Limit ~ Pr 0.1ng Necessary to exclude Molecular Ions Device:SEIKO Instruments: SPQ9000

32 Examination of Molecular Ions Pd 102(1%) 104 (11%) 105 (22%) 106 (27%) 108 (26%) 110 (12%) Pd(NO) PdO No molecular ions interfering Mass 141(Pr) in this system

33 No D 2 Gas Permeation Cs Pd Pd CaO Pr は検出されず

34 F.G.Data(1) Ion counts(counts/sec) 133 Cs 141 Pr:53.9ppt 38ng/cm 2 Mass Number

35 F.G.Data(2) Ion counts(counts/sec) 133 Cs 20ng/cm Pr:12.8ppt Mass Number

36 Analysis of the Standard Solution Ion counts(counts/sec) 133 Cs Standard solution Cs : 100ppt Pr : 20ppt 141 Pr Mass Number

37 Transmutation Dependence on the Element Addition Method 1V Pd Complex Pt Cs + CsNO3 Positive 1mM CsNO 3 /D 2 O solution Pd Complex Cs + Cs Positive Pd Complex CsNO3 Drop CsNO 3 Negative

38 Conjecture on D distribution in the Pd Complex D/Pd P D2 =1atm? Pd thin film D CaO/Pd ~1E-9(cm 2 /sec) CaO/Pd compound Pd bulk D Pd =1.5E-6(cm 2 /sec) FL=2sccm:D/Pd=0.17 FL=4sccm:D/Pd=0.34 P D2 =0 C t 2 C = D 2 x t = 0 C Q = A J = A D x C A DCaO / Pd x = A D D Pd C x Pd D CaO / Pd Pd CaO / Pd 40nm 100nm 0.1mm Depth C x CaO / Pd C x Pd

39 Cross Sectional View Suppressor Disk(Cu) D 2 Thin Pd film, CaO and Pd Layers Bulk Pd Chamber Vacuum Wall (Type 316L SS) Gasket(Viton) Heater

40 Passage of D 2 Gas Analyzed region by XPS D 2 gas Pd Complex Test Piece Chamber Wall

41 Change of XPS Spectrum of Cs Cs3d 5/2 Cs3d 3/2 t=0 t=48h t=120h Counts (cps) Binding Energy (ev)

42 Change of XPS Spectrum of Pr Pr3d 5/2 Pr3d 3/2 t=0 t=48h t=120h Counts (cps) Binding Energy (ev)

43 Time Variation in number of Cs and Pr atoms in the case of D 2 Permeation through thin film and bulk Pd with added Cs Number of atoms (/10 14 /cm 2 ) Cs D Pd Pd Time (h) Cs Pr

44 XPS Spectrum of Cs (No CaO) Pd/Pd/D2 Counts (cps) Cs3d 5/2 Cs3d 3/ Binding Energy (ev) t=0 t=116h

45 XPS Spectrum of Pr (No CaO) Pd/Pd/D2 Counts (cps) Pr3d 5/2 Pr3d 3/2 t=0 t=116h Binding Energy (ev)

46 Time Variation in number of Cs and Pr atoms in the case of H 2 Permeation through Pd Complex with added Cs Number of atoms (/10 14 /cm 2 ) Cs H Pd Pd CaO Cs Pr Time (h)

47 XPS Spectrum of Cs(H 2 Permeation) Pd/CaO/Pd/H2 Counts (cps) Cs3d 5/2 Cs3d 3/ Binding Energy (ev) t=0 t=116h

48 XPS Spectrum of Pr (H 2 Permeation) Pd/CaO/Pd/H2 Counts (cps) Pr3d 5/2 Pr3d 3/2 t=0 t=116h Binding Energy (ev)

49 Average Permeation Rate and Products Electrochemical Addition Ion Implantation 電解添加イオン注入添加 Pr (ng/cm2) Average D 2 gas permeation rate:fl(sccm)

50 Total Permeated D2 Gas and Conversion Rate 100 Electrochemical Addition Ion Implantation Conversion rateη (%) Total Permeated D2 gas (cm3)

51 Total Permeated D2 Gas and Products 120 Electrochemical Addition Ion Implantation 100 Pr (ng/cm2) Total Permeated D2 gas (cm3)

52 Change of XPS Spectrum of Sr Counts (cps) Sr D Pd CaO Pd Sr3d 5/2 Sr3d 3/2 t=0 t=72h t=240h t=408h Binding Energy (ev)

53 Change of XPS Spectrum of Mo Counts (cps) Sr D Pd CaO Pd Mo3d 5/2 Mo3d 3/2 t=0 t=72h t=240h t=408h Binding Energy (ev)

54 Time Variation in number of Sr and Mo atoms in the case of D 2 Permeation through thin film and bulk Pd with added Sr Number of atoms (/10 14 /cm 2 ) Sr D Pd Pd Sr Mo Time (h)

55 XPS Spectrum of Sr (No CaO) Pd/Pd/D2 Counts (cps) Sr3d 3/2 Sr3d 5/2 t=0 t=149h t=294h Binding Energy (ev)

56 XPS Spectrum of Mo (No CaO) Pd/Pd/D2 Counts (cps) Mo3d 5/2 Mo3d 3/2 t=0 t=149h t=294h Binding Energy (ev)

57 Time Variation in number of Sr and Mo atoms in the case of H 2 Permeation through Pd Complex with added Sr Number of atoms(/10 14 /cm 2 ) 10 Sr Mo 5 0 Sr H Pd Pd CaO Time(h)

58 XPS Spectrum of Sr (H 2 Permeation) Pd/CaO/Pd/H2 Counts(cps) Sr3d 5/2 Sr3d 3/2 t=0 t=122h t=406h Binding Energy(eV)

59 XPS Spectrum of Mo (H 2 Permeation) Pd/CaO/Pd/H Mo3d 5/2 Mo3d 3/2 t=0 t=122h t=406h Counts(cps) Binding Energy(eV)

60 Separation of the Products and Contaminants(3) 3. Variation of Detected Elements depending on the given Elements Cs Pr, Sr Mo Li Al, C S,Si Number of Atoms (X10 13 ) C Mg S No.3 Si C Pd/CaO/Pd Mg S Si C Mg Si S Time(hour) Number of Atoms (X10 13 ) (Li) F Al (C) Mg Si F No.5 Mg Pd, Li/CaO/Pd Al Si F Mg Al Si If the detected elements were contaminants, was it possible that the detected elements changed depending on the given elements?

61 The other observations C Mg Si C Mg S Li F Na Al

62 Necessary Conditions Necessary Conditions to Induce Low Energy Nuclear Reactions 1. Enough Deuterium Flux 2. Sufficient D on the Pd surface 3. Existence of a third element except Pd and D Experimental Results