Hydrogen Isotope Gas Absorption/Adsorption Characteristics of Pd Nanopowders

Size: px

Start display at page:

Download "Hydrogen Isotope Gas Absorption/Adsorption Characteristics of Pd Nanopowders"

Elfrieda Lloyd
5 years ago
Views:

1 Hydrogen Isotope Gas Absorption/Adsorption Characteristics of Pd Nanopowders A. Kitamura, Y. Miyoshi, H. Sakoh, A. Taniike (Division of Marine Engineering, Graduate School of Maritime Sciences, Kobe University) A.Takahashi, R. Seto, and Y. Fujita (Technova Inc) To be presented at ACS-NET 2011, Anaheim Kitamura ACSNET2011 1

2 Outline Extensive measurements of heat release under hydrogen isotope absorption/adsorption of 7 kinds (PP, PB, PZ, NZ, PNZ-I,PNZ-II, PNZ2B) of Pd nano-powders in a twin gas charging system have been made by Kobe group in Anomalies in heat and D(H)-absorption observed by Pd (and Pd-Ni) nano-powders dispersed into/onto ZrO2 support are briefly overviewed. Heat and absorption data for larger Pure Pd powder and Pd-Black are shown in concentration in the present report. Kitamura ACSNET2011 2

3 A1 A2 twin system for simultaneous D2/H2 absorption experiments. 3 Pressure gauge Vacuum gauge D 2 gas cylinder H 2 gas cylinder A 2 system A 1 system D 2 run H 2 run Reaction chamber Outer vacuum chamber Vacuum pumps Kitamura ACSNET2011 3

4 Reservoir tank Schematic of one of the twin absorption system. 4 Pressure gauge Super Needle valve Pressure gauge Vacuum pump Heater Reaction chamber Sample Insulation chamber Liq. N 2 trap T s T o T i Thermocouples H 2 or D 2 Vacuum pump Vacuum pump Chiller Kitamura ACSNET2011 4

5 Samples tested: 7 kinds 100nmf -Pd 99.5%, PP 100nmf Pd-black 99.9%, PB 300mesh mixed oxide PZ mixed oxide NZ mixed oxide PNZ mixed oxide PNZII mixed oxide PNZ2B Pd Ni Zr O Supplier Remarks (1.69) (3) (7) (0) (1.67) Nilaco Corp. Nilaco Corp. Santoku Corp. Santoku Corp. Santoku Corp. Santoku Corp. Dr. B. Ahern [1],[2], this report [1],[2], this report [1],[2],[3], ICCF16, ACS2011 [1] Phys. Lett. A, 373 (2009) [2] Low Eergy Nuclear Reactions, (AIP Conf. Proc. 1273, ed. Jan Marwan, 2010) to be changed to JCMNS4, [3] LENR Source Book 3, (ed. Jan Marwan, ACS) to be published. Kitamura ACSNET [2] [2] ICCF16, ACS2011 5

6 Experimental procedure Sample setup 6 Evacuation Baking (440K, 3h, vac.) Forced reduction {D 2 (H 2 ) gas charging at 570K for 24h} Forced oxidation {O 2 gas filling at 470K for 30h} Baking (570K, h, vac.) Evacuation (#2 run) (#3 run) (#1 run) (A/B run) Absorption run {D 2 (H 2 ) gas charging at R.T.} Data acquisition: Temp., Pressure, Radiation (neutron, ) Kitamura ACSNET2011 6

7 W D, W H (W) P D, P H (MPa) Heat Evolution appeared in Two Phases: for PZ Samples 0.4 Power D-PZ13#3 H-PZ14#3 D Pressure st phase 2 nd phase Time (min) Integration gives the 1 st phase specific output energy E 1. Kitamura ACSNET2011 7

8 Temperature [ ] Temperature [ ] Pressure [MPa] Pressure [MPa] Forced oxidization Time [min] Kitamura ACSNET2011 A1 T A2 T A1 Ps A2 Ps Dp D Time [min] 0.10 by introducing O 2 gas at a pressure of 0.2 MPa and a temperature of 470 K for 30 hours. The pressure difference Dp D is used to calculate the degree of oxidization, x for Pd+(x/2) O 2 PdO x 8

9 E 1 (ev/atom-pd) E 1 (ev/atom-pd) PZ11-14 sample (Pd:31.2% Zr:68.8%) PZ11,12#3run PdO/Pd(D2) : 86 PdO/Pd(H2) : D-PZ11 H-PZ PZ13,14#3run PdO/Pd(D2) : 73 PdO/Pd(H2) : 61 D-PZ13 H-PZ Bulk-like Data Bulk-like Data - - #1 #2 #3 #3d #3A #3Ad #3B 3Bd #1 #1d #1A #1Ad #1B #1Bd #2 #2d #3 #3d Comparison of the 1 st -phase specific output energy E 1 for the runs D(H)-PZ11(12)#1 through D(H)-PZ13(14)#3Bd Kitamura ACSNET2011 9

10 D/Pd, H/Pd D/Pd, H/Pd PZ11-14 sample (Pd:31.2% Zr:68.8%) 11 PZ11,12#3run PdO/Pd(D2) : 86 PdO/Pd(H2) : 54 PZ13,14#3run PdO/Pd(D2) : 73 PdO/Pd(H2) : 61 D-PZ11 H-PZ12 D-PZ13 H-PZ Bulk-like Data Bulk-like Data #1 #2 #3 #3A #3B #1 #1A #1B #2 #3 Comparison of the loading ratio D(H)/Pd for the runs D(H)-PZ11(12)#1 through D(H)-PZ13(14)#3Bd Kitamura ACSNET

11 Q D (ev/d), Q H (ev/h) Q D (ev/d), Q H (ev/h) PZ11-14 sample (Pd:31.2% Zr:68.8%) 12 PZ11,12#3run PdO/Pd(D2) : 86 PdO/Pd(H2) : 54 PZ13,14#3run PdO/Pd(D2) : 73 PdO/Pd(H2) : 61 D-PZ11 H-PZ12 D-PZ13 H-PZ14 Bulk-like Data Bulk-like Data #1 #2 #3 #3A #3B #1 #1A #1B #2 #3 Comparison of the hydridation energy Q D(H) for the runs D(H)-PZ11(12)#1 through D(H)-PZ13(14)#3Bd Kitamura ACSNET

12 W D(H) (W), h D(H) (ev/d(h)) W D(H) (W), h D(H) (ev/d(h)) W D(H) [W], h D(H) [ev/d(h)] W D(H) (W), h D(H) (ev/d(h)) Dynamic D(H)-Sorption Energy observed for PZ Samples: Larger for D-sorption in the Ia Phases h D D-PZ13#3 h H H-PZ14#3 W D W H Time Time (min) (min) h value for bulk Pd Time (min) 1a phase 1b phase 1a phase 1b phase Typical variation of the specific sorption energy, h D (h H ), compared with that of the power, W D (W H ), in the #3 run for the PZ13(14) sample. Kitamura ACSNET

13 W D(H) (W), h D(H) (ev/d(h)) W D(H) (W), h D(H) (ev/d(h)) W D(H) [W], h D(H) [ev/d(h)] W D(H) (W), h D(H) (ev/d(h)) #2 Run (After O-Reduction) for PZ Samples showed bulk-like data. D-PZ11#2 2.0 H-PZ12#2 17 h D h H W D Time Time (min) (min) h value for bulk Pd Time (min) W H 1b phase 1b phase Typical variation of the specific sorption energy, h D (h H ), compared with the power, W D (W H ), in the #2 run for the PZ11(12) sample. Kitamura ACSNET

14 W D(H) (W), P D(H) (MPa) Large Powder of Pure Pd :PP3,4#3 100-nmf Pd 18 - Significant Heat Peak After 0.19% Surface-PdO Formation Heat-Power Phase-I L H (t) L D (t) Pressure Phase-II Time (min) W-H W-D P-H P-D L-H L-D L D(H) - Kitamura ACSNET

15 E 1 [ev/atom-pd] PP3,4 sample (100-nmf Pd) ; Show the similar (but smaller) effect of oxidization O/Pd(D2) : 02 O/Pd(H2) : 02 D H -0.2 Bulk-like Data (Sorption-E = De-sorption-E) -0.3 PP3#1 PP3#1d PP3#2 PP3#2d PP3#3 PP3#3d PP3#3A Comparison of the 1 st -phase specific output energy E 1 for the runs D(H)-PP3(4)#1 through D(H)-PZ3(4)#3A Kitamura ACSNET

16 D/Pd, H/Pd PP3,4 sample (100-nmf Pd) ; Show the similar (but smaller) effect of oxidization O/Pd(D2) : 02 O/Pd(H2) : 02 D H PP3#1 PP3#1d PP3#2 PP3#2d PP3#3 PP3#3d PP3#3A Comparison of the loading ratio D(H)/Pd for the runs D(H)-PP3(4)#1 through D(H)-PZ3(4)#3A Kitamura ACSNET

17 Q D [ev/d], Q H [ev/h] PP3,4 sample (100-nmf Pd) ; Show the similar (but smaller) effect of oxidization O/Pd(D2) : 02 O/Pd(H2) : 02 D H Bulk-like Data PP3#1 PP3#1d PP3#2 PP3#2d PP3#3 PP3#3d PP3#3A Comparison of the hydridation energy QD(H) for the runs D(H)-PP3(4)#1 through D(H)-PZ3(4)#3A Kitamura ACSNET

18 η W D(H) (W) W D(H) (W) hd(h) (ev/d(h)) PP3,4 #1(right) and #3(left) (100-nmf Pd): Effect of slight PdO layer is great (Ia) cf. bulky (Ib) PP3,4#3 (After Oxidization) PP3,4#1 (As received, pure Pd) 2 Heat Power 0.9 1a phase 0.9 1b phase 1 1b phase Heat Power hd(h) (ev/d(h)) O/Pd(D2) : 02 O/Pd(H2) : 02 Time (min) h value for bulk Pd (ca. 0.3 ev) Time (min) Kitamura ACSNET

19 W D(H) (W), P D(H) (MPa) Palladium Black Samples PB5,6#1: Virgin Runs (10g each) Power D/Pd H/Pd W-H W-D P-H P-D L-H L-D L D(H) Time (min) -0.3 Kitamura ACSNET

20 W D(H) (W), η h D(H) (ev/d(h)) PB5,6#1; h-values vs. power Phase-Ia Phase-Ib Eta Eta-H Eta-D W-H W-D Power 0.2 Bulk Level Eta Time (min) Kitamura ACSNET

21 W D(H) (W), P D(H) (MPa) PB5,6#2; After Forced De-Oxidization 0.8 H/Pd Power D/Pd Pressure W-H W-D P-H P-D L-H L-D L D(H) Time (min) Kitamura ACSNET

22 η W D(H) (W), h D(H) (ev/d(h)) PB5,6#2 h-values vs. powers after De-oxidization Phase-Ib Only Eta-H 0.8 Power Eta-D W-H W-D Eta : Close to bulk values Time (min) Kitamura ACSNET

23 W D(H) (W), P D(H) (MPa) PB5,6#3: 2(D)-1.7(H)%PdO/Pd, After Oxidization 6.0 Ia Ib Phase-II D/Pd Power W-H W-D P-H P-D L-H L-D L D(H) Time (min) -0.2 Kitamura ACSNET

24 W D(H) (W), η h D(H) (ev/d(h)) PB5,6#3 h vs. Power: After Forced Oxidization (2-1.7%) Ia Phase Ib Phase Power Eta-H Eta-D W-H W-D Eta Time (min) Kitamura ACSNET

25 ev/atom-pd Integrated Heat Data for PB5,6 E D2 H Bulk-like Data #1 #1d #3 #3d #3A #3Ad #2 #2d #3_2 #3d_2 Kitamura ACSNET

26 Integrated Data for PB D2 H2 ev/atom-d(h) Absorption Energy per D(H) Saturated Loading Ratios D2 H Bulk-like Data L D, L H 0.8 Bulk-like Data #1 #1d #3 #3d #3A #3A #2 #2d #3_2 #3_2d 0 #1 #1d #3 #3d #3A #3A #2 #2d #3_2 #3_2d Kitamura ACSNET

27 Summary-1 PZ: 8-nmf Pd(31.2%) Zr(68.8%) (1)The 1st phase is found to be divided into sub-phases Ia and Ib; 1a phase; with rapid absorption/adsorption and high heat output. - Probably occurring in the near-surface region - Oxygen incorporation is necessary for this phase to appear. - h D value is larger than h H., several times in some cases. 1b phase; with a lower heat output nearly equal to the bulk value. (2) The 1a phase is observed only in #1 and #3 runs. (3)The as-received sample has very large 1 st -phase parameters; (specific output energy E 1D(H), the loading ratio D(H)/Pd~2.0, the hydridation energy Q D(H): (1.3) ev or more for D(H).) Forced reduction sample has given the significantly smaller 1 st -phase parameters (close to those for bulk Pd sample). Forced oxidization sample has substantially recovered the large values of the 1 st -phase parameters. Kitamura ACSNET

28 Summary-2 PP: 100-nmf Pd 99.5% (1) The similar effects are observed less prominently; - the existence of the 1a and 1b phases, and - increased absorption parameters by oxygen incorporation. - general trend is similar to the following PB behavior. PB: palladium black (1) Virgin (as received) samples gave high D(H)/Pd values (ca. ) and higher heat release than PP. (2) Slight PdO formation made more enhanced effect of initial large heat peak (QD(H): 1.2(1.1) ev/d(h)-sorption), Ia phase, and following Ib phase with bulky (ca. 0.3 ev/d(h)-sorption) heat power. (4) After the forced de-oxidization, heat levels and loading ratios gave bulk-like values (0.3 ev/d(h) and D(H)/Pd = ca. ) (5) The ratio of hd/hh is a little bit larger than for Ia phases. Kitamura ACSNET

29 Summary-3:Tested Metal/Ceramics Powders and Results 100nmf -Pd PP Pd-black PB 8-10nmf -Pd PZ mixed oxide NZ mixed oxide PNZ 2nmf-PdNi PNZ2B Pd Ni Zr O Supplier 995%, 100nmf 99.9%, 300mesh Nilaco Corp Nilaco Corp (1.64) Santoku Corp (1.64) Santoku Corp (1.64) Santoku Corp (1.67) Dr. B. Ahern Anomalies observed? [1],[2] No, bulk metal data, but PdO [1],[2] Yes, a little large heat & D/Pd [1],[2],[3], discussed in the present paper Yes, Heat and D/Pd reproducible [2] No heat and loading [2] Yes, but weak only briefly in the present paper Yes, very large heat and D(H)/M, reproducible [1] Phys. Lett. A, 373 (2009) Drastic change happens by Meso-Catalyst! Why? [2] Low Eergy Nuclear Reactions, (AIP Conf. Proc. 1273, ed. Jan Marwan, 2010). [3] LENR Source Book 3, (ed. Jan Marwan, ACS) to be published. Kitamura ACSNET

30 Supplement Data below Kitamura ACSNET

31 W D, W H (W) P D, P H (MPa) The 1 st phase is divided into the 1a-phase and the 1b-phase Power D-PZ13#3 H-PZ14#3 D Pressure st phase 2 nd phase 5 0 1a 0phase b phase Time (min) Kitamura ACSNET

32 L D, L H L D, L H As-received (#1) LD (D/Pd; D-PZ13#2) LH (H/Pd; H-PZ14#2) de-oxidized (#2) a phase P D, P H (kpa) LD (D/Pd; D-PZ13#1) LH (H/Pd; H-PZ14#1) 1b phase P D, P H (kpa) L D, L H P D, P H (kpa) Oxidized (#3) LD (D/Pd; D-PZ13#3) LH (H/Pd; H-PZ14#3) Time-dependent loading ratio, L D(H) (t), expressed as a function of pressure in the runs D(H)-PZ13(14)#3 through D(H)-PZ13(14)#3 Kitamura ACSNET

33 Time-resolved specific sorption energy, or differential heat of hydrogen uptake, defined as the output energy per one hydrogen isotope atom absorbed/adsorbed, h( t) t t t + D L( t W true + Dt) - ( t)dt L( t) 15 t t W ( t, )dt t ( t) + D h,, L( t + Dt) - L( t) W ( t, ) t + t W meas ( t) dt The values of W true (t) should be de-convoluted from the measured output power W meas (t), which has an indicial delay with a time constant of, and is approximated here by W(t, ) averaged over. The hydridation energy Q D(H) introduced earlier is equal to the integrated power over the 1 st phase divided by D(H)/Pd at the end of the 1 st phase in the absence of oxygen. The interval Dt is arbitrary, and chosen here to be 1 min. Kitamura ACSNET

34 W D(H) (W), P D(H) (MPa) PNZ2B3,4#1 Pd Ni Zr O Supplier (1.67) Dr. B. Ahern L D (t) Power L H (t) Pressure for H Pressure for D L D(H) L D, L H L(t) vs P H/PdNi (H-PNZ2B1#1) D/PdNi (D-PNZ2B2#1) Time (min) Pressure (kpa) Kitamura ACSNET

35 E 1 (ev/atom-pdni) E 1 (ev/atom-pdni) PNZ2B1-4 sample (Pd : 4% Ni : 29% Zr : 67%) ; Deoxidization works as well as oxidization PNZ2b1,2#3run PdO/Pd(D2) : 69 PdO/Pd(H2) : 72 H-PNZ2B1 D-PNZ2B #1 #1d #1A #1Ad #1B #1Bd #2 #2d #3 #3d H-PNZ2B3 D-PNZ2B4 PNZ2B3,4#3run PdO/Pd(D2) : 86 PdO/Pd(H2) : 87 #1 #1d #1A #1Ad #1B #1Bd #2 #2d #3 #3d Comparison of the 1 st -phase specific output energy E 1 for the runs D(H)-PNZ2B2(1)#1 through D(H)-PNZ2B4(3)#3d Kitamura ACSNET

36 PNZ2B1-4 sample (Pd : 4% Ni : 29% Zr : 67%) ; Deoxidization works as well as oxidization PNZ2b1,2#3run PdO/Pd(D2) : 69 PdO/Pd(H2) : H-PNZ2B1 D-PNZ2B H-PNZ2B3 D-PNZ2B4 PNZ2B3,4#3run PdO/Pd(D2) : 86 PdO/Pd(H2) : 87 L D, L H 2.0 L D, L H 2.0 #1 #1A #1B #2 #3 #1 #1A #1B #2 #3 Comparison of the loading ratio D(H)/[Pd Ni] for the runs D(H)-PNZ2B2(1)#1 through D(H)-PZ4(3)#3 Kitamura ACSNET

37 Q D (ev/atom-d), Q H (ev/atom-h) Q D (ev/atom-d), Q H (ev/atom-h) PNZ2B1-4 sample (Pd : 4% Ni : 29% Zr : 67%) ; Deoxidization works as well as oxidization 26 Larger energy Q D(H) for the D-runs D(H)-PNZ2B2(1)#1 through D(H)-PNZ2B4(3)#3 Kitamura ACSNET2011 PNZ2b1,2#3run PdO/Pd(D2) : 69 PdO/Pd(H2) : 72 PNZ2B3,4#3run PdO/Pd(D2) : 86 PdO/Pd(H2) : H-PNZ2B1 D-PNZ2B2 #1 #1A #1B #2 # H-PNZ2B3 D-PNZ2B4 #1 #1A #1B #2 #3 37

38 W D(H) (W), W D(H) h D(H) [W] (ev/d(h)) PNZ2B3,4#1 27 Absorption / desorption energies are constant and anomalously large, while Ni does not absorb D(H) at all at room temperature h value for bulk Pd W-D W-H Eta-D Eta-H Time (min) Kitamura ACSNET

39 W D(H) (W), P D(H) (MPa) PB5,6#3_2: 0.47%PdO/Pd The second forced-oxidization runs gave smaller Ia phase. 3.0 Ia Ib Power H/Pd W-H W-D P-H P-D L-H L-D L D(H) Time (min) -0.2 Kitamura ACSNET

40 W D(H) (W), h D(H) (ev/d(h)) PB5,6#3_2 h Ia Phase Ib Phase Eta-H Eta-D 2.0 W-H W-D Time (min) Kitamura ACSNET

41 PB5,6#1 h D /h H h(d)/h(h) Time (min) Kitamura ACSNET

42 PB5,6#2 h D /h H h ( D)/h (H) Time (min) Kitamura ACSNET

43 PB5,6#3 h D /h H h ( D)/h (H) Time (min) Kitamura ACSNET

44 PB5,6#3A h D /h H h ( D)/h (H) Time (min) Kitamura ACSNET

45 PB5,6#3_2 h D /h H h ( D)/h (H) Time (min) Kitamura ACSNET

46 PB5,6#1 PB5,6#3 PB5,6#3A PB5,6#2 PB5,6#3_2 PB5,6 Integrated Data Table 1st phase desorption PdO/Pd E1 QD xqr D(H)/Pd kj kj/g-pd ev/atom-pd ev/d(h) ev/atom-pd kj ev/atom-pd D2 unknown H2 unknown D H D H D H D H Kitamura ACSNET

47 Summary of the results obtained so far (1) PZ sample (Santoku; Pd 36 Zr 64 ) - very large specific energy of absorption/adsorption, E 1 ~ 2 ev/pd, - very large loading ratio, D(H)/Pd ~ - 2.3, - very large hydridation energy, Q D(H) ~ ev/d(h), - 1a-phase; near-surface phenomenon with h(1a) = 1.33(1.15) ev/d(h), while 1b-phase; bulk characteristics with h(1b) = 0.47(0.41) ev/d(h), - deteriorates after an absorption run, and recovers after forced oxidization. (2) PP sample (Nilaco; 0.1- mf) - E 1 ~ 0.2 ev/pd, D(H)/Pd ~, Q D(H) ~ 0.3 ev/d(h), - less prominent 1a-phase, and less effective enhancement by oxidization. (3) PB sample (Nilaco; Pd-black) - intermediate characteristic values. (4) PNZ (Santoku; Pd 11 Ni 25 Zr 64, Pd 2 Ni 44 Zr 54 ) and NZ (Ni 36 Zr 64 ) - absorption in proportion to Pd content. (5) PNZ2B (B.Ahern; Pd 4 Ni 29 Zr 67 ; melt spinning) - absorption occurs at R.T. with E 1 ~ 2.0 (1.8) ev/atom-[pd Ni], - D(H)/[Pd Ni] ~ 3.3 (3.3), - Q D(H) (and h) ~ 5 (0) ev/atom-d(h), - 1a-phase / 1b-phase ; indistinguishable, - modest deterioration after absorption runs. Kitamura ACSNET

Phenomenology of Nano-Particle/Gas-Loading Experiments

Phenomenology of Nano-Particle/Gas-Loading Experiments A.Takahashi 2*, A. Kitamura 1, Y. Miyoshi 1, H. Sakoh 1, A. Taniike 1, R. Seto 2 and Y. Fujita 2 1 Kobe University & 2 Technova Inc. ( presented at