Iwamura, Y., et al. Observation Of Surface Distribution Of Products By X-Ray Fluorescence Spectrometry During D2 Gas Permeation Through Pd Complexes. in The 12th International Conference on Condensed Matter Nuclear Science. 2005. Yokohama, Japan. OBSERVATION OF SURFACE DISTRIBUTION OF PRODUCTS BY X-RAY FLUORESCENCE SPECTROMETRY DURING D 2 GAS PERMEATION THROUGH PD COMPLEXES YASUHIRO IWAMURA, TAKEHIKO ITOH, MITSURU SAKANO, NORIKO YAMAZAKI, SHIZUMA KURIBAYASHI Advanced Technology Research Center, Mitsubishi Heavy Industries, Ltd., 1-8-1, Kanazawa-ku, Yokohama 236-8515, Japan YASUKO TERADA Japan Synchrotron Radiation Research Institute, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 Japan TETSUYA ISHIKAWA Coherent X-ray Optics Laboratory, RIKEN Harima Institute, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148, Japan In-situ measurement of transmutation of Cs into Pr was performed, and the surface distribution of Pr was investigated using XRF (X-Ray Fluorescence spectrometry) at SPring-8, a large synchrotron x-ray facility. The in-situ measurement indicated that Pr emerged and Cs decreased at some points after D 2 gas permeation, though any Pr cannot be observed before D 2 gas permeation at all the points on the Pd complex surface. Using small size X-ray beam in 100- and 500-micrometer squares, we obtained 2 dimensional XRF spectra for three permeated samples, from which we detected Pr. Pr was detected again by the two small x-ray beams as expected. The amount of Pr varied greatly at different locations of the Pd surface, however, a clear correlation between surface structures and distribution of Pr has not seen up to now. Experimental results suggest that nuclear transmutations do not occur uniformly but some uncertain factors, presumably condensed matter effects in the present Pd/D/CaO system, have a large effect on the rate or the process of the reactions. 1 Introduction Low energy nuclear transmutations in condensed matter have been observed in Pd complexes which are composed of Pd and CaO thin film and Pd substrate, induced by D 2 gas permeation through Pd multilayer complexes. We already reported transmutation reactions of Cs into Pr, Ba into Sm and Sr into Mo, respectively [1-5]. Fig. 1 shows schematic of our method. Our experimental method can be characterized by the permeation of D 2 gas through the Pd complex and the addition of an element that is specifically targeted to be transmuted. Permeation of deuterium is attained by exposing one side of the Pd complex to D 2 gas while maintaining the other side under vacuum conditions. On the D 2 gas side of the Pd complex, dissociative absorption causes the D 2 molecules to separate into D atoms, which diffuse through the Pd metal toward the vacuum side, where they emerge from the Pd metal, combine and are released as D 2 gas. The second feature is the addition of an element targeted to be transmuted. Our sample is a Pd complex composed of bulk Pd on the bottom, alternating CaO and Pd layers, and a Pd thin film on top. After fabricating a Pd complex, Cs, Ba, Sr or the other element is deposited on the surface of the top thin Pd layer. We can observe transmutation of the added Cs or Ba. In other words, with this composition, we can provide a deuterium flux through the Pd complex on which a target element is placed as a target to be transmuted. We perform elemental analyses of the given elements after D 2 gas permeation by exhausting the D 2 chamber. In this paper, in-situ measurement of transmutation of Cs into Pr and surface distribution are described. X-ray Fluorescence Spectrometry at SPring-8 (http://www.spring8.or.jp/e/) was used for this study. Transmutation reactions of Cs into Pr were confirmed by the in-situ measurement. Surface Pr distribution data were obtained and they showed that the amount of Pr changed greatly depending on the locations of the Pd surface. 1
D 2 gas D Permeation Cross Section of Pd Complex Cs,Ba, etc. D Flux Vacuum CaO 2nm Pd 40nm Pd substrate Figure 1. Schematic of our experimental approach. 2 Experimental Fabrication of Pd complex is basically the same as before [1]-[5]. A Pd was washed with acetone and annealed in vacuum (<10-7 torr) at 900 C for 10 h. It was then cooled to room temperature in furnace and washed with aqua regia to remove impurities on the surface of the Pd plate. The surface of the plate was covered by layers of CaO and Pd, which were obtained by five times alternatingly sputtering 20-Å-thick CaO and 200-Å -thick Pd layers. Then a 400-Å-thick Pd layer was sputtered on the surface of the CaO and Pd layers. These processes are performed by Ar ion beam sputtering method or magnetron sputtering method. After forming a Pd complex, Cs was deposited on the surface of the thin Pd layer. Cs was deposited by electrochemical method or ion implantation method. Figure 2 shows the experimental setup for in-situ measurement. Synchrotron orbital radiation X-ray (5.97keV) is introduced into the permeation chamber through a Be window and attacks on the surface of Pd complex sample. X-ray intensity is about from 10 12 to 10 13 photons/s. Cs-L and Pr-L lines can be detected by a Silicon Drift Detector (SDD). The SDD is covered by a Cl filter for suppression of Pd-L x-ray. We made D 2 gas permeated through a Pd complex with Cs for 10-14 days. D 2 gas pressure is about 170kPa and the temperature was 70 o C. XRF was performed during D 2 permeation in-situ at the beginning and the end of experiments. Detector Evacuation Be Window SOR X-ray Pd Complex Evacuation with Cs D Cl Filter Fluorescence X-ray Vacuum System TMP DP D 2 Gas Inlet Figure 2. Experimental setup for in-situ measurement. Surface distribution of Cs and Pr can be measured by the experimental setup shown in the Fig. 3. The synchrotron radiation x-ray is divided by slits and we get rectangular micro x-ray beam. In this study, we use 500-micron and 100-micron beams. The Pd complex sample is attached on a X-Y stage that can be moved by stepping motors. 2-dimentional XRF spectra can be obtained by this setup. Surface images can be taken by a microscope that is equipped for this 2-dimentional XRF spectrum analysis. We can obtain the information about correlation between distribution of elements and surface images. 2
Z Stage X Slit Slit Sample X-ray fluorescence Synchrotron Radiation X-ray SDD Micro Beam Detector Detector Sample Synchrotron X-ray Figure 3. Experimental setup for the measurement of surface distribution of Cs and Pr. 3 Results and Discussion First of all, we describe the results of in-situ measurement; sample name is SP-24. Initial (before D 2 gas permeation) and final (after D 2 gas permeation) XRF spectra are drawn in Fig. 4. Cs was deposited by the ion beam implantation method (voltage: 5kV, dose: 2.5 10 14 /cm 2 ). In this case, we use 1 mm square x-ray beam. As shown here, Cs peaks decreases and Pr peak emerge after D 2 gas permeation at the shown point. It can be seen that transmutation of Cs into Pr occurred at this point. However, no Cs was changed and no Pr was seen except this point in the case of SP-24. Figure 4. Confirmation of transmutation of Cs into Pr using ion beam implanted sample (SP-24) by in-situ measurement Another example of in-situ measurement is shown in Fig. 5. Electrochemical deposition [1] was applied to this sample (SP-33). Pr was detected at the points 2, 3, 8 and 9, although no Pr was detected at the points 4, 5, 6, 10, 11 and 12. We could not see initial Cs at the points 1, 7, 13, 14, 15 because Cs distribution is not uniform if we applied electrochemical Cs deposition method. Initial and final XRF spectra at point 2 are shown in Fig. 2. Cs peaks decreased and a Pr peak emerged after D 2 gas permeation. The ratio of minor peak of Cs-L to major peak of Cs-L is always constant, so we can judge that the peak near 5keV is attributed to Pr-L x-ray. This result also demonstrates that transmutation reaction of Cs into Pr occurs in this experimental system. 3
Figure 5. Confirmation of transmutation of Cs into Pr using electrochemically deposited sample (SP-33) by in-situ measurement Let us move on to the next point. Figure 6 shows Pr detection by XRF method performed in 2003. FG1 was fabricated by the Ar ion beam sputtering method and permeated for 97 hours by D 2 gas at 70 C. FG2 was made by the magnetron sputtering method and permeated for 96 hours by D 2 gas at 70 C. Pr-L lines were clearly in both foreground samples, while no Pr peak could be seen in the background sample. Figure 6. Detection of Pr by XRF in 2003 (FG1 and FG2; D2 permeated samples, BG; No permeated sample) Pr surface distribution measurements were done for FG1, FG2 and SP-24 by small size X-ray beams in 100- and 500-micrometer squares. Mapping data of Pr for FG1 analyzed by 500-micron x-ray beam is shown in Fig. 7 (a) Pr could be detected from all the points (400 points) in the analyzed region in 10mmX10mm. Detection of Pr is consistent with the above XRF measurement in 2003. In addition to Pr, we detected the other peaks for 27 points. A peak around 4.5keV can be seen at point 284. Levels of Pr seem to be almost uniform for these points. We can estimate that these peaks correspond to about 5x10 13 atoms/cm 2 by the comparison with XRF spectra using a reference sample in which Pr was already implanted. Figure 7 (c) shows corresponding surface image taken by a microscope. It seems that there are no specific or special features for the point 284 under this measurement condition. 4
20 19 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 40 39 38 37 36 35 34 33 32 31 30 29 28 27 26 25 24 23 22 21 60 59 58 57 56 55 54 53 52 51 50 49 48 47 46 45 44 43 42 41 80 79 78 77 76 75 74 73 72 71 70 69 68 67 66 65 64 63 62 61 100 99 98 97 96 95 94 93 92 91 90 89 88 87 86 85 84 83 82 81 120 119 118 117 116 115 114 113 112 111 110 109 108 107 106 105 104 103 102 101 140 139 138 137 136 135 134 133 132 131 130 129 128 127 126 125 124 123 122 121 160 159 158 157 156 155 154 153 152 151 150 149 148 147 146 145 144 143 142 141 180 179 178 177 176 175 174 173 172 171 170 169 168 167 166 165 164 163 162 161 200 220 240 199 219 239 198 218 238 197 217 237 196 216 236 195 215 235 194 214 234 193 213 233 192 212 232 191 211 231 190 210 230 189 209 229 188 208 228 187 207 227 186 206 226 185 205 225 184 204 224 183 203 223 182 202 222 181 201 221 10 mm 260 259 258 257 256 255 254 253 252 251 250 249 248 247 246 245 244 243 242 241 280 279 278 277 276 275 274 273 272 271 270 269 268 267 266 265 264 263 262 261 300 299 298 297 296 295 294 293 292 291 290 289 288 287 286 285 284 283 282 281 320 319 318 317 316 315 314 313 312 311 310 309 308 307 306 305 304 303 302 301 340 339 338 337 336 335 334 333 332 331 330 329 328 327 326 325 324 323 322 321 360 359 358 357 356 355 354 353 352 351 350 349 348 347 346 345 344 343 342 341 380 379 378 377 376 375 374 373 372 371 370 369 368 367 366 365 364 363 362 361 400 399 398 397 396 395 394 393 392 391 390 389 388 387 386 385 384 383 382 381 10 mm Detection of Pr only; 373points(93%) Detection of Pr and unidentified element;27points(7%) (a) (b) (c) Figure 7. Surface Distribution of Pr for FG1 using 500 micron x-ray beam; (a) Mapping of Pr and unidentified element, (b) XRF spectra for the points 281-285, (c) Surface image of FG1 for the points 282-286. Mapping data of Pr for FG2 analyzed by 500-micron x-ray beam is shown in Fig. 8 (a) Pr was observed at 61% points (74 points) in the analyzed region in 5.5mmX5.5mm. Detection of Pr is consistent with the 2003 XRF measurement shown Fig. 6. In this case, we could not see any unidentified peaks shown in Fig. 7 (FG1). No Pr was detected in 39% of the points. XRF spectra for points 75-79 by 500-micron beam are shown in Figure 9 (a). The strengths of Pr seem to be slightly changed depending on measured points, however, no clear difference seems to be seen as shown in Fig. 9 (b). XRF spectra using 100-micron beam for the point 27 are illustrated in Fig. 9 (c) and the surface image for the corresponding region is shown in Fig. 9 (d). The unidentified peak emerged at the point 5-1 in the point 27, although we could not observe the unidentified peak if we used a 500-micron beam. This fact suggests that the unidentified element was so localized and so small that the signal from the element was buried when we used large beam (500-micron). It also seems there are specific or special features for the point 5-1; or if there are specific structures, they might be much smaller than this image. Based on the XRF spectra, La, Ba and Ti are candidates for the unidentified peak. At the present stage, we cannot completely exclude the possibility that the peak is derived from a localized impurity. Further investigation by other measurement methods is necessary. 5
24 23 22 21 20 19 18 17 16 15 14 36 35 34 33 32 31 30 29 28 27 26 48 47 46 45 44 43 42 41 40 39 38 60 59 58 57 56 55 54 53 52 51 50 5.5 mm 72 84 96 108 71 83 95 107 70 82 94 106 69 81 93 105 68 80 92 104 67 79 91 103 66 78 90 102 65 77 89 101 64 76 88 100 63 75 87 99 62 74 86 98 120 119 118 117 116 115 114 113 112 111 110 132 131 130 129 128 127 126 125 124 123 122 144 143 142 141 140 139 138 137 136 135 134 5.5mm Detection of Pr only; 74points(61%) No Detection;47points(39%) Figure 8. Surface Distribution of Pr for FG2 using 500-micron and 100-micron x-ray beams, mapping of Pr by 500-micron beam. (a) (b) 6-1 5-1 2-1 (c) (d) Figure 9. Surface Distribution of Pr for FG2 using 500-micron and 100-micron x-ray beams, continued: (a) XRF spectra for the points 75-79 by 500-micron beam, (b) Surface image of FG2 for points 75-77, (c) XRF spectra using 100-micron beam for the point 27, (d) Surface image of FG2 for the point 27. Sample SP-24, originally measured in-situ, was analyzed by small size X-ray beams in 100- and 500- micrometer squares 5 months after the permeation experiment. Pr could be observed again in the same region as 6
the in-situ measurement. The surface distribution of Pr for SP-24 by 500-micron x-ray beam is shown in Fig. 9 (a). Pr was observed only at 6 points and the unidentified peak was observed at 2 points even though we used 500-micron x-ray beam. As for SP-24, reaction rate is lower than FG1 and FG2. At present, the authors cannot explain completely the difference of reaction rates between these 3 samples. It should be investigated further, since clarifying the factors that make influence on the transmutation rate is an important and valuable task to increase transmutation rate. Figure 9 (b) and (c) show surface distribution of Pr and XRF spectra obtained by 100-micron x-ray beam for point 13-4 shown in Fig. 9 (a). The amount of Pr changed greatly depending on the locations of the Pd surface. Pr is localized at the specific points shown in Fig. 9(c). Surface image for the corresponding region is shown in Fig. 9 (d). No clear correlation between the localized Pr and surface image could be observed. These experimental results suggests that transmutation reaction rate varies depend on the Pd surface region. And if we postulate that the unidentified peak is derived from a transmuted element, transmutation pass might be changed depending on location. Some uncertain factors, presumably relating to condensed matter effects in the present Pd/D/CaO system, must make a lot of effects on the rate or the process of the reactions. In order to make clear the uncertain factors, it would be necessary to use smaller X-ray beam, although it would take much more time for XRF measurement. 7
20-1 2-1 1-1 16-2 1-2 5-3 13-4 12-4 11-4 14-5 13-5 13-6 20-10 1-10 10mm Detection of Pr only; 6points(3%) Detection of Pr and unidentified element;2points (1%) No Detection;192points(96%) (a) X Y 1 2 3 4 5 6 1 2 3 4 5 6 100μm Much Pr detection Pr detection No Pr 13-4 100μm (b) (c) (d) Figure 10. Surface Distribution of Pr for SP-24 using 500-micron and 100-micron x-ray beams; (a) Mapping of Pr by 500-micron beam, (b) Mapping of Pr by 100-micron beam at point 13-4. (c) XRF spectra depending on location obtained by 100-micron beam, (d) Surface image of SP-24 corresponding to XRF spectra 4 Concluding Remarks One of our experimental apparatus was carried to SPring-8 for the purpose of in-situ measurement and we obtained clear Pr signals after D 2 gas permeation by the X-ray fluorescence method. According to the micro x- ray beam measurement, we noticed that Pr was localized greatly. At present, the correlation between products and the surface structures is not clear. Further investigations are necessary, for example, using smaller X-ray beam or analyzing these samples by the other methods. Acknowledgments The authors would like to acknowledge Prof. A. Takahashi, Prof J. Kasagi, Prof. T. Okano, Prof. K. Fukutani, Dr. F. Clelani, Dr. K. Grabowski, Prof. M. Melich, Dr. C. Catalina, Dr. C. Carmine, Prof. K. Okuno, Dr. Z. Yoshida, Dr. Y. Nagame and Prof. S. Iio for their valuable discussions. The authors also acknowledge for the support of TEET (The Thermal and Electric Energy Technology Foundation). 8
XRF experiments in this work were performed at the BL37XU in the SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Grant No. 2004B0456-NXb-np, 2005A0250-NXb-np, 2005A0409-NXb-np-Na). References 1. Y. Iwamura, M. Sakano and T. Itoh, Jpn. J. Appl. Phys. 41 (2002), pp. 4642-4648. 2. Y. Iwamura, T. Itoh, M. Sakano, S.Kuribayashi, Y. Terada, T. Ishikawa and J.Kasagi, Proc. ICCF11, Marseilles, France, Oct.31-Nov.5 (2004), World Scientific, pp.339-350. 3. Y. Iwamura, T. Itoh, M. Sakano, S. Sakai and S. Kuribayashi, Proc. ICCF10, Cambridge, USA, Aug.24-29 (2003), World Scientific, pp.435-446 4. Y. Iwamura, T. Itoh, M. Sakano and S. Sakai, Proc. of ICCF9 19-24 May 2002, Beijing (China); pp.141-146. 5. Y. Iwamura, T. Itoh and M. Sakano, Proc. of ICCF8, 21-26 May 200 Lerici (Italy), SIF Conf. Proc.Vol.70, pp.141-146. 9