<figure><img src="image_82.png" /></figure>

<table><thead><tr><th colspan="7">05-0519</th><th colspan="7">Wavelength= 1.5405</th></tr><tr><th>Bi</th><th></th><th></th><th></th><th></th><th></th><th></th><th>d(A)</th><th>Int</th><th>h</th><th>k</th><th>l</th><th>d(A)</th><th>Int</th><th>h</th><th>k</th><th>l</th></tr></thead><tbody><tr><td rowspan="3">Bismuth</td><td></td><td></td><td></td><td></td><td></td><td></td><td>3.95</td><td>9</td><td>0</td><td>0</td><td>3</td><td>.992</td><td>1</td><td>3</td><td>1</td><td>5</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>3.74</td><td>3</td><td>1</td><td>0</td><td>1</td><td>.9854</td><td>3</td><td>2</td><td>2</td><td>6</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>3.28</td><td>100</td><td>0</td><td>1</td><td>2</td><td>.9709</td><td>2</td><td>0</td><td>4</td><td>2</td></tr><tr><td rowspan="2">Bismuth, syn</td><td></td><td></td><td></td><td></td><td></td><td></td><td>2.37</td><td>40</td><td>1</td><td>0</td><td>4</td><td>.9455</td><td>2</td><td>2</td><td>0</td><td>11</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>2.273</td><td>41</td><td>1</td><td>1</td><td>0</td><td>.9301</td><td>4</td><td>3</td><td>0</td><td>9</td></tr><tr><td>Rad.: CuKa1: 1.5405</td><td>Filter: Ni</td><td>Beta</td><td>d-sp:</td><td></td><td></td><td></td><td>2.030</td><td>8</td><td>0</td><td>1</td><td>5</td><td>.9276</td><td>2</td><td>2</td><td>1</td><td>10</td></tr><tr><td>Cut off:</td><td>Int.: Diffract.</td><td>l/Cor.:</td><td></td><td></td><td></td><td></td><td>1.976</td><td>3</td><td>0</td><td>0</td><td>6</td><td>.9178</td><td>2</td><td>1</td><td>3</td><td>7</td></tr><tr><td rowspan="4">Ref: Swanson, Fuyat, Natl. Bur. Stand. (U.S.), Circ. 539, III, 20 (1954)</td><td></td><td></td><td></td><td></td><td></td><td></td><td>1.970</td><td>10</td><td>1</td><td>1</td><td>3</td><td>.9065</td><td>2</td><td>1</td><td>1</td><td>12</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>1.941</td><td>1</td><td>0</td><td>2</td><td>1</td><td>.8928</td><td>2</td><td>2</td><td>3</td><td>2</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>1.868</td><td>23</td><td>2</td><td>0</td><td>2</td><td>.8886</td><td>2</td><td>1</td><td>0</td><td>13</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>1.639</td><td>9</td><td>0</td><td>2</td><td>4</td><td>.8792</td><td>2</td><td>3</td><td>1</td><td>8</td></tr><tr><td>Sys.: Rhombohedral</td><td>S.G.: R3m (166)</td><td></td><td></td><td></td><td></td><td></td><td>1.556</td><td>6</td><td>1</td><td>0</td><td>7</td><td>.8731</td><td>2</td><td>1</td><td>2</td><td>11</td></tr><tr><td>a: 4.546</td><td>b:</td><td>c: 11.860</td><td>A:</td><td>C: 2.6089</td><td></td><td></td><td>1.515</td><td>2</td><td>2</td><td>0</td><td>5</td><td>.864</td><td>2</td><td>3</td><td>2</td><td>4</td></tr><tr><td>α:</td><td>β:</td><td>γ:</td><td>Z: 6</td><td>mp:</td><td></td><td></td><td>1.491</td><td>13</td><td>1</td><td>1</td><td>6</td><td>.8591</td><td>4</td><td>4</td><td>1</td><td>0</td></tr><tr><td rowspan="5">Ref: Ibid.</td><td></td><td></td><td></td><td></td><td></td><td></td><td>1.443</td><td>16</td><td>1</td><td>2</td><td>2</td><td>.8511</td><td>&lt;1</td><td>4</td><td>0</td><td>7</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>1.387</td><td>4</td><td>0</td><td>1</td><td>8</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>1.330</td><td>11</td><td>2</td><td>1</td><td>4</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>1.319</td><td>1</td><td>0</td><td>0</td><td>9</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>1.312</td><td>6</td><td>3</td><td>0</td><td>0</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Dx: 9.809</td><td>Dm: 9.765</td><td>SS/FOM: F30 = 47(.0187, 34)</td><td></td><td></td><td></td><td></td><td>1.284</td><td>2</td><td>0</td><td>2</td><td>7</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Color: Grayish white</td><td></td><td></td><td></td><td></td><td></td><td></td><td>1.261</td><td>2</td><td>1</td><td>2</td><td>5</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Pattern taken at 25 C. Sample from Johnson Matthey Company, Ltd.</td><td></td><td></td><td></td><td></td><td></td><td></td><td>1.246</td><td>1</td><td>3</td><td>0</td><td>3</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>CAS #: 7440-69-9. Spectroscopic analysis: &lt;0.001% Pb, Si, Cu, Fe, Al, Ca, Mg, Na. Opaque mineral optical data on specimen from unspecified locality, R3R% = 66.7, Disp.=Std., VHN100=15-18, Ref.: IMA</td><td></td><td></td><td></td><td></td><td></td><td></td><td>1.184</td><td>2</td><td>2</td><td>0</td><td>8</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Commission on Ore Microscopy QDF. Measured density from Dana's System of Mineralogy, 7th Ed., I 134. As type. Tetradymite group, arsenic subgroup. PSC: hR2. To replace 1-688, 1-699, 2-491 and 2-518. Deleted by 44-1246, better intensities, 12/95. Mwt: 208.98. Volume[CD]: 212.26.</td><td></td><td></td><td></td><td></td><td></td><td></td><td>1.139</td><td>4</td><td>1</td><td>1</td><td>9</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>1.136</td><td>4</td><td>2</td><td>2</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>1.117</td><td>2</td><td>2</td><td>1</td><td>7</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>1.093</td><td>4</td><td>3</td><td>0</td><td>6</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>1.073</td><td>5</td><td>3</td><td>1</td><td>2</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>1.050</td><td>2</td><td>1</td><td>2</td><td>8</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>1.039</td><td>2</td><td>0</td><td>1</td><td>11</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>1.024</td><td>3</td><td>1</td><td>3</td><td>4</td><td></td><td></td><td></td><td></td><td></td><td></td></tr></tbody></table>

1

<table><thead><tr><th colspan="7">05-0519</th><th colspan="7">Wavelength= 1.5405</th></tr><tr><th>Bi</th><th></th><th></th><th></th><th></th><th></th><th></th><th>2θ</th><th>Int</th><th>h</th><th>k</th><th>l</th><th>2θ</th><th>Int</th><th>h</th><th>k</th><th>l</th></tr></thead><tbody><tr><td>Bismuth</td><td></td><td></td><td></td><td></td><td></td><td></td><td>22.489</td><td>9</td><td>0</td><td>0</td><td>3</td><td>97.473</td><td>3</td><td>1</td><td>3</td><td>4</td></tr><tr><td rowspan="3">Bismuth, syn</td><td></td><td></td><td></td><td></td><td></td><td></td><td>23.770</td><td>3</td><td>1</td><td>0</td><td>1</td><td>101.876</td><td>1</td><td>3</td><td>1</td><td>5</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>27.163</td><td>100</td><td>0</td><td>1</td><td>2</td><td>102.826</td><td>3</td><td>2</td><td>2</td><td>6</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>37.931</td><td>40</td><td>1</td><td>0</td><td>4</td><td>104.997</td><td>2</td><td>0</td><td>4</td><td>2</td></tr><tr><td>Rad.: CuKa1: 1.5405</td><td>Filter: Ni</td><td>Beta</td><td>d-sp:</td><td></td><td></td><td></td><td>39.616</td><td>41</td><td>1</td><td>1</td><td>0</td><td>109.105</td><td>2</td><td>2</td><td>0</td><td>11</td></tr><tr><td>Cut off:</td><td>Int.: Diffract.</td><td>l/Cor.:</td><td></td><td></td><td></td><td></td><td>44.597</td><td>8</td><td>0</td><td>1</td><td>5</td><td>111.816</td><td>4</td><td>3</td><td>0</td><td>9</td></tr><tr><td rowspan="4">Ref: Swanson, Fuyat, Natl. Bur. Stand. (U.S.), Circ. 539, III, 20 (1954)</td><td></td><td></td><td></td><td></td><td></td><td></td><td>45.884</td><td>3</td><td>0</td><td>0</td><td>6</td><td>112.273</td><td>2</td><td>2</td><td>1</td><td>10</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>46.032</td><td>10</td><td>1</td><td>1</td><td>3</td><td>114.119</td><td>2</td><td>1</td><td>3</td><td>7</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>46.761</td><td>1</td><td>0</td><td>2</td><td>1</td><td>116.357</td><td>2</td><td>1</td><td>1</td><td>12</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>48.704</td><td>23</td><td>2</td><td>0</td><td>2</td><td>119.250</td><td>2</td><td>2</td><td>3</td><td>2</td></tr><tr><td rowspan="5">Ref: Ibid.</td><td></td><td></td><td></td><td></td><td></td><td></td><td>56.062</td><td>9</td><td>0</td><td>2</td><td>4</td><td>120.181</td><td>2</td><td>1</td><td>0</td><td>13</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>59.342</td><td>6</td><td>1</td><td>0</td><td>7</td><td>122.346</td><td>2</td><td>3</td><td>1</td><td>8</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>61.117</td><td>2</td><td>2</td><td>0</td><td>5</td><td>123.818</td><td>2</td><td>1</td><td>2</td><td>11</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>62.209</td><td>13</td><td>1</td><td>1</td><td>6</td><td>126.123</td><td>2</td><td>3</td><td>2</td><td>4</td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>64.523</td><td>16</td><td>1</td><td>2</td><td>2</td><td>127.424</td><td>4</td><td>4</td><td>1</td><td>0</td></tr><tr><td>Dx: 9.809</td><td>Dm: 9.765</td><td>SS/FOM: F30 = 47(.0187, 34)</td><td></td><td></td><td></td><td></td><td>70.780</td><td>11</td><td>2</td><td>1</td><td>4</td><td>129.648</td><td>&lt;1</td><td>4</td><td>0</td><td>7</td></tr><tr><td>Color: Grayish white</td><td></td><td></td><td></td><td></td><td></td><td></td><td>71.460</td><td>1</td><td>0</td><td>0</td><td>9</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Pattern taken at 25 C. Sample from Johnson Matthey Company, Ltd.</td><td></td><td></td><td></td><td></td><td></td><td></td><td>71.900</td><td>6</td><td>3</td><td>0</td><td>0</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>CAS #: 7440-69-9. Spectroscopic analysis: &lt;0.001% Pb, Si, Cu, Fe, Al, Ca, Mg, Na. Opaque mineral optical data on specimen from unspecified locality, R3R% = 66.7, Disp.=Std., VHN100=15-18, Ref.: IMA</td><td></td><td></td><td></td><td></td><td></td><td></td><td>73.723</td><td>2</td><td>0</td><td>2</td><td>7</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td>Commission on Ore Microscopy QDF. Measured density from Dana's System of Mineralogy, 7th Ed., I 134. As type. Tetradymite group, arsenic subgroup. PSC: hR2. To replace 1-688, 1-699, 2-491 and 2-518. Deleted by 44-1246, better intensities, 12/95. Mwt: 208.98. Volume[CD]: 212.26.</td><td></td><td></td><td></td><td></td><td></td><td></td><td>75.298</td><td>2</td><td>1</td><td>2</td><td>5</td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>76.366</td><td>1</td><td>3</td><td>0</td><td>3</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>81.141</td><td>2</td><td>2</td><td>0</td><td>8</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>85.020</td><td>4</td><td>1</td><td>1</td><td>9</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>85.307</td><td>4</td><td>2</td><td>2</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>87.104</td><td>2</td><td>2</td><td>1</td><td>7</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>89.592</td><td>4</td><td>3</td><td>0</td><td>6</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>91.666</td><td>5</td><td>3</td><td>1</td><td>2</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>94.362</td><td>2</td><td>1</td><td>2</td><td>8</td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td></td><td></td><td></td><td></td><td></td><td>95.582</td><td>2</td><td>0</td><td>1</td><td>11</td><td></td><td></td><td></td><td></td><td></td><td></td></tr></tbody></table>

<figure><img src="image_83.png" /></figure>
<figure><img src="image_84.png" /></figure>

26-0214

Wavelength= 1.54056

<table><thead><tr><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th></tr><tr><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th></tr><tr><th>Bi</th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th></tr><tr><th>Bismuth</th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th></tr><tr><th></th><th>d(A)</th><th>Int</th><th>h</th><th>k</th><th>l</th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th></tr></thead><tbody><tr><td></td><td>2.673</td><td>100</td><td>1</td><td>1</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>1.889</td><td>16</td><td>2</td><td>0</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>1.545</td><td>30</td><td>2</td><td>1</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>1.338</td><td>18</td><td>2</td><td>2</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>1.198</td><td>25</td><td>3</td><td>1</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>1.095</td><td>5</td><td>2</td><td>2</td><td>2</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>1.014</td><td>14</td><td>3</td><td>2</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>.949</td><td>2</td><td>4</td><td>0</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>.893</td><td>6</td><td>3</td><td>3</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>.850</td><td>14</td><td>4</td><td>2</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>.808</td><td>5</td><td>3</td><td>3</td><td>2</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></tbody></table>

Sys.: Cubic S.G.: 1m3m (229)

a: 3.795 b: c: A: C

α: β: γ: Z. 2 mp:

Ref: Ibid.

Dx: 12.698 Dm: SS/FOM: F₁₁ = 5 (0.208, 11)

CAS #: 7440-69-9. High pressure phase, examined at 90
kbar and room temperature. W type. PSC: cl2. Mwt: 208.98.
Volume[CD]: 54.66.

74-1374

Wavelength= 1.54060

<table><thead><tr><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th></tr><tr><th>Bi2O3</th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th></tr><tr><th>Bismuth Oxide</th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th></tr><tr><th></th><th>d(A)</th><th>Int</th><th>h</th><th>k</th><th>l</th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th><th></th></tr></thead><tbody><tr><td></td><td>7.7286</td><td>1</td><td>1</td><td>1</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>5.4650</td><td>1</td><td>2</td><td>0</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>4.5453</td><td>1</td><td>1</td><td>1</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>3.9179</td><td>4</td><td>2</td><td>0</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>3.8643</td><td>4</td><td>2</td><td>2</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>3.4563</td><td>17</td><td>3</td><td>1</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>3.1842</td><td>999*</td><td>2</td><td>2</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>2.9441</td><td>32</td><td>3</td><td>1</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>2.8100</td><td>136</td><td>0</td><td>0</td><td>2</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>2.7325</td><td>231</td><td>4</td><td>0</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>2.4990</td><td>1</td><td>2</td><td>0</td><td>2</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>2.4440</td><td>1</td><td>4</td><td>2</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>2.2726</td><td>1</td><td>2</td><td>2</td><td>2</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>2.2412</td><td>1</td><td>4</td><td>2</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>2.1803</td><td>17</td><td>3</td><td>1</td><td>2</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>2.1435</td><td>4</td><td>5</td><td>1</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>2.0028</td><td>10</td><td>5</td><td>1</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>1.9589</td><td>256</td><td>4</td><td>0</td><td>2</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>1.9321</td><td>113</td><td>4</td><td>4</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>1.8744</td><td>18</td><td>5</td><td>3</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>1.8744</td><td></td><td>0</td><td>0</td><td>3</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>1.8441</td><td>1</td><td>4</td><td>2</td><td>2</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>1.8272</td><td>1</td><td>4</td><td>4</td><td>1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr><tr><td></td><td>1.8216</td><td>1</td><td>6</td><td>0</td><td>0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td></tr></tbody></table>
Bibliographie

1. Sun,X., Zhang,Z. & Dresselhaus,M.S. Theoretical modeling of thermoelectricity in Bi nanowires. *Applied Physics Letters* 74, 4005-4007 (1999).

2. Mulvaney,P., Liz-Marzan,L.M., Giersig,M. & Ung,T. Silica encapsulation of quantum dots and metal clusters. *J. Mater. Chem.* **10**, 1259-1270 (2000).

3. Issi,J.-P. Low Temperature Transport properties of Groups V semimetals. *Aust. J. Phys.* 32, 585-628 (1979).

4. Issi,J.-P. Les semimétaux. *Revue des questions scientifiques* 146, 61-85 (1975).

5. Lin,Y.-M., Sun,X. & Dresselhaus,M.S. Theoretical investigation of thermoelectric transport properties of cylindrical Bi nanwires. *Physical review B* 62, 4610-4623 (2000).

6. Lin,Y.-M. & Dresselhaus,M.S. Thermoelectric properties of superlattice nanowires. *Physical review B* 68, 075304-1-075304-14 (2003).

7. Lutskii,V.N. *JETP Lett.* 2, 245 (1965).

8. Sandomirskii,V.B. *JETP Lett.* 25, 101 (1967).

9. He,M., Yuan,C.M., Ngo,N.Q. & Bu,J. Molecular-beam epitaxy growth of arsenic film and its semimetal to semiconductor transition. *Applied Physics Letters* 83, 5452-5454 (2003).

10. Xu,J.H. & Ting,C.S. Quantum size effect on optical absorption edge in thin antimony films. *Applied Physics Letters* 63, 129-133 (1993).

11. Dresselhaus,M.S. et al. Nanowires and nanotubes. *Materials science and engineering C* 23, 129-140 (2003).

12. Lin,Y.M., Sun,X. & Dresselhaus,M.S. Theoretical investigation of thermoelectric transport properties of cylindrical Bi nanowires. *Physical review B* 62, 4610-4623 (2000).

13. Franket,D.D. & Chu,H.T. Hole-majority condition in thin films of semimetal bismuth. *Physical review B* 61, 13183-13190 (2000).

14. Huber,T.E. et al. Confinement effects and surface-induced charge carriers in Bi quantum wires. *Applied Physics Letters* 84, 1326-1328 (2004).

15. Heremans,J. et al. Bismuth nanowire arrays : synthesis and galvanomagnetic properties. *Physical review B* 61, 2921-2930 (2000).

16. Golin,S. Band Structure of Bismuth : Pseudopotentieel Approach. *Physical Review* 166, 643-651 (1968).
17. Chu,H.T., Fang,N. & Zheng,QI. Double quantum size effects on the energy spectra of charge carriers in thin wires of pure bismuth. *J. Phys. Chem. Solids* **56**, 1069-1075 (1995).

18. Chu,H.T. Comment on "Semimetal-to-semiconductor transition in bismuth thin films". *Physical Review* **51**, 5532-5534 (1995).

19. Hengsberger,M., Segovia,P., Garnier,M., Purdie,D. & Baer,Y. Photoemission study of the carrier bands in Bi(111). *Eur. Phys. J. B* **17**, 603-608 (2000).

20. Zhang,Z., Sun,X., Dresselhaus,M.S., Ying,J.Y. & Heremans,J. Electronic transport properties of single-crystal bismuth nanowire arrays. *Physical review B* **61**, 4850-4861 (2000).

21. Oshima,Y., Takayanagi,K. & Hirayama,H. Structural anomaly of fine bismuth particles observed by ultra high-vacuum TEM. *Z. Phys. D* **40**, 534-538 (1997).

22. Yokozeki,A. & Stein,D.G. A metal cluster generator for gas-phase electron diffraction and its application to bismuth and indium: Variation in microcrystal structure with size. *J. Appl. Phys* **49**, 2224-2232 (1978).

23. Vossloh,C., Holdenried,M. & Micklitz,H. Influence of cluster size on the normal- and superconducting-state properties of granular Bi films. *Physical review B* **58**, 12422-12426 (1998).

24. Wurl,A., Hyslop,M., Brown,S.A., Hall,B.D. & Monot,R. Structure of unsupported bismuth nanoparticles. *Eur. Phys. J. D* **16**, 205-208 (2001).

25. Kapitza,P.L. Proc.R.Soc.London. *Ser A* **119**, 358 (1928).

26. Yang,F.Y. *et al*. Large magnetoresistance of electrodeposited single-crystal bismuth thin films. *Science* **284**, 13351337 (1999).

27. Cho,S. *et al*. Large magnetoresistance in postannealed Bi thin films. *Applied Physics Letters* **79**, 3651-3653 (2001).

28. Merkulov,V.I. & Lannin,J.S. Variations in atomic structure of liquid bismuth clusters. *Physical review B* **58**, 7373-7376 (1998).

29. Tanaka,A. *et al*. Bulk and surface electronique structures of the semimetal Bi studied by angle-resolved photoemission spectroscopy. *Physical review B* **59**, 1786-1791 (2005).

30. Foos,E.E., Stroud,R.M., Berry,A.D., Snow,A.W. & Armistead,J.P. Synthesis of nanocrystalline bismuth in reverse micelles. *J. Am. Chem. Soc.* **122**, 7114-7115 (2000).

31. Gutierrez,M. & Henglein,A. Nanometer-sized Bi particles in aqueous solution: absorption spectrum and some chemical properties. *J. Phys. Chem. C* **100**, 7656-7661 (1996).
32. Hicks,L.D. & Dresselhaus,M.S. Effect of Quantum-Well Structures on the Thermoelectric Figure of Merit. *Physical review B* 47, 12727-12731 (1993).

33. Dresselhaus,M.S. et al. Quantum Wells and Quantum Wires for Potential Thermoelectric Applications. *Semicond. Semimetals* 71, 1-121 (2001).

34. Shakouri,A. & Bowers,J.E. Heterostructure Integrated Thermionic Coolers. *Applied Physics Letters* 71, 1236 (1997).

35. Mahan,G.D. Thermoionic Refrigeration. *Semicond. Semimetal* 71, 157-174 (2001).

36. Venkatasubramanian,R. Phonon Blocking Electron Transmitting Superlattice Structure as Advanced Thin Film thermoelectric Materials. *Semicond. Semimetal* 71, 175-201 (2001).

37. Chen,G. Phonon Transport in low-Dimensional Structures. *Semicond. Semimetal* 71, 203-259 (2001).

38. Harman,T.C., Taylor,O.J., Walsh,M.P. & Laforge,B.E. Quantum Dot Superlattice Thermoelectric Materials and Devices. *Science* 297, 2229-2231 (2002).

39. Dresselhaus,M.S. et al. Low-dimension thermoelectric materials. *Phys. solid state* 41, 679-682 (1999).

40. Mahan,G.D. & SOFO,J.O. The best thermoelectric. (1996).

41. Heremans,J.P., Thrush,C.M., Morelli,D.T. & Wu,M.C. Thermoelectric Power of Bismuth Nanocomposites. *Physical Review Letters* 88, 216801-1-216801-4 (2002).

42. Khitun,A., Wang,K.L. & Chen,G. Thermoelectrique figure of merit enhancement in a quantum dot superlattice. *Nanotechnology* 11, 327-331 (2000).

43. Chen,G. Particularities of heat conduction in nanostructures. *Journal of Nanoparticle Research* 2, 199-204 (2000).

44. Parrott,J.E. Phonon-drag-mediated size-effect. *J. Phys. F: Met. Phys.* 1, 657-664 (1971).

45. Keghouche,N., Mostafavi,M., Delcourt,M.O. & Picq,G. Radiolyse de solutions aqueuses de polyacrylate d'argent: premiers clusters oligomères Agn (n=1 à 4). *J. Chim Phys* 90, 777-788 (1993).

46. Rele,M., Kapoor,S. & Mukherjee,T. Reduction, aggregation and physicochemical properties of silver nanoparticles in propan-2-ol : cyclohexane mixtures induced by a high energy electron beam. *Materials research bulletin* 37, 2275-2283 (2002).

47. Buxton,G.V., Greenstock,C.L., Helman,W.P. & Ross,A.B. Critical Review of Rate Constants for Reactions Hydrated Electrons, Hydrogen Atoms and Hydroxyl Radicals in Aqueous Solution. *J. Phys. Chem.* 17, 513-886 (1998).

48. Ferradini,C. & Pucheault,J. Biologie de l'action des rayonnements ionisants. *Masson* (1983).
49. Hickel, B. Biological. *Academia-Erasme* (1992).

50. Napper, D.H. Polymeric Stabilization of Colloidal dispersions. London, New-York, Paris, San Diego, San Francisco, Sydney, Tokyo, Toronto, (1993).

51. Rémita, S. Effet de ligands sur les propriétés thermodynamiques, cinétiques et spectrales d'agrégats métalliques synthétisés par radiolyse. Thèse (1995).

52. Fricke, H. & Morse, S. The chemical action of Röntgen rays on dilute ferrosulfate solutions as a measure of dose. *Am J Roentgenol Radium Ther* 18, 430 (1927).

53. Göltner, C.G., Henke, S., Weißenberger, M. & Antonietti, M. Mesoporöse Silicate aus lyotrop-flüssigkristallinen Blockcopolymertemplaten. *Angew. Chem.* 110, 633-636 (1998).

54. Zhao, D., Huo, Q., Feng, J., Chmelka, B. & Stucky, G. Nonionic Triblock and Star Diblock Copolymer and Oligomeric Surfactant Syntheses of Highly Ordered, Hydrothermally Stable, Mesoporous Silica Structures. *J. Am. Chem. Soc.* 120, 6024-6036 (1998).

55. Everette, D.H. Thermodynamics of multiphase fluids in porous media. *Journal of Colloid and Interface Science* 52, (1975).

56. Esparza, J.M. *et al*. N2 sorption scanning behavior of SBA-15 porous substrates. *Coll. Surf. A: Physicochem. Eng. Aspects* 241, 35-45 (2004).

57. Cullity, B.D. Elements of X-Ray Diffraction. (1978).

58. Graner, F. & Sillen, N.G. On the Hydrolysis of Bi<sup>3+</sup> Ion. *Acta Chem. Scand.* 1, 631-655 (1947).

59. Baes, C.F. & Mesmer, R.E. The hydrolysis of cations., pp. 375-383 Wiley-Interscience Publication (1976).

60. Keghouche, N., Mostafavi, M. & Delcourt, M.O. Etude des systemes aqueux Ag<sup>+</sup>/APA (acide polyacrylique) et Ag<sup>0</sup>/APA à l'équilibre. *J. Chim Phys* (1991).

61. Mostafavi, M., Delcourt, M.O., Keghouche, N. & Picq, G. Early steps of formation of silver/polyacrylate complexed oligomer clusters. A pulse radiolysis study. *Radiation physical Chemistry* 40, 445-450 (1992).

62. Mostafavi, M., Delcourt, M.O. & Picq, G. Study of the interaction between polyacrylate and silver oligomer clusters. *Radiation physical Chemistry* 41, 453-459 (1993).

63. Ershov, B.G., Ionova, G.V. & Kiseleva, A.A. Silver clusters: Calculations of Optical Transitions and the Formation and Properties of "Magic" Positively Charged Clusters. *Russian Journal of Physical Chemistry* 69, 239-248 (1995).

64. Ershov, B.G., Janata, E. & Henglein, A. Growth of silver particles in aqueous solution : long lived magic clusters and ionic strength. *J. Phys. Chem.* 97, 339-343 (1993).
65. Henglein, A., Linnert, T. & Mulvaney, P. Reduction of Ag⁺ in aqueous polyanion solution: some properties and reactions of long-lived oligomeric silver clusters and metallic silver particles. *Ber. Bunsenges. Phys. Chem.* **94**, 1449-1457 (1990).

66. Michaelis, M. & Henglein, A. Reduction of Pd(II) in aqueous solution : stabilization and reactions of an intermediate cluster and Pd colloid formation. *J. Phys. Chem.* **96**, 4719-4724 (1992).

67. Belloni, J., Mostafavi, M., Remita, H. & Marignier, J.L. Radiation-induced synthesis and applications of mono- and bi-metallic nanocolloids or supported clusters. Proc. Rad Tech Asia 318-319 (1998)

68. Kelm, M., Lilie, J., Henglein, A. & Janata, E. Pulse radiolytic study of Ni2+. Nickel-Carbon bond formation. *The Journal of Physical Chemistry* **78**, 882-887 (1974).

69. Kelm, M., Lilie, J. & Henglein, A. Pulse radiolytic investigation of the reduction of cadmium(II) ions. *Journal of the Chemical Society, Faraday transaction* **71**, 1132-1142 (1975).

70. Belloni, J., Delcourt, M.O., Marignier, J.L. & Mostafavi, M. Radiation-induced synthesis of mono and multimetallic clusters and nanocolloids. *New J. Chem.* 1239-1255 (1998).

71. Fultz, M.L. & DURST, R.A. Mediator compounds for the electrochemical study of biological redox systems : a compilation. *Analytica Chimica Acta* **140**, 1-18 (1982).

72. Louis, C. & Bessiere, J. Diagrammes potentiel-niveau d'acidité dans les milieu H2O-H3PO4- I Systemes electrochimiques ne faisant pas intervenir le proton. *Talanta* **34**, 763-769 (1987).

73. Faulkner, K.M., Bonaventura, C. & Crumbliss, A.L. A Spectroelectrochemical Method for Differentiation of steric and Electronic Effects in Hemoglobins and Myoglobins. *JCB* **270**, 13604-13612 (1995).

74. Katz, E., de Lacey, A.L. & Fernandez, V.M. Covalent binding of viologen to electrode surfaces coated with poly(acryl acid) formed by electropolymerisation of acrylate ions. effect of the ionoization state of polymeric coating on the formal potential of viologen. *J. Electroanal. Chem* **358**, 262-272 (1998).

75. Buxton, G.V., Greenstock, C.L., Helman, P.W., Ross, B.A. & Tsang, W. Critical Review of rate constants for reactions of hydrated electronsChemical Kinetic Data Base for Combustion Chemistry. Part 3: Propane. *J. Phys. Chem. Ref. Data* **17**, 513-886 (1988).

76. Shepard, D.S. *et al*. Bimetallic nanoparticle catalysts anchored inside mesoporous silica. *Angew. Chem. Int. Ed. Engl.* **36**, 2242-2245 (1997).

77. Zhang, W.H., Shi, J.L., Wang, L.Z. & Yan, D.S. Preparation and characterization of ZnO clusters inside mesoporous silica. *Chem. Mater.* **12**, 1408-1413 (2000).

78. Shan, Y. & Gao, L. Synthesis, characterisation and optical properties of CdS nanoparticles confined in SBA-15. *Materials Chemistry and Physics* **89**, 412-416 (2005).
79. Feng, Y., Yao, R. & Zhang, L. Synthesis and sensitivity properties of Pd-doped tin oxide nanoparticles dispersed in mesoporous silica. *Mat. Chem. Phys.* 89, 311-314 (2005).

80. Landmesser, H., Kosslick, H., Storek, W. & Fricke, R. Interior surface hydroxyl groups in ordered mesoporous silicates. *Solid State Ionics* 101–103, 271-277 (1997).

81. Jentys, A., Kleestorfer, K. & Vinek, H. Concentration of surface hydroxyl groups on MCM-41. *Microporous and Mesoporous Materials* 27, 321-328 (2005).

82. Naono, H., Hakuman, M., Tanaka, T., Tamura, N. & Nakai, K. Porous texture and surface character of dehydroxylated and rehydroxylated MCM-41 mesoporous silica - Analysis of adsorption isotherms of nitrogen gas and water vapor. *J. Colloid. Interface Sc.* 225, 411-420 (2000).

83. Fang, J., Stokes, K. L., Zhou, W. L., Dai, J. & O'Connor, C. J. Colloidal bismuth nanoparticles synthesis and UV-VIS absorption. Proceedings of ISCANI (International Symposium on Cluster and Nanostructure Interfaces), ed. By P. Jena, World Scientific Publishing, Singapore (2000).

84. Zhao, Y., Zhang, Z. & Dang, H. A simple way to prepare bismuth nanoparticles. *Mat. Letters* **58**, 790–793 (2004)

85. Chao, K.J., Cheng, M.H., Ho, H.F. & Liu, P.H. Preparation and characterization of highly dispersed gold nanoparticles within channels of mesoporous silica. *Catalysis today* 97, 49-53 (2004).

86. Hornebecq, V., Antonietti, M., Cardinal, T. & Treguer-Delapierre, M. Stable silver nanoparticles immobilized in mesoporous silica. *Chem. Mater.* **15**, 1993-1999 (2003).

87. Zhao, X.S., Lu, G.Q., Whittaker, A.K., Millar, G.J. & Zhu, H.Y. Comprehensive Study of Surface Chemistry of MCM-41 Using Si CP/MAS NMR, FTIR, Pyridine-TPD, *J. Phys. Chem. B* **101**, 6525-6531 (1997).

88. Lygin, V.I. IR-Spectroscopic Study of Changes in Silica Surface Structure on Thermal Dehydroxylation and Rehydroxylation in Water Vapors. *Russ. J. Gen. Chem.* **71**, 1368-1372 (2001).

89. Zhang, G., Mao, Y. & Thomas, J.K. Surface chemistry induced by high energy radiation in silica of small particle structures. *J. Phys. Chem. 101*, 7100-7113 (1997).

90. Schaufelberger, Ph., Merx, H. & Contre, M. *High. Temp. High Press.* **5**, 221-230 (2005).

91. Férey, G. *et al.* A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area. *Science* **309**, 2040-2042 (2005).
Résumé

À l'échelle nanométrique et plus précisément en dessous de 10 nm, le bismuth présente des modifications structurales qui, bien que peu étudiées, sont largement décrite dans la littérature comme source d'amélioration des propriétés thermoélectriques. L'objectif principal de ce travail a été de proposer une nouvelle méthode de synthèse permettant d'élaborer des nanoparticules de bismuth métal stable à l'air avec une taille inférieure à 10 nm. La première partie de nos recherches a été consacrée à l'étude des mécanismes de réduction radiolytique du perchlorate de bismuth en solution aqueuse avec et sans polymères. Puis à partir de ces résultats, nous avons mis au point un procédé original de synthèse de réseaux de nanoparticules métalliques dont l'essentiel consiste à réduire le sel précurseur *in situ* au sein d'une matrice de silice mésoporeuse par voie radiolytique. Ces réseaux, selon la nature de la silice, peuvent être désordonnés ou organisés. Dans ce dernier cas, de nouvelles perspectives s'ouvrent dans le développement des matériaux thermoélectrique basés sur le principe de la filtration des porteurs de charges et des phonons par confinement quantique.

Discipline – spécialité doctorale : Science et ingénierie des matériaux

Mots clés : bismuth, nanoparticule, radiolyse gamma, confinement quantique, semimétaux

Abstract

On length scales below 10 nm, bismuth exhibits structural modifications that are reported to improve its thermoelectric properties. The present work describes a new synthesis route that produces metallic Bi nanoparticles smaller than 10 nm and stable in air. We first discuss our studies of the radiolytic reduction of bismuth perchlorate in aqueous solution with and without polymers. Our results have enabled us to develop a completely new process for synthesizing networks of metallic nanoparticles in which the essential step is the reduction by radiolysis of the precursor salt inside a mesoporous silica matrix. Depending on the nature of the silica, these networks can be either disordered or ordered. The latter case opens up the prospect for developing novel thermoelectric materials with enhanced characteristics resulting from the quantum confinement of phonons and charge carriers.

Keywords : bismuth, nanoparticle, gamma radiolysis, quantum dot, semimetal.

Laboratoire : Centre de Recherche sur la Matière Divisée - CRMD
1 b rue de la Férollerie
45071 Orléans cedex