A7 d63 1 9 4 ____ B7 五、發明説明（1) " 發明之背吾_ 本發明係關於鈮粉末及使用鈮粉末之電解電容器，及製 造粉末與電解電容器之方法。 許多年來，因爲其氧化物之高介電常數與比較許多其他 金屬爲相當低之鈮價格，許多研究者之目標爲發展鈮電解 電容器。起初，此領域之研究者考慮使用鈮作爲鈕電容器 之取代物之可能性。因此，進行許多研究以決定以鈮取代 妲之適合性。 然而，在一些這些研究中，結論爲鈮具有需要解決之嚴 重基本缺陷，如此推論鈮爲鈕之不可接受取代物。（參見電 化學協會期刊，第408頁，1997年12月）。在另一個研究 中’由於各種物理與機械問題，如場結晶，得到之結論爲 叙在固態電解電容器之使用似乎非常不可能。（電阻件科 學與技術，第1卷，第27-37頁（1974))。此外，在另一個研 究中’研究者結論爲在陽極於銳上形成之純化膜異於以纽 元成之電性質’而且就之使用造成使用起並未存在複雜 性。（參見 Elecrochimica Act，第 40 卷，第 16 期，第 2623-26 頁 經濟部中央梯準局負工消費合作社印製 (1995))。因此’雖然起初有鈮可爲钽之適合取代之希望， 證據顯示鈮在電解電容器市場無法取代钽。 除了钽電解電容器’另有鋁電解電容器市場。然而，銘 電解電容器具有與輕電解電容器戲劇性地石同之性能特 徵。 今曰電子電路之驅動力爲朝較低等效序列電阻（ESR)與等 效序列電感（ESL)之增加移動。因1C性能隨次微米幾何増 本紙張尺度適用中國國家標率（CNS )八4規格（210x297公楚） 4 63194 a? ___________B7 五、發明説明（2 ) 〜 加，有較低電源電壓與雜訊界限之需求。同時，增加汇速 度需要較高之電力需求。這些衝突之要求產生較佳電力管 理之要求。其經需要較大電流以將雜訊分離之分散電源而 完成。增加1C速度亦表示較低之切換時間及較高之電流瞬 閘。因此，電4流亦必須設計成降低瞬間負載反應。如果電 路具有夠大之電容但是低ESR與ESL·，可符合此廣泛範圍 之要求。 鋁電容器一般提供全電容器型式之最大電容。ESR隨電 容增加而降低。因此，目前使用大型高電容鋁電容器以符 合以上之要求。然而，鋁電容器並非眞正滿足設計者之低 ESR與ESL需求。其具有液態電解質之機械構造有地產生 100s亮歐姆及高阻抗之ESR。 發明之概要 本發明之一個特點爲提供屑狀鈮粉末。 本發明之另一個特點爲提供鈮粉末，較佳爲具有使鈮粉 末形成具有高電容之電容器之高表面積及物理特徵。 本發明之另一個特點爲提供鈮粉末，其在形成電容器 時，具有低DC漏電。 經濟部中央標準局具工消费合作社印聚 本發明之額外特點爲提供降低由鈮粉末形成之電容器中 DC漏電之方法。 本發明之額外特點與優點部份敌述於以下之説明，及部 份由説明而顯而易知，或可由本發明之實務學習。 本發明係關於屑狀鈮粉末。本發明之另—種狀態係關於 具有至少約0·15平方米/克之BET表面積之任何鈮粉末。 本紙張尺度^ 4631)4 A7 -----------B7 五、發明説明（3 ) 本發明亦關於鈮粉末，其在形成電解電容器陽極性，陽 極具有30,000 cv/克至約61，000 CV/克之電容。 此外’本發明係關於具有至少約2,000 ppm之氧含量之鈮 粉末。 本發明亦關於降低由鈮粉末製成之鈮陽極中DC漏電之 方法’其包含以足量之氧摻雜鈮粉末以降低Dc漏電之步 驟。 應了解，以上之一般説明及以下之詳細説明僅爲例示 性’而且意圖提供如所請之本發明之進一步解釋。 圖式之簡要説明 圖1爲顯示形成陽極及在1750 »c之溫度燒結時，鈮粉末之 BET表面積及其各電容之圖表。 圖2爲顯示形成陽極及在i600 之溫度燒結時，銳粉末 之BET表面積及其各電容之圖表。 圖3爲顯示形成陽極及在145〇。(：之溫度燒結時，鈮粉末 之BET表面積及其各電容之圖表。 圖4爲顯示形成陽極及在I300 之溫度燒結時，起粉末 之BET表面積及其各電容之圖表。 經濟部中央標準局負工消贽合作社印紫 圖5爲顯示鈮陽極之各種燒結溫度及其計算之最大電六、 圖表。 各l 圖6爲敘述在使用50伏特之形成電壓以下不同溫度形成 陽極及燒結時’艇粉末之乳捧雜含量及其各DC漏電之圖 表。 圖7爲顯示在使用30伏特之形成電壓以不同溫度形成陽 6- 本紙張尺度適用中國國家標準（) Λ4規格（210 X 2?7公釐_)~~ '—_ 經濟部中央標準局員工消费合作社印掣 4 63 1 9 4 A7 _____ B7 五、發明説明（4 ) 極及燒結時，具有各種氧摻雜程度之鈮粉末及各DC溫電 之圖表。 圖8爲顯示形成陽極時，摻雜於鈮粉末之各種磷程度之 效果及其各電容之圖表。 圖9爲顯示形成陽極時，摻雜於鈮粉末之各種磷程度之 效果及其各DC漏電之圖表。 本發明之詳細説明 本發明之一種狀態係關於屑狀鈮粉末。屑狀鈮粉末特徵 爲平坦、板形、及/或小板。屑狀鈮粉末亦具有约3至約 300，較佳爲約3至約30之縱橫比（直徑對厚度之比例）。屑 狀鈮粉末由於其形態而增加表面積。較佳爲，屑狀鈮粉末 之BET表面積爲至少0.15平方米/克而且更佳爲至少約1.0平 方米/克’而且甚至更佳爲至少約2.0平方米/克。屑狀鈮粉 末之BET表面積之較佳範圍爲约1.0半方米/克至約5.0平方 米/克而且更佳爲約2.0平方米/克至約5.0平方米/克或約2.0 平方米/克至約4.0平方米/克。BET範圍爲以預黏聚屑狀鈮 粉末爲主。 屑狀鈮粉末可黏聚。屑狀鈮粉末亦可氫化或非氫化〇屬 狀鈮粉末較佳爲具有低於約35克/立方英叫·，而且更佳爲 低於約12，而且最佳爲低於约5克/立方英叶之]5cott密度。 較佳爲，黏聚之屑狀銳粉末具有大於80毫克/秒，更佳爲 約80毫克/秒至約500毫克/秒之流速。 屑狀統粉末可藉由取銳鍵塊及使其接受氫氣以氫化而使 錠塊變脆。氫化之錠塊然後壓碎，例如，使用顎夾軋碎 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公t ) ί^^閱讀背面之ίΐφ^φ項再填寫本頁} .裝 訂 A7 B7 經濟部中央標华局員工消费合作社印裝 五、發明説明（5) 機，而形成圓形粉末。然後藉由在眞空中加熱而去除氫， 而且脱氣之圓形粉末然後接受研磨，如使用揽拌球磨機， 粉末在此分散於如乙醇之流體介質中（水性或非水性），藉 轉動棒之作用移動之不鎊鋼球之衝擊而形成屑狀粉末。各 種大小之屑可藉氫脆化繼而使屑接受衝擊研磨，例如，使 用流體化床噴射研磨機、Vortec研磨、或其他適合之研磨 步驟，而完成。 肩狀魏粉末可視情況地具有高氧含量，如藉捧雜。氧捧 雜含量之量可爲至少約2,000 ppm。更佳爲，屑狀鈮粉末具 有約2,000 ppm至約20,000 ppm而且更佳爲約2,750 ppm至約 10,000 ppm，而且最佳爲約4,000 ppm至約9,000 ppm之氧含 量。鈮，末與氧之摻雜可以各種方式完成，其包括但不限 於在眞空中於900 °C重複加熱及於空氣中冷卻。 此外，屑狀鈮粉末亦可單獨或與氧摻雜嶙。屑狀起粉末 與鱗之挣雜亦爲視情ί兄的。在本發明之一個具體實施例 中’鈮粉末之磷摻雜量爲低於約400 ppm而且較佳爲低於約 100 ppm，而且最佳爲低於約25 ppm。 基於上述之實例，摻雜之磷量關於由具有各種鱗程度作 爲摻雜物之鈮粉末形成之陽極之DC漏電及電容爲不重要 的。因此，在一個具體實施例中，由於磷關於由鈮粉末形 成之特定陽極對DC漏電與電容具有小或無益處，而存在 低量之磷及甚至可忽略量或無磷。 在本發明之另一個具體實施例中，本發明係關於具有足 夠程度之氧存在於鈮粉末中之鈮粉末（例如，屑狀、圓 (請先閲讀背面之注意事項#填寫本頁〕 .裴A7 d63 1 9 4 ____ B7 V. Description of the invention (1) " Invention of the invention_ This invention relates to niobium powder and electrolytic capacitors using niobium powder, and a method for manufacturing powder and electrolytic capacitors. For many years, because of the high dielectric constant of its oxides and the relatively low price of niobium compared to many other metals, many researchers have aimed to develop niobium electrolytic capacitors. Initially, researchers in this field considered the possibility of using niobium as a substitute for button capacitors. Therefore, many studies have been conducted to determine the suitability of replacing niobium with niobium. However, in some of these studies, it was concluded that niobium has serious basic flaws that need to be addressed, so it is deduced that niobium is an unacceptable substitute for buttons. (See Journal of the Electrochemical Society, p. 408, December 1997). In another study, 'due to various physical and mechanical problems, such as field crystallization, it was concluded that the use of solid electrolytic capacitors seems very unlikely. (Resistance Science and Technology, Vol. 1, pp. 27-37 (1974)). In addition, in another study, the 'researcher concluded that the purification film formed on the anode is different from the electrical properties of the new element' and that there is no complexity in use due to its use. (See Elecrochimica Act, Vol. 40, No. 16, pp. 2623-26. Printed by the Consumers' Cooperatives of the Central Government of the Ministry of Economic Affairs (1995)). So 'though initially there was hope that niobium could be a suitable replacement for tantalum, evidence shows that niobium cannot replace tantalum in the electrolytic capacitor market. In addition to tantalum electrolytic capacitors, there is also an aluminum electrolytic capacitor market. However, Ming electrolytic capacitors have the same performance characteristics as light electrolytic capacitors. Today, the driving force of electronic circuits is to increase towards lower equivalent sequence resistance (ESR) and equivalent sequence inductance (ESL). Due to 1C performance with sub-micron geometry, the paper size is applicable to China National Standards (CNS) 8 4 specifications (210x297 cm) 4 63194 a? ___________B7 5. Description of the invention (2) ~ plus, there are lower power supply voltage and noise boundaries Demand. At the same time, increasing the exchange rate requires higher power demand. These conflicting requirements result in better power management requirements. This is done via a distributed power supply that requires a large current to separate the noise. Increasing the speed by 1C also means lower switching time and higher current trip. Therefore, the electric current must also be designed to reduce the transient load response. If the circuit has large enough capacitance but low ESR and ESL ·, it can meet this wide range of requirements. Aluminum capacitors generally provide the maximum capacitance of the full capacitor type. ESR decreases with increasing capacitance. Therefore, large high-capacity aluminum capacitors are currently used to meet the above requirements. However, aluminum capacitors are not meeting designers' low ESR and ESL needs. Its mechanical structure with liquid electrolyte generates 100s bright ohms and high impedance ESR. SUMMARY OF THE INVENTION It is a feature of the present invention to provide crumb niobium powder. Another feature of the present invention is to provide a niobium powder, preferably having a high surface area and physical characteristics that enable the niobium powder to form a capacitor having a high capacitance. Another feature of the present invention is to provide a niobium powder which has a low DC leakage when forming a capacitor. The Central Standards Bureau of the Ministry of Economic Affairs, Industrial and Consumer Cooperatives, Printed Poly An additional feature of the present invention is to provide a method for reducing DC leakage in capacitors formed from niobium powder. The additional features and advantages of the present invention are partly described in the following description, and part is obvious from the description, or can be learned from the practice of the present invention. The present invention relates to crumb niobium powder. Another aspect of the present invention relates to any niobium powder having a BET surface area of at least about 0.15 m2 / g. Standard of this paper ^ 4631) 4 A7 ----------- B7 V. Description of the invention (3) The present invention also relates to niobium powder, which is used to form the anode of electrolytic capacitors, and the anode has a capacity of 30,000 cv / g to about 61,000 CV / g capacitor. In addition, the present invention relates to a niobium powder having an oxygen content of at least about 2,000 ppm. The present invention also relates to a method for reducing DC leakage in a niobium anode made of niobium powder ', which comprises the step of doping the niobium powder with a sufficient amount of oxygen to reduce the Dc leakage. It should be understood that the above general description and the following detailed description are merely exemplary 'and are intended to provide further explanation of the invention as requested. Brief Description of the Drawings Figure 1 is a graph showing the BET surface area of niobium powder and its capacitance when the anode is formed and sintered at a temperature of 1750 »c. Figure 2 is a graph showing the BET surface area of sharp powders and their capacitances when forming anodes and sintering at i600 temperature. FIG. 3 shows the formation of the anode and at 1450. (: Graph of BET surface area of niobium powder and its capacitance when sintered at temperature. Figure 4 is a graph showing the BET surface area of powder and its capacitance when anode is formed and sintered at I300. Central Bureau of Standards, Ministry of Economic Affairs Figure 5 is a diagram showing various sintering temperatures of niobium anodes and their calculated maximum electric voltages. Figures 6 are diagrams describing the formation and sintering of anodes at different temperatures below the formation voltage of 50 volts. Graph of the content of milk powder and its DC leakage. Figure 7 shows the formation of anodes at different temperatures using a formation voltage of 30 volts. 6-This paper size applies Chinese national standard () Λ4 size (210 X 2 ~ 7 mm)厘 _) ~~ '—_Stamps of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 63 1 9 4 A7 _____ B7 V. Description of the Invention (4) Niobium powder and various DCs with various oxygen doping levels during electrode and sintering Graph of thermoelectricity. Figure 8 is a graph showing the effects of various phosphorus levels doped with niobium powder and its capacitance when forming an anode. Figure 9 is a graph showing the effects of various phosphorus levels doped with niobium powder when forming an anode. And its DC leakage chart. Detailed description of the present invention One aspect of the present invention relates to crumb niobium powder. The crumb niobium powder is characterized by flatness, plate shape, and / or small plate. The crumb niobium powder also has about 3 To about 300, preferably about 3 to about 30, aspect ratio (ratio of diameter to thickness). Chip-shaped niobium powder increases surface area due to its morphology. Preferably, chip-shaped niobium powder has a BET surface area of at least 0.15 square meters And more preferably at least about 1.0 square meter per gram 'and even more preferably at least about 2.0 square meter per gram. A preferred range of BET surface area for crumb niobium powder is from about 1.0 half square meter per gram to about 5.0 square meters. M / g and more preferably about 2.0 square meters / gram to about 5.0 square meters / gram or about 2.0 square meters / gram to about 4.0 square meters / gram. The BET range is mainly pre-adhesive crumb-like niobium powder. The niobium powder may be cohesive. The crumb niobium powder may also be hydrogenated or non-hydrogenated. The metal niobium powder preferably has a content of less than about 35 g / cm3, more preferably less than about 12, and most preferably Less than about 5 grams per cubic inch of leaf] 5cott density. Preferably, the cohesive sharp powder has a large 80 mg / sec, more preferably a flow rate of about 80 mg / sec to about 500 mg / sec. The crumb powder can be made brittle by taking sharp bond blocks and subjecting it to hydrogen to hydrogenate. The hydrogenated ingots The pieces are then crushed, for example, using jaws to crush the paper. The size of the paper applies the Chinese National Standard (CNS) A4 specification (210X297g t). ^^ Read the ΐΐ ^^ φ item on the back and fill out this page}. Binding A7 B7 Ministry of Economy Printed by the Consumer Standards Cooperative of the Central Standardization Bureau of the People's Republic of China (5) to form a circular powder. Then the hydrogen is removed by heating in the air, and the degassed circular powder is then subjected to grinding, such as mixing In a ball mill, the powder is dispersed in a fluid medium such as ethanol (aqueous or non-aqueous), and the impact of non-pound steel balls moved by the action of a rotating rod forms a chip-like powder. Chips of various sizes can be made by hydrogen embrittlement and then subject the chips to impact grinding, for example, using a fluidized bed jet mill, Vortec grinding, or other suitable grinding steps. The shoulder-shaped Wei powder may optionally have a high oxygen content, such as borrowing impurities. The amount of oxygen impurity can be at least about 2,000 ppm. More preferably, the crumb niobium powder has an oxygen content of about 2,000 ppm to about 20,000 ppm and more preferably about 2,750 ppm to about 10,000 ppm, and most preferably about 4,000 ppm to about 9,000 ppm. Doping of niobium, oxygen, and oxygen can be accomplished in various ways, including but not limited to repeated heating at 900 ° C in the air and cooling in the air. In addition, the crumb niobium powder may be doped with oxygen alone or with oxygen. The crumb-like powder and scales are mixed as brothers. In a specific embodiment of the present invention, the phosphorus doping amount of the 'niobium powder is less than about 400 ppm, preferably less than about 100 ppm, and most preferably less than about 25 ppm. Based on the above example, the amount of doped phosphorus is not important with respect to the DC leakage and capacitance of the anode formed from niobium powder with various scales as dopants. Therefore, in a specific embodiment, because phosphorus has little or no benefit for DC leakage and capacitance with respect to a particular anode formed from niobium powder, there is a low amount of phosphorus and even negligible or no phosphorus. In another specific embodiment of the present invention, the present invention relates to a niobium powder (for example, crumbs, rounds, etc.) that has a sufficient degree of oxygen in the niobium powder (please read the precautions on the back first # Fill this page].
、1T 線 本纸張尺度適用中國國家標準（CNS ) Λ4規格（2]0X297公釐) 經濟部中央標準局員工消費合作社印製 4 63 19 4 A7 _______ B7 五、發明説明（6 ) 形、卽狀、及其混合物）。氧程度可以上述之相同方法而 得。較佳爲，鈮粉末中之氧量爲至少約2,oooppm，而且更 佳爲約2,000 ppm至約2〇,〇〇〇 ppm。鈮粉末中氧含量之其他較 佳範圍爲約2,750 ppm至約1〇,〇〇〇 ppm，及约4,〇〇〇 ppm至約9,〇〇〇 ppm之程度。關於這些鈮粉末，如有關僅屑狀鈮粉末之具 體實施例，鈮粉末中之磷程度對於特定乏具體實施例可爲 相當低。較佳爲，在此具體實施例中，磷程度（如摻雜物） 低於约400ppm，而且更最佳爲低於約1〇〇ppm，而且最佳爲 低於約25 ppm。 在另一個具體實施例中’本發明係關於具有至少0·5平方 米/克而且較佳爲至少約1.0平方米/克，而且更佳爲約1〇 至約5.0平方米/克’而且最佳爲約2 〇至約5 〇平方米/克之 BET表面積之鈮粉末（例如，屑狀、圓形、節狀、及其混 合物）。BET範園爲以預黏聚鈮粉末爲主。鈮粉末可氫化 或非氫化。鈮粉末亦可黏聚。此具體實施例中之鈮粉末可 摻雜氮。對於特定之用途，鈮粉末亦可具有低於約2,〇〇〇 ppm之氧含量。 關於製造屑狀粉末或具有任何形態與BET表面積之鈮粉 末’實例顯示形成鈮粉末之較佳步驟，其然後可製成屑或 其他形態。通常’此方法如下及實例提供製造本發明鈮粉 .末之較佳具體實施例之特定細節。 通常，在製備具有至少0.5平方米/克之BET表面積之鈮 粉末’鈮錠塊藉由在眞空中加熱而氫化以形成變脆之錠 塊’其壓碎成末。粉末中g氫視情沉地藉由在眞空中將粒 -9- 本紙乐尺度制f顧I：料（CNS ) 格（2mx 297公 (請先閱讀背面之注意事項名填寫本頁) 裝 訂-------線—：；---ri-丨 463194 經濟部中央標準局ΐ工消費合作社印製 五、發明説明（7 ) 子加熱而去除。各種BET表面積可藉由使粉末研磨而得， 幸又佳爲藉磨粉機研磨法。粉末之BET表面積越高通常需要 越長疋研磨時間。例如，約60分鐘之研磨時間可得約1.〇 平万米克之BET表面積。爲了得到甚至更高之BET表面 積，、需要較長之研磨時間，而且爲了得到約4約5平方米/ 克或更大之BET表面積，在磨粉機中約24小時或更多之研 磨時間爲使此鈮粉末具有高BET表面積範圍之唯一方法。 在製造此高表面積時，較佳爲使用15000磅3/16"SS介質及約 80磅鈮粉末之30-SL聯合方法磨粉機，研磨機設於約13〇印⑺ 之轉動。研磨機亦含足量之介質，如13或更多加佘之級數 之乙醇。研磨後，鈮粉末然後接受熱處理而且較佳爲鈮粉 末可具有在熱處理時助於減少表面積降低之磷含量。熱處 理了爲足以大致造成黏聚而且不降低表面積之任何溫度。 可使用之熱處理溫度爲約1100。(： 30分鐘。然而，溫度與時 間可修改以確定並未降低高BET表面積。 上述之各種鈮粉末可藉由使用本發明鈮粉末之電容器之 形成生成之電性質進一步特徵化。通常，本發明之起粉末 可籍由將統粉末壓成陽極及在適當之溫度燒結所壓鈮粉 末，然後將陽極化以製造然後可試驗電性質之電解電容器 陽極，而試驗電性質。 因此，本發明之另一個具體貫施例係關於由本發明之銳 粉末形成之電容器。由一些本發明之鈮粉末形成之陽極可 具有30,000 CV/克至約61，000 CV/克之電容。在形成本發明之 電容器陽極中’使用可形成具有所需性質之電容器之燒妹 -10- (請先閏讀背面之注意事項男填寫本頁) 裝- 、νβ1. The paper size of the 1T line is applicable to the Chinese National Standard (CNS) Λ4 specification (2) 0X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 63 19 4 A7 _______ B7 V. Description of the invention (6) Shape, and mixtures thereof). The degree of oxygen can be obtained in the same manner as described above. Preferably, the amount of oxygen in the niobium powder is at least about 2.0 ppm, and more preferably from about 2,000 ppm to about 20,000 ppm. Other preferable ranges of the oxygen content in the niobium powder are in the range of about 2,750 ppm to about 10,000 ppm, and about 4,000 ppm to about 9,000 ppm. Regarding these niobium powders, for example, regarding the specific embodiment of the chip-like niobium powder only, the degree of phosphorus in the niobium powder may be relatively low for a specific embodiment. Preferably, in this embodiment, the degree of phosphorus (such as dopant) is less than about 400 ppm, and more preferably less than about 100 ppm, and most preferably less than about 25 ppm. In another specific embodiment, the invention relates to having at least 0.5 square meters per gram and preferably at least about 1.0 square meters per gram, and more preferably about 10 to about 5.0 square meters per gram, and most Preferably, the niobium powder has a BET surface area of about 20 to about 50 square meters per gram (eg, crumb, round, nodular, and mixtures thereof). BET Fanyuan is mainly based on pre-bonded polyniobium powder. Niobium powder can be hydrogenated or non-hydrogenated. Niobium powder can also be cohesive. The niobium powder in this embodiment may be doped with nitrogen. For specific applications, niobium powders can also have an oxygen content of less than about 2,000 ppm. With regard to the manufacture of crumb-like powder or niobium powder having any morphology and BET surface area, examples show a preferred procedure for forming niobium powder, which can then be made into crumb or other shapes. Generally, this method is as follows and the examples provide specific details of the preferred embodiments of manufacturing the niobium powder of the present invention. In general, a niobium powder ' niobium ingot having a BET surface area of at least 0.5 m2 / g is prepared by hydrogenation in the air to form a brittle ingot ' which is crushed into powder. The hydrogen in the powder is immersed in the air by taking the granules in the air. 9- The paper scale made by Gu scale I: material (CNS) grid (2mx 297 male (please read the precautionary name on the back first and fill in this page) binding- ------ Line— :; --- ri- 丨 463194 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Printed by the Masonry Consumer Cooperative. V. Description of the Invention (7) The heating and removal of various BET surface areas can be achieved by grinding the powder. Fortunately, it is better to use a mill to grind. The higher the BET surface area of the powder, the longer the grinding time is usually required. For example, a grinding time of about 60 minutes can obtain a BET surface area of about 1.0 square meters. In order to obtain Even higher BET surface area requires longer grinding time, and in order to obtain a BET surface area of about 4 to about 5 square meters per gram or more, the grinding time of about 24 hours or more in a mill is such that Niobium powder is the only method with a high BET surface area range. When manufacturing this high surface area, it is preferred to use a 30-SL combined method mill with 15000 pounds of 3/16 " SS medium and about 80 pounds of niobium powder. The rotation of about 13 ％ of the seal. The grinder also contains a sufficient amount of medium, such as 13 or more Add more grades of ethanol. After grinding, the niobium powder is then subjected to heat treatment and preferably the niobium powder may have a phosphorus content that helps reduce surface area reduction during heat treatment. Any heat treatment is sufficient to substantially cause cohesion without reducing surface area. Temperature. The heat treatment temperature that can be used is about 1100. (: 30 minutes. However, the temperature and time can be modified to ensure that the high BET surface area is not reduced. The various niobium powders described above can be produced by the formation of a capacitor using the niobium powder of the present invention. The electrical properties are further characterized. Generally, the powder of the invention can be obtained by pressing the powder into an anode and sintering the pressed niobium powder at an appropriate temperature, and then anodizing to produce an electrolytic capacitor anode that can then be tested for electrical properties. And test the electrical properties. Therefore, another specific embodiment of the present invention relates to a capacitor formed from the sharp powder of the present invention. An anode formed from some of the niobium powder of the present invention may have 30,000 CV / g to about 61,000 CV / Gram of capacitance. In the formation of the capacitor anode of the present invention, 'use a capacitor which can form a capacitor having the desired properties. Sister-10- (please read the back of a leap male precautions Complete this page) loaded -, νβ
線 ί1---N J 本紙浪尺度適用中國國家梂準（CNS ) Λ4規格（2ΙΟΧ297公釐） 463194 經濟部中央標準居*;工消費合作社印製 A7 B7 五、發明説明（8 ) 溫度。較佳爲，燒結溫度爲約1200 °C至約1750 X，而且更 佳爲约1200 Ό至約H00 τ，而且最佳爲约1250 °C至約1350 °C。 由本發明之鈮粉末形成之陽極較佳爲以低於約6〇伏特， 而且較佳爲約30至約50伏特而且更佳爲約40伏特之電壓形 成。較佳爲’由本發明之鈮粉末形成之陽極之作業電壓爲 約4至約16伏特而且更佳爲約4至約1〇伏特。由本發明之 銳粉末形成之陽極亦較佳爲具有低於約5.0 na/CV之dc漏 電。在本發明之一個具體實施例中，由一些本發明之鈮粉 末形成之陽極具有約5.0na/CV至約0_50na/CV之DC漏電。 本發明亦有關依照本發明在其表面上具有氧化鈮膜之電 容器。較佳爲，氧化鈮膜包含五氧化鈮膜。 本發明之電容器可用於許多最終用途，如自動電子零 件；行動電話；電腦，如監視器、主機板等；消費者電子 零件，其包括TV與CRT ;印表機/影印機；電源；數據 機；筆記型電腦；及磁碟機。 本發明由以下之實例進一步説明，其意圖爲本發明之例 7JC 〇 試驗方法 陽極举ΐ告 大小-0.197”直徑 3.5 Dp 粉末重量=341毫克 歷極燒結 -11 - 本紙張尺度適用中國國家標率（CNS ) A4規格（210X297公釐〉 ----.---^----装------ir------$ ,:♦ (- (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作社印製 〇 3 1 9 4· A7 B7 五、發明説明（9 ) 1300 度 C * 10’ 1450 度 C * 10' 1600 度 C * 10_ 1750 度 C * 10' 30VEf陽極化 30V E嗯60度C/O.l% H3P04電解質20 mA/克固定電流 DC漏電/電容-ESR試驗： DC漏電試驗--- 70% Ef (21 VDC)試驗電壓 60秒充電時間 i0%H3PO4@21 度 C 電容-DF試驗： 18%H2S04@21 度 C 120 Hz 50V Ef再形成陽極化： 50V Ef @ 60度C/0.1%H3PO4電解質20 mA/克固定電流 DC漏電/電容-ESR試驗： DC漏電試驗--- 70%Ef (35 VDC)試驗電壓 60秒充電時間 10% H3P〇4 @21 度 C 電容-DF試驗： 18%氏804@21度0 120 Hz -12- 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X 297公釐） (請先閲讀背面之注意事項另填寫本頁) .裝. 線 463 A7 B7 五、發明説明（1〇) 75VEf再形成陽極化： 75VEf @ 60度C/O.l% H3P〇4電解質20 mA/克固定電流 DC漏電/電容-ESR試驗： DC漏電試驗— 70%Ef (52.5 VDC)試驗電壓 60秒充電時間 I0%H3PO4 @21 度 C 電容-DF試驗； 18%邮04@21度0 120 Hz 依照敘述於美國專利5,011，742 ; 4,960,471 ;與4,964,906之步 驟，其均全部在此併入作爲參考，測定Scott密度、氧分 析、磷分析、與BET分析。 實例1 經濟部中央標嗥局員工消资合作社印來 此實例描述包含圓形鈮粉末之本發明具體實施例。電子 束製造之鈮錠塊藉由在10-4托耳之眞空中加熱錠塊至850 °C 120分鐘而氫化。眞空以21 kPa之氫氣沖洗取代足夠之時 間，以使錠塊變脆。眞空然後泵低至-28"汞然後以氬回充 至-5” Hg。壓力維持直到以作業熱偶測量之溫度安定。增 壓時逐漸引入空氣，使得作溫度不上升。變脆之錠塊在顎 夾軋碎機中壓碎成圓形粉末及藉抽取粉末而分類，其通過 325號篩網（等於44微米粒度）。藉由在眞空中將粒予加熱 至850 °C，直到壓力不再受自粒子放射之氫影響，而自大 小降低之含氳粒子去除氫，以提供具有10.6微米之Fisher次 -13- 本紙張尺度適用中國國家標孪（CNS ) Λ4規格（2I0X297公釐） 4 63 A7 B7 經濟部中央標準局員工消资合作社印策 五、發明説明（11) 篩度、2.67克/ cc (43_8克/立方英叶）之Scott密度、0.17平方 米/克之預黏聚BET表面積、與1700 ppm氧之叙金屬圓形粉 末；乳對BET表面積之比例爲l〇,4〇〇 ppm 0 /平方米/克，及 流速爲19毫克/秒。0.34克未黏聚圓形鈮粉末之樣品壓入圍 繞0.6毫米直徑鈮引線之直徑5毫米之陽擇模型成3.5克/ cc 之密、度。所壓說粉末之樣品在眞空（低於1 〇.3 pa )於四種不 同溫度燒結10分鐘，即，1300、1450、1600與1750 °C，然後 藉由以50 V施加20 mA/克固定電流至浸於〇·]重量。/〇磷酸之 陽極而陽極化’以製造電解電容器陽極，其清況及乾燥。 在浸於18重量％硫酸之陽極之測量評估之電容器性能特徵 報告於表1。以120赫茲之頻率測定之電容以每克之微法拉 第伏特（CV/克）與每立方公分陽極體積之微法拉第伏特 (CV/cc)之單位報告；1分鐘35伏特電後測量之dc漏電以每 微法拉第伏特之奈安培(nA/CV)之單位報告。 實例2 此實例描述本發明粉末之具體實施例，其包含圓形與屑 狀粉末之黏聚混合物。2.5磅以本質上實例1之方法製備之 脱氣圓形粉末在l-s聯合方法壓粉機攪拌球磨機中處理（285 ipm90分鐘），在此粉末分散於2,4〇〇毫升乙醇介質中，而且 40磅3/16_i440SS介質藉由以轉動棒之作用移動之不銹鋼球 之衝擊形成於屑狀粉末中。在屑之所需變形後，然後去除 鈮粉末及清洗以去除存在之任何醇。鈮粉末然後以去離子 水、氫氟酸與氫氣酸各爲500毫升/時、4毫升/镑與250毫 升/磅之鈮之混合物（18.6%含22毫升/公斤HF之HC1 )清洗， -14- 本紙ί良尺度適用中國g；家標率（CNS ) Λ4規格（2Ι0Χ297公p ----'--------裝------訂------線 丨 - „ (請先閱讀背面之注意事項声乐寫本頁) Α7 B7 五、發明説明（12 ) 閱 讀 背 面 之 注 意 事 項 再一 填 弇裝 本衣 頁 訂 線 經濟部中央標準局員工消费合作杜印製 以去除金屬污染（例如，因與不銹鋼球接觸轉移之鐵、 鎳、路等）。然後，鈮粉末再以去離子水清洗及乾燥。經 酸清洗之屑狀粉末在空氣中於85T(3(TC)乾燥，並且具有5〇 至70之範圍之縱橫比（由顯微鏡察）。屑狀粉末摻合起始圓 形粉末（以30 : 70之重量比例）及提供6〇 ppm之磷之量之含 磷粉末，即’ NHJF6，其作顆粒阻止劑以在以後之黏聚用 熱處理減少表面積之降低。預黏聚之BET表面積爲〇·31平 方米/克。混合粉末藉由在眞空中於1100 X加熱3〇分鐘以 形成黏聚塊而黏聚。黏聚步驟及使得物質泵低至高眞空及 以3 C /分鐘之上升速率加熱至700，並且保持出氣直到 得到鬲壓之方式實行。加熱在爐中於高壓下以8。〇/分鐘之 上升速率持績至1100 °C並且保持30分鐘《此物質然後在爐 中冷卻及藉由暴露於空氣中而人工地鈍化。此物質然後藉 顎夾壓碎而降低至較小之黏聚粒子；通過5〇號篩度之降低 粒子（等於300微米之最大黏聚粒度）呈現u克/ cc (2L7克/ 立方英吋）之Scott密度、〇·26平方米/克之BET表面積、3693 ppm之氧含量與25 ppm之磷含量；氧對BE丁表面積之比例爲 14,OOOppmO/平方米/克及22毫克/秒之流速。黏聚之粉末以 實例1之方法製成陽極及試驗電性質，其報告於表1。 實例3 此實例描述本發明之具體實施例’其包含黏聚之屑狀粉 末。本質上如實例2所述（60分鐘之循環時間）製備具有約 50至70之縱橫比之經酸瀝濾屑狀粉末，除了鈮粉末藉由在 20_7 kPa (3 psig)與850°C暴露於氫而二次氫化，以提供變脆之 -15- 本紙張尺度適用中国國家標準（CNS ) Λ4規格（2]0x 297公漦） 經濟部中央標準局負工消资合作社印製 4 63 19 4 A7 B7 五、發明説明（13) 屑，其冷卻及藉由在流體化床噴射研磨機（得自Hosokawa微 米粉末系統，Summit ’紐澤西州）中之自我衝擊而降低大 小成具有6微米之中間粒度（由雷射粒度掃描測定）之屑狀 粉末，預黏聚BET表面積爲0.62平方米/克。降低大小之屑 狀粉末藉由在眞空爐下以l〇°C/分鐘之速率將爐加熱至1〇5〇 °C並且保持此溫度直到爐壓降低至低於1〇〇微米，而在氫 氣中加熱。以1 Nb對1-1.5 Ta之重量比例使用钽粗片（10-20篩 目）作爲獲氧物。爐以氫回充而得360毫米汞之壓力，而且 爐溫然後增至1200 °C並且保持1小時。氫然後抽氣直到爐 壓降至低於1微米，及使爐冷卻至室溫。鈮粉末然後在空 氣中鈍化30個循環，其中操作壓力在各循環增加20托耳並 且在開始次一空氣回充之前保持2分鐘。黏聚之鈮粉末藉 顎夹軋碎機降低大小成黏聚粒子；降低之黏聚屑狀鈮粉末 藉由經50號篩度濾網過濾而分離（等於3〇〇微米之最大黏聚 屑狀粒度），並且呈現1.21克/cc (20.4克/立方英吋）之Scott密 度、0.46平方米/克之BET表面積、8760 ppm之氧含量；氧 對BET表面積之比例爲19,〇〇〇 ppm 0 /平方米/克、及低於1毫 克/秒之流速。黏聚之粉末以實例1之方法製成陽極及試驗 電性質，並且報告於表1。 實例4 此實例描述本發明粉末之另一個具體實施例，其包含高 表面積、低氧、黏聚鈮屑狀粉末。鈮粉末以如實例3之相 同方法製備，除了鈮粉末以磨粉機研磨90分鐘，而且熱處 理在眞空中於1150 X：進行30分鐘。預黏聚BET表面積爲 -16- 本紙張尺度適财(⑽）罐格（2IGx297公势) ' i"^---裝------訂------線 .:: ί.. 一 (請先閱讀背面之注意事項孑填寫本頁) 4 63 19 4 A7 B7 五、發明説明（14) 0.85平方米/克β以本質上實例3之方法製備之屑狀鈮粉末 之量之氧含量藉由在氬氣下於750至850 °C範圍之溫度加熱 捧合4至5重量％鎮粉之叙粉末2小時而降低。鐵含量以起 粉末中氧化學計量之量之2至3倍範圍而建立。冷卻後， 殘餘之鎂與氧化物藉硝酸瀝濾自黏聚屑狀鈮去除。去氧屑 狀鈮以水清洗、乾燥、及藉由經50號篩度濾網過濾而分 離。過濾之鈮屑呈現1.47克/ cc(24.1克/立方英吋）之Scott密 度、0.96方米/克之BET表面積、3130 ppm之氧含量；氧對 BET表面積之比例爲3260 ppm 0 /平方米/克、及76毫克/秒 之流速。黏聚之粉末以實例1之方法製成陽極及試驗電性 (請先閱讀背面之注意事項再填寫本I) .裝. 經濟部中央標準局貝工消费合作社印製 質，並且報靠於表1。 表1 燒結溫度 1300°C 1450〇C 實例1 : 電容 1600°C 1750°C (CV/ 克） 8400 7500 6400 5500 (CV/cc) DC漏電 40900 37000 33400 30000 (na/CV 燒結密度 5 3 2.8 2.3 2.4 (克/cc) 實例2 電容 4.9 5.0 5.2 5.5 *-* -17- 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X297公釐） A7 經濟部中央標準局貝工消费合作社印製 4 63 1 94 __B7 五、發明説明（15 ) (CV/ 克） 13600 11900 10000 8200 (CV/cc) 46000 41600 36900 33400 DC漏電 (na/CV) 25 1.7 2.1 2.5 燒結密度 (克 /cc ) 3.4 3.5 3.7 4.1 實例3 : 電容 (CV/ 克） 32500 21400 13400 7100 (CV/cc) 114100 94300 73600 45800 DC漏電 (na/CV) 5.8 4.1 2.4 2.0 燒結密度 (克 / CC) 3.5 4.4 5.5 6.4 實例4 電容 (CV/ 克） 31,589 21,059 12,956 7,254 (CV/cc) 110,562 88,448 64,780 42,699 DC漏電 (na/CV 5.8 5.3 2.6 1.4 燒結密度 (克 / cc) 3.5 * 4.2 5.0 5.9 實例5 以如實例4之相同方法製備鈮粉末，除了熱處理發生於 (請先閱讀背面之注意事項"填寫本頁) -18- 本紙ί長尺度適用中國國家標準（CNS ) Λ4規格（210X 297公釐） A7 經濟部中央標準局員工消费合作社印製 463194 __B7 五、發明説明（15 ) (CV/ 克） 13600 11900 10000 8200 (CV/cc) DC漏電 46000 41600 36900 33400 (na/CV) 燒結密度 25 1.7 2.1 2.5 (克 /cc) 實例3 : 電容 3.4 3.5 3.7 4.1 (CV/ 克） 32500 21400 13400 7100 (CV/cc) DC漏電 114100 94300 73600 45800 (rWCV) 燒結密度 5.8 4.1 2.4 2.0 (克 / CC) 實例4 電容 3.5 4.4 5.5 6.4 (CV/ 克） ‘31,589 21,059 12,956 7,254 (CV/cc) DC漏電 110,562 88,448 64,780 42,699 (na/CV ' 燒結密度 5.8 5.3 2.6 1.4 (克 / CC) 3.5 4.2 5.0 5.9 實例5 以如實例4之相同方法製備鈮粉末，除了熱處理發生於 (請先閱讀背面之注意事項"填寫本頁) •裝_ 線 -18- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 463194 A7 B7 五、發明説明（16) 1250 °C之眞空中30分鐘。預黏聚BET表面積爲0.78平方米/ 克。粉末如實例1形成陽極並且具有以下之性能特徵。 CV/ 克 @ 50 VF 燒結密度，克/ cc DC 漏電，na/Cv BET，平方米/克 氧，ppm Scott密度，克/立方英叶 流速，毫克/秒 19,600(1450°C) 4.8(1450〇C ) 2.33(1450°C ) 0.S0 2,815 24.0 97 31,040(1300°C) 請 先-閱 讀 背.. 面* 之. 注 意* 事 項 填I裝 頁 實例6 以如實例4之相同方法製備鈮粉末，除了鈮粉末於磨粉 機150分鐘及熱處理於眞空爐中，在此壓力泵低至1微米然 後溫度以50°C /分鐘增至950 °C並且保持直到得到高眞空。 溫度然後以15 °C階段增加直到達到125〇 "c之溫度，而且此 溫度保持30分鐘。此物質然後在眞空下冷卻至室溫及鈍化 30個循環，其中壓力在各循環增加2〇托耳並且在開始次一 2氣回充之則保持2分鐘。此物質然後在5〇篩目顎夾軋碎 機中壓碎並且以4 % w/w鎂金屬摻合粉末及將物質置於蒸餾 爐中及泵低至1〇〇微米而去氧。預黏聚BET表面積爲1〇5平 方米/克。爐然後以氬回充至8〇〇托耳之壓力而且壓力增至 800 °C並且保持2小時。此物質然後冷卻至室溫及如上述實 例3之相同方法在空氣中鈍化3〇個循環。此物質然後以去 離子水（500 ¾升/磅）、氫氟酸（4毫升/磅）與硝酸（25〇毫升/ 镑）之混合物清洗。粉末然後以去離子水清洗及乾澡。銳 -19- 本紙張尺賴;种@醉辟 訂 線 經濟部中央標準局員工消f合作社印裝 五、發明説明（17) 經濟部中央標牟局貝工消f合作社印掣 粉末然後如實例1形成陽極 ’並且具有以下之性能特徵。 CV/克@50VF(燒結溫度 24,300(1450°C) 41,700 (1300°C) 燒結密度，克/ CC 4.0(145(TC ) DC 漏電，na/Cv 1.5(1450°C ) BET，平方米/克 1.11 氧，ppm 3,78 Scott密度，克/立方英吋 24.4 流速，毫克/秒 112 實例7 以如實例6之相同方法製備鈮粉末，除了鈮粉末在熱處 理前摻合磷以得到56 jipm之磷負載。預黏聚BET表面積爲 1.05平方米/克。此物質如實例3氫化，及如實例6壓碎' 熱處理 '與去氧。鈮粉末然後如實例1形成陽極並且具有 以下之性能特徵。 CV/ 克 @ 50 VF 29,900(1450°C) 45,400 (1300°C) 燒結密度，克/ CC 3,7(1450〇C ) DC 漏電，na/Cv 1.3(1450〇C ) BET，平方米/克 1.07 氧，ppm 3,690 Scott密度，克/立方英吋 23.2 流速，毫克/秒 76 實例8 以如實例4之相同方法製備鈮粉末，除了鈮粉末在30S磨 粉研磨機（130 ηρηι)藉由使用1,000镑之3/16'_ SS介質、80镑之 -20- 本紙乐尺度速用中國國家標準（CNS ) Λ4規格（2IOX29·?公釐） Δ 6319 4 Λ7 ___ 五、發明説明（18) 鈮粉末、與13加侖之乙醇研磨8小時。研磨之粉末以如前 户斤述之相同方法酸遊滤及清洗，而且物質具有以下之性能 特徵。 BET，平方米/克 139 氧，ppm 8,124Line ί1 --- N J This paper wave scale is applicable to China National Standard (CNS) Λ4 specification (2IO × 297 mm) 463194 Central Standard House of the Ministry of Economic Affairs *; printed by the Industrial and Consumer Cooperatives A7 B7 V. Description of the invention (8) Temperature. Preferably, the sintering temperature is about 1200 ° C to about 1750 X, and more preferably about 1200 ° C to about H00 τ, and most preferably about 1250 ° C to about 1350 ° C. The anode formed from the niobium powder of the present invention is preferably formed at a voltage of less than about 60 volts, and more preferably about 30 to about 50 volts, and more preferably about 40 volts. It is preferred that the anode formed from the niobium powder of the present invention has an operating voltage of about 4 to about 16 volts and more preferably about 4 to about 10 volts. The anode formed from the sharp powder of the present invention also preferably has a dc leakage below about 5.0 na / CV. In a specific embodiment of the present invention, an anode formed from some of the niobium powder of the present invention has a DC leakage of about 5.0na / CV to about 0-50na / CV. The present invention also relates to a capacitor having a niobium oxide film on its surface according to the present invention. Preferably, the niobium oxide film includes a niobium pentoxide film. The capacitor of the present invention can be used in many end uses, such as automatic electronic parts; mobile phones; computers, such as monitors, motherboards, etc .; consumer electronic parts, including TVs and CRTs; printers / photocopiers; power supplies; modems ; Laptops; and disk drives. The present invention is further illustrated by the following example, which is intended to be Example 7JC of the present invention. Test method Anode lifting obituary size -0.197 "diameter 3.5 Dp powder weight = 341 mg calendar pole sintering-11-This paper standard is applicable to China's national standard (CNS) A4 specification (210X297mm) ----.--- ^ ---- installation ------ ir ------ $,: ♦ (-(Please read the note on the back first Please fill in this page again) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 0 3 1 9 4 · A7 B7 V. Description of Invention (9) 1300 degrees C * 10 '1450 degrees C * 10' 1600 degrees C * 10_ 1750 degrees C * 10 '30VEf anodized 30V E 60 degrees C / Ol% H3P04 electrolyte 20 mA / g fixed current DC leakage / capacitance-ESR test: DC leakage test --- 70% Ef (21 VDC) test voltage 60 seconds charging Time i0% H3PO4 @ 21 ° C Capacitance-DF test: 18% H2S04 @ 21 ° C 120 Hz 50V Ef re-formed anodizing: 50V Ef @ 60 ° C / 0.1% H3PO4 electrolyte 20 mA / gram fixed current DC leakage / capacitance -ESR test: DC leakage test --- 70% Ef (35 VDC) test voltage 60 seconds charging time 10% H3P〇4 @ 21 degrees C capacitance-DF test: 18% 804 @ 21 degrees 0 120 Hz -12- Paper ruler Applicable to Chinese National Standard (CNS) Λ4 specification (210X 297 mm) (Please read the notes on the back and fill in this page). Assembly. Line 463 A7 B7 V. Description of the invention (1〇) 75VEf and then anodized: 75VEf @ 60 ° C / Ol% H3P〇4 electrolyte 20 mA / g fixed current DC leakage / capacitance-ESR test: DC leakage test — 70% Ef (52.5 VDC) test voltage 60 seconds charging time I0% H3PO4 @ 21 degrees C capacitor -DF test; 18% post 04 @ 21 degrees 0 120 Hz in accordance with the procedures described in US Patent Nos. 5,011,742; 4,960,471; and 4,964,906, all of which are incorporated herein by reference for determination of Scott density, oxygen analysis, phosphorus analysis, Analysis with BET. Example 1 Printed by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, this example describes a specific embodiment of the present invention containing circular niobium powder. Niobium ingots manufactured by electron beam are emptied by 10-4 Torr. The ingots were heated to 850 ° C for 120 minutes and hydrogenated. The air was flushed with 21 kPa of hydrogen for a sufficient time to make the ingots brittle. Empty and then pump down to -28 " Hg and then recharge to -5 "Hg with argon. The pressure is maintained until the temperature measured by the operating thermocouple is stable. Air is gradually introduced during pressurization so that the operating temperature does not rise. Brittle ingots It is crushed into a circular powder in a jaw crusher and classified by extracting the powder, which passes through a 325 mesh screen (equal to a particle size of 44 microns). The pellets are preheated to 850 ° C in the air until the pressure is not Affected by the hydrogen emitted from the particles, the hydrogen is removed from the reduced particles of thorium-containing particles to provide Fisher times of 10.6 microns. 13- This paper size applies to the Chinese National Standard (CNS) Λ4 specification (2I0X297 mm) 4 63 A7 B7 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (11) Sieve density, Scott density of 2.67 g / cc (43_8 g / cubic British leaf), pre-cohesive BET surface area of 0.17 m2 / g And metal round powder with 1700 ppm oxygen; the ratio of milk to BET surface area is 10,400 ppm 0 / m 2 / g, and the flow rate is 19 mg / s. 0.34 g of non-adhesive round niobium powder The sample was pressed into a straight line around a 0.6 mm diameter niobium lead. The 5 mm anode selection model has a density and degree of 3.5 g / cc. The sample of the pressed powder is sintered in air (below 10.3 Pa) at four different temperatures for 10 minutes, that is, 1300, 1450, 1600 and 1750 ° C, and then anodized by applying a fixed current of 20 mA / g at 50 V to an anode immersed in a weight of 0.] phosphoric acid to produce an anode of an electrolytic capacitor, which is conditioned and dried. Immersion in 18 The performance characteristics of the capacitors for the measurement and evaluation of anodes by weight% sulfuric acid are reported in Table 1. Capacitance measured at a frequency of 120 Hz is measured in microfaradic volts per gram (CV / g) and microfaradic volts per cubic centimeter of anode volume (CV / cc ) Unit report; dc leakage measured after 35 volts of electricity for 1 minute is reported in units of nanoamperes (nA / CV) per microfarady volt. Example 2 This example describes a specific embodiment of the powder of the present invention, which includes a circular shape and Cohesive mixture of crumb-like powder. 2.5 lbs of degassed round powder prepared in accordance with essentially the method of Example 1 was processed in a ls combined method powder press stirring ball mill (285 ipm for 90 minutes), and the powder was dispersed in 2,4. 〇mL ethanol medium, and 40 pounds of 3 / 16_i440SS medium is formed in the crumb powder by the impact of a stainless steel ball moving by the action of a rotating rod. After the desired deformation of the crumb, the niobium powder is then removed and washed to remove any alcohol present. The niobium powder is then Wash with a mixture of deionized water, hydrofluoric acid and hydroacid at 500 ml / h, 4 ml / lb and 250 ml / lb of niobium (18.6% HC1 containing 22 ml / kg HF), -14- paper Good standards apply to China g; house standard rate (CNS) Λ4 specification (2Ι0 × 297 male p ----'-------- installation ------ order ------ line 丨-„( Please read the notes on the back first and write this page on the vocal) Α7 B7 V. Description of the invention (12) Read the notes on the back and fill out the booklet and booklet again. This item is printed by the Consumer Standards Department of the Central Standards Bureau of the Ministry of Economic Affairs. Contamination (for example, iron, nickel, roads, etc. transferred by contact with stainless steel balls). Then, the niobium powder is washed and dried with deionized water. The acid-washed crumb powder is dried in air at 85T (3 (TC) and has an aspect ratio in the range of 50 to 70 (observed by a microscope). The crumb powder is blended with the starting round powder (with 30: 70% by weight) and a phosphorus-containing powder that provides 60ppm of phosphorus, ie, 'NHJF6', which acts as a particle inhibitor to reduce the surface area reduction by heat treatment in the subsequent cohesion. The BET surface area of the pre-cohesion is 0 · 31 square meters per gram. The mixed powder is agglomerated by heating at 1100 X for 30 minutes in the air to form a cohesive mass. The cohesion step and the substance pump are lowered to a high air and heated at a rate of 3 C / min to 700, and keep the gas out until the pressure is achieved. Heating in a furnace under high pressure at a rising rate of 8. 0 / min is maintained at 1100 ° C and held for 30 minutes. "This substance is then cooled in the furnace and by It is artificially passivated by exposure to air. This substance is then reduced to smaller cohesive particles by crushing by jaws; reduced particles passing through a No. 50 sieve (equivalent to a maximum cohesive particle size of 300 microns) exhibit ug / cc (2L7g / cubic inch) Scott dense BET surface area of 0.26 square meters per gram, oxygen content of 3693 ppm and phosphorus content of 25 ppm; the ratio of oxygen to BE but surface area is 14.000 ppmO / square meter per gram and a flow rate of 22 mg / second. The powder was made into anodes and tested for electrical properties by the method of Example 1, which is reported in Table 1. Example 3 This example describes a specific embodiment of the present invention 'which contains cohesive crumb-like powder. Essentially as described in Example 2 (60 Cycle time in minutes) to prepare acid-leached crumb-like powders having an aspect ratio of about 50 to 70, except that the niobium powders were rehydrogenated by exposure to hydrogen at 20_7 kPa (3 psig) and 850 ° C to provide a variable Brittle -15- This paper size applies to Chinese National Standards (CNS) Λ4 specifications (2) 0x 297 gong) Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Capital Cooperatives 4 63 19 4 A7 B7 V. Description of the invention (13) Crumbs, which are cooled and reduced in size to have an intermediate particle size of 6 micrometers (determined by laser particle size scanning by self-impact in a fluidized bed jet mill (from Hosokawa Micron Powder System, Summit 'New Jersey)) ) Chip powder, BET surface area is 0.62 square meters per gram. Reduced size crumb powder by heating the furnace to 1050 ° C at a rate of 10 ° C / min under an empty furnace and maintaining this temperature until the furnace pressure is lowered below 1.0. 〇micron, and heated in hydrogen. The weight ratio of 1 Nb to 1-1.5 Ta was used as tantalum coarse flakes (10-20 mesh). The furnace was recharged with hydrogen to obtain a pressure of 360 mmHg, and The furnace temperature was then increased to 1200 ° C and held for 1 hour. Hydrogen was then evacuated until the furnace pressure dropped below 1 micron and the furnace was allowed to cool to room temperature. The niobium powder was then passivated in air for 30 cycles, where the operating pressure was increased by 20 Torr in each cycle and held for 2 minutes before the next air refill was started. The cohesive niobium powder is reduced to a cohesive particle by a jaw crusher; the reduced cohesive niobium powder is separated by filtering through a No. 50 sieve filter (equivalent to a maximum cohesive chip of 300 microns). Particle size) and exhibits a Scott density of 1.21 g / cc (20.4 g / cubic inch), a BET surface area of 0.46 square meters per gram, and an oxygen content of 8760 ppm; the ratio of oxygen to BET surface area is 19,000 ppm 0 / M2 / g, and flow rates below 1 mg / s. The cohesive powder was made into anodes and tested for electrical properties by the method of Example 1 and reported in Table 1. Example 4 This example describes another specific embodiment of the powder of the present invention which comprises a high surface area, low oxygen, cohesive niobium crumb powder. The niobium powder was prepared in the same manner as in Example 3, except that the niobium powder was ground with a pulverizer for 90 minutes, and the heat treatment was performed in the air at 1150 X for 30 minutes. The surface area of the pre-adhesive BET is -16- This paper is suitable for standard (⑽) cans (2IGx297) and it is' i " ^ --- installation ------ order ------ line. :: ί .. 1 (Please read the precautions on the back and fill in this page first) 4 63 19 4 A7 B7 V. Description of the invention (14) 0.85 m2 / g β The amount of crumb niobium powder prepared by the method of Example 3 in essence The oxygen content is reduced by heating the powder of 4 to 5% by weight of ballast powder for 2 hours at a temperature in the range of 750 to 850 ° C under argon. The iron content is established in a range of 2 to 3 times the amount oxidized in the powder. After cooling, residual magnesium and oxides were removed from the cohesive niobium by leaching of nitric acid. Deoxygenated niobium is washed with water, dried, and separated by filtering through a No. 50 sieve. The filtered niobium filings exhibited a Scott density of 1.47 g / cc (24.1 g / cubic inch), a BET surface area of 0.96 m2 / g, and an oxygen content of 3130 ppm; the ratio of oxygen to BET surface area was 3260 ppm 0 / m2 / g , And a flow rate of 76 mg / sec. The cohesive powder was made into anode by the method of Example 1 and tested for electrical properties (please read the notes on the back before filling in this I). Packing. Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, and reported to the table 1. Table 1 Sintering temperature 1300 ° C 1450 ° C Example 1: Capacitance 1600 ° C 1750 ° C (CV / g) 8400 7500 6400 5500 (CV / cc) DC leakage 40900 37000 33400 30000 (na / CV sintering density 5 3 2.8 2.3 2.4 (g / cc) Example 2 Capacitance 4.9 5.0 5.2 5.5 *-* -17- This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) A7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 63 1 94 __B7 V. Description of the invention (15) (CV / g) 13600 11900 10000 8200 (CV / cc) 46000 41600 36900 33400 DC leakage (na / CV) 25 1.7 2.1 2.5 Sintered density (g / cc) 3.4 3.5 3.7 4.1 Example 3: Capacitance (CV / g) 32500 21400 13400 7100 (CV / cc) 114100 94300 73600 45800 DC leakage (na / CV) 5.8 4.1 2.4 2.0 Sintered density (g / CC) 3.5 4.4 5.5 6.4 Example 4 Capacitance (CV / G) 31,589 21,059 12,956 7,254 (CV / cc) 110,562 88,448 64,780 42,699 DC leakage (na / CV 5.8 5.3 2.6 1.4 sintered density (g / cc) 3.5 * 4.2 5.0 5.9 Example 5 Prepare niobium powder in the same manner as in Example 4, In addition to the heat treatment that occurs (please read the precautions on the back first) (This page) -18- The long scale of this paper applies the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) A7 Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 463194 __B7 V. Description of the invention (15) (CV / g) 13600 11900 10000 8200 (CV / cc) DC leakage 46000 41600 36900 33400 (na / CV) Sintered density 25 1.7 2.1 2.5 (g / cc) Example 3: Capacitance 3.4 3.5 3.7 4.1 (CV / g) 32500 21400 13400 7100 (CV / cc) DC leakage 114100 94300 73600 45800 (rWCV) Sintered density 5.8 4.1 2.4 2.0 (g / CC) Example 4 Capacitance 3.5 4.4 5.5 6.4 (CV / g) '31, 589 21,059 12,956 7,254 (CV / cc) DC leakage 110,562 88,448 64,780 42,699 (na / CV 'Sintered density 5.8 5.3 2.6 1.4 (g / CC) 3.5 4.2 5.0 5.9 Example 5 Niobium powder was prepared in the same way as in Example 4, except that the heat treatment occurred (please read the precautions on the back first " fill out this (Page) • Installation_ Line-18- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297mm) 463194 A7 B7 V. Description of the invention (16) 30 minutes in the air at 1250 ° C. The pre-bonded BET surface area was 0.78 m2 / g. The powder formed the anode as in Example 1 and had the following performance characteristics. CV / g @ 50 VF sintered density, g / cc DC leakage, na / Cv BET, m2 / g oxygen, ppm Scott density, g / cubic leaf flow rate, mg / s 19,600 (1450 ° C) 4.8 (1450. C) 2.33 (1450 ° C) 0.S0 2,815 24.0 97 31,040 (1300 ° C) Please read the back first: face * of. Note * Note Fill in page Example 6 Prepare niobium powder in the same way as in Example 4 Except for the niobium powder in the mill for 150 minutes and heat treatment in the hollow furnace, the pressure pump is lowered to 1 micron and the temperature is increased to 50 ° C at 50 ° C / minute and maintained until a high hollow is obtained. The temperature was then increased in 15 ° C steps until a temperature of 125 ° C was reached, and this temperature was maintained for 30 minutes. This material was then cooled to room temperature and passivated for 30 cycles in a vacuum, where the pressure increased by 20 Torr at each cycle and was maintained for 2 minutes after the second gas refill was initiated. This material was then crushed in a 50 mesh jaw crusher and the powder was blended with 4% w / w magnesium metal and the material was placed in a distillation furnace and pumped down to 100 microns to deoxygenate. The pre-cohesive BET surface area was 105 m2 / g. The furnace was then backfilled with argon to a pressure of 800 Torr and the pressure was increased to 800 ° C and held for 2 hours. This material was then cooled to room temperature and passivated in air for 30 cycles in the same manner as in Example 3 above. This material was then washed with a mixture of deionized water (500 ¾ l / lb), hydrofluoric acid (4 ml / lb) and nitric acid (25 ml / lb). The powder was then washed with deionized water and dried. Rui-19- This paper rule is based on the kind of @ 辟 沛 定 线 Employees of the Central Standards Bureau of the Ministry of Economic Affairs, the cooperatives printed on the Fifth, the description of the invention (17) The Central Bureau of the Ministry of Economic Affairs, the Ministry of Economics and the Fifth Cooperatives printed powder, and then as an example 1 forms the anode 'and has the following performance characteristics. CV / g @ 50VF (sintering temperature 24,300 (1450 ° C) 41,700 (1300 ° C) sintering density, g / CC 4.0 (145 (TC)) DC leakage, na / Cv 1.5 (1450 ° C) BET, square meter / g 1.11 Oxygen, ppm 3,78 Scott density, g / cubic inch 24.4 flow rate, mg / s 112 Example 7 Niobium powder was prepared in the same manner as in Example 6, except that the niobium powder was doped with phosphorus to obtain 56 jipm of phosphorus. Load. The pre-cohesive BET surface area is 1.05 square meters per gram. This material is hydrogenated as in Example 3 and crushed 'heat treated' and deoxygenated as in Example 6. The niobium powder then forms the anode as in Example 1 and has the following performance characteristics. CV / G @ 50 VF 29,900 (1450 ° C) 45,400 (1300 ° C) sintered density, g / CC 3,7 (1450 ° C) DC leakage, na / Cv 1.3 (1450 ° C) BET, square meter / g 1.07 Oxygen, ppm 3,690 Scott density, g / cubic inch 23.2 flow rate, mg / s 76 Example 8 Niobium powder was prepared in the same manner as in Example 4, except that the niobium powder was milled in a 30S mill (130 ηρηι) by using 1,000 pounds 3 / 16'_ SS medium, 80 pounds -20- Chinese paper standard Quick Use Chinese National Standard (CNS) Λ4 Regulation (2IOX29 ·? Mm) Δ 6319 4 Λ7 ___ V. Description of the invention (18) Niobium powder, ground with 13 gallons of ethanol for 8 hours. The ground powder is filtered and washed by acid in the same way as described in the previous section And the substance has the following performance characteristics: BET, m2 / g 139 oxygen, ppm 8,124
Scott密度，克/立方英吋3 實例9 圖1、2、3與4顯示具有一定範圍之βΕΤ之各種灿粉末 之CV/克相對BET ^各圖表示在指定燒結溫度測定之粉末 之CV/克測量。如圖所示，燒結溫度越高，陽極之表面積 損失越大，而且對於任何特定粉末樣品，在較高燒結溫度 試驗樣品時亦有CV/克之一般降低（cv/克與燒結後陽極之 殘餘表面積比成正比）。 經濟部中央標隼局員工消费合作社印製 如圖1至4所描述，對於任何指定之燒結溫度，所得之 CV/克對樣之起始bet有關係。如所示，低bet產生低淨 CV/克而且隨BET上升CV/克亦上升。對於具有高BET之物 質，燒結時表面積損失之程度大到鍍滅許多表面積，在燒 結後僅留下小邵份之原始高BET可表現，所以cv/克隨最 高BET下降。因此，CV/克相對BET之反應顯示在燒結後保 存大部份表面積比之BET値最大。通常，如圖所示，較低 之燒結溫度得最適CV/克與較高之BET物質；於是，對 小、高BET粒子爲非常破壞性之高燒結溫度得到最適cv/ 克與較低BET粉末。 通系對於在任何指定燒結溫度均有最適bet ;而且所有 -21 - 本紙張尺度適用中國國家標毕（CNS ) A4規格（210X297公釐） 五、發明説明（19) A7 B7 Μ濟部中央標準局負工消资合作社印紫 最適BET組形成有關燒結溫度之反應表面。如圖所示， CV/克通常與BET成正比，及CV/克顯示對燒結溫度之關 係。因此，圖5顯示相對燒結溫度由圖1至3繪製之各燒結 溫度之CV/克。圖5顯示在1300 °C燒結得到之CV/克在約 61，000之級數。 圖5之製備爲基於測定得自各圖1至3之最大CV/克之目 的與數學修正步驟。因爲觀察各至3中CV/克相對BET 之反應呈現最大，此要求由對於各圖之數據發現最佳功能 符合之最大値而解決。CV/克對BET之實際反應爲複雜之 變數函數；然而，函數之Taylor序列膨脹敎示所有之函數 可由獨立變數之有限域内Taylor序列之前三項（在此情形爲 BET)趨近。此量趨近在任何所選X値之有限相鄰内有效之 二次方程式（F(x)=ax2+bx+c)之函數。只要X値在相鄰内，此 計算爲有效的。各情形之最適BET作爲BET域相鄰中心， 使得趨近對於接近此値之BET最有效；及，因此取符合數 據之最大二次方程式爲圖1至3中數據之尖峰CV/克之最佳 估計。因此，在圖1至3使用微軟Excel v 5.0之曲線符合工具 對二次方程式實行數據之最佳符合，其產生重疊圖1至3 之測量數據之抛物線曲線。使用符合圖1至3拋物線之最 大値作爲輸入數據而產生圖5。 圖5之最CV/大克相對燒結溫度數據之组其次使用微軟 Exce中v 5.0之曲線符合工具符合指數衰減函數。選擇指數 衰減作爲最大CV/克相對燒結溫度之反應之最佳趨近之原 因乃因爲，如圖所示，CV/克隨燒結溫度增加而降低；然 -22- 本紙張尺度適用中國國家樣準（CNS ) Λ4規格（2丨0'乂 297公釐） 請 k ~ 閲 背. 面· i ' 事 項 填 寫 本 頁 裝 訂 線 A7 — ______B7 五、發明説明（2〇) 而，CV/克原則上從不低於〇.丨，因爲表面積比無法小於零 (热法爲負的）。不對稱衰減至零之指數函數爲圖5之數據 可使用之最簡單函數形式’其並不預測負CV/克。微軟 Excel v 5.0決定之指數曲線之最佳符合加入圖5之數據，而 且其允許最大CV/克之計算，其如上解釋基於圖1至3之所 有數據以1300 °C之燒結溫度得到。 圖4爲在1300 C燒結試驗之可得Na樣品之實際數據；然 而，在圖4可見到’數據並非尖峰，因爲並無樣品對13〇〇 C燒結具有最適BET。數據恰如用於圖1至3符合二次方程 式函數’而且重疊圖4所示之結果顯示，應依照圖I至3之 尖峰之觀察存在尖峰：及，尖峰出現於CV/克>55,000及 BET>1.7。明顯地’在圖4之情形，使用用以製造圖5之數 據之相同分析預測之尖峯CV/克敘述非常接近圖5估計獨 立衍生最大値之最大CV/克。兩個在1300 °C燒結之最大CV/ 克之分別測定間之一致符合，而且澄清在1300T：燒結條件 時’以BET > 1.7完成之物質（2或更高級數之BET )呈現cv/ 克 >55,000 (60,000 級數之 CW 克）。 (請先閱讀背面之注意事項4填寫本頁) -裝 經濟部中央標_局貝工消费合作社印製 -23- 本紙張尺度適用中國國家樣準（CNS ) Λ4规格（2i〇X297公釐） 4 63 19 4 A7 B7 五、發明説明（21) 表2 用於圖1至4之實例數捷 ^sssssxaass^= 1300 1300 1450 1 —1 .Λ 1450 1600 1600 1750 1750 BET cv/g BET CV/g BET CV/g BET cv/g 0.8 30,302 0.8 22,757 0.8 14,433 0.8 7,972 0.8 30,423 0.8 22,982 0.8 14,754 0.8 8,517 1.16 45,440 1.16 29,916 1.16 16,495 1.16 7,785 0.96 40,797 0.96 29,868 0.96 18,480 0.96 9,958 0.96 35,350 0.96 27,959 0.96 17,742 0.96 9,611 0.96 40,235 0.96 30,147 0.96 18,707 0.96 9,989 0.96 35,481 0.96 27,667 0.96 17,977 0.96 9,611 實例10 經濟部中央標準局貝工消费合作社印製 研究氧對鈮粉末之影響。試驗各稱重丨磅之五個屑狀鈮 粉末樣品（如實例5製備）。樣品之一爲對照及四個其餘樣 品以增加鈮粉末中氧含量之方式處理。特別地，四個樣品 在爐中於900 °C熱處理30分鐘。粉末然後以類似以上實例 5寸論之空氣純化在空氣中純化。然後，去除四個樣品之一 而且其餘二個樣品再以上述之相同方法熱處理及鈍化。如 别，此二個樣品之一然後去除而且再對兩個其餘樣品重複 步驟。然後，再去除樣品之一而且最終其餘樣品再如前熱 處理及鈍化。如此，製備五個樣品’其中實行〇、1、2 ' 3、或4個熱處理循環。在試驗這些樣品各個之氧含量之 前’樣品個別地通過4〇篩目滤網。 粉末然後黏聚及在各種溫度燒結，並且基於三種不同電 -24- 本纸張尺度適用中國國家榡準（CNS ) A4現格（210x297公釐） 463194 A7 B7五、發明説明（气 壓形成陽極，如表3所示。DC漏電之結果敘述於表3。如 由表3之結果及圖6與7所示，DC漏電隨鈮之氧含量增加 而逐漸降低。DC漏電之降低在如30與50伏特之形成電壓 特別明顯。 表3 顯示02對na/CV於30,50與60伏特之影響之數據 經濟部中夬標準局員工消费合作社印製 30 Vf 1300 1450 1600 1750 氧 na/CV na/CV na/CV na/CV 2725 4.47 1.86 0.89 0.47 4074 3.96 1.41 0.62 0.47 4870 3.49 1.29 0.58 0.45 5539 2.7 1.04 0.55 0.45 6499 2.38 0.95 0.54 0.45 8909 2.25 0.88 0.57 0.54 50 Vf 1600 1750 氧 na/CV na/CV na/CV na/CV 2725 4.31 3.07 1.84 1.08 4074 4.47 2.55 1.46 1.01 4870 3.96 2.51 1.42 0.99 5539 3.26 2.21 1.29 0.97 6499 3.5 2.09 1.23 0.97 8909 3.85 2.02 1.26 0.97 60 Vf 1600 1750 氧 na/CV na/CV na/CV na/CV 2725 22.16 25.06 28.64 27.08 4074 19.78 24.07 28.51 28.78 4870 19.11 24.71 28.51 27.67 5539 17.84 21.75 26.62 27.37 6499 17.88 22.37 24.88 25.69 8909 25.2 29.67 33.2 28.99 -25- (請先閲讀背面之注意事3^/填寫本頁) .裝. 線 本纸張尺度適用中國國家標準（CNS ) A4規格（2〗0X297公釐） A7 B7 五、發明説明（23) 實例11 然後檢驗磷對鈮粉末之影響。試驗以如實例5之方法製 備之六個级粉末樣品。樣品之一作爲對照及其餘五個具有 加入足夠磷酸以得到各5 ppm、10 ppm、30 ppm、1〇〇 ppm、與5〇〇 Ppm之鱗程度。碟酸如使用150毫升之去離子水之稀釋溶液 加入。ί粦酸溶液與粉末混合而JL樣品在眞空烤箱中乾燥。 乾燥後，樣品個別地摻合及試驗磷程度。結果敘述於表 4。如由表4及圖8與9所見到，有磷摻雜造成之小效果， 而且注意到較高量之磷摻雜未必改良DC漏電之性質。 (請先閲讀背面之注意事項再填筇本頁j -裝· —線 經濟部中央標準局員工消费合作社印裝 -26- 本紙弦尺度適用中國國家標準（CNS ) A*!規格（210X297公釐ΐ A7 f 4-631Scott Density, g / cubic inch 3 Example 9 Figures 1, 2, 3 and 4 show the CV / gram relative BET of various brilliant powders with a certain range of β ET ^ The figures show the CV / gram of powder measured at a specified sintering temperature measuring. As shown in the figure, the higher the sintering temperature, the greater the loss of surface area of the anode, and for any specific powder sample, the CV / g is generally reduced when the sample is tested at a higher sintering temperature (cv / g and the residual surface area of the anode after sintering) Proportionally). Printed by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs As shown in Figures 1 to 4, for any given sintering temperature, the resulting CV / gram is related to the initial bet of the sample. As shown, a low bet produces a low net CV / gram and CV / gram rises as the BET rises. For materials with a high BET, the surface area loss during sintering is so great that many surface areas are plated out. After sintering, only the original high BET leaving only a small amount can be expressed, so cv / g decreases with the highest BET. Therefore, the response of CV / g to BET shows that the BET 値 that retains most of the surface area ratio after sintering is the largest. Generally, as shown in the figure, the lower sintering temperature is the most suitable CV / g and the higher BET substance; therefore, the small and high BET particles are very destructive and the high sintering temperature is the best cv / g and the lower BET powder . The general system is the most suitable bet at any given sintering temperature; and all -21-This paper size applies to China National Standard Complete (CNS) A4 specifications (210X297 mm) V. Description of invention (19) A7 B7 Μ Central Standard The optimized BET group of the Yinzizi Cooperative of the local labor and consumer cooperatives formed a reaction surface related to the sintering temperature. As shown, CV / gram is usually directly proportional to BET, and CV / gram shows a relationship to sintering temperature. Therefore, Fig. 5 shows the CV / gram of each sintering temperature plotted from Figs. 1 to 3 with respect to the sintering temperature. Figure 5 shows a CV / g order of about 61,000 obtained by sintering at 1300 ° C. The preparation of Figure 5 is based on the determination of the maximum CV / gram obtained from each of Figures 1 to 3 and the mathematical correction steps. Because the maximum CV / gram response to BET was observed in each of 3 to 3, this requirement was solved by finding the maximum function that best matched the data in each figure. The actual response of CV / gram to BET is a complex variable function; however, the Taylor sequence expansion of the function indicates that all functions can be approached by the first three terms (in this case, BET) of the Taylor sequence in a finite field of independent variables. This quantity approaches a function of the quadratic equation (F (x) = ax2 + bx + c) that is valid within the finite neighbors of any selected X 値. As long as X 値 is within the neighborhood, this calculation is valid. The optimal BET in each case is the adjacent center of the BET domain, so that the approximation is most effective for BETs close to this ；; and therefore, the largest quadratic equation that fits the data is the best estimate of the peak CV / gram of the data in Figures 1 to 3. . Therefore, the curve coincidence tool of Microsoft Excel v 5.0 is used in Figures 1 to 3 to implement the best fit of the data for the quadratic equation, which produces a parabolic curve that overlaps the measured data of Figures 1 to 3. Fig. 5 is generated using the largest 符合 that conforms to the parabola of Figs. 1 to 3 as input data. The group of the most CV / Dake relative sintering temperature data in Fig. 5 is followed by the curve conformance tool of Microsoft Exce v 5.0 which conforms to the exponential decay function. The reason why the exponential decay is chosen as the best approach to the response of the maximum CV / gram to the sintering temperature is because, as shown in the figure, CV / gram decreases as the sintering temperature increases; (CNS) Λ4 specification (2 丨 0 '乂 297mm) Please k ~ read the back. Please fill in the binding line A7 on this page. ______B7 V. Description of the invention (2〇) In principle, CV / gram starts from Not lower than 0.1, because the surface area ratio cannot be less than zero (the thermal method is negative). The exponential function of asymmetric decay to zero is the simplest form of function that can be used for the data in Figure 5 'which does not predict negative CV / gram. The best fit of the exponential curve determined by Microsoft Excel v 5.0 fits the data added in Figure 5, and it allows the calculation of the maximum CV / gram, which is explained above based on all the data in Figures 1 to 3 at a sintering temperature of 1300 ° C. Figure 4 is the actual data of the available Na sample at the 1300 C sintering test; however, it can be seen in Figure 4 that the 'data is not a spike because no sample has an optimal BET for 1300 C sintering. The data is exactly the same as used in Figures 1 to 3 for the function of the quadratic equation 'and the results shown in Figure 4 are superimposed. There should be peaks according to the observations of the peaks in Figures 1 to 3: and the peaks appear at CV / g > 55,000 and BET ; 1.7. Obviously, in the case of Fig. 4, the description of the peak CV / gram predicted using the same analysis used to make the data of Fig. 5 is very close to the estimated maximum CV / gram of the independently derived maximum chirp in Fig. 5. Consistent agreement between two separate determinations of the maximum CV / g sintered at 1300 ° C, and clarified that at 1300T: sintering conditions, 'substances completed with BET > 1.7 (BET of 2 or higher) present cv / g & gt 55,000 (60,000 series of CW grams). (Please read the Note 4 on the back first to fill in this page)-Install the central standard of the Ministry of Economic Affairs_Printed by the Bureau of Consumer Industry Cooperatives -23- This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (2i × 297mm) 4 63 19 4 A7 B7 V. Description of the invention (21) Table 2 Examples used in Figures 1 to 4 ^ sssssxaass ^ = 1300 1300 1450 1 —1 .Λ 1450 1600 1600 1750 1750 BET cv / g BET CV / g BET CV / g BET cv / g 0.8 30,302 0.8 22,757 0.8 14,433 0.8 7,972 0.8 30,423 0.8 22,982 0.8 14,754 0.8 8,517 1.16 45,440 1.16 29,916 1.16 16,495 1.16 7,785 0.96 40,797 0.96 29,868 0.96 18,480 0.96 9,958 0.96 35,350 0.96 27,959 0.96 17,742 0.96 9,611 0.96 9,611 0.96 0.96 30,147 0.96 18,707 0.96 9,989 0.96 35,481 0.96 27,667 0.96 17,977 0.96 9,611 Example 10 The impact of oxygen on niobium powder was printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Five crumb niobium powder samples (prepared in Example 5) were weighed and weighed one pound each. One of the samples was a control and the four remaining samples were processed in such a way as to increase the oxygen content in the niobium powder. Specifically, four samples were heat-treated in a furnace at 900 ° C for 30 minutes. The powder was then purified in air using a 5 inch air purifier similar to the example above. Then, one of the four samples was removed and the remaining two samples were heat-treated and passivated in the same manner as described above. Otherwise, one of these two samples is then removed and the steps are repeated for the two remaining samples. Then, one of the samples is removed and finally the remaining samples are heat treated and passivated as before. In this way, five samples 'were prepared in which 0, 1, 2' 3, or 4 heat treatment cycles were performed. Prior to testing the oxygen content of each of these samples, the samples were individually passed through a 40 mesh screen. The powder is then agglomerated and sintered at various temperatures and is based on three different electrical -24- This paper size is applicable to China National Standard (CNS) A4 (210x297 mm) 463194 A7 B7 V. Description of the invention (pressure forming the anode, As shown in Table 3. The results of DC leakage are described in Table 3. As shown by the results in Table 3 and Figures 6 and 7, DC leakage decreases gradually as the oxygen content of niobium increases. The reduction of DC leakage is between 30 and 50 The formation voltage of volts is particularly obvious. Table 3 shows the effect of 02 on na / CV at 30, 50, and 60 volts. Printed by the Ministry of Economic Affairs, China Standards Bureau, Employee Consumer Cooperative, 30 Vf 1300 1450 1600 1750 oxygen na / CV na / CV na / CV na / CV 2725 4.47 1.86 0.89 0.47 4074 3.96 1.41 0.62 0.47 4870 3.49 1.29 0.58 0.45 5539 2.7 1.04 0.55 0.45 6499 2.38 0.95 0.54 0.45 8909 2.25 0.88 0.57 0.54 50 Vf 1600 1750 oxygen na / CV na / CV na / CV na / CV 2725 4.31 3.07 1.84 1.08 4074 4.47 2.55 1.46 1.01 4870 3.96 2.51 1.42 0.99 5539 3.26 2.21 1.29 0.97 6499 3.5 2.09 1.23 0.97 8909 3.85 2.02 1.26 0.97 60 Vf 1600 1750 oxygen na / CV na / CV na / CV V 2725 22.16 25.06 28.64 27.08 4074 19.78 24.07 28.51 28.78 4870 19.11 24.71 28.51 27.67 5539 17.84 21 The paper size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (2 0x297 mm) A7 B7 V. Description of the invention (23) Example 11 Then check the effect of phosphorus on the niobium powder. The test is performed as in Example 5. Six grade powder samples were prepared. One of the samples served as a control and the remaining five had scale levels sufficient to add 5 ppm, 10 ppm, 30 ppm, 100 ppm, and 500 Ppm each. Dish acid is added as a diluted solution using 150 ml of deionized water. The acid solution was mixed with the powder and the JL samples were dried in an air oven. After drying, the samples were individually blended and tested for phosphorus levels. The results are described in Table 4. As can be seen from Table 4 and Figures 8 and 9, there are small effects caused by phosphorus doping, and it is noted that higher amounts of phosphorus doping do not necessarily improve the DC leakage properties. (Please read the precautions on the back before filling in this page. J -Installation · —Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-26-This paper string size applies to Chinese National Standards (CNS) A *! Specifications (210X297 mm ΐ A7 f 4-631
7 B 五、發明説明（24) 表4 接雜P之紅樣品之數據 掺雜P (ppm) 陽極P (ppm) CV/g(1300eC) na/CV (1300°C) 16 13 33009 22.96 26 13 33614 21.77 69 100 33676 19.53 200 58 33915 21.83 400 204 34213 20.65 CV/g(1450〇C) na/CV (1420〇C) 16 0 24095 25.06 26 20 24375 23.4 62 72 24459 24.33 200 50 25348 26.09 400 339 25664 24.69 0 CV/g(1600°C) na/CV (I600°C) 16 15757 25.51 26 0 15974 24.82 62 0 16131 24.57 200 56 16736 25.83 400 415 17011 27.18 16 CV/g(1750〇C) na/CV (1750CC) 8575 16.39 26 9176 16.69 62 9315 17.35 200 9551 16.54 400 9670 18.74 由在此揭示之本發明説明書與實務，本發明之其他具體 經濟部中央標準局員工消費合作社印製 {請先閱讀背面之注意事項名填寫本頁) 實施例對熟悉此技藝者爲明顯的。其意圖使説明書與實例 僅爲例示，本發明之眞正範圍與精神由以下之申請專利範 圍指示。 -27-本紙乐尺度適用中國國家榇準（CNS ) A4規格（2!0Χ 297公釐）7 B V. Description of the invention (24) Table 4 Data of red sample doped with P Doped P (ppm) Anode P (ppm) CV / g (1300eC) na / CV (1300 ° C) 16 13 33009 22.96 26 13 33614 21.77 69 100 33676 19.53 200 58 33915 21.83 400 204 34213 20.65 CV / g (1450 ° C) na / CV (1420 ° C) 16 0 24095 25.06 26 20 24375 23.4 62 72 24459 24.33 200 50 25348 26.09 400 339 25664 24.69 0 CV / g (1600 ° C) na / CV (I600 ° C) 16 15757 25.51 26 0 15974 24.82 62 0 16131 24.57 200 56 16736 25.83 400 415 17011 27.18 16 CV / g (1750〇C) na / CV (1750CC ) 8575 16.39 26 9176 16.69 62 9315 17.35 200 9551 16.54 400 9670 18.74 Printed by the specification and practice of the invention disclosed here, and other specific inventions of the Ministry of Economic Affairs Central Standards Bureau employee consumer cooperatives {Please read the notes on the back first Name fill in this page) Examples are obvious to those skilled in the art. It is intended that the specification and examples are merely examples, and the true scope and spirit of the present invention is indicated by the following patent application scope. -27-The paper scale is applicable to China National Standard (CNS) A4 (2! 0 × 297 mm)