TW201200472A - Si powder and method for producing same - Google Patents

Abstract

Disclosed is an Si powder which contains 0-2% by mass of Fe with the balance made up of Si and unavoidable impurities. The Si powder has an average circularity of 0.75-1.00 and a relative density of 65% or more as calculated by the formula below. The Si powder has high contact resistance when used in filling, molding, coating and the like.

Description

201200472 六、發明說明： 關聯申請案的相互參照 本申請案係以20 10年2月I7日申請的日本發明專利申 請第2010-31907號、2010年3月30日申請的日本發明專利 申請第2010-76700號、2010年4月19日申請的日本發明專 利申請第201 0-95 630號爲基礎而主張優先權者，藉由參昭 彼等全體的揭示內容而納入本說明書中。 【發明所屬之技術領域】 本發明關於在用於塡充、成形 '塗佈等之際，接觸電 阻高的矽粉末者’尤其關於具有高的電阻之軟磁性燒結構 件或軟磁性壓粉體等中所用的接觸電阻高之矽粉末。又， 本發明的一態樣係關於接觸電阻、塡充密度、流動性及分 散性高的矽粉末，尤其關於需要高的接觸電阻之電子零件 材料’或在介質中的分散性高之Si原料所用的矽粉末及其 製造方法。再者’本發明的另一態樣係關於作爲粉末塡充 體的電流遮斷性與導熱性高，而且塡充密度高、便宜的電 子零件材料用矽粉末。 【先前技術】201200472 VI. INSTRUCTIONS: CROSS-REFERENCE TO RELATED APPLICATIONS This application is a Japanese invention patent application No. 2010-31907 filed on February 1, 2010, and Japanese Patent Application No. 2010 filed on March 30, 2010 The priority of the Japanese Patent Application No. 201-95 630, filed on Apr. 19, 2010, the entire disclosure of which is incorporated herein by reference. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tantalum powder having a high contact resistance when used for filling, forming, coating, etc., particularly regarding a soft magnetic sintered member or a soft magnetic powder having a high electrical resistance. The tantalum powder with high contact resistance used in the above. Further, an aspect of the present invention relates to a tantalum powder having high contact resistance, enthalpy density, fluidity and dispersibility, in particular, an electronic component material requiring high contact resistance or a Si material having high dispersibility in a medium. The tantalum powder used and its method of manufacture. Further, another aspect of the present invention relates to a tantalum powder for an electronic component material which has high current interruption property and thermal conductivity as a powder filler and which has a high tantalum density and is inexpensive. [Prior Art]

Si係半導體，具有固有電阻高的大特徵，若與Fe或Ni 等的金屬比較’則亦大2〜5位數。又，若與Fe或Ni等的金 屬比較，則爲具有塑性變形能力極小，或真密度低等的各 式各樣特徵之元素。 -5- 201200472 另一方面，粉末狀的Si，若Si本身的固有電阻高，則 在塡充其時，由於粉末彼此變成點接觸，故具有粉末塡充 體才有的接觸電阻高之特徵。利用此特徵，粉末狀的Si係 可在電流不宜流動的2個金屬體之間塡充、塗佈等而使用 〇 又，將軟磁性金屬粉未與矽粉末混合及成形，避免軟 磁性金屬粉末彼此之接觸，則即使在已減低渦電流損失的 壓粉芯等，也可使用矽粉末。再者，如日本特開2005- 608 3 0號公報（專利文獻1 )中所揭示，亦有提案在軟磁性 金屬粉末中混合矽粉末，將此燒結的高電阻軟磁性燒結構 件等。於如此的用途中，要求矽粉末彼此的接觸電阻高。 於日本特開2 008-2 8 8 525號公報（專利文獻2 )中，提案一 種由含有Fe、44〜5〇質量％的Ni與2〜6質量％的3丨之組成 所構成’在粒子間S i偏在的燒結軟磁性粉末所成之成形體 〇 於如上述專利文獻1之製造粉末成形體的用途中，一 般地粉末的塡充密度及流動性愈高愈佳。又，作爲壓粉芯 用的原料粉末使用時，爲了與各式各樣的樹脂混煉成形， 樹脂中的原料粉末之分散性愈高愈佳。 特開2008- 1 1 776 1號公報（專利文獻3 )中揭示，爲了 得到鋰離子電池用負極材料，將由矽粉末與其它粉末所混 合成的混合粉末浸在水溶性等的溶劑中進行處理。此混合 粉末係在以球磨機或磨碎機（attritor)處理機械合金時， 通常作爲原料。此時，溶劑中的粉末之分散性亦愈好愈佳 -6- 201200472 如此地’要求接觸電阻、塡充密度、流動性、分散性 優異的砂粉末。然而’通常的矽粉末係將塊狀體機械地粉 碎者，此等特性係不充分。 還有’ S i的固有電阻係大幅受到雜質的影響。特別地 ’ Fe係與Si生成化合物，而降低固有電阻的雜質元素。通 常’使用於電子零件等的矽粉末，由於係將母材的半導體 或太陽電池中所使用的矽晶圓等高純度的塊狀體粉碎而製 造，故以Fe爲主體的雜質之量係低，但製造成本相當高昂 。此等砂晶圓的純度一般的爲5N( 99.999%)以上》 因此’本發明者著眼於主要在鐵鋼材料的製造之際作 爲添加材料所使用的矽原料’其係便宜的砂原料，通常不 使用作爲高純度S i的原料。然而’此原料雖然便宜，但純 度爲98〜99 %程度的極低，尤其含有許多的Fe當作雜質。 因此’以此爲原料的經粉碎之矽粉末，無法期待高的固有 電阻。如此地’使用便宜的Si原料來製作具有高的固有電 阻之矽粉末者，以往係困難》 又’ 一般市售的矽粉末係將矽晶圓等的塊狀體粉碎者 ，爲不定形狀。因此，塡充密度低。使用矽粉末的塡充體 當作絕緣性散熱體時，導熱性變重要，但矽粉末的塡充密 度對此導熱性的影響大。推測此係因爲在一定的體積中， 塡充多的導熱之矽粉末，則塡充體的導熱性變良好。然而 ’於塊狀體的粉碎粉末中，敲緊密度係真密度約60%以下 的低’導熱性低。如此地，雖然希望由便宜的Si原料所構 201200472 成，其塡充體的電流遮斷性與導熱性高之矽粉末，但現狀 爲無法實現具有充分的特性之矽粉末。 如此的矽粉末，例如係如特開2005-608 3 0號公報（專 利文獻1)中揭示，使用於在軟磁性粉未表面上被覆矽粉 末的電子零件等。 [先前技術文獻] [專利文獻] 專利文獻1 :特開2005-60830號公報 專利文獻2:特開2008-288525號公報 專利文獻3 :特開2008-117761號公報 【發明內容】 [發明所欲解決的問題] 對使用於專利文獻1記載的軟磁性燒結構件或專利文 獻2記載的燒結軟磁性粉末所成之成形體等，重視保持高 的電阻之純矽粉末來說，茲認爲塡充時是否不流動任何程 度的電流（以下記載爲電流遮斷性）係極重要的特性。然 而’此任一專利文獻皆無法解決純矽粉末的塡充體中之電 流遮斷性。 因此’本發明者對於上述塡充的純矽粉末之電流遮斷 性’進行專心致力的檢討。通常市售的純矽粉末，由於係 將塊狀體機械地粉碎而製造之粉碎粉末，故其形狀爲不定 形狀。本發明者著眼於對純矽粉末塡充體的電流遮斷性造 成影響的純矽粉末之形狀依賴性，製作平均圓形度及相對 -8- 201200472 密度經若干程度變化的純矽粉末，評價此等的電流遮斷性 。結果發現藉由使用具有指定的平均圓形度及相對密度之 純矽粉末當作塡充體，而具有高的電流遮斷性。又，本發 明者亦發現即使含有最大到2質量％爲止的Fe之矽粉末，也 可與純矽粉末同樣地具有高的電流遮斷性。再者，所謂的 圓形度，就是由粒子影像來測定面積（A)與周圍長（p) ，將此測定値代入（圓形度）=4πΑ/(ρ2)的式中而算出。愈 接近真球形狀的粉末，圓形度的數値愈大，隨著形狀偏離 真球，圓形度變成小値。 即，本發明者得到以下知識：含有〇〜2質量％的F e， 剩餘部分爲Si及無可避免的雜質所成之矽粉末，具有0.75 〜1.00的平均圓形度及65%以上的相對密度者，係在使用 於塡充、成形、塗佈等之際，顯示高的接觸電阻。此高的 接觸電阻，對重視保持高的電阻之用途所用的純Si來說， 係極重要的特性，意味電流遮斷性優異。 因此’本發明之目的爲可提供一種純矽粉末，其在塡 充、成形、塗佈等使用之際，顯示高的接觸電阻。 即’若依照本發明，可提供一種砂粉末，其含有〇〜2 質量％的Fe ’剩餘部分爲Si及無可避免的雜質所成之矽粉 末，前述矽粉末具有0.75〜1.00的平均圓形度及下式所算 出的6 5 %以上之相對密度D r，The Si-based semiconductor has a large characteristic of high specific resistance, and is larger by 2 to 5 digits when compared with a metal such as Fe or Ni. Further, when compared with a metal such as Fe or Ni, it is an element having various characteristics such as extremely small plastic deformation ability or low true density. -5-201200472 On the other hand, in the case of powdered Si, if the inherent resistance of Si itself is high, since the powders are in point contact with each other, the contact resistance of the powdered ruthenium is high. According to this feature, the powdery Si-based can be used for filling, coating, and the like between two metal bodies in which current is not suitable to flow, and the soft magnetic metal powder is not mixed and formed with the tantalum powder to avoid soft magnetic metal powder. In contact with each other, tantalum powder can be used even in a powder core or the like which has reduced eddy current loss. Further, as disclosed in Japanese Laid-Open Patent Publication No. 2005-60830 (Patent Document 1), it is also proposed to mix a niobium powder in a soft magnetic metal powder, and to sinter the sintered high-resistance soft magnetic structure. In such applications, it is required that the contact resistance of the tantalum powders is high. Japanese Patent Publication No. 2 008-2 8 8 525 (Patent Document 2) proposes a composition of a composition containing Fe, 44 to 5% by mass of Ni, and 2 to 6% by mass of 3 丨. In the use of the molded body of the sintered soft magnetic powder in which the S i is biased, the use of the powder molded body in the above-described Patent Document 1 is generally preferable as the bulk density and fluidity of the powder are higher. Further, when used as a raw material powder for a powder core, in order to knead and knead various types of resins, the dispersibility of the raw material powder in the resin is preferably as high as possible. In order to obtain a negative electrode material for a lithium ion battery, a mixed powder obtained by mixing a cerium powder and another powder is immersed in a solvent such as water-soluble to be treated. This mixed powder is usually used as a raw material when a mechanical alloy is treated by a ball mill or an attritor. At this time, the dispersibility of the powder in the solvent is also better. -6-201200472 Thus, a sand powder excellent in contact resistance, enthalpy density, fluidity, and dispersibility is required. However, the usual enamel powder is a mechanically pulverized block, and these characteristics are insufficient. Also, the inherent resistance of 'S i is greatly affected by impurities. In particular, the Fe-based compound forms a compound with Si and lowers the inherent resistance of the impurity element. In general, the tantalum powder used for electronic components and the like is produced by pulverizing a high-purity bulk material such as a semiconductor of a base material or a tantalum wafer used in a solar cell, so that the amount of impurities mainly composed of Fe is low. But the manufacturing cost is quite high. The purity of the sand wafers is generally 5 N (99.999%) or more. Therefore, the present inventors focused on the raw materials used as the additive materials mainly in the production of iron and steel materials, which are inexpensive sand materials. Raw materials as high purity Si are not used. However, although this raw material is inexpensive, the purity is extremely low at a level of 98 to 99%, and particularly contains a large amount of Fe as an impurity. Therefore, the high specific resistance cannot be expected as the pulverized tantalum powder which is used as a raw material. In the case of using a low-cost Si raw material to produce a tantalum powder having a high intrinsic resistance, it has been conventionally difficult. The commercially available tantalum powder is an indefinite shape in which a massive body such as a tantalum wafer is pulverized. Therefore, the charge density is low. When the ruthenium powder is used as the insulating heat sink, the thermal conductivity becomes important, but the enthalpy density of the ruthenium powder has a large influence on the thermal conductivity. It is presumed that this is because the thermal conductivity of the ruthenium is improved because a large amount of thermally conductive ruthenium powder is filled in a certain volume. However, in the pulverized powder of the lump, the knock-tightness is low in the true density of about 60% or less, and the thermal conductivity is low. In this way, it is desirable to form a ruthenium powder having a high electrical current barrier property and a high thermal conductivity from a low-cost Si raw material of 201200472. However, it is currently impossible to realize a ruthenium powder having sufficient characteristics. Such a ruthenium powder is disclosed, for example, in Japanese Laid-Open Patent Publication No. 2005-60830 (Patent Document 1), and is used for an electronic component or the like which is coated with a ruthenium powder on the surface of the soft magnetic powder. [Prior Art] [Patent Document] Patent Document 1: JP-A-2005-60830, JP-A-2008-288525 (Patent Document 3) The problem of the problem is that the soft magnetic sintered component described in Patent Document 1 or the molded soft magnetic powder described in Patent Document 2 is considered to have a high electrical resistance. Whether or not current flows at any time during charging (hereinafter referred to as current interruption) is an extremely important characteristic. However, none of the patent documents can solve the current interrupting property in the ruthenium of pure tantalum powder. Therefore, the inventors of the present invention have devoted themselves to the review of the current occlusion of the above-mentioned pure bismuth powder. The commercially available pure tantalum powder has a shape which is indefinite due to the pulverized powder which is produced by mechanically pulverizing the bulk. The present inventors focused on the shape dependence of a pure tantalum powder which affects the current interruption property of a pure tantalum powder, and produced a pure tantalum powder having a degree of circularity and a relative density of -8-201200472, and evaluated. These currents are interrupted. As a result, it was found to have high current interruption by using a pure tantalum powder having a specified average circularity and relative density as a ruthenium. Further, the present inventors have found that even if it contains a Fe powder of up to 2% by mass, it can have high current interrupting properties similarly to pure tantalum powder. In addition, the circularity is calculated by measuring the area (A) and the surrounding length (p) from the particle image, and substituting this measurement into the equation of (circularity) = 4π Α / (ρ2). The closer to the shape of the true sphere, the greater the degree of circularity, and as the shape deviates from the true sphere, the circularity becomes small. That is, the inventors obtained the following knowledge: a bismuth powder containing 〇2 to 2% by mass of Fe, and the remainder being Si and inevitable impurities, having an average circularity of 0.75 to 1.00 and a relative degree of 65% or more. The density is a high contact resistance when used for charging, forming, coating, and the like. This high contact resistance is a very important characteristic for pure Si used for applications in which high resistance is maintained, and it means excellent current interruption. Therefore, the object of the present invention is to provide a pure niobium powder which exhibits high contact resistance upon use in charging, forming, coating, and the like. That is, according to the present invention, it is possible to provide a sand powder containing 〇2 to 2% by mass of Fe' remaining as Si and an inevitable impurity, and the above-mentioned cerium powder has an average circular shape of 0.75 to 1.00. Degree and the relative density D r of 65% or more calculated by the following formula,

Dr(%) = l 〇〇xDt/Da (式中’ Dr係相對密度’ Dt係前述矽粉末的敲緊密度 (Mg/m3) ’ Da係 Si的真密度 2.33Mg/m3 ) » -9- 201200472 【實施方式】 [實施發明的形態] 接觸電阻高的矽粉末 本發明的矽粉末係含有〇〜2質量％的Fe，剩餘部分爲 Si及無可避免的雜質所成。砂粉末亦可爲不含Fe的純矽粉 末’也可爲含有最大到2質量％爲止的Fe之政粉末。而且’ 矽粉末具有0.75〜1.00的平均圓形度及65 %以上的相對密 度。 本發明的矽粉末具有0.75〜1.00、較佳0.85〜1.00的 平均圓形度。圓形度係顯示粉末的形狀是否接近球狀的數 値，由於接近真球的粉末係成爲高的値，故完全的真球爲 1.00。此圓形度的平均値未達0.75的純矽粉末，係塡充體 的電流遮斷性變差。又，平均圓形度超過1 .00者係不符原 理的。 如實施例中所後述，同時評價純矽粉末的敲緊密度， 結果在敲緊密度的大的粉末，看見電流遮斷性有良好的傾 向。直覺上，認爲敲緊密度愈高，則粉末彼此的接觸點愈 多，粉末塡充體的電流遮斷性變差，但亦明瞭與此直覺相 異者係出乎預料。 本發明的矽粉末具有65%以上、較佳65〜80%、更佳 65〜74%的相對密度。若爲此範圍內，則得到電流遮斷性 良好的供試粉末。另一方面，相對密度若未達65，尤其供 試粉末的相對密度未達60〜65%的供試粉末，則電流遮斷 -10- 201200472 性差。可知此係因爲相對密度比較高者具有良好的電流遮 斷性。 另一方面，以氣體霧化（gas-atomizing )所製造的粉 末一般爲大致球形狀，藉由將其粉碎，形狀係偏離球形狀 。再者，用粉碎前大致球形狀的粒度不同之粉末，進行粉 碎，同樣分級成106μιη以下，可有意圖地使形狀變化。據 此，將以氣體霧化所製造的粉末粉碎，分級成106 μιη以下 ，對當時的形狀進行各種測定。例如，將以氣體霧化所製 造的粉末之粉碎前爲大致球形狀且粒徑爲200μπι的粉末粉 碎成爲約ΙΟΟμιη時，估計其形狀係大致球形狀粉末成爲W8 ***的程度。相對於此，將粉碎前爲大致球形狀且粒徑爲 ΙΟΟΟμιη的粉末粉碎而成爲約ΙΟΟμιη時，估計原本的球形狀 係幾乎看不到而爲大致完全的不定形狀粉末。 如上述，藉由將以氣體霧化所製造的粉末粉碎，形狀 係偏離球形狀。將以氣體霧化所製造的大致球狀的粉末分 級成不同的粒徑，將此等不同粒徑的粉末粉碎，最終分級 成106 μιη以下。對於如此所得之粉末的各個粒子，測定平 均圓形度，測定當時的電流遮斷性及相對密度。 於本發明的較佳態樣中，矽粉末係僅由Si及無可避免 的雜質所構成，爲接觸電阻高的純矽粉末。藉此，可提供 一種接觸電阻高的純矽粉末，其使用於具有高的電阻之軟 磁性燒結構件或軟磁性壓粉體等。 接觸電阻、塡充密度、流動性及分散性高的矽粉末 -11 - 201200472 若依照本發明的較佳態樣，可提供一種氧分析値對比 表面積的比爲0.2〜10，且接觸電阻、塡充密度、流動性 及分散性優異之矽粉末。與粉碎粉末比較下，本態樣的矽 粉末係表面氧化被膜厚，接觸電阻高，且在水溶液中的分 散性優異，故可提供接觸電阻、塡充密度、流動性及分散 性高的矽粉末。本態樣的矽粉末亦宜尙具有0.75〜1.00的 平均圓形度及65%以上的相對密度。 與本態樣有關的技術背景係如以下。首先，如本說明 書的背景技術所述的通常之矽粉末係將塊狀體機械地粉碎 者，於要求高的接觸電阻之電子零件材料，或在介質中要 求高的分散性之矽粉末中，得不到充分的特性係實際狀況 。爲了消除此問題，在作爲塡充密度及流動性優異的粉末 ，本發明者首先著眼於製作大致球形狀的粉末之氣體霧化 法，而不是市售的不定形狀之粉碎粉末。再者，發現與粉 碎粉末比較下，以氣體霧化法所製作的矽粉末係表面氧化 被膜厚，粉末間接觸電阻（以下稱爲接觸電阻）高，且在 水溶液中的分散性優異，而達成本態樣》 具體地，在作爲塡充密度及流動性優異的粉末，本發 明者首先著眼於製作大致球形狀的粉末之霧化法，而不是 市售的不定形狀之粉碎粉末。霧化法之內的得到大致粒徑 狀的粉末之方法中，已知氣體霧化法或離心霧化、圓盤霧 化法、混合霧化法、高壓水霧化法等。 本發明係不受此等揭示的方法所限定，但一般已知在 量產性之點，氣體霧化法係最合適，在球形狀之點，離心 -12- 201200472 霧化或圓盤霧化法、混合霧化法係合適。又，在表面氧化 之點，亦考慮高壓水霧化法》此處實際上，以氣體霧化法 所製作的矽粉末係成爲大致球狀，如後述的實施例，塡充 密度及流動性優異。此一般地係與Fe或Ni等之氣體霧化粉 末的特徵同樣。圖1顯示以氣體霧化法所製作的純矽粉末 之外觀SEM影像，圖2顯示將塊狀體粉碎而製作的通常純 矽粉末之外觀SEM影像。 本發明者發現以氣體霧化法所製作的矽粉末係更具有 Si特有的以下二個特徵。即，詳細調査氣體霧化法的矽粉 末與粉碎法的矽粉末，結果可知氣體霧化矽粉末係即使不 施予氧化處理，「氧分析値/比表面積」也比粉碎粉末高 。於是，判斷氣體霧化矽粉末係表面的氧化物層比粉碎粉 末厚。因此，發現（1)在對所塡充的粉末施加壓力之際 ，粉末間的接觸電阻高，且（2)在水等的溶劑中之分散 性優異的特徵。 關於上述（1 )的效果，係如以下地考量。g卩，判斷 於如Fe或Ni之具有塑性變形能力的金屬粉未中，若對粉末 的塡充體施加壓力，則粉末變形，粉末彼此的接觸部之氧 化物被破壞，故表面的氧化皮膜提高接觸電阻的效果係不 很大。相對於此，推測由於矽粉末係極高硬度且亦沒有塑 性變形能力，故粉末表面的氧化皮膜不易被破壞，提高接 觸電阻的效果高。 其次，（2)的效果之原理雖然未確定，但推測Si本 來對水等溶劑的潤濕性差，生成氧化皮膜的Si02對水等的 -13- 201200472 溶劑之潤濕性良好，故改善分散性。又，與Fe或Ni比較下 ，Si係比重低到1/3〜1/4左右。因此，當粉末表面對溶劑 的潤濕性差時，不能分散在溶劑中，而亦會浮在溶劑液面 。如此地，氣體霧化法的矽粉末，由於不僅塡充密度及流 動性高，而且同時顯示只有Si才有的（1)及（2)之特徵 ，故適合作爲高電阻軟磁性燒結構件等的電子零件材料或 鋰離子電池負極活物質之原料粉末等。 「氧分析値/比表面積」係粉末表面的氧化物層厚度 之指標。於本合適態樣的矽粉末中，此氧分析値/比表面 積爲0·2〜10，較佳爲0.3〜5。若未達0.2，則由於表面的 氧化物層薄，故接觸電阻變低，而且在溶劑中的分散性亦 變差。然而，由於超過1 〇則必須高溫的氧化處理，燒結係 與氧化同時進行。因此，在氧化處理後將粉末粉碎，會損 害氣體霧化的特徵之球狀，塡充密度或流動性差。再者， 氧分析値的單位爲m a s s %，比表面積係以Β Ε Τ法評價，單 位爲m2 / g。 將以氣體霧化法所製作的矽粉末分級後，亦可進行在 5 00〜1000 °C、較佳在600〜800 °C的溫度之氧化處理。其理 由爲與粉碎粉末比較下，雖然以氣體霧化法所製作的矽粉 末係表面氧化被膜厚，接觸電阻高，且在水溶液中的分散 性優異，但視情況而定，若「氧分析値/比表面積」未達 0.2，則表面氧化被膜薄，可能得不到接觸電阻、塡充密 度、流動性及分散性的特性。於此情況下，藉由在上述溫 度範圍內進行氧化處理，更形成表面氧化被膜，可進一步 -14- 201200472 提高上述效果。氧化處理溫度若未達500°C，在表面氧化 被膜的形成係不充分，若爲超過1 000°c的溫度，則其效果 飽和。 較佳的氧化處理時間爲10〜600分鐘，更佳爲30〜90 分鐘。氧化處理時間若未達1 0分鐘，則表面氧化被膜的形 成可能不充分，另一方面，超過600分鐘的程度之氧化處 理時間係沒有特別的必要。 含Fe的矽粉末 若依照本發明的較佳態樣，可提供一種含有Fe : 0.01 〜2質量％ ’剩餘部分爲Si及無可避免的雜質所成，內部生 成的膜狀不純相之厚度爲2μηι以下，爲球形狀或大致球形 狀的電子零件材料用矽粉末。若依照本態樣，可提供作爲 粉末塡充體的電流遮斷性與導熱性高，且塡充密度高的便 宜矽粉末。本態樣的矽粉末亦宜具有0.75〜1.00的平均圓 形度及6 5 %以上的相對密度。 與本態樣有關的技術背景係如以下。首先，於如本說 明書的背景技術所述的技術中，如專利文獻1中記載之使 用於絕緣的矽粉末’或作爲散熱體使用的矽粉末，在電流 遮斷性與導熱性係未達到充分的特性。爲了消除此問題， 本發明者進行專心致力的開發，結果提供一種作爲粉末塡 充體的電流遮斷性與導熱性高，且塡充密度高之便宜矽粉 末。該態樣的要旨在於一種電子零件材料用矽粉末，其含 有Fe : 0.01〜2質量％ ’剩餘部分爲si及無可避免的雜質所 -15- 201200472 成，內部生成的膜狀不純相之厚度爲2μιη以下，爲球形狀 或大致球形狀。 具體地，作爲塡充密度高的粉末，本發明者首先著眼 於製作大致球形狀的粉末之氣體霧化法，而不是市售的不 定形狀之粉碎粉末。實際上，以氣體霧化法所製作的矽粉 末係成爲大致球狀，如後述的實施例，塡充密度優異。此 係與一般的Fe或Ni等之氣體霧化粉末的特徵同樣。 然而，發現以氣體霧化法所製作的矽粉末更具有Si才 有的下述特徵。詳細調査氣體霧化法的矽粉末與粉碎法的 矽粉末，結果可知與含有相同程度的Fe當作雜質的塊狀體 粉碎粉末比較下，氣體霧化矽粉末係電流遮斷性優異。 此現象的詳細要因雖然不明，但推測如下。Fe不僅與 Si的化合物之固有電阻低，而且如由Si-Fe系2元狀態圖可 知，完全不固溶於Si固體相中。因此，即使僅含有些微Fe 量當作雜質，在使Si的熔融液凝固之際，也邊將Fe排出到 殘液部，邊將Si的結晶當作固體結晶出，Fe係被濃縮在Si 的結晶間，於Si結晶間生成厚膜狀的化合物。 如此地，茲認爲Si中的Fe不僅爲雜質之量，而且化合 物容易生成膜狀者，亦成爲容易影響固有電阻的主要因素 。此處，推測因爲氣體霧化粉末係經由噴霧氣體而急冷凝 固，故含有同程度的Fe當作雜質，因此即使生成同程度之 量的膜狀化合物，膜厚也比較薄，被分散，而顯示高的固 有電阻。 本態樣的矽粉末含有〇.〇1〜2質量％的Fe，較佳含有 -16- 201200472 〇_〇1〜1.0質量％。由於Fe係給予雜質的不利影響之元素（ 以下稱爲Fe雜質），故該Fe量未達0.01%的Si原料係價格 高，另一方面，若超過2%則電流遮斷性變差。 於本態樣的矽粉末中，其內部生成的膜狀不純相之厚 度爲2μηι以下。內部生成的膜狀不純相（主要爲含有Fe雜 質的相）之厚度若超過2 μπι，則電流遮斷性變差。又，本 態樣的矽粉末係球形狀或大致球形狀。此係因爲由塊狀體 而來的如粉碎粉之不定形狀的粉末係導熱性變差，故成爲 球形狀或大致球形狀者。如此的粉末係藉由氣體霧化法或 旋轉圓盤霧化法等方法而獲得。Dr(%) = l 〇〇xDt/Da (where 'Dr is relative density' Dt is the knock-tightness of the above-mentioned tantalum powder (Mg/m3) 'The true density of Da-type Si is 2.33Mg/m3) » -9- 201200472 [Embodiment] Embodiment of the invention The niobium powder having high contact resistance The niobium powder of the present invention contains Fe to 2% by mass of Fe, and the remainder is Si and inevitable impurities. The sand powder may be a pure cerium powder containing no Fe, or may be a chemical powder containing Fe up to 2% by mass. Further, the 矽 powder has an average circularity of 0.75 to 1.00 and a relative density of 65% or more. The niobium powder of the present invention has an average circularity of from 0.75 to 1.00, preferably from 0.85 to 1.00. The circularity indicates whether the shape of the powder is close to a spherical shape, and since the powder close to the true ball becomes a high enthalpy, the total true sphere is 1.00. The average tantalum of this circularity is less than 0.75 pure tantalum powder, and the current blocking property of the plug is deteriorated. Also, the average circularity of more than 1,000 is not the same. As will be described later in the examples, the knocking degree of the pure niobium powder was evaluated at the same time, and as a result, a large powder having a tightness in tapping was observed to have a good tendency for current interruption. Intuitively, it is considered that the higher the knocking degree, the more the contact points of the powders are, and the current occlusion of the powder ruthenium is deteriorated, but it is also apparent that the intuition is unexpected. The tantalum powder of the present invention has a relative density of 65% or more, preferably 65 to 80%, more preferably 65 to 74%. If it is within this range, a test powder having good current interrupting properties is obtained. On the other hand, if the relative density is less than 65, especially if the relative density of the test powder is less than 60 to 65% of the test powder, the current is interrupted -10- 201200472. It can be seen that this is because the relative density is relatively high and has good current blocking property. On the other hand, the powder produced by gas-atomizing is generally in the shape of a substantially spherical shape, and by pulverizing it, the shape is deviated from the spherical shape. Further, the powder having a particle size different from that of the substantially spherical shape before the pulverization is pulverized, and is also classified into 106 μm or less, and the shape can be intentionally changed. According to this, the powder produced by gas atomization was pulverized and classified into 106 μm or less, and various shapes were measured for the shape at that time. For example, when the powder prepared by gas atomization is pulverized into a substantially spherical shape and the particle diameter of 200 μm is pulverized to about ΙΟΟμηη, it is estimated that the shape is a degree that the substantially spherical powder becomes W8 split. On the other hand, when the powder having a substantially spherical shape and having a particle diameter of ΙΟΟΟμηη was pulverized to about ΙΟΟμηη, it was estimated that the original spherical shape was almost invisible and was substantially completely indefinite shape powder. As described above, the shape is deviated from the spherical shape by pulverizing the powder produced by gas atomization. The substantially spherical powder produced by gas atomization is classified into different particle diameters, and the powders having different particle diameters are pulverized and finally classified into 106 μm or less. For each particle of the powder thus obtained, the average circularity was measured, and the current interrupting property and relative density at that time were measured. In a preferred aspect of the invention, the tantalum powder is composed only of Si and inevitable impurities, and is a pure tantalum powder having a high contact resistance. Thereby, a pure tantalum powder having a high contact resistance can be provided, which is used for a soft magnetic sintered member or a soft magnetic green compact having a high electric resistance. Tantalum powder with high contact resistance, enthalpy density, fluidity and dispersibility-11 - 201200472 According to a preferred aspect of the present invention, an oxygen analysis 値 contrast surface area ratio of 0.2 to 10, and contact resistance, 塡 can be provided. A fine powder with excellent density, fluidity and dispersibility. In comparison with the pulverized powder, the ruthenium powder of this aspect has a thick surface oxide film, high contact resistance, and excellent dispersibility in an aqueous solution, so that bismuth powder having high contact resistance, enthalpy density, fluidity, and dispersibility can be provided. The niobium powder of this aspect should also have an average circularity of 0.75 to 1.00 and a relative density of 65% or more. The technical background related to this aspect is as follows. First, the conventional tantalum powder as described in the background of the present specification mechanically pulverizes the bulk body, in an electronic component material requiring high contact resistance, or in a tantalum powder which requires high dispersibility in a medium, The lack of sufficient characteristics is the actual situation. In order to eliminate this problem, the present inventors first focused on a gas atomization method for producing a substantially spherical powder, instead of a commercially available pulverized powder of an indefinite shape, as a powder excellent in enthalpy density and fluidity. In addition, it was found that the tantalum powder produced by the gas atomization method has a surface oxide film thickness, a contact resistance between powders (hereinafter referred to as contact resistance), and excellent dispersibility in an aqueous solution. In particular, in the case of a powder excellent in enthalpy density and fluidity, the inventors of the present invention first focused on an atomization method for producing a substantially spherical powder, instead of a commercially available pulverized powder of an indefinite shape. Among the methods for obtaining a powder having a substantially particle size within the atomization method, a gas atomization method, a centrifugal atomization method, a disk atomization method, a mixed atomization method, a high pressure water atomization method, or the like is known. The present invention is not limited by the methods disclosed herein, but it is generally known that at the point of mass productivity, the gas atomization method is most suitable, at the point of the spherical shape, centrifugation-12-201200472 atomization or disk atomization The method of mixing and atomization is suitable. Further, in the point of surface oxidation, high-pressure water atomization method is also considered. Actually, the tantalum powder produced by the gas atomization method has a substantially spherical shape, and is excellent in tantalum density and fluidity as in the examples described later. . This is generally the same as the characteristics of the gas atomized powder of Fe or Ni. Fig. 1 shows an external SEM image of a pure tantalum powder produced by a gas atomization method, and Fig. 2 shows an external SEM image of a normal pure tantalum powder produced by pulverizing a bulk. The present inventors have found that the tantalum powder system produced by the gas atomization method has the following two characteristics unique to Si. In other words, the tantalum powder of the gas atomization method and the tantalum powder of the pulverization method were examined in detail. As a result, it was found that the gas atomized tantalum powder was higher in "oxygen analysis / specific surface area" than the powder after the oxidation treatment. Thus, it was judged that the oxide layer on the surface of the gas atomized cerium powder was thicker than the pulverized powder. Therefore, it is found that (1) the contact resistance between the powders is high when pressure is applied to the powder to be charged, and (2) the dispersibility in a solvent such as water is excellent. The effect of the above (1) is considered as follows. g卩, judged in a metal powder having a plastic deformation ability such as Fe or Ni, if pressure is applied to the powder of the powder, the powder is deformed, and the oxide of the contact portion between the powders is destroyed, so the surface oxide film The effect of increasing the contact resistance is not large. On the other hand, it is presumed that since the niobium powder has extremely high hardness and no plastic deformation ability, the oxide film on the surface of the powder is not easily broken, and the effect of improving the contact resistance is high. Next, although the principle of the effect of (2) is not determined, it is presumed that Si has poor wettability with respect to a solvent such as water, and SiO 2 which forms an oxide film has good wettability with water of -13-201200472 such as water, thereby improving dispersibility. . Further, in comparison with Fe or Ni, the specific gravity of the Si system is as low as about 1/3 to 1/4. Therefore, when the surface of the powder is poor in wettability to the solvent, it cannot be dispersed in the solvent but also floats on the surface of the solvent. In this way, the tantalum powder of the gas atomization method is suitable as a high-resistance soft magnetic sintered member because it has not only the high density and fluidity but also the characteristics of (1) and (2) which are only available in Si. The electronic component material or the raw material powder of the negative active material of the lithium ion battery. "Oxygen analysis 値 / specific surface area" is an index of the thickness of the oxide layer on the surface of the powder. In the niobium powder of the present aspect, the oxygen analysis has a specific surface area of from 0.2 to 10, preferably from 0.3 to 5. If it is less than 0.2, since the oxide layer on the surface is thin, the contact resistance becomes low, and the dispersibility in the solvent also deteriorates. However, since it exceeds 1 Torr, high temperature oxidation treatment is required, and the sintering system is simultaneously performed with oxidation. Therefore, the powder is pulverized after the oxidation treatment, and the spherical shape of the gas atomization is impaired, and the enthalpy density or fluidity is poor. Furthermore, the unit of oxygen analysis enthalpy is m a s s %, and the specific surface area is evaluated by the Β Τ method, and the unit is m2 / g. The cerium powder prepared by the gas atomization method may be subjected to oxidation treatment at a temperature of 500 to 1000 ° C, preferably 600 to 800 ° C. The reason for this is that the tantalum powder produced by the gas atomization method has a surface oxide thickness, a high contact resistance, and excellent dispersibility in an aqueous solution, as the case of the pulverized powder. When the specific surface area is less than 0.2, the surface oxide film is thin, and the characteristics of contact resistance, enthalpy density, fluidity, and dispersibility may not be obtained. In this case, by performing oxidation treatment in the above temperature range, the surface oxide film is further formed, and the above effect can be further improved by -14 - 201200472. If the oxidation treatment temperature is less than 500 °C, the formation of the surface oxide film is insufficient, and if it is a temperature exceeding 1 000 °C, the effect is saturated. The preferred oxidation treatment time is from 10 to 600 minutes, more preferably from 30 to 90 minutes. If the oxidation treatment time is less than 10 minutes, the formation of the surface oxide film may be insufficient. On the other hand, the oxidation treatment time of more than 600 minutes is not particularly necessary. The Fe-containing cerium powder according to a preferred aspect of the present invention can provide a film containing Fe: 0.01 to 2% by mass. The remainder is Si and inevitable impurities, and the thickness of the film-like impure phase formed inside is 2 μηι or less, a bismuth powder for a spherical or substantially spherical electronic component material. According to this aspect, it is possible to provide a powder which is high in current and thermal conductivity and has a high enthalpy density as a powder entangled body. The niobium powder of this aspect preferably has an average circularity of 0.75 to 1.00 and a relative density of 65% or more. The technical background related to this aspect is as follows. First, in the technique described in the background art of the present specification, the tantalum powder used in the insulation described in Patent Document 1 or the tantalum powder used as the heat sink does not sufficiently satisfy the current interruption property and the thermal conductivity system. Characteristics. In order to solve this problem, the inventors of the present invention have devoted themselves to development, and as a result, have provided an inexpensive niobium powder having a high current interruption property and thermal conductivity as a powder ruthenium and having a high enthalpy density. This aspect is intended to be an enamel powder for electronic component materials, which contains Fe: 0.01 to 2% by mass 'the remainder is si and the unavoidable impurities are -15-201200472. The thickness of the film-like impure phase formed internally It is 2 μm or less, and is a spherical shape or a substantially spherical shape. Specifically, as a powder having a high enthalpy density, the inventors of the present invention first focused on a gas atomization method for producing a substantially spherical powder, instead of a commercially available pulverized powder of an irregular shape. In fact, the tantalum powder produced by the gas atomization method has a substantially spherical shape, and is excellent in the tantalum density as in the examples described later. This is the same as that of a general gas atomized powder of Fe or Ni. However, it has been found that the tantalum powder produced by the gas atomization method has the following characteristics which are unique to Si. When the tantalum powder of the gas atomization method and the tantalum powder of the pulverization method were examined in detail, it was found that the gas atomized tantalum powder was excellent in current interrupting property as compared with the bulk crushed powder containing the same degree of Fe as an impurity. Although the detailed cause of this phenomenon is unknown, it is presumed as follows. Fe is not only low in the intrinsic resistance of the compound of Si, but also is completely insoluble in the Si solid phase as is known from the Si-Fe system state diagram. Therefore, even if only a small amount of Fe is contained as an impurity, when the melt of Si is solidified, Fe is discharged as a solid crystal while the Fe is discharged to the residual liquid portion, and Fe is concentrated in Si. A thick film-like compound is formed between the crystals of the crystal. As such, it is considered that Fe in Si is not only an amount of impurities, but also a compound which is likely to form a film, and which is a major factor that easily affects the inherent resistance. Here, it is estimated that since the gas atomized powder is rapidly solidified by the spray gas, Fe contains the same level of Fe as an impurity. Therefore, even if a film-like compound of the same amount is formed, the film thickness is relatively thin and dispersed, and the display is performed. High inherent resistance. The niobium powder of this aspect contains 〜1〇2% by mass of Fe, preferably -16-201200472 〇_〇1 to 1.0% by mass. Since Fe is an element which adversely affects impurities (hereinafter referred to as Fe impurity), the Si raw material having a Fe content of less than 0.01% is expensive, and on the other hand, if it exceeds 2%, the current blocking property is deteriorated. In the tantalum powder of the present aspect, the thickness of the film-like impure phase formed inside is 2 μηι or less. When the thickness of the film-like impure phase (mainly the phase containing Fe impurities) generated inside exceeds 2 μm, the current interruption property is deteriorated. Further, the tantalum powder of the present aspect is a spherical shape or a substantially spherical shape. In this case, since the thermal conductivity of the powder of an indefinite shape such as pulverized powder due to the lumpy body is deteriorated, it is a spherical shape or a substantially spherical shape. Such a powder is obtained by a gas atomization method or a rotary disk atomization method.

實施例 例A 以下，藉由實施例來具體說明接觸電阻高的矽粉末。 首先，爲了製作平均圓形度不同的數種類之純矽粉末，將 以氣體霧化法所製作的純矽粉末分級成106μηι以下、106〜 3 00 μπι ' 300 〜500μπι、500 〜700μηι、700 〜ΙΟΟΟμπι，藉由 行星式球磨機將106μιη以下的以外粉末粉碎。粉碎條件係 在內徑100mm、深度70mm的瑪瑙製壺中，置入50g已分級 成各粒度的純矽粉末、80個直徑10mm的瑪瑙製球，以 300rpm粉碎2分鐘。使粉碎的粉末成爲106μπι以下，當作 供試粉末。106 μπι以下的氣體霧化粉末係直接當作供試粉 末。又，來自市售的塊狀體之粉碎粉末亦分級成106 μπι以 下’當作比較粉末。再者，藉由混合平均圓形度不同的粉 -17- 201200472 末，亦評價平均圓形度已變化的粉末。 作爲平均圓形度的評價，測定純矽粉末的平均圓形度 。平均圓形度係藉由SEI SHIN企業公司製的PIT A-1進行評 價。其原理的槪略係如以下》使載體液連同粒子流到小室 (cell )內，用CCD照相機攝入大量的粒子影像，由各個 粒子影像來測定面積（A)與周圍長（p)。藉由此等，以 (圓形度）=4 π Α/(ρ2)進行評價。再者，於真球的情況，由 於C CD照相機所取入的影像爲真圓，故若此直圓的半徑爲！· ，貝ljA = 7ir2，ρ = 2πΓ，（圓形度）=4π(πΓ2)/(2πΓ)2=1·00。又 ，愈接近真球的形狀之粉末則圓形度的數値愈大，隨著形 狀偏離真球，圓形度變成小値。對每供試粉末，測定各自 25 00〜3 5 00個粒子的圓形度，將其平均値當作平均圓形度 〇 又，作爲相對密度（敲緊密度）的評價，對各供試粉 末測定敲緊密度，除以純Si的真密度2.3 3 Mg/m3，將乘以 1 〇〇後之値以相對密度（％ )表示。其結果係在表1顯示供 試粉末的製程、平均圓形度、電流遮斷性、相對密度。又 ，表1中，將106μηι以下的粒度記載爲-106μηι。將X〜Υμηι 的粒度記載爲-Υ/ + Χμηι。 再者，作爲電流遮斷性的評價，準備2片直徑3 0mm、 厚度2mm的銅製圓盤，於上下配置的此圓盤之間夾入0.5 g 的各供試粉末，在上圓盤載置l〇〇g的秤錘。於此狀態下將 端子連接於上下的銅圓盤，施加10V的電壓時，將電流値 未達ΙμΑ者評價爲〇，將電流値爲ΙμΑ以上者評價爲X。 -18- 201200472 [表 Al] 表A 1EXAMPLES Example A Hereinafter, a tantalum powder having a high contact resistance will be specifically described by way of examples. First, in order to produce a plurality of pure tantalum powders having different average circularities, the pure tantalum powder produced by the gas atomization method is classified into 106 μηη or less, 106 to 300 μπι '300 to 500 μπι, 500 to 700 μηι, 700 〜 ΙΟΟΟμπι, the powder other than 106 μηη was pulverized by a planetary ball mill. The pulverization conditions were carried out in an agate pot having an inner diameter of 100 mm and a depth of 70 mm, and 50 g of pure enamel powder classified into respective particle sizes and 80 agate balls having a diameter of 10 mm were placed and pulverized at 300 rpm for 2 minutes. The pulverized powder was made 106 μm or less as a test powder. A gas atomized powder of 106 μm or less is directly used as a test powder. Further, the pulverized powder from the commercially available lump was also classified into 106 μm or less as a comparative powder. Further, by mixing powders having different average circularities, -17-201200472, powders having an average circularity change were also evaluated. As the evaluation of the average circularity, the average circularity of the pure cerium powder was measured. The average circularity was evaluated by PIT A-1 manufactured by SEI SHIN Corporation. The principle of the principle is as follows: The carrier liquid and the particles are flowed into the cell, and a large number of particle images are taken up by the CCD camera, and the area (A) and the surrounding length (p) are measured from the respective particle images. By this, it is evaluated by (circularity) = 4 π Α / (ρ2). Furthermore, in the case of a real ball, since the image taken by the C CD camera is a true circle, the radius of this straight circle is! · , 贝 ljA = 7ir2, ρ = 2πΓ, (circularity) = 4π(πΓ2) / (2πΓ) 2 = 1·00. Further, the powder which is closer to the shape of the real ball has a larger degree of circularity, and as the shape deviates from the true sphere, the circularity becomes a small flaw. For each test powder, the circularity of each of the 25 00 to 3,500 particles was measured, and the average enthalpy was taken as the average circularity 〇, and as the relative density (knock tightness), the test powder was applied. The tap density was measured and divided by the true density of pure Si of 2.3 3 Mg/m3, which was multiplied by 1 〇〇 and expressed as relative density (%). The results are shown in Table 1 for the process of the test powder, the average circularity, the current interruption, and the relative density. Further, in Table 1, the particle size of 106 μm or less was described as -106 μηι. The particle size of X~Υμηι is described as -Υ/ + Χμηι. Further, as evaluation of current interruption property, two copper discs having a diameter of 30 mm and a thickness of 2 mm were prepared, and 0.5 g of each test powder was placed between the discs disposed above and below, and placed on the upper disc. L〇〇g's scale hammer. In this state, the terminal was connected to the upper and lower copper discs, and when a voltage of 10 V was applied, the current 値 was not evaluated as 〇, and the current 値 was ΙμΑ or more as X. -18- 201200472 [Table Al] Table A 1

材 料 製程 平均 圓形度 相對密度 (96) 電流 遮斷性 備 註 A 氣體霧化一分級成· 1 〇6mm 0.92 74 〇 本 發 明 例 B 氣體霧化—分級成-300/+106// m—粉碎―分級成-106" m 0.76 70 〇 C 以3:1的重量比混合粉末A與粉末F 0.86 69 〇 D 以1:1重量比混合粉未A與粉末F 0.79 65 〇 £ 氣體霧化—分級成-500/+300 /m-*粉碎—分級成-106 /m 0.71 64 X 比 較 例 F 氣體霧化―分級成-700/+500 zm—粉碎—分級成-106/m 0.70 62 X G 氣體霧化—分級成-1000/+700/m—粉碎—分級成-106/z m 0.69 60 X Η (市售的純政粉末)塊狀體—粉碎—分級成-106弘m 0.66 60 X I 以3:1的重量比混合粉末A與粉末F 0.73 63 X 註）底線係本發明條件外 表A1中所示的試料No.A〜D係本發明例，試料No.E〜 I係比較例。 如表A1中所示，可知比較例試料No.E〜I由於皆平均 圓形度未達0.75且相對密度未達65%，故電流遮斷性差。 相對於此，可知本發明例試料No.A〜D由於皆平均圓形度 爲0.75以上且相對密度爲65 %以上，故具有良好的電流遮 斷性。 如上述，對重視保持高的電阻之目的所用的純Si，具 有特別高的電阻之軟磁性燒結構件或軟磁性壓粉體等中所 用的純Si來說，在用於塡充、成形、塗佈等之際，可提供 電流遮斷性的接觸電阻高之純矽粉末，達成工業上極優異 的效果。Material Process Average Circularity Relative Density (96) Current Interruption Remarks A Gas atomization is classified into 1 〇6mm 0.92 74 〇Inventive Example B Gas atomization-classification into -300/+106// m- pulverization ―Classified into -106" m 0.76 70 〇C Mix powder A and powder F in a weight ratio of 3:1 0.86 69 〇D Mix 1:1 by weight powder A and powder F 0.79 65 〇 Gas atomization - grading -500/+300 /m-* pulverization - classification into -106 /m 0.71 64 X Comparative Example F Gas atomization - classification into -700/+500 zm - pulverization - classification into -106/m 0.70 62 XG gas mist - Classification into -1000/+700/m - Crushing - Classification into -106/zm 0.69 60 X Η (commercially pure powder) Blocks - Crushing - Classification into -106 Hong 0.66 60 XI to 3: The weight ratio of 1 is the mixed powder A and the powder F 0.73 63 X. The bottom line is the sample No. A to D shown in the condition of the present invention, and the sample No. A to D is a comparative example of the sample No. E to I. As shown in Table A1, it was found that the comparative examples Nos. E to I had an average circularity of less than 0.75 and a relative density of less than 65%, so that the current interrupting property was poor. On the other hand, in the samples No. A to D of the present invention, since the average circularity was 0.75 or more and the relative density was 65% or more, it was found that the samples had good current blocking properties. As described above, pure Si used for the purpose of maintaining high electric resistance, pure Si used in soft magnetic sintered members or soft magnetic powders having particularly high electric resistance, is used for charging, forming, and In the case of coating, etc., it is possible to provide a pure tantalum powder having a high current contact resistance and an excellent industrial effect.

例B -19- 201200472 以下，藉由實施例來具體說明接觸電阻、塡充密度、 流動性及分散性高的矽粉末。首先，爲了製作表B1中所示 的「氧分析値/比表面積」不同的數種類之矽粉末，將以 氣體霧化法所製作的純矽粉末分級成150μπι以下，在大氣 中以500〜1 l〇〇°C進行1小時的氧化處理。又，市售的粉碎 粉末亦同樣地分級成150μηι以下，在大氣中以500〜1 100°C 進行1小時的氧化處理。對於此等氧化處理前後的粉末， 進行以下的評價。 比表面積的評價（BET法）係用氪氣吸附法評價。又 ，作爲粉末間接觸電阻的評價，準備2片直徑3 0mm、厚度 2mm的銅製圓盤，於上下配置的此圓盤之間夾入0.5 g的各 供試粉末，在上圓盤載置l〇〇g的秤錘。於此狀態下將端子 連接於上下的銅圓盤，施加10V的電壓時，將電流値未達 ΙμΑ者評價爲〇，將ΙμΑ以上者評價爲X。 又，作爲塡充密度（相對密度）的評價，對各供試粉 末測定敲緊密度，除以純Si的真密度2.3 3Mg/m3，將乘以 100後之値當作相對密度（％ )，將65%以上評價爲〇，將 未達65 %評價爲X。再者，作爲流動性的評價，對於各供試 粉末依照JIS-Z2502的方法進行試驗。此試驗係將流動者 價評價爲〇’將不流動者評價爲x。 關於水中的分散性，係將1 00ml的水加入燒杯中，於 其中加入5g各供試粉末’用不銹鋼製匙攪拌5次。然後， 目視確認水中的粉末之凝聚狀態。將幾乎沒有看到凝聚者 評價〇，將看到許多凝聚者評價爲x。 -20- 201200472 作爲平均圓形度的評價，測定矽粉末的平均圓形度。 平均圓形度係藉由SEISHIN企業公司製的PITA-1進行評價 。其原理的槪略係如以下。使載體液連同粒子流到小室（ cell )內，用CCD照相機攝入大量的粒子影像，由各個粒 子影像來測定面積（A )與周圍長（p )。藉由此等，以（ 圓形度）=4πΑ/(ρ2)進行評價。再者，於真球的情況，由於 CCD照相機所取入的影像爲真圓，故若此直圓的半徑爲r， 貝 ljA = 7ir2，ρ = 2 π r ' (圓开多度）=4π(πΓ2)/(2πΓ)2 = 1.〇〇° 又， 愈接近真球的形狀之粉末則圓形度的數値愈大，隨著形狀 偏離真球，圓形度變成小値。對每供試粉末，測定各自 2500〜3 500個粒子的圓形度，將其平均値當作平均圓形度 [表 Β1] 表Β 1Example B -19-201200472 Hereinafter, the tantalum powder having high contact resistance, enthalpy density, fluidity, and dispersibility will be specifically described by way of examples. First, in order to produce a plurality of types of cerium powders having different "oxygen analysis enthalpy / specific surface area" shown in Table B1, the pure cerium powder produced by the gas atomization method is classified into 150 μm or less, and 500 to 1 in the atmosphere. l 〇〇 ° C for 1 hour of oxidation treatment. Further, the commercially available pulverized powder was also classified into 150 μm or less in the same manner, and subjected to oxidation treatment at 500 to 1 100 ° C for 1 hour in the air. The following evaluations were performed on the powders before and after the oxidation treatment. The evaluation of the specific surface area (BET method) was evaluated by a helium gas adsorption method. Further, as evaluation of contact resistance between powders, two copper discs having a diameter of 30 mm and a thickness of 2 mm were prepared, and 0.5 g of each test powder was placed between the discs arranged vertically, and placed on the upper disc. 〇〇g's scale hammer. In this state, the terminal was connected to the upper and lower copper discs, and when a voltage of 10 V was applied, the current 値μ达 was evaluated as 〇, and the ΙμΑ or higher was evaluated as X. Further, as the evaluation of the enthalpy density (relative density), the knocking degree of each test powder was measured, and the true density of pure Si was divided by 2.3 3 Mg/m 3 , and the enthalpy after multiplied by 100 was regarded as the relative density (%). More than 65% were evaluated as 〇, and less than 65% were evaluated as X. Further, as evaluation of fluidity, each test powder was tested in accordance with the method of JIS-Z2502. In this test, the liquidity price was evaluated as 〇', and the non-flowing person was evaluated as x. With respect to the dispersibility in water, 100 ml of water was added to a beaker, and 5 g of each test powder was added thereto, and the mixture was stirred 5 times with a stainless steel spoon. Then, the state of aggregation of the powder in the water was visually confirmed. There will be almost no evaluation of cohesives, and many cohesers will be evaluated as x. -20- 201200472 As the evaluation of the average circularity, the average circularity of the cerium powder was measured. The average circularity was evaluated by PITA-1 manufactured by SEISHIN Corporation. The strategy of the principle is as follows. The carrier liquid and the particles were flowed into the cell, and a large number of particle images were taken by a CCD camera, and the area (A) and the surrounding length (p) were measured from the respective particle images. By this, the evaluation was performed with (circularity) = 4π Α / (ρ2). Furthermore, in the case of a true ball, since the image taken by the CCD camera is a true circle, if the radius of the straight circle is r, the shell ljA = 7ir2, ρ = 2 π r ' (circle openness) = 4π (πΓ2)/(2πΓ)2 = 1.〇〇° Also, the closer to the shape of the true sphere, the larger the degree of circularity, and the circularity becomes smaller as the shape deviates from the true sphere. For each test powder, the circularity of each of 2500 to 3 500 particles was measured, and the average enthalpy was regarded as the average circularity [Table ] 1] Table 1

No 製程 氧分析 値/比表 面積 粉末間 接觸電 阻 塡充 密度 流 動 性 分 散 性 備 註 1 氣體霧化—分級成-150 0.3 〇 〇 〇 〇 2 氣體霧化一分級成-150 " m—以500*t氧化 0.4 0 0 〇 〇 古 3 氣體霧化—分級成-150// m—以700TC氧化 2 〇 〇 〇 〇 4 氣體霧化-> 分級成-150只以9001C氧化 7 〇 〇 〇 〇 级 5 氣體霧化—分級成-250 // m—以6001C氧化 1 〇 〇 〇 〇 明 6 氣體霧化—分級成-106 /z m->以8001C氧化 5 〇 〇 〇 〇 例 7 氣體霧化—分級成-106 " m—以lOOffC氧化 10 〇 〇 〇 〇 8 氣體霧化β分級成-150 /z m—以1100ΐ氣化 25 〇 X X 〇 9 (市售)塊狀體粉碎粉—分級成150/m 0.1 X X X X 10 (市售)塊狀體粉碎粉—分級成-150/zm-*以500t氧化 0.15 X X X X 比 11 (市售)塊狀體粉碎粉—分級成150//m—以700°C氧化 3 〇 X X 〇 較 12 (市售)塊狀體粉碎粉—分級成150"m—以900TC氧化 8 〇 X X 〇 例 13 沛售)塊狀體粉碎粉-分娜50"m-►以1100TC氧化 13 〇 X X 〇 註）底線係本發明條件外 表Β1中顯示供試粉末的製程、「氧分析値/比表面積 -21 - 201200472 」、粉末間接觸電阻、塡充密度、流動性、分散性的評價 結果。又，表B1中將150μιη以下的粒度記載爲_15〇μπ^ 又，表Β2中顯示供試粉末的平均圓形度及相對密度。 [表 Β2] 表Β 2No Process Oxygen Analysis 値/Specific Surface Area Powder Contact Resistance 塡 Charge Density Fluidity Dispersion Remarks 1 Gas Atomization—Classified into -150 0.3 〇〇〇〇2 Gas atomization is classified into -150 " m—to 500* t oxidation 0.4 0 0 〇〇古 3 gas atomization - classification into -150 / / m - oxidation with 700TC 2 〇〇〇〇 4 gas atomization - > graded into -150 only 9001C oxidation 7 〇〇〇〇 grade 5 Gas atomization - classification into -250 // m - oxidation at 6001C 1 〇〇〇〇6 gas atomization - classification into -106 /z m-> oxidation at 8001C 5 〇〇〇〇7 gas atomization - Classification into -106 " m - oxidation with lOOffC 10 〇〇〇〇 8 gas atomization β classification into -150 / zm - gasification at 1100 25 25 〇 XX 〇 9 (commercially available) block pulverized powder - classified into 150/m 0.1 XXXX 10 (commercially available) block pulverized powder - classified into -150/zm-* with 500t oxidation 0.15 XXXX ratio 11 (commercially available) block pulverized powder - graded into 150//m - at 700 °C oxidation 3 〇 XX 〇 compared to 12 (commercially available) block pulverized powder - graded into 150 " m - oxidized at 900 TC 8 〇 XX 〇 13 沛 ) ) 块 块 块 块 块 块 块 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 - 201200472 》, evaluation results of contact resistance, enthalpy density, fluidity, and dispersibility between powders. Further, in Table B1, the particle size of 150 μm or less is described as _15 〇 μπ^, and in Table 2, the average circularity and relative density of the test powder are shown. [Table Β 2] Table Β 2

No· 平均0形度 相對密度(％) 1 0.87 74 2 0.87 74 3 0. 85 70 4 0.90 73 5 0.90 72 6 0. 93 69 7 0,91 70 如表Β 1中所示，Ν ο · 1〜7係本發明例，Ν 〇 . 8〜1 3係比 較例。比較例Ν 〇 · 8由於「氧分析値/比表面積」的値大， 故塡充密度（相對密度）低，且流動性差。比較例No.9由 於市售的塊狀體粉碎粉且「氧分析値/比表面積」的値小 ，故接觸電阻（粉末間）小，塡充密度（相對密度）低， 流動性差’且分散性差。比較例Ν ο · 1 0係與比較例Ν 〇 . 9同 樣’由於市售的塊狀體粉碎粉且「氧分析値/比表面積」 的値小’故接觸電阻（粉末間）小，塡充密度（相對密度 )低’流動性差，且分散性差。 比較例Ν〇·11係與比較例No.9、10同樣，由於是市售 的塊狀體粉碎粉，故塡充密度（相對密度）低，流動性差 。比較例No. 12係與比較例No.9〜11同樣，由於是市售的 塊狀體粉碎粉，故塡充密度（相對密度）低，流動性差。 比較例Ν 〇 . 1 3係與比較例ν 〇 . 9〜1 2同樣，由於市售的塊狀 -22- 201200472 體粉碎粉且「氧分析値/比表面積」的値大’故塡充密度 (相對密度）低，流動性差。 相對於此，本發明例之No.1〜7由於皆滿足本發明的 條件，故可知「氧分析値/比表面積」、接觸電阻（粉末 間）、塡充密度、流動性及分散性的特性優異。 如以上，「氧分析値/比表面積」未達〇·2時，表面氧 化被膜係薄，得不到接觸電阻（粉末間）、塡充密度、流 動性及分散性的特性。又，於使「氧分析値/比表面積」 超過1 〇爲止時，必須高溫的氧化處理，燒結係與氧化同時 進行，另外需要粉碎步驟，因此球形狀崩塌，成爲塡充密 度等降低的結果。No· Average 0 degree relative density (%) 1 0.87 74 2 0.87 74 3 0. 85 70 4 0.90 73 5 0.90 72 6 0. 93 69 7 0,91 70 As shown in Table 1, Ν ο · 1 ~7 is an example of the present invention, Ν 〇. 8~1 3 is a comparative example. Comparative Example 〇 8 8 Since the "oxygen analysis 値 / specific surface area" is large, the enthalpy density (relative density) is low and the fluidity is poor. In Comparative Example No. 9, the commercially available bulk pulverized powder had a small "oxygen analysis enthalpy / specific surface area", so the contact resistance (between powders) was small, the enthalpy density (relative density) was low, and the fluidity was poor' and dispersed. Poor sex. Comparative example ο · 1 0 series and comparative example 〇 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 Low density (relative density) 'poor flowability and poor dispersion. In the same manner as in Comparative Examples Nos. 9 and 10, the comparative example No. 11 and 10 were commercially available bulk pulverized powders, so that the enthalpy density (relative density) was low and the fluidity was poor. In Comparative Example No. 12, similarly to Comparative Examples No. 9 to 11, since the commercially available bulk pulverized powder was used, the enthalpy density (relative density) was low and the fluidity was poor. Comparative Example 〇 1. 1 3 series and comparative example ν 〇. 9~1 2 Similarly, due to the commercially available bulk -22-201200472 body pulverized powder and "larger oxygen analysis 値 / specific surface area" (relative density) is low and fluidity is poor. On the other hand, in Examples 1 to 7 of the present invention, since the conditions of the present invention are satisfied, the characteristics of "oxygen analysis enthalpy / specific surface area", contact resistance (between powders), enthalpy density, fluidity, and dispersibility are known. Excellent. As described above, when the "oxygen analysis 値/specific surface area" is less than 〇2, the surface oxidation film is thin, and the contact resistance (between powders), the enthalpy density, the fluidity, and the dispersibility are not obtained. In addition, when the "oxygen analysis enthalpy / specific surface area" is more than 1 Torr, high-temperature oxidation treatment is required, and the sintering system is simultaneously performed with oxidation, and a pulverization step is required. Therefore, the spherical shape collapses and the enthalpy density is lowered.

例C 以下，藉由實施例來具體說明含Fe的矽粉末。首先， 作爲表C1中所示的供試粉末之製造，爲了製作內部生成的 膜狀不純相之厚度不同的數種類之矽粉末，在石墨坩堝中 溶解Fe含量不同的Si原料，以氣體霧化法製作矽粉末，分 級成不同的粒度。又，作爲比較，同樣地溶解Fe含量不同 的Si原料，將直接凝固的鑄錠粉碎、分級，分級成不同的 粒度。粉碎係用金屬製鎚粗粉碎至約5mm以下後，再使用 乳鉢將其微粉碎。對於此等供試粉末，進行以下的評價。 表C1中顯示其結果。即，顯示供試粉末的製程、內部的膜 狀不純相之厚度、塡充體的電流遮斷性、塡充體的導熱性 、塡充密度的評價結果。又，表C1中例如將150μιη以下的 -23- 201200472 粒度記載爲-150μπι。 作爲矽粉末的外觀，藉由SEM觀察進行評價，將球狀 或大致球狀者當作〇，將不定形狀者當作X。又，關於矽 粉末內部的膜狀不純相之厚度，係以樹脂埋藏供試粉末進 行硏磨，拍攝隨意選出的10粒之粉末的Compo影像，測定 各粉末的膜狀不純相之最大厚度，將此平均爲2 μηι以下者 當作〇，將超過2 μηι者當作X。圖3 Α及3 Β中顯示如此所拍 攝的Compo影像之例。即，圖3 A及3 B係顯示矽粉末的截面 Compo影像之顯微鏡照片，圖3A係低倍率者，圖3B係高倍 率者。 關於塡充體的電流遮斷性，係準備2片直徑30mm、厚 度2 mm的銅製圓盤，於上下配置的此圓盤之間夾入〇.5g的 各供試粉末，在上圓盤載置l〇〇g的秤錘。於此狀態下將端 子連接於上下的銅圓盤，施加10V的電壓時，將電流値未 達1 μΑ者評價爲〇，將1 μΑ以上者評價爲X。 關於塡充體的導熱性，係於外徑60mm、內徑50mm、 高度50mm的銅製容器中振動塡充供試粉末，將此置於已 加熱到1 00°C的熱板之上。再者，將溫度計***矽粉末塡 充部中央以測定溫度’以升溫速度的迅速度評價塡充體的 導熱性。將***粉末塡充體中的溫度計達到70它爲止的時 間比表C 1的No. 1之供試粉末慢的粉末當作x，將與no . 1同 等或快的粉末當作〇。 作爲塡充密度的評價’將供試粉末的敲緊密度除以Si 的真密度之2.3 3 Mg/m3，然後乘以i 〇〇的相對密度（％ )爲 -24- 201200472 6 5 %以上者當作〇，將未達6 5 %者當作χ。 作爲平均圓形度的評價，測定矽粉末的平均圓形度。 平均圓形度係藉由SEISHIN企業公司製的PITA-1進行評價 。其原理的槪略係如以下。使載體液連同粒子流到小室（ cell )內，用CCD照相機攝入大量的粒子影像，由各個粒 子影像來測定面積（A )與周圍長（p )。藉由此等，以（ 圓形度）=4πΑ/(ρ2)進行評價。再者，於真球的情況，由於 CCD照相機所取入的影像爲真圓，故若此直圓的半徑爲r， 則 Α = πΓ2，ρ = 2πΓ，（圓形度）=4 π( 7tr 2 )/( 2 τη*) 2 = 1 · Ο 0。又， 愈接近真球的形狀之粉末則圓形度的數値愈大，隨著形狀 偏離真球，圓形度變成小値。對每供試粉末，測定各自 2500〜3500個粒子的圓形度，將其平均値當作平均圓形度 -25- 201200472 [表 Cl] 表c 1Example C Hereinafter, Fe-containing cerium powder will be specifically described by way of examples. First, as the production of the test powder shown in Table C1, in order to produce a plurality of kinds of cerium powders having different thicknesses of the film-shaped impure phase formed therein, Si raw materials having different Fe contents are dissolved in the graphite crucible, and atomized by gas. The enamel powder is prepared and classified into different particle sizes. Further, as a comparison, Si raw materials having different Fe contents were dissolved in the same manner, and ingots directly solidified were pulverized, classified, and classified into different particle sizes. The pulverization was coarsely pulverized to about 5 mm or less with a metal hammer, and then finely pulverized using a mortar. The following evaluations were performed on these test powders. The results are shown in Table C1. That is, the evaluation results of the process of the test powder, the thickness of the inner film-like impure phase, the current interruption of the ruthenium, the thermal conductivity of the ruthenium, and the enthalpy density were displayed. Further, in Table C1, for example, the -23-201200472 particle size of 150 μm or less is described as -150 μm. The appearance of the enamel powder was evaluated by SEM observation, and a spherical or substantially spherical shape was regarded as 〇, and an indefinite shape was regarded as X. Further, regarding the thickness of the film-like impure phase in the tantalum powder, a immersion test powder was used for honing, and a Compo image of 10 randomly selected powders was taken, and the maximum thickness of the film-like impure phase of each powder was measured. This average is 2 μηι or less as 〇, and more than 2 μηι is considered as X. An example of such a captured Compo image is shown in Figure 3 and Figure 3. That is, Fig. 3A and Fig. 3B show micrographs of the cross-sectional Compo image of the tantalum powder, Fig. 3A is a low magnification, and Fig. 3B is a high magnification. For the current interrupting property of the sputum, two copper discs having a diameter of 30 mm and a thickness of 2 mm were prepared, and each of the test powders of 〇5 g was placed between the discs arranged above and below, and the upper disc was placed on the upper disc. Set l〇〇g's scale hammer. In this state, the terminal was connected to the upper and lower copper discs, and when a voltage of 10 V was applied, the current 値 was less than 1 μΑ, and it was evaluated as 〇, and the 1 μΑ or more was evaluated as X. Regarding the thermal conductivity of the ferrule, the test powder was shaken in a copper container having an outer diameter of 60 mm, an inner diameter of 50 mm, and a height of 50 mm, and placed on a hot plate heated to 100 °C. Further, a thermometer was inserted into the center of the mash powder portion to measure the temperature. The thermal conductivity of the ruthenium was evaluated by the rapid rate of temperature increase. The powder which was inserted into the powder entangled body reached 70. The powder which was slower than the test powder of No. 1 of Table C1 was regarded as x, and the powder which was equal or faster than No. 1 was regarded as 〇. As the evaluation of the enthalpy density, the knocking degree of the test powder is divided by 2.3 3 Mg/m3 of the true density of Si, and then the relative density (%) of i 〇〇 is -24 - 201200472 6 5 % or more. As a cockroach, less than 65% of people will be treated as cockroaches. As an evaluation of the average circularity, the average circularity of the cerium powder was measured. The average circularity was evaluated by PITA-1 manufactured by SEISHIN Corporation. The strategy of the principle is as follows. The carrier liquid and the particles were flowed into the cell, and a large number of particle images were taken by a CCD camera, and the area (A) and the surrounding length (p) were measured from the respective particle images. By this, the evaluation was performed with (circularity) = 4π Α / (ρ2). Furthermore, in the case of a true ball, since the image taken by the CCD camera is a true circle, if the radius of the straight circle is r, then Α = π Γ 2, ρ = 2π Γ, (circularity) = 4 π ( 7tr 2 ) / ( 2 τη*) 2 = 1 · Ο 0. Further, the powder which is closer to the shape of the true ball has a larger circularity, and as the shape deviates from the true ball, the circularity becomes a small flaw. For each test powder, the circularity of each of 2500 to 3500 particles was measured, and the average enthalpy was regarded as the average circularity -25 - 201200472 [Table Cl] Table c 1

No 製程 形 狀 Fe量 (質量％) 膜狀不純相原 (um) 電流 遮斷性 導熱 性 塡充 密度 備 註 1 氣體霧化——5 3 xm 〇 0.11 0.2 〇 0 〇 2 氣體霧化〇6/+53//m 〇 0.11 0.3 〇 〇 〇 3 氣體霧化—2 1 2/+ 1 0 6 wm 〇 0.11 0.3 〇 〇 〇 4 氣體霧化--5 0 0/+2 1 2 jum 〇 0.11 0.5 〇 〇 〇 本 5 氣體霧化1 〇 6/+ 5 3tfm 〇 0.01 未達〇· U) 〇 〇 〇 發 6 氣體霧化—-J 0 6/+ 5 3jum 〇 0.05 未達0.10 〇 〇 0 明 7 氣體親化――1 〇6/+53jum 〇 0.52 1.2 〇 〇 〇 例 8 氣體霧化一-2 1 2/+1 0 6 itm 〇 1.55 1.4 Ο 〇 〇 9 氣體霧化一2 1 2/+1 0 6；im 〇 1.97 1.8 〇 〇 〇 10 鑄造粉碎一-53/m _x_ 0.11 3.1 X X X 11 鏡造粉碎1 〇6/+53#ιη _x_ 0.11 4.1 X X X 12 @造粉碎一-2 1 2/+ 1 0 6 //m X O.li 3.7 X X X J3 鑄造粉碎—5 0 0/+ 2 1 2 /rn _x_ 0.11 ZZ X X X 比 14 鑄造粉碎—1 〇 65 3 xm 0.01 未達〇· 10 〇 X X 較 15 鑄造粉碎-一 1 0 6/十5 _x_ 0.05 1.7 〇 X X 例 16 鑄造粉碎一 1 0 6/+5 3//m _x_ 0.52 4.4 X X X 17 鑄造粉碎·*- 2 1 2/+ 1 0 6 wm X 1.55 4.0 X X X 18 鑄造粉碎—2 1 2/+ 1 0 6 1.97 5.3 X X X 19 氣體S化一-1 0 0 0/+5 0 Otfm 〇 1.97 2.5 X 〇 〇 20 氣體毅化—-l〇6/+53;/m 〇 2.54 2.8 X 〇 〇 註）底線係本發明條件外 如表C1中所示，No. 1〜9係本發明例，No. 10〜20係比 較例。 又，表C2中顯示供試粉末的平均圓形度及相對密度。 -26- 201200472 [表 C2] 表C 2No Process shape Fe amount (% by mass) Membrane impure phase (um) Current interrupting thermal conductivity Charge density Remarks 1 Gas atomization - 5 3 xm 〇0.11 0.2 〇0 〇2 Gas atomization 〇6/+53 //m 〇0.11 0.3 〇〇〇3 gas atomization—2 1 2/+ 1 0 6 wm 〇0.11 0.3 〇〇〇4 gas atomization--5 0 0/+2 1 2 jum 〇0.11 0.5 〇〇〇 5 gas atomization 1 〇 6 / + 5 3tfm 〇 0.01 not reached 〇 · U) 〇〇〇 6 gas atomization - J 0 6 / + 5 3jum 〇 0.05 not up to 0.10 〇〇 0 Ming 7 gas ——1 〇6/+53jum 〇0.52 1.2 〇〇〇Example 8 Gas atomization--2 1 2/+1 0 6 itm 〇1.55 1.4 Ο 〇〇9 Gas atomization one 2 1 2/+1 0 6; Im 〇1.97 1.8 〇〇〇10 Casting pulverization-53/m _x_ 0.11 3.1 XXX 11 Mirror crushing 1 〇6/+53#ιη _x_ 0.11 4.1 XXX 12 @造碎一-2 1 2/+ 1 0 6 / /m X O.li 3.7 XXX J3 Casting smash - 5 0 0/+ 2 1 2 /rn _x_ 0.11 ZZ XXX than 14 casting smash -1 〇65 3 xm 0.01 not up to 〇· 10 〇XX compared to 15 casting smash-one 1 0 6/10 5 _x_ 0.05 1.7 〇 XX cases 16 Casting smashing 1 0 6/+5 3//m _x_ 0.52 4.4 XXX 17 Casting smashing·*- 2 1 2/+ 1 0 6 wm X 1.55 4.0 XXX 18 Casting smashing—2 1 2/+ 1 0 6 1.97 5.3 XXX 19 Gas S-I-1 0 0 0/+5 0 Otfm 〇1.97 2.5 X 〇〇20 Gas 毅化--l〇6/+53;/m 〇2.54 2.8 X 〇〇) Bottom line is the invention The conditions are shown in Table C1, Nos. 1 to 9 are examples of the present invention, and Nos. 10 to 20 are comparative examples. Further, Table C2 shows the average circularity and relative density of the test powder. -26- 201200472 [Table C2] Table C 2

No. 平均圓形度 相對密度(%) 1 0.93 70 2 0. 88 69 3 0. 84 70 4 0. 80 67 5 0. 85 68 6 0. 86 68 7 0. 82 67 8 0.81 66 9 0. 82 69 比較例No · 1 0〜1 8由於皆將以鑄造方法所製造的鑄錠 粉碎、分級，而分級成不同的粒度者，故比較例No.10〜 13係形狀爲不定形狀，由於內部的膜狀不純相之厚度係厚 ，故電流遮斷性、導熱性及塡充密度差》比較例No. 14由 於係形狀爲不定形狀，故導熱性及塡充密度差。 比較例N 〇 . 1 5係與比較例Ν ο · 1 4同樣，由於形狀爲不定 形狀，故導熱性及塡充密度差。比較例No.16、17、18由 於形狀爲不定形狀，內部的膜狀不純相之厚度係厚，故電 流遮斷性、導熱性及塡充密度差。比較例No. 1 9由於內部 的膜狀不純相之厚度係厚，故電流遮斷性差。比較例 No.20由於Fe含量多，內部的膜狀不純相之厚度係厚，故 電流遮斷性差。 如以上，藉由將原料的F e含量限制在0.0 1〜2質量％， 同時藉由以霧化法使成爲球形狀或大致球形狀之矽粉末， 而塡充密度高，即使爲便宜的Si原料，也可提高固有電阻 ’而且藉由使以矽粉末內部的Fe爲主體的不純相之膜厚成 -27- 201200472 爲2 μιη以下，可提高固有電阻，可提供使用於電子零件的 絕緣性散熱材等中所用的矽粉末。 【圖式簡單說明】 圖1係顯示以氣體霧化法所製作的純矽粉末之外觀 S Ε Μ影像。 圖2係顯示以粉碎法所製作的純矽粉末之外觀SEM影 像。 圖3 A係顯示矽粉末的截面c〇mp〇影像之低倍率照片。 圖3B係顯示矽粉末的截面c〇mp〇影像之高倍率照片。 -28 -No. Average circularity relative density (%) 1 0.93 70 2 0. 88 69 3 0. 84 70 4 0. 80 67 5 0. 85 68 6 0. 86 68 7 0. 82 67 8 0.81 66 9 0. 82 69 Comparative Example No. 1 0 to 1 8 Since the ingots produced by the casting method were pulverized and classified, and classified into different sizes, the comparative examples No. 10 to 13 were indefinite shape, and the inside was internal. Since the thickness of the film-like impure phase is thick, the current interruption property, the thermal conductivity, and the enthalpy density difference are compared. In Comparative Example No. 14, since the shape is an indefinite shape, the thermal conductivity and the enthalpy density are inferior. Comparative Example N 〇 . 1 5 is similar to the comparative example ο 1 1 4 in that the shape is an indefinite shape, so that the thermal conductivity and the enthalpy density are inferior. In Comparative Examples Nos. 16, 17, and 18, since the shape was an indefinite shape, the thickness of the inner film-shaped impure phase was thick, so that the current interrupting property, the thermal conductivity, and the enthalpy density were inferior. In Comparative Example No. 19, since the thickness of the inner film-shaped impure phase was thick, the current interrupting property was poor. Comparative Example No. 20 has a large Fe content, and the thickness of the internal film-like impure phase is thick, so that the current interrupting property is poor. As described above, by limiting the Fe content of the raw material to 0.01 to 2% by mass, and by making the spherical or substantially spherical niobium powder by the atomization method, the crucible density is high, even if it is inexpensive Si In addition, the thickness of the impure phase mainly composed of Fe in the niobium powder can be increased by -27-201200472 to 2 μm or less, and the specific resistance can be improved, and insulation for electronic parts can be provided. A tantalum powder used in a heat sink or the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the appearance of a pure tantalum powder produced by a gas atomization method. Fig. 2 is a view showing the appearance of an SEM image of a pure tantalum powder produced by a pulverization method. Fig. 3 A shows a low-magnification photograph of the cross-section c〇mp〇 image of the tantalum powder. Fig. 3B is a high magnification photograph showing a cross section c〇mp〇 image of the tantalum powder. -28 -

Claims (1)

201200472 七、申請專利範圍： 1. 一種砂粉末，其係含有0〜2質量％的Fe，剩餘部分 爲Si及無可避免的雜質所成之矽粉末， 前述矽粉末具有0.75〜1.00的平均圓形度及由下式所 算出的65 %以上之相對密度Dr， Dr(%) = l 00xDt/Da (式中，Dr係相對密度，Dt係前述矽粉末的敲緊密度（ tapdensity) (Mg/m3)，Da係Si的真密度2.33Mg/m3)。 2. 如申請專利範圍第1項之矽粉末，其中前述矽粉末 係僅由Si及無可避免的雜質所成之接觸電阻高的純矽粉末 〇 3 .如申請專利範圍第2項之矽粉末，其中前述相對密 度爲6 5〜8 0 %。 4. 如申請專利範圍第2或3項之矽粉末，其係經由氣體 霧化法所製造。 5. 如申請專利範圍第1項之矽粉末，其氧分析値對比 表面積的比爲0.2〜10，而且其接觸電阻、塡充密度、流 動性及分散性優異。 6. 如申請專利範圍第5項之矽粉末，其具有球狀或大 致球狀的形狀。 7. —種矽粉末之製造方法，該矽粉末係接觸電阻、塡 充密度、流動性及分散性優異，其特徵爲將經由霧化法所 製作的矽粉末分級，以使得氧分析値對比表面積的比成爲 0.2 〜1 0。 -29- 201200472 8. —種矽粉末之製造方法’該矽粉末係接觸電阻、塡 充密度、流動性及分散性優異’其特徵爲將經由霧化法所 製作的矽粉末分級’在5 0 0〜1 0 0 0 °C進行氧化處理，以使 得氧分析値對比表面積的比成爲〇·2〜10。 9. 如申請專利範圍第1項之矽粉末，其中 前述Fe的含量爲0.01〜2質量％， 前述矽粉末具有生成於其內部的厚度爲2 μιη以下之膜 狀不純相，而且係球形狀或大致球形狀，用於電子零件材 料者。 -30-201200472 VII. Patent application scope: 1. A sand powder containing 0 to 2% by mass of Fe and the balance being Si and an inevitable impurity. The above-mentioned tantalum powder has an average circle of 0.75 to 1.00. The shape and the relative density of more than 65% calculated by the following formula Dr, Dr (%) = l 00xDt / Da (wherein Dr is the relative density, Dt is the tapdensity of the aforementioned tantalum powder (Mg / M3), the true density of Da-based Si is 2.33 Mg/m3). 2. The powder according to item 1 of the patent application, wherein the tantalum powder is a pure tantalum powder having a high contact resistance formed by only Si and inevitable impurities. 3. The powder of the second item of claim 2 Wherein the aforementioned relative density is from 6 5 to 80%. 4. A powder according to item 2 or 3 of the patent application, which is produced by a gas atomization method. 5. For the powder of the first application of the patent scope, the ratio of the oxygen analysis to the comparative surface area is 0.2 to 10, and the contact resistance, the enthalpy density, the fluidity and the dispersibility are excellent. 6. The powder of claim 5, which has a spherical or substantially spherical shape. 7. A method for producing a cerium powder, which is excellent in contact resistance, enthalpy density, fluidity, and dispersibility, and is characterized in that cerium powder produced by an atomization method is classified so that oxygen is analyzed for 値 contrast surface area. The ratio becomes 0.2 to 1 0. -29- 201200472 8. The method for producing a bismuth powder is characterized by excellent contact resistance, enthalpy density, fluidity, and dispersibility, which is characterized by classifying cerium powder produced by an atomization method at 50 Oxidation treatment was carried out at 0 to 1 0 0 ° C so that the ratio of the comparative surface area of the oxygen analysis was 〇·2 to 10. 9. The powder according to claim 1, wherein the content of the Fe is 0.01 to 2% by mass, and the cerium powder has a film-like impure phase having a thickness of 2 μm or less formed therein, and is a spherical shape or A roughly spherical shape for use in electronic parts materials. -30-