TWI720523B - Metal powder and its manufacturing method - Google Patents

Metal powder and its manufacturing method Download PDF

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TWI720523B
TWI720523B TW108122839A TW108122839A TWI720523B TW I720523 B TWI720523 B TW I720523B TW 108122839 A TW108122839 A TW 108122839A TW 108122839 A TW108122839 A TW 108122839A TW I720523 B TWI720523 B TW I720523B
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sulfur
metal
aforementioned
gas
concentration
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TW202000344A (en
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西島一元
小林諒太
六角廣介
淺井剛
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日商東邦鈦股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/28—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from gaseous metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel

Abstract

問題之一在於要提供包含硫之濃度或其分布受到控制之金屬粒子的金屬粉體及其製造方法。提供一種製造金屬粉體的方法。此方法包含：藉由透過氯的金屬之氯化來生成金屬氯化物的氣體，以及藉由在包含硫之氣體的存在下將係為氣體的前述金屬氯化物還原來生成金屬粒子。還原係以金屬粒子的硫之總體濃度成為0.01重量%以上且1.0重量%以下，金屬粒子在自表面起算4nm之位置的硫之局部濃度成為2原子%以上的方式來進行。總體濃度與局部濃度係分別藉由感應耦合電漿發光分光分析裝置及掃描穿透式電子顯微鏡所具備的能量色散型X射線分光分析器來估計。 One of the problems is to provide a metal powder containing metal particles whose concentration or distribution of sulfur is controlled, and a manufacturing method thereof. A method of manufacturing metal powder is provided. The method includes: generating a metal chloride gas by chlorination of a metal permeating chlorine, and generating metal particles by reducing the aforementioned metal chloride as a gas in the presence of a gas containing sulfur. The reduction is performed so that the total sulfur concentration of the metal particles is 0.01% by weight or more and 1.0% by weight or less, and the local sulfur concentration of the metal particles at a position 4 nm from the surface of the metal particles is 2 atomic% or more. The overall concentration and the local concentration are respectively estimated by the energy dispersive X-ray spectrometer equipped in the inductively coupled plasma emission spectrometer and the scanning transmission electron microscope.

Description

金屬粉體與其製造方法 Metal powder and its manufacturing method

本發明之實施型態之一係關於金屬粉體及其製造方法。或者，本發明之實施型態之一係關於金屬粉體之品質管理方法、金屬粉體之特性推定方法或燒結溫度之預測方法。 One of the embodiments of the present invention relates to metal powder and its manufacturing method. Alternatively, one of the implementation modes of the present invention relates to a method for quality management of metal powder, a method for estimating characteristics of metal powder, or a method for predicting sintering temperature.

包含微細之金屬粒子的集合體(下稱金屬粉體)已利用於各種領域，銅或鎳、銀等顯現高導電性之金屬的金屬粉體，已廣泛利用於作為例如堆疊陶瓷電容器(MLCC)之內部電極等電子部件的原始材料。MLCC已具有包含介電質材料之陶瓷層與包含金屬之內部電極的堆疊作為基本結構。此堆疊係藉由將包含介電質材料之分散液與包含金屬粉體之分散液交互塗布之後進行加熱，將介電質材料與金屬粉體燒結而形成。舉例而言，在專利文獻1或2已揭露用以控制加熱時之金屬粉體之燒結特性的方法。 Aggregates containing fine metal particles (hereinafter referred to as metal powders) have been used in various fields. Metal powders of metals that exhibit high conductivity, such as copper, nickel, and silver, have been widely used as, for example, stacked ceramic capacitors (MLCC) The original material for internal electrodes and other electronic components. MLCC already has a stack of a ceramic layer containing a dielectric material and an internal electrode containing a metal as a basic structure. The stack is formed by alternately coating a dispersion liquid containing a dielectric material and a dispersion liquid containing a metal powder, and then heating, to sinter the dielectric material and the metal powder. For example, Patent Literature 1 or 2 has disclosed a method for controlling the sintering characteristics of metal powder during heating.

『專利文獻』 『Patent Literature』

《專利文獻1》：日本專利公開第H11-80816號公報 "Patent Document 1": Japanese Patent Publication No. H11-80816

《專利文獻2》：日本專利公開第2014-189820號公報 "Patent Document 2": Japanese Patent Publication No. 2014-189820

本發明之實施型態之一，其問題之一在於要提供包含硫之濃度或其分布受到控制之金屬粒子的金屬粉體及其製造方法。或者，本發明之實施型態之一，其問題之一在於要提供具有 高燒結起始溫度的金屬粉體及其製造方法。或者，本發明之實施型態之一，其問題之一在於要提供燒結起始溫度之偏差小的金屬粉體及其製造方法。或者，本發明之實施型態之一，其問題之一在於要提供金屬粉體之品質管理方法或金屬粉體之特性推定方法，或燒結溫度之預測方法。 One of the problems of one of the embodiments of the present invention is to provide a metal powder containing metal particles whose concentration or distribution of sulfur is controlled, and a manufacturing method thereof. Or, one of the problems of one of the implementation modes of the present invention is to provide Metal powder with high sintering starting temperature and its manufacturing method. Alternatively, one of the problems of one of the embodiments of the present invention is to provide a metal powder with a small deviation of the sintering start temperature and a method for manufacturing the same. Alternatively, one of the problems of one of the embodiments of the present invention is to provide a method for quality management of metal powder, a method for estimating characteristics of metal powder, or a method for predicting sintering temperature.

本發明相關的實施型態之一係金屬粉體。此金屬粉體包含：金屬與包含硫之金屬粒子。金屬粒子中的硫之總體濃度為0.01重量%以上且1.0重量%以下，金屬粒子在自表面起算4nm之位置的硫之局部濃度為2原子%以上。總體濃度與局部濃度係分別藉由感應耦合電漿發光分光分析裝置及掃描穿透式電子顯微鏡所具備的能量色散型X射線分光分析器來估計。 One of the embodiments related to the present invention is metal powder. The metal powder contains metal and metal particles containing sulfur. The overall concentration of sulfur in the metal particles is 0.01% by weight or more and 1.0% by weight or less, and the local concentration of sulfur at a position 4 nm from the surface of the metal particles is 2 atomic% or more. The overall concentration and the local concentration are respectively estimated by the energy dispersive X-ray spectrometer equipped in the inductively coupled plasma emission spectrometer and the scanning transmission electron microscope.

本發明相關的實施型態之一係製造金屬粉體的方法。此方法包含：藉由透過氯的金屬之氯化來生成金屬氯化物的氣體，以及藉由在包含硫之氣體的存在下將係為氣體的金屬氯化物還原來生成金屬粒子。還原係以金屬粒子的硫之總體濃度成為0.01重量%以上且1.0重量%以下，金屬粒子在自表面起算4nm之位置的硫之局部濃度成為2原子%以上的方式來進行。總體濃度與局部濃度係分別藉由感應耦合電漿發光分光分析裝置及掃描穿透式電子顯微鏡所具備的能量色散型X射線分光分析器來估計。 One of the related embodiments of the present invention is a method of manufacturing metal powder. The method includes generating metal chloride gas by chlorination of metal permeating chlorine, and generating metal particles by reducing the metal chloride which is a gas in the presence of a gas containing sulfur. The reduction is performed so that the total sulfur concentration of the metal particles is 0.01% by weight or more and 1.0% by weight or less, and the local sulfur concentration of the metal particles at a position 4 nm from the surface of the metal particles is 2 atomic% or more. The overall concentration and the local concentration are respectively estimated by the energy dispersive X-ray spectrometer equipped in the inductively coupled plasma emission spectrometer and the scanning transmission electron microscope.

本發明相關的實施型態之一係預測金屬粉體之燒結溫度的方法。此方法包含量測選自金屬粉體之金屬粒子在自表面起算4nm之位置的硫之局部濃度。硫之局部濃度係使用具備有 能量色散型X射線分光分析器的掃描穿透式電子顯微鏡來量測。 One of the related embodiments of the present invention is a method of predicting the sintering temperature of metal powder. This method includes measuring the local concentration of sulfur in metal particles selected from the metal powder at a position 4 nm from the surface. The local concentration of sulfur is used with Scanning transmission electron microscope of energy dispersive X-ray spectrometer for measurement.

110:還原裝置 110: restore device

112:還原爐 112: Reduction furnace

114:加熱器 114: heater

116:第1輸送管 116: The first delivery pipe

118:第1氣體導入管 118: The first gas introduction pipe

120:閥 120: Valve

122:第2氣體導入管 122: The second gas inlet pipe

124:閥 124: Valve

126:第3氣體導入管 126: The third gas introduction pipe

128:閥 128: Valve

130:第2輸送管 130: 2nd delivery pipe

〈圖1〉：本發明之實施型態之一相關的金屬粉體製造裝置之還原爐的剖面示意圖。 <Figure 1>: A schematic cross-sectional view of a reduction furnace of a metal powder manufacturing device related to one of the embodiments of the present invention.

〈圖2〉：繪示實施例及比較例之金屬粉體所包含之金屬粒子的硫濃度之態勢的圖。 <Figure 2>: A graph showing the state of the sulfur concentration of the metal particles contained in the metal powder of the embodiment and the comparative example.

〈圖3〉：繪示實施例及比較例之金屬粉體的燒結起始溫度與硫之總體濃度之關係的圖。 <Figure 3>: A graph showing the relationship between the sintering start temperature of the metal powders of the Examples and Comparative Examples and the overall concentration of sulfur.

以下參照圖式等同時說明本發明之各實施型態。惟本發明在不脫離其要旨的範圍中可以各式各樣的態樣實施，並非受以下示例之實施型態的記載內容限定解釋者。 Hereinafter, each embodiment of the present invention will be described with reference to the drawings and the like. However, the present invention can be implemented in various forms without departing from the scope of the gist thereof, and is not limited by the description of the following examples of implementation forms.

為使說明更為明確，圖式相較於實際態樣，其關於各部分之幅寬、厚度、形狀等雖有示意表示的情形，但終究為一例，並非限定本揭露之解釋者。在本說明書與各圖中，對於具備與有關於已出現之圖而已說明者同樣功能的要件，有時會標註相同符號，省略重複的說明。 In order to make the description clearer, compared with the actual state, although the schematic representation of the width, thickness, shape, etc. of each part is shown in the drawing, it is an example after all and does not limit the interpreter of this disclosure. In this specification and the drawings, the same reference numerals are sometimes attached to the elements that have the same functions as those described in the drawings that have already appeared, and repeated descriptions are omitted.

〈第1實施型態〉 <First implementation type>

在本實施型態，說明係為本發明相關的實施型態之一之金屬粉體的結構與特性。 In this embodiment, the description is of the structure and characteristics of the metal powder, which is one of the embodiments related to the present invention.

1.結構 1. Structure

金屬粉體係多個金屬粒子的集合體，金屬粒子包含金屬與硫。金屬係選自鎳、銅、銀等，典型上係鎳。金屬粉體之數量平均粒徑可為50nm以上且400nm以下、100nm以上且300nm以下，或100nm以上且250nm以下。換言之，選自金屬粉體之多個(例如600個)金屬粒子之粒徑的平均值，得落在上述範圍作為金屬粉體之數量平均粒徑。作為上述數量平均粒徑，舉例而言，可透過掃描式電子顯微鏡觀察金屬粉體所包含之金屬粒子，量測多個粒子(例如600個)的粒徑，採用其平均值。粒徑係內切粒子之最小圓的直徑。 The metal powder system is an aggregate of a plurality of metal particles, and the metal particles contain metal and sulfur. The metal is selected from nickel, copper, silver, etc., and is typically nickel. The number average particle size of the metal powder may be 50 nm or more and 400 nm or less, 100 nm or more and 300 nm or less, or 100 nm or more and 250 nm or less. In other words, the average particle size of a plurality of (eg, 600) metal particles selected from the metal powder should fall within the above range as the number average particle size of the metal powder. As the above-mentioned number average particle size, for example, the metal particles contained in the metal powder can be observed through a scanning electron microscope, the particle size of a plurality of particles (for example, 600) can be measured, and the average value thereof can be used. The particle size is the diameter of the smallest circle of inscribed particles.

金屬粉體含有硫。具體而言，金屬粉體的硫之總體濃度為0.01重量%以上且1.0重量%以下，或較0.01重量%還高且0.6重量%以下，或0.15重量%以上且0.6重量%以下，或0.16重量%以上且0.6重量%以下。換言之，選自金屬粉體之多個(例如相當於0.5g的個數)金屬粒子的硫之總體濃度的平均值，落在於上已述之範圍。於此所謂硫之總體濃度，係於金屬粒子之重量中硫之重量所佔的比例。選自金屬粉體之一個金屬粒子的硫之總體濃度，或多個金屬粒子的硫之總體濃度的平均，係算出作為金屬粉體之總體濃度。 Metal powder contains sulfur. Specifically, the total concentration of sulfur in the metal powder is 0.01% by weight or more and 1.0% by weight or less, or higher than 0.01% by weight and 0.6% by weight or less, or 0.15% by weight or more and 0.6% by weight or less, or 0.16% by weight % Or more and 0.6% by weight or less. In other words, the average value of the total concentration of sulfur in a plurality of metal particles (for example, the number equivalent to 0.5 g) selected from the metal powder falls within the above-mentioned range. The total concentration of sulfur referred to here refers to the proportion of the weight of sulfur in the weight of the metal particles. The total concentration of sulfur in one metal particle selected from the metal powder, or the average of the total concentration of sulfur in a plurality of metal particles, is calculated as the total concentration of the metal powder.

硫之總體濃度，可藉由感應耦合電漿發光分光來量測。舉例而言，使用SII NanoTechnology股份有限公司製之感應耦合電漿發光分光分析裝置(SPS 3100)量測即可。若要示例具體的量測方法，首先以酸使金屬粉體溶解之後，在量測波長 182.036nm進行ICP發光分光分析，藉此可獲得硫之總體濃度。 The overall concentration of sulfur can be measured by inductively coupled plasma emission spectroscopy. For example, the inductively coupled plasma emission spectrometer (SPS 3100) manufactured by SII NanoTechnology Co., Ltd. can be used for measurement. To illustrate the specific measurement method, first dissolve the metal powder with acid, and then measure the wavelength ICP emission spectrophotometric analysis was performed at 182.036nm, thereby obtaining the overall concentration of sulfur.

金屬粒子不僅於表面附近，於自表面朝向粒子內側相對遠離的內部亦含有硫。具體而言，硫之濃度雖自金屬粒子之表面隨著接近內部而減少，但在自表面起算4nm之位置的硫之濃度(以下將金屬粒子在特定位置的硫之濃度稱作局部濃度)為2原子%以上。此外，在自該表面起算4nm之位置的硫之濃度可為4原子%以下。選自金屬粉體之多個(例如10個)金屬粒子在上述位置的硫之局部濃度的平均值，落在於上已述之範圍。 The metal particles not only contain sulfur near the surface, but also in the interior relatively far away from the surface toward the inside of the particle. Specifically, although the concentration of sulfur decreases from the surface of the metal particle as it approaches the inside, the concentration of sulfur at a position 4nm from the surface (hereinafter the concentration of sulfur at a specific position of the metal particle is referred to as the local concentration) is 2 atomic% or more. In addition, the concentration of sulfur at a position of 4 nm from the surface may be 4 atomic% or less. The average value of the local concentration of sulfur in the above-mentioned positions of a plurality of (for example, 10) metal particles selected from the metal powder falls within the above-mentioned range.

並且，具有在金屬粒子之表面的硫之局部濃度的二分之一之局部濃度的位置(以下稱減半深度)，得存在於自表面起算2nm以上且4nm以下的範圍。亦即，選自金屬粉體之多個(例如10個)金屬粒子之減半深度的平均值，得落在於上已述之範圍。 In addition, a position having a local concentration of one-half of the local concentration of sulfur on the surface of the metal particle (hereinafter referred to as the halved depth) must exist in a range from the surface of 2 nm to 4 nm. That is, the average value of the halved depth of a plurality of (for example, 10) metal particles selected from the metal powder must fall within the above-mentioned range.

於上已述的硫之局部濃度，可藉由例如掃描穿透式電子顯微鏡所具備的能量色散型X射線分光分析器(STEM-EDS：Scanning Transmission Electron Microscope-Energy Dispersive X-ray Spectroscope)來估計。若要示例具體的量測方法，首先將金屬粉體分散於樹脂，將樹脂固化。之後，使用截面拋光機(CP)使剖面露出，使用聚焦離子束(FIB)製作藉由平面取樣的薄膜試樣。試樣的厚度做成100nm左右，藉此金屬粒子可成形為具有此厚度之薄膜。之後，對於所獲得之薄膜在穿過金屬粒子之中央的直線上進行EDS量測，藉此可獲得局部濃度。作為EDS量測的 條件，可選擇例如加速電壓200kV、探針徑1nm、間距幅寬3nm、每一點之量測時間15秒鐘的條件。 The above-mentioned local concentration of sulfur can be estimated by, for example, the Scanning Transmission Electron Microscope-Energy Dispersive X-ray Spectroscope (STEM-EDS: Scanning Transmission Electron Microscope-Energy Dispersive X-ray Spectroscope). . To illustrate a specific measurement method, first disperse the metal powder in the resin and cure the resin. After that, a cross-section polisher (CP) was used to expose the cross-section, and a focused ion beam (FIB) was used to prepare a thin film sample sampled by a plane. The thickness of the sample is made about 100 nm, whereby the metal particles can be formed into a thin film with this thickness. After that, the obtained film is measured by EDS on a straight line passing through the center of the metal particle, thereby obtaining a local concentration. As measured by EDS The conditions can be selected such as accelerating voltage of 200kV, probe diameter of 1nm, pitch width of 3nm, and measurement time of 15 seconds per point.

2.特性 2. Features

包含金屬粒子的金屬粉體，由於具有高的硫之總體濃度一事，以及金屬粒子在表層部的硫之廣泛分布，而具有高燒結起始溫度，於例如600℃以上的範圍顯現燒結起始溫度。此外，燒結起始溫度亦可為700℃以下。依據以上之特性，量測金屬粒子之表層部的硫之局部濃度，在局部濃度滿足於上已述之條件的情況下，係為此金屬粒子之集合體的金屬粉體能夠判斷為具有高燒結起始溫度。因此，藉由本實施型態，可提供用以預估金屬粉體之特性的有效方法。 The metal powder containing metal particles has a high overall concentration of sulfur and the wide distribution of sulfur in the surface layer of the metal particles, and therefore has a high sintering start temperature, which shows a sintering start temperature in the range of 600°C or higher, for example. . In addition, the sintering start temperature may also be 700°C or lower. Based on the above characteristics, the local concentration of sulfur in the surface layer of metal particles is measured. When the local concentration meets the above-mentioned conditions, the metal powder that is an aggregate of this metal particle can be judged to have high sintering. Starting temperature. Therefore, with this embodiment, an effective method for predicting the characteristics of the metal powder can be provided.

如實施例所示，硫之廣泛分布與高的總體濃度，與金屬粉體之高燒結起始溫度相關之情事受到默示。此外，倘若在硫之總體濃度為相同的情況下，於硫分布廣泛(在表層直至深處存在有硫)與改善燒結起始溫度的觀點上為有利。若利用此事，則能夠藉由量測硫在表層之分布或總體濃度，來推定或估計金屬粉體的燒結起始溫度。舉例而言，藉由STEM-EDS分析任意選自金屬粉體的金屬粒子，於滿足金屬粒子在自表面起算4nm之位置的硫之局部濃度為2原子%以上之條件的情況下，能夠推定包含此金屬粒子的金屬粉體之燒結溫度為600℃以上。換言之，藉由本實施型態，即使不進行金屬粉體之燒結，仍可透過量測表面層之硫濃度來推定金屬粉體之燒結行為，而可提供用以管理金屬粉 體之品質的有效方法。 As shown in the examples, the wide distribution and high overall concentration of sulfur are implied that the high sintering start temperature of the metal powder is related. In addition, if the overall concentration of sulfur is the same, it is advantageous from the viewpoints of wide distribution of sulfur (the presence of sulfur in the surface layer to the depth) and the improvement of the sintering start temperature. If this is used, the sintering start temperature of the metal powder can be estimated or estimated by measuring the distribution or overall concentration of sulfur on the surface. For example, by STEM-EDS analysis of metal particles arbitrarily selected from metal powders, when the local concentration of sulfur at a position of 4 nm from the surface of the metal particles is 2 atomic% or more, it can be estimated that The sintering temperature of the metal powder of the metal particles is 600°C or higher. In other words, with this embodiment, even if the sintering of the metal powder is not carried out, the sintering behavior of the metal powder can be estimated by measuring the sulfur concentration of the surface layer, which can be used to manage the metal powder. An effective method for the quality of the body.

如上所述，在例如使用金屬粉體作為MLCC之內部電極用之原始材料的情況下，將包含介電質之分散液與包含金屬粉體之分散液交互塗布之後進行燒製。於包含介電質之分散液，包含有Ba或Ti系之氧化物粉末或作為黏結劑發揮功能的高分子材料、溶媒、分散劑等，於包含金屬粉體之分散液，亦不僅金屬粉體還包含有黏結劑或溶媒、分散劑等。燒製時，此等黏結劑或溶媒、分散劑會蒸發或分解，同時氧化物粉末或金屬粉體會燒結而分別給予介電質膜與內部電極。通常介電質之燒結起始溫度較金屬粉體之燒結起始溫度還高，故燒製時金屬粉體之燒結會先開始。其結果，燒製時於介電質與內部電極間會產生間隙，有時會由於此間隙而在內部電極與介電質膜間發生剝離，此事招致MLCC之特性或良率的下降。 As described above, in the case of using metal powder as the original material for the internal electrode of MLCC, for example, the dispersion liquid containing the dielectric substance and the dispersion liquid containing the metal powder are alternately coated and then fired. In the dispersion liquid containing the dielectric substance, it contains Ba or Ti-based oxide powder or the polymer material that functions as a binder, solvent, dispersant, etc., in the dispersion liquid containing the metal powder, it is not only the metal powder It also contains binders or solvents, dispersants, etc. During firing, these binders, solvents, and dispersants will evaporate or decompose, and the oxide powder or metal powder will be sintered to give the dielectric film and the internal electrode, respectively. Generally, the sintering start temperature of the dielectric material is higher than the sintering start temperature of the metal powder, so the sintering of the metal powder will start first during firing. As a result, a gap may be formed between the dielectric and the internal electrode during firing, and peeling may occur between the internal electrode and the dielectric film due to the gap, and this may cause a decrease in the characteristics or yield of the MLCC.

相對於此，本實施型態相關的金屬粉體顯現高燒結起始溫度，故燒結會在更為接近氧化物粉末等之燒結起始溫度的溫度下開始。其結果，在燒製時於內部電極與介電質之間可確保高密合性，可抑制剝離。是故，金屬粉體能夠利用作為具有優異特性之用以提供各種電子部件的原料。 In contrast, the metal powder related to the present embodiment exhibits a high sintering start temperature, so the sintering starts at a temperature closer to the sintering start temperature of the oxide powder or the like. As a result, at the time of firing, high adhesion can be ensured between the internal electrode and the dielectric substance, and peeling can be suppressed. Therefore, the metal powder can be used as a raw material for providing various electronic components with excellent characteristics.

如以上所述，藉由本實施型態，即使不進行燒結仍可推定金屬粉體之燒結行為，故能夠提供用以製造具有高可靠性之金屬粉體作為MLCC之電極用材料的品質管理方法。 As described above, with this embodiment, the sintering behavior of the metal powder can be estimated even without sintering, so it is possible to provide a quality control method for producing highly reliable metal powder as an electrode material for MLCC.

〈第2實施型態〉 <Second Implementation Type>

在本實施型態，說明金屬粉體之製造方法之一例。 In this embodiment, an example of the manufacturing method of metal powder is described.

金屬粉體係利用氣相法來製造。亦即，藉由在含硫氣體的存在下將「將金屬氯化而獲得之金屬氯化物(以下亦簡記為氯化物)的蒸氣」或「將金屬氯化物加熱而獲得的蒸氣」還原來製造。惟因可獲得高純度之氯化物蒸氣且可將氯化物蒸氣的供給量穩定化，故以藉由金屬之氯化來生成氯化物之蒸氣為較佳。用以將金屬氯化之裝置(氯化爐)利用眾所周知者即可，故勉予省略說明。 The metal powder system is manufactured by the gas phase method. That is, it is produced by reducing "vapor of metal chloride (hereinafter also referred to as chloride) obtained by chlorination of metal" or "vapor obtained by heating metal chloride" in the presence of a sulfur-containing gas . However, since high-purity chloride vapor can be obtained and the supply amount of chloride vapor can be stabilized, it is preferable to generate chloride vapor by chlorination of metal. A well-known device (chlorination furnace) for chlorinating metals can be used, so the description is reluctantly omitted.

係為用以將氯化物還原之裝置的還原裝置110之剖面示意圖繪示於圖1。還原裝置110具有在將氯化物還原而生成金屬粉體的同時將硫導進金屬粒子的功能。還原裝置110具備還原爐112、用以將還原爐112加熱的加熱器114，作為基本的構造。於還原爐112連結有第1輸送管116，可中介之而對還原爐112導入金屬氯化物的氣體。於還原爐112更設置有用以供給係為還原性氣體之氫氣或肼、氨、甲烷等的第1氣體導入管118。於第1氣體導入管118接續有未圖示的還原氣體供給源。閥120裝設於第1氣體導入管118，藉此可控制還原氣體的供給量。 A schematic cross-sectional view of a reduction device 110 which is a device for reducing chloride is shown in FIG. 1. The reducing device 110 has a function of reducing the chloride to produce metal powder and at the same time introducing sulfur into the metal particles. The reduction device 110 includes a reduction furnace 112 and a heater 114 for heating the reduction furnace 112 as a basic structure. The reduction furnace 112 is connected to the first delivery pipe 116, and the metal chloride gas can be introduced into the reduction furnace 112 via the intermediary. The reduction furnace 112 is further provided with a first gas introduction pipe 118 for supplying hydrogen, hydrazine, ammonia, methane, etc., which are reducing gas. A reducing gas supply source (not shown) is connected to the first gas introduction pipe 118. The valve 120 is installed in the first gas introduction pipe 118, whereby the supply amount of the reducing gas can be controlled.

於第1輸送管116設置有用以供給含硫氣體的第2氣體導入管122。於第2氣體導入管122中介閥124而接續有未圖示的含硫氣體供給源，可藉由閥124調整其供給量。藉由此構造，可使還原性氣體接觸於氯化物之氣體與含硫氣體的混合氣體。第1氣體導入管118、第2氣體導入管122亦可更與惰性氣體 (inert gas)供給源接續，藉此可將作為載體氣體之惰性氣體混合而將還原性氣體或含硫氣體供給至還原爐112。藉由此構造，氯化物之氣體與含硫氣體的混合氣體可供給至還原爐112。雖未圖示，但亦可使第2氣體導入管122接續於還原爐112，將氯化物之氣體與含硫氣體個別供給至還原爐112，而非與第1輸送管116接續。 A second gas introduction pipe 122 for supplying sulfur-containing gas is provided in the first delivery pipe 116. A sulfur-containing gas supply source (not shown) is connected to the second gas introduction pipe 122 via a valve 124, and the supply amount of the sulfur-containing gas can be adjusted by the valve 124. With this structure, the reducing gas can be brought into contact with the mixed gas of the chloride gas and the sulfur-containing gas. The first gas introduction pipe 118 and the second gas introduction pipe 122 may be more compatible with inert gas The (inert gas) supply source is connected, whereby the inert gas as the carrier gas can be mixed to supply the reducing gas or the sulfur-containing gas to the reduction furnace 112. With this structure, the mixed gas of the chloride gas and the sulfur-containing gas can be supplied to the reduction furnace 112. Although not shown, the second gas introduction pipe 122 may be connected to the reduction furnace 112, and the chloride gas and the sulfur-containing gas may be separately supplied to the reduction furnace 112 instead of being connected to the first delivery pipe 116.

在利用加熱器114加熱之還原爐112內，氯化物會透過還原性氣體還原，藉此生成金屬粒子，同時對金屬粒子導入源自含硫氣體的硫。此外，氯化物氣體以將在圖示省略之氯化爐生成者導入而非經單獨分離者為佳。藉由建構此種型態，可連續進行氯化與還原，而能有效率製造金屬粉體。 In the reduction furnace 112 heated by the heater 114, the chloride is reduced by the reducing gas to generate metal particles, and at the same time, sulfur derived from the sulfur-containing gas is introduced into the metal particles. In addition, the chloride gas is preferably introduced into the chlorination furnace that is omitted from the figure rather than separated separately. By constructing this type, chlorination and reduction can be performed continuously, and metal powder can be produced efficiently.

於還原爐112更具備有用以對還原爐112供給冷卻氣體的第3氣體導入管126。第3氣體導入管126以設置於遠離第1輸送管116的位置為佳。舉例而言，在將第1輸送管116設置於還原爐112之上部的情況下，第3氣體導入管126設置於還原爐112之下部。作為冷卻氣體，可使用氮氣或氬氣等惰性氣體，此等氣體之供給源(未圖示)接續於第3氣體導入管126。冷卻氣體的流量可藉由閥128控制。藉由供給冷卻氣體，可控制在還原爐112形成之金屬粒子的成長。金屬粉體係藉由冷卻氣體通過第2輸送管130往分離裝置或回收裝置輸送，並單獨分離、純化。 The reduction furnace 112 is further provided with a third gas introduction pipe 126 for supplying cooling gas to the reduction furnace 112. The third gas introduction pipe 126 is preferably provided at a position away from the first delivery pipe 116. For example, when the first transport pipe 116 is installed in the upper part of the reduction furnace 112, the third gas introduction pipe 126 is installed in the lower part of the reduction furnace 112. As the cooling gas, an inert gas such as nitrogen or argon can be used, and a supply source (not shown) of these gases is connected to the third gas introduction pipe 126. The flow rate of the cooling gas can be controlled by the valve 128. By supplying the cooling gas, the growth of the metal particles formed in the reduction furnace 112 can be controlled. The metal powder system is transported to the separation device or recovery device by the cooling gas through the second delivery pipe 130, and is separated and purified separately.

進行還原時，藉由加熱器114將還原爐112加熱，中介第1輸送管116與第2氣體導入管122將金屬氯化物之氣體 與含硫氣體導進還原爐112，同時通過第1氣體導入管118將還原性氣體供給至還原爐112內。還原爐112之加熱溫度以較金屬之熔點還低為佳，例如選自800℃至1100℃的範圍。藉此，可將在還原爐112生成之金屬做成固體狀的金屬粒子並取出。供給至還原爐112之還原性氣體的量，係使用閥120調整成在化學計量上與所供給之金屬氯化物等量或略為過剩。 During the reduction, the reduction furnace 112 is heated by the heater 114, and the metal chloride gas is transferred between the first conveying pipe 116 and the second gas introduction pipe 122. While the sulfur-containing gas is introduced into the reduction furnace 112, the reducing gas is supplied into the reduction furnace 112 through the first gas introduction pipe 118. The heating temperature of the reduction furnace 112 is preferably lower than the melting point of the metal, for example, selected from the range of 800°C to 1100°C. Thereby, the metal produced in the reduction furnace 112 can be made into solid metal particles and taken out. The amount of the reducing gas supplied to the reduction furnace 112 is adjusted by using the valve 120 to be stoichiometrically equivalent to or slightly surplus to the supplied metal chloride.

作為含硫氣體，係包含選自硫化氫、二氧化硫或鹵化硫之成分的氣體。作為鹵化硫，可列舉：SnCl2(n為2以上之整數)、SF6、SF5Cl、SF5Br等。其中，以處理容易的二氧化硫為佳。含硫氣體的流量，係使用閥124調整成相對於供給至還原爐112之每單位時間自氯化物生成之金屬粉體為0.01重量%以上且1.0重量%以下。 The sulfur-containing gas is a gas containing a component selected from hydrogen sulfide, sulfur dioxide, and sulfur halide. Examples of the sulfur halide include S n Cl 2 (n is an integer of 2 or more), SF 6 , SF 5 Cl, SF 5 Br, and the like. Among them, sulfur dioxide, which is easy to handle, is preferred. The flow rate of the sulfur-containing gas is adjusted using the valve 124 to be 0.01% by weight or more and 1.0% by weight or less with respect to the metal powder generated from the chloride per unit time supplied to the reduction furnace 112.

藉由採用於上已述之方法，可將硫之總體濃度與局部濃度控制於在第1實施型態已述的範圍內，可製造不僅於表面附近，於遠離表面之內部亦以高濃度含有硫的金屬粒子，以及包含金屬粒子的金屬粉體。 By adopting the method described above, the overall concentration and local concentration of sulfur can be controlled within the range described in the first embodiment, and it can be manufactured not only near the surface, but also in the interior away from the surface at a high concentration. Sulfur metal particles, and metal powders containing metal particles.

『實施例』 "Example"

1.實施例1 1. Example 1

在本實施例，揭示應用於第2實施型態已述的製造方法製造金屬粉體之例。 In this embodiment, an example of applying the manufacturing method described in the second embodiment to the production of metal powder is disclosed.

在氯化爐中，使鎳與氯氣反應以使氯化鎳氣體生成，將還原爐112加熱至1100℃，自接續於氯化爐的第1輸送管116 將氯化鎳氣體、係為含硫氣體的二氧化硫氣體及氮氣的混合氣體以2.8m/秒鐘(1100℃換算)的流速導進還原爐112。同時自第1氣體導入管118將氫氣以2.2m/秒鐘(1100℃換算)的流速導進還原爐112。作為冷卻氣體，使用氮氣並自第3氣體導入管126供給。所獲得之鎳粉體(數量平均粒徑190nm)係使用未圖示之生成裝置等來純化。所獲得之鎳粉體的硫之總體濃度為0.15重量%。 In the chlorination furnace, nickel and chlorine gas are reacted to generate nickel chloride gas, and the reduction furnace 112 is heated to 1100°C from the first transfer pipe 116 connected to the chlorination furnace A mixed gas of nickel chloride gas, sulfur dioxide gas which is a sulfur-containing gas, and nitrogen gas is introduced into the reduction furnace 112 at a flow rate of 2.8 m/sec (1100° C. conversion). At the same time, hydrogen gas is introduced into the reduction furnace 112 from the first gas introduction pipe 118 at a flow rate of 2.2 m/sec (calculated at 1100° C.). As the cooling gas, nitrogen gas is used and is supplied from the third gas introduction pipe 126. The obtained nickel powder (number-average particle size 190nm) was purified using a production device not shown in the figure. The overall concentration of sulfur in the obtained nickel powder was 0.15% by weight.

作為相對於此實施例1的比較例1，使用對於在不存在含硫氣體的情況下進行氯化鎳之還原而獲得之鎳粉體進行硫處理而製作的鎳粉體，量測其硫濃度。比較例1之鎳粉體，係藉由在上述實施例中未將含硫氣體導進還原爐112即製作鎳粉體並於之後進行以下之後處理來製作。 As a comparative example 1 relative to this example 1, a nickel powder prepared by sulfur treatment on a nickel powder obtained by reducing nickel chloride in the absence of a sulfur-containing gas was used, and the sulfur concentration was measured . The nickel powder of Comparative Example 1 was produced by preparing the nickel powder without introducing the sulfur-containing gas into the reduction furnace 112 in the above-mentioned embodiment, and then performing the following post-processing.

亦即，對於將在不存在含硫氣體的情況下製作之鎳粉體(數量平均粒徑190nm)純化的過程中獲得之漿液，以硫含有率相對於鎳粉體成為0.15重量%的方式加入硫脲水溶液，攪拌30分鐘。之後，利用氣流乾燥機將漿液乾燥，藉此獲得比較例1的鎳粉體。 That is, the slurry obtained during the purification of nickel powder (number average particle size 190nm) produced in the absence of sulfur-containing gas is added so that the sulfur content relative to the nickel powder becomes 0.15% by weight The thiourea aqueous solution was stirred for 30 minutes. After that, the slurry was dried with an airflow dryer, thereby obtaining the nickel powder of Comparative Example 1.

對於實施例1與比較例1的鎳粉體，使用STEM-EDS自表面沿深度方向量測硫之局部濃度。量測係使用具備能量色散型X射線分光分析器(日本電子股份有限公司製之JED-2300T)的掃描穿透式電子顯微鏡(日本電子股份有限公司製之JEM-2100F)來進行。所獲得之結果揭示於表1與圖2。 For the nickel powders of Example 1 and Comparative Example 1, the local concentration of sulfur was measured from the surface along the depth direction using STEM-EDS. The measurement was performed using a scanning transmission electron microscope (JEM-2100F manufactured by JEOL Ltd.) equipped with an energy dispersive X-ray spectrometer (JED-2300T manufactured by JEOL Ltd.). The results obtained are shown in Table 1 and Figure 2.

Figure 108122839-A0305-02-0013-1
Figure 108122839-A0305-02-0013-1

如表1與圖2所示，可知於比較例1的鎳粉體，其在表面的硫之局部濃度雖較實施例1的鎳粉體還高，但會隨著自表面起算的深度增大--亦即隨著更接近內部--而急劇減少。相對於此，實施例1的鎳粉體可確認到，其在表面的硫之局部濃度雖低，但沿深度方向之減少率小，硫亦分布於鎳粉體內部。在此實施例1，其減半深度為3.2nm。 As shown in Table 1 and Figure 2, it can be seen that in the nickel powder of Comparative Example 1, the local concentration of sulfur on the surface is higher than that of the nickel powder of Example 1, but it increases with the depth from the surface. --That is, it decreases sharply as it gets closer to the inside. In contrast, in the nickel powder of Example 1, it was confirmed that although the local concentration of sulfur on the surface was low, the reduction rate in the depth direction was small, and sulfur was also distributed inside the nickel powder. In this example 1, the halved depth is 3.2 nm.

由此等結果，可知藉由使用本發明之實施型態相關的製造方法，可獲得硫分布至更深之位置的金屬粉體。 From these results, it can be seen that by using the manufacturing method related to the embodiment of the present invention, a metal powder in which sulfur is distributed to a deeper position can be obtained.

2.實施例2 2. Example 2

在本實施例2，針對硫之總體濃度對於燒結起始溫度造成的影響進行研究。應用與實施例1相同的方法，使含硫氣體的流量自1.7m/秒鐘變化至2.2m/秒鐘(1100℃換算)，製作具有各種的硫之總體濃度的鎳粉體。同樣地，使用與於實施例1已述之比較例1相同的方法，使硫脲水溶液的濃度或添加量變化，製作具有各種的硫之總體濃度的鎳粉體作為比較例2。硫之總體 濃度的量測，係以與實施例1相同的方法進行。 In Example 2, the effect of the overall concentration of sulfur on the starting temperature of sintering was studied. Using the same method as in Example 1, the flow rate of the sulfur-containing gas was changed from 1.7 m/sec to 2.2 m/sec (converted at 1100°C) to produce nickel powders having various overall concentrations of sulfur. Similarly, using the same method as that of Comparative Example 1 described in Example 1, the concentration or addition amount of the thiourea aqueous solution was changed to produce nickel powders having various overall concentrations of sulfur as Comparative Example 2. Total Sulfur The measurement of the concentration was carried out in the same way as in Example 1.

燒結起始溫度的量測，係藉由具備加熱台(Gatan公司製，Murano 525 heating stage)的掃描式電子顯微鏡(Hitachi High-Technologies Corporation製之SU-5000)來進行。若要示例具體的方法，首先將金屬粉體成形為ø5mm×1mm的顆粒，接合於加熱台，導進掃描式電子顯微鏡。將加熱台自室溫階段性升溫至800℃，同時以掃描式電子顯微鏡進行觀察。伴隨著升溫，金屬粒子開始燒結，但將視野內之鎳粉體之半數以上燒結時的溫度定為燒結起始溫度。結果揭示於圖3。 The measurement of the sintering start temperature was performed with a scanning electron microscope (SU-5000 manufactured by Hitachi High-Technologies Corporation) equipped with a heating stage (manufactured by Gatan Corporation, Murano 525 heating stage). To illustrate a specific method, first, the metal powder is formed into ø5mm×1mm particles, joined to a heating stage, and guided into a scanning electron microscope. The heating stage was gradually raised from room temperature to 800°C, while observation was carried out with a scanning electron microscope. As the temperature rises, the metal particles start to sinter, but the temperature at which more than half of the nickel powder in the field of view is sintered is set as the sintering start temperature. The results are shown in Figure 3.

在比較例2，可知隨著硫之總體濃度增大，燒結起始溫度上升。然而，亦如於實施例1所述，在比較例2之金屬粉體，因硫未以高濃度分布至金屬粒子之內部，故硫之總體濃度存有上限。恐由於此事，而硫之總體濃度為最大約0.2重量%，燒結起始溫度停留在500℃至600℃左右。 In Comparative Example 2, it can be seen that as the overall concentration of sulfur increases, the sintering start temperature rises. However, as described in Example 1, in the metal powder of Comparative Example 2, since sulfur is not distributed in the metal particles at a high concentration, there is an upper limit on the overall concentration of sulfur. Because of this, the total concentration of sulfur is about 0.2% by weight at the maximum, and the sintering start temperature stays at about 500°C to 600°C.

相對於此，可知實施例2的鎳粉體比起比較例2，燒結起始溫度較高。並且，在實施例2，硫分布至鎳粒子之內部，故若與比較例2的鎳粉體相比，則較可實現高的硫之總體濃度。例如在本實施例2，可獲得硫之總體濃度超過0.2重量%的，甚或具有0.3重量%以上的硫之總體濃度的金屬粉體。由於此事，實施例2的鎳粉體之燒結起始溫度可達成超過600℃，亦達到約700℃。並且，可知在硫之總體濃度為相同的情況下，藉由應用本實施型態之製造方法，可製作更高燒結起始溫度的鎳粉體。 In contrast, it can be seen that the nickel powder of Example 2 has a higher sintering start temperature than that of Comparative Example 2. In addition, in Example 2, sulfur is distributed inside the nickel particles. Therefore, compared with the nickel powder of Comparative Example 2, a higher overall sulfur concentration can be achieved. For example, in Example 2, a metal powder with a total sulfur concentration of more than 0.2% by weight, or even a metal powder with a total sulfur concentration of more than 0.3% by weight, can be obtained. Because of this, the sintering start temperature of the nickel powder of Example 2 can reach more than 600°C and also reach about 700°C. In addition, it can be seen that when the overall concentration of sulfur is the same, by applying the manufacturing method of this embodiment, a nickel powder with a higher sintering start temperature can be manufactured.

此處應注意之點，係在實施例2中若硫之總體濃度成為0.15重量%以上則燒結起始溫度為600℃以上，甚或可以高概率實現超過600℃這點。是故，藉由將金屬粉體中的硫之總體濃度做成0.15重量%以上，即使硫之總體濃度顯著變化，對於燒結起始溫度亦不會表現出影響，可有效抑制燒結起始溫度的變動。換言之，藉由本實施型態之製造方法，能夠提供燒結起始溫度之偏差小的金屬粉體。 The point to be noted here is that if the total concentration of sulfur in Example 2 becomes 0.15 wt% or more, the sintering start temperature is 600° C. or higher, or it can even exceed 600° C. with a high probability. Therefore, by making the total concentration of sulfur in the metal powder more than 0.15 wt%, even if the total concentration of sulfur changes significantly, it will not affect the sintering start temperature, which can effectively suppress the sintering start temperature. change. In other words, with the manufacturing method of this embodiment, it is possible to provide a metal powder with a small deviation of the sintering start temperature.

依據本發明之實施型態，本發明所屬技術領域中具有通常知識者進行適當構成要件的追加、刪除或設計變更者，或者進行工序的追加、省略或條件變更者，只要具備本發明之要旨，亦即為本發明之範圍所包含。 According to the embodiments of the present invention, those with ordinary knowledge in the technical field to which the present invention pertains to add, delete, or change the design of appropriate constituent elements, or to add, omit, or change the conditions of the process, as long as they have the gist of the present invention, That is, it is included in the scope of the present invention.

即使係與藉由於上已述之各實施型態之態樣所帶來之作用效果相異的其他作用效果，對於由本說明書之記載可明瞭者，或在本發明所屬技術領域中具有通常知識者中得輕易預測者，自當理解為藉由本發明所促成者。 Even if it is other effects that are different from the effects brought about by the various implementation modes described above, those who are clear from the description of this specification, or those who have general knowledge in the technical field of the present invention Those who are easy to predict should be understood as those facilitated by the present invention.

Claims (11)

一種金屬粉體，其包含：含有金屬及總體濃度為0.01重量%以上且1.0重量%以下之硫的金屬粒子；其中前述金屬粒子在自表面起算4nm之位置的硫之局部濃度為2原子%以上；前述金屬粒子的數量平均粒徑為50nm以上且400nm以下；在前述金屬粒子之前述表面的硫之前述局部濃度減半的位置存在於自前述表面起算2nm以上且4nm以下的範圍；前述總體濃度與前述局部濃度係分別藉由感應耦合電漿發光分光分析裝置及掃描穿透式電子顯微鏡所具備的能量色散型X射線分光分析器來估計。 A metal powder comprising: metal and metal particles with a total concentration of 0.01% by weight or more and 1.0% by weight or less of sulfur; wherein the local concentration of sulfur in the aforementioned metal particles at a position 4nm from the surface is 2 atomic% or more The number average particle size of the aforementioned metal particles is 50nm or more and 400nm or less; the position where the aforementioned local concentration of sulfur on the aforementioned surface of the aforementioned metal particles is halved exists in the range of 2nm or more and 4nm or less from the aforementioned surface; the aforementioned overall concentration The local concentration and the aforementioned local concentration are respectively estimated by the energy dispersive X-ray spectrometer equipped in the inductively coupled plasma emission spectrometer and the scanning transmission electron microscope. 如請求項1所述之金屬粉體，其中前述金屬粉體之燒結起始溫度為600℃以上。 The metal powder according to claim 1, wherein the sintering start temperature of the metal powder is 600°C or higher. 如請求項1所述之金屬粉體，其中前述金屬係鎳、銅或銀。 The metal powder according to claim 1, wherein the aforementioned metal is nickel, copper or silver. 如請求項1所述之金屬粉體，其中硫之前述局部濃度自前述金屬粒子的前述表面連續減少。 The metal powder according to claim 1, wherein the local concentration of sulfur continuously decreases from the surface of the metal particle. 如請求項1所述之金屬粉體，其中硫分布至自前述金屬粒子的前述表面起算14nm之深度。 The metal powder according to claim 1, wherein the sulfur is distributed to a depth of 14 nm from the surface of the metal particle. 一種製造金屬粉體的方法，其包含：藉由透過氯的金屬之氯化來生成金屬氯化物的氣體；以及 藉由在包含硫之氣體的存在下將係為氣體的前述金屬氯化物還原來生成金屬粒子；其中前述還原係以前述金屬粒子的硫之總體濃度成為0.01重量%以上且1.0重量%以下，前述金屬粒子在自表面起算4nm之位置的硫之局部濃度為2原子%以上，前述金屬粒子的數量平均粒徑為50nm以上且400nm以下，在前述金屬粒子之前述表面的硫之前述局部濃度減半的位置存在於自前述表面起算2nm以上且4nm以下的範圍的方式來進行；前述總體濃度與前述局部濃度係分別藉由感應耦合電漿發光分光分析裝置及掃描穿透式電子顯微鏡所具備的能量色散型X射線分光分析器來估計。 A method of manufacturing metal powder, comprising: generating a gas of metal chloride by chlorination of a metal that permeates chlorine; and Metal particles are produced by reducing the aforementioned metal chloride, which is a gas, in the presence of a gas containing sulfur; wherein the aforementioned reduction system is such that the total concentration of sulfur in the aforementioned metal particles becomes 0.01% by weight or more and 1.0% by weight or less, the aforementioned The local concentration of sulfur at a position 4nm from the surface of the metal particles is 2 atomic% or more, the number average particle size of the metal particles is 50 nm or more and 400 nm or less, and the local concentration of sulfur on the surface of the metal particles is halved The position of is present in the range of 2nm or more and 4nm or less from the aforementioned surface; the aforementioned overall concentration and the aforementioned local concentration are respectively determined by the energy of the inductively coupled plasma emission spectrometer and scanning transmission electron microscope Dispersive X-ray spectroscopic analyzer to estimate. 如請求項6所述之方法，其中前述還原係在不單獨分離前述金屬氯化物的情況下進行。 The method according to claim 6, wherein the aforementioned reduction is performed without separate separation of the aforementioned metal chloride. 如請求項6所述之方法，其中前述包含硫之氣體係包含二氧化硫之氣體。 The method according to claim 6, wherein the aforementioned sulfur-containing gas system contains sulfur dioxide-containing gas. 如請求項6所述之方法，其中前述還原係以硫之前述局部濃度自前述金屬粒子的前述表面連續減少的方式進行。 The method according to claim 6, wherein the reduction is performed in a manner that the local concentration of sulfur continuously decreases from the surface of the metal particle. 如請求項6所述之方法，其中前述還原係以硫分布至自前述金屬粒子的前述表面起算14nm之深度的方式進行。 The method according to claim 6, wherein the reduction is performed in a manner that sulfur is distributed to a depth of 14 nm from the surface of the metal particle. 如請求項6所述之方法，其中前述還原係藉由將前述金屬氯化物之前述氣體及含硫之前述氣體的混合氣體與還原性氣體處理來進行。 The method according to claim 6, wherein the reduction is performed by treating a mixed gas of the metal chloride gas and the sulfur-containing gas with a reducing gas.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005008981A (en) * 2003-06-16 2005-01-13 Jfe Mineral Co Ltd Nickel alloy powder, and its production method
CN1968773A (en) * 2004-06-16 2007-05-23 东邦钛株式会社 Nickel powder and manufacturing method thereof
TW201129434A (en) * 2009-09-24 2011-09-01 Sumitomo Metal Mining Co Nickel powder and production method thereof
US20160203911A1 (en) * 2013-08-13 2016-07-14 Jx Nippon Mining & Metals Corporation Surface-treated metal powder, and method for producing same
TW201736617A (en) * 2016-01-12 2017-10-16 東邦鈦股份有限公司 Nickel powder

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69735130T2 (en) * 1996-12-02 2006-08-31 Toho Titanium Co., Ltd., Chigasaki METHOD AND DEVICE FOR PRODUCING METAL POWDERS
JPH1180816A (en) 1997-09-10 1999-03-26 Sumitomo Metal Mining Co Ltd Nickel powder for conductive paste and its production
JP4611464B2 (en) * 1998-06-12 2011-01-12 東邦チタニウム株式会社 Method for producing metal powder
JP3492672B1 (en) * 2002-05-29 2004-02-03 東邦チタニウム株式会社 Metal powder manufacturing method and manufacturing apparatus
KR100671250B1 (en) * 2002-09-30 2007-01-19 도호 티타늄 가부시키가이샤 Method and apparatus for producing metal powder
JP4392283B2 (en) * 2004-04-12 2009-12-24 日機装株式会社 Carbon nanofiber manufacturing method and carbon nanofiber post-processing method
US7344584B2 (en) * 2004-09-03 2008-03-18 Inco Limited Process for producing metal powders
JP5067312B2 (en) 2008-08-18 2012-11-07 住友金属鉱山株式会社 Nickel powder and its manufacturing method
JP2010043345A (en) * 2008-08-18 2010-02-25 Sumitomo Electric Ind Ltd Nickel powder or alloy powder composed mainly of nickel and method for producing the same, conductive paste, and multilayer ceramic capacitor
JP5768322B2 (en) * 2010-03-19 2015-08-26 住友金属鉱山株式会社 Nickel fine powder and method for producing the same
CN101857276A (en) * 2010-06-21 2010-10-13 中国科学院苏州纳米技术与纳米仿生研究所 Method for preparing general nano metal sulphide
KR20120049026A (en) * 2010-11-08 2012-05-16 삼성전기주식회사 A nickel powder coated by sulfur, a paste for inner electrode, a laminated ceramic electronic parts by using the same and a process thereof
TWI597112B (en) * 2012-04-06 2017-09-01 東邦鈦股份有限公司 Nickel metal powder and process for production thereof
JP5962562B2 (en) 2013-03-22 2016-08-03 住友金属鉱山株式会社 Nickel powder and its manufacturing method
JP5826204B2 (en) 2013-03-26 2015-12-02 大陽日酸株式会社 Method for producing metal fine particles
CN106457379B (en) * 2014-04-08 2020-12-08 东邦钛株式会社 Nickel powder
JP6746321B2 (en) * 2016-02-05 2020-08-26 株式会社村田製作所 Ni powder, method of manufacturing Ni powder, internal electrode paste, and electronic component
CN107768609A (en) * 2016-08-16 2018-03-06 中国科学院上海硅酸盐研究所 A kind of na chloride positive electrode for battery material and its preparation method and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005008981A (en) * 2003-06-16 2005-01-13 Jfe Mineral Co Ltd Nickel alloy powder, and its production method
CN1968773A (en) * 2004-06-16 2007-05-23 东邦钛株式会社 Nickel powder and manufacturing method thereof
TW201129434A (en) * 2009-09-24 2011-09-01 Sumitomo Metal Mining Co Nickel powder and production method thereof
US20160203911A1 (en) * 2013-08-13 2016-07-14 Jx Nippon Mining & Metals Corporation Surface-treated metal powder, and method for producing same
TW201736617A (en) * 2016-01-12 2017-10-16 東邦鈦股份有限公司 Nickel powder

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