TW201542832A - Nickel powder - Google Patents

Nickel powder Download PDF

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TW201542832A
TW201542832A TW104108717A TW104108717A TW201542832A TW 201542832 A TW201542832 A TW 201542832A TW 104108717 A TW104108717 A TW 104108717A TW 104108717 A TW104108717 A TW 104108717A TW 201542832 A TW201542832 A TW 201542832A
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gas
nickel powder
nickel
sulfur
powder
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TW104108717A
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TWI638051B (en
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Hirosuke Rokkaku
Tsuyoshi Asai
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Toho Titanium Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16Metallic particles coated with a non-metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00Metallic composition of the powder or its coating
    • B22F2301/15Nickel or cobalt

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Ceramic Capacitors (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

Provided is a nickel powder having excellent sintering properties in a manufacturing process for laminated ceramic capacitors, and capable of preventing the occurrence of defects in laminated ceramic capacitors such as cracking in an electrode layer and separating between the electrode layer and a dielectric layer. The nickel powder contains 1.0-5.0 mass% of sulfur, and 50% of particles therein have a size of less than or equal to 0.09 [mu]m.

Description

鎳粉末 Nickel powder

本發明係有關適合使用於電子零件等之導電膏用途的鎳粉末,特別是有關用在疊層陶瓷電容器的內部電極用途之導電膏而適合的鎳粉末。 The present invention relates to a nickel powder suitable for use as a conductive paste for electronic parts and the like, and more particularly to a nickel powder suitable for use as a conductive paste for internal electrode use of a laminated ceramic capacitor.

由於以智慧型手機、平板終端為代表的行動通信終端係伴隨著多機能化、高機能化而消耗電力變大,電池的容量亦變大,因此在有限的框體內搭載有電子零件的主電路板有變小的傾向。另一方面,搭載於主電路板的電子零件數有增加的傾向。因此,搭載於主電路板的疊層陶瓷電容器被要求要小型且大容量。 The mobile communication terminal represented by the smart phone and the tablet terminal is equipped with a large number of functions and high power consumption, and the power consumption is increased, and the capacity of the battery is also increased. Therefore, the main circuit of the electronic component is mounted in a limited casing. The board has a tendency to become smaller. On the other hand, the number of electronic components mounted on the main circuit board tends to increase. Therefore, the multilayer ceramic capacitor mounted on the main circuit board is required to be small and large in capacity.

伴隨著疊層陶瓷電容器的小型化、大容量化,疊層陶瓷電容器的內部電極亦被要求薄層化、低電阻化等。因此,被使用在內部電極的鎳粉末,其一次粒子的個數50%直徑當然是0.3μm以下,且被要求為0.2μm以下,甚至是0.1μm以下的超微粉末。 With the miniaturization and increase in capacity of the multilayer ceramic capacitor, the internal electrodes of the multilayer ceramic capacitor are also required to have a thin layer and a low resistance. Therefore, the nickel powder used in the internal electrode has a diameter of 50% of the primary particles of 0.3 μm or less, and is required to be 0.2 μm or less, or even 0.1 μm or less.

一般而言,與用在疊層陶瓷電容器的介電體之陶瓷粉末相較下,鎳粉末的燒結開始溫度低,熱收縮大。因此,在疊層陶瓷電容器的製造步驟中進行燒成時,有所謂在電極層與介電體層之間的剝離或在電極層的裂 痕產生之類缺陷容易產生的問題。又,若鎳粉末中存在有超過一次粒子的個數50%直徑3倍的粗大粒子或由粒子彼此凝結而成的凝集粒子,則電極層表面的凹凸會變大,而成為電極層間的短路或疊層陶瓷電容器的耐電壓降低的原因。 In general, compared with the ceramic powder used for the dielectric body of the laminated ceramic capacitor, the nickel powder has a low sintering start temperature and a large heat shrinkage. Therefore, when firing is performed in the manufacturing step of the laminated ceramic capacitor, there is a so-called peeling between the electrode layer and the dielectric layer or cracking in the electrode layer. Problems such as defects are easy to produce. In addition, when there are coarse particles in which the number of primary particles exceeds 50% of the diameter of the primary particles or the aggregated particles which are condensed by the particles, the unevenness on the surface of the electrode layer becomes large, and the electrode layer is short-circuited or The reason why the withstand voltage of the laminated ceramic capacitor is lowered.

在因應上述燒成時所產生的缺陷之手段方面,例如日本特開平11-80817號公報中揭示一種含硫黃率是0.02~1.0重量%的鎳粉末。又,日本特開2008-223145號公報中揭示一種在表面上形成有硫化鎳或硫酸鎳的被覆膜之鎳粉末。 For example, a nickel powder having a sulfur content of 0.02 to 1.0% by weight is disclosed in Japanese Laid-Open Patent Publication No. Hei 11-80817. Further, Japanese Laid-Open Patent Publication No. 2008-223145 discloses a nickel powder in which a coating film of nickel sulfide or nickel sulfate is formed on the surface.

然而,上述習知技術中,若鎳粉末的個數50%直徑小於0.1μm,則防止鎳粉末在燒成時產生缺陷的效果不充分,而被要求再改善。 However, in the above-mentioned conventional technique, if the number of nickel powders is 50% and the diameter is less than 0.1 μm, the effect of preventing the nickel powder from being defective at the time of firing is insufficient, and it is required to be further improved.

因此,本發明之目的在於獲得一種個數50%直徑小於0.1μm的鎳粉末,其在疊層陶瓷電容器的製造步驟中具有優異的燒結特性,可防止疊層陶瓷電容器的電極層與介電體層之間的剝離或電極層的裂痕之類缺陷的產生。 Accordingly, it is an object of the present invention to obtain a nickel powder having a diameter of 50% and a diameter of less than 0.1 μm, which has excellent sintering characteristics in the manufacturing step of the laminated ceramic capacitor, and can prevent the electrode layer and the dielectric layer of the laminated ceramic capacitor. The generation of defects such as peeling or cracking of the electrode layer.

再者,本發明之目的在於提供一種個數50%直徑小於0.1μm的鎳粉末,其在疊層陶瓷電容器的製造步驟中可抑制凝集粒子的產生,可防止電極層間的短路或耐電壓降低之類不良情況的發生。 Further, an object of the present invention is to provide a nickel powder having a diameter of 50% and a diameter of less than 0.1 μm, which can suppress the generation of aggregated particles in the manufacturing step of the laminated ceramic capacitor, and can prevent short circuit or voltage withstand between the electrode layers. The occurrence of a bad situation.

本發明的鎳粉末之特徵為,含有1.0~5.0質量%的硫黃,個數50%直徑是0.09μm以下。 The nickel powder of the present invention is characterized in that it contains 1.0 to 5.0% by mass of sulfur, and the number of 50% is 0.09 μm or less.

依據本發明,透過含有1.0~5.0質量%的硫黃,即使個數50%直徑是0.09μm以下亦可改善鎳粉末的燒結舉動(behavior),可解決因燒結所致疊層陶瓷電容器的特性劣化等之問題點。 According to the present invention, by containing 1.0 to 5.0% by mass of sulfur, even if the number is 50% and the diameter is 0.09 μm or less, the sintering behavior of the nickel powder can be improved, and the deterioration of the characteristics of the laminated ceramic capacitor due to sintering can be solved. Wait for the problem.

依據本發明的鎳粉末,得以在疊層陶瓷電容器的製造步驟中具有優異的燒結特性,可防止在疊層陶瓷電容器的電極層與介電體層之間的剝離或電極層的裂痕之類缺陷的產生。再者,本發明的鎳粉末可抑制凝集粒子的產生,可抑制在電極層間的短路或耐電壓降低之類不良情況的發生。 According to the nickel powder of the present invention, it is possible to have excellent sintering characteristics in the manufacturing steps of the laminated ceramic capacitor, and it is possible to prevent peeling or cracking of the electrode layer between the electrode layer and the dielectric layer of the laminated ceramic capacitor. produce. Further, the nickel powder of the present invention can suppress the generation of aggregated particles, and can suppress the occurrence of defects such as short-circuiting between the electrode layers and reduction in withstand voltage.

10‧‧‧還原爐 10‧‧‧Reduction furnace

11‧‧‧氯化鎳氣體噴嘴 11‧‧‧NiChin gas nozzle

12‧‧‧氫氣噴嘴 12‧‧‧ Hydrogen Nozzle

13‧‧‧冷卻氣體噴嘴 13‧‧‧Cooling gas nozzle

14‧‧‧回收管 14‧‧‧Recycling tube

F‧‧‧光焰 F‧‧‧光焰

P‧‧‧鎳粉末 P‧‧‧ Nickel powder

第1圖係顯示在實施例及比較例所使用之鎳粉末製造裝置的概略圖。 Fig. 1 is a schematic view showing a nickel powder producing apparatus used in the examples and comparative examples.

本發明的鎳粉末包含依各種製造方法所製造之鎳粉末與以鎳為主成分的鎳合金粉末。而關於鎳合金粉末方面,有在鎳中添加有用以賦與耐氧化性等或提升導電係數之鉻、矽、硼、磷或稀土類元素、貴金屬元素等所成的合金粉末。 The nickel powder of the present invention contains nickel powder produced by various production methods and nickel alloy powder containing nickel as a main component. As for the nickel alloy powder, an alloy powder obtained by adding chromium, bismuth, boron, phosphorus or a rare earth element or a noble metal element which is useful for imparting oxidation resistance or the like to increase the conductivity is added to nickel.

本發明的鎳粉末的個數50%直徑為0.09μm以下。本發明的鎳粉末的個數50%直徑之下限並未特別限制,但從通常的鎳粉末之生產成本、用途的觀點,以0.01μm以上為較佳。 The number of nickel powders of the present invention is 50% and the diameter is 0.09 μm or less. The lower limit of the 50% diameter of the nickel powder of the present invention is not particularly limited, but is preferably 0.01 μm or more from the viewpoint of the production cost and use of the usual nickel powder.

本發明的鎳粉末的個數50%直徑,係利用掃瞄電子顯微鏡拍攝鎳粉末的照片,使用影像分析軟體從該照片測定約1,000個粒子的粒徑,由所獲得之鎳粉末的粒度分布,算出其個數50%直徑者。在此情況,粒徑係將粒子包入之最小圓的直徑。 The number of nickel powders of the present invention is 50% by diameter, and a photograph of nickel powder is taken by a scanning electron microscope, and the particle size of about 1,000 particles is measured from the photograph using an image analysis software, and the particle size distribution of the obtained nickel powder is Calculate the number of 50% of the diameter. In this case, the particle size is the diameter of the smallest circle in which the particles are enclosed.

本發明的鎳粉末係透過含硫黃1.0~5.0重量%。透過將硫黃濃度設成1.0重量%以上,可改善鎳粉末的燒結舉動。另一方面,若硫黃濃度超過5.0重量%,則會發生在燒結時產生腐蝕性氣體而使疊層陶瓷電容器的特性劣化等之問題。鎳粉末中的硫黃濃度更佳為1.2~4.0重量%,再佳為1.5~3.0重量%。 The nickel powder of the present invention transmits 1.0 to 5.0% by weight of sulfur-containing yellow. By setting the sulfur concentration to 1.0% by weight or more, the sintering behavior of the nickel powder can be improved. On the other hand, when the sulfur concentration exceeds 5.0% by weight, there is a problem that a corrosive gas is generated during sintering to deteriorate the characteristics of the laminated ceramic capacitor. The sulfur concentration in the nickel powder is more preferably from 1.2 to 4.0% by weight, still more preferably from 1.5 to 3.0% by weight.

又,本發明的鎳粉末,其存在於粉末表面之硫黃中以硫酸離子存在的硫黃與以硫化物存在的硫黃之莫耳比(硫酸離子/硫化物離子比)是以0.10以下為較佳,若為0.05以下則更佳。透過將以硫酸離子存在的硫黃與以硫化物離子存在的硫黃之莫耳比設為上述範圍,可防止在製造鎳粉末膏時產生凝集粒子。此外,鎳粉末表面的以硫酸離子存在的硫黃與以硫化物離子存在的硫黃之比(硫酸離子/硫化物離子比)係從使用X射線光電分光儀所測定之S2p光譜的168eV的峰值與162eV的峰值之強度比算出。 Further, in the nickel powder of the present invention, the sulfur present in the sulfur on the surface of the powder, the sulfur present in the sulfuric acid ion, and the molar ratio of the sulfur in the sulfide (sulfuric acid/sulfide ion ratio) are 0.10 or less. Preferably, it is more preferably 0.05 or less. By setting the molar ratio of sulfur present in the presence of sulfate ions to sulfur in the presence of sulfide ions to the above range, generation of aggregated particles during the production of the nickel powder paste can be prevented. Further, the ratio of sulfur in the presence of sulfate ions on the surface of the nickel powder to sulfur in the presence of sulfide ions (sulfate ion/sulfide ion ratio) is 168 eV from the S 2p spectrum measured by an X-ray photoelectron spectrometer. The ratio of the peak value to the peak intensity of 162 eV is calculated.

又,本發明的鎳粉末,其鎳粉末中所含具有個數50%直徑3倍以上的粒徑之粒子(以下,有時記載為「粗大粒子」)的存在率以個數基準計是以100ppm以下為較佳,若為50ppm以下則更佳。藉由將粒度分布設在 此範圍,在製造疊層陶瓷電容器時可使電極層平滑。此外,粗大粒子的存在率之評價,係與前述同樣地利用掃瞄電子顯微鏡拍攝鎳粉末的照片,使用影像分析軟體從該照片計數在約100,000個粒子當中粒徑超過前述求得之個數50%直徑3倍的粒子數而算出。 In addition, the nickel powder of the present invention has a particle diameter of particles having a particle diameter of three times or more and three times or more (hereinafter referred to as "coarse particles") in the nickel powder. 100 ppm or less is preferable, and if it is 50 ppm or less, it is more preferable. By setting the particle size distribution In this range, the electrode layer can be made smooth when manufacturing a laminated ceramic capacitor. Further, in the evaluation of the existence rate of the coarse particles, a photograph of the nickel powder was taken by a scanning electron microscope in the same manner as described above, and the image analysis software used the image analysis software to count the number of particles in the range of about 100,000 particles from the photograph. Calculated by the number of particles having a diameter of 3 times.

本發明的鎳粉末係例如能以氣相法或液相法等已知的方法製造。特別是透過使氯化鎳氣體與還原性氣體接觸而生成鎳粉末的氣相還原法、或將熱分解性的鎳化合物噴霧而進行熱分解的噴霧熱分解法,在可容易地控制要生成的金屬微粉末之粒徑,進而可有效率地製造球狀的粒子之點而言是較佳的。特別是使氯化鎳氣體與還原性氣體接觸的氣相還原法,從可精密地控制要生成的鎳粉末的粒徑,進而可防止粗大粒子產生之點而言是較佳的。 The nickel powder of the present invention can be produced, for example, by a known method such as a vapor phase method or a liquid phase method. In particular, a vapor phase reduction method in which nickel powder gas is brought into contact with a reducing gas to form a nickel powder, or a spray pyrolysis method in which a thermally decomposable nickel compound is sprayed and thermally decomposed is easily controlled to be generated. It is preferable that the particle diameter of the metal fine powder is further capable of efficiently producing spherical particles. In particular, a gas phase reduction method in which a nickel chloride gas is brought into contact with a reducing gas is preferable from the viewpoint of precisely controlling the particle diameter of the nickel powder to be produced and preventing the generation of coarse particles.

氣相還原法係使氣化的氯化鎳氣體與氫等之還原性氣體反應。在此情況亦可加熱固體的氯化鎳並使之蒸發而生成氯化鎳氣體。然而,若考慮到防止氯化鎳氧化或吸濕、及能源效率,則較有利係:使金屬鎳接觸氯氣而使之連續地產生氯化鎳氣體,並將此氯化鎳氣體直接供給到還原步驟,接著使之與還原性氣體接觸而將氯化鎳氣體連續地還原而製造鎳微粉末之方法。 The gas phase reduction method reacts a vaporized nickel chloride gas with a reducing gas such as hydrogen. In this case, the solid nickel chloride can also be heated and evaporated to form nickel chloride gas. However, if it is considered to prevent oxidation or moisture absorption of nickel chloride, and energy efficiency, it is advantageous to contact the metal nickel with chlorine gas to continuously generate nickel chloride gas, and directly supply the nickel chloride gas to the reduction. The step of subsequently producing a nickel fine powder by continuously reducing the nickel chloride gas by bringing it into contact with a reducing gas.

使用在將鎳作為主成分的合金粉末的製造方法之情況的氯化鎳氣體以外的氣體,可例舉:三氯化矽(III)氣體、四氯化矽(IV)氣體、單矽烷氣體、氯化銅(I)氣體、氯化銅(II)氣體、氯化銀氣體、氯化鉬氣體(III) 氣體、氯化鉬(V)氣體、氯化鐵(II)氣體、氯化鐵(III)氣體、氯化鉻(III)氣體、氯化鉻(VI)氣體、氯化鎢(II)氣體、氯化鎢(III)氣體、氯化鎢(IV)氣體、氯化鎢(V)氣體、氯化鎢(VI)氣體、氯化鉭(III)氣體、氯化鉭(V)氣體、氯化鈷氣體、氯化錸(III)氣體、氯化錸(IV)氣體、氯化錸(V)氣體、乙硼烷氣體、磷氣體等及此等的混合氣體。 Examples of the gas other than the nickel chloride gas in the case of the method for producing an alloy powder containing nickel as a main component include ruthenium (III) chloride gas, ruthenium tetrachloride (IV) gas, and monodecane gas. Copper (I) chloride, copper (II) chloride, silver chloride, and molybdenum chloride (III) Gas, molybdenum chloride (V) gas, iron (II) chloride gas, iron (III) chloride gas, chromium (III) chloride gas, chromium (VI) chloride gas, tungsten (II) chloride gas, Tungsten (III) chloride gas, tungsten (IV) chloride gas, tungsten (V) chloride gas, tungsten (VI) chloride gas, ruthenium (III) chloride gas, ruthenium chloride (V) gas, chlorination Cobalt gas, ruthenium (III) chloride gas, ruthenium (IV) chloride gas, ruthenium (V) chloride gas, diborane gas, phosphorus gas, and the like, and a mixed gas thereof.

又,還原性氣體,可例舉:氫氣、硫化氫氣體、氨氣、一氧化碳氣體、甲烷氣體及此等的混合氣體。特佳為氫氣、硫化氫氣體、氨氣、及此等的混合氣體。 Further, the reducing gas may, for example, be hydrogen gas, hydrogen sulfide gas, ammonia gas, carbon monoxide gas, methane gas or a mixed gas thereof. Particularly preferred are hydrogen, hydrogen sulfide gas, ammonia gas, and a mixed gas thereof.

在利用氣相還原反應之鎳粉末的製造過程中,氯化鎳氣體與還原性氣體接觸的瞬間會生成鎳原子,而藉由鎳原子彼此衝撞、凝集,使鎳粒子生成並成長。而且,會依據在還原步驟的氯化鎳氣體的分壓或溫度等之條件而決定生成之鎳粉末的粒徑。依據上述鎳粉末的製造方法,因為會產生對應於氯氣的供給量之量的氯化鎳氣體,故藉由控制氯氣的供給量,可調整供給至還原步驟之氯化鎳氣體的量,藉此可控制所生成之鎳粉末的粒徑。 In the production process of the nickel powder by the vapor phase reduction reaction, nickel atoms are generated at the moment of contact between the nickel chloride gas and the reducing gas, and the nickel atoms are collided and aggregated to form and grow the nickel particles. Further, the particle diameter of the produced nickel powder is determined depending on the conditions of the partial pressure or temperature of the nickel chloride gas in the reduction step. According to the method for producing a nickel powder, since the amount of nickel chloride gas corresponding to the supply amount of chlorine gas is generated, the amount of the nickel chloride gas supplied to the reduction step can be adjusted by controlling the supply amount of the chlorine gas. The particle size of the produced nickel powder can be controlled.

再者,因為氯化鎳氣體係由氯氣與金屬之反應而產生,故不同於由固體氯化鎳之加熱蒸發而產生氯化鎳氣體的方法,不僅能減少載氣的使用,亦可依製造條件而不使用。因此,氣相還原反應較能因載氣的使用量減低及其所伴隨之加熱能源減低而謀求製造成本的削減。 Furthermore, since the nickel chloride gas system is produced by the reaction of chlorine gas and metal, the method of generating nickel chloride gas by heating and evaporation by solid nickel chloride can not only reduce the use of carrier gas, but also manufacture. Conditions are not used. Therefore, the gas phase reduction reaction can reduce the manufacturing cost due to the decrease in the amount of carrier gas used and the accompanying reduction in heating energy.

又,透過將非活性氣體混合於在氯化步驟產生的氯化鎳氣體,可控制在還原步驟中之氯化鎳氣體的分壓。如此,透過控制氯氣的供給量或供給至還原步驟之氯化鎳氣體的分壓,可控制鎳粉末的粒徑,可控制粒徑的不均,同時並可任意地設定粒徑。 Further, by mixing the inert gas with the nickel chloride gas generated in the chlorination step, the partial pressure of the nickel chloride gas in the reduction step can be controlled. Thus, by controlling the supply amount of chlorine gas or the partial pressure of the nickel chloride gas supplied to the reduction step, the particle diameter of the nickel powder can be controlled, the unevenness of the particle diameter can be controlled, and the particle diameter can be arbitrarily set.

依據上述氣相還原法之鎳粉末的製造條件係以個數50%直徑成為0.09μm以下之方式作任意設定,但例如是出發原料的金屬鎳之粒徑係以約5~20mm的粒狀、塊狀、板狀等較佳,又,其純度係以概略是99.5%以上較佳。將此金屬鎳先與氯氣反應而生成氯化鎳氣體,為使反應充分進行,那時的溫度係設為800℃以上且設為鎳的熔點1453℃以下。若考慮反應速度與塩化爐的耐久性,則實用上以900℃~1100℃的範圍較佳。 The production conditions of the nickel powder according to the vapor phase reduction method are arbitrarily set so that the number of diameters is 50% and the diameter is 0.09 μm or less. For example, the particle diameter of the metallic nickel of the starting material is about 5 to 20 mm. The block shape, the plate shape, and the like are preferable, and the purity thereof is preferably 99.5% or more. This metal nickel is first reacted with chlorine gas to form a nickel chloride gas, and in order to sufficiently carry out the reaction, the temperature at that time is 800 ° C or higher and the melting point of nickel is 1453 ° C or lower. In consideration of the reaction rate and the durability of the crucible furnace, it is preferably in the range of 900 ° C to 1100 ° C.

接著,將此氯化鎳氣體直接供給到還原步驟,使之與氫氣等之還原性氣體接觸反應。那時,將氯化鎳氣體以適宜的氬、氮等之非活性氣體稀釋可控制氯化鎳氣體的分壓。透過控制氯化鎳氣體的分壓,可控制在還原部生成之金屬粉末的粒度分布等之品質。藉此可任意地設定所生成的金屬粉末之品質,同時並可使品質穩定。通常,為獲得個數50%直徑是0.09μm以下的鎳粉末,係將氯化鎳氣體的分壓控制成30kPa以下。還原反應的溫度只要是足以完成反應的溫度以上即可。因為生成固體狀的鎳粉末之處理較為容易,故設為鎳的熔點以下較佳,若考慮經濟性則900℃~1100℃是實用的。 Next, this nickel chloride gas is directly supplied to a reduction step, and is brought into contact with a reducing gas such as hydrogen to react. At that time, the partial pressure of the nickel chloride gas can be controlled by diluting the nickel chloride gas with an inert gas such as argon or nitrogen. By controlling the partial pressure of the nickel chloride gas, the quality of the particle size distribution of the metal powder generated in the reducing portion can be controlled. Thereby, the quality of the produced metal powder can be arbitrarily set, and the quality can be stabilized. Usually, in order to obtain a nickel powder having a diameter of 50% and a diameter of 0.09 μm or less, the partial pressure of the nickel chloride gas is controlled to 30 kPa or less. The temperature of the reduction reaction may be at least a temperature sufficient to complete the reaction. Since the treatment for forming a solid nickel powder is relatively easy, it is preferably set to be equal to or lower than the melting point of nickel, and 900 to 1100 ° C is practical in consideration of economy.

如此生成經還原反應後的鎳粉末之後,冷卻所生成之鎳粉末。為了防止在冷卻之際因所生成的鎳之一次粒子彼此凝集而生成二次粒子,俾獲得期望的粒徑之鎳粉末,以透過吹入氮氣等之非活性氣體將還原反應終了之1000℃附近的氣體流急速冷卻至400~800℃程度較為理想。之後,將所生成的鎳粉末,例如利用袋式過濾器等分離、回收。 After the nickel powder after the reduction reaction is thus formed, the produced nickel powder is cooled. In order to prevent the primary particles of the generated primary particles from agglomerating to form secondary particles during cooling, the nickel powder having a desired particle diameter is obtained, and the reduction reaction is terminated by 1000 ° C by blowing an inert gas such as nitrogen gas. The gas flow is rapidly cooled to a temperature of 400 to 800 ° C. Thereafter, the produced nickel powder is separated and recovered, for example, by a bag filter or the like.

在利用噴霧熱分解法之鎳粉末的製造方法中,係將熱分解性的鎳化合物作為原料。具體言之,含有硝酸鹽、硫酸鹽、氧硝酸鹽、氧硫酸鹽、氯化物、銨錯合物、磷酸鹽、羧酸鹽、烷氧化合物等之1種或2種以上。將含有此鎳化合物的溶液進行噴霧而製作微細的液滴。這時的溶媒是使用水、乙醇、丙酮、乙醚等。又,噴霧的方法係利用超音波或雙層噴射噴嘴等之噴霧方法進行。照這樣形成微細的液滴,並以高溫加熱,而將金屬化合物熱分解,生成鎳粉末。此時的加熱溫度係所使用之特定的鎳化合物會熱分解的溫度以上,較佳為金屬的熔點附近。 In the method for producing a nickel powder by a spray pyrolysis method, a thermally decomposable nickel compound is used as a raw material. Specifically, it may contain one or more of a nitrate, a sulfate, an oxynitrate, an oxysulfate, a chloride, an ammonium complex, a phosphate, a carboxylate, and an alkoxide. The solution containing this nickel compound was sprayed to prepare fine droplets. The solvent at this time is water, ethanol, acetone, diethyl ether or the like. Further, the spraying method is carried out by a spraying method such as an ultrasonic wave or a double jet nozzle. Fine droplets are formed in this manner, and heated at a high temperature to thermally decompose the metal compound to form a nickel powder. The heating temperature at this time is preferably higher than the temperature at which the specific nickel compound used is thermally decomposed, and is preferably near the melting point of the metal.

在利用液相法之鎳粉末的製造方法中,係將含硫酸鎳、氯化鎳或鎳錯合物的鎳水溶液添加於氫氧化鈉等之鹼金屬氫氧化物中等使之接觸而生成鎳氫氧化物,接著以聯胺等之還原劑還原鎳氫氧化物而獲得金屬鎳粉末。如此生成的金屬鎳粉末為獲得均一的粒子而視需要進行破碎處理。 In the method for producing a nickel powder by a liquid phase method, a nickel aqueous solution containing nickel sulfate, nickel chloride or a nickel complex is added to an alkali metal hydroxide such as sodium hydroxide to form a nickel-hydrogen. The oxide is then reduced with a reducing agent such as hydrazine to obtain a metallic nickel powder. The metal nickel powder thus produced is subjected to a crushing treatment as needed to obtain uniform particles.

為了去除殘留的原料,按以上的方法獲得之鎳粉末係以分散於液相中並進行洗淨較佳。例如,係使按以上的方法獲得之鎳粉末在經控制pH、溫度之特定條件下懸浮於碳酸水溶液中而進行處理。透過以碳酸水溶液進行處理,附著在鎳粉末的表面的鹽等之雜質會被充分去除,且因存在於鎳粉末的表面之氫氧化鎳等氫氧化物或粒子彼此的摩擦等而自表面離開所形成之微粒子會被去除,故表面可形成均一的氧化鎳被膜。就利用碳酸水溶液的處理方法而言,有將鎳粉末與碳酸水溶液混合的方法,或於以純水將鎳粉末暫時洗淨後的水漿中吹入碳酸氣體,或於以純水將鎳粉末暫時洗淨後的水漿中添加碳酸水溶液作處理亦可。 In order to remove residual raw materials, the nickel powder obtained by the above method is preferably dispersed in a liquid phase and washed. For example, the nickel powder obtained by the above method is treated by suspending in an aqueous solution of carbonic acid under specific conditions of controlled pH and temperature. By treating with a carbonated aqueous solution, impurities such as salts adhering to the surface of the nickel powder are sufficiently removed, and the hydroxide or particles such as nickel hydroxide present on the surface of the nickel powder are separated from the surface by friction or the like. The formed fine particles are removed, so that the surface can form a uniform nickel oxide film. In the treatment method using the aqueous solution of carbonic acid, there is a method of mixing nickel powder with an aqueous solution of carbonic acid, or blowing carbon dioxide gas into a water slurry in which nickel powder is temporarily washed with pure water, or nickel powder in pure water. It is also possible to add an aqueous solution of carbonic acid to the water slurry after the temporary washing.

使本發明的鎳粉末含有硫黃之方法未特別限定,例如可採用以下的方法。 The method of containing the sulfur in the nickel powder of the present invention is not particularly limited, and for example, the following method can be employed.

(1)上述還原反應中添加含硫黃氣體之方法 (1) Method for adding sulfur-containing gas in the above reduction reaction

(2)使鎳粉末與含硫黃氣體接觸處理之方法 (2) Method for contacting nickel powder with sulfur-containing gas

(3)將鎳粉末與固體的含硫黃化合物以乾式混合之方法 (3) a method of dry mixing nickel powder with solid sulfur-containing yellow compound

(4)於液相中分散著鎳粉末的漿液中添加含硫黃化合物溶液之方法 (4) A method of adding a sulfur-containing compound solution to a slurry in which a nickel powder is dispersed in a liquid phase

(5)於液相中分散著鎳粉末的漿液中使含硫黃氣體起泡之方法 (5) A method for foaming a sulfur-containing gas in a slurry in which a nickel powder is dispersed in a liquid phase

特別是從可精密地控制含硫黃量之點及可均一地添加硫黃的觀點,(1)及(4)的方法為較佳。(1)、(2)、(5)的 方法中所使用之含硫黃氣體未特別限定,可將在還原步驟的溫度下屬於氣體的硫黃蒸氣、二氧化硫氣體、硫化氫氣體等直接使用或稀釋後使用。其中從在常溫是氣體而容易控制流量之點、雜質混入的疑慮低之點,二氧化硫氣體及硫化氫氣體是有利的。 In particular, from the viewpoint of precisely controlling the amount of sulfur content and uniformly adding sulfur, the methods (1) and (4) are preferred. (1), (2), (5) The sulfur-containing gas to be used in the method is not particularly limited, and may be used by directly using or diluting sulfur vapor, sulfur dioxide gas, hydrogen sulfide gas or the like which is a gas at the temperature of the reduction step. Among them, sulfur dioxide gas and hydrogen sulfide gas are advantageous from the point that the gas is easily controlled at a normal temperature and the point of contamination is low.

(1)的方法,透過將此等的氣體與氯化鎳氣體、非活性氣體、還原性氣體任一混合,可使藉還原反應生成的鎳粉末均一地含有硫黃。又,藉由控制氯化鎳氣體與含硫黃氣體之流量比,可控制鎳粉末的含硫黃量。 In the method of (1), by mixing the gases with any of nickel chloride gas, an inert gas, and a reducing gas, the nickel powder produced by the reduction reaction uniformly contains sulfur. Further, by controlling the flow ratio of the nickel chloride gas to the sulfur-containing gas, the amount of sulfur contained in the nickel powder can be controlled.

(3)、(4)的方法中所使用之含硫黃化合物未特別限定,可使用三硫醇、2-巰基苯幷噻唑、硫脲等之含硫黃化合物。其中使用硫脲的方法最具效果。 The sulfur-containing yellow compound used in the methods (3) and (4) is not particularly limited, and three types can be used. A sulfur-containing yellow compound such as mercaptan, 2-mercaptobenzothiazole or thiourea. Among them, the method using thiourea is most effective.

(4)的方法,係將鎳漿液與含硫黃化合物的溶液混合後,進行攪拌或超音波處理等。進行上述處理時之液溫的範圍為20~60℃,更佳為20~40℃。藉由調整含硫黃化合物的添加量,可任意地調整鎳粉末的含硫黃量。在將(4)的方法適用於藉氣相還原法所獲得之鎳粉末的情況,以於前述的洗淨步驟之後進行硫黃添加處理較佳。 The method of (4) is a method of mixing a nickel slurry with a solution containing a sulfur compound, followed by stirring or ultrasonic treatment. The liquid temperature in the above treatment is in the range of 20 to 60 ° C, more preferably 20 to 40 ° C. The amount of sulfur contained in the nickel powder can be arbitrarily adjusted by adjusting the amount of the sulfur-containing yellow compound added. In the case where the method of (4) is applied to the nickel powder obtained by the vapor phase reduction method, it is preferred to carry out the sulfur addition treatment after the above-described washing step.

於前述的洗淨步驟及硫黃添加步驟之後,將鎳粉末漿液乾燥。乾燥方法未特別限定,可使用已知的方法。具體言之,可例舉:使與高溫的氣體接觸而乾燥之氣流乾燥、加熱乾燥、真空乾燥等。其中,由於氣流乾燥没有因為粒子彼此衝撞而破壞含硫黃層而較佳。 After the aforementioned washing step and the sulfur addition step, the nickel powder slurry is dried. The drying method is not particularly limited, and a known method can be used. Specifically, a gas stream which is dried by contact with a gas having a high temperature, dried by heating, dried by vacuum, or the like can be exemplified. Among them, since the air flow is dried, it is preferable that the sulfur-containing layer is destroyed because the particles collide with each other.

本發明的鎳粉末在上述的乾燥步驟之後,於環境氣體控制下進行加熱處理。加熱處理在還原環境氣體中是100~400℃,較佳為100~250℃,更佳為於150~250℃的溫度下進行0.5~10小時的加熱處理。還原環境氣體,例如可例舉氮、氬等之非活性氣體與氫氣的混合氣體之環境氣體。還原環境氣體中的氫分壓為0.001~0.01MPa。藉此處理,將存在於鎳粉末的表面之硫酸離子變換成硫化物離子,可將鎳粉末表面的以硫酸離子存在的硫黃與以硫化物離子存在的硫黃的莫耳比(硫酸離子/硫化物離子比)穩定而設為0.10以下。 The nickel powder of the present invention is subjected to heat treatment under the control of ambient gas after the above drying step. The heat treatment is 100 to 400 ° C, preferably 100 to 250 ° C in the reducing atmosphere, and more preferably 0.5 to 10 hours at 150 to 250 ° C. The reducing atmosphere gas may, for example, be an ambient gas of a mixed gas of an inert gas such as nitrogen or argon and hydrogen. The partial pressure of hydrogen in the reducing ambient gas is 0.001 to 0.01 MPa. By this treatment, the sulfate ions present on the surface of the nickel powder are converted into sulfide ions, and the molar ratio of sulfur in the presence of sulfate ions on the surface of the nickel powder to sulfur in the presence of sulfide ions (sulfate ions/ The sulfide ion ratio is stable and is set to 0.10 or less.

第1圖係顯示用以製造鎳粉末的裝置之圖。第1圖中的符號10為還原爐。還原爐10係呈有底圓筒狀,在其上游側安裝有氯化鎳氣體噴嘴11,呈現為得以朝還原爐10內供給氯化鎳氣體、二氧化硫氣體及濃度調整用的氮氣。又,在還原爐10的上游側側壁安裝有氫氣噴嘴12。藉由從氫氣噴嘴12被供給至還原爐10內的氫氣,使氯化鎳被還原而生成鎳粉末P。在還原爐10的下游側側壁安裝有冷卻氣體噴嘴13,藉由從冷卻氣體噴嘴13被供給至還原爐10內的氮氣等之非活性氣體而生成的鎳粉末P會被迅速地冷卻,防止鎳粉末P粗大化。在還原爐10的下游側安裝有回收管14,鎳粉末P係流通在回收管14而被送至回收裝置。 Fig. 1 is a view showing a device for producing nickel powder. Reference numeral 10 in Fig. 1 is a reduction furnace. The reduction furnace 10 has a bottomed cylindrical shape, and a nickel chloride gas nozzle 11 is attached to the upstream side thereof to supply nickel chloride gas, sulfur dioxide gas, and nitrogen gas for concentration adjustment into the reduction furnace 10. Further, a hydrogen gas nozzle 12 is attached to the upstream side wall of the reduction furnace 10. The nickel chloride is reduced by the hydrogen gas supplied from the hydrogen nozzle 12 to the reduction furnace 10 to generate nickel powder P. The cooling gas nozzle 13 is attached to the downstream side wall of the reduction furnace 10, and the nickel powder P generated by the inert gas such as nitrogen gas supplied from the cooling gas nozzle 13 to the reduction furnace 10 is rapidly cooled to prevent nickel. The powder P is coarsened. A recovery pipe 14 is attached to the downstream side of the reduction furnace 10, and the nickel powder P is sent to the recovery pipe 14 and sent to a recovery device.

實施例 Example

(實施例1、2、比較例1~3) (Examples 1, 2, and Comparative Examples 1 to 3)

使用第1圖所示的鎳粉末製造裝置以氣相還原法製作個數50%直徑是0.03μm程度且使含硫黃率作各種變化後的鎳粉末。 Using the nickel powder production apparatus shown in Fig. 1, a nickel powder having a diameter of 50% and a diameter of 0.03 μm and varying the sulfur content was produced by a vapor phase reduction method.

利用氯化鎳氣體噴嘴11將氯化鎳氣體、二氧化硫氣體及氮氣的混合氣體以2.8m/秒(1,100℃換算)流速導入於經加熱器設為1,100℃的環境氣體溫度之還原爐10內。同時從氫氣噴嘴12以2.2m/秒(1,100℃換算)的流速將氫氣導入於還原爐10內,在還原爐10內還原氯化鎳氣體而獲得鎳粉末P。 The mixed gas of nickel chloride gas, sulfur dioxide gas, and nitrogen gas was introduced into the reduction furnace 10 at an ambient gas temperature of 1,100 ° C by a heater at a flow rate of 2.8 m/sec (1,100 ° C) by a nickel chloride gas nozzle 11. At the same time, hydrogen gas was introduced into the reduction furnace 10 from the hydrogen nozzle 12 at a flow rate of 2.2 m/sec (1,100 ° C), and nickel chloride gas was reduced in the reduction furnace 10 to obtain nickel powder P.

在此情況,係藉由控制氯化鎳氣體與二氧化硫氣體之流量比,而調整鎳粉末的含硫黃量。此外,在進行鎳生成反應時,依反應熱而生成的鎳粉末係被加熱直到1,200℃,而含有所生成的鎳粉末之氣體流係因鎳粉末的黑體輻射而被觀察到與烴等之氣體燃料的燃燒炎相似的光焰F。所生成的鎳粉末P係與從冷卻氣體噴嘴13以鎳粉末的平均單位時間生成量之200倍的質流量導入的25℃的氮氣混合,在被冷卻到400℃以下之後,藉由回收管14引導至未圖示之袋式過濾器,將鎳粉末分離、回收。比較例3係不將二氧化硫氣體添加於氯化鎳氣體而製作鎳粉末。 In this case, the sulfur content of the nickel powder is adjusted by controlling the flow ratio of the nickel chloride gas to the sulfur dioxide gas. Further, in the nickel formation reaction, the nickel powder produced by the reaction heat is heated up to 1,200 ° C, and the gas stream containing the produced nickel powder is observed as a gas with hydrocarbons due to black body radiation of the nickel powder. The combustion of the fuel is similar to the flame F. The produced nickel powder P is mixed with nitrogen gas introduced at a mass flow rate of 200 times the average production time per unit time of the nickel powder from the cooling gas nozzle 13, and after being cooled to 400 ° C or lower, the recovery pipe 14 is passed through the recovery pipe 14 The bag is guided to a bag filter (not shown) to separate and recover the nickel powder. In Comparative Example 3, a nickel powder was produced by not adding sulfur dioxide gas to nickel chloride gas.

回收的鎳粉末係進行反覆5次的在水中分散、沉降之洗淨步驟而去除殘留的氯化鎳後,以含水率成為0.5%以下之方式利用氣流乾燥裝置進行乾燥處理。接著在2體積%氫-氬的還原環境氣體下(氫分壓:2kPa)進行3小時的150℃之熱處理,獲得實施例1、2及比較例1~3的鎳粉末。 The recovered nickel powder is subjected to a washing step of dispersing and sedimenting in water for five times to remove residual nickel chloride, and then dried by a gas flow drying device so that the water content is 0.5% or less. Subsequently, heat treatment was performed at 150 ° C for 3 hours under a reducing atmosphere of hydrogen gas (hydrogen partial pressure: 2 kPa) of 2% by volume of hydrogen-argon to obtain nickel powders of Examples 1 and 2 and Comparative Examples 1 to 3.

針對所獲得之鎳粉末,利用以下的方法來評價個數50%直徑、硫黃濃度、鎳粉末表面的硫酸離子/硫化物離子比、粗大粒子率、燒結舉動及凝集舉動。 With respect to the obtained nickel powder, the following method was used to evaluate the number of 50% diameter, the sulfur concentration, the sulfate ion/sulfide ion ratio on the surface of the nickel powder, the coarse particle ratio, the sintering behavior, and the agglutination behavior.

a.個數50%直徑 a. Number 50% diameter

利用掃瞄電子顯微鏡(Hitachi High-Technologies Corp.製,商品名S-4700)拍攝金屬鎳粉末的照片,使用影像分析軟體(mountech.co.,ltd製,商品名MacView4.0)從該照片測定約1,000個粒子的粒徑,算出其個數50%直徑。此外,粒徑係為將粒子包入之最小圓的直徑。 A photograph of the metallic nickel powder was taken by a scanning electron microscope (manufactured by Hitachi High-Technologies Corp., trade name: S-4700), and the image analysis software (manufactured by Mountech. Co., Ltd., trade name MacView 4.0) was used for the photograph. The particle size of about 1,000 particles was calculated to be 50% of the diameter. Further, the particle diameter is the diameter of the smallest circle in which the particles are enclosed.

b.硫黃濃度 b. sulfur concentration

使用感應耦合電漿原子發射光譜儀(SII nanotechnology Co.,Ltd.製,商品名SPS3100)作測定。 The measurement was carried out using an inductively coupled plasma atomic emission spectrometer (manufactured by SII Nanotechnology Co., Ltd., trade name SPS3100).

c.鎳粉末表面的硫酸離子/硫化物離子比 c. Sulfate ion/sulfide ion ratio on the surface of nickel powder

從使用X射線光電分光儀(ULVAC-PHI,INCORPORATED製,商品名QVuantum2000)所測定之S2p光譜的168eV的峰值與162eV的峰值之強度比算出鎳粉末表面的硫酸離子/硫化物離子比。 The sulfate ion/sulfide ion ratio on the surface of the nickel powder was calculated from the intensity ratio of the peak of 168 eV and the peak of 162 eV of the S 2p spectrum measured by an X-ray photoelectric spectrometer (ULVAC-PHI, INCORPORATED, trade name: QVuantum 2000).

d.粗大粒子率 d. Gross particle rate

利用掃瞄電子顯微鏡(Hitachi High-Technologies Corp.製,商品名S-4700)拍攝金屬鎳粉末的照片,使用影像分析軟體(mountech.co.,ltd製,商品名MacView4.0)從該照片測定在約100,000個粒子當中,粒徑是個數50%直徑的3倍以上的粗大粒子數並求得粗大粒子率。 A photograph of the metallic nickel powder was taken by a scanning electron microscope (manufactured by Hitachi High-Technologies Corp., trade name: S-4700), and the image analysis software (manufactured by Mountech. Co., Ltd., trade name MacView 4.0) was used for the photograph. Among the approximately 100,000 particles, the particle diameter is a number of coarse particles of three times or more the number of diameters of 50% and a coarse particle ratio is obtained.

e.燒結舉動 e. Sintering behavior

將鎳粉末1g、樟腦3重量%及丙酮3重量%混合,將此混合物填充於內徑5mm、長度10mm的圓柱狀金屬容器,以500MPa進行壓縮而製作試驗圓球(Pellet)。針對此試驗圓球的熱收縮舉動,使用熱機械分析儀(Rigaku Corporation製,商品名TMA8310)在1.5體積%氫-氮的還原環境氣體下以昇溫速度5℃/分鐘的條件測定。從測定結果求得5%收縮溫度,按照表1那樣來評價鎳粉末的燒結舉動。 1 g of nickel powder, 3 wt% of camphor, and 3 wt% of acetone were mixed, and this mixture was filled in a cylindrical metal container having an inner diameter of 5 mm and a length of 10 mm, and compressed at 500 MPa to prepare a test pellet (Pellet). The heat shrinkage behavior of the test pellet was measured using a thermomechanical analyzer (manufactured by Rigaku Corporation, trade name TMA8310) under a reducing atmosphere of 1.5% by volume of hydrogen-nitrogen at a temperature elevation rate of 5 ° C /min. From the measurement results, the 5% shrinkage temperature was determined, and the sintering behavior of the nickel powder was evaluated as shown in Table 1.

f.凝集粒子 f. agglutinated particles

於鎳粉末0.5g添加聚羧酸系分散劑5重量%水溶液100ml,使用超音波分散機(gin-sen.Corporation製,商品名GSD600AT)在輸出600W、振幅寬30μm之條件下於60秒分散。於分散後,使用膜片過濾器(孔徑1μm,過濾器徑25mm)(GE health care bioscience Co.,Ltd.製,商品名Nuclepore membrane)並以吸引壓0.1MPa進行吸引過濾,從那時的通過時間,按照表2那樣評價鎳粉末的凝集舉動。 To a 0.5 g portion of a nickel powder, 100 ml of a 5% by weight aqueous solution of a polycarboxylic acid-based dispersant was added, and the mixture was dispersed in an ultrasonic wave disperser (manufactured by Gin-sen. Corporation, trade name: GSD600AT) under the conditions of an output of 600 W and an amplitude of 30 μm for 60 seconds. After the dispersion, a membrane filter (pore size: 1 μm, filter diameter: 25 mm) (manufactured by GE Health Care Bioscience Co., Ltd., trade name: Nuclepore membrane) was used, and suction filtration was performed at a suction pressure of 0.1 MPa, and passed through at that time. At the time, the agglutination behavior of the nickel powder was evaluated as in Table 2.

實施例1、2及比較例1~3的測定結果及評價結果表示於表3。此外,比較例3係硫黃濃度是檢出限界以下,針對鎳粉末表面之硫黃的狀態亦無法評價。 The measurement results and evaluation results of Examples 1 and 2 and Comparative Examples 1 to 3 are shown in Table 3. Further, in Comparative Example 3, the sulfur concentration was below the detection limit, and the state of sulfur on the surface of the nickel powder could not be evaluated.

(實施例3~5) (Examples 3 to 5)

製作個數50%直徑是0.09μm程度、含硫黃率1.5%程度且使表面的硫黃之狀態作各種變化後鎳粉末。使用第1圖所示的鎳粉末製造裝置,對於不將二氧化硫氣體施加於氯化鎳氣體所製造而成的不含硫黃的鎳粉末,進行反覆5次的在水中分散、沉降之洗淨步驟而去除殘留的氯化鎳。之後,以含硫黃率相對於鎳粉末是1.5%的方式添加硫脲的乙醇溶液,且在35℃下進行30分鐘攪拌處理。接著,以含水率成為0.5%以下的方式利用氣流乾燥裝置進行乾燥處理之後,為改變鎳粉末表面的硫黃之狀態,將於2體積%氫-氬的還原環境氣體下(氫分壓:2kPa)之200℃的熱處理的處理時間變化為0.5~3小時而進行,獲得實施例3~5的鎳粉末。實施例3~5的測定結果及評價結果表示於表3。 A nickel powder having a diameter of 50% of a diameter of about 0.09 μm, a sulfur content of about 1.5%, and various changes in the state of sulfur on the surface was produced. Using the nickel powder manufacturing apparatus shown in Fig. 1, the sulfur-free nickel powder produced by applying sulfur dioxide gas to nickel chloride gas is subjected to a washing step of dispersing and sedimenting in water for five times. The residual nickel chloride is removed. Thereafter, an ethanol solution of thiourea was added so that the sulfur content was 1.5% with respect to the nickel powder, and the mixture was stirred at 35 ° C for 30 minutes. Next, after drying treatment by a gas flow drying device so that the water content is 0.5% or less, in order to change the state of sulfur on the surface of the nickel powder, it will be under a reducing atmosphere of 2% by volume of hydrogen-argon (hydrogen partial pressure: 2 kPa). The treatment time of the heat treatment at 200 ° C was changed to 0.5 to 3 hours, and nickel powders of Examples 3 to 5 were obtained. The measurement results and evaluation results of Examples 3 to 5 are shown in Table 3.

(比較例4) (Comparative Example 4)

除了將實施例3之洗淨步驟後的在硫脲的乙醇溶液中進行攪拌處理後的步驟,於洗淨步驟後以含水率成為0.5%以下之方式利用氣流乾燥裝置進行乾燥處理後,在石英反應管中於1.5體積%氫-5體積%硫化氫-氮環境氣體下(氫分壓:1.5kPa,硫化氫分壓:5kPa)以230℃進行10分鐘的硫化處理外,其餘同實施例3地獲得鎳粉末。比較例4的測定結果及評價結果表示於表3。 In addition to the step of stirring the thiourea in an ethanol solution after the washing step of Example 3, after the washing step, the water content is 0.5% or less, and the drying treatment is performed by a gas flow drying device, followed by quartz. The reaction tube was subjected to a vulcanization treatment at 230 ° C for 10 minutes under a 1.5 volume% hydrogen-5 vol% hydrogen sulfide-nitrogen atmosphere (hydrogen partial pressure: 1.5 kPa, hydrogen sulfide partial pressure: 5 kPa), and the same as in Example 3 Nickel powder was obtained. The measurement results and evaluation results of Comparative Example 4 are shown in Table 3.

針對所獲得之鎳粉末,利用先前述及的方法來評價個數50%直徑、硫黃濃度、鎳粉末表面的硫酸離子/硫化物離子比、粗大粒子率、燒結舉動及凝集舉動。其結果一併載於表3。 With respect to the obtained nickel powder, the number of 50% diameter, the sulfur concentration, the sulfate ion/sulfide ion ratio on the surface of the nickel powder, the coarse particle ratio, the sintering behavior, and the agglutination behavior were evaluated by the method described above. The results are shown in Table 3.

從表3可明瞭,實施例1、2的鎳粉與比較例1~3相較下,儘管個數50%直徑是相同程度,但因硫黃濃度是在1.0~5.0重量%的範圍內,故得知燒結舉動優異。又實施例3、4的鎳粉與實施例5、比較例4相較下,儘管個數50%直徑是相同程度,但因硫黃濃度是在上述範圍內且硫酸離子/硫化物離子比是0.10以下,故得知產生凝集粒子的情況少。此外,實施例5由於凝集舉動之評價是「△」,更重要的燒結舉動之評價是「○」,故就本發明的性能而言是充分的。 As can be seen from Table 3, the nickel powders of Examples 1 and 2 were compared with Comparative Examples 1 to 3, and although the number of the 50% diameters was the same, the sulfur concentration was in the range of 1.0 to 5.0% by weight. Therefore, it is known that the sintering behavior is excellent. Further, in the nickel powders of Examples 3 and 4, compared with Example 5 and Comparative Example 4, although the number of the 50% diameters was the same, the sulfur concentration was within the above range and the sulfate ion/sulfide ion ratio was When it is 0.10 or less, it is known that the amount of aggregated particles is small. Further, in Example 5, since the evaluation of the aggregation behavior was "△", and the evaluation of the more important sintering behavior was "○", it was sufficient in terms of the performance of the present invention.

依以上結果,本發明的鎳粉末在疊層陶瓷電容器的製造步驟中具有優異的燒結特性,結果證實在防止疊層陶瓷電容器的電極層與介電體層之間的剝離、電 極層的裂痕之類缺陷的發生是具效用的。而且,具有防止凝集粒子發生的效果,結果證實在防止電極層間的短路、耐電壓降低之類不良情況的發生是具效用的。 According to the above results, the nickel powder of the present invention has excellent sintering characteristics in the manufacturing steps of the laminated ceramic capacitor, and as a result, it has been confirmed that the peeling and electric electricity between the electrode layer and the dielectric layer of the laminated ceramic capacitor are prevented. The occurrence of defects such as cracks in the polar layer is effective. Further, it has an effect of preventing the occurrence of aggregated particles, and as a result, it has been confirmed that it is effective to prevent the occurrence of defects such as short-circuiting between the electrode layers and reduction in withstand voltage.

本發明作為疊層陶瓷電容器的內部電極用途之導電膏用的鎳粉末是有用的。 The present invention is useful as a nickel powder for a conductive paste for use as an internal electrode of a laminated ceramic capacitor.

Claims (3)

一種鎳粉末,其特徵為含有1.0~5.0質量%的硫黃,個數50%直徑是0.09μm以下。 A nickel powder characterized by containing 1.0 to 5.0% by mass of sulfur, and the number of 50% is 0.09 μm or less. 如請求項1之鎳粉末,其中存在於前述鎳粉末的表面之硫黃中以硫酸離子存在的硫黃與以硫化物離子存在的硫黃之莫耳比是0.10以下。 The nickel powder of claim 1, wherein the sulfur present in the sulfur of the surface of the nickel powder, the sulfur present in the sulfuric acid ion and the sulfur in the sulfide ion are 0.10 or less. 如請求項1或2之鎳粉末,其中具有前述鎳粉末的個數50%直徑3倍以上的粒徑之粗大粒子的存在率以個數基準計是100ppm以下。 The nickel powder according to claim 1 or 2, wherein the presence ratio of the coarse particles having a particle diameter of 50% or more of three times the diameter of the nickel powder is 100 ppm or less on a unit basis.
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