TW418142B - Composite nickel fine powder and method for preparing the same - Google Patents
Composite nickel fine powder and method for preparing the same Download PDFInfo
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碰 濟 部 智 慧 財 產 局 消 費 合 作 社 印 製 1 Α7 Β7 五、發明說明(1 ) [發明技術領域] 本發明係關於複合鎳微細粉末及製備複合微細粉末之 方法;其中複合鎳微細粉末具有適合使用作為製備層壓陶 瓷電容器之内電極材料的顯著性質,具有優異之金屬鎳氧 化抗性及氧化鎳擴散抗性,特別是於黏合劑移除期間,亦 具有優異之熱收縮性質,因此當製造大尺寸的層壓陶瓷電 容器時,可防止發生脫層及形成裂紋,且可製造包括陶瓷 介電層及内電極之薄、小尺寸的多層陶瓷電容器,而未損 害其介電性質及電性質》 [技藝背景] 層壓陶瓷電容器係由分層交互放置陶瓷介電材料及内 電極,施予壓力使彼等相連接,接著以烘烤使彼等單一化 而製造。在此方面,該層壓陶瓷電容器之内電極一般係由 下述製造:使作為内電極材料之金屬微細粉末形成糊狀 物,於陶瓷底材上印製糊狀物層,分層放置複數個此等印 製底材,其後以壓縮及加熱使彼等相互連接而得到單一化 產物,最後在減壓下加熱及烘烤。關於該内電極之材料, 舉例而言,已使用鉑與鈀,但最近已開發且推動使用车金 屬(例如鎳)取代貴金屬(例如鉑與把)之技術。 然而,S使用金屬鎳微細粉末作為内電極材料時雖 然熱收縮傾向視粉末之粒度而定,但在溫度高於約400至 500 C下,其具有經歷迅速熱收縮之傾向。根據此項理由, 方使用金屬鎳微細粉末作為内電極材料,則例如上述夂單 ^一化產物,於烘烤期間’因為陶莞底材及金屬鎳微細粉末 張尺度通用中國國家標準(CNS)A4規格(21G χ 297公- -------- 310997 -------------裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 4 1 8 1 4 2 A7 —— B7 五、發明說明(2 ) 層之間對於熱收縮特徵的差異,易於引起脫層與/或裂紋 形成,且此已變成嚴重的問題。 為了解決此等問題’本發明之發明人已開發以特定範 圍之量’合併鎮與/或約於金屬錄微細粉末中,以改善金 屬鎳微細粉末之熱收縮特徵之技術,且已申請專利(日本 專利申請案號平9-342793)。在溫度高於400至500〇c下, 此技術可抑制前述之迅速熱收縮(該迅速熱收縮為習知的 金屬鎳微細粉末所觀察到者),可將該迅速熱收縮之起始 溫度改變至接近約600至700t範圍之較高溫度區域。 然而’為了防止烘烤期間發生脫層與/或形成裂紋, 希望改變内電極材料之迅速熱收縮起始溫度至更高的溫度 區域。這是因為製備層壓陶瓷電容器之烘烤溫度可視陶竟 介電材料之成分而改變’但用於鈦酸鋇陶瓷電介質之供烤 溫度一般為約1200至1400eC範圍間。 此外’當進行烘烤而陶瓷底材開始接觸金屬時,一般 會使金屬氧化’所得金屬氧化物具有高於陶磁底材之擴散 係數。因此’在晶粒邊界處,易引起具有高擴散係數之金 屬氧化物相擴散至具有低擴散係數之陶瓷相。 更詳言之’當使用含有習知金屬鎳微細粒子之糊狀物 時’部份金屬鎳微細粒子會氧化,且所得氧化鎳擴散至陶 曼介電材料中。結果’部份欲成形之内電極有消失之傾向, 於内電極中形成缺陷,且由於形成鐵酸鹽之故,部份陶曼 介電層具有損害其介電特徵之傾向。因此,相當難以製造 包括陶曼介電材料層及内電極層之薄、小尺寸的層壓陶竞 (請先閱讀背面之注意事項再填寫本頁} -------訂---------線— 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS〉G規格⑽x 297公楚) 2 310997 A7 五、發明說明(3 ) 電容器’而不損害其介電性質及帶電性質。 [發明揭示j 如上述詳細之討論,相軎番亜 製備糊肤物r用㈣ 相*重要的疋金屬鎳微細末作為 製備掬狀物(用於製備層屋陶竟電容器)之材料,必 粉末氧化’及在供烤期間,防止任何氧化 m且同時可以將金屬錄微細粉末之迅速 熱收縮起始溫度改變至更高的溫度區《,以使鎳微細粉末 之熱收縮曲線接近陶瓷底材之熱收縮曲線。 因此,本發明之目的係提供複合鎳微細粉末,其具有 適合使用作為製備層壓陶瓷電容器之内電極材料的顯著性 質,特別是於黏合劑移除期間,具有優異之金屬鎳氧化抗 性及氧化鎳擴散抗性,具有近乎與陶瓷底材相同之熱收縮 曲線,因此當製造大尺寸的層壓陶瓷電容器時,可防止發 生脫層及形成裂紋,且可製造包括陶瓷介電層及内電極之 薄、小尺寸的多層陶瓷電容器,而未損害其介電特徵及電 性質。 本發明之另一目的係提供製備該複合鎳微細粉末之方 煃濟部智慧財產局員工消費合作社印製 法。 本發明之發明人已進行廣泛研究而完成前述目的,已 發現具有前述顯著性質之複合鎳微細粉末,可將特定金屬 元素之氧化物及/或錯合氧化物固定於金屬鎳微細粒子之 表面而獲得,並發現該複合鎳微細粉末可經由濕承載加 工、乾承載加工、或半乾承載加工予以製備’因此根據此 等發現完成本發明。 ’ 3L0997 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 418142 - A7 --------— B7 —_ 五、發明說明(4 ) 根據本發明之第一目的,係提供一種複合錄微細粉 末其特徵為將至少一員選自氧化物及錯合氧化物承載至 金屬鎳微細粒子表面上,其令該氧化物或錯合氧化物係包 括至少一種具有原子序範圍為12至56或82且屬於週期 表中第2至14族之金屬元素。 根據本發明之另-目的,係提供一種製備複合錄微細 粉末之方法,包括下列步驟:在含有金屬鎳微細粒子或表 面被氧化的金屬鎳微細粒子之漿液中,添加含有至少一員 選自金屬元素(各具有原子序範圍為12至56或82且屬於 週期表中第2至14族)之水溶性鹽的水溶液;接著以酸或 鹼調節混合物之pH值,因而將水溶性鹽衍生之金屬氧化 物與/或錯合氧化物承載至金屬鎳微細粒子表面上。 根據本發明之進一步目的,亦提供一種製備複合鎳微 細粉末之方法,包括下列步驟:將至少一員選自氧化物及 錯合氧化物之超微細粒子暫時承載至金屬鎳微細粒子或表 面被氧化的金屬鎳微細粒子之表面上,其中該氧化物或錯 合氧化物係含有至少一種具有原子序範圍為12至56或82 且屬於週期表中第2至14族之金屬元素;使暫時承載黏 著其上的超微細粒子之鎳微細粒子相互碰撞或與其它物體 碰撞’如此可將超微細粒子承載至金屬鎳微細粒子之表面 上。 根據本發明之又另一目的,係提供一種製備複合鎳微 細粉末之方法,包括下列步驟:利用加熱,將其中分散有 至少一員選自氧化物及錯合氣化物的超微細粒子之懸浮液 (請t閱讀背面之注意事項再填寫本頁) -I ---------訂---------線 — , 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 4 310997 A7 '---------§1________ 五、發明說明(5 ) (請先閱讀背面之注意事項再填寫本頁) 與金屬鎳微細粒子或表面被氧化的金屬鎳微細粒子混合, 其令該氧化物或錯合氧化物係含有至少一種具有原子序範 圍為12至56或82且屬於週期表中第2至14族之金屬元 素,移除懸浮液之介質,如此可將超微細粒子暫時承載至 金屬鎳微細粒子之表面上;使暫時帶有黏著其上的超微細 粒子之鎳微細粒予相互碰撞或與其它物體碰揸,如此可將 超微細粒子承載至金屬鎳微細粒子之表面上。 [特別具體實例說明】 根據本發明之複合鎳微細粉末包括金屬鎳微細粒子及 至少一員選自氧化物及錯合氧化物,後者係承載至金屬鎳 微細粒子之表面上;其中該氧化物或錯合氧化物含有至少 一種具有原子序範圍為12至56或82且屬於週期表中第 2至14族之金屬元素,因此,本發明之複合鎳微細粉末 具有與陶瓷底材十分類似之熱收縮特徵,如此可在製造大 尺寸層壓陶磁電容器時,防止發生脫層及形成裂紋。另外, 複合鎳微細粉末於黏合劑移除期間,具有優異之氧化抗性 及擴散抗性,因此可製造包括陶瓷介電材料及内電極之 •經濟部智慧財產局員工消費合作社印製 薄、小尺寸的多層層壓陶瓷電容器,而未損害電容器之介 電特徵及電性質。 當製造包括陶瓷介電材料及内電極之薄、小尺寸的多 層層壓陶瓷電容器且未損害電容器之介電特徵及電性質, 而使用含有本發明複合鎳微細粉末之糊狀物時,可在黏合 劑移除期間’充分防止金屬鎳微細粉末氧化及防止氧化鎳 之任何擴散至陶磁介電層’或由於部分欲成形之内電極消 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 5 310997 4 Ί 8 1 4 2」从 A7 ---- B7 五、發明說明(6 ) 失及陶瓷介電層功能部分損壞,亦可防止内電極之任何損 害;本發明之複合鎳微細粉末較好包括金屬鎳微細粒子及 至少一員選自氧化物及錯合氧化物,該氧化物或錯合氧化 物含有至少一種*具有原子序範圍為12至56或82且屬於 週期表中第2至7族或第13至14族之金屬元素;且該複 合鎳微細粉末更好包括金屬鎳微細粒子及至少一員選自氧 化物及錯合氧化物,該氧化物或錯合氧化物含有至少一種 具有原子序範圍為12至56或82且屬於週期表中第2、3、 4、7、13或14族之金屬元素;其中氧化物或錯合氧化物 係承載至金屬鎳微細粒子表面上。 再者,最好使用包括金屬鎳微細粒子與至少一員選自 屬於週期表中第2族、Y、Zr、A卜及Si之金屬元素氧化 物之複合鎳微細粉末,後者係承載至金屬鎳微細粒子之表 面上〇 關於前述複合氧化物,本發明可使用包含前述任一種 及下列之多種複合氧化物。 當使用本發明複合鎳微細粉末作為層壓陶兗電容器之 内電極材料時,本發明之複合鍊微細粉末可經由將至少— 員選自例如上列之氧化物及錯合氧化物,及至少_貢選自 鑭系之氧化物,黏著至金屬鎳微細粒子表面上而獲得。 當使用本發明複合鎳微細粉末作為層壓陶曼電容器之 内電極材料時’本發明之複合鎳微細粉末較佳包括金屬錄 微細粉末及至少一員選自以下列通式表示之錯合敦化物: 本紙張尺度適用令國國家標準(CNS)A4規格(210 «297公釐) (請也閲讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Health, Japan 1 Α7 Β7 V. Description of the Invention (1) [Technical Field of the Invention] The present invention relates to a composite nickel fine powder and a method for preparing the composite fine powder; wherein the composite nickel fine powder is suitable for use as Significant properties of the internal electrode material for the preparation of laminated ceramic capacitors, which have excellent resistance to metal nickel oxidation and diffusion of nickel oxide, especially during the removal of the adhesive, also has excellent heat shrinkage properties, so when manufacturing large sizes Laminated ceramic capacitors can prevent delamination and crack formation, and can produce thin, small-sized multilayer ceramic capacitors including ceramic dielectric layers and internal electrodes without compromising their dielectric and electrical properties "[技艺Background] Laminated ceramic capacitors are manufactured by placing ceramic dielectric materials and internal electrodes alternately in layers, applying pressure to connect them, and then singulating them by baking. In this regard, the internal electrode of the laminated ceramic capacitor is generally manufactured by forming a paste of the fine metal powder as an internal electrode material, printing a paste layer on a ceramic substrate, and placing a plurality of layers in layers. These printed substrates are then connected to each other by compression and heating to obtain singularized products, and finally heated and baked under reduced pressure. Regarding the material of the internal electrode, for example, platinum and palladium have been used, but a technology of replacing a precious metal (such as platinum and a handle) with a car metal (such as nickel) has been recently developed and promoted. However, although S uses a metallic nickel fine powder as an internal electrode material, although the heat shrinkage tendency depends on the particle size of the powder, it has a tendency to undergo rapid heat shrinkage at a temperature higher than about 400 to 500 ° C. For this reason, Fang uses fine metal nickel powder as the internal electrode material. For example, during the baking process, because the ceramic substrate and the fine metal nickel powder have a common Chinese national standard (CNS) during baking, A4 specification (21G χ 297 male--------- 310997 ------------- install -------- order --------- line (Please read the precautions on the back before filling this page) 4 1 8 1 4 2 A7 —— B7 V. Description of the invention (2) Differences in heat shrinkage characteristics between layers are likely to cause delamination and / or crack formation, And this has become a serious problem. In order to solve these problems, the inventors of the present invention have developed a combination of the town and / or the metal fine powder in a specific amount to improve the heat shrinkage characteristics of the metal nickel fine powder. Technology and has applied for a patent (Japanese Patent Application No. Hei 9-342793). At temperatures above 400 to 500 ° C, this technology can suppress the aforementioned rapid thermal shrinkage (the rapid thermal shrinkage is a conventional metal nickel) (Observed by fine powder), can change the rapid thermal shrinkage onset temperature to approximately 600 to 700t High temperature region. However, 'in order to prevent delamination and / or crack formation during baking, it is desirable to change the rapid thermal shrinkage starting temperature of the internal electrode material to a higher temperature region. This is because of the baking of laminated ceramic capacitors. The temperature may vary depending on the composition of the ceramic dielectric material, but the baking temperature for barium titanate ceramic dielectrics is generally in the range of about 1200 to 1400eC. In addition, when baking is performed and the ceramic substrate begins to contact the metal, it will generally The oxidation of the metal has a diffusion coefficient higher than that of the ceramic magnetic substrate. Therefore, at the grain boundary, it is easy to cause a metal oxide phase with a high diffusion coefficient to diffuse to a ceramic phase with a low diffusion coefficient. More details "When using a paste containing the conventional metal nickel fine particles" part of the metal nickel fine particles will be oxidized, and the obtained nickel oxide will diffuse into the Taumann dielectric material. As a result, some of the internal electrodes to be formed disappear. The tendency is to form defects in the internal electrodes, and due to the formation of ferrites, part of the Taurman dielectric layer has a tendency to damage its dielectric characteristics. It is quite difficult to manufacture a thin, small-size laminated ceramic ceramic including a Taoman dielectric material layer and an internal electrode layer (please read the precautions on the back before filling this page) ------- Order ----- ---- Line — Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with Chinese National Standards (CNS> G Specification ⑽x 297 Gongchu) 2 310997 A7 V. Description of Invention (3) Capacitors' without damaging its media Electrical properties and charging properties. [Invention of the invention j As discussed in detail above, the phase is used to prepare pastes, and the phase is used as the important metal nickel fine powder as a preparation material (used for the production of laminated ceramics capacitors). ), The material must be oxidized, and during baking, it can prevent any oxidation m and at the same time can change the rapid thermal shrinkage starting temperature of the metal powder to a higher temperature zone ", in order to make the nickel fine powder heat shrink The curve is close to the heat shrinkage curve of the ceramic substrate. Therefore, the object of the present invention is to provide a composite nickel fine powder, which has remarkable properties suitable for use as an internal electrode material for preparing laminated ceramic capacitors, and particularly has excellent resistance to metal nickel oxidation and oxidation during binder removal. Nickel diffusion resistance, which has almost the same heat shrinkage curve as ceramic substrates, can prevent delamination and crack formation when manufacturing large-size laminated ceramic capacitors, and can manufacture ceramic dielectric layers and internal electrodes. Thin, small-sized multilayer ceramic capacitors without compromising their dielectric characteristics and electrical properties. Another object of the present invention is to provide a method for preparing the composite nickel fine powder by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The inventors of the present invention have carried out extensive research to accomplish the foregoing object, and have found that the composite nickel fine powder having the aforementioned remarkable properties can fix oxides and / or complex oxides of specific metal elements on the surface of the metal nickel fine particles. Obtained, and found that the composite nickel fine powder can be prepared via wet-loaded processing, dry-loaded processing, or semi-dry-loaded processing ', thus completing the present invention based on these findings. '3L0997 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 418142-A7 --------— B7 —_ 5. Description of the invention (4) According to the first purpose of the present invention The system provides a composite recording fine powder characterized in that at least one member selected from oxides and complex oxides is supported on the surface of metallic nickel fine particles, so that the oxide or complex oxide system includes at least one atomic range A metal element that is 12 to 56 or 82 and belongs to groups 2 to 14 of the periodic table. According to another object of the present invention, there is provided a method for preparing a composite fine powder, comprising the steps of adding at least one member selected from metal elements to a slurry containing fine metal nickel particles or fine metal nickel particles whose surface is oxidized. An aqueous solution of a water-soluble salt (each having an atomic range of 12 to 56 or 82 and belonging to groups 2 to 14 of the periodic table); then the pH of the mixture is adjusted with an acid or a base, thereby oxidizing the metal derived from the water-soluble salt The complex and / or the complex oxide are supported on the surface of the metallic nickel fine particles. According to a further object of the present invention, there is also provided a method for preparing a composite nickel fine powder, including the following steps: temporarily carrying at least one member of ultrafine particles selected from oxides and complex oxides to metal nickel fine particles or the surface of which is oxidized On the surface of metallic nickel fine particles, the oxide or complex oxide system contains at least one metal element having an atomic range of 12 to 56 or 82 and belonging to groups 2 to 14 of the periodic table; making it temporarily bear and adhere to it The nickel fine particles of the ultrafine particles on the collision with each other or with other objects' so that the ultrafine particles can be carried on the surface of the metallic nickel fine particles. According to still another object of the present invention, there is provided a method for preparing a composite nickel fine powder, comprising the steps of: dispersing at least one member of a suspension of ultrafine particles selected from oxides and complex gaseous substances by heating ( Please read the precautions on the back and fill in this page) -I --------- Order --------- line —, printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs China National Standard (CNS) A4 Specification (210 X 297 mm) 4 310997 A7 '--------- §1 ________ V. Description of Invention (5) (Please read the precautions on the back before filling this page) Mixed with metallic nickel fine particles or metallic nickel fine particles whose surface is oxidized, the oxide or complex oxide system contains at least one having an atomic range of 12 to 56 or 82 and belongs to groups 2 to 14 of the periodic table. Metal element, removing the medium of the suspension, so that the ultrafine particles can be temporarily carried on the surface of the metal nickel fine particles; the nickel fine particles temporarily with the ultrafine particles adhered thereto can collide with each other or with other objects Bump, so you can make ultrafine particles Carried to the upper surface of nickel fine particles. [Specific specific example description] The composite nickel fine powder according to the present invention includes metal nickel fine particles and at least one member selected from oxides and complex oxides, the latter being carried on the surface of metal nickel fine particles; The composite oxide contains at least one metal element having an atomic range of 12 to 56 or 82 and belonging to Groups 2 to 14 of the periodic table. Therefore, the composite nickel fine powder of the present invention has a heat shrinkage characteristic very similar to that of a ceramic substrate. In this way, delamination and crack formation can be prevented when manufacturing large-scale laminated ceramic magnetic capacitors. In addition, the composite nickel fine powder has excellent oxidation resistance and diffusion resistance during the removal of the binder, so it can be manufactured including ceramic dielectric materials and internal electrodes. Multilayer multilayer ceramic capacitors without compromising the dielectric characteristics and electrical properties of the capacitors. When manufacturing thin, small-size multilayer laminated ceramic capacitors including ceramic dielectric materials and internal electrodes without compromising the dielectric characteristics and electrical properties of the capacitors, the paste containing the composite nickel fine powder of the present invention can be used in During the removal of the adhesive, 'to fully prevent the oxidation of the fine nickel metal powder and prevent any diffusion of nickel oxide to the ceramic magnetic dielectric layer' or due to the elimination of some internal electrodes to be formed. The paper dimensions are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 5 310997 4 Ί 8 1 4 2 ″ from A7 ---- B7 V. Description of the invention (6) Loss of the functional part of the ceramic dielectric layer can also prevent any damage to the internal electrode; the compound of the invention The nickel fine powder preferably includes metal nickel fine particles and at least one member selected from the group consisting of oxides and complex oxides, the oxides or complex oxides containing at least one type * having an atomic range of 12 to 56 or 82 and belonging to the periodic table Group 2 to 7 or Group 13 to 14 metal elements; and the composite nickel fine powder preferably includes metal nickel fine particles and at least one member selected from the group consisting of oxides and complex oxides. The oxide contains at least one metal element having an atomic range of 12 to 56 or 82 and belonging to Group 2, 3, 4, 7, 13 or 14 of the Periodic Table; wherein the oxide or complex oxide is supported on metallic nickel Fine particles on the surface. Furthermore, it is preferable to use a composite nickel fine powder including metal nickel fine particles and at least one member selected from metal element oxides belonging to Group 2, Y, Zr, Ab and Si in the periodic table, the latter being carried to the metal nickel fine On the surface of the particle. Regarding the foregoing composite oxide, the present invention can use a plurality of composite oxides including any one of the foregoing and the following. When the composite nickel fine powder of the present invention is used as the internal electrode material of a laminated ceramic capacitor, the composite chain fine powder of the present invention can be selected from at least-members such as the oxides and complex oxides listed above, and at least _ The oxide is selected from lanthanide oxides and is adhered to the surface of fine particles of metallic nickel. When the composite nickel fine powder of the present invention is used as an internal electrode material of a laminated Taunman capacitor, the composite nickel fine powder of the present invention preferably includes a metal fine powder and at least one member selected from the complex compounds represented by the following general formula: This paper size applies the national standard (CNS) A4 specification (210 «297 mm) (Please also read the precautions on the back before filling out this page)
-I --------訂·-------I I 經濟部智慧財產局員工消費合作社印製 310997 經濟部智慧財產局員工消費合作社印製 A7 B7 ____________ 五、發明說明(7 ) (式中’ X表示sr、Ca、Mg或Pb ; z表示Zr、γ、Sn或 Ge;m為0至1範圍間之數字;η為〇至i範圍間之數字), 該錯合氧化物係承載至金屬鎳微細粒子之表面上。在此方 面,前述錯合氧化物可單獨使用或組合至少兩種使用,或 錯合氧化物可進一步包括,舉例而言,至少一員選自前述 多種氡化物、鑭系族元素之氧化物、氧化鉍及氧化组,作 為視情況之次要成分。 舉例而言’前述氧化物及錯合氧化物可為.Mg〇、Ca〇、-I -------- Order · ------- II Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 310997 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 ____________ V. Description of Invention (7 ) (Where 'X represents sr, Ca, Mg or Pb; z represents Zr, γ, Sn or Ge; m is a number in the range of 0 to 1; η is a number in the range of 0 to i), the complex oxidation The object is carried on the surface of fine particles of metallic nickel. In this regard, the aforementioned complex oxides may be used alone or in combination of at least two kinds, or the complex oxides may further include, for example, at least one member selected from the foregoing various halide compounds, oxides of lanthanoids, and oxides Bismuth and oxidation group, as the minor components as appropriate. For example, the aforementioned oxide and complex oxide may be .Mg〇, Ca〇,
SrO、BaO、ZnO、Al2〇3、Ga2.03、Y2〇3、si〇2、Ti〇2、Zr02、SrO, BaO, ZnO, Al2O3, Ga2.03, Y2O3, si02, Ti02, Zr02,
Cr203、Mn02、Mn304、Nb2〇5、BaTi〇3、CaTi03、SrTi03、 BaZr03、CaZr03、SrZr03、(Mg、Ca)Ti〇3、(Ba、Ca)(Ti、Cr203, Mn02, Mn304, Nb205, BaTi〇3, CaTi03, SrTi03, BaZr03, CaZr03, SrZr03, (Mg, Ca) Ti〇3, (Ba, Ca) (Ti,
Zr)03、PbTi03、Pb(Zr、Ti)〇3、(Pb、Ca)Ti〇3、MgAl2〇4 及BaTi4〇9 ’其可組合使用。此外’此等氧化物及錯合氧 化物可摻雜有例如,Nb、W、La、Y及Mo之氧化物。 舉例而言’前述鑭系族元素之氧化物可為Nd2〇3、Zr) 03, PbTi03, Pb (Zr, Ti) 〇3, (Pb, Ca) Ti03, MgAl2O4, and BaTi4 09 'can be used in combination. In addition, these oxides and complex oxides may be doped with, for example, oxides of Nb, W, La, Y, and Mo. For example, the oxide of the aforementioned lanthanide group element may be Nd203,
Sm203、Dy203、Er203 及 Ho203。 當本發明之複合錄微,細粉末或粒子以糊狀物的形式, 用於製造層壓陶瓷電容器之内電極時,較佳可具有不大於 5em之粒度,更佳為不大於lym。 此外’相對於複合鎳微細粉末之總量,前述欲承載至 金屬鎳微細粒子上之至少一員選自前述氧化物或錯合氧化 物之總量範圍較佳為0.05至10重量%,更佳〇·5至i〇重 量% ’特佳為1至10重量%。此係因為若承載的氧化物 及/或錯合氧化物之總量少於〇.〇5重量%,則氧化物及/或 -------------裝---I----訂-------線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 x 297公髮) 7 310997 A7 418142 五、發明說明(8 ) 錯合氧化物之效果不足,而若其超過1〇重量%,且該複 合錄微細粉末係使用作為製造層壓陶瓷電容器之内電極材 料,則此等氧化物對所得電容器之介電特徵有不良影響。 使用於本發明方法中之金屬鎳微細粒子或表面被氧化 的金屬鎳微細粒子,可由乾處理(例如以鎳鹽蒸氣進行汽 相氫還原)’或濕處理(係於特定條件下,自含有鎳鹽之水 溶液以還原劑還原,使金屬錄微細粒子沉殿)予以製備。 當本發明之複合鎳微細粉末以糊狀物的形式,用於製造層 壓陶瓷電容器之内電極時,欲使用之金屬鎳微細粉末較佳 具有不大於5/zm之粒度,更佳為不大於iym。 根據本發明之複合鎳微細粉末可經由濕承載加工或乾 承載加工、或進一步半-乾承載加工予以製備,包括下列 步驟.將金屬氧化物或錯合氧化物之超微細粒子水性懸浮 液與金屬鎳微細粒子混合,而將超微細粒子承載至金屬鎳 微細粒子之表面上,接著乾燥該承載超微細粒子的金屬鎳 微細粒子。 若本發明之複合鎳微細粉末係由濕承栽加工製備,則 在含有金屬鎳微細粒子或表面被氧化的金屬鎳微細粒子之 漿液中,添加含有至少一員選自金屬元素(各具有原子序 範圍為12至56或82且屬於週期表中第2至14族)之水 溶性鹽的水溶液,接著以酸或鹼調節混合物值因 而將水;谷性鹽衍生之金屬氡化物與/或錯合氣化物承載至 金屬錄微細粒子表面上。 若本發明之複合鎳微細粉末係由濕承載加工製備, (請先閱讀背面之注意事項再填寫本頁) 訂---------線丨 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用尹國國家標準(CNS)A4規格(21〇 χ 297公釐) 8 310997 A7 五、發明說明(9 ) 作為原料之金屬錄微細粒子可為經Sm203, Dy203, Er203, and Ho203. When the composite micro-recorder of the present invention is used in the form of a paste to manufacture an internal electrode of a laminated ceramic capacitor, it may preferably have a particle size of not more than 5em, more preferably not more than lym. In addition, with respect to the total amount of the composite nickel fine powder, at least one member of the foregoing nickel fine particles to be carried on the metal nickel fine particles is preferably selected from the foregoing oxides or complex oxides in a range of 0.05 to 10% by weight, more preferably. -5 to 10% by weight 'Extremely preferred is 1 to 10% by weight. This is because if the total amount of supported oxides and / or complex oxides is less than 0.055% by weight, then the oxides and / or ------------- install --- I ---- Order ------- line (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (21〇x 297) 7 310997 A7 418142 V. Description of the invention (8) The effect of the complex oxide is insufficient, and if it exceeds 10% by weight, and the composite fine powder is used as an internal electrode material for manufacturing a laminated ceramic capacitor, these oxide pairs The dielectric characteristics of the resulting capacitor have an adverse effect. The metallic nickel fine particles used in the method of the present invention or the metallic nickel fine particles whose surface is oxidized may be subjected to dry treatment (for example, vapor phase hydrogen reduction with nickel salt vapor) or wet treatment (under specific conditions, which contains nickel) The aqueous salt solution is reduced with a reducing agent, and the fine particles of the metal particles are allowed to sink. When the composite nickel fine powder of the present invention is used in the form of a paste for manufacturing an internal electrode of a laminated ceramic capacitor, the metal nickel fine powder to be used preferably has a particle size of not more than 5 / zm, more preferably not more than iym. The composite nickel fine powder according to the present invention can be prepared through wet load-bearing processing or dry load-bearing processing, or further semi-dry load-bearing processing, including the following steps. An ultrafine particle aqueous suspension of metal oxide or complex oxide and metal The nickel fine particles are mixed, the ultrafine particles are carried on the surface of the metal nickel fine particles, and then the metal nickel fine particles carrying the ultrafine particles are dried. If the composite nickel fine powder of the present invention is prepared by wet-supporting processing, at least one member selected from metal elements (each having an atomic range) is added to the slurry containing the metal nickel fine particles or the surface-oxidized metal nickel fine particles. It is an aqueous solution of water-soluble salts of 12 to 56 or 82 and belongs to groups 2 to 14 of the periodic table, and then adjusts the value of the mixture with acid or alkali to thereby convert water; metal salts and / or complex gases derived from cereal salts. The compound is carried on the surface of the metal particles. If the composite nickel fine powder of the present invention is prepared by wet load processing, (please read the precautions on the back before filling this page) Order --------- Online 丨 Printed by the staff consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The size of this paper applies Yin National Standard (CNS) A4 (21〇χ 297 mm) 8 310997 A7 V. Description of the invention (9) Fine particles of metal recorded as raw materials can be
^ ^ U. ^ ^ A 或濕處理所激I 者。在此方面,複合錄微細粉末可在低成 ,倚 整的濕處理操作而製傷,.根據上述之濕處理 完 微細粒子作為原料,視情況由濕處理以適 2屬鎳 化金屬鎳微細粒子,接著根據濕承 、4略巩 微細粉末之方法。就此而論,當使用?^進订製備複兮錄 使表面略氧化的金屬鎳微細粒子時, 的氧化劑 a κ此 町則刖述氧化物與/或 錯^氧化物容易形成在金屬鎳微細粒子表面上。 一 用於本發明複合鎳微細粉末製造 古之别述水溶性as (其根據濕承載加工進行)並無特別限制,只要彼等可溶: 水且可轉化為水不溶性氧化物或錯合氧化物即可。其^例 為前述金屬元素之齒化物、硝酸鹽、硫酸鹽、草酸鹽、: 化物、及磁性金屬鹽,例如鋁酸鹽與矽酸鹽。 當本發明之複合鎳微細粉末製造方法係由濕承載加工 進行時,pH調節劑可視前述所使用的水溶性鹽種類而定 而選酸或鹼,所用之此等酸及鹼之種類並無特別限制。<舉 例而言,若括弧中之氧化物係經由使用下述水溶性鹽而形 成’則可使用氫氧化鈉水溶液: 硫酸鈦(Ti02);硫酸錳(Μη02); 氣化絡(Cr2〇3);氣化釔(Υ2〇3); 氣化鍅氧化物(Zr02)。 此外,若括弧中之氧化物係經由使用下述水溶性逢而 形成’則可使用稀硫酸: 鋁睃鈉(αι2ο3);矽酸鈉(Si02)。 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 訂 濟 部 智 慧 財 產 局 消 費 合 作 社 印 製 310997 4 18 1 五、發明說明(10 ) 前述水溶性鹽會轉化為彼等氧化物或錯合氧化物,並 如以上所討論之調節水溶性鹽溶液之pH值,沉積及承載 在金屬錄微細粒子表面上,獲得本發明之複合鎳微細粉, 末。 - 右本發明之複合鎳微細粉·末製造方法係根據濕承載加 工進行,則除了前述處理步驟外,尚可進一步包括隨後的 洗滌及/或乾燥步驟。然而,前述水溶性登衍生之金屬氧. 化物及/或錯合氧化物根據濕承載加工承載至金屬鎳微細 粒子表面上,然後洗滌及乾燥’接著其上承載有氧化物及 /或錯合氧化物承載之金屬鎳微細粒子可進行額外步驟, 例如以器械處理’如〇ng研磨機、雜混機、械械熔融 (Mechanofusion)、Coat Mizer、Disper Coat、或 Jet Mizer, 其中使金屬鎳微細粒子相互碰撞或與其它物體碰撞,而將 超微細粒子緊密承載至金屬鎳微細粒子表面上。 根據乾承載加工所進行之本發明複合鎳微細粉末製造 方法中,將至少一員選自氧化物及錯合氧化物之超微細粒 子暫時承載至金屬鎳微細粒子或表面被氡化的金屬鎳微細 粒子表面上,其中該氧化物或錯合氧化物係含有至少一種 具有原子序範圍為12至56或82且屬於週期表中第2至 14族之金屬元素’接著使暫時承載黏著其上的超微細粒 子之鎳微細粒子相互碰撞或與其它物體碰撞,而將超微細 粒子承載至金屬鎳微細粒子表面上。 當本發明之複合鎳微細粉末製造方法係根據乾承載加 工進行,且所得複合鎳微細粉末以糊狀物的形式,用於製 木紙張尺度適用中國國家標率(CNS)A4規格(210x 297公着)— (請先閱讀背面之注·1^·項再填寫本頁) 訂---------線丨, 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(11 造層壓陶变電容器之内電極時,可用於發明方法中之金屬 錄微細粒子或表面氧化的金屬冑微細粒子較佳具有不大於 以m之粒度,更佳為不大於此外,此等氧化物及 /或錯合氧化物之超微細粒子粒度愈小,其可均勻承載至 金屬鎳微細粒子之所需量愈小。根據此項理由,其粒度較 佳不大於0.5am,更佳不大於〇 ,最佳不大於〇〇5ym。 ) 為了將前述金屬氧化物及/或錯合氧化物之超微細粒 子承載至金屬錄微細粒子或表面被氧化&金屬錄微細粒子 之表面上’則需要混合前者及後者’接著使暫時承載超微 細粒子之金屬鎳微細粒子相互碰撞或與其它物體碰撞,而 可確保超微細粒子黏著至金屬鎳微細粒子之表面上。或 者,將金屬鎳微細粒子及金屬氧化物及/或錯合氧化物之 超微細粒子充填於器械中,例如〇ng研磨機、雜混機、 機械熔融、Coat Mizer、Disper c〇at、或 Jet Mizer,而可 同時混合且承載後者至前者上。 k 濟 部 智 .慧 財 產 局 員 X 消 費 合 ΐ 社 印 製 根據半-乾承載加工所進行之本發明複合鎳微細粉末 製造方法令,利用加熱,將含有至少一員分散其中且選自 氧化物及錯合氧化物的超微細粒子之懸浮液與金屬鎳微細 粒子或表面被氧化的金屬鎳微細粒子混合,其中該氧化物 或錯合氧化物係含有至少一種具有原子序範圍為12至56 或82且屬於週期表中第2至14族之金屬元素接著移除 懸浮液之介質,而將超微細粒子暫時承載至金屬鎳微細粒 子表面上,並使暫時承載有黏著其上的超微細粒子之金屬 錄微細粒子相互碰撞或與其它物體碰撞’而將超微細粒子 11 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公笼) 310997 (請先閱讀背面之注意事項再填寫本頁)^ ^ U. ^ ^ A or I induced by wet treatment. In this respect, the composite recording fine powder can be wound in a low-temperature, uniform wet treatment operation. According to the above-mentioned wet treatment, the fine particles are used as raw materials, and if appropriate, the wet treatment is used to adapt the nickel fine particles of the 2 gens of nickelized metals. Then, according to the method of wet bearing, 4 slightly fine powder. In this regard, when to use? When the complex is prepared, the oxidizing agent a of the metallic nickel fine particles that slightly oxidizes the surface is described as oxides and / or oxides are easily formed on the surface of the metallic nickel fine particles. A kind of water-soluble as (which is performed according to wet-bearing processing) used in the production of the composite nickel fine powder of the present invention is not particularly limited as long as they are soluble: water and can be converted into water-insoluble oxides or complex oxides Just fine. Examples thereof include the dentate, nitrate, sulfate, oxalate, sulfide, and magnetic metal salts of the aforementioned metal elements, such as aluminate and silicate. When the method for manufacturing the composite nickel fine powder according to the present invention is performed by wet-bearing processing, the pH adjuster may be selected as an acid or an alkali depending on the type of the water-soluble salt used above, and the types of these acids and alkalis are not particularly limit. < For example, if the oxides in the parentheses are formed by using the following water-soluble salts, then an aqueous sodium hydroxide solution can be used: titanium sulfate (Ti02); manganese sulfate (Μη02); gasification complex (Cr203) ); Vaporized yttrium (rhenium 203); vaporized samarium oxide (Zr02). In addition, if the oxides in the parentheses are formed by using the following water-soluble compounds, dilute sulfuric acid may be used: sodium aluminum sulfonate (αι2ο3); sodium silicate (Si02). This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Development 310997 4 18 1 5. Description of the invention (10) The aforementioned water-soluble salts will be converted to their oxidation Or complex oxides, and the pH value of the water-soluble salt solution is adjusted as discussed above, deposited and carried on the surface of the metal fine particles to obtain the composite nickel fine powder of the present invention. -The manufacturing method of the composite nickel fine powder and powder according to the present invention is performed according to wet load processing. In addition to the aforementioned processing steps, it may further include subsequent washing and / or drying steps. However, the aforementioned water-soluble dendrite-derived metal oxides and / or complex oxides are carried on the surface of metallic nickel fine particles according to wet-loading processing, and then washed and dried 'followed by carrying oxides and / or complex oxides thereon. Fine particles of metallic nickel carried by the substrate may be subjected to additional steps, such as processing with a device such as a 0ng grinder, a hybrid machine, a mechanofusion, a Coat Mizer, a Disper Coat, or a Jet Mizer, in which the metallic nickel fine particles are made Collision with each other or with other objects, and the ultrafine particles are tightly supported on the surface of the metallic nickel fine particles. In the method for producing a composite nickel fine powder according to the present invention, which is carried out according to dry load processing, at least one member of ultrafine particles selected from oxides and complex oxides is temporarily carried to metal nickel fine particles or metal nickel fine particles having a surface that has been denatured. On the surface, the oxide or complex oxide system contains at least one metal element having an atomic range of 12 to 56 or 82 and belonging to groups 2 to 14 of the periodic table. The nickel fine particles of the particles collide with each other or with other objects, and the ultrafine particles are carried on the surface of the metallic nickel fine particles. When the method for manufacturing the composite nickel fine powder according to the present invention is performed according to dry load processing, and the obtained composite nickel fine powder is used in the form of a paste for wood making paper, the size of the Chinese national standard (CNS) A4 (210x 297 mm) is applicable. By) — (Please read the note on the back · 1 ^ · item before filling out this page) Order --------- line 丨, printed by A7 of the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs V. Invention Description (11 When manufacturing the internal electrode of the laminated ceramic capacitor, the metal particles or surface oxidized metal particles used in the method of the invention preferably have a particle size of not more than m, more preferably not more than these oxides. The smaller the particle size of the ultrafine particles of the complex oxide and / or the smaller the required amount for uniformly supporting the metal nickel fine particles. According to this reason, the particle size is preferably not more than 0.5am, more preferably not more than 0. , The best is not more than 0.05mm.) In order to carry the aforementioned ultrafine particles of metal oxides and / or complex oxides onto the metal fine particles or the surface is oxidized & the surface of the metal fine particles, then mixing is required. Former and later That is, the metallic nickel fine particles temporarily carrying the ultrafine particles collide with each other or with other objects, thereby ensuring that the ultrafine particles adhere to the surface of the metallic nickel fine particles. Alternatively, metal nickel fine particles and ultrafine particles of metal oxides and / or complex oxides are filled in a device, such as a ng mill, a hybrid, a mechanical fusion, a Coat Mizer, a Disper Coat, or a Jet Mizer, while mixing and carrying the latter onto the former. k Member of the Ministry of Economic Affairs, Intellectual Property, X, and Consumer Goods Co., Ltd. Printed the manufacturing method of the composite nickel fine powder according to the present invention, which was carried out according to semi-dry load processing, and used heating to disperse at least one member and selected from oxides and oxides. A suspension of ultrafine particles of a complex oxide is mixed with fine particles of metallic nickel or fine particles of metallic nickel whose surface is oxidized, wherein the oxide or complex oxide contains at least one having an atomic range of 12 to 56 or 82 and Metal elements belonging to groups 2 to 14 of the periodic table are then removed from the suspension medium, and the ultrafine particles are temporarily carried on the surface of the metal nickel fine particles, and the metal records temporarily holding the ultrafine particles adhered thereto Fine particles collide with each other or collide with other objects' while ultrafine particles will be used. 11 This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 male cage) 310997 (Please read the precautions on the back before filling this page)
41«142 五、發明說明(l2 ) 承載至金屬絲微細粒子表面上。 可用於前述半-乾承載加工中之金屬鎳黴細粒子或表 面氧化的金屬鎳微細粒子以及金屬氧化物及/或錯合氧化 物之超微細粒子與前述乾承載加工作所者相同。另外·,懸 浮超微細粒子之介質並無特別限制,一般使用例如灰、酸 性水溶液、驗性水溶液、醇或其它有機溶劑。此製造方法 中,使用的懸浮液可由下列步驟製備:將所欲的氧化物或 錯合氧化物之超微細粒子分散成預定固體含量之濃度,或 舉例而言,可為商業上購得的二氧化矽溶膠、氧化鋁溶膠、 氧化鈦溶膠、及鈦酸鋇溶膠,若需要,可稀釋以調節其濃 度至所欲的程度》 茲以下列實施例、比較例、及製備例於下文中更詳細 敘述本發明’但本發明完全未局限於此等特定實施例。 比較例1 將244克固體主要氫氧化鈉溶於純水,然後以純水稀 釋所得溶液至總體積為430毫升,而獲得氫氧化鈉水溶 液。另一方面,將448克硫酸鎳(NiS04 . 0H20 ;具有品 質程度為22.2重量%之產物)溶於純水(使用溫水以;保立 刻且完全溶解)’然後以純水稀釋所得溶液至總體積為1〇〇〇 毫升’而獲得硫酸銻水溶液。以添加速率為20毫升/分鐘, 將所得硫酸鎳水溶液以50分鐘内添加至前述氫氧化鈉水 溶液中。如此製備的含氫氧化物漿液溫度升高達60°c後, 將420克聯胺單水合物一次添加至漿液中以還原氩氧化 物。以純水洗滌所得金屬鎳微細粉末,持續以水洗滌直到 1-1—^---vk--------訂---------線 <請先閲讀背面ta..t事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) 12 310997 A7 A7 Μ 濟 部 智 慧 財 產 局 消 費 合 作 社 印 製 五、發明說明(U ) 洗滌液之pH值達到不大於1〇之程度,接著根據習用方 法過濾及乾燥而獲得金屬鎳微細粉末。所得金屬鎳微細粉 末以SEM觀測判定具有平均粒度(Feret,s直徑:主要粒子 之平均粒度)為0.2 ,且發現其具微觀不均勻表面。 比較例2 除了將420克用於還原加熱至6(rc的含氫氧化物裝 液之聯胺單水合物以20分鐘内連續添加至漿液中,而替 代一次添加以外,重複比較例1使用之相同步驟以製備鎳 微細粉末。所得金屬鎳微細粉末以SEM觀測判定具有平 均粒度(Feret’s直徑)為0,2em,且發現其具微觀不均勻 表面。 比較例3 充填由比較例1製備的金屬鎳微細粉末所組成之鎳微 細粉末(其具微觀不均勻表面)至雜混機(Hybridizer)(購自 奈良機械製造所(Nara Kikai Seisakusho)),並使其在機器 中以8000 rpm循環5分鐘而進行處理。處理後獲得的金 屬鎳微細粒子以SEM觀測判定具有平均粒度^“以、直徑) 為0.2/zm’且發現其具平滑表面。 比較例4 充填由比較例2製備的金屬鎳微細粉末所組成之鎳微 細粉末(其具微觀不均勻表面)至雜混機(購自奈良機械製 造所),並使其在機器中以8000 rpm循環5分鐘而進行處 理◎處理後獲得的金屬鎳微細粒子以SEM觀測判定具有 平均粒度(Feret’s直徑)為〇.5(am,且發現其具平滑表面。 I本紙張尺度適用中國國家標準(CNS)A4規格(21G X 297公餐) 丨-— 13 310997 請 先 閱 讀 背 之 注 意 事 項 · 再 I 填 · $裝 頁 訂 線 0142 A7 ---- B7 五、發明說明(W ) 製備例1 將1〇〇克比較例1製備的金屬鎳微細粉末添加於1升 純水中’接著予以攪拌而獲得漿液。漿液攪拌30分鐘後,' 將100克過氡化氫水溶液一次添加其中.當終止產生氣泡 (此表不反應完成)時即停止攪拌,接著過濾及乾燥而獲得 表面被氧化的金屬鎳微細粉末。所得金屬鎳微細粉末以 SEM觀測判定發現具有平均粒度(Feret,s直徑)為〇 2以瓜。 製備例2 將100克比較例2製備的金屬鎳微細粉末添加於J升 純水中,接著予以攪拌而獲得漿液。漿液攪拌30分鐘後, 將100克過氧化氫水溶液一次添加其中。當終止產生氣泡 (此表不反應完成)時即停止攪拌,接著過濾及乾燥而獲得 表面被氧化的金屬鎳微細粉末。所得金屬鎳微細粉末以 SEM觀測判定發現具有平均粒度(Feret,s直徑)為〇 5以瓜。 實施例1 將1〇〇克製備例1所製備表面被氧化的金屬鎳微細粉 末添加於1升純水中,接著予以攪拌而獲得漿液,漿液加 熱至6〇t並使漿液維持在此溫度。19 2克硫酸鈥(具有Ti a量為5重量%之產品)一次添加於漿液中,並添加氫氧 化鈉水溶液(Na0H·· 1N)以調節混合物之pH值至8。在彼 料件下持續攪拌】小時,接著過濾及乾燥而獲得帶有黏 著於金屬鎳粒子表面上的Ti〇2之複合鎳微細粉末。 實施例2 __將100克製備例2所製備表面氧化的金屬鎳微細粉末 衣紙張尺度適用中國國家標準(CNS)A4規格(2iQ χ ----------- W 310997 A7 - — - B7 五、發明說明(I5 ) 添加於1升純水中,接著予以搜摔而獲得衆液,衆液加熱 至60 C並使衆液維持在此溫度。由5克氣化絡溶於毫 升純水所製備之水溶液一次添加於後液中,並添加氮氧化 納水溶液(NaOH: 1N)以調節混合物之pH值至7。在彼等 條件下持續挽拌1小時,接著過渡及乾燥而獲得帶有黏著 於金屬鎳粒子表面上的CqO3之複合鎳微細粉末。 實施例3 ) Μ 100克製備例1所製備表面氧化的金屬鎳微細粉末 添加於1升純水中,接著予以授掉而獲得裝液,聚液加熱 至60 C並使漿液維持在此溫度。由6 5克矽酸鈉(水玻璃) 溶於60毫升純水所製備之水溶液一二欠添加於漿液中並 添加稀硫酸以調節混合物之ρΗ值至6。在彼等條件下持 績挽拌1小時,接著過遽及乾燥而獲得帶有黏著於金屬錄 粒子表面上的Si〇2之複合鎳微細粉末。 實施例4 j 將100克製備例1所製備表面氧化的金屬鎳微細粉末 添加於1升純水中,接著予以攪拌而獲得漿液,漿液加熱 至60°C並使漿液維持在此溫度。由3 5克氣化釔溶於5〇 毫升純水所製備之水溶液-次添加中,&添加氮氧 化鈉水溶液(NaOH : 1N)以調節混合物ipH值至6。在彼 等條件下持續攪拌1小時,接著過濾及乾燥而獲得帶有黏 著於金屬鎳粒子表面上的ΙΑ之複合鎳微細粉末。 實施例5 將克製備例1所製備表面氧化的金屬鎳微細粉末 15 310997 (請先.閱讀背面之注意事項再填寫本頁) ^紙張尺度適用中國國家標準(CNS)A4規格咖x 297公笼)---------- 經濟部智慧財產局員工消費合作社印製 A 1 〇 ^ A ^ A7 ------____ _ 五、發明說明(l6 ) 添加於1升純水中,接著予以授掉而獲得設液,激液加熱 至60 C並使衆液維持在此溫度β由3 5克氣化錯溶於% 毫升純水所製備之水溶液一次添加於梁液中,並添加氣氧 化鈉水溶液(Na〇H: 1Ν)以調節混合物之ρΗ值至6。在彼 等條件下持績搜拌1小時,接著過滅及乾燥而獲得帶有黏 著於金屬鎳粒子表面上的Zr〇2之複合鎳微細粉末。 實施例6 將100克製倩例1所製備表面氧化的金屬鎳微細粉末 添加於1升純水令’接著予以攪拌而獲得漿液’漿液加熱 至60C,並一次添加3.9克硫睃鈦水溶液(Ti含量:5重 量%)。進一步於漿液中添加氫氧化鈉水溶液(Na〇H : ιΝ) 以調節其pH值至8,接著攪拌1小時。然後過濾漿液, 一旦再漿化,即再予以過濾。將如此獲得的濾餅添加於1 升純水中以獲得漿液。接著由2.62克氧化鋇溶於溫水所 製備之溶液一次添加於漿液中,並添加氫氧化鈉水溶液 (NaOH : 1N)以調節混合物之pH值至不少於12。在彼等 條件下持續挽拌1小時,接著過遽及乾燥而獲得帶有黏著 於金屬鎳粒子表面上的BaTi03之複合錄微細粉末。 實施例7 將1〇〇克製備例2所製備表面氧化的金屬鎳微細粉末 添加於1升純水中,接著予以攪拌而獲得漿液,漿液加熱 至60°C並使漿液維持在此溫度。由15.7克硫酸錳溶於1〇〇 毫升純水所製備之水溶液一次添加於漿液中,並添加氫氧 化鈉水溶液(NaOH ·· 1N)以調節混合物之pH值至8。在彼 本紙張尺度適用令國國家標準(⑽A4規格⑵㈣7公⑻ 16 310997 --------訂---------線 ί請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 310997 A7 B7 五、發明說明(l7 ) 等條件下持續攪拌1小時,接著過濾及乾燥而獲得帶有黏 著於金屬錄粒子表面上的Μπ02之複合錄微細粉末。 實施例8 將10〇克製備例2所製備表面氧化的金屬鎳微細粉末 添加於1升純水中’接著予以攪拌而獲得漿液,漿液加熱 至50°C並使襞液維持在此溫度。由5 5克鋁酸鈉溶於1〇〇 毫升純水所製備之水溶液一次添加於漿液中,並添加稀硫 酸以調節混合物之pH值至8。在彼等條件下持績攪拌】 小時’接著過濾及乾燥而獲得帶有黏著於金屬鎳粒子表面 上的A丨2〇3之複合錄微細粉末。 實施例9 將100克製備例2所製備表面氧化的金屬鎳微細粉末 添加於1升純水中,接著攪拌而獲得漿液,漿液加熱至 60 C並使漿液維持在此溫度。由1〇 4克硝酸鎵溶於 毫升純水所製備之水溶液一次添加於漿液中並添加氫氧 化鈉水溶液(NaOH : 1N)以調節混合物之pH值至9。在彼 等條件下持續搜拌!小時,接著過遽及乾燥而獲得帶有黏 著於金屬鎳粒子表面上的Ga2〇3之複合鎳微細粉末。 實施例10 將⑽S製備例2所製備表面氡化的金屬鋒微細粉末 添加於1升純水中’接著予以授掉而獲得聚液聚液加熱 至〇6(TC,並一次添加3 9克硫酸鈦水溶液(τι含量:$重 量進步於漿液中添加氩氧化鈉水溶液(Na〇f^ 1N) 以調節其pH值至8,蛀基她秘, __接著攪拌1小時。然後過濾漿液,41 «142 V. Description of the invention (l2) Carried on the surface of fine particles of metal wire. The metal nickel mold fine particles or surface-oxidized metal nickel fine particles and ultrafine particles of metal oxides and / or complex oxides that can be used in the aforementioned semi-dry load processing are the same as those in the aforementioned dry load plus work station. In addition, the medium for suspending ultrafine particles is not particularly limited, and generally, for example, ash, an acidic aqueous solution, a test aqueous solution, an alcohol, or other organic solvents are used. In this manufacturing method, the suspension used can be prepared by dispersing ultrafine particles of the desired oxide or complex oxide to a predetermined solid content concentration, or, for example, commercially available two The silica sol, alumina sol, titania sol, and barium titanate sol can be diluted if necessary to adjust the concentration to a desired level. The following examples, comparative examples, and preparation examples are described in more detail below. The invention is described, but the invention is not limited to these specific embodiments at all. Comparative Example 1 244 g of solid main sodium hydroxide was dissolved in pure water, and the resulting solution was then diluted with pure water to a total volume of 430 ml to obtain a sodium hydroxide aqueous solution. On the other hand, 448 grams of nickel sulfate (NiS04. 0H20; a product with a quality level of 22.2% by weight) was dissolved in pure water (use warm water; ensure immediate and complete dissolution) 'and then the resulting solution was diluted with pure water to the total The volume was 1,000 ml 'to obtain an antimony sulfate aqueous solution. The obtained nickel sulfate aqueous solution was added to the aforementioned sodium hydroxide aqueous solution at a rate of 20 ml / min over a period of 50 minutes. After the temperature of the hydroxide-containing slurry thus prepared rose by up to 60 ° C, 420 g of hydrazine monohydrate was added to the slurry at one time to reduce argon oxide. Wash the obtained metallic nickel fine powder with pure water, and continue washing with water until 1-1 — ^ --- vk -------- Order --------- line < Please read the back ta first ..t matters, please fill out this page again) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Cooperative, this paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 public love) 12 310997 A7 A7 Μ Consumer Property Cooperative of the Ministry of Economic Affairs Printing 5. Description of the invention (U) The pH value of the washing liquid reaches a level of not more than 10, and then it is filtered and dried according to conventional methods to obtain a fine metal nickel powder. The obtained metallic nickel fine powder was judged by SEM observation to have an average particle size (Feret, s diameter: average particle size of major particles) of 0.2, and it was found to have a microscopic uneven surface. Comparative Example 2 Except that 420 g of the hydrazine monohydrate containing the hydroxide-containing liquid used for reduction heating to 60 ° C. was continuously added to the slurry within 20 minutes, instead of one time addition, the same was used as in Comparative Example 1. The same steps were used to prepare nickel fine powder. The obtained metallic nickel fine powder was judged by SEM observation to have an average particle size (Feret's diameter) of 0,2em, and it was found to have a micro uneven surface. A fine nickel powder (having a micro uneven surface) composed of a fine powder to a Hybridizer (purchased from Nara Kikai Seisakusho), and circulated in the machine at 8000 rpm for 5 minutes, and The treatment was performed. The fine particles of metallic nickel obtained after the treatment were judged to have an average particle size by SEM observation of 0.2 / zm ′ and were found to have a smooth surface. Comparative Example 4 A metallic nickel fine powder prepared in Comparative Example 2 was filled. The composed nickel fine powder (which has a microscopic uneven surface) is passed to a hybrid machine (purchased from Nara Machinery Manufacturing Co., Ltd.) and circulated in the machine for 5 minutes at 8000 rpm. ◎ The metallic nickel fine particles obtained after the treatment have an average particle size (Feret's diameter) of 0.5 (am) and are found to have a smooth surface by SEM observation. I This paper size applies the Chinese National Standard (CNS) A4 specification ( 21G X 297 public meal) 丨 -— 13 310997 Please read the notes of the back first, then I fill in the $ binding page 0142 A7 ---- B7 V. Description of the invention (W) Preparation Example 1 100 g The metallic nickel fine powder prepared in Comparative Example 1 was added to 1 liter of pure water 'followed by stirring to obtain a slurry. After stirring the slurry for 30 minutes, 100 g of an aqueous hydrogen peroxide solution was added thereto at a time. When the generation of air bubbles was terminated (this table When the reaction is not completed), stirring is stopped, followed by filtration and drying to obtain fine metal nickel powder with an oxidized surface. The obtained fine metal nickel powder was found to have an average particle size (Feret, s diameter) of 0.02 by SEM observation. Preparation Example 2 100 g of the metallic nickel fine powder prepared in Comparative Example 2 was added to J liters of pure water, followed by stirring to obtain a slurry. After the slurry was stirred for 30 minutes, 100 g of an aqueous hydrogen peroxide solution was used. It is added twice. When the generation of air bubbles is stopped (the reaction is complete), the stirring is stopped, and then the surface is oxidized to obtain fine metal nickel powder. The obtained fine metal nickel powder is found to have an average particle size by SEM observation. , S diameter) is 0. 5 melons. Example 1 100 g of finely oxidized metal nickel powder prepared in Preparation Example 1 was added to 1 liter of pure water, followed by stirring to obtain a slurry, and the slurry was heated to 6 0t and the slurry was maintained at this temperature. 19 2 g of sulfuric acid '(a product having a Ti a content of 5% by weight) was added to the slurry at one time, and an aqueous sodium hydroxide solution (NaOH ·· 1N) was added to adjust the pH of the mixture to 8. Stirring was continued for another hour], followed by filtration and drying to obtain a composite nickel fine powder with Ti0 2 adhered to the surface of the metal nickel particles. Example 2 __ 100 grams of surface-oxidized metallic nickel fine powder coated paper prepared in Preparation Example 2 was applied to the Chinese National Standard (CNS) A4 specification (2iQ χ ----------- W 310997 A7- —-B7 V. Description of the Invention (I5) Added to 1 liter of pure water, and then searched to obtain the liquid, the liquid was heated to 60 C and the liquid was maintained at this temperature. Dissolved from 5 g of gasification complex The aqueous solution prepared by the pure water was added to the subsequent solution at one time, and an aqueous solution of sodium oxynitride (NaOH: 1N) was added to adjust the pH value of the mixture to 7. Under these conditions, stirring was continued for 1 hour, followed by transition and drying. A composite nickel fine powder with CqO3 adhered to the surface of the metal nickel particles was obtained. Example 3) 100 g of the finely oxidized metal nickel powder prepared on the surface prepared in Preparation Example 1 was added to 1 liter of pure water, and was then given off to A charge was obtained, and the polymer was heated to 60 C and the slurry was maintained at this temperature. An aqueous solution prepared by dissolving 65 g of sodium silicate (water glass) in 60 ml of pure water was added to the slurry and dilute sulfuric acid was added to adjust the pH of the mixture to 6. Under these conditions, the mixture was stirred for 1 hour, followed by drying and drying to obtain a composite nickel fine powder with SiO2 adhered to the surface of the metal recording particles. Example 4 j 100 g of the surface-oxidized metallic nickel fine powder prepared in Preparation Example 1 was added to 1 liter of pure water, followed by stirring to obtain a slurry. The slurry was heated to 60 ° C and the slurry was maintained at this temperature. An aqueous solution prepared by dissolving 35 g of yttrium vaporized solution in 50 ml of pure water, and adding an aqueous solution of sodium hydroxide (NaOH: 1N) to adjust the ipH value of the mixture to 6. Stirring was continued for 1 hour under these conditions, followed by filtration and drying to obtain a composite nickel fine powder with IA adhered to the surface of the metal nickel particles. Example 5 The surface-oxidized metal nickel fine powder 15 310997 prepared in Preparation Example 1 (please read the precautions on the back before filling out this page) ^ Paper size applies Chinese National Standard (CNS) A4 size coffee x 297 male cages ) ---------- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A 1 〇 ^ A ^ A7 ------____ _ V. Description of the invention (l6) Added to 1 liter of pure water Then, it is taught to obtain the setting liquid, the stimulus is heated to 60 C and the liquid is maintained at this temperature β. The aqueous solution prepared by 35 g of gasification and dissolved in% ml of pure water is added to the beam liquid at a time, and Aqueous sodium oxide solution (NaOH: 1N) was added to adjust the pH value of the mixture to 6. Under these conditions, they were searched and mixed for 1 hour, followed by quenching and drying to obtain a composite nickel fine powder with ZrO2 adhered to the surface of the metal nickel particles. Example 6 100 g of the surface-oxidized metallic nickel fine powder prepared in Example 1 was added to 1 liter of pure water and then 'stirred to obtain a slurry'. The slurry was heated to 60 C, and 3.9 g of an aqueous titanium thiosulfate solution (Ti Content: 5% by weight). An aqueous solution of sodium hydroxide (NaOH: 1N) was further added to the slurry to adjust its pH to 8, followed by stirring for 1 hour. The slurry is then filtered, and once reslurried, it is filtered again. The filter cake thus obtained was added to 1 liter of pure water to obtain a slurry. Then, a solution prepared by dissolving 2.62 g of barium oxide in warm water was added to the slurry at one time, and an aqueous sodium hydroxide solution (NaOH: 1N) was added to adjust the pH of the mixture to not less than 12. Under these conditions, stirring was continued for 1 hour, followed by mashing and drying to obtain a composite fine powder with BaTi03 adhered to the surface of the metallic nickel particles. Example 7 100 g of the finely oxidized metallic nickel powder prepared in Preparation Example 2 was added to 1 liter of pure water, followed by stirring to obtain a slurry. The slurry was heated to 60 ° C and the slurry was maintained at this temperature. An aqueous solution prepared by dissolving 15.7 g of manganese sulfate in 100 ml of pure water was added to the slurry at one time, and an aqueous sodium hydroxide solution (NaOH ·· 1N) was added to adjust the pH of the mixture to 8. The national standard of the ordering country is applied to the size of the paper (4A4 size⑵㈣7⑵㈣⑻ 16 310997 -------- Order --------- line, please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 310997 A7 B7 V. Description of the invention (l7) Continue stirring for 1 hour, and then filter and dry to obtain a composite fine powder with Μπ02 adhered to the surface of the metal record particles . Example 8 100 g of the finely oxidized metallic nickel powder prepared in Preparation Example 2 was added to 1 liter of pure water ', followed by stirring to obtain a slurry. The slurry was heated to 50 ° C and the mash was maintained at this temperature. An aqueous solution prepared by dissolving 55 g of sodium aluminate in 100 ml of pure water was added to the slurry at one time, and dilute sulfuric acid was added to adjust the pH of the mixture to 8. Stirring under these conditions] hours', followed by filtration and drying to obtain a composite fine powder with Al 2 O 3 adhered to the surface of metallic nickel particles. Example 9 100 g of the finely oxidized metallic nickel powder prepared in Preparation Example 2 was added to 1 liter of pure water, followed by stirring to obtain a slurry. The slurry was heated to 60 C and the slurry was maintained at this temperature. An aqueous solution prepared by dissolving 104 g of gallium nitrate in ml of pure water was added to the slurry at one time and an aqueous sodium hydroxide solution (NaOH: 1N) was added to adjust the pH of the mixture to 9. Continue to search under their conditions! After 1 hour, the mixture was dried and dried to obtain a composite nickel fine powder with Ga203 bonded to the surface of the metal nickel particles. Example 10 The finely powdered metal front of the surface prepared by ⑽S Preparation Example 2 was added to 1 liter of pure water ', and then the mixture was obtained to obtain a polymer solution, and the solution was heated to 0 ° C and 39 g of sulfuric acid was added at a time Titanium aqueous solution (τι content: $ weight improvement) Add slurry of sodium argon oxide aqueous solution (NaOf ^ 1N) to adjust its pH to 8, and then stir it for 1 hour. Then filter the slurry,
参紙f尺度適用中^㈣靴NS)A4規格(心,公I I— — — — — — — — —— — — · I I I I I I I . I — I— I — II (請先閱讀背面之注意事項再填寫本頁) A7 4i b 1 4 2 -----B7 " -—--- 五、發明說明(IS ) 一旦再漿化’即再予以過濾。將如此獲得的濾餅添加於j 升純水中以獲得漿液《接著由2.0克氣化锶溶於溫水所製 備之溶液一次添加於漿液中,並添加氫氧化鈉水溶液 (NaOH : 1N)以調節混合物之pH值至不少於12。在彼等 條件下持續攪拌1小時,接著過濾及乾燥而獲得帶有黏著 於金屬鎳粒#表面上的SrTi03之複合鎳微細粉末。 上列實施例1至10製備之複合鎳微細粉末及前述比 較例1至2製儀之金屬鎳微細粉末,利用形變熱分析器(購 自理學電機株式會社(Rigaku Denki K.K·)),在氮氣壓下, 以加熱速率為l〇°C/分鐘,檢驗熱收縮率。如此獲得的結 果詳列於下表1中。 表1 實施例Feret’s氧化物黏著量熱收縮率(〇/〇)Refer to the paper f scale for medium ^ boots NS) A4 specifications (heart, male II — — — — — — — — — — — IIIIIII. I — I— I — II (Please read the precautions on the back before filling (This page) A7 4i b 1 4 2 ----- B7 " ---------- V. Description of the invention (IS) Once it is re-slurry ', it will be filtered. The filter cake thus obtained is added to j liters Obtaining a slurry in water "Then a solution prepared by dissolving 2.0 g of strontium gas in warm water was added to the slurry at one time, and an aqueous sodium hydroxide solution (NaOH: 1N) was added to adjust the pH of the mixture to not less than 12. Under these conditions, stirring was continued for 1 hour, followed by filtration and drying to obtain a composite nickel fine powder with SrTi03 adhered to the surface of the metal nickel particles #. The composite nickel fine powder prepared in Examples 1 to 10 above and the aforementioned comparison The fine metal nickel powders of the apparatuses of Examples 1 to 2 were tested for heat using a deformation thermal analyzer (purchased from Rigaku Denki KK ·) under a nitrogen pressure at a heating rate of 10 ° C / min. Shrinkage. The results thus obtained are detailed in Table 1 below. Table 1 Example Fere t ’s oxide adhesion calorimetric shrinkage (〇 / 〇)
編號 直徑 種類(%) 500°C 700°C 900°C ll〇〇°C 1 0.20 Ti02 0.97 -0.25 -0.17 -1.92 -7.08 2 0.20 Cr,0, 0.95 -1.25 -2.29 -6.96 -11.96 3 0.20 Si〇2 0.90 -0.63 -0.02 -0.83 -3.46 4 0.20 Y203 0.95 -1.08 -0.83 -3.06 -4.83 5 0.20 Zr02 0.98 -0.77 -0.58 -6.38 -11.83 6 0.20 BaTi03 0.96 -1.25 -1.45 -3.96 -14.08 7 0.50 Μη02 2.88 -0.92 -0.98 -5.83 -12.92 8 0.50 Α12〇3 0.89 -1.35 -0.98 -1.46 -8.04 9 0.50 Ga203 0.88 -1.28 -2.17 -4.52 -9.58 10 0.50 SrTiO, 0.91 -1.04 -1.99 -2.75 -5.09 1* 0.20 — — -0.83 -1.98 -9.69 -15.35 2* 0.50 — — -0.56 -0.69 -7.88 -14.46 氺:比較例 由詳列於表1令之數據可發現,與比較例1至2之金 c請先閱讀背面之沒意事項再填寫本頁) 訂---------線- 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用令國國家標準(CNS)A4規格(210 X 297公釐) 18 310997 A7 A7 •經濟部智慧財產局員工消費合作社印製 310997 五、發明說明(i9 ) 屬鎳微細粉末相較,實施例丨至10之複合鎳微細粉末(本 發明)在高溫下具有相當低之熱大尺寸率。 管施例11 將500克比較例2製備之金屬錄微細粉末及35克超 微細氧化鋁粒子(自日本埃羅矽株式會社(Nipp〇n Aer〇sii Co·,Ltd.)購買之氧化鋁c ;主要粒子之平均粒度:13 nm ; 相對於金屬鎳微細粉末之混合比率:7重量%)攪4混合i5 分鐘,以獲得包括暫時承載至金屬鎳微細粒子表面上的氧 化銘超微細粒子之錄微細敕子。此外,將粉末充填至雜混 機(購自奈良機械製造所),並使粉末在機器中以8〇〇〇 rpm 循環5分鐘而進行處理,以獲得包括承載至金屬錄微細粒 子表面上的氧化鋁超微細粒子之複合鎳微細粉末。 因為氧化鋁超微細粒子係承載在所得複合鎳微細粉末 之金屬鎳微細粒子表面上,所以即使在水中添加氧化鋁超 微細粒子(在粉末係利用攪拌簡單混合而獲得之情況下, 氧化鋁超微細粒子係懸浮於水中且水會變得混濁),亦未 觀察到任何氧化鋁超微細粒子之移除及浮動。另外,所得 複合鎳微細粉末藉由SEM觀測檢驗,並證實氧化鋁超微 細粒子係均勻承載至複合鎳微細粒子表面上,且證實複合 粒子之粒度在黏著步驟前後幾乎相等。 實施例12 除了以2.5克超微細氧化鋁粒子(相對於金屬鎳微細 粉末之混合比率:〇_5重量取代實施例丨丨使用之35克 超微細氧化鋁粒子外,重複如實施例丨丨使用之相同步驟, I紙張尺度適用中國國豕標準(CNS>A4規格(21G X 297公餐 — 丨·!1—1111—1 ^^ . I —---— I 訂.----I I (請先閱讀背面之注意事項再填寫本頁) Α7Number Diameter Type (%) 500 ° C 700 ° C 900 ° C ll00 ° C 1 0.20 Ti02 0.97 -0.25 -0.17 -1.92 -7.08 2 0.20 Cr, 0, 0.95 -1.25 -2.29 -6.96 -11.96 3 0.20 Si 〇2 0.90 -0.63 -0.02 -0.83 -3.46 4 0.20 Y203 0.95 -1.08 -0.83 -3.06 -4.83 5 0.20 Zr02 0.98 -0.77 -0.58 -6.38 -11.83 6 0.20 BaTi03 0.96 -1.25 -1.45 -3.96 -14.08 7 0.50 Μη02 2.88 -0.92 -0.98 -5.83 -12.92 8 0.50 Α12〇3 0.89 -1.35 -0.98 -1.46 -8.04 9 0.50 Ga203 0.88 -1.28 -2.17 -4.52 -9.58 10 0.50 SrTiO, 0.91 -1.04 -1.99 -2.75 -5.09 1 * 0.20 — — -0.83 -1.98 -9.69 -15.35 2 * 0.50 — — -0.56 -0.69 -7.88 -14.46 氺: Comparative examples can be found from the data listed in the order in Table 1, and gold c in Comparative Examples 1 to 2 please Read the unintentional matter on the back before filling this page) Order --------- line-Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs This paper applies the national standard (CNS) A4 specification (210 X 297 mm) 18 310997 A7 A7 • Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 310997 V. Description of Invention (i9) Compared with nickel fine powder, implemented Shu to nickel composite fine powder (Invention) 10 having the large heat of a relatively low ratio at a high temperature. Tube Example 11 500 g of the fine metal powder prepared in Comparative Example 2 and 35 g of ultrafine alumina particles (alumina c purchased from Nippon Aerosii Co., Ltd.) ; Average particle size of main particles: 13 nm; Mixing ratio with respect to metal nickel fine powder: 7% by weight) Stir for 4 minutes and mix for 5 minutes to obtain a record including ultrafine particles of oxide particles temporarily carried on the surface of metal nickel fine particles Fine duster. In addition, the powder was filled into a hybrid machine (purchased from Nara Machinery Manufacturing Co., Ltd.), and the powder was processed by circulating the powder in the machine at 8000 rpm for 5 minutes to obtain oxidation including loading on the surface of the fine particles of the metal recorder. Composite nickel fine powder of aluminum ultrafine particles. Since alumina ultrafine particles are supported on the surface of metallic nickel fine particles of the obtained composite nickel fine powder, even if alumina ultrafine particles are added to water (in the case of powder systems obtained by simple mixing with stirring, alumina ultrafine The particles were suspended in water and the water became cloudy), and no removal and floating of any alumina ultrafine particles was observed. In addition, the obtained composite nickel fine powder was examined by SEM observation, and it was confirmed that the alumina ultrafine particles were uniformly carried on the surface of the composite nickel fine particles, and it was confirmed that the particle size of the composite particles was almost equal before and after the adhesion step. Example 12 Except replacing the 35 grams of ultrafine alumina particles used in Example 丨 with 2.5 grams of ultrafine alumina particles (mixing ratio with respect to metallic nickel fine powder: 0-5 weight), repeat the use as in Examples 丨 丨For the same steps, I paper size applies the Chinese National Standard (CNS > A4 specification (21G X 297 public meal — 丨 ·! 1-1111—1 ^^. I —---— I order .---- II ( (Please read the notes on the back before filling out this page) Α7
五、發明說明(Μ ) 以獲得包括承載至金屬錄微細粒子表面上的氧化銘超微細 粒子之複合鎳微細粉末β . 會施例13至26 4 ! d I ^! · 2 經濟部智慧財產局員工消費合作社印製 將500克比較例2製備之金屬鎳微細粉末及25克(相 對於金屬錄微細粉末之混合比率:5重量%)或5克(相對 於金屬錄微細粉末之混合比率:1重量%)下列超微細粒子 攪拌混合15分鐘:超微細氧化鈦粒:f (自曰本埃羅參株式 會社購買之!>25;主要粒子之平均粒度:13nm)、超微細 二氧化矽粒子(自曰本埃羅矽株式會社購買之3〇〇CF ;主 要粒子之平均粒度:7 nm)、超微細氧化鎂粒子(自宇部材 料株式會社(Ube Material Co.,Ltd·)購買之1〇〇A;主要粒 子之平均粒度:10 rim)、超微細氧化釔粒子(自CI化學工 業株式會社(Cl Chemical Industries,Ltd.)構買;主要粒子 之平均粒度:10 nm)、超微細鈦酸鋇粒子(根據溶膠_凝膠 法,使用過氧化鈦及過氧化鋇予以製備;主要粒子之平均 粒度:30 nm)、超微細鈦酸鳃粒子(根據溶膠_凝膠法,使 用過氧化鈦及過氧化鋇予以製備;主要粒子之平均粒度: 10 nm)、或超微細鈦酸锶鋇(Ba〇 9Sr() i)Ti〇3粒子(根據溶膠 -凝膠法製備;主要粒子之平均粒度:1〇nm),以獲得包 括暫時承載至金屬鎳微細粒子表面上的前述任一種超微細 粒子之金屬鎳微細粒子。此外,將粉末充填至雜混機(購 自奈良機械製造所),並使粉末在機器中以8〇〇〇 rpm循環 5分鐘而進行處理’以獲得包括承載至金屬鎳微細粒子表 面上的前述任一種超微細粒子之複合鎳微細粉末。 ------------I I ' I ---—II --------^ C請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用争國國家標準(CNS)A4規格(21〇x 297公釐) 20 310997 A7 B7 ,經濟部智慧財產局員工消費合作社印制衣 五、發明說明() 實施例27 除了以機械熔融機(購自細川微米株式會社(H〇s〇kawa Micron Co.,Ltd·))取代實施例11使用之雜混機(購自奈良 機械製造所)’並使粉末在機器中以3000 rpm循環30分 鐘而進行處理外,重複如實施例11使用之相同步驟,以 獲得包括承載至金屬鎳微細粒子表面上的氧化鋁超微細粒 子之複合鎳微細粉末。 因為氧化銘超微細粒子係承載在所得複合鎳微細粉末 之金屬錄微細粒子表面上,所以即使在水中以攪拌添加氧 化铭超微細粒子’亦未觀察到任何氧化鋁超微細粒子之移 除及浮動。另外,所得複合鎳微細粉末藉由SEM觀測檢 驗’並證實氧化鋁超微細粒子係均勻承載至複合粉末表面 上’且證實複合粒子之粒度於黏著步驟前後幾乎相等。 實施例28 將二氧化5夕溶膠(Snow Tex 0,購自曰產化學工業株 式會社(Nissan Chemical Industries, Ltd.);主要粒子之平 均粒度:10 nm)以水稀釋20倍而獲得之於2.5升溶液(二 氧化矽含量:10克/升)中,添加500克製備例2所製備的 金屬鎳微細粉末,接著加熱並充分攪拌。逐漸蒸發水成分, 最後獲得乾燥粉末。將粉末充填至雜混機(購自奈良機械 製造所),並使粉末在機器中以8000 rpm循環5分鐘而進 行處理,如此可獲得包括承載至金屬鎳微細粒子表面上的 超微細二氧化矽粒子之複合鎳微細粉末。 所得複合鎳微細粉末藉由SEM觀測檢驗,並證實二 I--------裝-------- 訂---I-----線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用申國國家標準(CNS)A4規格(2〗0 X 297公釐〉 21 310997 A7 ^10142 •------ ' '___ B7_ 五、發明說明(22 ) 氧化矽超微W粒子係均勻承載至複合粉末表面上,且證實 嘈合粒子之粒.度於黏著步驟前後幾乎相等。發現相對於金 屬鎳微細粉末之重量,承載至複合鎳微細粒子表面上之二 氧化碎粒子量為5重量。/〇。此外,二氧化石夕超微細粒子係 承載在所得複合鎳微細粉末之金屬鎳微細粒子表面上,因 此,即使在水中以拌.添々二氧化矽超微細粒子·,亦未觀 察到任何氧化鋁超橛細粒子之移除及浮動。 實施例29 將500克製備例2所製備的金屬鎳微細粉末以充分攪 拌添加於超分散機容器(購自三井礦山株式會社(Mitsui Mining Co.,Ltd.))中,以熱蒸氣加熱容器,接著自容器頂 端,滴加氧化鋁溶膠(125克;自曰產化學工業株式會社 購貝之氧化銘溶膠520;粒度:10至20 nm),以獲得包 括暫時承載至金屬鎳微細粒子表面上的氧化鋁超微細粒子 之金屬鎳微細粉末。將粉末充填至雜混機(購自奈良機械 製造所),並使粉末在機器中以8000 rpm循環5分鐘而進 行處理’如此可獲得包括承載至金屬鎳微細粒子表面上的 超微細氧化鋁粒子之複合鎳微細粉末。所得複合鎳微細粉 末藉由SEM觀測檢驗’並證實超微細粒子係承載至金屬 鎳微細粒子表面上’且發現相對於金屬鎳微細粉末之重 量,承載至金屬鎳微細粒子表面上之超微細粒子量為5重 量%。 上列實施例11至29製備之複合鎳微細粉末及前述比 較例3至4製備之金屬鎳微細粉末(其具有平滑表面,但 --II— —.1 I I I I I ^ i I I I I I I ^ - - - - - ----|( (請先閱讀背面;之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 22 310997 A7 B7 五、發明說明(23 ) 其上未黏著任何氧化物或錯合氧化物),利用形變熱分析 器(購自精工電機工業株式會社(Seiko Electronic Industries,Ltd.)之TMA/SS6000),在氮氣壓下,以加熱速 率為10°C/分鐘,檢驗熱大尺寸率。如此獲得的結果詳列 於下表2中。在此方面,觀察比較例1至2製備之金屬鎮 微細粉末(其不具有平滑表面,且其上未黏著任何氧化物 或錯合氧化物)之熱大尺寸率詳列於前述表1中。 表2 實施氧化物種類 混合熱收縮率(%) 例編 比例 5〇o°c 7〇o°c 9〇o°c TToot" 號 --------------裝— (請先閱讀背面之注意事項再填寫本頁) -經濟部智慧財產局員工消費合作社印製 11 ai2o3 7 -0.34 -0.41 -0.41 -0.49 12 0.5 -0.52 -0.61 -0.63 -1.81 13 Ti〇2 1 -0.57 -0.63 -2.90 -8.67 14 Τΐ02 5 -0.49 -0.54 -2.41 -7.97 15 Si02 1 -0.52 -0.63 -0.95 -1.46 16 Si〇2 5 -0.49 -0.63 -0.70 -1.13 17 MgO 1 -0.58 -0.30 -0.33 -0.24 18 MgO 5 -0.55 -0.35 -0.39 -0.28 19 Y203 1 -0.32 -0.48 0.53 -1.87 20 Y2〇3 5 -0.45 -0.49 -0.58 -1.52 21 BaTi03 1 -0.48 -0.51 -0.68 -0.69 22 BaTi03 5 -0.51 -0.52 -0.63 -0.66 23 SrTi〇3 1 -0.38 -0.44 -0.81 -2.14 24 SrTi〇3 5 -0.32 -0.39 -0.52 -1.90 25 (B^OgSlo 1)Ti〇3 1 -0.25 -0.41 -0.60 -1.86 26 (Ba0 9Sr01)Ti03 5 -0.32 -0.37 0.51 -0.95 27 AI2O3 7 -0.37 -0.46 -0.54 -0.79 28 Si02 5 -0.26 -0.36 -0.59 -0.80 29 Al2〇3 5 -0.43 -0.46 -0.56 -0.59 3* 一 — -0.81 -1.94 -9.56 -15.08 4* 一 一 -0.54 -0.66 -7.79 -14.30 氺:比較例 訂 線 本紙張尺度適用中國國家標準(CNS)A4規格(210x 297公釐) 23 310997 A7 4 I b 1 4 2 ___-____B7___ 五、發明說明(24 ) 由詳列於表1及2中之數據清楚可知,與比較例ι至 4之金屬鎳微細粉末相比,實施例u至29之複合鎳微細 粉末(本發明)在高溫下具有相當低之熱大尺寸率。 實施例11至26獲得之複合鎳微細粉末及比較例2及 4之金屬鎳微細粉末,在空氣下埠行熱重分析。更詳言之, • 在分析前判定各樣品的重量,然後以速率為丨〇<>c /分鐘加 熱樣ucr達4 0 0 C ’並在4 0 0 C維持2小時。此階段,相對 於測量開始時觀察的重量(起始重量),判定各樣品的重 量’如此可計算重量増加率Α(%ρ其後,樣品的溫度提 高達1000°C (此階段’所有鎳似乎轉化為氧化鎳),相對於 起始重量,判定此階段各樣品的重量,如此可獲得重量增 加率B(%)。測定A/B之比率,其定義為各樣品(即鎳粉末) 在400°C維持2小時後之氧化程度》如此獲得的結果簡單 說明於下表3中。 -------------^ ---I----訂.!------|( (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 24 310997 五、發'明說明(25 A7 B7 表3 實施例編號氧化物種類 混合比例各樣品400°C下維持 _2小時後之氧化程度 234567890123456* * n 1 lx 1 1 IX 11 11 2 2 2 2 2 2 2 4. % /Ό /Ό /Ό /Ό /Ό /Ό /Ό Λ^/ 7 Ti 1i 11 1X c—w 11 11 3 3 o o ♦1 *1 T T \ly \)/ 1 11 o o :030303o:sr9sr 2o2oo2020202gogoo303aT-aTlTiTiaoao aattssmmyybbss(b(b 25899813013975393 3 56766586765455658 8V. Description of the invention (M) to obtain a composite nickel fine powder including oxidized ultrafine particles carried on the surface of the fine particles of the metal record β. Examples 13 to 26 4! D I ^! · 2 Bureau of Intellectual Property, Ministry of Economic Affairs Employee Consumer Cooperative printed 500 grams of metal nickel fine powder prepared in Comparative Example 2 and 25 grams (mixing ratio with respect to metal recording fine powder: 5% by weight) or 5 grams (mixing ratio with respect to metal recording fine powder: 1 % By weight) The following ultrafine particles are stirred and mixed for 15 minutes: ultrafine titanium oxide particles: f (purchased from Japan Erosin Corporation!> 25; average particle size of main particles: 13nm), ultrafine silicon dioxide particles (300CF purchased from Japan Eros Silicon Co., Ltd .; average particle size of main particles: 7 nm), ultra-fine magnesium oxide particles (1 purchased from Ube Material Co., Ltd.) 〇A; average particle size of main particles: 10 rim), ultrafine yttrium oxide particles (purchased from CI Chemical Industries, Ltd .; average particle size of main particles: 10 nm), ultrafine titanic acid Barium particles Prepared according to the sol-gel method using titanium peroxide and barium peroxide; the average particle size of the main particles: 30 nm), ultrafine gill titanate particles (based on the sol-gel method, using titanium peroxide and barium peroxide) Prepared; average particle size of main particles: 10 nm), or ultrafine barium strontium titanate (Ba〇9Sr () i) Ti03 particles (prepared according to sol-gel method; average particle size of main particles: 10 nm ) To obtain metallic nickel fine particles including any of the foregoing ultrafine particles temporarily carried on the surface of metallic nickel fine particles. In addition, the powder was filled into a hybrid machine (purchased from Nara Machinery Manufacturing Co., Ltd.), and the powder was processed by circulating the powder in the machine at 8000 rpm for 5 minutes to obtain the foregoing including loading onto the surface of metallic nickel fine particles. Any kind of ultra-fine particles of composite nickel fine powder. ------------ II 'I ----- II -------- ^ C Please read the notes on the back before filling this page) This paper size applies to the national standards of the competing countries (CNS) A4 specification (210 × 297 mm) 20 310997 A7 B7, printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention () Example 27 Except for a mechanical melting machine (purchased from Hosokawa Micron Co., Ltd.) (Hosokawa Micron Co., Ltd.)) Instead of the hybrid machine (purchased from Nara Machinery Manufacturing Co., Ltd.) used in Example 11 ', the powder was cycled in the machine for 30 minutes at 3000 rpm, and the process was repeated. The same procedure was used as in Example 11 to obtain a composite nickel fine powder including alumina ultrafine particles supported on the surface of metallic nickel fine particles. Because the oxide ultrafine particles are carried on the surface of the metal fine particles of the obtained composite nickel fine powder, even if the oxide ultrafine particles are added by stirring in water, no removal and floating of alumina ultrafine particles is observed. . In addition, the obtained composite nickel fine powder was examined by SEM observation and confirmed that the alumina ultrafine particles were uniformly carried on the surface of the composite powder 'and that the particle size of the composite particles was almost equal before and after the adhesion step. Example 28 Dioxide of 5 nd sol (Snow Tex 0, purchased from Nissan Chemical Industries, Ltd .; average particle size of major particles: 10 nm) was diluted by 20 times with water to obtain 2.5. In a liter solution (silica dioxide content: 10 g / L), 500 g of the fine metal nickel powder prepared in Preparation Example 2 was added, followed by heating and stirring sufficiently. The water component was gradually evaporated, and finally a dry powder was obtained. The powder was filled into a hybrid machine (purchased from Nara Machinery Manufacturing Co., Ltd.), and the powder was processed by circulating the powder in the machine at 8000 rpm for 5 minutes, thereby obtaining ultrafine silicon dioxide including the surface of fine particles of metallic nickel. Particles of composite nickel fine powder. The obtained composite nickel fine powder was examined by SEM observation and confirmed that the two I -------- installation -------- order --- I ----- line (please read the note on the back first) Please fill in this page again for the items) This paper size applies to the National Standard of China (CNS) A4 (2〗 0 X 297 mm> 21 310997 A7 ^ 10142 • ------ '' ___ B7_ V. Description of the invention (22 ) The silicon oxide ultrafine W particles are uniformly carried on the surface of the composite powder, and it is confirmed that the particles of the noisy particles are almost equal before and after the adhesion step. It is found that the weight relative to the weight of the metal nickel fine powder is carried on the surface of the composite nickel fine particles. The amount of crushed particles of the particles is 5 wt.%. In addition, the ultrafine particles of the silica dioxide are supported on the surface of the metal nickel fine particles of the obtained composite nickel fine powder. Silicon ultrafine particles. No removal or floating of alumina ultrafine particles was observed. Example 29 500 grams of the metallic nickel fine powder prepared in Preparation Example 2 was added to the ultra-disperser container (purchased with sufficient stirring). From Mitsui Mining Co., Ltd.), hot steamed The vessel was heated by gas, and then from the top of the vessel, an alumina sol (125 g; oxidized sol 520 purchased from Japan Chemical Industry Co., Ltd .; particle size: 10 to 20 nm) was obtained to obtain fine particles including a temporary load on metallic nickel. Metal nickel fine powder of alumina ultrafine particles on the particle surface. Fill the powder into a hybrid machine (purchased from Nara Machinery Manufacturing Co., Ltd.), and let the powder be processed in the machine at 8000 rpm for 5 minutes for processing. A composite nickel fine powder including ultrafine aluminum oxide particles carried on the surface of metal nickel fine particles. The obtained composite nickel fine powder was examined by SEM observation and 'confirmed that the ultrafine particles were carried on the surface of metal nickel fine particles' and it was found that the relative Based on the weight of the metal nickel fine powder, the amount of ultrafine particles carried on the surface of the metal nickel fine particles is 5% by weight. The composite nickel fine powder prepared in the above Examples 11 to 29 and the metal nickel prepared in the aforementioned Comparative Examples 3 to 4 Fine powder (it has a smooth surface, but --II---. 1 IIIII ^ i IIIIII ^--------- | ((Please read the back first; note Please fill in this page for further information) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 mm) 22 310997 A7 B7 V. Description of the invention (23) Any oxide or complex oxide), using a deformation thermal analyzer (TMA / SS6000 purchased from Seiko Electronic Industries, Ltd.) under a nitrogen pressure at a heating rate of 10 ° C / Minutes, check the thermal large size ratio. The results thus obtained are detailed in Table 2 below. In this regard, the thermal large size ratios of the metal ball fine powders (which do not have a smooth surface and which do not have any oxides or complex oxides adhered thereto) prepared in Comparative Examples 1 to 2 are listed in Table 1 above. Table 2 Mixed thermal shrinkage rate of implementation oxide types (%) Example compilation ratio 50o ° c 70o ° c 90o ° c TToot " No. -------------- equipment— (Please read the precautions on the back before filling this page)-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 11 ai2o3 7 -0.34 -0.41 -0.41 -0.49 12 0.5 -0.52 -0.61 -0.63 -1.81 13 Ti〇2 1 -0.57 -0.63 -2.90 -8.67 14 Τΐ02 5 -0.49 -0.54 -2.41 -7.97 15 Si02 1 -0.52 -0.63 -0.95 -1.46 16 Si〇2 5 -0.49 -0.63 -0.70 -1.13 17 MgO 1 -0.58 -0.30 -0.33 -0.24 18 MgO 5 -0.55 -0.35 -0.39 -0.28 19 Y203 1 -0.32 -0.48 0.53 -1.87 20 Y2〇3 5 -0.45 -0.49 -0.58 -1.52 21 BaTi03 1 -0.48 -0.51 -0.68 -0.69 22 BaTi03 5 -0.51 -0.52 -0.63 -0.66 23 SrTi〇3 1 -0.38 -0.44 -0.81 -2.14 24 SrTi〇3 5 -0.32 -0.39 -0.52 -1.90 25 (B ^ OgSlo 1) Ti〇3 1 -0.25- 0.41 -0.60 -1.86 26 (Ba0 9Sr01) Ti03 5 -0.32 -0.37 0.51 -0.95 27 AI2O3 7 -0.37 -0.46 -0.54 -0.79 28 Si02 5 -0.26 -0.36 -0.59 -0.80 29 Al2〇3 5 -0.43 -0.46 -0.56 -0.59 3 * one--0.81 -1.94 -9.56 -15.08 4 * one -0.54 -0. 66 -7.79 -14.30 氺 : Comparison setting. The paper size is applicable to Chinese National Standard (CNS) A4 (210x 297 mm) 23 310997 A7 4 I b 1 4 2 ___-____ B7___ V. Description of the invention (24) Details The data listed in Tables 1 and 2 clearly show that the composite nickel fine powders of the examples u to 29 (the present invention) have a relatively low heat large size at high temperatures compared to the metal nickel fine powders of Comparative Examples ι to 4. rate. The composite nickel fine powders obtained in Examples 11 to 26 and the metal nickel fine powders of Comparative Examples 2 and 4 were subjected to thermogravimetric analysis in the air. In more detail, • Determine the weight of each sample before analysis, and then heat the sample at a rate of 0 < > c / min to ucr for 4 0 C 'and maintain it at 4 0 C for 2 hours. At this stage, relative to the weight (starting weight) observed at the beginning of the measurement, determine the weight of each sample 'so that the weight increase rate A (% ρ) can be calculated. Thereafter, the temperature of the sample has increased by 1000 ° C (all nickel at this stage') (Seems to be converted to nickel oxide), relative to the starting weight, determine the weight of each sample at this stage, so that the weight increase rate B (%) can be obtained. The A / B ratio is determined, which is defined as each sample (ie, nickel powder) in The degree of oxidation after maintaining at 400 ° C for 2 hours "The results thus obtained are briefly explained in Table 3 below. ------------- ^ --- I ---- Order.!- ---- | ((Please read the notes on the back before filling out this page) Printed on the paper by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 24 310997 V. Instructions (25 A7 B7 Table 3 Example No. Oxidation Type Mixing Ratio Each sample is maintained at 400 ° C for 2 hours after oxidation 234567890123456 * * n 1 lx 1 1 IX 11 11 2 2 2 2 2 2 2 4.% / Ό / Ό / Ό / Ό / Ό / Ό / Ό Λ ^ / 7 Ti 1i 11 1X c—w 11 11 3 3 oo ♦ 1 * 1 TT \ ly \) / 1 11 oo: 0 30303o: sr9sr 2o2oo2020202gogoo303aT-aTlTiTiaoao aattssmmyybbss (b (b 25899813013975393 3 56766586765455658 8
I --------------裳--------訂. f請先閱讀背面之注音?事項再填寫本頁:> '經濟部智慧財產局員H消費合作社印製 * :比較例 由詳列於表3中之據數可清楚表示,與比較例2及4 之金屬鎳微細粉末相比,根據本發明實施例11至2 6之複 合鎳微細粉末具優異之抗氧化性。特別清楚是,承載至錦 表面之氧化物與/或錯合氧化物的比率愈高,複合鎳微細 粉末之抗酸性愈高。此係因為承載至鎳微細粉末表面之氧 化物與/或錯合氧化物,而顯現防止複合鎳微細粉末氧化 之效果。 前述實施例11獲得之複合錄微細粉末及比較例4之 金屬錄微細粉末進一步進行熱重分析。測定各樣品重量 後,以加熱速率為1.5 °C/分鐘加熱樣品達1〇〇〇艺,並將 本紙張尺度適用令國國家標準(CNS)A4規格(21〇 X 297公爱) 25 310997 A7 B7_______ 五、發明說明(26 ) 此測定的重量増加率製成溫度之函數圖。因此,測定所達 到1 000°C觀察之一半重量增加率之溫度。此係表示5 0% 錄氧化之溫度。發現比較例4之金屬錄粉末的溫度為 429°C,而聲現前述實施例u獲得之複合鎳微細粉末的溫 度為452°C,表示需要氧化50%鎳之溫度增加23°C。 關於上述之詳細說明,本發明之複合鎳微細粉末具優 異之抗氧.化性、具有對氧化低敏感性之結構、迅速熱大尺 寸起始溫度移動至不低於700eC,且對多數試驗情況而言 為不低於900°C,因此複合粉末相當適合使用作為形成層 壓電容器之内電極材料。換言之,本發明之複合鎳微細粉 末於黏合劑移除期間,具有優異之金屬鎳氧化抗性及氧化 鎳擴散抗性,表現近乎與陶瓷底材的熱大尺寸曲線相同之 熱大尺寸性質,當製造大尺寸的層壓陶瓷電容器時,可根 據本發明防止發生脫層及形成裂紋,且可製造包括陶瓷介 電層及内電極之薄、小尺寸的多層陶瓷電容器,而未損害 其介電特徵及電性質。 > ;-------------訂-----1---線 — {請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用t國國家標準(CNS)A4規格(210 X 297公爱) 26 310997I -------------- Shang -------- Order. F Please read the phonetic on the back first? Please fill in this page again: > 'Printed by H Consumer Cooperative, Member of Intellectual Property Bureau, Ministry of Economic Affairs *: The comparative example can be clearly shown by the data detailed in Table 3, compared with the fine nickel metal powders of Comparative Examples 2 and 4. The composite nickel fine powders according to Examples 11 to 26 of the present invention have excellent oxidation resistance. It is particularly clear that the higher the ratio of the oxide and / or complex oxide carried on the surface of the brocade, the higher the acid resistance of the composite nickel fine powder. This is because the oxides and / or complex oxides carried on the surface of the nickel fine powder have an effect of preventing oxidation of the composite nickel fine powder. The composite fine powder obtained in the aforementioned Example 11 and the fine fine powder of the metal recorded in Comparative Example 4 were further subjected to thermogravimetric analysis. After measuring the weight of each sample, the sample was heated at a heating rate of 1.5 ° C / min for 1,000 hours, and the paper size was adapted to the national standard (CNS) A4 specification (21OX 297 public love) 25 310997 A7 B7_______ 5. Description of the invention (26) The measured weight increase rate is made as a function of temperature. Therefore, the temperature at which one-half the weight increase rate observed at 1 000 ° C was measured was measured. This is the temperature at which 50% of oxidation is recorded. It was found that the temperature of the metal powder of Comparative Example 4 was 429 ° C, and the temperature of the composite nickel fine powder obtained in the foregoing Example u was 452 ° C, indicating that the temperature required to oxidize 50% of nickel was increased by 23 ° C. Regarding the above detailed description, the composite nickel fine powder of the present invention has excellent oxidation resistance, chemical resistance, a structure with low sensitivity to oxidation, rapid thermal large-scale starting temperature shift to not less than 700eC, and for most test cases In terms of not less than 900 ° C, the composite powder is quite suitable for use as an internal electrode material for forming a laminated capacitor. In other words, the composite nickel fine powder of the present invention has excellent metal nickel oxidation resistance and nickel oxide diffusion resistance during the removal of the binder, and exhibits a thermal large size property that is almost the same as the thermal large size curve of the ceramic substrate. When manufacturing a large-size laminated ceramic capacitor, delamination and crack formation can be prevented according to the present invention, and a thin, small-sized multilayer ceramic capacitor including a ceramic dielectric layer and an internal electrode can be manufactured without impairing its dielectric characteristics. And electrical properties. >; ------------- Order ----- 1 --- line — {Please read the notes on the back before filling this page) The paper size of the paper is applicable to the national standard (CNS) A4 (210 X 297 public love) 26 310997
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JP4001438B2 (en) * | 1999-05-31 | 2007-10-31 | 三井金属鉱業株式会社 | Method for producing composite copper fine powder |
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WO2015153584A1 (en) * | 2014-04-01 | 2015-10-08 | Pneumaticoat Technologies Llc | Passive electronics components comprising coated nanoparticles and methods for producing and using the same |
JP5978371B2 (en) * | 2015-09-10 | 2016-08-24 | 株式会社ノリタケカンパニーリミテド | Core-shell particle and conductor-forming composition |
JP6431650B1 (en) | 2017-03-31 | 2018-11-28 | 東邦チタニウム株式会社 | Method for producing metal powder |
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1999
- 1999-03-31 JP JP09212299A patent/JP4076107B2/en not_active Expired - Lifetime
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Cited By (2)
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CN102867564A (en) * | 2011-07-07 | 2013-01-09 | 三星电机株式会社 | Conductive paste composition for internal electrodes and multilayer ceramic electronic component including the same |
CN109550940A (en) * | 2017-09-27 | 2019-04-02 | 财团法人金属工业研究发展中心 | Metal-base composites |
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JP2000282102A (en) | 2000-10-10 |
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