TW450857B

TW450857B - Method of synthesizing nickel fibers and the nickel fibers so prepared

Info

Publication number: TW450857B
Application number: TW89114015A
Authority: TW
Inventors: Geng-Sheng Jou; Jie-Tsung Luo; Chiang-Yu Ren
Original assignee: Nat Science Council
Priority date: 2000-07-13
Filing date: 2000-07-13
Publication date: 2001-08-21

Abstract

The present invention discloses s novel synthesis method of nickel fibers. The method of the present invention involves reducing nickel ions with a reducing agent in an aqueous solution containing nickel ions and in the presence of a base and a pH buffer at a temperature of 80-100 DEG C for a period of time, wherein a pH value of the aqueous solution is not less than 11.0 during the period of time, so that nickel fibers are formed in the aqueous solution. The nickel fibers synthesized in the present invention have a diameter ranging from sub-micron microns, and a length up to centimeters.

Description

h 4 5 0857 A7 I B7 五、發明說明（1 ) 發明領域 <請先閲讀背面之注意事項再填寫本頁) 本發明係有關一種鎳絲的合成方法，尤其有關一種利用氧化還原的鎳絲的化學合成方法。發明背景過去幾年來，鎳金屬在工業上被廣泛應用，其主要應用於製備機械合金材料、陶瓷材料、磁性材料和觸媒方面。在電子產品中，鎳金靥亦應用於導電黏著劑、電磁干擾屏蔽（EMI shielding)和抗靜電材料上。無論是在導電黏著劑或電磁干擾屏蔽的材料中，鎳金屬皆被用來作爲導電塡充物。此種導電塡充物在基質中的濃度達到一臨界値時，電阻會有劇烈下降的現象，使得整體的材料從絕緣體變爲導體，此臨界値稱爲滲透門檻（percolation threshold)。然而此種導電塡充物在與樹脂或塑膠作摻合時，常會因混合效果不佳而導致了塡充物的臨界値有變大的現象，因此在製程時，爲了控制品質的·-定，一般商品粒子塡充量皆達到70體積％以上，不過粒子塡充量的增加意味著成本的提升。經濟部智慧財產局貝工消费合作社印製根據文獻中的報導，降低金屬粒子臨界體積用量的方法，大致包括了：改善金屬與基質的混合方式、使用表面積更大的粉末（換言之即使用更細微的粉末）、或者使用縱橫比（aspect ratio)較高的粒子，例如片狀（flake)或絲狀 (fiber or filament)的微粒。目前金屬粉末材料的合成法有物理合成法與化學合成 -4 - 本紙張尺度適用中國國家標準（CNS>A4規格（210 X 297公釐) I 4 5 0857 A7 i B7 五、發明說明（2 ) 法兩大類，物理合成法常見的有粉碎法、濺鍍法等：而化學合成法則有溶膠凝膠（sol-gel)法、氣相沈積法與氧化還原法。以鎳爲例，在文獻或專利中，無有關鎳絲製程方法的記載，而只找到有關鎳粉體合成的方法。在鎳粉體合成法中，一般常見的合成法爲在高溫下通入氣體還原鎳的前驅物，例如美國專利 4,673,430; 5,584,908; 3,850,612號。 T-ray照射還原法是以Co6°爲放射源，經照射至NiS04 水溶液後，可以還原鎳離子生成鎳金屬微粒。本法的特色是必須另外添加0H自由基的淸除劑（scavenger)，目的爲在溶液相的反應中，避免一價鎳離子氧化爲二價離子，否則產率會降低=另外提高反應液pH値亦有利於產率的提高。文獻的記載有：h 4 5 0857 A7 I B7 V. Description of the invention (1) Field of invention < Please read the notes on the back before filling out this page) The present invention relates to a method for synthesizing nickel wire, especially a nickel wire using redox Chemical synthesis method. BACKGROUND OF THE INVENTION In the past few years, nickel metal has been widely used in industry. It is mainly used for the preparation of mechanical alloy materials, ceramic materials, magnetic materials and catalysts. In electronic products, nickel-gold is also used in conductive adhesives, EMI shielding, and antistatic materials. Whether in conductive adhesives or electromagnetic interference shielding materials, nickel metal is used as a conductive filler. When the concentration of such a conductive filler in the matrix reaches a critical threshold, the resistance will drop drastically, causing the overall material to change from an insulator to a conductor. This critical threshold is called the percolation threshold. However, when such conductive fillers are blended with resin or plastic, the criticality of the fillers tends to increase due to the poor mixing effect. Therefore, in order to control the quality during the manufacturing process, In general, the particle charge of commercial products reaches more than 70% by volume, but the increase in particle charge means an increase in cost. Printed by the Shelley Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs According to reports in the literature, the method for reducing the critical volume of metal particles roughly includes: improving the mixing method of the metal and the matrix, and using a powder with a larger surface area (in other words, using finer particles) Powder), or particles with a high aspect ratio, such as flake or fiber or filament particles. At present, the synthesis methods of metal powder materials include physical synthesis and chemical synthesis-4-This paper size applies to Chinese national standards (CNS > A4 specification (210 X 297 mm) I 4 5 0857 A7 i B7 V. Description of the invention (2) There are two major types of physical methods: physical synthesis methods such as pulverization method and sputtering method. Chemical synthesis methods include sol-gel method, vapor deposition method and redox method. Take nickel as an example. In the patent, there is no description of the nickel wire manufacturing method, but only the method of nickel powder synthesis. In the nickel powder synthesis method, the common synthesis method is generally a precursor that reduces the nickel by passing a gas at a high temperature, such as US patents 4,673,430; 5,584,908; 3,850,612. The T-ray irradiation reduction method uses Co6 ° as a radiation source. After irradiation to NiS04 aqueous solution, nickel ions can be reduced to generate nickel metal particles. The characteristic of this method is that 0H radicals must be additionally added Scavenger, the purpose is to avoid the oxidation of monovalent nickel ions into divalent ions in the reaction of the solution phase, otherwise the yield will decrease = In addition, increasing the pH of the reaction solution will also help to increase the yield The records in the literature are:

Marignier 等人[Marignier，J.L,，J·Belloni，M.O·Marignier et al. [Marignier, J.L ,, J. Belloni, M.O.

Delcourt and J.P. Chevalier, Microaggregates of Non-noble Metals and Bimetallic Alloys Prepared by Radiation-induced Reduction, Nature, 317, 344 (1985)]以 NiS04 爲前驅物，異丙醇爲淸除劑及PVA爲界面活性劑，經r -ray照射所生成的產物粒徑爲10-20nm，而粒子呈Ni面心晶體結構：Delcourt and JP Chevalier, Microaggregates of Non-noble Metals and Bimetallic Alloys Prepared by Radiation-induced Reduction, Nature, 317, 344 (1985)] with NiS04 as the precursor, isopropanol as the scavenger and PVA as the surfactant, The particle size of the product produced by r-ray irradiation is 10-20nm, and the particles have a Ni face-centered crystal structure:

Zhu等人[Zhu，YJ·，Qian Y.，Zhang M.W., Chen Z.Y.， Chen M. and Zhou G., Preparation and Characterization of Nanocrystalline Nickel Powders by the γ Radiation Method, J. Mater. Sci. Lett” 13, 1243 (1994)]則是在反應液中加入 SDS 作爲界面活性劑，另外添加NH40H作爲鹸化劑，使溶液pH 値在反應過程中維持在10-11之間，抑制了再氧化的現象，本紙張尺度適用中國國家標準（CNS)A4規格（210 * 297公釐） A9 讀背 Si 之注項再填寫本頁經濟部智慧財產局員工消货合作社印製 A7 f 450857 5 B7 五、發明說明（3 ) 產率可達90%。其產物爲Ni面心結構，平均粒徑爲8-9nm。 (請先閱讀背面之沒意事項再填窝本頁) 至於在氧化還原法中，其反應溶劑分爲去離子水與醇類兩種。以醇類作爲溶劑的合成方法又稱爲多醇法（polyol process)，溶劑在多醇法中亦作爲還原劑之用。在水相反應中：美國專利4,089,676號以聯胺還原鎳的前驅物，並加入 Union.Carbide的消泡劑（antifoam agent)及一驗，在 88-96°C 環境下可合成微米級的鎳微粒：美國專利3,923,496號在氮氣或二氧化碳環境下，以草酸還原硝酸鎳，可得到0.5 a m以上的鎳微粒。若添加抑制劑（如：氧化鎂），則可減小粒徑至0.1// m。至於多醇法合成鎳微粒則有：經濟部智慧財產局員工消费合作社印製Zhu et al. [Zhu, YJ ·, Qian Y., Zhang MW, Chen ZY, Chen M. and Zhou G., Preparation and Characterization of Nanocrystalline Nickel Powders by the γ Radiation Method, J. Mater. Sci. Lett "13, 1243 (1994)] is adding SDS as a surfactant in the reaction solution, and NH40H as a tritiation agent, so that the pH of the solution is maintained between 10-11 during the reaction, and the phenomenon of reoxidation is suppressed. Standards are applicable to China National Standard (CNS) A4 specifications (210 * 297 mm) A9 Read back the note of Si and then fill in this page Printed by the Consumer Goods Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 f 450857 5 B7 V. Description of the invention (3 ) The yield can reach 90%. Its product is Ni face-centered structure with an average particle size of 8-9nm. (Please read the unintentional matter on the back before filling in this page) As for the redox method, the reaction solvent is It is two kinds of deionized water and alcohols. The synthesis method using alcohols as solvents is also called the polyol process. The solvents are also used as reducing agents in the polyol method. In the water phase reaction: US patent No. 4,089,676 for reduction of nickel with hydrazine Precursor, adding antifoam agent of Union.Carbide and first test, it can synthesize micron-sized nickel particles at 88-96 ° C environment: US Patent No. 3,923,496 under nitrogen or carbon dioxide environment, reduced with oxalic acid Nickel nitrate can obtain nickel particles of more than 0.5 am. If an inhibitor (such as magnesium oxide) is added, the particle size can be reduced to 0.1 // m. As for the synthesis of nickel particles by the polyol method, there are: Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Employee Consumer Cooperative

Hegde等人[Hedge, M.S” D. Larcher，L. Dupont, B. Beaudoin, K. Tekaia-Elhsissen and J.M. Tarascon, Synthesis and Chemical Reactivity of Polyol Prepared Monodispersed Nickel Powders, Solid State Ionics, 93，33 (1997)]是在乙二醇中加入Pd或Pt爲成核劑、PVP爲保護劑，在198t的環境中持溫30-40分鐘，便可將氫氧化鎳還原成135 nm的鎳粒子；Hegde et al. [Hedge, MS ”D. Larcher, L. Dupont, B. Beaudoin, K. Tekaia-Elhsissen and JM Tarascon, Synthesis and Chemical Reactivity of Polyol Prepared Monodispersed Nickel Powders, Solid State Ionics, 93, 33 (1997) ] Is to add Pd or Pt as a nucleating agent, PVP as a protective agent in ethylene glycol, and maintain the temperature in a 198t environment for 30-40 minutes to reduce nickel hydroxide to nickel particles at 135 nm;

Kurhara 等人[Kurihara，L.K_, G.M. Chow and P.E· Schoen, Nanocrystalline Metallic Powders and Films Produced by the Polyol Method, Nanostructured Mater., 5(6), 607 (1995)]認爲當硝酸鎳濃度在0.02-0.2M之間時，在120°C 下反應1小時後，即可得到粒徑約20nm的晶粒。本紙張尺度適用中國國家標準（CNS)A4規格（210*297公釐) 45〇8 57 A7 B7 五、發明說明（4 ) 至於在鎳絲的合成法中，工業界常用的方法爲： (a) 將鎳金屬熔融後，直接抽絲而成，不過需要很高的加熱溫度，而且所抽得的金屬絲，直徑不會太細。 (b) Shui及 Chung [Shui, X.P. and D.D.L· Chung, Submicron Nickel Filaments Made by Electroplating Carbon Filaments as a New Filler Material for Electromagnetic Interference Shielding, J. Electronic Mater., 24 (2), 107 (1995)]則是將鎳金屬以電鍍的方法鍍在碳纖維上，所合成的鎳絲中，鎳的體積分率爲94%時，鎳絲的直徑爲0.4私 m、長度可至100 jum，不過其先決條件須要使用碳纖維，而且也將受限於碳纖維的尺寸。而且使用電鍍的方式時，會因爲電場分佈的原因，較難得到十分均勻的結果，此外 '本文所製得的鎳絲，仍然具有碳心（carbon core) 1所以它的導電性較純的鎳絲爲差。本篇文章所合成的鎳絲，主要用途在於電磁波的遮蔽（EMI)效應，而根據理論，金屬絲的直徑越小，其效果越佳。Kurhara et al. [Kurihara, L.K_, GM Chow and PE · Schoen, Nanocrystalline Metallic Powders and Films Produced by the Polyol Method, Nanostructured Mater., 5 (6), 607 (1995)] considered that when the concentration of nickel nitrate was 0.02 At -0.2M, after reacting at 120 ° C for 1 hour, crystal grains with a particle diameter of about 20nm can be obtained. This paper size applies the Chinese National Standard (CNS) A4 specification (210 * 297 mm) 45〇8 57 A7 B7 V. Description of the invention (4) As for the synthesis method of nickel wire, the commonly used method in the industry is: (a ) After the nickel metal is melted, it is directly drawn. However, it requires a high heating temperature, and the drawn wire does not have a too small diameter. (b) Shui and Chung [Shui, XP and DDL · Chung, Submicron Nickel Filaments Made by Electroplating Carbon Filaments as a New Filler Material for Electromagnetic Interference Shielding, J. Electronic Mater., 24 (2), 107 (1995)] Nickel metal is plated on carbon fibers by electroplating. When the volume fraction of nickel in the synthesized nickel wire is 94%, the diameter of the nickel wire is 0.4 μm and the length can reach 100 jum, but its prerequisites are required. The use of carbon fibers will also be limited by the size of the carbon fibers. Moreover, when using the electroplating method, it is difficult to obtain very uniform results because of the electric field distribution. In addition, the nickel wire produced in this article still has a carbon core 1 so its conductivity is relatively pure nickel. The silk was poor. The main purpose of the nickel wire synthesized in this article is the electromagnetic wave shielding (EMI) effect. According to the theory, the smaller the diameter of the metal wire, the better the effect.

Ichiki等人[Ichiki，M·，J. Akedo，K. Mori and Y. Ishikawa, Microstructure of Nickel Whiskers Produced by the Gas Deposition Method, J. Mater. Sci. Lett., 16, 531 (1997)] 則是利用氣相沈積的方法，先將鎳微粒高溫（1700°C)蒸發後，通以鈍氣（例如Ar或He)冷卻後，再經由噴嘴沈積在基材上，鎳會以whisker方式成長，而且長成狐尾（foxtail)形狀。氣相沈積法製得的鎳絲直徑爲100# m、長度爲3mm。然而氣相沈積法在設備上的成本較高，且因爲氣相的濃度本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 -___— — — — —______ {請先W讀背面之注意事項再填寫本I) 訂.-Ichiki et al. [Ichiki, M., J. Akedo, K. Mori and Y. Ishikawa, Microstructure of Nickel Whiskers Produced by the Gas Deposition Method, J. Mater. Sci. Lett., 16, 531 (1997)] are By vapor deposition, nickel particles are first evaporated at a high temperature (1700 ° C), cooled with a passive gas (such as Ar or He), and then deposited on the substrate through a nozzle. Nickel will grow in a whisker manner, and Grow into a foxtail shape. The nickel wire prepared by the vapor deposition method has a diameter of 100 # m and a length of 3mm. However, the cost of the vapor deposition method on the equipment is high, and because of the concentration of the vapor phase, the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -___— — — — —______ {Please W Read the notes on the back and fill in this I) order.-

A 經濟部智慧財產局貝工消費合作社印製五、發明說明（5 ) 低，所以產率不會太高 A7 B7 經濟部智慧財產局員工消费合作社印製發明要旨本發明的主要目的在提供一種鎳絲的化學合成方法，尤其是溶液相的氧化還原方法。具體而言•本發明主要以聯胺作爲還原劑，鎳的鹽類溶液爲前驅物，並加入適當添加劑，在ioo°c以下進行鎳離子的還原反應，其中藉由控制溶液中的pH値：或調整聯胺的濃度：或調整反應溫度：或調整一界面活性劑的濃度：或使用一磁場，使得上述還原反應生成的成品爲鎳絲狀態•而非粉末，且鎳絲的長度可至數公分，且不會有反應過快，以致於部分還原的鎳金屬鍍在反應器器壁上的現象，導致產率的下降。本發明方法所合成的鎳絲在將反應混合物經過簡單的分離及乾燥步驟後即可獲得，且其直徑介於微米至次微米，長度可達公分級。本發明所提出的合成方法，是溶液相的氧化還原法，與前述文獻中提及的鎳絲製法相比較，氧化還原法在設備的成本上較低，且反應快速，而且得到鎳絲後，也十分容易與母液分離，因此適合工業上的大量製程。圖示之簡單說明圖一爲本發明實施例一所合成的鎳絲，以掃描式電子顯微鏡（scan electron microscopy，簡稱 SEM)放大 500倍的照片。 <請先Μ讀背面之注項再填寫本頁) V)- ,ΧΜ. 訂本紙張尺度適用中國國家標準（CNS)A4規格（210 * 297公釐）A Printed by the Shelley Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The invention description (5) is low, so the yield will not be too high. A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The main purpose of the present invention is to provide a Chemical synthesis method of nickel wire, especially redox method in solution phase. Specifically, the present invention mainly uses hydrazine as a reducing agent, a nickel salt solution as a precursor, and adds an appropriate additive to perform a reduction reaction of nickel ions below 100 ° C, in which the pH in the solution is controlled by: Or adjust the concentration of hydrazine: or adjust the reaction temperature: or adjust the concentration of a surfactant: Or use a magnetic field to make the finished product generated by the above reduction reaction into a state of nickel wire instead of powder, and the length of the nickel wire can be several digits Cm, and there is no phenomenon that the reaction is too fast, so that partially reduced nickel metal is plated on the reactor wall, resulting in a decrease in yield. The nickel wire synthesized by the method of the present invention can be obtained after the reaction mixture is subjected to simple separation and drying steps, and has a diameter ranging from micrometers to submicrons and a length of up to a common grade. The synthesis method proposed by the present invention is a solution-phase redox method. Compared with the nickel wire production method mentioned in the aforementioned document, the redox method has lower equipment cost and quick reaction, and after the nickel wire is obtained, It is also very easy to separate from the mother liquor, so it is suitable for a large number of industrial processes. Brief Description of the Drawings Figure 1 is a photograph of a nickel wire synthesized in Example 1 of the present invention, which is 500 times magnified with a scanning electron microscope (SEM). < Please read the notes on the back before filling in this page) V)-, × Μ. The paper size is applicable to China National Standard (CNS) A4 (210 * 297 mm)

圖二爲本發明實施例一所合成的鎳絲被放大2500倍的 SEM照片。經濟部智慧財產局員工消費合作社印製發明之詳細說明本發明提供了一種鎳絲的合成方法，包含：在一含有鎳離子的水溶液中，在一鹼及一pH緩衝劑存在下，及一磁場或一界面活性劑存在下，以一還原劑在一介於80-100°C溫度，較佳地80-90°C，還原該鎳離子一段時間，較佳地，該段時間大於5分鐘，而於該水溶液中形成鎳絲，其中該水溶液的pH値在該段時間內不小於11.0，較佳地，介於11.5至13.0。較佳地，該含有鎳離子的水溶液係將一鎳鹽加入水中而形成，其中該鎳鹽爲可於一鹸性水溶液中形成氫氧化鎳 (II)的任一種鎳鹽。較佳地，該鎳鹽爲氯化鎳，硝酸鎳，醋酸鎳，碳酸鎳，硫酸鎳，硫酸銨錬或其等之水合物》更佳地，該鎳鹽爲 NiCl2,6H2〇。較佳地，該還原劑爲聯胺，聯胺水合物或聯胺鹽。更佳地，該還原劑爲Ν2Η4·Η20。較佳地，該鹸具有一化學式ΜΟΗ，該pH緩衝劑具有一化學式Μ2ΗΡ04，其中Μ爲鹼金屬。更佳地，該鹼金屬氫氧化物爲ΚΟΗ，該pH緩衝劑爲Κ2ΗΡ〇4。於本發明方法的一較佳具體實施例中，該ΚΟΗ於該含有鎳離子的水溶液的濃度爲0.125Μ，及該Κ2ΗΡ04Μ該水溶本紙張尺度適用中0因家標準（CNS>A4規格（210 X 297公釐）閲面之注項再填寫本頁 Ρ 訂 450857 A7 _ B7 五、發明說明（7 ) 液中的濃度爲0.25M。 (請先《讀背面之注意事項再填寫本頁) 較佳地，於本發明方法中，該還原劑以超過還原該鎳鹽所需的化學量存在於該含有鎳離子的水溶液中。當該還原劑爲聯胺，聯胺水合物或聯胺鹽時，較佳地，該還原劑於該含有鎳離子的水溶液的濃度大於1.5M。當該還原劑爲 Ν2Η4‘Η20及該鎳鹽爲NiCl2*6H20,較佳地，Ν2Η4·Η20於該含有鎳離子的水溶液中的濃度小於10Μ。於本發明方法的一較佳具體實施例中，NiCl2‘6H20於該含有鎳離子的溶液中的濃度爲約0.05M，Ν2Η4·Η20於該含有鎳離子的水溶液中的濃度爲約2.3Μ。較佳地，於本發明方法中，一鹼金屬碳酸鹽及一鹸金屬碳酸氫鹽被加入於該含有鎳離子的水溶液。該鹸金屬碳酸鹽可以爲K2C03及該鹼金屬碳酸氫鹽可以爲KHC03。該尺2(：03及1^11(：03於該含有鎳離子的水溶液中的一合適濃度均爲0.25Μ。較佳地|於本發明方法中，該鎳離子的還原係在一磁場存在下進行》經濟部智慧財產局貝工消f合作社印製較佳地，於本發明方法中，該鎳離子的還原係在一界面活性劑存在下進行該界面活性劑於該含有鎳離子的水溶液中的一合適濃度介於lx 1〇_4Μ至1 X10+2M。較佳地，於本發明方法中*該鎳離子的還原係在一磁場及一界面活性劑均存在下進行。本發明同時提供一種藉由本發明方法所合成的鎳絲。較佳地，該鎳絲具有一介於0.1至20微米的直徑，及一介於 -10- 本紙張尺度適用令國國家標準（CNS)A4規格（2〗0 X 297公;Ϊ ) 45〇857 A7 r- i、發明說明（8 ) 1-100毫米的長度。更佳地，該鎳絲具有一介於0.5至5微米的直徑，及一介於0.5-50毫米的長度。經濟部智慧財產局員工消費合作社印製實施例一將10ml的含鎳離子溶液，其中包含0.45M的KHC03、 0.65M的 Ν2Η4.Η20、0.50M的 K2C03、0.10M的 NiCl2.6H20、 0.50\1的1；：21^〇4及 0.25M的 KOH，與 8ml的去離子水於 100ml 的燒杯中混合，再置於一預熱80°C的水浴中，該水浴被置於PMC 500系列型號502多點熱盤及攪拌器上及將溫度控制在 80-90°C 之間（PMC 500 series analog hotplate-stirrers Model No. 502 from Barnstead/Thermolyne，Iowa, US)。在該杯置於80t環境下加熱的同時，立即加入2ml的98% N2H4_H20 (hydrazine hydrate)與 0.0046g (7.98xlO_4M)的癸苯碼酸鈉鹽（sodium dodecylbenzene sulfonate，簡稱 SDS)。加熱10分鐘後，溶液顏色由淡藍色轉爲暗藍色I此時漸有鎳絲生成，待加熱20分鐘後，溶液變爲無色，此時推測反應完成《產率可達90%以上。生成的鎳絲大部分沈澱在容器底部，少部分合成長度較短的鎳絲則仍浮在溶液上層。反應完的反應混合物經過濾，及乾燥所獲得固體後，即可得到鎳絲》本實施例所合成的鎳絲，由電子顯微鏡觀察其長度數百微米以上，直徑則介於微米至次微米之間，如圖一的掃描式電子顯微鏡（scan electron microscopy ’簡稱SEM)照片所示。鎳絲表面有許多長條狀之結晶，如圖二的SEM照片 -11- 本纸張尺度適用中國因家標準（CNS>A4規格(210 * 297公爱）閲讀背面之注項再填窝本頁訂 ▲ 450857 A7 B7 五、發明說明（9 ) 所示》本實施例所合成的鎳絲亦經X射線繞射分析（XRD)觀察其結晶型態，發現其結晶型態十分良好。此樣品比表面積約 2.73 m2/g » 實施例二在本實施例中，我們改變反應溫度，藉以觀察鎳絲在不同溫度下的生長情形•此處的溶液組成皆與實施例一相同。而所謂的反應完成時間，係指當溶液由藍色變爲無色時的瞬間。反應結果如下： (請先闓讀背面之注意事項再填寫本頁) 組別反應湄度反應完成時間鎮絲特件 RT1 60-70°C 150分形成一完整的網狀結構 RT2 80-90°C 20分鎳絲長度可達數公分 RT3 100-110°C 12分多麵總壁上，少數長成絲狀訂：經濟部智慧財產局員工消费合作社印製反應溫度在60-70°C之間時，所有的鎳絲是以反應器底部的某一處爲成核中心，成長爲網狀結構*並無任何鎳絲懸浮在溶液上層。當反應溫度在80-90X：之間時，合成的鎳絲同樣以反應器底部的某一處爲成核中心，但有部分的鎳絲懸浮在溶液上層。此現象應爲鎳絲成長時，由於速度較快，因而使得部分鎳絲的直徑較小，受到溶液對流作用後，容易斷裂成爲長度較短的鎳絲懸浮在溶液上層。當反應溫度增高到lOO-UOt之間時，反應在5分鐘後，器壁即鍍上了一層鎳。反應完成後，大部分生成的鎳皆銨在反應器器壁上，少部分則長成鎳絲，並與鍍在器壁的鎳連接在 -12- 本紙張尺度適用中困Η家標準（CNS)A4規格（210 X 297公釐） A7 B7 五、發明說明（10 ) —起，顯然非理想的反應條件。此一實施例表示，當反應溫度過高時，反應加速，造成鎳過飽合，因而促使鎳在器壁上成核，得到類似銀鏡的結果。本組實驗中，RT1的產率爲86.9%，其樣品比表面積爲11.8 m2/g。實施例三此實施例的目的爲說明在不同的SDS濃度下的鎳絲生成情形，合成的程序與條件與實施例一相同，唯一改變的只有界面活性劑SDS的濃度。界面活性劑SDS濃度介於 1Μ0·4-8χ10·3Μ之間》反應條件及結果，如後所述： -------------— <請先閱讀背面之注意事碩再填*本頁) 組別 TSDS1 (Μ) 反應完成時間鏤絲特件 SCI: 0 20分長度可至數公分 SC2: 2.93χ104 90分長度只有數微米至毫米 SC3: 7.98χ10_4 20分長度可至數公分 SC4: Ι.όΟχΙΟ·3 20分長度可至數公分 SC5: 3.99χ10*3 10分多數鍍在器壁，少數長度數公分 SC6: 7.98x10° 5分多數鍍在器壁*少數長度數公分訂· 經濟部智慧財產局貝工消費合作社印製在SCI、SC3與SC4三組中，溶液由藍色變爲無色的反應時間皆約20分鐘，生成的鎳絲部分懸浮在溶液的上層，部分則與反應器的底部某一處連接一起，亦即連結處應爲鎳絲的成核中心。然而在SC5與SC6兩組中，反應所需時間則較短，而且大部分被還原的鎳皆鍍在反應器的器壁上， -13- 本紙張尺度適用令國國家標準（CNS>A4規格（210 * 297公釐） 4δ〇8 57 Α7 Β7 i、發明說明（11 ) 只有少部分的鎳以鎳絲方式存在，由此可見SDS的添加量如果太低，則會降低反應的速率，如SC2組，除了反應時間較長外，其形成的鎳絲長度亦較短。但添加量也不宜太多，否則也將促進成核的作用，如SC5、SC6組別所示》 SCI與SC4組的產率分別爲81.7%及92.5%，而SC4樣品的比表面積則爲7.3 m2/g。實施例四在前三實施例中所使用的界面活性劑爲陰離子型界面活性劑，其對反應所造成的影響爲提高了反應速率，但當添加濃度過高時，則有銀鏡反應》此實施例中，合成的程序與條件與實施例一相同，除了我們採用了陽離子型與非離子型界面活性劑。在此實施例中所使用的陽離子型界面活性劑爲C16TABr (十六基三甲基銨溴化物 (hexadecyltrimethyl-ammonium bromide)):非離子型界面活性劑爲Tween80 (聚氧伸乙基花楸醣單油酸酯 (polyoxyethylenesorbitan monooleate)。此處的反應溫度在 80-90°C間。反應結果如下： <請先W讀背面之注意事項再填寫本頁) 一-BI · 經濟部智慧財產局貝工消费合作社印數界面活性剖種類及濃度 [C16TABr] = 9.60x10^ Μ 反應時間鏤絲特忡 5盼長度可至數公分 [C16TABr] = 9.60xia3M 10分多醒在器壁•少願度數般 [Tween 80] = 1.74xl0'3 M 195分長度可至數公分 [Tween 80] = 9.80χΐσ3Μ 15分長度可至數健 [Tween 80] = 9.83xl0'2 M 5分多數鍍在器壁，少數長度數公分 -14- 本紙張尺度適用中困國家標準(CNS)A4规格（210 X 297公釐） 1 450857 A7 B7 經濟部智慧財產局貝工消費合作社印製五、發明說明（12 ) 對C16TABr與Tween 80兩種添加物而言，顯然濃度增加都會加速反應的進行。在較低的濃度組別中，其反應速率較不添加時爲慢•不過所生成的鎳絲|部分懸浮在溶液上層，部分則以反應器底部的某一處爲成核中心，成長爲鎳絲的結構，但並無鍍在反應器器壁的現象，因此以過濾乾燥收集鎳絲成品時，其收集較易且量較多。當濃度增高時，其反應速率明顯增快，但大部分被還原的鎳皆鍍在反應器器壁，只有少部分的鎳絲生成。以上的數據顯示，如果反應速率過快，則無法得到理想的鎳絲爲產品。減緩反應速率，雖然仍然可以得到鎳絲，但恐怕不利於生產的速率。此處的產率約在82-86%間，第一組的比表面積爲 10.0 m2/g。實施例五此一實施例爲在不同還原劑（聯胺）濃度下的鎳絲生長情形。合成的程序與條件與實施例一相似，其中溶液總體積皆固定在20 m卜藉調整去離子水的體積而達成聯胺濃度的改變。反應溫度控制在80-90°C，並無添加任何界面活性劑。反應結果如下： -15- 本紙張尺度適用中國國家標準（CNS)A4規格<210 X 297公釐） <請先閲讀背面之注意事項再填寫本頁) 訂. 4508 5 7 A7 B7 五、發明說明（13 ) 組別聯胺濃度(M) 反應完成時間鎳絲特性 .. HC1 0 > 8小時長度只有數微米至數毫米 HC2 1.325 85分長度只有數微米至數毫米 HC3 2.325 2盼長度可至數妙 HC4 5.325 2盼長航至數公分 HC5 8.325 1吩長度可至數公分 HC6 10.325 21分長度可至數公分經濟部智慧財產局貝工消费合作社印製由以上的數據可知，當聯胺的濃度低時，反應速率慢，且生成的鎳絲短。然而當濃度提高到2.325 Μ後，鎳絲的生成速率，以及反應速率就不會再受到聯胺濃度的影響了。實施例六在此實施例中，我們探討了反應物溶液的組成對於鎳絲形成的影響。在實施例一的反應物溶液組成中，包括了： KHC03、Ν2Η4·Η20、K2C03、NiCl2.6H20、Κ2ΗΡ04、Κ〇Η以及界面活性劑。在此實施例中，我們採取逐漸刪減一種添加物的方式·其餘條件則與實施例一相同（但未添加界面活性劑）。反應結果如下： \-/· __ _ _ _ ____I__i I <請先《讀背面之注意事項再填寫本頁) 訂- -16 - 本紙張尺度適用中圉國家標準(CNS)A4規格（210 X 297公釐） A7 B7 五、發明說明（14 ) 組別溶液組成反應完成時間 20分鎳絲特件FIG. 2 is a SEM photograph of a nickel wire synthesized in Example 1 of the present invention at a magnification of 2500 times. Detailed description of the invention printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics The present invention provides a method for synthesizing nickel wire, comprising: in an aqueous solution containing nickel ions, in the presence of an alkali and a pH buffer, and a magnetic field Or in the presence of a surfactant, a reducing agent at a temperature between 80-100 ° C, preferably 80-90 ° C, reduces the nickel ion for a period of time, preferably, the period of time is greater than 5 minutes, and A nickel wire is formed in the aqueous solution, wherein the pH of the aqueous solution is not less than 11.0 during the period, preferably, between 11.5 and 13.0. Preferably, the nickel ion-containing aqueous solution is formed by adding a nickel salt to water, wherein the nickel salt is any kind of nickel salt capable of forming nickel (II) hydroxide in an alkaline aqueous solution. Preferably, the nickel salt is nickel chloride, nickel nitrate, nickel acetate, nickel carbonate, nickel sulfate, ammonium sulfate or the hydrate thereof, and more preferably, the nickel salt is NiCl2, 6H2O. Preferably, the reducing agent is hydrazine, hydrazine hydrate or hydrazine salt. More preferably, the reducing agent is N2Η4 · Η20. Preferably, the fluorene has a chemical formula M0Η, and the pH buffering agent has a chemical formula M2ΗP04, where M is an alkali metal. More preferably, the alkali metal hydroxide is KOH and the pH buffer is K2HPO4. In a preferred embodiment of the method of the present invention, the concentration of the KOΗ in the aqueous solution containing nickel ions is 0.125M, and the K2ΗP04M is water soluble. The paper size is applicable in accordance with the domestic standard (CNS > A4 specification (210 X 297mm) Please fill in this page before filling out the page. Order 450857 A7 _ B7 V. Description of the invention (7) The concentration in the liquid is 0.25M. (Please read the “Notes on the back side before filling this page”) Better In the method of the present invention, the reducing agent is present in the nickel ion-containing aqueous solution in a chemical amount exceeding the required amount for reducing the nickel salt. When the reducing agent is a hydrazine, a hydrazine hydrate or a hydrazine salt, Preferably, the concentration of the reducing agent in the aqueous solution containing nickel ions is greater than 1.5 M. When the reducing agent is N2Η4'Η20 and the nickel salt is NiCl2 * 6H20, preferably, N2Η4 · Η20 is used in the nickel ion-containing solution. The concentration in the aqueous solution is less than 10M. In a preferred embodiment of the method of the present invention, the concentration of NiCl2'6H20 in the nickel ion-containing solution is about 0.05M, and N2Η4 · Η20 in the nickel ion-containing aqueous solution. The concentration is about 2.3M. Preferably, in the method of the present invention, an alkali metal carbonate and a hafnium metal bicarbonate are added to the aqueous solution containing nickel ions. The hafnium metal carbonate may be K2C03 and the alkali metal bicarbonate may be KHC03. A suitable concentration of the ruler 2 (: 03 and 1 ^ 11 (: 03) in the aqueous solution containing nickel ions is 0.25M. Preferably | In the method of the present invention, the reduction of the nickel ion exists in a magnetic field It will be printed by "Beijing Consumer Cooperative Co., Ltd., Intellectual Property Bureau of the Ministry of Economic Affairs. Preferably, in the method of the present invention, the reduction of nickel ions is performed in the presence of a surfactant in the aqueous solution containing nickel ions. A suitable concentration is between 1 × 10-4M to 1 X10 + 2M. Preferably, in the method of the present invention * the reduction of nickel ions is performed in the presence of a magnetic field and a surfactant. The present invention is also A nickel wire synthesized by the method of the present invention is provided. Preferably, the nickel wire has a diameter between 0.1 and 20 micrometers, and a range between -10- and -10. The paper size is applicable to the national standard (CNS) A4 specification (2 〖0 X 297 male; Ϊ) 45〇857 A7 r-i. Description of the invention (8) 1-100 mm length. More preferably, the nickel wire has a diameter of 0.5 to 5 microns and a length of 0.5-50 mm. Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs The cooperative prints the first example. 10 ml of a solution containing nickel ions, including 0.45M KHC03, 0.65M N2Η4.Η20, 0.50M K2C03, 0.10M NiCl2.6H20, 0.50 \ 1 of 1 ;: 21 ^ 〇 4 and 0.25M KOH, mixed with 8ml of deionized water in a 100ml beaker, and placed in a preheated 80 ° C water bath, which was placed in a PMC 500 series model 502 multi-point hot plate and agitator And control the temperature between 80-90 ° C (PMC 500 series analog hotplate-stirrers Model No. 502 from Barnstead / Thermolyne, Iowa, US). While the cup was heated in an 80t environment, 2 ml of 98% N2H4_H20 (hydrazine hydrate) and 0.0046 g (7.98xlO_4M) of sodium dodecylbenzene sulfonate (SDS) were immediately added. After heating for 10 minutes, the color of the solution changed from light blue to dark blue. At this time, nickel wires gradually formed. After heating for 20 minutes, the solution became colorless. At this time, the reaction was estimated to be complete. The yield reached 90% or more. Most of the generated nickel wire was deposited on the bottom of the container, and a small portion of the synthesized nickel wire was still floating on the upper layer of the solution. After the reaction mixture is filtered and the solid obtained is dried, the nickel wire can be obtained. The nickel wire synthesized in this example is observed by an electron microscope to have a length of several hundred microns or more and a diameter ranging from micrometers to submicrons. In the meantime, as shown in the scanning electron microscope (scan electron microscopy 'SEM') picture of FIG. There are many long strips of crystals on the surface of the nickel wire, as shown in the SEM photo of Figure 2. 11- This paper size is in accordance with Chinese standards (CNS > A4 specification (210 * 297 public love)) Page order ▲ 450857 A7 B7 V. Description of the invention (9) "The nickel wire synthesized in this example was also observed by X-ray diffraction analysis (XRD) for its crystalline form and found that its crystalline form was very good. This sample Specific surface area is about 2.73 m2 / g »Example 2 In this example, we changed the reaction temperature to observe the growth of nickel wires at different temperatures. The solution composition here is the same as in Example 1. The so-called reaction Completion time refers to the moment when the solution changes from blue to colorless. The reaction results are as follows: (Please read the precautions on the back before filling out this page) Group reaction Maede reaction completion time Zhensi special RT1 60- 70 ° C 150 minutes to form a complete network structure RT2 80-90 ° C 20 minutes Nickel wire length can reach several centimeters RT3 100-110 ° C 12 minutes on the multi-faceted total wall, a few grow into filaments Order: Ministry of Economic Affairs Printed by Intellectual Property Bureau Staff Consumer Cooperatives When the reaction temperature is between 60-70 ° C, all the nickel wires grow with a nucleation center at a certain place at the bottom of the reactor, and grow into a network structure. * No nickel wires are suspended in the upper layer of the solution. When the reaction temperature Between 80-90X :, the synthesized nickel wire also takes a certain bottom of the reactor as the nucleation center, but some of the nickel wires are suspended in the upper layer of the solution. This phenomenon should be caused when the nickel wire grows, because the speed is relatively high. Fast, so that the diameter of some nickel wires is small. After being subjected to the convection of the solution, it is easy to break into short nickel wires suspended in the upper layer of the solution. When the reaction temperature increases to 100-UOt, the reaction takes 5 minutes. The wall of the vessel is plated with nickel. After the reaction is completed, most of the nickel produced is ammonium on the vessel wall, and a small part is grown into nickel wires, which are connected to the nickel plated on the vessel wall. The scale applies to the CNS A4 specification (210 X 297 mm) A7 B7 5. From the description of the invention (10), it is obviously not ideal reaction conditions. This example shows that when the reaction temperature is too high , The reaction accelerates, causing nickel to oversaturate, which promotes Nucleation on the wall of the device yielded results similar to silver mirrors. In this set of experiments, the yield of RT1 was 86.9%, and the specific surface area of the sample was 11.8 m2 / g. Example 3 The purpose of this example is to illustrate the difference in SDS For the formation of nickel wire at a concentration, the synthesis procedure and conditions are the same as in Example 1. The only change is the concentration of the surfactant SDS. The concentration of the surfactant SDS is between 1M0 · 4-8 × 10 · 3M. Reaction conditions and The results are as follows: -------------— < Please read the notes on the back before filling in this page) Group TSDS1 (Μ) Response completion time SCI: 0 20 centimeters in length to several centimeters SC2: 2.93χ104 90 centimeters in length only a few microns to millimeters SC3: 7.98χ10_4 20 centimeters in length to centimeters SC4: Ι.όΟχΙΟ · 3 20 centimeters in length to SC5: 3.99 χ10 * 3 Most of 10 points are plated on the wall, a few centimeters in length SC6: 7.98x10 ° 5 points are mostly plated on the wall * A few centimeters in length are ordered · Printed by the Shelley Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs on SCI, SC3 and In the three groups of SC4, the reaction time of the solution from blue to colorless was about 20 minutes. The part of the generated nickel wire is suspended in the upper layer of the solution, and the part is connected with the bottom of the reactor somewhere, that is, the junction should be the nucleation center of the nickel wire. However, in the SC5 and SC6 groups, the reaction time is shorter, and most of the reduced nickel is plated on the wall of the reactor. -13- This paper is applicable to national standards (CNS > A4 specifications) (210 * 297 mm) 4δ〇8 57 Α7 B7 i. Description of the invention (11) Only a small amount of nickel exists in the form of nickel wire, which shows that if the amount of SDS added is too low, the reaction rate will be reduced, such as In addition to the longer reaction time, the length of the nickel wire formed in the SC2 group is also shorter. However, the addition amount should not be too much, otherwise it will promote the nucleation effect, as shown in the SC5 and SC6 groups. SCI and SC4 The yields were 81.7% and 92.5%, respectively, and the specific surface area of the SC4 sample was 7.3 m2 / g. Example 4 The surfactant used in the first three examples is an anionic surfactant. The effect is to increase the reaction rate, but when the concentration is too high, there is a silver mirror reaction. In this example, the synthesis procedures and conditions are the same as in Example 1, except that we use cationic and nonionic interface activities.剂。 Made in this example The cationic surfactant is C16TABr (hexadecyltrimethyl-ammonium bromide): the non-ionic surfactant is Tween80 (polyoxyethylenesorbitan monooleate ). The reaction temperature here is between 80-90 ° C. The reaction results are as follows: < Please read the precautions on the back before filling out this page) I-BI · Printed interface of Shelley Consumer Cooperative, Intellectual Property Bureau, Ministry of Economic Affairs Kind and concentration of active profile [C16TABr] = 9.60x10 ^ Μ Response time Wire length 5 can reach several centimeters [C16TABr] = 9.60xia3M More than 10 minutes wake up on the wall • Less willingness [Tween 80] = 1.74 xl0'3 M 195 centimeters in length can be several centimeters [Tween 80] = 9.80χΐσ3M 15 centimeters in length can be several centimeters [Tween 80] = 9.83xl0'2 M 5 cents are mostly plated on the wall, a few centimeters are 14- This paper size is applicable to the National Standard for Difficulties (CNS) A4 (210 X 297 mm) 1 450 857 A7 B7 Printed by the Shell Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (12) Adding both C16TABr and Tween 80 In terms of material, obviously the concentration increases Accelerate the reaction. In the lower concentration group, the reaction rate is slower than when it is not added. • However, the nickel wire generated is partially suspended in the upper layer of the solution, and some is nucleated at a certain position at the bottom of the reactor. In the center, it grows into a structure of nickel wire, but there is no phenomenon of plating on the reactor wall. Therefore, when the finished nickel wire is collected by filtration and drying, it is easy to collect and has a large amount. When the concentration is increased, the reaction rate is significantly faster, but most of the reduced nickel is plated on the reactor wall, and only a small amount of nickel wire is generated. The above data shows that if the reaction rate is too fast, the ideal nickel wire cannot be obtained as a product. Slowing down the reaction rate, although nickel wire can still be obtained, it is probably not conducive to the production rate. The yield here is about 82-86%, and the specific surface area of the first group is 10.0 m2 / g. Example 5 This example shows the growth of nickel wires under different reducing agent (diamine) concentrations. The synthesis procedure and conditions are similar to those in Example 1, in which the total volume of the solution is fixed at 20 m, and the concentration of hydrazine is changed by adjusting the volume of deionized water. The reaction temperature was controlled at 80-90 ° C without adding any surfactant. The results of the reaction are as follows: -15- This paper size applies to Chinese National Standard (CNS) A4 specifications < 210 X 297 mm < Please read the precautions on the back before filling this page) Order. 4508 5 7 A7 B7 V. Description of the invention (13) Group Hydrazine concentration (M) Response completion time Nickel wire characteristics: HC1 0 > 8 hours length is only a few microns to a few millimeters HC2 1.325 85 minutes length is only a few microns to a few millimeters HC3 2.325 2 hope length Can reach the number HC4 5.325 2 I hope long flight to several centimeters HC5 8.325 1 phen length can reach several centimeters HC6 10.325 21 centimeters can be printed to the number of centimeters HC6 10.325 21 centimeters length Printed by the above-mentioned data When the concentration of amine is low, the reaction rate is slow and the nickel wire formed is short. However, when the concentration is increased to 2.325 M, the rate of nickel wire formation and the reaction rate will no longer be affected by the concentration of hydrazine. Example 6 In this example, we investigated the effect of the composition of the reactant solution on the formation of nickel wires. The composition of the reactant solution in Example 1 includes: KHC03, N2Η4 · Η20, K2C03, NiCl2.6H20, K2ΗΡ04, K〇Η, and a surfactant. In this embodiment, we adopt the method of gradually deleting an additive. The remaining conditions are the same as those in the first embodiment (but no surfactant is added). The reaction results are as follows: \-/ · __ _ _ _ ____I__i I < Please read the "Cautions on the back side before filling out this page) Order--16-This paper is applicable to the China National Standard (CNS) A4 specification (210 X 297 mm) A7 B7 5. Description of the invention (14) Group solution composition reaction completion time 20 minutes Ni wire special parts

ELC1 KHC03' Ν2Η4.Η20 ' K3CO3' NiCl2.6H20 ' K2HP〇4以及 KOH ELC2 Ν2Η4·Η20、NiCl2_6H20 20分、K2HP04以及KOH ELC3 N2H4,H20、NiCl2.6H20 5分以及KOH 長度可至數公分長度可至數公分長度只有數微米 <請先Μ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聯胺與碳酸氫鉀添加的目的是爲在溶液中形成穩定的聯胺碳酸鹽（hydrazine carboxylate)，以避免聯胺與鎳離子在儲藏時提前產生鎳的還原反應。碳酸鉀的功用爲有助於聯胺碳酸鹽在溶液中的穩定。如果溶液中沒有碳酸根離子，會明顯生成氫氧化鎳的沈澱，但這對於鎳絲的生成並未造成任何影響，此可由ELC2的結果得知。同時這也說明，氫氧化鎳爲反應過程的中間產物，因此任何鎳的鹽類*例如氯化鎳，硝酸鎳等，只要加入鹼液後，也會產生氫氧化鎳，就都應該得到類似的結果。但如果不添加磷酸根離子作爲緩衝劑時，則反應明顯加快，使得鎳絲變爲極短，如ELC3所示，這也表示溶液的pH値應該也是重要的實驗參數。實施例七在本實施例中，合成的程序與條件與實施例一相似’ -17- 本紙張尺度適用中@國家標準（CNS)A4規格<210 X 297公釐） Η 4508 5 7 Α7 Β7 五、發明說明（丨5 ) (請先《讀背面之注意事項再填寫本頁) 但反應物溶液的組成只包含聯胺水合物作爲還原劑、 NiCl2_6H20爲鎳的前驅物，Κ2ΗΡ04作爲緩衝劑，KOH作爲鹸》本實施例提供pH値對於鎳絲生成的影響，其中PH値以 KOH濃度控制。反應結果如下：溶液啓誠値反應完成時間鎳絲特性 14.24 6分長度難米至數毫米 13.16 1盼長度數微米至數毫米 12.88 14分長度爲數般 12.24 (未量測）長度爲數公分 11.79 20分長度數毫米 11.39 長度數毫米*但產率極低 10.95 7小時以上未反應無鎳絲生成 (未添加KOH) 經濟部智慧財產局員工消費合作社印製 pH値爲13.16以上時，鎳絲生成速率較快，長度亦較短，當pH値至14.24，生成的鎳絲上同時會有些微鎳箔生成。pH値爲11.79與12.88兩組中，鎳絲生成長度長，較適於作爲導電塡充物。當pH値小於11時，反應7小時以上溶液未有任何反應產生。pH = 12.88組別的產率經量測爲 90.3%。實施例八在本實施例中，重覆實施例一的步驟’除了我們不使 -18- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 45〇8 57 A7 B7 五、發明說明（16 ) 用實施例一中的PMC 500系列型號502多點熱盤及攪拌器，而將該水浴置於一無磁場的加熱盤上，藉以観察鎳絲在無磁場下的生長情形》結果爲反應完成時間增長至90分，所生成的鎳絲具有數公分長度。對照例一在本實施例中，重覆實施例六中組別ELC1，ELC2及 ELC3的實驗，除了我們不使用實施例一中的PMC 500系列型號502多點熱盤及攪拌器，而將該水浴置於一無磁場的加熱盤上，藉以觀察鎳絲在無磁場下的生長情形。結果發現在反應時間2小時時反應仍不完全，且僅得長度數微米的細小絲狀產品。 I ---丨！一！1 1— — ！丨訂！一一 — _ I 線-- (請先《讀背面之注項再填寫本頁) 經濟部智慧財產局員工消費合作杜印製本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱）ELC1 KHC03 'Ν2Η4.Η20' K3CO3 'NiCl2.6H20' K2HP〇4 and KOH ELC2 Ν2Η4 · Η20, NiCl2_6H20 20 minutes, K2HP04 and KOH ELC3 N2H4, H20, NiCl2.6H20 5 minutes and KOH lengths can be up to several centimeters in length The length of a few centimeters is only a few micrometers. <Please read the notes on the back before filling out this page.) The employee cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints hydrazine and potassium bicarbonate. The purpose of the addition is to form a stable hydrazine in solution. Carbonate (hydrazine carboxylate), in order to avoid the reduction reaction of nickel and nickel ions in advance during storage. The function of potassium carbonate is to help stabilize hydrazine carbonate in solution. If there are no carbonate ions in the solution, precipitation of nickel hydroxide will obviously occur, but this has no effect on the formation of nickel wires, which can be known from the results of ELC2. At the same time, it also shows that nickel hydroxide is an intermediate product of the reaction process, so any salt of nickel * such as nickel chloride, nickel nitrate, etc., as long as nickel hydroxide is added to the alkaline solution, it should be similar. result. However, if no phosphate ion is added as a buffer, the reaction will be significantly accelerated, making the nickel wire extremely short, as shown by ELC3, which also indicates that the pH of the solution should also be an important experimental parameter. Example 7 In this example, the synthetic procedure and conditions are similar to those of Example 1. '-17- This paper size is applicable @National Standard (CNS) A4 Specification < 210 X 297 mm) 508 4508 5 7 Α7 Β7 V. Description of the invention (丨 5) (Please read the “Notes on the back side before filling out this page”) However, the composition of the reactant solution only contains hydrazine hydrate as the reducing agent, NiCl2_6H20 is the precursor of nickel, and Κ2ΗΡ04 is the buffering agent. KOH as 鹸 "This example provides the effect of pH 値 on the formation of nickel wire, where pH 控制 is controlled by the KOH concentration. The results of the reaction are as follows: The time of completion of the solution. The reaction time of the nickel wire is 14.24. The length is 6 meters to several millimeters. 13.16. The length is from several micrometers to several millimeters. 12.88 The length is 14 to 12.24 (not measured). The length is 11.79 centimeters. 20 minutes length several millimeters 11.39 length several millimeters * but the yield is extremely low 10.95 7 hours or more without reaction without nickel wire formation (without KOH added) When the pH value printed by the employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is 13.16 or higher, nickel wire generation The rate is faster and the length is shorter. When the pH is 値 14.24, some micro-nickel foil will be generated on the generated nickel wire. In the two groups of pH 値 11.79 and 12.88, the length of nickel wire generation is long, which is more suitable as a conductive charge. When the pH is less than 11, no reaction occurs in the solution for more than 7 hours. The yield in the pH = 12.88 group was measured at 90.3%. Example 8 In this example, the steps of Example 1 are repeated, except that we do not make -18- this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 45〇8 57 A7 B7 5 Explanation of the invention (16) Using the PMC 500 series model 502 multi-point hot plate and agitator in the first embodiment, the water bath was placed on a magnetic field-free heating plate to observe the growth of the nickel wire in the absence of a magnetic field. 》 The result is that the reaction completion time is increased to 90 minutes, and the nickel wire produced has a length of several centimeters. Comparative Example 1 In this example, the experiments of the groups ELC1, ELC2, and ELC3 in Example 6 were repeated, except that we did not use the PMC 500 series model 502 multi-point hot plate and agitator in Example 1. The water bath was placed on a magnetic field-free heating plate to observe the growth of the nickel wire in the absence of a magnetic field. As a result, it was found that the reaction was still incomplete at the reaction time of 2 hours, and only a fine filamentous product having a length of several micrometers was obtained. I --- 丨! One! 1 1—!丨 Order! ONE — _ I Line-(Please read the “Notes on the back side before filling out this page”) The consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs Du printed this paper The size of the paper is applicable to China National Standard (CNS) A4 (210 X 297) Love)

Claims

Μ 4^08 5 7Μ 4 ^ 08 5 7

A8明C8D6 1. —種鎳絲的合成方法，包含：在一含有鎳離子的水溶液中在一鹼、一 pH緩衝劑及一磁場存在下，以一還原劑在一介於80-100°C溫度還原該鎳離子一段時間，而於該水溶液中形成鎳絲，其中該水溶液的pH値在該段時間內不小於Π.0。 2. 如申請專利範圍第1項的方法，其中該pH値介於 11.5至 13.0。 3. 如申請專利範圍第1項的方法，其中該溫度介於80-90t。 4. 如申請專利範圍第1項的方法*其中該段時間大於 5分鐘。 5. 如申請專利範圍第1項的方法，其中該含有鎳離子的水溶液係將一鎳鹽加入水中而形成*其中該鎳鹽爲可於一鹼性水溶液中形成氫氧化鎳（II)的鎳鹽。 6. 如申請專利範圍第5項的方法’其中該鎳鹽爲氯化鎳，硝酸鎳，醋酸鎳，碳酸鎳，硫酸鎳，硫酸銨鎳或其等之水合物。 7. 如申請專利範圍第6項的方法，其中該鎳鹽爲 •20· 本紙張尺度適用中囲囲家標準（CNS>A4规格（210 X 297公釐） <請先《讀背面之注意事項再螇寫本頁) 訂- 經濟部智慧財產局員工消費合作社印製A8 Ming C8D6 1. A method for synthesizing nickel wire, comprising: in the presence of a base, a pH buffer, and a magnetic field in an aqueous solution containing nickel ions, a reducing agent at a temperature between 80-100 ° C The nickel ions are reduced for a period of time, and nickel wires are formed in the aqueous solution, wherein the pH of the aqueous solution is not less than Π.0 during the period of time. 2. The method according to item 1 of the patent application, wherein the pH is between 11.5 and 13.0. 3. The method according to item 1 of the patent application range, wherein the temperature is between 80-90t. 4. The method according to item 1 of the scope of patent application *, where the period is greater than 5 minutes. 5. The method according to item 1 of the patent application, wherein the aqueous solution containing nickel ions is formed by adding a nickel salt to water *, wherein the nickel salt is nickel that can form nickel (II) hydroxide in an alkaline aqueous solution. salt. 6. The method according to item 5 of the patent application, wherein the nickel salt is nickel chloride, nickel nitrate, nickel acetate, nickel carbonate, nickel sulfate, nickel ammonium sulfate, or a hydrate thereof. 7. For the method of applying for the scope of patent No. 6, where the nickel salt is • 20 · This paper size is applicable to the Chinese standard (CNS > A4 size (210 X 297 mm)) < Please read the precautions on the back first (Reprinted on this page) Order-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

5 8 ο ASSC8DS 六、申請專利範圍 NiCl2.6H2〇。 8.如申請專利範圍第1項的方法，其中該還原劑爲聯胺，聯胺水合物或聯胺鹽。 9·如申請專利範圍第8項的方法，其中該還原劑爲 ν2η4·η2ο 〇 10. 如申請專利範圍第8項的方法，其中該鹼具有一化學式ΜΟΗ，其中Μ爲鹼金屬。 11. 如申請專利範圍第10項的方法，其中該鹼金屬氫氧化物爲ΚΟΗ。 12. 如申請專利範圍第10項的方法，其中該PH緩衝劑具有一化學式Μ2ΗΡ04，其中Μ的定義同申請專利範圍第10 項。 13. 如申請專利範圍第11項的方法，其中該pH緩衝劑爲 Κ2ΗΡ04。 14. 如申請專利範圍第13項的方法，其中該KOH於該含有鎳離子的水溶液的濃度爲0.125M，及該Κ2ΗΡ04於該水溶液中的濃度爲0.25M。 -21- 本紙張尺度適用中國國冢標準（CNS)A4規袼（210 X 297公釐> <請先Η讀背面之注f項再填寫本頁) 訂.' -線. 經濟部智慧財產局員工消費合作社印裂 5 8 ο 5 4 A8B8C8D8 六、申請專利範圍 15. 如申請專利範圍第5項的方法，其中該還原劑以超過還原該鎳鹽所需的化學量存在於該含有鎳離子的水溶 .液中。 16. 如申請專利範圍第15項的方法，其中該還原劑爲聯胺，聯胺水合物或聯胺鹽，及該還原劑於該含有鎳離子的水溶液的濃度大於1.5M。 17. 如申請專利範圍第16項的方法，其中該還原劑爲 Ν2Η4·Η20及該鎳鹽爲NiCl2_6H20，其中Ν2Η4_Η20於該含有鎳離子的水溶液中的濃度小於10M。 18. 如申請專利範圍第Π項的方法，其中NiCl2‘6H20 於該含有鎳離子的溶液中的濃度爲0.05M 1 Ν2Η4·Η20於該含有鎳離子的水溶液中的濃度爲2.3Μ " 19. 如申請專利範傰第17項的方法，其中該鹼具有一化學式ΜΟΗ，其中Μ爲鹼金屬。 20. 如申請專利範圍第19項的方法’其中該鹼金屬氫氧化物爲ΚΟΗ。 21. 如申請專利範圍第19項的方法’其中該pH緩衝劑具有一化學式M2HP04，其中Μ的定義同申請專利範圍第19 -22- 本紙張尺度適用中0國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注$項再填寫本頁) 訂·- 線經濟部智慧財產局員工消費合作杜印製 i 45〇8s5 8 ο ASSC8DS 6. Application scope NiCl2.6H2〇. 8. The method according to item 1 of the patent application scope, wherein the reducing agent is hydrazine, hydrazine hydrate or hydrazine salt. 9. The method according to item 8 of the patent application, wherein the reducing agent is ν2η4 · η2ο 10. The method according to item 8 of the patent application, wherein the base has a chemical formula M0Η, where M is an alkali metal. 11. The method of claim 10, wherein the alkali metal hydroxide is KOH. 12. The method as claimed in claim 10, wherein the pH buffer has a chemical formula M2HP04, and the definition of M is the same as that in claim 10. 13. The method according to item 11 of the scope of patent application, wherein the pH buffering agent is K2HP04. 14. The method according to item 13 of the patent application scope, wherein the concentration of the KOH in the aqueous solution containing nickel ions is 0.125M, and the concentration of the K2ΗΡ04 in the aqueous solution is 0.25M. -21- This paper size is subject to the Chinese National Standard (CNS) A4 Regulations (210 X 297 mm > < Please read the note f on the back before filling out this page) Order. '-Line. Ministry of Economy Wisdom Property Bureau employee consumer cooperative print 5 8 ο 5 4 A8B8C8D8 6. Application for patent scope 15. For the method of patent application No. 5 wherein the reducing agent is present in the nickel-containing nickel in a chemical amount exceeding the amount required to reduce the nickel salt Ions are soluble in water. 16. The method of claim 15 in which the reducing agent is hydrazine, hydrazine hydrate or hydrazine salt, and the concentration of the reducing agent in the aqueous solution containing nickel ions is greater than 1.5M. 17. The method of claim 16 in which the reducing agent is N2Η4 · Ν20 and the nickel salt is NiCl2_6H20, and the concentration of N2Ν4_Η20 in the aqueous solution containing nickel ions is less than 10M. 18. The method of claim No. Π, wherein the concentration of NiCl2'6H20 in the nickel ion-containing solution is 0.05M 1 Ν2Η4 · Η20 in the nickel ion-containing aqueous solution is 2.3M " 19. For example, the method of claim 17 in the patent application, wherein the base has a chemical formula M0, where M is an alkali metal. 20. The method according to item 19 of the scope of patent application, wherein the alkali metal hydroxide is KOΗ. 21. If the method of applying for the scope of the patent No. 19 'wherein the pH buffer has a chemical formula M2HP04, where the definition of M is the same as the scope of the patent application No. 19 -22- This paper is applicable to the National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back before filling out this page) Order ·-Consumption Cooperation of Employees of the Intellectual Property Bureau of the Ministry of Online Economy Du printed i 45〇8s

六、申請專利範固 A8B8C8D8 項。 22. 如申請專利範圍第20項的方法，其中該pH緩衝劑爲1^即04。 23. 如申請專利範圍第22項的方法，其中該koh於該含有鎳離子的水溶液的濃度爲0.125M，及該Κ2ΗΡ04於該水溶液中的濃度爲0.25M。 24. 如申請專利範圍第1項的方法，其中一界面活性劑被加入於該含有鎳離子的水溶液》 25. 如申請專利範圍第24項的方法，其中該界面活性劑於該含有鎳離子的水溶液中的濃度介於1X10'4M至1X10_ 2M。 26. 如申請專利範圍第9項的方法，其中一鹼金屬碳酸鹽及一鹼金屬碳酸氫鹽被加入於該含有鎳離子的水溶液。 27. 如申請專利範圍第17項的方法，其中一鹼金屬碳酸鹽及一鹼金靥碳酸氫鹽被加入於該含有鎳離子的水溶液。 -23- 本紙張尺度適用中固固家標準（CNS>A4规格<210 * 297公釐〉 (請先Μ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 45〇86. Apply for patent Fangu A8B8C8D8. 22. The method as claimed in claim 20, wherein the pH buffer is 1 ^, that is, 04. 23. The method of claim 22, wherein the concentration of the koh in the aqueous solution containing nickel ions is 0.125M, and the concentration of the K2ΚΡ04 in the aqueous solution is 0.25M. 24. The method according to claim 1 in which a surfactant is added to the aqueous solution containing nickel ions "25. The method according to claim 24 in which the surfactant is applied to the nickel-containing solution The concentration in the aqueous solution is between 1X10'4M and 1X10_2M. 26. The method of claim 9 in which an alkali metal carbonate and an alkali metal bicarbonate are added to the aqueous solution containing nickel ions. 27. The method according to item 17 of the patent application, wherein an alkali metal carbonate and an alkali metal sulfonium bicarbonate are added to the aqueous solution containing nickel ions. -23- This paper size applies to the China Solid Goods Standard (CNS > A4 Specifications < 210 * 297mm) (please read the precautions on the back before filling this page) Printed by Consumer Cooperatives

28_如申請專利範圍第26項的方法，其中該鹼金屬碳酸鹽爲K2C03&該鹼金屬碳酸氫鹽爲KHC03。 29_如申請專利範圍第27項的方法，其中該鹼金屬碳酸鹽爲【2003及該鹼金屬碳酸氫鹽爲KHC03。 30.如申請專利範圍第28項的方法，其中該1<：2(：03及 KHC03於該含有鎳離子的水溶液中的濃度均爲0.25M 〇 3丨.如申請專利範圍第29項的方法，其中該〖2(：0;及 KHC03於該含有鎳離子的水溶液中的濃度均爲0.25M < 1 I— — I-.!— —I _ I <請先《讀背面之項再填寫本頁) 訂·- 32. —種藉申請專利範圍第1至31項中任一項所_的方法所合成的鎳絲。28_ The method of claim 26, wherein the alkali metal carbonate is K2C03 & the alkali metal bicarbonate is KHC03. 29_ The method of claim 27 in the scope of patent application, wherein the alkali metal carbonate is [2003 and the alkali metal bicarbonate is KHC03. 30. The method as claimed in item 28 of the patent application, wherein the concentrations of the 1 <: 2 (: 03 and KHC03 in the nickel ion-containing aqueous solution are both 0.25 M. 03. The method as claimed in item 29 of the patent application scope , Where the concentrations of [2 (: 0) and KHC03 in the nickel ion-containing aqueous solution are both 0.25M < 1 I— — I-.! — —I _ I < Fill in this page) Order ·-32. — A nickel wire synthesized by the method described in any one of claims 1 to 31.

緣· 經濟部智慧財產局員工消費合作杜印製 34. 如申請專利範圍第33項的鎳絲，其中該鎳絲具有 —介於0.5至5微米的直徑，及一介於0.5-50毫米的長度。 35. —種鎳絲的合成方法，包含：在一含有鎳離子的水溶液中在一鹸、一pH緩衝劑及一界面活性劑存在下，以—還原劑在—介於80-100°C溫度還 -24- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐>Yuan · Intellectual Property Cooperation, Intellectual Property Bureau of the Ministry of Economic Affairs, printed by Du. 34. For example, the nickel wire in the scope of patent application No. 33, wherein the nickel wire has a diameter of 0.5 to 5 microns and a length of 0.5 to 50 mm . 35. A method for synthesizing nickel wire, comprising: in a solution containing nickel ions in the presence of a tritium, a pH buffer, and a surfactant, at a temperature of -reducing agent at -80-100 ° C Also-24- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm >

六、申請專利範圍原該鎳離子一段時間，而於該水溶液中形成鎳絲，其中該水溶液的pH値在該段時間內不小於11.0。 36. 如申請專利範圍第35項的方法，其中該PH値介於 11.5 至 13.0。 37. 如申請專利範圍第35項的方法，其中該溫度介於 80-90°C。 38_如申請專利範圍第35項的方法，其中該段時間大於5分鐘。 39. 如申請專利範圍第35項的方法，其中該含有鎳離子的水溶液係將一鎳鹽加入水中而形成，其中該鎳鹽爲可於一鹼性水溶液中形成氫氧化鎳（II)的鎳鹽。 40. 如申請專利範圍第39項的方法，其中該鎳鹽爲氯化鎳，硝酸鎳，醋酸鎳*碳酸鎳，硫酸鎳，硫酸銨鎳或其等之水合物。 41. 如申請專利範圍第40項的方法’其中該鎳鹽爲 NiCl2.6H20。 42. 如申請專利範圍第35項的方法，其中該還原劑爲 -25- 本紙張尺度用中®國家標準（CNS>A4規格（210 * 297公« )' (請先《讀背面之注意事項再填寫本頁) 訂： A 經濟部智慈財產局員工消費合作社印製 5 8ο 5 4 A8B8C8D8 六、申請專利範圍聯胺，聯胺水合物或聯胺鹽。 43. 如申請專利範圍第42項的方法，其中該還原劑爲 Ν2Η4·Η20。 44. 如申請專利範圍第42項的方法’其中該驗具有一化學式ΜΟΗ，其中Μ爲鹸金靨。 45. 如申請專利範圍第44項的方法，其中該鹼金屬氫氧化物爲ΚΟΗ。 46. 如申請專利範圍第44項的方法，其中該PH緩衝劑具有一化學式Μ2ΗΡ04，其中Μ的定義同申請專利範圍第44 項。 LVL --------------/Μ--- (請先閲讀背面之注項再f本I ) 訂· 經濟部智慧財產局消費合作社印製 47. 如申請專利範圍第45項的方法，其中該pH緩衝劑 gK2HP04。 48. 如申請專利範圍第47項的方法，其中該ΚΟΗ於該含有鎳離子的水溶液的濃度爲0.125Μ，及該Κ2ΗΡ〇4於該水溶液中的濃度爲0.25Μ。 49. 如申請專利範圍第39項的方法，其中該還原劑以超過還原該鎳鹽所需的化學量存在於該含有鎳離子的水溶 -線- -26- 857 A8B8C8D8 六、申請專利範圍液中。 50. 如申請專利範圍第49項的方法，其中該還原劑爲聯胺，聯胺水合物或聯胺鹽，及該還原劑於該含有鎳離子的水溶液的濃度大於1.5M。 51. 如申請專利範圍第50項的方法，其中該還原劑爲 Ν2Η4·Η20及該鎳鹽爲NiCl2‘6H20，其中Ν2Η4·Η20於該含有鎳離子的水溶液中的濃度小於10Μ。 52. 如申請專利範圍第51項的方法，其中NiCl2_6H20 於該含有鎳離子的溶液中的濃度爲0.05M，Ν2Η4·Η20於該含有鎳離子的水溶液中的濃度爲2.3Μ。 (請先《讀背面之注意事項再填寫本頁) 訂· 經濟部智慧財產局貝工消費合作社印製 53.如申請專利範圍第52項的方法•其中該鹸具有一化學式MOH *其中Μ爲鹼金屬。 54_如申請專利範圍第53項的方法，其中該鹼金屬氫氧化物爲ΚΟΗ。 55.如申請專利範圍第53項的方法，其中該pH緩衝劑具有一化學式Μ2ΗΡ04，其中Μ的定義同申請專利範圍第53 項。 ____-27- 本紙張尺度適用中國0家標準（CNS)A4规格<210 X 297公爱> .線.· 5 8 ο 5 4 Aacw 經濟部智慧財產局貝工消費合作社印製六、申請專利範圍 56. 如申請專利範圍第54項的方法，其中該pH緩衝劑爲 Κ2ΗΡ04。 57. 如申請專利範圍第54項的方法，其中該KOH於該含有鎳離子的水溶液的濃度爲0.125M，及該Κ2ΗΡ04於該水溶液中的濃度爲0.25M。 58. 如申請專利範圍第35項的方法，其中該界面活性劑於該含有鎳離子的水溶液中的濃度介於1 Χ10·4Μ至1 X 10· 2Μ。 59. 如申請專利範圍第43項的方法，其中一鹸金屬碳酸鹽及一鹼金屬碳酸氫鹽被加入於該含有鎳離子的水溶液。 60. 如申請專利範圍第51項的方法，其中一鹼金屬碳酸鹽及一鹼金屬碳酸氫鹽被加入於該含有鎳離子的水溶液。 61. 如申請專利範圍第59項的方法，其中該鹸金屬碳酸鹽爲〖2(：03及該鹼金屬碳酸氫鹽爲KHC03 » 62. 如申請專利範圍第60項的方法，其中該鹼金屬碳酸鹽爲K2C03及該鹼金屬碳酸氫鹽爲KHC03。 -28- 本紙張尺度適用中固國家標準（CNS)A4規格（210 X 297公釐） — — — — —一11^¾^ ·1!! —訂線 (請先《讀背面之注$項再填寫本頁)6. Scope of patent application: The nickel ions are formed for a period of time, and nickel wires are formed in the aqueous solution, and the pH of the aqueous solution is not less than 11.0 during the period. 36. The method of claim 35, wherein the pH is between 11.5 and 13.0. 37. The method of claim 35, wherein the temperature is between 80-90 ° C. 38_ The method according to item 35 of the patent application, wherein the period is more than 5 minutes. 39. The method of claim 35, wherein the aqueous solution containing nickel ions is formed by adding a nickel salt to water, and the nickel salt is nickel that can form nickel (II) hydroxide in an alkaline aqueous solution. salt. 40. The method of claim 39, wherein the nickel salt is nickel chloride, nickel nitrate, nickel acetate * nickel carbonate, nickel sulfate, nickel ammonium sulfate, or a hydrate thereof. 41. The method of claim 40, wherein the nickel salt is NiCl2.6H20. 42. If the method of applying for the scope of the patent No. 35, wherein the reducing agent is -25- this paper size for the national standard (CNS > A4 specifications (210 * 297 public «) ') (Please read" Notes on the back " (Fill in this page again) Order: A Printed by the Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs 5 8ο 5 4 A8B8C8D8 6. Application scope of patents Hydrazine, Hydrazine Hydrate or Hydrazine Salt 43. If you apply for patent No. 42 Method, wherein the reducing agent is N2Η4 · Η20. 44. The method of claim 42 in the scope of patent application, wherein the test has a chemical formula ΜΟΗ, where M is 鹸鹸靥. 45. The method of scope 44 in the patent application, Wherein, the alkali metal hydroxide is KOΗ. 46. For example, the method of the scope of application of the patent No. 44 wherein the pH buffer has a chemical formula M2ΗΡ04, where the definition of M is the same as the scope of the scope of the patent application No. 44. LVL ---- ---------- / Μ --- (Please read the note on the back before f this I) Order · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Wherein the pH buffer gK2HP04. 48. Such as The method of claim 47, wherein the concentration of the KO in the aqueous solution containing nickel ions is 0.125M, and the concentration of the KO2 in the aqueous solution is 0.25M. 49. As for the 39 Method, wherein the reducing agent is present in the nickel-containing water-soluble-line- -26- 857 A8B8C8D8 in a chemical amount exceeding the chemical amount required to reduce the nickel salt. 6. Apply for a patent scope. Method, wherein the reducing agent is hydrazine, hydrazine hydrate or hydrazine salt, and the concentration of the reducing agent in the aqueous solution containing nickel ions is greater than 1.5M. 51. The method of claim 50, wherein The reducing agent is N2Η4 · Η20 and the nickel salt is NiCl2'6H20, wherein the concentration of N2Η4 · Η20 in the aqueous solution containing nickel ions is less than 10M. 52. For example, the method of claim 51 in the scope of patent application, wherein NiCl2_6H20 is contained in the solution. The concentration of nickel ions in the solution is 0.05M, and the concentration of N2Η4 · Η20 in the aqueous solution containing nickel ions is 2.3M. (Please read the "Cautions on the back side before filling this page") Printed by the Industrial and Commercial Shellfish Consumer Cooperatives. 53. For example, the method of applying for the scope of the patent No. 52 • Where the 鹸 has a chemical formula MOH * where M is an alkali metal. 54_ As for the method of the scope of applying for the patent No. 53, where the alkali metal The hydroxide is KO. 55. The method according to item 53 of the patent application, wherein the pH buffering agent has a chemical formula M2HP04, where M has the same definition as item 53 of the patent application. ____- 27- This paper size is applicable to 0 Chinese Standards (CNS) A4 specifications < 210 X 297 Public Love > .line. · 5 8 ο 5 4 Aacw Printed by Shellfish Consumer Cooperative, Intellectual Property Bureau, Ministry of Economic Affairs Patent scope 56. The method according to item 54 of the patent scope, wherein the pH buffering agent is K2HP04. 57. The method according to item 54 of the patent application, wherein the concentration of the KOH in the aqueous solution containing nickel ions is 0.125M, and the concentration of the K2ΗΡ04 in the aqueous solution is 0.25M. 58. The method of claim 35, wherein the concentration of the surfactant in the nickel ion-containing aqueous solution ranges from 1 × 10 · 4M to 1 × 10 · 2M. 59. The method according to item 43 of the patent application, wherein a hafnium metal carbonate and an alkali metal bicarbonate are added to the aqueous solution containing nickel ions. 60. The method of claim 51, wherein an alkali metal carbonate and an alkali metal bicarbonate are added to the aqueous solution containing nickel ions. 61. The method according to the scope of patent application 59, wherein the rhenium metal carbonate is [2 (: 03) and the alkali metal bicarbonate is KHC03 »62. The method according to scope 60 of the patent application, wherein the alkali metal The carbonate is K2C03 and the alkali metal bicarbonate is KHC03. -28- This paper size applies the National Solid State Standard (CNS) A4 specification (210 X 297 mm) — — — — —-11 ^ ¾ ^ · 1! ! — Ordering (please read "Note $ on the back side before filling out this page)

六、申請專利範圍 63. 如申請專利範圍第61項的方法，其中該1^<：03及 KHC03於該含有鎳離子的水溶液中的濃度均爲0.25m ^ 64. 如申請專利範圍第62項的方法，其中該1(2003及 KHC03於該含有鎳離子的水溶液中的濃度均爲0.25M。 65. —種藉申請專利範圍第35至64項中任一項所述的方法所合成的鎳絲· 66. 如申請専利範圍第65項的鎳絲，其中該鎳絲具有 —介於0.1至20微米的直徑，及一介於1-100毫米的長度。 67. 如申請專利範圍第66項的鎳絲，其中該鎳絲具有一介於0.5至5微米的直徑，及一介於0.5-50毫米的長度。 — — — — —--· I I (請先閲讀背面之注$項再填寫本頁) 訂- ，線. 經濟部智慧財產局員工消費合作杜印製 I 9 2 本紙張尺度適用中國Η家楳準（CNS)A4規格（210 X 297公釐） /Sixth, the scope of patent application 63. For the method of scope 61 of the patent application, the concentration of 1 ^ <: 03 and KHC03 in the aqueous solution containing nickel ions are both 0.25m ^ 64. Such as the scope of patent application No. 62 The method of item 1, wherein the concentrations of 1 (2003 and KHC03 in the nickel ion-containing aqueous solution are 0.25 M. 65.-a method synthesized by the method described in any one of the claims 35 to 64 Nickel wire · 66. If the nickel wire of the 65th scope of the application is filed, the nickel wire has a diameter of between 0.1 to 20 microns and a length of 1 to 100 millimeters. Nickel wire, wherein the nickel wire has a diameter between 0.5 and 5 microns and a length between 0.5 and 50 mm. — — — — ——— · (Please read the note on the back before filling in this page ) Order-, line. Consumer cooperation of Intellectual Property Bureau of the Ministry of Economic Affairs Du printed I 9 2 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) /