TW200902193A - Method of producing fine particle copper powders - Google Patents

Abstract

Methods for producing finely divided copper or copper alloy powders are described, from compositions containing metal ions and an alkanolamine, preferably monoethanolamine, wherein the alkanolamine acts as a primary reducing agent. In preferred embodiments the methods for producing micron and submicron copper powder utilize precursor compositions containing copper ions in the form of submicron particles of copper carbonate, copper hydroxide, copper oxides, or any combination thereof, and utilize monoethanolamine (or optionally but less preferably hydrazine), and preferably additionally containing caustic and a reducing sugar.

Description

200902193 IX. INSTRUCTIONS RELATED APPLICATIONS This application filed the application No. 60/672,979 on April 20, 2005 and the application number of 11/342,605 on January 31, 2006. The content is all Break into this article. TECHNICAL FIELD OF THE INVENTION The present invention relates to a square copper salt of a synthetic copper metal powder to a desired particle size, converting the ground copper, copper oxide or a mixture thereof, and subsequently to a preferred system. The copper oxide particles are converted into copper powder in the presence of a caustic, a reducing sugar and a reducing agent in the presence of monoethanolamine or hydrazine, and preferably in the form of a sub-reducing organic acid such as a formate. The method is carried out batchwise by exemplifying copper sulphate particles, reducing sugars, caustic and 1.5 to maintain a temperature above about 1000 (for example, between i 〇 3 3 ). [Prior Art] Micro-copper ( Cu) powders have many uses, such as field emission displays, lights, and the like. For example, copper conductive metal pastes that are compressed or replaceable, wherein the paste is used in multilayer passive components (please require the United States) The method disclosed in the US Provisional Application for Temporary Application is based on the fact that the wet copper salt is at a temperature of osmium oxide and on the other hand (there is no ammonia and low concentration on the other hand, the reducing agent is used in the reactor) 2 g of monoethanolamine ^ 1 1 〇 °c ) can be used in the plasma display panel, the powder is prepared into a sintered, electrically conductive, for example, a multilayer ceramic crystal-4-200902193 chip capacitor. Usually 'micron size The particles are used in a conductive paste, such as those described in, for example, U.S. Patent No. 4,735,676, U.S. Patent No. 4,997,674, and U.S. Patent No. 5,011,546. A submicron copper powder having a size of from 8 μm to about 0.1 μm is used, for example, to produce a conductive material for internal electrodes on an integrated circuit. Many differences have been made in the synthesis of copper powder used in the above-mentioned conductive paste. Methods, but such methods are generally classified as gas phase processes or liquid phase processes. Conventional methods of making metal powders have many problems, such as wide particle size distribution, large particles, low sphericity, and uncontrolled oxidation levels. The gas phase process (also known as gas atomization) involves forcing a high pressure inert gas and molten copper to "atomicize" the liquid metal through the nozzle at a sufficient velocity, and the liquid metal is cooled to produce a metal. Powder. Although the method is suitable for mass production, it is difficult to produce a nanometer-sized powder having a commercially acceptable yield (e.g., particles having a diameter of 0.15 micrometer or less) by the method. The product, the oversized particles must be separated from the particles of the preferred range, because the powder often has an irregular shape. The method is difficult 'so difficult to separate. There is also a gas phase thermal decomposition method' in which a copper-containing salt has a weak bonding force between a metal and an anion, and a gas reducing agent is used to thermally decompose the copper-containing salt and Honing to obtain a metal powder. The method provides a fine metal powder. However, the metal powder may burn during heat treatment and the burned powder needs to be honed and classified. Therefore, the yield of the method is lower than liquid phase reduction-5 - 200902193 The method is low. In the vapor phase evaporation method, the evaporation substance is evaporated by heating with an inert gas or an active gas such as CH4 and NH4, and the evaporated gas system is reduced by hydrogen and condensed to obtain a fine metal powder. This method is used to prepare metal powders having a particle size of 5 nm to several micrometers. However, the yield is extremely low and therefore the metal powder is extremely expensive. The liquid phase reduction method is a conventional chemical method for producing metal powder. This liquid phase reduction method makes it easier to control the shape of the powder. Typically, the method of preparing a metal powder comprises 1) forming a soluble first intermediate product, 2) producing an insoluble intermediate product, and 3) adding a reducing agent. A conventional liquid phase reduction method for preparing a copper powder is first carried out by adding sodium hydroxide (NaOH) to an aqueous copper sulfate solution to precipitate copper oxide (the copper hydroxide is subsequently dehydrated to form CuO), and then filtering the slurry. The particles are separated from the liquid. In the second step, a stable Cu20 solution is obtained by reacting the CuO with glucose or another monosaccharide containing 6 carbons and aldehyde groups. When the color of the resulting solution turned dark red due to the formation of Cu20, glycine and arabic gum were added to control the size and surface shape of the final copper powder. Subsequently, a reducing agent (typically, formalin or hydrazine) is added to reduce Cu20 to obtain a copper powder. The particle size of the copper powder varies depending on the conditions under which a plurality of reagents and additives are added, and thus it is difficult to control the particle size. U.S. Patent No. 6,87 5,25 2 teaches a method of making a copper powder having an average particle size of from not less than 0. 1 micron to less than 1.5 micron (preferably between 1.2 microns). However, the example described by the method described in the patent shows that the minimum particle size obtained is actually -6-200902193 〇 8 μm, and the minimum particle size obtained by the prior art method is 0.6 μm. The copper oxyhydroxide is reduced to a metallic copper powder by a wet reduction reaction in the presence of ammonia or an ammonium salt to produce a copper powder. The size of the copper powder is related to the size of the copper hydroxide formed in the first step and also to the size of the copper (I) oxide formed in the second reduction reaction. Specifically, an aqueous solution of a copper salt is reacted with a base to precipitate copper (II) hydroxide. The first reduction step is then carried out in the suspension to reduce the resulting copper oxyhydroxide (11) to copper pentoxide. This first reduction step is carried out by a conventional method by adding glucose as a reducing agent to the obtained suspension of copper (II) hydroxide, thereby reducing copper (II) hydroxide to copper pentoxide. This first reduction step is preferably carried out under an inert gas and an elevated temperature (50 to 90 °C). By blowing an oxygen-containing gas into one of the copper oxide suspensions produced by the first reduction step, the particle diameter is increased but the particle size distribution range is narrowed. Subsequently, a second reduction step is carried out in the suspension to reduce the obtained copper oxide to metal copper ' by adding about 0.01 to 0.1 mol ammonia/mole copper and 1.1 times the chemical equivalent. The bismuth oxyhydroxide is reduced to the hydrazine hydrate required for the metallic copper to initiate the second reduction step. The high-density smooth surface metal particles produced by this method allow the electrode to be sintered at a low temperature into a solid sintered body having few voids. U.S. Patent No. 6,673,134 teaches a method of producing a sheet-like copper powder having an average major axis diameter of 4 to 1 micron and a sheeting property of 2 to 20, wherein the sheet-like copper powder is produced by being dispersed in A copper slurry of fine copper particles having an average particle diameter of 3 to 5 μm in water is introduced into a bead mill containing cerium oxide beads having a diameter of 0.3 to 1.0 mm and honed to 200902193 to flatten the copper powder. . This patent describes the prior art: "The wet synthesis method provides a copper powder having an adjusted average particle size of between about 2 and 4 microns and having a narrow particle size distribution, but involves high cost and economics. The problem is that the patent teaches that after honing, "the powdered copper powder is graded by a classifier (and) to release the desired fine copper powder and by a cyclone or internal surface scraper. The blister copper powder is collected (at the same time) and fed to the honing chamber and pulverized again. This method does not provide the desired narrow particle size and does not provide the desired solid (non-flake) particles. US Published Patent Application No. 2004022 1 685 (now abandoned) describes a method of producing a copper powder by a wet reduction method comprising adding an appropriate amount of sodium hydroxide and hydrazine to an aqueous solution of copper chloride to finally obtain particles Copper powder of 0.1 micron size. The first method for producing the copper powder comprises the steps of: (1) adding sodium hydroxide to an aqueous solution of copper chloride to form an aqueous solution containing copper oxide and copper hydroxide; and (2) adding ruthenium To the aqueous solution, the copper oxide and copper hydroxide are reduced to copper powder, wherein the composition is maintained at a temperature of from 40 to 80 °C. In an alternative method, in the intermediate step, the obtained CuO is reacted with an aldose (a monosaccharide containing 6 carbons and aldehyde groups; such as glucose) to obtain a stabilized Cu20 solution. An amino acid (e.g., glycine) and gum arabic are added to the Cu2 solution to control the size and surface shape of the final copper powder. This published patent application also describes the formation of a complex of hydrazine (amine) with a soluble copper salt and subsequent precipitation of copper powder by mixing a base therein. U.S. Patent No. 5,094,686 teaches a method of making a powder comprising thermally decomposing anhydrous copper formate having a solid phase of 200,902,193 in a non-oxidizing gas at a temperature between 150 and 300 ° C, thereby producing a primary particle size. A fine copper powder having a specific aforesaid surface area of 5 to 0.5 m 2 /g and a small agglomerability of 0.2 to 1 μm.

Kimchenko, Y. I. Et al., in the paper Poroshkovaya Metallurgiya, No. 5 ( 245 ), pages 14-19 (May 1 983; entitled "Preparation of very finely dispersed copper by thermal decomposition of copper formate monoethanolamine complex" (Preparation A method for producing copper powder by thermal decomposition of copper-monoethanolamine formate complex by thermal decomposition of copper formate is described and compared in the Very Finely Divided Copper By The Thermal Decomposition Of Copper Formate Monoethanolamine Complexes). MEA) is a conventional substitute for the formation of ammonia in water-soluble copper complexes. To obtain a high concentration of dissolved complex in solution, an anion for the formation of a stable copper-MEA-anion complex should be supplied, and commercially The anion is a carbonate, a chloride, a nitrate, a borate, a citrate, a sulfate, an acetate or the like. Low molecular weight organic acids such as formic acid and oxalic acid are conventionally known as reducing agents. In this document, as formic acid When the copper dihydrate is dissolved in the linear MEA to form the starting mixture, the composition does not contain a significant amount of water. By copper formate dihydrate (or can be substituted It is known from the thermal decomposition of copper oxalate to form metallic copper. When copper formate is decomposed, differential thermal analysis shows the presence of two isotherms. The first isotherm (up to a maximum temperature of about 3 80 °K (107t) )) is the dehydration of the dihydrate, and the second isotherm (at the highest temperature of about 453 °K (180t)) corresponds to the decomposition of formate and the formation of metallic copper. When copper-monoethanolamine is used - For the formate brine, differential thermal analysis showed five endothermic effects. The first isotherm at 38CK ( -9- 200902193 1 1 1 °C) was related to dehydration at 405. Separation and removal of two isotherms from the MEA; f and the formation of a third isotherm and complex 5 with metallic copper at 419 °K (146 °C) (at low temperatures) The isotherms associated with the formation of 1391 are related to the boiling removal/coagulation of residual organic matter. This method is useful, but the use of copper formate as a precursor is also repeated. 'This document states that the copper powder produced is not compensated. As a result of the surface, it contains a lattice in an unbalanced state, which contains a giant stress. Powders require a cost effective method, one or more low molecular weight organic acids (such as formate and / or oxalic acid) or a reducing agent that is expensive and unstable for each copper ion (such as [invention]] A novel method for preparing micron to submicron particles (copper powder) of copper metal. A product of copper powder of different particle sizes, and there is a considerable need to reduce the manufacturing cost of the copper powder to have a very narrow particle size distribution. Copper powder with a value of 0. 04 to 0. 2 micron narrow particle size distribution (total granule size) of copper powder (preferably having an average particle size of 〇. 〇 4 microns, 0, 07 to 0. 095 micron, 0. 1 to 0. 15 microns and 0. 1 micron copper powder) has other advantages. By narrow particle size, we measured 90% by weight of each sample (preferably 94 weights today 1 3 2〇C ίOff': decomposition. The rest is expensive. The force and the micro-energy need . Collectively referred to as different 1 pressures. There is a center = quantity pair to 0. 07 5 to 0. 2 'Distribution, i) Copper -10- 200902193 The powder particles have an effective diameter falling within 30% (preferably 20%) of the average diameter. The copper powder is formed by blending a slurry of micron to submicron particles of copper oxide (preferably copper pentoxide) with a reducing agent. The reducing agent can be monoethanolamine and/or hydrazine, but monoethanolamine provides a substantial cost advantage. The copper particle size, particle size distribution and particle morphology can be further refined by wet milling the copper oxide particles prior to converting the copper oxide particles to copper powder. However, it has been found that the minimum particle size of the final copper metal powder product is limited to particle growth/agglomeration that occurs during the final reduction step of converting copper pentoxide to copper powder. The copper pentoxide can be prepared by a method known in the art (for example, by reacting copper sulfate with a caustic solution and then converting the copper hydroxide slurry to copper oxychloride by adding glucose). Advantageously, the reaction is carried out under a reducing gas or an inert gas. In a preferred system of the invention, the copper oxide slurry is added to a reactor containing a hot (>100 ° C) monoethanolamine solution, and the monoethanolamine is used as a reduction within 30 minutes of the addition. The agent is used to form a copper powder. In the foregoing reaction, the amount of monoethanolamine added is at least 3 (typically at least 3 · 5 ) molyl monoethanolamine / moor copper (which is about equivalent to g monoethanolamine / g copper). We have noticed that a simple conversion reaction using monoethanolamine requires a high temperature and a reaction time of about 30 minutes, and ignores the particle size of the starting copper oxide (the average diameter of which is one-half the diameter of the particle weight is larger than the average The diameter of one-half of the weight of the particles is smaller than the average 値), and it is difficult to obtain a particle size smaller than 0.  1 5 micron copper powder. Obviously, the dissolution and reprecipitation of the particles will increase the average particle size of the total -11 - 200902193. However, we have surprisingly found that if the presence of reducing sugars (such as glucose) and a small amount of caustic agent, the average diameter is between, for example, zero. 05 to 0. The reaction of one of the 4 micrometers of copper oxide particles requires only about one. 5 to 2 g (for example, 1·6 to 2 g or 1. 7 to 1. 8 g, typically only 1. 75 g) monoethanolamine to completely reduce 1 g of copper. The reaction of copper oxide with monoethanolamine (in which the monoethanolamine-based reducing agent; that is, the low molecular weight reducing acid, hydrazine and the like are not present, and the sugar and caustic are also absent) requires a temperature higher than 1 20 ° C to reach Industrially useful reaction rates. In addition, the reaction takes from 20 to 30 minutes to complete. However, at 1. In the presence of 75 g of monoethanolamine/g of copper, reducing sugars (such as glucose) and a small amount of caustic, the reduction of one of the micron-sized cuprous oxides is carried out rapidly at a temperature of only 101 to 106 ° C (for example, at 1). Within minutes). As a result, the particle growth system during the conversion of copper oxide to copper metal is greatly reduced, and the average particle size has been obtained as 0. 12 micron copper powder. Previous attempts have been made to add dispersants to the slurry. This addition is not particularly beneficial because the dispersant appears to increase particle growth during the reduction reaction. It has also been found that in order to avoid the multiple flushing required to remove traces of sulfate, it is advantageous to use a copper salt of non-copper sulfate as a starting material to form a cuprous oxide system. The preferred starting material is basic copper carbonate, which if it is present as a large particle, can be rapidly wet-milled by a honing medium having a sub-millimeter zircon substrate to an average particle size of less than 0. 2 microns. A small amount of sodium hydroxide and glucose added to the slurry of the sub-millimeter particles of alkaline copper carbonate will convert the basic carbonic acid-12-200902193 copper into copper oxide, and the residual copper sulfate has no residual sulfate residue. salt. Alternatively, the starting material may be a wet micronized submicron hydroxide (12. 9% Cu, 0. 1 1 micron). A small amount of sodium hydroxide and glucose added to the submicron slurry of copper hydroxide will convert the copper oxyhydroxide, and the copper oxydioxide does not have sulfate or other hydrazine remaining. As described above, we have found To obtain a small average particle size, a small amount of caustic is added to the slurry before the reduction reaction. The amount of caustic added is small (sufficient to bring the pH between 1 C, preferably between 10. 5 to 1 1. 5, for example about 1 1 ). After the addition of the caustic, the oxygen can be converted to copper powder by simply adding hydrazine. The reaction is carried out at a low temperature, and the reaction is still quite rapid at a low temperature (30 minutes to 1 hour). Even though the particle size distribution of the resulting product is in two forms, this result is due to the agglomeration caused by the reduction of cuprous oxide to copper metal. Beneficially, if one of the starting copper oxide muds is down to 0-1 and if the reaction is for example 55 to 80. (: (for example, at 60 to 70 ° C, the resulting powder may be as low as 0.15. It is also possible to produce copper powder of a large micron size. By containing a caustic agent and about 1. A solution of 75 g of monoethanolamine/g of dissolved copper was slowly boiled in a copper sulfate solution and then subjected to high temperature cooking for a period of time to form a copper powder having a particle size of 3 μm. Or other copper mud rice granules copper is a small residual salt, which is beneficial to the system. Even if it is 12 bismuth copper, it is considered to be a micron powder of 5 micrometers. - 200902193 Description of the preferred system of choice A preferred system of the invention typically comprises self-contained copper ions (in solution or in the form of a salt or oxide) and an alkanolamine (preferably monoethanolamine) and optionally A method of producing finely dispersed copper by thermal decomposition of a composition of water, a salt, and/or an inorganic base (wherein the alkanolamine is used as a main reducing agent). A preferred system of the invention comprises a method of reducing copper ions mismatched by ethanolamine in the precursor composition to copper metal. More particularly, the present invention relates to compositions and methods for making micron and submicron copper metal powders from compositions comprising or consisting essentially of copper ions, inorganic anions, inorganic bases, monoethanolamine, and optionally water. In one aspect, the invention provides a method of making a micron to submicron size copper powder comprising the steps of providing a precursor composition comprising more than 5% by weight copper ions and greater than 20% by weight monoethanolamine The solution, only below 0. 8 mole of low molecular weight organic acid/mole copper ion; and heating the precursor composition to a temperature at which copper ions are converted into copper powder, the powder containing more than 90% by weight of copper and having an average diameter of About 0. 02 microns to about 5 microns. The invention may include several preferred systems. The reduction reaction is carried out at a temperature of from 90 to 15 (TC, preferably from 130 to 1 55 ° C.) Preferably, the composition contains less than 〇. 4 Moer's low molecular weight organic acid / Mo Er copper ion. The composition may further comprise a total of low molecular weight organic acid and lanthanum less than 0. 4 mol / Mo Er copper ion. Preferably, less than 0 is present in the precursor composition. 4 Mo's 胼 / Mo Er copper ion. Preferably, the precursor composition comprises less than 0. 1 mole of -14-200902193 low molecular weight organic acid/mole copper ion. Most preferably, the composition does not contain the low molecular weight organic acid and/or hydrazine. The reduction reaction can be carried out under the particle form of at least a portion of the copper ion of the precursor composition being a copper salt, copper, copper oxide, or a mixture or composition thereof. The reduction reaction is based on monoethanolamine to copper ions at least 1. 5: 1 is carried out. The reduction is carried out by consuming at least 丨moethanolamine/forming 1 mole of copper powder. The copper powder produced has a mean diameter of about 0. 2 microns to about 1. 3 microns. Advantageously and preferably the precursor composition comprises more than 12% copper, more than 25% single B and above 0. 2% of the counter ion, wherein less than half of the counter ion is a low molecular weight organic acid. In another aspect, the invention provides a method of making a micron-sized to sub-sized copper powder comprising the steps of providing a precursor composition comprising copper and a monoethanolamine, the monoethanolamine to copper ion ratio system being at least Is 1, and the total of low molecular weight organic acids per mole of copper ions is less than 0. 4mol; and heating the precursor composition to a temperature at which the copper ions are converted to copper powder, the powder containing more than 90% of the copper and having an average diameter of about 0. 02 microns to about 5 microns. This aspect may include several preferred systems. The reduction is carried out by adding the precursor composition to a general reducing agent. The precursor group contains less than 〇.  Preferably, the precursor composition is substantially free of low molecular weight organic compounds. The reduction reaction is between 90 and 150 ° C (preferably between 1303). °C) at the temperature. The reduction reaction is based on the consumption of at least 1 mole of which the ratio of the hydroxide to the ear is flat, the amount of the alkanolamine, and the amount of the micron ion, which is the amount of the product. acid. 155 Monoethyl -15- 200902193 Alcoholamine / produced 1 mole of copper powder under the reduction reaction. In a third aspect, the present invention provides a method of making a micron to sub-sized copper powder comprising the steps of: providing a precursor material which is actually selected from copper ions, monoethanolamine, inorganic counter ions, and Optionally consisting of a reducing sugar composition wherein the monoethanolamine pair has a molar ratio of at least 1:1; and heating the precursor composition to a temperature at which the copper ion is converted to copper powder, the powder comprising greater than 90 weight copper And its average diameter is about 0. 02 microns to about 5 microns. This aspect may include several preferred systems. The reduction is carried out by adding the precursor composition to a general reducing agent. Preferably, the reaction is based on the precursor composition comprising less than zero. 1 Moule's low molecular weight is carried out under machine acid/mole copper ions. Preferably, the reduction is carried out under conditions in which the precursor composition is substantially free of low molecular weight organic acids. The reaction is carried out at a temperature of from 90 to 150 ° C (preferably at a temperature of from 1 30 to 15 5 ° C. The reduction reaction is carried out by consuming at least 1 mol of single g to form 1 mol. The reduction reaction of the copper powder is carried out. The reduction reaction is at least 1 molar ratio of ethanolamine to copper ion. 5: 1 is carried out. The present invention comprises a method of producing a fine particle copper powder, which comprises 1) providing a precursor composition comprising copper ions, finely divided salts, finely dispersed one of copper oxide particles, or any combination thereof and an alkanolamine (preferably ethanolamine and more preferably monoethanolamine) and the copper ion is reduced by thermally decomposing the precursor composition. Yes, the composition contains reducing sugars and is sufficient to maintain a pH between 10 and 12. 5 to 1 1 .  5) The caustic dose. An advantageous and preferred micron composition, the amount of copper which is from the middle of the reduction, the reduction of the reduction amount of the indole amine / in the single-system copper, 2) (more than 200,902,193) It is carried out under conditions which do not contain other reducing agents (for example, formate, oxalate, hydrazine and the like). It is advantageous and preferred to reduce the copper ions which are mis-synthesized or present in solid form in the precursor composition. The reaction system produces fine, micron to submicron copper metal particles. The initial experiment is carried out in a water soluble copper MEA carbonate composition, and the method involves heating the composition to about 70 ° C (which The temperature is slowly increased to a temperature of up to about 140 to 150 ° C. This method produces a uniform copper powder having a primary particle size of 1 to 2 μm. In the water-soluble copper MEA carbonate composition, water is the carrier and copper is the wrong a metal, MEA is a mismatched ligand and carbonate is a counter ion. The invention also includes a method of forming copper alloy particles. The precursor solution or slurry only needs to contain other metal ions capable of forming an alloy, such metal The precursor may be reduced under conditions for reducing copper ions. If the precursor solution is a slurry of copper salt, copper hydroxide or copper oxide, it is beneficial that the non-copper metal forming the alloy is dispersed in the solid phase. The amount of any non-copper metal present is limited to a few percent by weight or less than the total weight of the alloy powder product. Advantageously and preferably copper ions, non-copper metal ions (such as nickel ions), optional The reduction reaction of the tin ion, optionally the zinc ion, or any combination thereof, is carried out under conditions which do not contain other reducing agents such as formate 'oxalate' and the like. Ethanolamine (preferably) Monoethanolamine is used as the main reducing agent. In some preferred systems, glucose or the like can be added to the composition containing copper (II) ions, because of the cost-effective manufacturing of copper (〗 Method of ionizing. In some preferred systems, a caustic agent is added to the composition to aid in the reduction of the reaction -17-200902193, to minimize particle growth during the reduction reaction, or both. In a preferred system, an alkanolamine (preferably monoethanolamine) serves as the primary reducing agent for the reduction of copper (I) ions to copper metal. If the reduction process of the present invention is not carried out completely, it may be obtained or actually oxidized. Copper (I), or a mixture of copper (I) and copper metal. Unless otherwise specified, all % used in the present invention means % by weight of a preferred system (wherein the precursor composition) In an aqueous solution comprising a misaligned copper (II) ion, the precursor composition comprises at least 8% copper (preferably at least 10% copper and more preferably at least 12% copper). The article advantageously comprises at least 3 moles (preferably between about 3. 5 to about 4 moles of monoethanolamine per mole of copper (II) ions to be misaligned. If the precursor composition comprises copper (I) ions, the composition advantageously additionally comprises at least one.  5 moles (preferably between about 1 · 7 5 and about 2 moles) of monoethanolamine / mole of copper (I) ions to be misaligned. Excessive monoethanolamine does not have a negative effect, except that the process ultimately requires energy to remove excess monoethanol fe from the reaction mixture, e.g., by evaporation. In this preferred system, nickel may partially or completely replace copper, with nickel replacing copper with a molar to molar basis. In another preferred system, up to about half, but more preferably less than a quarter and more preferably less than one-sixth of the copper ion mole number can be used by other metals (eg, town, zinc, tin And similar) replaced. These mixtures can be used to prepare alloy powders having a melting temperature lower than, for example, the melting temperature of copper. In some preferred systems in which all metal ions (e.g., copper ions) -18-200902193 are mismatched and in solution to the precursor composition, there is a 2. 5 to 4 moles of ethanolamine (preferably monoethanolamine) / moles of metal ions (e.g., copper) to be reduced to metal powder. In an alternative preferred embodiment, the invention also encompasses a preferred system wherein up to one half, but preferably one third or less than one third of the monoethanolamine molars in the precursor composition It is substituted with other alkanolamines (eg, diethanolamine, triethanolamine, and/or isopropanolamine) that are capable of interfering with the copper ions in the water soluble composition. In some preferred systems, it is preferred to include triethanolamine and/or diethanolamine and a precursor composition of MEA. Under certain conditions, we believe that the higher OH ratio of the alkanolamines to the OH of the formula is advantageous for the reduction of copper. In other preferred systems, the composition is substantially free of (e.g., contains less than 2%) such other alkanolamines, and the monoethanolamine-based major reducing agent is advantageously at least 1 mole (preferably At least 1 . 5 moles of alkanolamine (preferably ethanolamine and more preferably monoethanolamine) / moles of metal ions to be reduced to metal powder. For a metal ion such as a copper (I) ion having a positive charge, it is advantageous to have at least 1 mole (preferably at least 1. 5 moles of ethanolamine (preferably monoethanolamine) / mole metal ion. For metal ions such as copper (II) ions having two positive charges, it is advantageous to have at least 1.5 moles (preferably 2 moles) of ethanolamine (preferably monoethanolamine) / mole metal ions . Reducing sugars or other non-alkanolamines, which are used to reduce copper (I) ions to copper (I) ions, will reduce the amount of alkanolamine required to completely convert the metal ions to metal powder. Preferably, the composition is substantially free of (e.g., contains less than -19 - 200902193 1% and more preferably less than 0. 1% or 〇%) of ammonia. Alternatively, the reaction comprises between 0. 00 1 to 0. 1 mole of ammonia / mole of gold to be reduced, such as copper) ions. Copper is known to be directly soluble in ethanolamine. This dissolution is extremely economical, and is disclosed, for example, in U.S. Patent Nos. 6,905,53, and 6,90 5,5, the disclosure of each of each of each of The compositions made by the methods described in these patents contain significant amounts of water. It is generally less suitable to be present in the precursor composition, wherein the copper system is in a soluble form. Most of the water is distilled from the composition prior to the temperature required to carry out the reduction reaction of copper or nickel at a useful rate by monoethanolamine. For this reason, it is advantageous that the composition is less than 50% water, preferably less than 35% water and more preferably less than 20% water. The caustic and reducing salts may also alleviate this problem to some extent. The lower temperature to obtain an industrially acceptable rate of copper ion reduction reaction is less desirable for the presence of reduced organic acids such as formic acid. The formic acid in monoethyl will reduce the copper ion to copper metal, but a detailed analysis of the stagnation zone during the reaction showed that monoethanolamine did not participate in the reduction, at least until the formic acid had been consumed. Therefore, most, if not all, of the monoethanolamine of the precursor composition is not used for copper ions, and the cost of the reaction is due to the inclusion of expensive but unaffected components. The solid copper salt and/or copper oxide can be contacted with an alcohol amine in the precursor composition. Then, it is believed that the particle size of the precursor salt has a strong influence on the degree of copper ionization to copper metal conversion and also on the generated mixture (as described in the patent case, the water mision precursor is included. The original reaction in the warm reaction of sterolamine has a strong effect on the particle size of the alkane-transferred copper salt-20-200902193. However, if desired, the average particle size is less than 〇. 2 microns (e.g., copper powder having an average particle size between about 〇·04 and 〇_07 microns (as described in the Examples below), with an average particle size of 0. 07 to 0. 095 micron copper powder or average particle size is between 〇. 1 to 0. The 1 9 micron copper powder) has a strong influence on the final particle size by agglomeration or by the dissolution/reprecipitation procedure or by particle growth caused by the two during the reduction reaction. As used herein, the particle diameter can be expressed as "dXX", where "XX" is a weight percent equal to or less than the weight percent of the component of the dxx (or alternatively, the volume %). d 5 0 means the diameter, wherein 50% by weight of the component is a particle having a diameter equal to or smaller than the d50, and only less than 50% by weight of the component is a particle having a diameter larger than the d50. Greater than 0. The 2 micron particle diameter is preferably determined in the fluid by the particle settling velocity of Stokes's law (for example, using the LA 700 model sold by Horiba Ltd. or the CAPATM 700 or the SedigraphTM manufactured by Micromeritics). 5 1 00T, which uses X-ray detection and is based on the calculation of Shrek's law) to a size as small as about 0.  1 5 microns. The smaller particle size can be determined by dynamic light scattering methods and preferably by means of a laser scattering device, or can be determined by directly measuring the diameter of a representative number of particles in the SEM print. Between about 0 · 0 1 micron to about 〇.  1 5 micron particles, the particle size can be measured by SEM of representative particles in the size range and the diameter of the representative sample (for example, 100 particles to about 400 particles) is measured in two directions ( And using its arithmetic mean) to determine 'the relative weight of the particles in this portion is assumed to be the weight of the spherical particles of the diameter of the second measured diameter equal to the average of the diameter of the second measured diameter - 21 - 200902193. Wet ball honing of copper salts and/or copper oxide (or equivalent honing method) particles which are larger than 1 micron in size can be easily removed by abrasion. The size distribution of the particles is advantageously a majority of the particles (e.g., at least about 95 weight 0 / Torr, preferably at least about 99 9% by weight, more preferably at least about 9 9. The average diameter of 5% by weight) is less than about 1 micron' and it is advantageous that the particles are not rod-shaped in a single long dimension. The solid precursor metal salt or oxide should have a d99 of less than 2 microns, preferably less than 丨 after the honing procedure. 4 microns, more preferably less than 1 micron; d9 8 is less than 2 microns, preferably less than i microns, more preferably less than 〇 8 microns; d 5 0 is less than 0. 9 microns, preferably less than 〇.  7 microns, more preferably less than 〇·5 microns, for example between about 0. 06 to 0. 17 microns or between 0. 1 to micron. There are many different ways of honing. Preferably, it is by a sand mill or a wet ball honing machine (which is loaded, for example, by a diameter of about 〇.  2 to about 0. 9 mm (usually about 0. 5 mm) of zirconium silicate and/or zirconia beads are subjected to wet honing, or alternatively by a rotary sand mill (which is loaded, for example, having a diameter of from about 〇·2 to about 0. 9 mm (typically about 0. 5 mm) of sour pin and/or zirconia beads are wet honed at a stirring of, for example, about 1 rpm. In a preferred embodiment of the invention, the metal salt and/or oxide particles are advantageously tied to a ball mill comprising a honing medium (sphere) which preferably comprises a zirconium compound such as zirconium silicate or more preferably chromium oxide. Medium wet grinding. If the particle system is present in the precursor composition, the size of the salt honing material is important in order to obtain an industrially acceptable product (honed in an industrially acceptable time, such as less than 30 minutes). And even critical. -22- 200902193 The honing medium does not need to be a composition or size. Furthermore, not all honing materials need to be preferred materials, i.e. having a range from 0 J to 〇 8 mm (preferably between 0. 2 to 0. 7 mm and more preferably between 〇·3 and 0. 6 mm) preferred diameter and equal to or greater than 3. 8 g/cm3 (preferably greater than or equal to 5. A density of 5 g/cm 3 and more preferably greater than or equal to 6 g/cm 3 ). In fact, a very small amount of the medium (such as 10%) will provide effective honing. Preferably, the amount of honing medium can be between 5% and 100%, based on the total weight of the medium in the honing machine, advantageously between 丨〇% and i 〇〇%, and preferably Between 2 5 % and 90 % ', for example, between about 40% and 80%. Media which are not in this preferred category may be somewhat larger, such as those having a diameter between 1 and 4 mm, preferably between 1 and 2 mm, and advantageously also equal to or greater than 3. Density of 8 g/cm3. Preferably, at least about 10% (preferably about 25%, or at least about 30%, such as from about 50% to about 99%) of the media has an average diameter of about 0. 1 to about 〇 · 8 mm (preferably between about 0. 3 to about 0 · 6 mm, or between about 〇. 3 to about 〇. 5mm). A preferred honing procedure includes wet milling, which is typically carried out at a honing machine setting of from about 600 to about 4000 rpm (e.g., from about 1 rpm to about 255 rpm). Faster speeds provide shorter processing times to achieve minimum product particle size. In general, a person skilled in the art based on the present invention can easily determine the honing speed (which includes the speed of the magnified industrial honing machine) without undue experimentation. The copper (Π) precursor composition (such as copper hydroxide slurry) may contain at least 0. 5 molar hydrogen oxide ions (preferably between about 〇·75 and 2. 5 moles of hydroxide ions/molar copper (II) ions. However, it is advantageous that even the oxygen--23-200902193 bismuth copper mud precursor composition contains a base (hydroxide source). For example, the hydroxide source is such as sodium hydroxide, hydrogen peroxide, potassium hydroxide, and the like, or any mixture thereof, or a combination thereof. The source of the hydroxide can be added to the solution as an aqueous solution or added to the solution as a solid and then dissolved in water. If the copper powder is to be used in a microelectronic material, it is preferably a hydrogen peroxide or a gas oxidized bromine. Advantageously, the reaction composition is substantially free of typical reducing agents (e.g., hydrazine). Substantially free of a general reducing agent means that the precursor composition contains less than about 1 mole per mole (preferably less than 〇 · 〇 5 moles, more preferably less than 〇. 〇 1 Mo or 〇 Mo) General Reducing Agent / Mo Er Copper Ion. In other preferred systems, reducing salts and hydrazine are used as the primary reducing agents. In certain preferred systems, the reaction composition is substantially free of weak primary reducing agents (e.g., aldohexose, such as glucose). Substantially free of a conventional reducing agent means that the precursor composition contains less than about 0. 02 mole (more preferably less than 0. 01 Moer or 〇 Mo ear) weak main reducing agent / Mo Er copper ion. However, the preferred method uses reducing sugars. Optionally, prior to or during dissolution, a certain amount of a weak primary reducing agent is added under conditions such as conversion of copper (II) ions to copper (I) ions, such as typically at temperatures greater than about 50 ° C. It is sufficient to add a part of an aldohexose (such as glucose) to a slurry containing one part of copper and 3 to 4 parts of water. However, the preferred method uses reducing sugars. In other preferred systems, the reaction composition comprises a weak primary reducing agent (e.g., an aldohexose such as glucose). Before the reduction reaction by thermal decomposition of the alkanolamine, the precursor -24-200902193 composition usually contains about 0. 03 to about 0. 4 Moer (one! 0. The weak main reducing agent/mole copper ion of 1 mole is sufficient to convert copper (II) ions into copper (I) ions. Unrestricted by theory, Xianxin monoethanolamine is mainly responsible for the original copper metal. MEA is used to reduce copper (I) and/or copper (one or both to copper metal powder. Copper oxide (CuO, Cu20 or both) is in a single ethyl (eg water soluble monoethanolamine composition) Reduction. During the reduction reaction, the copper salt, copper hydroxide or oxidation is at least partially dissolved in the monoethanolamine composition (eg, water soluble composition). In still another preferred system, one or more such as a soluble salt such as copper sulfate, copper chloride and the like, an insoluble copper salt (such as copper carbonate, basic copper carbonate, alkali Including, in particular, tribasic copper sulfate, basic copper nitrate, copper borate and basic copper borate, or any mixture thereof, is dissolved in a monoethanolamine composition (eg, water soluble monoethanolamine to form the precursor composition. Alternatively, the salts may be precipitated with hydroxide by the addition of a caustic agent, and the reverse is a slurry of copper hydroxide. Most of the precursor composition comprises water and excess alkane. The material is rarely saturated with copper, and usually copper! Copper can be at least partially dissolved in the precursor composition. The method involves heating the precursor composition to form a ruthenium system. 〇4 to a large amount of copper amine ion II) ion alkanol composition copper soluble (single monoethanolamine copper salt (one or more kinds of copper sulfate (copper hypochlorite, dissolved or part of the composition) The solution I and/or the oxidizing composition which dissolves and conforms to the composition of the alcohol amine. -25- 200902193 Typically, the excess water and the by-product of the reaction are vaporized. Usually, it is not exposed to the air, although Even if exposed to air, the process can be carried out 'only its exposure to oxygen is minimal. See, for example, U.S. Patent No. 5,492,6 8 1, if the water-soluble copper amide composition is placed in an excess of ammonium and oxygen. The mixture is subsequently stirred and heated to a temperature of between about 70 t: and 130 ° C to form copper oxide particles. The process can be at atmospheric pressure, under vacuum or pressurized (eg, between about 1 and 6). In some preferred systems, the thermal decomposition reaction can be carried out under an inert environment or in a low oxygen environment (for example, containing one or more inert gases such as helium or nitrogen, water vapor, or Monoethanolamine and / Or the organic environment of the organic reaction by-products. The boiling point of the MEA at 1 atm is about 170 ° C. The flash point of the MEA (in the open cup) is only about 93 ° C. Therefore, it is not in the air. In an oxidizing environment, this thermal decomposition will produce vaporizable by-products that can be burned or exploded. Eliminating oxygen is a concern to eliminate flammability/explosive mixtures and will also help prevent or delay the production of copper oxide on the surface of newly produced copper powder. The reduction reaction is carried out at a temperature of between about 95 and 150 ° C (more likely, between about 100 and 14 〇t). If a reducing sugar and/or caustic is present, An industrially acceptable reaction rate is obtained at temperatures between 100 and 1 〇 ° C. If there are no such additional components, then the range is between 130 and 140. Acceptable reaction rate. It may be advantageous to carry out the thermal decomposition under pressurized or reduced pressure. If carried out under reduced pressure, the volatiles may be removed under cooling. Carrying out, it will save a lot of water for vaporization of water and ethanolamine -26- 200902193 Energy, because the components can be maintained in a fluid form without being vaporized. For example, the thermal decomposition can be carried out in an inert environment containing one or more of water vapor, ME A vapor, helium or nitrogen. It is carried out under an absolute pressure of 5 bar, and very little water will be evaporated, so that a lot of energy can be saved when compared with the energy required to distill the water from the reaction mixture before reaching the reaction temperature. Usually, the reduction reaction is carried out. Water is required. Removal of water by distillation involves high energy costs. It may be advantageous to remove a portion of the water from the precursor composition by, for example, when the composition is more soluble in water and less soluble in ethanol. Applying pressure (reverse osmosis) to the composition upon contact, contacting (absorbing) the precursor composition with a dehydrating agent (such as anhydrous calcium sulfate and/or copper sulfate) or electrodialysis pretreatment (wherein the precursor is concentrated) Under the conditions of the active ingredient (particularly copper ion and MEA), a voltage is applied to the ion exchange membrane in contact with the precursor composition. Of course, other options use a source of Μ E A containing very little water or water. Generally, the method involves heating the precursor composition to a temperature of from about 70 to about 17 ° C (e.g., from about 90 to about 155 t). The reaction occurs when the temperature is about 95 to 150 ° C, and it is more likely that the visible copper powder begins to form when the temperature exceeds 10 ° C. It is advantageous to remove water and reaction by-products from the reaction composition by vaporization. Reusable materials such as water/monoethanolamine vapor can be coagulated and reused. It is important to note that the reduction of copper ions by monoethanolamine alters the structure of monoethanolamine (possibly reducing 1 mole of copper will consume at least 1 mole of monoethanolamine), making this part of the monoethanolamine no longer available. There may be monoethanolamine that is not involved in the reduction reaction. This MEA can be recovered and reused at -27-200902193. In contrast, when a formate or other reducing agent is used, most or all of the MEA can be recovered and reused because the MEA will not change its structure. The method is advantageously carried out in a fluid composition. In a preferred system, the stream system is converted to an aerosol and the thermal conversion reaction is carried out in an oven. The particle size of the copper produced can be affected by the particle size of the individual droplets of the precursor composition introduced into the oven. The oven can be maintained at a certain temperature or the oven can have different temperatures at different locations to maximize the reaction rate while preventing the droplets from breaking apart and the volatiles vaporizing too quickly. Typically, the process produces high purity copper metal particles of variable particle size (depending on process conditions), but the particle size that can be easily fabricated cannot be less than about 0.1 micron and cannot be greater than about 10 microns. Typical process conditions and adjuvants can produce sizes between about 〇.  2 to about 1 · 5 μm spherical or round particles. It is not a large particle size distribution. It is apparent that at least 80% of the particle diameter of the total weight of the particles produced falls within about 50% of the average weight particle diameter. The present invention describes a novel method for synthesizing a copper metal powder by honing a copper salt to a desired particle size, converting the honed copper salt to copper monoxide (or copper oxide), and The copper oxychloride particles are then converted to copper powder by a reducing agent. Different preferred systems include one or more of the following: 1) addition of reducing sugars; 2) addition of surfactants (such as glycine, gum arabic, tri" and the like), and preferably to copper Before the powder is produced; 3) adding a surfactant (such as azole), and preferably after the copper powder is produced; and 4) converting a part of the misaligned copper (II) -28-200902193 ion into copper (I) Before or at the same time, copper is added to the copper-MEA precursor composition to dissolve additional copper. In a preferred embodiment of the invention, the copper (II) ion can be obtained by exposing the copper (Π) ion to a weak reducing agent (for example, exposing copper (Π) ions to a reducing sugar such as glucose). Reduction to copper (I) ions. At this time, the precursor composition may be contacted with another copper metal, copper oxide and/or copper salt (the conversion of copper (II) ions into copper (I) ions is compared with the amount of MEA required to dissolve the copper. Excess ME A). Alternatively, the thermal decomposition reaction may be carried out directly from the reaction composition by adding a reducing sugar to the reaction composition, and one or more surfactants may be added to the reaction mixture to stabilize the copper powder and Blocks surface oxidation. Copper powder is typically used to create electrical contacts, and the copper oxide layer on the surface of the particles increases the chances of failure of the resulting product. Exemplary surfactants include azoles and substituted derivatives thereof, particularly aromatic azoles (which include diazoles, triazoles, and tetramines), such as benzotriazole, tolyltriazole, 2,5-(amine Benzymidazole, oxobenzoquinone, such as oleoyl porphyrin; thiazide, such as thiothibenzothiazole, 1-phenyl-5-hydrothiotetrazole; Thiadiazole, anti-halogen, and combinations thereof. The thiadiazole substituted with a thiol group and/or an amine group on the ring and the triazole group substituted with a thiol group and/or an amine group are effective. Examples of anti-halazoles include 5,6-dimethyl-benzotriazole, 5,6-diphenylbenzotriazole, 5-benzoyl-benzotriazole, 5-benzylbenzotriazole And 5-phenylbenzotriazole. Alkyl-substituted aromatic diazoles such as tolyltriazole are preferred. The azole is useful for copper-containing powders (such as pure copper or copper alloys such as zinc copper) -29-200902193. The compounds form a film on the particles and are advantageously dissolved in a solvent and contacted with the copper particles. The particle size of the copper powder can be reduced by honing after the copper powder is formed. U.S. Patent No. 6,432,3 20 describes a process for the manufacture of a refrigerant. A 05 micron powder method by ball milling of spherical 1 to 5 micron particle size copper particles commercially available. In an important preferred system, the invention includes a method of making a micron to submicron size copper powder comprising the steps of: 1) providing a precursor composition comprising or substantially greater than 5% by weight a solution of copper and a solution of greater than 20% by weight of monoethanolamine; and 2) heating the precursor composition to a temperature at which the copper monoethanolamine complex is converted to copper powder. Another preferred system comprises 1) providing a precursor composition comprising or consisting essentially of greater than 5% by weight copper, greater than 20% by weight monoethanolamine and greater than zero. 2% by weight of carbonate as a solution of carbon dioxide; and 2) heating the precursor composition to a temperature at which the copper monoethanolamine complex is converted to copper powder. A third important preferred system comprises 1) providing a precursor composition comprising or consisting essentially of greater than 12% copper, greater than 25% monoethanolamine and greater than ruthenium.  The composition of the 2% counterion is composed of a lower half of the low molecular weight organic acid; and 2) the temperature at which the precursor composition is heated to convert the copper monoethanolamine complex into copper powder. In each of the above preferred systems, it is advantageous that the precursor composition does not contain or is added with a general reducing agent; the precursor composition comprises less than zero.  1 mole low molecular weight organic acid / Moer dissolved copper; the precursor composition is substantially free of low molecular weight organic acid (ie below 〇.  1 mole low molecule -30- 200902193 amount of organic acid / Mo Er copper): the precursor composition contains at least 0. 5 mole hydrogen oxide/mole copper ions; and, advantageously, heated to a temperature of from about 95 to about 150 ° C (more advantageously from about 105 to about 140 ° C). In each of the above preferred systems, it is advantageous that at least 1 mole of monoethanolamine is consumed by the reduction reaction produced per mole of copper powder. [Embodiment] Certain preferred systems and certain advantages of the present invention are illustrated by the following non-limiting embodiments. While the invention has been described by way of example only, the embodiments of the invention may Example 1: Bismuth oxide was prepared by reacting copper sulfate with a caustic solution and then converting the copper hydroxide slurry to copper monoxide by adding glucose under an inert gas. The resulting copper oxide slurry is added to a reactor containing a hot monoethanolamine solution. The copper pentoxide was converted to copper powder within 30 minutes after the addition. The copper powder was recovered and measured to have an average particle size of 〇·1 26 μm. However, the particle size distribution is in two forms, wherein the center of the particle size distribution of a small portion of the particles is several times the median size of the particle size of the slurry. Example 2: Copper powder was prepared in the same manner as in Example 1 except that a small amount of dispersant (Ultrazine NA) was added before the conversion of copper pentoxide to copper powder. The average particle size of the generated copper powder is 0. 158 microns. -31 - 200902193 Example 3: Using a sub-millimeter vermiculite as a substrate for the honing medium, the acid copper slurry to an average particle size of 〇.  1 5 microns. A small amount of hydrogen was added to the slurry and the slurry was converted to di-copper by the addition of glucose. The particle size of one of the obtained copper oxides is about 〇.  1 〇 The copper pentoxide is converted into copper by MEA, and the obtained copper powder has a particle size of 0. 147 microns. Example 4: Preparation of abraded copper hydroxide in a beaker (500 ml) reactor (38. 6 g, 12. 9% Cu, 0. 11 microns) and go (100 g) of puree. A reducing solution was prepared by dissolving D-glucose (22 g) in water (50 ml). After the glucose was dissolved in the stirred copper carbonate slurry (under nitrogen) and the reaction was maintained at 60 to 70 ° C for 1 hour, a copper oxide slurry was obtained. At the end of the process, the pH of the slurry is 8. 2. By adding a 50% caustic solution (2.) before converting the oxidized bismuth powder. 4 g) to adjust the pH of the oxidized copper slurry to 11. At the beginning of the reaction by a 肼 (2. 8 g, 80% active) and a second reduction reaction in nitrogen and at 65 to 80 ° C in the same reactor to reduce the copper oxychloride to copper. The average particle size of the resulting particle size determined by Microtrac is 0. 11 microns. However, the size distribution is clearly in two forms, wherein the particle has a diameter of about 1 介于 of about 0. 4 to 1 micron (the center is about 〇.  6 micro-particles of about 87% by weight of the diameter is between about 0. 2 to 0.  扫描 9 The scanning electron micrograph (SEM) of the copper particles is shown in Fig. 1. Example 5: wet-grinding alkaline copper carbonate (25 g, wet-milled sodium carbonate-micron. The end of the flat wet-ion ion deionized liquid is poured into the temperature between the anti-copper and copper. When the temperature is added, the particles are converted to copper powder by 1% by weight and micrometers. 2 0 % C u, -32- 200902193 0. 10 micron particle size) and deionized water (100 g) carrying a. The slurry was stirred under nitrogen and heated to 65 ° C before addition of a solution of glucose (22 g) water (50 ml). The reaction was maintained at a temperature of 57.5 ° C for 6 hours until the slurry transition was light to indicate submicron copper oxide. In the same reactor, 肼 (2. 8 g, 80% active) Conversion of the copper pentoxide to copper The reaction took 50 minutes. Microtrac analysis shows an average of 0. 04 5 microns. However, the particle size distribution is about two types of particles. 5 wt% of the diameter is about 0. 2 microns and the 90% by weight diameter is between about 〇·3 and 0. 12 microns. Example 6: A copper sulfate solution which had been heated to about 103 to 106 ° C was charged into the reactor. A solution containing glucose, monoethanolamine (about 1.7 g) / g of dissolved copper was added to the solution. Maintain the temperature between 1 0 3 and 1 0 6 . C and the resulting copper particles are 3 microns in size. Examples 7 to 16: Table 1 below is an excerpt from many of the examples. In these examples, monoethanolamine: the molar of copper ions. 5 changes to about 3. 5. Glucose: The molar ratio of copper is about 0 0. 35. The recovery of copper is usually greater than 98%. The deionized ion in the reactor is in the range of 60 to yellow (which is added by adding. The size of the transforming particles is in a state in which the important boiling ratio of the caustic of the particles and the boiling powder of the particles is changed from about to about - 33- 200902193 Table 1 Example MEA/Cu Mohr Ratio Cu Recovery Glucose/Cu Ratio Anion Method Diameter (μm) 7 3. 5 92% 0 C〇3 CMC+AH/vac 1-2 8 3. 5 98% 0 C〇3 CMC+gum+AH/vac ~1 9 3. 5 98% 0. 04 C〇3 CMC+glu+AH/vac <1 10 3.5 98% 0.07 C03 CMC+glu+AH/vac <1 11 2.4 97% 0.05 co3/oh CMCH-CuC03+glu+AH/vac NM 12 2.5 98% 0 C03/OH CMC+AH/vac+CuC03/Cu(0H)2 1.3* +AH/vac 13 1.5 NM 0 SOVOH CuS04+NaOH+AH/vac 0.3-0.4 14 7.8 0.35 SOVOH CuS04+NaOH+glu+AH/vac 0.2 +MEA+AH/vac (3AGG) 15 1.5 0.34 so4 CuS〇4+NaOH+glu+MEA + AH/vac ~0.9 16 3.5 99.6 % C03/OH CMC+AH/vac+NaOH+AH/vac ~1 (3.6AGG) * Self-surface area estimation Example 7: Stirring and heating in a beaker at boiling temperature 25 g of copper monoethanolamine carbonate (CMC) aqueous solution (d = 1.25 g/cc, 9.6% copper and 32.5% MEA). After the solution is vaporized as a whole, the decomposition of C M C spontaneously begins and brown mud is produced. The brown powder was separated from the slurry by filtration. The powder is washed with deionized water and finally washed with acetone (hereinafter referred to as standard method). After drying in an oven at 50 ° C, the copper in the powder was analyzed by iodine titration. The copper content was found to be 94%. The CMC solution contained 32.5 wt% MEA, 9.6% wt copper, up to about 1 wt% carbon dioxide (expressed as carbonate), and the remainder (e.g., about 50 wt%) contained water. Most of the water has been evaporated from the CMC solution before the reaction occurs, presumably the reaction is carried out at a faster rate than the temperature above 100 °C. -34- 200902193 Example 8: The same CMC solution (about 25 5 g) used in Example 7 was placed in a conical filter bottle (500 ml). The solution was stirred and heated under partial vacuum (using a water pump) until the composition began to boil. After evaporation of water (about 100 to 150 g), brown particles begin to appear in the reaction medium. The evaporation and decomposition of the CMC solution lasted for about 10 minutes until the reaction medium turned into a brown slurry with some visible white smoke on the surface of the slurry. After the copper powder is separated from the slurry, the powder is washed and dried by standard. About copper (24. 5 g) was formed in the composition of the c M C precursor and the recovered dry copper powder (22.5 g) was recovered by about 92%. The copper content of the powder was found to be about 1 〇 5% by iodine titration. SEM photographs of the obtained copper powder showed that the particles were agglomerated with a uniform primary particle size of 1 to 2 μm. Example 9: This experiment was similar to Example 8, but before starting the thermal decomposition reaction, CMC (252 g) ) mixed with RodoPo1 23 (Sanxianjiao; 〇·25 g). About copper (2 4 _ 2 g ) in the composition of the c M c precursor and recovered dry copper powder (23·9 S) 'recovery rate greater than 98% ° compared with the particles of Example 8' The particle size was slightly reduced (visual). Example 10: This experiment was similar to Example 8, except that CMC (250 g) was mixed with glucose (2.5 g) to form a precursor composition. The dry copper powder (about 23.3 g) was recovered and the recovery rate was 97%. The particle size of the powder was significantly reduced (visual) compared to the previous batch. Example 1 1 : This experiment was similar to Example 1 'but using glucose (5 g). The recovered copper powder (about 23.8 g) was recovered at a yield of about 99%. The particle size of the powder was slightly smaller than that of Example 10 (visual), but -35-200902193 was again significantly less than those of Examples 7 to 9. Example 12: This experiment was similar to Example 1 but blended with CMC (251 g), glucose (5 g) and copper carbonate (22 g, 56% Cu) to form a precursor composition. The composition appeared to form a solution. Thus, the precursor composition contained copper (about 12.3 g) from the copper carbonate added and copper (24.1 g) from the CMC solution, sharing copper (36.5 g). The dried copper powder (about 34.5 g) was recovered, and the recovery rate was 94%. Example 1 3: A C M C solution (about 10 k g, 9.5% copper) was weighed and boiled until about one and a half of the original volume remained. Basic copper carbonate (about 860 g) was added to the reactor and continued to boil. When the reaction temperature reached about 150 ° C, the reaction to convert into copper powder was completed. A fine powder (1,350 g) having a surface area of 0.47 m2/g and a particle size of about 1.5 μm was obtained. Example 14: MEA (about 340 g) and deionized water (23 0 g) were mixed in a beaker and then stirred. Copper sulfate pentahydrate (CSP; about 273 g) was added and completely dissolved in the MEA solution. Subsequently, a caustic solution (477 g, 1 8%) was added and the solution in the beaker was converted into a viscous slurry. The slurry is heated and evaporated to a boiling temperature of about 150 °C. The reaction was completed after maintaining the temperature above 150 °C for several minutes. The copper particles were filtered and washed with deionized water, followed by final cleaning with acetone (15 ml). A copper powder that is somewhat purple (probably because the particles are small rather than surface oxidized). The copper powder contained 97.7% copper and had a surface area of 2.11 m2/g and a particle size of less than 0.5 μm. Example 15: CSP (about 20 g) was weighed and dissolved in deionized water (60 m 1 ). A solution of 18% N a Ο ( (about 36 g) was added to form a copper hydroxide slurry with good agitation of -36-200902193. Glucose (5 g) was then added to the slurry. The slurry is heated to near boiling temperature. The slurry gradually turned from blue copper hydroxide to green, then yellowed and eventually pale pink copper oxide. At this time, a MEA solution (39 g, 85%) was added to the reactor and the slurry was continuously heated and subjected to a conversion reaction. Copper powder having a particle size distribution of two forms (0.2 and 3 μm, respectively) was obtained. The 3 micron particles are actually agglomerated by smaller copper particles. Example 16: CSP (about 80 g) was mixed with deionized water (250 ml) until all C S P crystals dissolved. Glucose (about 20 g) and MEA (100 g) were added. The solution is heated to near boiling temperature. The solution slowly turned into yellow, red and then purple slurry. The copper powder obtained had a surface area of 0.76 m2/g and a particle size of less than 1 μm. Example 1 7: A c M C solution (about 3 177 g, 9 · 5 % copper) was weighed and allowed to evaporate until a reddish precipitate formed in the solution. Subsequently, a 18% NaOH solution (5 1 5 g) was added to the solution. The caustic reacts with concentrated CMC to form a viscous green slurry. After the slurry has continued to evaporate, the color of the slurry turns yellow, then reddish, and dark red when eventually converted to copper particles. After the powder was washed and dried, copper powder (300 g) was collected. After the powder was deagglomerated by honing, the particle size determined by Micro track was 3.6 μm. Under the microscope, it was found that each particle was agglomerated with 1 to 3 copper particles adhered together. Example 18: The nickel sulfate was dissolved in the MEA and NaOH solution and subsequently heated to boiling temperature. It was visually observed that a metal powder was present on the magnetic stir bar, and a metal layer was deposited on the side of the beaker to indicate the formation of nickel metal. -37- 200902193 [Simple description of the diagram] The included drawings provide further graphical illustrations of the data and photos of the particles. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a scanning electron micrograph of a copper powder produced by the method of the present invention described in Example 4. Because the machine appeared to be out of focus, it was not clear, so it did not get sharpness. Fig. 2 shows details of particle size analysis of copper powder produced by the method of the present invention described in Example 4. Fig. 3 shows details of particle size analysis of copper powder produced by the method of the present invention described in Example 5. Figure 4 is a scanning electron micrograph of a copper powder produced by the method of the present invention described in Example 5. Because the machine appeared to be out of focus, it was not clear, so it did not get sharpness. -38-

Claims (1)

200902193 X. Patent Application No. 1. A method for producing a finely divided copper or copper alloy powder comprising adding monoethanolamine to a slurry comprising finely divided particles comprising a solid copper precursor compound, the precursor containing solid copper The compound is selected from the group consisting of copper salts, copper carbonates, copper hydroxides, copper oxides, copper pentoxide or any combination thereof, wherein the temperature is between 90 and 150 ° C and is sufficient to convert the precursor compound to copper over a period of time. The time of the powder. 2. A method of producing a finely divided copper or copper alloy powder according to the first aspect of the patent application, the slurry additionally comprising a caustic and a reducing sugar. 3. A method of producing a finely divided copper or copper alloy powder according to claim 2, wherein the caustic is used to raise the pH of the slurry to between 10.5 and 11.5. 4. A method of producing a finely divided copper or copper alloy powder according to claim 2, wherein the monoethanolamine is used in an amount of from 1 to 5 g to 2 g of monoethylamine/g copper. 5. The method of producing a finely divided copper or copper alloy powder according to item 2 of the patent application, wherein the monoethanolamine is used in an amount of from 1.7 to 1.8 g of monoethylamine/g copper. 6. A method of producing a finely divided copper or copper alloy powder according to claim 2, wherein the copper powder has an average particle size of between 0.04 and 0.07 μm. 7. A method of producing a finely divided copper or copper alloy powder according to claim 2, wherein the copper powder has an average particle size of between 0.07 and 0.095 micron. -39- 200902193 8. A method of producing a finely divided copper or copper alloy powder according to claim 2, wherein the copper powder has an average particle size of between 0.1 and 0.2 microns. 9. A method of making a finely divided copper or copper alloy powder according to claim 1 wherein the solid precursor copper precursor is copper pentoxide. I. The method of producing a finely divided copper or copper alloy powder according to the first aspect of the invention, further comprising adding a caustic and a reducing sugar before the reaction of the copper-containing precursor compound with the monoethanolamine. II. A method of producing a finely divided copper or copper alloy powder according to claim 1 of the patent, the slurry additionally comprising a caustic and a reducing sugar. A method for producing a finely divided copper or copper alloy powder according to the first aspect of the invention, wherein the copper precursor compound is copper pentoxide, the method further comprising before the reaction of the copper oxydioxide with the monoethanolamine The copper oxychloride is wet milled. 1 3 - A method for producing a finely divided copper or copper alloy powder according to claim 1, wherein the copper-containing precursor compound has an average particle size of from 0.05 to 44 micrometer of cuprous oxide, the slurry The mud additionally contains caustic and reducing sugars. 1 4. The method of producing a finely divided copper or copper alloy powder according to claim 1, wherein the copper precursor compound is copper oxide and wherein the copper oxide is added after adding monoethanolamine. Minute or less than 10 minutes converted to copper powder. I5. A method for producing a finely divided copper or copper alloy powder, the method of -40-200902193 comprising a caustic agent for reducing sugar, causing the pH of the slurry to be as high as 10 to 12, and hydrazine to be added to contain solid copper In the slurry of the finely divided particles of the precursor compound, the solid precursor containing the solid copper is selected from the group consisting of copper salt, copper carbonate, copper hydroxide, copper oxide, copper oxide or any combination thereof. 5 5 to 80 ° C and for a period of time sufficient to convert the precursor compound to copper powder. The method of claim 15, wherein the solid precursor copper precursor is selected from the group consisting of copper salts, copper carbonates, copper hydroxides or mixtures thereof, wherein the inclusions are added prior to the addition of the hydrazine and caustic The solid copper precursor compound reacts with the reducing sugar. -41 -