CN101096053B - Preparation method of ferro-cobalt ultra-fine powder - Google Patents
Preparation method of ferro-cobalt ultra-fine powder Download PDFInfo
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Abstract
The invention relates to a preparation method for Co-Fe ultra-fine alloy powder. Soluble slat solution of Co and Fe is used to adjust PH in 3.5-5.0 under the existence of polymeric surfactant. Hydrazine hydrate or hexmethylene tetramine is added to make Co and Fe ion for ball-like hydroxide co-precipitation. Filtering is carried out. Precipitation is washed by deionized water. The precipitation isbeaten by ethanol solution of fatty acid. Hydrate grain surface is modified. Then filtering is carried out again. Obtained hydrate filtered residue is heated by H2. the filtered residue is dried under 60-90deg.C and is deoxidized under 300-600deg.C. Ball-like Co-Fe ultra-fine alloy powder, of which grain diameter is distributed in 0.5-5mum is prepared. By adjusting the proportion of soluble slatof Co and Fe Co-Fe ultra-fine alloy powder with different proportion can be prepared and different requirements can be satisfied.
Description
Technical field
Disclosed in this invention is a kind of preparation method of ferro-cobalt ultra-fine powder, is meant the method for preparation average grain diameter at the ferro-cobalt powder of 0.5～5 mu m range especially, belongs to new material technology category.
Background technology
The impregnated with diamond goods, as be applied to the diamond bit of geological drilling and the diamond saw blade of processing of stone, generally adopt the preparation of " pressure sintering " sintering; Under the identical condition of diamond quality, the quality of diamond composition depends on the performance of carcass material (comprising: hardness, intensity, to the adamantine performance etc. that plates).
The carcass of impregnated with diamond goods is made up of framework ingredient and bonding component, and bonding component also claims binding agent, generally is meant the low-melting-point metal in the carcass.Make the impregnated with diamond goods have good performance, binding agent must meet the following conditions:
(1) liquid state of bonding phase will have good flowability, to soak into skeleton phase and diamond effectively;
(2) sintering temperature must be selected the low zone of diamond fire damage degree, is generally 800～1100 ℃, surpasses 20～50 ℃ of the eutectic temperatures of bonding phase, and bonding is melted mutually;
(3) alloying component is evenly distributed, and avoids the composition segregation phenomena.
In metal, cobalt is to adamantine wetting relatively good, itself has good comprehensive performances, rigid, intensity, toughness, high temperature oxidation corrosion resistance power as high temperature, diamond tool metallic bond both domestic and external, mostly being the cobalt that pure cobalt-based, high cobalt-based contain cobalt 70-80%, middle cobalt-based (containing cobalt 35-50%) greatly is metal alloy.
The framework material carbide alloy (as WC) that adds in pure cobalt powder and the impregnated with diamond goods, its conventional knot technology sintering temperature is in the graphited humidity province of diamond high speed more than 1350 ℃.And as the multiple metal of binding agent, if add through mechanical mixture with powder type, the carcass sintering temperature is higher, often can not reach complete alloying, and the carcass composition is also inhomogeneous, influences the overall performance such as timeliness, service life of diamond composition.
In addition, cobalt is crucial strategic material, costs an arm and a leg, therefore, diamond tool at home and abroad widely launches to replace the research and the trial of cobalt-based carcass with in the metal adhesive field, mainly contain the research and the application of iron-based and copper base replacement cobalt-based, to reduce cost.Iron is identical with the outermost electron number average with the electronic shell number of cobalt, position in the periodic table of elements is adjacent, their chemical property and physical property are rather close, and iron, cobalt, nickel are referred to as iron family element in chemistry, and the hot pressed sintering temperature of the metal dust of the two also is more or less the same.But what should particularly point out is, the crystal structure of cobalt and iron is different, and is different with the ability of other metal alloyization, and the performance after the alloying is also different.Especially high-temperature behavior, cobalt have that good high temperature is rigid, heat resistance, high temperature oxidation corrosion resistance power.Facts have proved that in a large number in actual use, alloying iron-binding agent improperly exists the problem of following several respects:
(1) sintering temperature height, controllable process narrow range, strict to sintering temperature;
(2) iron is easy to the etch diamond when hot pressed sintering, makes carcass and diamond surface form the loose graphite linings of one deck, weakens carcass to adamantine adhesion, causes the stock-removing efficiency of diamond tool to descend and the reduction in service life;
(3) the iron powder activity is very big, the particularly thin easier oxidation of iron powder, and oxygen content can have a strong impact on sintering quality near 1% iron powder;
(4) simple lower for the wearability of cobalt carcass with iron.
Therefore, in research with iron during for the carcass of cobalt, must be at above problem, method or other technology method by alloyings such as iron cobalt, iron cobalt copper are solved the effect that can receive.
The binder alloy powder of preparation carcass is according to the proportioning that designs at present, is smelted into alloy in advance, and atomizing is dusted then, obtains the alloy powder of desired particle size, is referred to as pre-alloyed powder.The pre-alloyed powder that this method obtains, each powder particle all comprise the various metallic elements of component alloy, and composition is quite even.The prealloy powder eutectic point, more much lower than single element fusing point in the alloy, in the sintering process, as long as temperature reaches above 20～50 ℃ of the liquidus curve of pre-alloyed powder, the powder smelting of whole binding metal composition is beneficial to the reduction sintering temperature, reduces adamantine graphitization trend, and it is molten earlier with enrichment, easily the difficult control etc. in sintering process of oxidation and volatile metal influence the factor of tyre-e/or performance, the diamond mean compressive strength behind the raising sintering gravity segregation, low-melting-point metal can not to occur.In the process of preparation impregnated with diamond goods, use pre-alloyed powder to have following remarkable advantage:
(1) impregnated with diamond goods adopt prealloy powder to be evenly distributed than the element of mechanical mixture powder, have fundamentally avoided the composition segregation;
(2) the prealloy powder alloying is abundant, even tissue, the diamond tool that adopts pre-alloyed powder to make, the compactness and the uniformity of carcass tissue have been improved, thereby improve the state of wear of diamond tool tyre case, improved resistance to compression, the bending strength of sintered article greatly, the requirement of diamond composition tyre-e/or performance is content with very little;
(3) alloying greatly reduces the required activation energy of the diffusion of metallic atom in the sintering process in advance, has reduced sintering temperature, has shortened sintering time, helps avoiding the diamond high-temperature damage;
(4) the prealloy powder oxidation resistance is strong, and it is convenient to preserve, and sintering character is good, can simplify the manufacturing process of diamond tool, reduces cost;
(5) the prealloy powder carcass has high rigidity and high impact;
(6) prealloy powder can improve carcass to adamantine ability of plating and hold, improves the sharpness of diamond tool, prolongs the service life of instrument;
(7) under the identical situation of cutting performance, use prealloy powder can reduce diamond concentration 15%-20%, make production cost cheaper;
(8) can select different binding agents for use according to the difference of target performance, improve specific aim, work limitation and service life that diamond tool uses.
Cobalt-based prealloy powder, especially ferro-cobalt powder are one of main materials of impregnated with diamond goods carcass material.At present, adopting water atomization, the preparation of aerosolization technology usually, mainly is the water atomization product that cost is low, output is big.But the particle of atomised product is wide ranges respectively, and pattern is irregular, water atomization ferro-cobalt powder especially, and great majority are dendriforms, and mobile poor, particle is (average grain diameter is between 10～100 μ m) greatly, and there is certain oxide-film on the surface; Although than the carcass binding agent of the mechanical mixture of one pack system metal dust, on performance, to improve a lot, in the hot pressed sintering process, still there is negative effect in compactness, the intensity of carcass, limited the further raising of impregnated with diamond product properties.
Therefore, preparation cost is low, uniform particles, particle size distribution range narrow (mainly at 0.5～5 mu m range), content of surface oxygen are low, the ferro-cobalt ultra-fine powder of subglobular or class sphere, as the carcass binding agent of impregnated with diamond goods, will be the key that increases substantially impregnated with diamond goods combination property.
In order to overcome the above problems, in order to overcome the above problems, set about from the preparation method of ferro-cobalt ultra-fine powder, adopt cobalt, the hydroxide co-precipitation of iron, H2 to reduce mode, prepare the spherical ferro-cobalt ultra-fine powder of class that particle diameter is distributed in 0.5～5 mu m range, the spy finishes the present invention.
Summary of the invention
In order to achieve the above object, the technical solution used in the present invention is: adopt the soluble-salt solution of cobalt, iron, in the presence of high molecular surfactant, regulate pH to 3.5～5.0, add hydrazine hydrate or hexamethylenetetramine, make cobalt, iron ion form the spherical hydroxide co-precipitation of class, filter, use deionized water rinsing, precipitation is pulled an oar with the ethanol solution of aliphatic acid, to the hydroxide particles surface modification, and then filter, gained hydroxide filter residue leads to H
2The spherical ferro-cobalt ultra-fine powder of class that particle diameter is distributed in 0.5～5 mu m range is prepared in heat drying, reduction.
Specifically be prepared according to the following steps:
1. the soluble-salt of cobalt, iron is mixed with total concentration and is not more than the 3M mixed solution, wherein the ratio of the soluble-salt of cobalt, the iron proportion requirement of pressing the ferro-cobalt powder is added, and quality is than iron: cobalt is 10: 1～1: 4; Wherein:
(1), in preparation mixed solution process, for preventing hydrolysis, add small amount of hydrochloric acid pH value of solution remained between 2～4;
(2), the cobalt soluble-salt is hydrochloride, nitrate, sulfate, acetate a kind of of divalent cobalt ion at least;
(3), the soluble-salt of iron is hydrochloride, nitrate, sulfate, acetate a kind of of the iron ion of divalence, trivalent ion at least;
2. adding high molecular surfactant, addition is 0.01～1% of a reaction solution cumulative volume, stirs; Wherein high molecular surfactant is that mean molecule quantity is no less than a kind of of 5000 poly-α-vinyl pyrrolidone, polyacrylic acid, α-vinyl pyrrolidone and styrol copolymer, α-vinyl pyrrolidone and acrylic acid copolymer at least;
3. dropping ammonia is regulated pH value to 3.5～5.0 under constantly stirring, and continues to stir heating then;
4. when the temperature of mixed solution rises to 60～70 ℃, adding under constantly stirring is a kind of of hydrazine hydrate, hexamethylenetetramine at least, and cobalt, the total mol ratio of iron are in addition and the reaction system: (hydrazine hydrate+hexamethylenetetramine): (iron+cobalt) is 5.0: 1～1.1: 1;
5. continue heating, stirring reaction 30～180 minutes, system temperature are controlled between 60～90 ℃; Wherein, when precipitating reagent adopted hydrazine hydrate, 30～60 minutes reaction time got final product; If precipitating reagent is the mixture of hexamethylenetetramine or hydrazine hydrate and hexamethylenetetramine, the reaction time should be between 120～180 minutes, and reaction temperature is advisable with 85～90 ℃;
6. filter, precipitate at least three times with deionized water rinsing;
7. after filtering, solid is pulled an oar with 0.2～3.0% aliphatic acid ethanol solution; Wherein:
(1), the aliphatic acid that is adopted is oleic acid, stearic acid, soft ester acid, palmitic acid, lauric a kind of at least;
(2), the pull an oar volume ratio of solid and aliphatic acid ethanol solution of washing is (V/V): 1: 1～1: 10;
8. filter once more, filter residue is at logical H
2Drying is 30～90 minutes under the condition, and baking temperature is 90～105 ℃;
9. continue logical H
2, continuing heating reduction, reduction temperature is 300～600 ℃; Recovery time is 4～8 hours;
10. after reduction finishes, continue the logical H of adding
2, being cooled to below 45 ℃, the aluminium foil vacuum packaging is used in discharging.
In technique scheme:
The mixed solution of first step preparation cobalt, iron, in preparation mixed solution process, the watery hydrochloric acid that can adopt 0.001M is separated the generation of reaction to prevent water, and pH value of solution is remained between 2～4 as solvent; It is difficult greater than 3M that soluble-salt is mixed with total concentration, otherwise there is certain difficulty in dissolving, and unfavorable to the pattern control of reacting the end product that forms; Because the carcass binding agent of different impregnated with diamond goods requires different, the ratio of alloying component is a quality than iron in the ferro-cobalt powder: cobalt is 10: 1～1: 4, can add on request in corresponding stoichiometry mode and add, because precipitation reaction is more complete, the residual quantity of Fe, Co all is not more than 0.0005M in the post precipitation solution, and the residual quantity in the solution does not produce appreciable impact to the deviation of component; Wherein the cobalt soluble-salt of Cai Yonging is hydrochloride, nitrate, sulfate, acetate a kind of of divalent cobalt ion at least, but it is more suitable with hydrochloride, nitrate, acetate, because sulfate residual sulfate ion be difficult for removing, unless the washing time in the increase filter process, otherwise residual sulfate ion has negative effect to the performance of follow-up impregnated with diamond goods; The soluble-salt of iron is hydrochloride, nitrate, sulfate, acetate a kind of of the iron ion of divalence, trivalent ion at least, bivalent ions soluble-salt with iron is good, because ferric hydroxide easily forms colloid, not easily separated, for the same reason, hydrochloride, nitrate, the acetate with ferrous ion is good.
In second step, add 0.01～1% high molecular surfactant of reaction solution cumulative volume, by the coordinating group that contains N, O atom of high molecular surfactant, to Co in the solution
2+, Fe
2+Selective absorption, make in the solution metal ion Local enrichment phenomenon to occur, thereby preferentially produce precipitation reaction in the part of enrichment from micro-scale, realize pattern control to cobalt, iron hydroxide; Wherein high molecular surfactant is that mean molecule quantity is no less than a kind of of 5000 poly-α-vinyl pyrrolidone, polyacrylic acid, α-vinyl pyrrolidone and styrol copolymer, α-vinyl pyrrolidone and acrylic acid copolymer at least.
In the 3rd step, adopt ammoniacal liquor to regulate the pH value, be for fear of introducing metal cation, improve the purity of product, pH being transferred to 3.5～5.0, be preferably between 4.5～5.0, can save the addition of precipitating reagent, continue then to stir, be heated to 60～70 ℃, the hydroxide that reaction forms in hot system filters easily.
In the 4th step, form the precipitating reagent of hydroxide as cobalt, iron ion, can in follow-up heat drying nuclear reduction process, residual precipitating reagent be removed fully, can not influence the purity of product with hydrazine hydrate, hexamethylenetetramine; When the temperature of mixed solution rises to 60～70 ℃, under constantly stirring, add, the guarantee system reaction is even, and cobalt, the total mol ratio of iron are in addition and the reaction system: (hydrazine hydrate+hexamethylenetetramine): (iron+cobalt) is 5.0: 1～1.1: 1.
In the 5th step, system temperature should be controlled between 60～90 ℃, and the temperature height helps shortening the reaction time, produces but have a large amount of bubbles when adding hydrazine hydrate, can drip a spot of ethanol for avoiding bumping; Wherein, when precipitating reagent adopted hydrazine hydrate, reaction temperature was in the time of 70～80 ℃, and 30～60 minutes reaction time got final product; If precipitating reagent is the mixture of hexamethylenetetramine or hydrazine hydrate and hexamethylenetetramine, the reaction time should be between 120～180 minutes, and reaction temperature is advisable with 85～90 ℃.
In the 6th step, reaction should be filtered after finishing while hot; In the filtration, with deionized water rinsing for several times, can remove the zwitterion that adsorbs in the precipitation.
In the 7th step, with the precipitation after filtering, just said solid disperses with the making beating of 0.2～3.0% aliphatic acid ethanol solution once more, is for modification is carried out in the absorbing fats acid of hydroxide particles surface, avoid in dry and sintering process, cause the particle increase even harden; Wherein the aliphatic acid that is adopted is oleic acid, stearic acid, soft ester acid, palmitic acid, lauric a kind of at least, what be convenient on the market buy is fatty acid mixed, normally oleic acid, stearic mixture, contain a small amount of (≤1%) soft ester acid etc., low price, adopt the ethanol solution of fatty acid mixed, can reduce production costs; For divalence cobalt, ferrous precipitation of hydroxide, the solid of the washing of pulling an oar and the volume ratio of aliphatic acid ethanol solution are with (V/V): be advisable in 1: 3～1: 5; For divalence cobalt, ferric precipitation of hydroxide, the solid of the washing of pulling an oar and the volume ratio of aliphatic acid ethanol solution are with (V/V): be advisable in 1: 4～1: 9.Making beating, the aliphatic acid ethanol solution after filtering are added aliphatic acid after can be after testing, recycle.
In the 8th step,, be logical H under 90～105 ℃ of conditions in temperature with filter residue---the ferro-cobalt precipitation of hydroxide after filtering
2Dry 30～90 minutes, remove the small amount of moisture and the ethanol of particle surface absorption, avoid ferro-cobalt hydroxide oxidized simultaneously.
In the 9th step, continue logical H
2, continue to be warming up to 300～600 ℃, ferro-cobalt hydroxide is reduced ultra-fine ferro-cobalt powder; Recovery time is 4～8 hours.
In the tenth step, because that ultra-fine ferro-cobalt powder at high temperature is easy to is oxidized, must logical H
2Lower the temperature, be cooled to below 45 ℃, discharging, and use the aluminium foil vacuum packaging, avoid contacting and oxidation with air, moisture in storage, transportation midium or long term.
Because the utilization of technique scheme, the present invention compares with existing atomizing preparation pre-alloyed powder technology, has following advantage:
1. can be under gentle relatively condition, the preparation ferro-cobalt ultra-fine powder need not the high melt facility;
2. controlled to the ultra-fine ferro-cobalt powder pattern of realizing synthesizing, be the class sphere substantially, its distribution of particles is at 0.5～5 mu m range, and distribution is very narrow;
3. the composition of ultra-fine ferro-cobalt powder is even, and component ratio can be regulated as required;
4. preparation technology is succinct.
In sum, core technology of the present invention is: the pattern that adopts high molecular surfactant control product, soluble-salt solution with cobalt, iron, with hydrazine hydrate or hexamethylenetetramine reaction, form the spherical cobalt of class, the co-precipitation of iron ion hydroxide, to the hydroxide particles surface modification, guarantee that oven dry, reduction process particle can not increase and harden, logical H with the ethanolic solution washing precipitation of aliphatic acid
2Add thermal reduction, prepare the spherical ferro-cobalt ultra-fine powder of class that particle diameter is distributed in 0.5～5 mu m range.The ratio of the soluble-salt by adjusting cobalt, iron can prepare the ferro-cobalt ultra-fine powder of different proportion of composing, satisfies different demands.
Description of drawings
Accompanying drawing 1: ferro-cobalt ultra-fine powder field emission scan (SEM) picture of hydrazine hydrate reduction system preparation, enlargement ratio (15000 times);
Accompanying drawing 2:(hydrazine hydrate+hexamethylenetetramine) the ferro-cobalt ultra-fine powder field emission scan (SEM) of reduction system preparation
Picture, enlargement ratio (5000 times);
Accompanying drawing 3:(hydrazine hydrate+hexamethylenetetramine) the EDAX analysis result of the ferro-cobalt ultra-fine powder of reduction system preparation;
Accompanying drawing 4: implementing process flow chart of the present invention.
The specific embodiment
Below in conjunction with specific embodiments and the drawings the present invention is further described:
Technological process with reference to figure (4) is implemented.
Embodiment 1:
In the ferro-cobalt mass ratio is 18: 82 alloy composition ratio design, prepares ultra-fine ferro-cobalt powder:
Take by weighing 9.133g FeCl
2, adding 50.0mL 0.001M HCl, heating for dissolving adds 20.0mL 0.75MCoCl
2Add the 1.00mL 5%PVP-K30 aqueous solution, mix, continuing to begin heating under the stirring, the ammoniacal liquor that drips 1: 1 (V/V) when mixeding liquid temperature reaches 70 ℃ is regulated pH value to 4.5～5.0, add 5.0M hydrazine hydrate 25.0mL then, continue heating, temperature is controlled at 75 ± 3 ℃, stirs 60 minutes, suction filtration, during with deionized water rinsing 3 times; Must precipitate and be about about 10mL, the gained solid sediment with the making beating of 50.0mL 1% fatty acid mixed ethanol solution, was stirred suction filtration, solid spontaneous combustion drying 5 minutes.
The solid sampling remains in logical H
2Under the condition, 100 ℃ were heated 60 minutes, were warming up to 450 ℃, were incubated 5 hours, then at logical H
2Cool off under the condition, take out during to room temperature, get the 4.6g ferro-cobalt ultra-fine powder, sem analysis, remaining sample aluminium foil Vacuum Package are done in sampling.SEM result shows that the pattern of ferro-cobalt ultra-fine powder is the class sphere, and distribution of particles concentrates between 0.5～0.8 μ m, referring to figure (1).
The EDAX analysis result shows that the cobalt of superfine alloy particle surface, iron component ratio (mass ratio) are 17.6: 82.4; The result is very desirable, and the result is referring to table (1).
Embodiment 2:
In the ferro-cobalt mass ratio is 16: 84 alloy composition ratio design, prepares ultra-fine ferro-cobalt powder:
Take by weighing 10.533g FeCl
2, adding 50.0mL 0.001M HCl, heating for dissolving adds 20.0mL 0.75MCoCl
2Add the 1.00mL 5%PVP-K30 aqueous solution, mix, continuing to begin heating under the stirring, the ammoniacal liquor that drips 1: 1 (V/V) when mixeding liquid temperature reaches 70 ℃ is regulated pH value to 4.5～5.0, add 5.0M hydrazine hydrate 15.0mL then, 2.0M hexamethylenetetramine solution 30.0mL continues heating, temperature is controlled at 85 ± 3 ℃, stirred 60 minutes, suction filtration, during with deionized water rinsing 3 times; Must precipitate and be about about 10mL, the gained solid sediment with the making beating of 50.0mL 1% fatty acid mixed ethanol solution, was stirred suction filtration, solid spontaneous combustion drying 5 minutes.
The solid sampling remains in logical H
2Under the condition, 100 ℃ were heated 60 minutes, were warming up to 300 ℃, were incubated 5 hours, then at logical H
2Cool off under the condition, take out during to room temperature, get the 5.2g ferro-cobalt ultra-fine powder, sem analysis, remaining sample aluminium foil Vacuum Package are done in sampling.SEM result shows that the pattern of ferro-cobalt ultra-fine powder is the class sphere, and distribution of particles concentrates between 1.5～2.0 μ m, because temperature is lower, still has the thread organic matter that does not decompose fully in the powder, referring to figure (2).
The EDAX analysis result shows that referring to table (1), the cobalt of superfine alloy particle surface, iron component ratio (mass ratio) are 14.7: 85.3; Ideal as a result, EDAX collection of illustrative plates and scanning constituency are respectively referring to figure (3a) with scheme (3b).
Table 1, ultra-fine ferro-cobalt surface composition EDAX analysis result
Claims (8)
1. the preparation method of a ferro-cobalt ultra-fine powder, it is characterized in that: the soluble-salt solution that adopts cobalt, iron, add high molecular surfactant, regulate pH to 3.5～5.0, add precipitating reagent with ammoniacal liquor, heating, stirring, make the reaction of cobalt, iron ion form the hydroxide co-precipitation, after filtration, flushing, with the ethanol solution of aliphatic acid to precipitation making beating modification, filter, gained hydroxide filter residue leads to H
2Heat drying, reduction, the preparation ferro-cobalt ultra-fine powder;
Wherein said:
(1), the cobalt soluble-salt is hydrochloride, nitrate, sulfate, acetate a kind of of divalent cobalt ion at least;
(2), the soluble-salt of iron is hydrochloride, nitrate, sulfate, acetate a kind of of the iron ion of divalence, trivalent ion at least;
(3), high molecular surfactant is that mean molecule quantity is no less than a kind of of 5000 poly-α-vinyl pyrrolidone, polyacrylic acid, α-vinyl pyrrolidone and styrol copolymer, α-vinyl pyrrolidone and acrylic acid copolymer at least;
(4), precipitating reagent is a kind of of hydrazine hydrate and hexamethylenetetramine at least;
(5), aliphatic acid is oleic acid, stearic acid, soft ester acid, palmitic acid, lauric a kind of at least;
(6), reaction temperature is controlled between 60～90 ℃, the reaction time was controlled at 30～180 minutes;
(7), logical H
2The heat drying temperature is between 90～105 ℃, and drying time was at 30～90 minutes;
(8), logical H
2The heating reduction temperature is at 300～600 ℃, and the recovery time is 4～8 hours.
2. the preparation method of a kind of ferro-cobalt ultra-fine powder as claimed in claim 1 is characterized in that the total concentration of the soluble-salt mixed solution of described cobalt, iron is not more than 3M.
3. the preparation method of a kind of ferro-cobalt ultra-fine powder as claimed in claim 1, the addition that it is characterized in that described high molecular surfactant is 0.01～1% of a reaction solution cumulative volume.
4. the preparation method of a kind of ferro-cobalt ultra-fine powder as claimed in claim 1, it is characterized in that cobalt in described precipitating reagent addition and the reaction system, the total mol ratio of iron are (precipitating reagents): (iron+cobalt) is 5.0: 1～1.1: 1.
5. the preparation method of a kind of ferro-cobalt ultra-fine powder as claimed in claim 1, the aliphatic acid volume by volume concentration that it is characterized in that described aliphatic acid ethanol solution is 0.2～3.0%.
6. the preparation method of a kind of ferro-cobalt ultra-fine powder as claimed in claim 1 or 2, the quality that it is characterized in that cobalt, iron in the soluble-salt mixed solution of described cobalt, iron are than iron: cobalt is 10: 1～1: 4.
7. the preparation method of a kind of ferro-cobalt ultra-fine powder as claimed in claim 1 or 2 is characterized in that the soluble-salt mixed solution of described cobalt, iron adding small amount of hydrochloric acid control pH between 2～4.
8. as the preparation method of claim 1 or 5 described a kind of ferro-cobalt ultra-fine powders, it is characterized in that the volume ratio of cobalt, iron hydroxide solid and the aliphatic acid ethanol solution of described making beating is (V/V): 1: 1～1: 10.
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| CN102000830B (en) * | 2010-11-18 | 2012-07-04 | 深圳市格林美高新技术股份有限公司 | Superfine cobalt alloy powder and preparation method thereof |
| CN102366839B (en) * | 2011-09-28 | 2014-04-02 | 哈尔滨电机厂有限责任公司 | Method for preparing rod-like ferrocobalt alloy powder without adopting template |
| CN103725886A (en) * | 2013-12-04 | 2014-04-16 | 刘军亮 | Method for preparing multicomponent alloy by using copper, nickel, chromium, zinc and ferrum in silt |
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| CN111266602A (en) * | 2018-12-04 | 2020-06-12 | 荆门市格林美新材料有限公司 | Preparation method of superfine cobalt-nickel powder for hard alloy |
| CN113070483A (en) * | 2021-03-25 | 2021-07-06 | 东北大学 | Method for preparing FeCoNi intermediate entropy alloy with low cost and short process |
| CN114636304B (en) * | 2022-04-27 | 2023-10-24 | 合肥八维七度新材料科技有限公司 | Energy-saving environment-friendly metal powder cold pressing and drying system capable of being recycled |
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