CN108103538A - A kind of cobalt-nickel-phosphor amorphous alloy powder preparation process - Google Patents

A kind of cobalt-nickel-phosphor amorphous alloy powder preparation process Download PDF

Info

Publication number
CN108103538A
CN108103538A CN201711451593.3A CN201711451593A CN108103538A CN 108103538 A CN108103538 A CN 108103538A CN 201711451593 A CN201711451593 A CN 201711451593A CN 108103538 A CN108103538 A CN 108103538A
Authority
CN
China
Prior art keywords
nickel
amorphous alloy
cobalt
mol
amorphous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201711451593.3A
Other languages
Chinese (zh)
Inventor
刘志红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201711451593.3A priority Critical patent/CN108103538A/en
Publication of CN108103538A publication Critical patent/CN108103538A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/04—Electroplating with moving electrodes
    • C25D5/06—Brush or pad plating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15341—Preparation processes therefor
    • H01F1/1535—Preparation processes therefor by powder metallurgy, e.g. spark erosion

Abstract

A kind of cobalt nickel-phosphorus amorphous alloy powder process, comprises the following steps：（1）Metal substrate selects and is plated the processing on surface；（2）Cobalt nickel phosphorus non-crystal alloy layer is prepared using brush electroplating method, anode uses graphite cake or stainless steel plate, and the current density of electrode is 0.5 5 A/mm2（It is preferred that 1.5 3 A/mm2）, electrode speed of related movement is 5 20 m/min（It is preferred that 10 15m/min）, titrating hydrochloric acid or sulfuric acid solution makes plating solution Ph values be less than 3, and plating temperature is 30 85 DEG C；（3）Using plastic deformation methods such as alternating bending, rollings amorphous alloy coating is made to come off from metallic substrate surfaces；（4）It is crushed using modes such as ball mill, particle breakers；When broken, ball mill, particle breaker should use and force the type of cooling or interval work mode；（5）The cobalt nickel phosphorus non-crystal alloy powder of different thicknesses is sieved into using sieve.

Description

A kind of cobalt-nickel-phosphor amorphous alloy powder preparation process
Technical field
The present invention relates to a kind of amorphous powdered alloys, and work is prepared more particularly, to a kind of cobalt-nickel-phosphor amorphous alloy powder Skill.
Background technology
With the development of electron electric power, communication industry, electronic component is sent out to miniaturization, high frequency and high current direction Exhibition, and the requirement to the Electro Magnetic Compatibility of electronic equipment is also higher and higher, traditional amorphous band iron core, soft magnetic ferrite And metal magnetic powder core etc. has been unable to meet demand.Common magnetic material performance deficiency is mainly manifested in：(1) amorphous band iron core In high-frequency work, inductive loop causes loss very big, limits its application in high frequency field；(2) soft magnetic ferrite high frequency damages Consume low, but saturation induction density and magnetic conductivity are low, it is impossible to meet the growth requirement of miniaturization and high current；(3) metallic magnetic Powder core limits its application range there is the problems such as high-frequency loss is high, DC superposition characteristic is poor or expensive.Amorphous knot Structure has longrange disorder, the structure of shortrange order, and powder is made to have many unique performances.Amorphous Magnaglo is excellent due to its Soft magnet performance, various electronic component stabilisations, miniaturization, high frequency, high current, high-power demand, energy can be met It is greatly facilitated the development of the hi-tech industries such as automobile, electronics, aerospace field.And cobalt base amorphous alloy powder is removed with excellent Different magnetic property also with the performances such as high temperature resistant, resistance to exhaust gas corrosion, wear-resisting, anti-corrosion, obtains in electronics, coating and hard alloy To extensive use.
Up to the present, the preparation process of amorphous powdered alloy mainly has water fog method, aeroponics and using amorphous thin ribbon The technique for crushing powder processed.Water fog method has big cooldown rate, can meet the requirement for preparing amorphous powder.However, in water mist During change, the powder obtained easily forms oxide, and oxygen content is high, furthermore upon solidification of the molten metal, the vapor of generation The surface of molten metal can be covered in, the presence of the vapor film reduces the core metal intensity of cooling for causing melting, so as to Prevent the problem of powder central part is from obtaining amorphous structure, influence device performance.Aeroponics are since intensity of cooling is limited, only The strong amorphous powdered alloy of amorphous formation ability can be prepared, and production cost is high.The advantages of direct crush method, is to material Selectivity is not strong, and stock utilization is high, but brittle annealing need to be carried out to amorphous thin ribbon, it is easy to since annealing unevenness causes strip Internal crystallization change it is uneven, and the powder particle with acute angle is easily generated after broken, is the following process of powder Bring difficulty.
And compared with liquisol quenching method, sputtering method prepare amorphous alloy material, galvanoplastic are more economical, and application range is also more To be wide.The formation of Resisting Property of Brush Electroplating Coating plating of inherently making peace is identical, is all the metal ion in solution in cathode（Workpiece） The process of upper electric discharge crystallization.But compared with plating, plated pen and workpiece have relative motion in Brush Plating, thus plated surface is not It is whole that metal ion reduction crystallization, the knot but plated surface each point sparks when plated pen is in contact with it occur simultaneously It is brilliant.Therefore, Brush Electroplating Technique has its unique distinction in process aspect, and feature can be summarized as follows：
1st, equipment is simple, and coating bath is not required, easy to carry, suitable for field and field repair.Particularly with large-scale, precision equipment Scene do not disintegrate repair it is more with practical value；
2nd, simple for process, operation is flexible, and the position that need not be plated not use many material protections；
3rd, in operating process, cathode has relative motion with anode, therefore allows using higher current density, it is used than slot plating Current density is several times greater to tens times；
4th, metal ion content is high in plating solution, so deposition velocity is fast（It is 5 times~10 times faster than slot plating）；
5th, have a plated pen of different model, and equipped with shape is different, insoluble anode not of uniform size, to various different geometries and Complicated parts can all be repaired；
6th, expense is low, and economic benefit is big.
The content of the invention
In view of the above-mentioned problems, amorphous alloy powder is made the present invention is based on Brush Plating+stripping+broken, one kind is provided Cobalt-nickel-phosphor amorphous alloy powder preparation process.
The ingredient of cobalt-nickel-phosphor amorphous powdered alloy of the present invention is cobalt 45-90wt %, nickel 5-30 wt%, phosphorus 5-25 wt%。
Cobalt of the present invention-nickel-phosphor amorphous alloy powder preparation process.Comprise the following steps：
（1）Metal substrate selects and is plated the processing on surface：The elongation percentage at normal temperatures of metal substrate is not less than 10%, is plated Mechanically or chemically derusting, degreasing can be used in surface；
（2）The composition of electric brush plating liquor：Cobalt chloride or cobaltous sulfate 3-7.5 mol/L（It is preferred that 4-6 mol/L）, phosphoric acid 0.5-1.5 Mol/L, nickel sulfate or nickel chloride 0.5-3 mol/L, phosphorous acid 0.2-2 mol/L, additive 1-8g/L, soluble sulphate or Chlorate 10-50 g/L, excess water；
Additive described in above-mentioned electric brush plating liquor is saccharin and the mixture of lauryl sodium sulfate；
3 kinds of salt using identical anionic, that is, are soluble sulphate or chlorate described in above-mentioned electric brush plating liquor；
Reducing agent is water-soluble described in above-mentioned electric brush plating liquor；
（3）The preparation of cobalt-nickel-phosphor amorphous alloy coating：Cobalt-nickel-phosphor amorphous alloy coating, anode are prepared using brush electroplating method Using graphite cake or stainless steel plate, the current density of electrode is 0.5-5 A/mm2（It is preferred that 1.5-3 A/mm2）, electrode relative motion Speed is 5-20 m/min（It is preferred that 10-15m/min）, titrating hydrochloric acid or sulfuric acid solution makes plating solution Ph values be less than 3, and plating temperature is 30-85℃；
（4）Using plastic deformation methods such as alternating bending, rollings amorphous alloy coating is made to come off from metallic substrate surfaces；
（5）Amorphous Alloy Grain crushes, and the amorphous alloy coating to come off is broken using modes such as ball mill, particle breakers It is broken.When broken, ball mill, particle breaker should use and force the type of cooling or interval work mode, prevent Amorphous Alloy Grain Larger Wen Sheng is generated when broken, crystallization change occurs for powder；
（6）Cobalt-nickel-phosphor amorphous powdered alloy of different thicknesses is sieved into using sieve.
Compared with prior art, the present invention has the following advantages：
1. compared with aeroponics and direct crush method, this technique has equipment investment few, simple for process, and energy is formed to non-crystaline amorphous metal The features such as power is of less demanding；
2. compared with water fog method, powder will not lead to the problem of oxidation and partial amorphization；
3. compared with direct crush method, due to depositing under the conditions of using pH value smaller, cause to generate larger planted agent in coating Power and compared with concrete dynamic modulus, coating is i.e. tear-away with broken without embrittlement annealing, and will not generate the powder particle with acute angle；
4. compared with galvanoplastic+crush method prepares amorphous powdered alloy method, due to having relative motion between two electrode of Brush Plating, electroplate Liquid is also flow regime, therefore, does not electroplate the concentration polarization problem of generation, can use the current density of opposite bigger, carry The production efficiency of high powder；
5. for conventional brush plating, because not requiring coating stress and surface quality, therefore the electric current of bigger can be used Density had both improved the preparation speed of amorphous alloy coating, was also beneficial to obtain amorphous more loose and with bigger internal stress Alloy layer is removed so as to be more easy to carry out amorphous alloy coating rolling pressure；
6. this method can match somebody with somebody without considering the amorphous formation ability to material by adjusting the concentration of each main component of electroplate liquid Than the amorphous powdered alloy of different constituent elements compositions and ratio can be obtained, and therefore, the applicability of this method is more extensive, operable Property is stronger, can meet requirement of the different occasions to amorphous powdered alloy performance.
Specific embodiment
The invention will be further described with reference to embodiments.
The preparation of 1 Co75Ni18P6 amorphous powdered alloys of embodiment
Its preparation process, comprises the following steps：
（1）The pretreatment of metallic substrate surfaces：Metal substrate selects 08F steel plates, thickness of slab 1mm, and plated substrate surface passes through respectively Sodium hydroxide solution and hydrochloric acid solution cleaning, to remove grease and oxidation；
（2）Electric brush plating liquor forms：5 mol/L of cobalt chloride, 0.8 mol/L of phosphoric acid, 1.2 mol/L of nickel chloride, phosphorous acid 0.4 Mol/L, additive 3g/L, 15 g/L of potassium chloride, excess water；
Above-mentioned additive is saccharin and lauryl sodium sulfate mass ratio is 2:1 mixture；
（3）The preparation of amorphous alloy coating：Pretreated plating piece accesses cathode, and anode uses graphite cake, stirs electroplate liquid, electricity The current density of pole is 1.5 A/mm2, plating temperature is 65 DEG C, and titration hydrochloric acid makes electroplate liquid Ph values be 2；
（4）Amorphous alloy coating is removed using rolling reductions method, rolling reduction ratio is 8%；
（5）Amorphous Alloy Grain crushes, and using planetary ball mill crusher machine, Amorphous Alloy Grain is broken in argon gas protection, ball milling 2h, ratio of grinding media to material 5:1, ball milling method uses interval work mode, and ball mill avoids non-crystalline flour per ball milling 3min, rest 10min End generates larger Wen Sheng；
（6）It is sieved into the Co75Ni18P6 amorphous powdered alloys of different thicknesses.
The preparation of 2 Co77Ni15P8 amorphous powdered alloys of embodiment
Its preparation process, comprises the following steps：
（1）The pretreatment of metallic substrate surfaces：Metal substrate selects brass sheet, and thickness of slab 1mm is plated substrate surface respectively through hydrogen Sodium hydroxide solution and hydrochloric acid solution cleaning, to remove grease and oxidation；
（2）Electric brush plating liquor forms：4.5 mol/L of cobaltous sulfate, 0.5 mol/L of phosphoric acid, 0.8 mol/L of nickel sulfate, phosphorous acid 0.4 Mol/L, additive 3g/L, 22 g/L of potassium sulfate, excess water；
Above-mentioned additive is saccharin and lauryl sodium sulfate mass ratio is 1:1 mixture；
（3）The preparation of amorphous alloy coating：Pretreated plating piece accesses cathode, and anode uses graphite cake, stirs electroplate liquid, electricity The current density of pole is 2 A/mm2, plating temperature is 65 DEG C, and titrated sulfuric acid solution makes electroplate liquid Ph values be 1；
（4）Amorphous alloy coating is removed using rolling reductions method, rolling reduction ratio is 8%；
（5）Amorphous Alloy Grain crushes, and using planetary ball mill crusher machine, Amorphous Alloy Grain is broken in argon gas protection, ball milling 3h, ratio of grinding media to material 5:1, ball milling method uses interval work mode, and ball mill avoids non-crystalline flour per ball milling 3min, rest 10min End generates larger Wen Sheng；
（6）It is sieved into the Co77Ni15P8 amorphous powdered alloys of different thicknesses.

Claims (5)

1. a kind of cobalt-nickel-phosphor amorphous alloy powder preparation process, the ingredient of powder is cobalt 45-90wt %, nickel 5-30 wt%, Phosphorus 5-25 wt%, powder are amorphous structure.
2. cobalt-nickel-phosphor amorphous alloy powder preparation process, which is characterized in that comprise the following steps：
（1）Metal substrate selects and is plated the processing on surface：The elongation percentage at normal temperatures of metal substrate is not less than 10%, is plated Mechanically or chemically derusting, degreasing can be used in surface；
（2）The composition of electric brush plating liquor：Cobalt chloride or cobaltous sulfate 3-7.5 mol/L（It is preferred that 4-6 mol/L）, phosphoric acid 0.5-1.5 Mol/L, nickel sulfate or nickel chloride 0.5-3 mol/L, phosphorous acid 0.2-2 mol/L, additive 1-8g/L, soluble sulphate or Chlorate 10-50 g/L, excess water；
（3）The preparation of cobalt-nickel-phosphor amorphous alloy coating：Cobalt-nickel-phosphor amorphous alloy coating, anode are prepared using brush electroplating method Using graphite cake or stainless steel plate, the current density of electrode is 0.5-5 A/mm2（It is preferred that 1.5-3 A/mm2）, electrode relative motion Speed is 5-20 m/min（It is preferred that 10-15m/min）, titrating hydrochloric acid or sulfuric acid solution makes plating solution Ph values be less than 3, and plating temperature is 30-85 DEG C,；
（4）Using plastic deformation methods such as alternating bending, rollings amorphous alloy coating is made to come off from metallic substrate surfaces；
（5）Amorphous Alloy Grain crushes, and the amorphous alloy coating to come off is broken using modes such as ball mill, particle breakers It is broken；When broken, ball mill, particle breaker should use and force the type of cooling or interval work mode；
（6）Cobalt-nickel-phosphor amorphous powdered alloy of different thicknesses is sieved into using sieve.
3. additive described in electric brush plating liquor described in claim 2 is saccharin and the mixture of lauryl sodium sulfate.
4. 3 kinds of salt using identical anionic, that is, are soluble sulphate or chlorination described in claim 2 electric brush plating liquor Salt.
5. reducing agent is water-soluble in electric brush plating liquor described in claim 2.
CN201711451593.3A 2017-12-27 2017-12-27 A kind of cobalt-nickel-phosphor amorphous alloy powder preparation process Pending CN108103538A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711451593.3A CN108103538A (en) 2017-12-27 2017-12-27 A kind of cobalt-nickel-phosphor amorphous alloy powder preparation process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711451593.3A CN108103538A (en) 2017-12-27 2017-12-27 A kind of cobalt-nickel-phosphor amorphous alloy powder preparation process

Publications (1)

Publication Number Publication Date
CN108103538A true CN108103538A (en) 2018-06-01

Family

ID=62213747

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711451593.3A Pending CN108103538A (en) 2017-12-27 2017-12-27 A kind of cobalt-nickel-phosphor amorphous alloy powder preparation process

Country Status (1)

Country Link
CN (1) CN108103538A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106381510A (en) * 2016-12-06 2017-02-08 刘志红 Preparing technology of Ni-Fe-P alloy-based compound coating
CN106756641A (en) * 2016-12-14 2017-05-31 刘志红 A kind of Fe based amorphous alloy powders and its preparation technology

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106381510A (en) * 2016-12-06 2017-02-08 刘志红 Preparing technology of Ni-Fe-P alloy-based compound coating
CN106756641A (en) * 2016-12-14 2017-05-31 刘志红 A kind of Fe based amorphous alloy powders and its preparation technology

Similar Documents

Publication Publication Date Title
CN106893953B (en) A kind of cobalt base amorphous alloy powder and production method
CN106756641B (en) A kind of Fe based amorphous alloy powder and its preparation process
CN106893954B (en) A kind of Co based amorphous alloy powders and its preparation process
CN100577891C (en) Anodic oxidation method for raising rigidity and corrosion resistance of plated aluminum on surface of metal base
CN105177572B (en) A kind of method for preparing anti-corrosion composite coating in surface of steel plate
CN104561877A (en) Thermal spraying nickel-based self-fused alloy amorphous coating
CN108149158A (en) A kind of Co-Ni-P amorphous powders preparation process
CN114411125B (en) High-entropy metal oxide coating and preparation method and application thereof
CN108193146B (en) Nickel-based amorphous alloy powder and production method thereof
CN106048667B (en) A kind of connection method of the same race or dissimilar metal based on plating
CN108103539A (en) A kind of Ni-Fe-phosphorus amorphous powder production method
CN108145149A (en) One kind is based on electroplated Ni-Co-P amorphous powder preparation methods
CN107937945A (en) A kind of galvanoplastic prepare Ni Fe P amorphous powder techniques
CN108103538A (en) A kind of cobalt-nickel-phosphor amorphous alloy powder preparation process
CN108220825A (en) A kind of Ni based amorphous alloy powders and its preparation process
CN108060440A (en) A kind of brush plating production method of iron-nickel-phosphor powder
CN108118265A (en) A kind of technique of brush plating method production iron-phosphorus amorphous powder
CN108145150A (en) One kind is based on amorphous nickel plating-phosphor powder production technology
CN108179365A (en) A kind of production technology of brush plating method Ni-Co-P amorphous powders
CN108145148A (en) A kind of production technology based on brush nickel plating alloy amorphous powder
CN108149159A (en) A kind of Co-Ni-Fe-phosphorus non-crystalline alloy powder production method
CN108165899A (en) A kind of production method of Co-Fe-Ni-P powder
CN108179366A (en) A kind of production method of the alloy amorphous state powder of Ni
CN108161014A (en) A kind of galvanoplastic prepare Ni-Fe-P amorphous powder techniques
CN108176847A (en) A kind of production technology of Ni-P powder

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20180601

WD01 Invention patent application deemed withdrawn after publication