CN108118265A - A kind of technique of brush plating method production iron-phosphorus amorphous powder - Google Patents

A kind of technique of brush plating method production iron-phosphorus amorphous powder Download PDF

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CN108118265A
CN108118265A CN201711494738.8A CN201711494738A CN108118265A CN 108118265 A CN108118265 A CN 108118265A CN 201711494738 A CN201711494738 A CN 201711494738A CN 108118265 A CN108118265 A CN 108118265A
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amorphous
phosphorus
mol
alloy coating
powder
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罗奕兵
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    • 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
    • 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
    • C22C45/008—Amorphous alloys with Fe, Co or Ni as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
    • 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
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

Abstract

A kind of ingredient of ferronickel phosphorus non-crystalline alloy powder is 40 90 wt% of nickel, and 5 35 wt% of iron, 5 25 wt% of phosphorus, powder is amorphous structure.Production method is it is characterised in that it includes following steps：（1）The elongation percentage of metal substrate at normal temperatures is not less than 10%, and substrate is plated the derusting on surface, ungrease treatment；（2）The preparation of ferronickel phosphorus non-crystalline alloy coating：Ferronickel phosphorus non-crystalline alloy coating 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 40 85 DEG C；（3）Using the difference of substrate and amorphous deposit plastic deformation ability, using the methods of rolling, bending, shot-peening amorphous alloy coating is made to come off；（4）The amorphous alloy coating to come off is crushed using modes such as ball mill, particle breakers, and ball mill, particle breaker should use and force the type of cooling or interval work mode.This is simple for process, workable.

Description

A kind of technique of brush plating method production iron-phosphorus amorphous powder
Technical field
The present invention relates to a kind of production methods of ferrous alloy amorphous powder, are produced more particularly, to a kind of brush plating method The technique of iron-phosphorus amorphous powder.
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 magnet Oxysome
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 inductive loop in high-frequency work causes loss very big, limits its application in high frequency field；(2) soft magnetic ferrite is high Frequency is lost low, but saturation induction density and magnetic conductivity are low, it is impossible to meet the growth requirement of miniaturization and high current；(3) it is golden Belong to powder core there is the problems such as high-frequency loss is high, DC superposition characteristic is poor or expensive, limit its application range.It is non- Crystal structure has longrange disorder, the structure of shortrange order, and powder is made to have many unique performances.Amorphous Magnaglo is due to it Excellent soft magnet performance can meet various electronic component stabilisations, miniaturization, high frequency, high current, high-power need It asks, the development of the hi-tech industries such as automobile, electronics, aerospace field can be greatly facilitated.And cobalt base amorphous alloy powder removes With excellent magnetic property, also with the performances such as high temperature resistant, resistance to exhaust gas corrosion, wear-resisting, anti-corrosion, closed in electronics, coating and hard It is used widely in gold.
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 without 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 plating product speed 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 powder is made the present invention is based on Brush Plating+stripping+broken, a kind of brush is provided The technique of the plating production non-crystalline flour powder of iron-phosphorus.
The ingredient of iron-phosphorus alloy non-crystal powder of the present invention is iron 70-95wt%, phosphorus 5-30 wt%.
The technique of iron of the present invention-phosphorus alloy non-crystal powder, which is characterized in that comprise the following steps：
（1）Its elongation percentage is not less than 5% to the selection of metal substrate material at normal temperatures, and plated surface is derusted, ungrease treatment；
（2）The composition of electric brush plating liquor：Frerrous chloride or ferrous sulfate 3-7.5 mol/L（It is preferred that 4-6 mol/L）, phosphoric acid 0.5- 1.5 mol/L, phosphorous acid or hypophosphites 0.5-3.5 mol/L, additive 1-8g/L, soluble sulphate or chlorate 10- 50 g/L, reducing agent 1-8g/L, excess water；
Above-mentioned additive is the mixture of lauryl sodium sulfate, neopelex or both；
Above-mentioned reducing agent is water-soluble；
（3）The preparation of iron-phosphorus alloy non-crystal coating：Iron-phosphorus alloy non-crystal coating is prepared using brush electroplating method, anode uses stone Black plate 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 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 Brush Plating bath temperature is 50-75 DEG C,；
（4）Using the difference of substrate and amorphous deposit plastic deformation ability, close amorphous using the methods of rolling, bending, shot-peening Gold plate comes off；
（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, to prevent non-crystaline amorphous metal Grain generates larger Wen Sheng, generation crystallization change when broken；
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 the alloy amorphous powders of 1 Fe92P8 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 frerrous chloride, 0.8 mol/L of phosphoric acid, 0.5 mol/L of phosphorous acid, additive 3g/L, 15 g/L of potassium chloride, 4 g/L of reducing agent, excess water；
Above-mentioned additive is lauryl sodium sulfate；
Above-mentioned reducing agent is ascorbic acid；
（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, electrode speed of related movement is 5 m/min, and Brush Plating solution temperature is 65 DEG C, 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 4h, ratio of grinding media to material 3:1, 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）The screening of amorphous powdered alloy.
The preparation of 2 Fe87P13 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 ferrous sulfate, 0.5 mol/L of phosphoric acid, 0.5 mol/L of sodium hypophosphite, additive 3g/L, 22 g/L of potassium sulfate, 3 g/L of reducing agent, excess water；
Above-mentioned additive is lauryl sodium sulfate and neopelex mass ratio is 1:1 mixture；
Above-mentioned reducing agent is ascorbic acid；
（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, electrode speed of related movement is 10 m/min, and bath temperature is 65 DEG C, and titration hydrochloric acid makes electricity Plating solution Ph values are 1；
（4）Amorphous alloy coating is removed using alternating bending method, bending radius is 0.2 m；
（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.
The preparation of 3 Fe84P16 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 ferrous sulfate, 0.5 mol/L of phosphoric acid, 1 mol/L of phosphorous acid, additive 2g/L, 22 g/L of potassium sulfate, 3 g/L of reducing agent, excess water；
Above-mentioned additive is neopelex；
Above-mentioned reducing agent is potassium iodide；
（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, electrode speed of related movement is 12 m/min, and bath temperature is 80 DEG C, and titration hydrochloric acid makes Electroplate liquid Ph values are 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 2h, ratio of grinding media to material 10:1, ball milling method uses interval work mode, and ball mill avoids amorphous per ball milling 3min, rest 10min Powder generates larger Wen Sheng.

Claims (5)

1. a kind of ingredient of Ni-Fe-phosphorus non-crystalline alloy powder is nickel 40-90 wt%, iron 5-35 wt%, phosphorus 5-25 wt%, powder For amorphous structure.
2. the production method of Ni-Fe-phosphorus non-crystalline alloy powder, which is characterized in that comprise the following steps：
（1）The elongation percentage of metal substrate at normal temperatures is not less than 10%, and substrate is plated the derusting on surface, ungrease treatment；
（2）The composition of electric brush plating liquor：Nickel chloride or nickel sulfate 3-7.5 mol/L（It is preferred that 4-6 mol/L）, phosphoric acid 0.5-1.5 Mol/L, ferrous sulfate or frerrous chloride 0.5-3.5 mol/L, phosphorous acid or hypophosphites 0.2-2 mol/L, additive 1-8g/ L, soluble sulphate or chlorate 10-50 g/L, reducing agent 1-8g/L, excess water；
（3）The preparation of Ni-Fe-phosphorus non-crystalline alloy coating：Ni-Fe-phosphorus non-crystalline 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 40-85 DEG C,；
（4）Using the difference of substrate and amorphous deposit plastic deformation ability, close amorphous using the methods of rolling, bending, shot-peening Gold plate comes off；
（5）The amorphous alloy coating to come off is crushed using modes such as ball mill, particle breakers, ball mill, Particle Breakage Machine should use and force the type of cooling or interval work mode；
（6）Ni-Fe-phosphorus non-crystalline alloy powder of different thicknesses is sieved into using sieve.
3. the additive described in claim 2 is the mixture of tartaric acid, sodium acetate or both.
4. 3 kinds of salt described in claim 2 are homo-ion type, that is, it is soluble sulphate or chlorate.
5. the reducing agent described in claim 2 is water-soluble.
CN201711494738.8A 2017-12-31 2017-12-31 A kind of technique of brush plating method production iron-phosphorus amorphous powder Pending CN108118265A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103436944A (en) * 2013-08-22 2013-12-11 北京科技大学 Amorphous iron-phosphorus alloy/V8C7 composite coating and and electroplating technique thereof
CN106756641A (en) * 2016-12-14 2017-05-31 刘志红 A kind of Fe based amorphous alloy powders and its preparation technology
CN108103539A (en) * 2017-12-29 2018-06-01 刘志红 A kind of Ni-Fe-phosphorus amorphous powder production method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103436944A (en) * 2013-08-22 2013-12-11 北京科技大学 Amorphous iron-phosphorus alloy/V8C7 composite coating and and electroplating technique thereof
CN106756641A (en) * 2016-12-14 2017-05-31 刘志红 A kind of Fe based amorphous alloy powders and its preparation technology
CN108103539A (en) * 2017-12-29 2018-06-01 刘志红 A kind of Ni-Fe-phosphorus amorphous powder production method

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