CN108149158A - A kind of Co-Ni-P amorphous powders preparation process - Google Patents

A kind of Co-Ni-P amorphous powders preparation process Download PDF

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Publication number
CN108149158A
CN108149158A CN201711448209.4A CN201711448209A CN108149158A CN 108149158 A CN108149158 A CN 108149158A CN 201711448209 A CN201711448209 A CN 201711448209A CN 108149158 A CN108149158 A CN 108149158A
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amorphous
mol
amorphous alloy
plating
electroplate liquid
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刘志红
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刘志红
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F1/00Special treatment of metallic powder, e.g. to facilitate working, to improve properties; Metallic powders per se, e.g. mixtures of particles of different composition
    • B22F1/0003Metallic powders per se; Mixtures of metallic powders; Metallic powders mixed with a lubricating or binding agent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/04Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • C22C45/04Amorphous alloys with nickel or cobalt as the major constituent
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys
    • C25D3/562Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt

Abstract

A kind of Co Ni P amorphous powder preparation processes, include 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 electro-plating method, anode uses graphite cake or stainless steel plate, and the current density of electrode is 0.05 0.5 A/mm2, titrating hydrochloric acid solution makes plating solution Ph values be less than 3, and plating temperature is 25 75 DEG C;(3)Amorphous alloy coating is made to come off from metallic substrate surfaces using the methods of rolling, bending, shot-peening;(4)Amorphous Alloy Grain crushes, and the amorphous alloy coating to come off carries out being broken into Co Ni P amorphous powdered alloys using modes such as ball mill, particle breakers.

Description

A kind of Co-Ni-P amorphous powders preparation process
Technical field
The present invention relates to a kind of amorphous powdered alloy, more particularly, to a kind of Co-Ni-P amorphous powders preparation process.
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 scope of application.It is non- Structure of the crystal structure with longrange disorder, shortrange order, makes powder 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 leading to 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 It is 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, electroplating technology has its unique distinction in process aspect, simple with equipment, simple for process, and operation is flexible, alloy Ingredient control is big.
Invention content
In view of the above-mentioned problems, the present invention is based on the principle of plating+stripping+broken, a kind of Co-Ni-P amorphous powders are provided Preparation process.
The ingredient of cobalt-nickel-phosphor alloy powder of the present invention is Co 45-90 wt %, Ni 5-35 wt%, P5-20 wt%; Its powder is amorphous structure.
The present invention provides a kind of Co-Ni-P amorphous powders preparation process.Include 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 electroplate liquid:Cobaltous sulfate or cobalt chloride 1.5-5 mol/L(It is preferred that 1.5-2.5 mol/L), nickel sulfate or chlorination Nickel 0.2-2.5 mol/L, phosphorous acid 0.25-1.5 mol/L, phosphoric acid 0.5-1.5 mol/L, additive 1-8g/L, soluble sulphur Hydrochlorate or chlorate 10-50 g/L, reducing agent 1-8g/L, excess water;
Additive described in above-mentioned electroplate liquid liquid is saccharin and the mixture of lauryl sodium sulfate;
3 kinds of salt are simultaneously sulfate or chlorate using identical anionic, i.e. three kinds of substances in above-mentioned electroplate liquid;
Reducing agent is water-soluble in above-mentioned electroplate liquid;
(3)Cobalt-nickel-phosphor amorphous alloy coating is prepared using electro-plating method, anode uses graphite cake or stainless steel plate, the electricity of electrode Current density is 0.05-0.5 A/mm2, titrating hydrochloric acid solution makes plating solution Ph values be less than 3, and plating temperature is 25-75 DEG C;
(4)Amorphous alloy coating is made to come off from metallic substrate surfaces using the methods of rolling, bending, shot-peening;
(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;
(6)It is sieved into the Co-Ni-P amorphous powdered alloys of different thicknesses.
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 produce 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 preparing galvanization coating, the present invention does not require coating stress and surface quality, therefore bigger can be used Current density had both improved the preparation speed of amorphous alloy coating, was also beneficial to obtain more loose and with bigger internal stress Amorphous alloy coating removes amorphous alloy coating and is come off so as to be more easy to;
6. compared with chilling method prepares amorphous powdered alloy, the present invention need not consider the amorphous formation ability of material, can pass through tune The concentration proportioning of whole each main component of electroplate liquid can obtain the amorphous powdered alloy of different constituent elements compositions and ratio, therefore, we The applicability of method is more extensive, and operability 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 Co68Ni22P10 amorphous powdered alloys of embodiment
Preparation process includes the following steps:
(1)The pretreatment of metallic substrate surfaces:Metal substrate selects 08F steel plates, and it is molten through sodium hydroxide respectively to be plated substrate surface Liquid and hydrochloric acid solution cleaning, to remove grease and oxidation;
(2)Electroplate liquid forms:2.2 mol/L of cobalt chloride, 0.6 mol/L of phosphoric acid, nickel chloride 0.8mol/L, phosphorous acid 0.35 Mol/L, 2.5 g/L of additive, 15 g/L of soluble chlorine salt dissolving, excess water;
Above-mentioned additive is saccharin and lauryl sodium sulfate mass ratio is 1:1 mixture;
Above-mentioned soluble chlorine salt dissolving is potassium chloride;
Above-mentioned reducing agent is ascorbic acid;
(3)The preparation of amorphous alloy coating:Pretreated metallic plate accesses cathode, and anode uses graphite cake, stirs electroplate liquid, The current density of electrode is 0.05 A/mm2, plating temperature is 65 DEG C, and titration hydrochloric acid makes electroplate liquid Ph values be 1;
(4)Amorphous alloy coating is removed using bending method, bending radius is 0.2 m;
(5)Amorphous Alloy Grain crushes, and Amorphous Alloy Grain is crushed under protection of argon gas using planetary ball mill, 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 Co68Ni22P10 amorphous powdered alloys.
The preparation of 2 Co75Ni16P9 amorphous powdered alloys of embodiment
Preparation process includes the following steps:
(1)The pretreatment of metallic substrate surfaces:Metal substrate selects brass sheet, and plate thickness 1mm is plated substrate surface respectively through hydrogen Sodium hydroxide solution and hydrochloric acid solution cleaning, to remove grease and oxidation;
(2)Electroplate liquid forms:1.8 mol/L of cobaltous sulfate, 0.7 mol/L of phosphoric acid, 0.45 mol/L of nickel sulfate, phosphorous acid 0.3mol/L, additive 3g/L, 20 g/L of sodium sulphate, excess water;
Above-mentioned additive is saccharin and lauryl sodium sulfate mass ratio is 1:2 mixture;
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 0.1 A/mm2, plating temperature is 75 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 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 Co75Ni16P9 amorphous powdered alloys.

Claims (5)

1. a kind of Co-Ni-P amorphous powders preparation process, the ingredient of powder is Co 45-90 wt %, Ni 5-35 wt%, P5-20 Wt%, powder are amorphous structure.
2. a kind of Co-Ni-P amorphous powders preparation process, which is characterized in that include 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 electroplate liquid:Cobaltous sulfate or cobalt chloride 1.5-5 mol/L(It is preferred that 1.5-2.5 mol/L), nickel sulfate or chlorination Nickel 0.2-2.5 mol/L, phosphorous acid 0.25-1.5 mol/L, phosphoric acid 0.5-1.5 mol/L, additive 1-8g/L, soluble sulphur Hydrochlorate or chlorate 10-50 g/L, reducing agent 1-8g/L, excess water;
(3)Cobalt-nickel-phosphor amorphous alloy coating is prepared using electro-plating method, anode uses graphite cake or stainless steel plate, the electricity of electrode Current density is 0.05-0.5 A/mm2, titrating hydrochloric acid solution makes plating solution Ph values be less than 3, and plating temperature is 25-75 DEG C;
(4)Amorphous alloy coating is made to come off from metallic substrate surfaces using the methods of rolling, bending, shot-peening;
(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)It is sieved into the Co-Ni-P amorphous powdered alloys of different thicknesses.
3. additive described in claim 2 electroplate liquid is saccharin and the mixture of lauryl sodium sulfate.
4. for 3 kinds of salt described in claim 2 electroplate liquid using identical anionic, i.e. three kinds of substances are simultaneously sulfate or chlorine Salt dissolving.
5. reducing agent is water-soluble described in claim 2 electroplate liquid.
CN201711448209.4A 2017-12-27 2017-12-27 A kind of Co-Ni-P amorphous powders preparation process Pending CN108149158A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109023464A (en) * 2018-07-27 2018-12-18 淮阴工学院 Ni-based chalcogenide film of amorphous cobalt and its preparation method and application
CN109097811A (en) * 2018-09-13 2018-12-28 济南东方结晶器有限公司 Electroplate liquid of Co-Ni-P- diamond coating and preparation method thereof and electro-plating method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106757287A (en) * 2016-12-06 2017-05-31 刘志红 A kind of preparation technology of Fe Ni P base composite claddings
CN106756641A (en) * 2016-12-14 2017-05-31 刘志红 A kind of Fe based amorphous alloy powders and its preparation technology
CN106893954A (en) * 2017-03-21 2017-06-27 长沙理工大学 A kind of Co based amorphous alloy powders and its preparation technology
CN106893953A (en) * 2017-03-21 2017-06-27 长沙理工大学 A kind of cobalt base amorphous alloy powder and production method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106757287A (en) * 2016-12-06 2017-05-31 刘志红 A kind of preparation technology of Fe Ni P base composite claddings
CN106756641A (en) * 2016-12-14 2017-05-31 刘志红 A kind of Fe based amorphous alloy powders and its preparation technology
CN106893954A (en) * 2017-03-21 2017-06-27 长沙理工大学 A kind of Co based amorphous alloy powders and its preparation technology
CN106893953A (en) * 2017-03-21 2017-06-27 长沙理工大学 A kind of cobalt base amorphous alloy powder and production method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109023464A (en) * 2018-07-27 2018-12-18 淮阴工学院 Ni-based chalcogenide film of amorphous cobalt and its preparation method and application
CN109097811A (en) * 2018-09-13 2018-12-28 济南东方结晶器有限公司 Electroplate liquid of Co-Ni-P- diamond coating and preparation method thereof and electro-plating method
CN109097811B (en) * 2018-09-13 2020-09-22 济南东方结晶器有限公司 Electroplating solution for Co-Ni-P-diamond coating and preparation method and electroplating method thereof

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Application publication date: 20180612