CN108103531A - The technique that a kind of galvanoplastic prepare the alloy amorphous state powders of Fe - Google Patents

The technique that a kind of galvanoplastic prepare the alloy amorphous state powders of Fe Download PDF

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Publication number
CN108103531A
CN108103531A CN201711493521.5A CN201711493521A CN108103531A CN 108103531 A CN108103531 A CN 108103531A CN 201711493521 A CN201711493521 A CN 201711493521A CN 108103531 A CN108103531 A CN 108103531A
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amorphous
mol
alloy
plating
broken
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罗奕兵
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罗奕兵
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • C22C45/02Amorphous alloys with iron as the major constituent
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions

Abstract

Amorphous powdered alloy is made for plating+stripping+broken in a kind of production method of Co Fe Ni P powder, technological principle, which is characterized in that comprises the following steps:(1)Metal substrate selects and is plated the processing on surface;(2)Cobalt ferronickel phosphorus non-crystalline alloy coating 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 40 85 DEG C;(3)Using the methods of rolling, bending, shot-peening amorphous alloy coating is made to come off from metallic substrate surfaces;(4)The amorphous alloy coating to come off 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)It is sieved into the Co Fe Ni P amorphous powdered alloys of different thicknesses.

Description

The technique that a kind of galvanoplastic prepare the alloy amorphous state powders of Fe
Technical field
The present invention relates to a kind of amorphous powdered alloys, and the alloy amorphous state powders of Fe are prepared more particularly, to a kind of galvanoplastic Technique.
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 alloy powder of amorphous formation ability can be prepared, and production cost is high.The advantages of direct crush method, is to material Selectivity it is not strong, stock utilization is high, but brittle annealing need to be carried out to amorphous thin ribbon, it is easy to due to annealing unevenness cause it is thin The powder particle of acute angle is carried with the uneven of internal crystallization change, and in broken rear easily generation, is that the follow-up of powder adds Work brings 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, electroplating technology has its unique distinction in process aspect, and feature can be summarized as follows:
1st, equipment is simple, simple for process, and operation is flexible;
2nd, expense is low, and economic benefit is big;
3rd, the controllable scope of powder metallurgy component ratio is big.
The content of the invention
In view of the above-mentioned problems, the present invention is based on the principle of plating+stripping+broken, provide a kind of galvanoplastic and prepare Fe and close The technique of golden amorphous powder.
It is Fe 32-86 wt %, Ni 5-35 wt%, P 6- that the present invention, which provides a kind of ingredient of the alloy amorphous state powders of Fe, 25 wt%, Co 3-8%;Its powder is amorphous structure.
The preparation process of the alloy amorphous state powders of Fe of the present invention, it is characterised in that comprise the following steps:
(1)Its elongation percentage is not less than 10% to the selection of metal substrate material at normal temperatures, is plated derusting, the ungrease treatment on surface;
(2)The composition of electroplate liquid:Soluble ferrite 1-4 mol/L(It is preferred that 1.5-2.5 mol/L), soluble nickel salt 0.2- 1.2 mol/L, phosphorous acid or hypophosphites 0.1-0.6 mol/L, cobaltous sulfate or cobalt chloride 0.05-0.4 mol/L, phosphoric acid 0.3- 1.5 mol/L, additive 1-8g/L, soluble strong acid salt 10-50 g/L, reducing agent 1-8g/L, excess water;
Above-mentioned additive is lauryl sodium sulfate, carboxylate etc.;
Above-mentioned reducing agent is water-soluble;
(3)The alloy amorphous state coating of Fe is prepared using electro-plating method, anode uses graphite cake or stainless steel plate, and the electric current of electrode is close It spends for 0.05-0.5 A/mm2, titrating strong acid solution makes plating solution Ph values be less than 3, and electroplating solution temperature is 55-90 DEG C;
(4)Using the methods of rolling, bending, shot-peening 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 Broken, ball mill, particle breaker should use and force the type of cooling or interval work mode.
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 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 Fe66 Ni21P9Co4 amorphous powdered alloys of embodiment
Preparation process comprises 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 dilute hydrochloric acid solution cleaning, to remove grease and oxidation;
(2)Electroplate liquid forms:1.8 mol/L of frerrous chloride, 0.3 mol/L of phosphoric acid, 0.5 mol/L of nickel chloride, phosphorous acid 0.25mol/L, cobaltous sulfate 0.1mol/L, 1.5 g/L of additive, 15 g/L of soluble chlorine salt dissolving, 1.5 g/L of reducing agent, surplus Water;
Above-mentioned additive is sodium acetate 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, electroplating solution 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 mill uses interval work mode, per ball milling 3min, rest 10min.
The preparation of 2 Fe73 Ni14P6Co7 amorphous powdered alloys of embodiment
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)Electroplate liquid forms:1.8 mol/L of ferrous sulfate, 0.7 mol/L of phosphoric acid, 0.3 mol/L of nickel sulfate, cobaltous sulfate 0.15 Mol/L, 0.2 mol/L of phosphorous acid, additive 3g/L, 20 g/L of soluble sulphate, 3 g/L of reducing agent, excess water;
Above-mentioned additive is lauryl sodium sulfate;
Above-mentioned soluble chlorine salt dissolving is sodium sulphate;
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, electroplating solution 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 mill uses interval work mode, per ball milling 3min, rest 10min.

Claims (4)

1. the ingredient that a kind of galvanoplastic prepare the alloy amorphous state powders of Fe is Fe 32-86 wt %, Ni 5-35 wt%, P 6-25 Wt%, Co 3-8%;Its powder is amorphous structure.
The preparation process of the alloy amorphous state powders of 2.Fe, which is characterized in that comprise the following steps:
(1)Its elongation percentage is not less than 10% to the selection of metal substrate material at normal temperatures, is plated derusting, the ungrease treatment on surface;
(2)The composition of electroplate liquid:Soluble ferrite 1-4 mol/L(It is preferred that 1.5-2.5 mol/L), soluble nickel salt 0.2- 1.2 mol/L, phosphorous acid or hypophosphites 0.1-0.6 mol/L, cobaltous sulfate or cobalt chloride 0.05-0.4 mol/L, phosphoric acid 0.3- 1.5 mol/L, additive 1-8g/L, soluble strong acid salt 10-50 g/L, reducing agent 1-8g/L, excess water;
(3)The alloy amorphous state coating of Fe is prepared using electro-plating method, anode uses graphite cake or stainless steel plate, and the electric current of electrode is close It spends for 0.05-0.5 A/mm2, titrating strong acid solution makes plating solution Ph values be less than 3, and electroplating solution temperature is 55-90 DEG C;
(4)Using the methods of rolling, bending, shot-peening 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 Broken, ball mill, particle breaker are using the pressure type of cooling or interval work mode.
3. additive described in claim 2 is lauryl sodium sulfate, carboxylate etc..
4. reducing agent described in claim 2 is water-soluble.
CN201711493521.5A 2017-12-30 2017-12-30 The technique that a kind of galvanoplastic prepare the alloy amorphous state powders of Fe Pending CN108103531A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (1)

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

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Application publication date: 20180601