CN108193146B - Nickel-based amorphous alloy powder and production method thereof - Google Patents
Nickel-based amorphous alloy powder and production method thereof Download PDFInfo
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- CN108193146B CN108193146B CN201611118716.7A CN201611118716A CN108193146B CN 108193146 B CN108193146 B CN 108193146B CN 201611118716 A CN201611118716 A CN 201611118716A CN 108193146 B CN108193146 B CN 108193146B
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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
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- 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
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- 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
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- 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
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- 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
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- 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 Ni-base amorphous alloy powder contains Ni (40-95 wt.%), and the alloy elements (P, Fe, Cr, Co, Mo, W and Re) which can be electrodeposited together with Ni. The production method of the nickel-based amorphous alloy powder comprises the following steps: (1) pretreating the plated surface of the metal substrate; (2) the electroplating solution comprises the following components: nickel salt, sodium hypophosphite or phosphorous acid, complexing agent and alloy element additive; (3) preparing an amorphous alloy coating by adopting an electric brush plating method; (4) the amorphous alloy coating is peeled off by adopting a mechanical or physical method; (5) ball milling of amorphous alloy particles; (6) and sieving the amorphous alloy powder into nickel-based amorphous alloy powder with different thicknesses.
Description
Technical Field
The invention relates to amorphous alloy powder, in particular to nickel-based amorphous alloy powder and a production method thereof.
Background
With the development of electronic power and communication industries, electronic components are miniaturized, high frequency and high current
At present, the requirements for the electromagnetic compatibility of electronic equipment are higher and higher, and the traditional amorphous strip iron core and soft magnetic ferrite
And metal magnetic powder cores and the like cannot meet the requirements, and the application is limited. The main points are as follows: (1) amorphous strip iron core working at high frequency
The loss caused by the induced eddy current is very large, so that the application of the high-frequency induction eddy current in the high-frequency field is limited; (2) the soft magnetic ferrite has low high-frequency loss, but has low saturation magnetic induction intensity and magnetic conductivity, and can not meet the development requirements of miniaturization and large current; (3) the metal magnetic powder core has the problems of high-frequency loss, poor direct-current superposition characteristics or high price and the like, and the application range of the metal magnetic powder core is limited. The amorphous magnetic powder can meet the requirements of various electronic components on stabilization, miniaturization, high frequency, large current and high power due to excellent soft magnetic performance, and can greatly promote the development of high and new technology industries in the fields of automobiles, electronics, aerospace and the like.
Up to now, the preparation process of amorphous alloy powder mainly includes water mist method, gas mist method and the process of crushing amorphous thin strip into powder. The water mist method has a large cooling rate and can meet the requirement of preparing amorphous powder. However, in the water atomization process, the obtained powder is easy to form oxides, the oxygen content is high, and when the molten metal is solidified, the surface of the molten metal is covered with generated water vapor, and the existence of the water vapor film causes the cooling strength of the molten core metal to be reduced, so that the central part of the powder cannot obtain an amorphous structure, and the device performance is affected. The aerosol method is limited in cooling strength, and can only prepare amorphous alloy powder with strong amorphous forming ability, and the production cost is high. The direct crushing method has the advantages that the selectivity to materials is not strong, the material utilization rate is high, but an amorphous thin strip needs to be subjected to embrittlement annealing, the nonuniform crystallization transformation inside the thin strip is easily caused by nonuniform annealing, and powder particles with acute angles are easily generated after crushing, so that the subsequent processing of the powder is difficult.
Compared with the liquid quenching method and the sputtering method for preparing the amorphous alloy material, the electroplating method is more economical and has wider application range. The formation of the brush plating layer is essentially the same as the plating, and is a process in which metal ions in a solution are crystallized by discharge on a negative electrode (workpiece). However, compared with electroplating, in brush plating, the plating pen and the workpiece move relatively, so that the plated surface does not wholly and simultaneously undergo metal ion reduction crystallization, but all points of the plated surface generate instantaneous discharge crystallization when the plating pen contacts the plated surface. Therefore, the brush plating technology has unique characteristics in the process aspect, and the characteristics can be summarized as follows:
1. the equipment is simple, does not need a plating bath, is convenient to carry, and is suitable for field and field repair. The method has practical value especially for on-site non-disassembly repair of large and precise equipment;
2. the process is simple, the operation is flexible, and the parts which do not need to be plated are not protected by a plurality of materials;
3. in the operation process, the cathode and the anode move relatively, so that higher current density is allowed to be used, which is several times to dozens of times greater than that used in the bath plating;
4. the plating solution has high metal ion content, so the plating speed is fast (5 to 10 times faster than the bath plating);
5. plating pens with different models are provided, insoluble anodes with different shapes and sizes are provided, and various parts with different geometric shapes and complex structures can be repaired;
6. low cost and great economic benefit.
Disclosure of Invention
Aiming at the problems, the invention provides nickel-based amorphous alloy powder with wider composition and proportion selection range of amorphous alloy material components and a production method thereof based on the principle of brush plating.
The nickel-based amorphous/alloy powder comprises 40-95 wt% of Ni, and the alloy elements are elements which can be electrodeposited together with Ni, such as one or a combination of more of P, Fe, Cr, Co, Mo, W, Re and the like.
The production method of the nickel-based amorphous alloy powder comprises the following steps:
(1) pretreatment of the plated surface of the metal substrate: the plated surface of the metal substrate can be derusted and degreased by adopting a mechanical or chemical method;
(2) the electroplating solution comprises the following components: 1-4.5mol/L (preferably 2-3.5 mol/L) of nickel salt (nickel sulfate, nickel chloride or a mixture of the nickel salt and the nickel chloride), 0.2-1mol/L of acid, 0.5-5g/L of complexing agent, 0.2-2mol/L of alloying element additive and the balance of water;
in the alloy element additive, iron is added in the form of ferrous sulfate or ferrous chloride (needing to be provided with a reducing agent), chromium is added in the form of chromic anhydride, molybdenum is added in the form of sodium molybdate, cobalt is added in the form of cobalt sulfate, tungsten is added in the form of sodium tungstate, phosphorus is added in the form of phosphorous acid or soluble hypophosphite, and Re is added in the form of Re soluble salt;
the above acids include boric acid, phosphoric acid, carboxylic acids, etc.;
the complexing agent comprises tartaric acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, citrate and the like;
(3) preparing an amorphous alloy coating: preparing amorphous alloy coating by brush plating method, wherein the anode is made of graphite, and the current density of the electrode is 0.4-1.5A/mm2(preferably 0.8-1.2A/mm)2) The relative movement speed of the electrode is 5-20m/min (preferably 10-15 m/min), the strong acid solution is titrated to ensure that the Ph value of the plating solution is less than 1, and the plating temperature is 30-60 ℃;
(4) stripping the amorphous alloy coating by mechanical or physical methods, such as rolling and rolling, shot blasting, scraping and the like;
(5) ball milling of amorphous alloy particles, wherein the ball milling of the peeled amorphous particles is carried out under the protection of vacuum or inert gas, the ball milling can be carried out by a ball mill, a planetary ball mill and the like, the ball milling time is 2-24h, and the ball-to-material ratio is 3-10: 1;
(6) sieving the amorphous alloy powder into Ni-based amorphous alloy powder with different thicknesses.
Compared with the prior art, the invention has the following advantages:
1. compared with an aerosol method and a direct crushing method, the process has the characteristics of less equipment investment, simple process, low requirement on amorphous alloy forming capacity and the like;
2. compared with a water mist method, the powder does not generate the problems of oxidation and partial amorphization;
3. compared with a direct crushing method, the method has the advantages that the large internal stress and the large number of pores are generated in the coating layer due to the fact that deposition is carried out under the condition that the PH value is small, the coating layer does not need to be embrittled, annealed and crushed, and powder particles with acute angles cannot be generated;
4. compared with the method for preparing the amorphous alloy powder by an electroplating method and a crushing method, the method has the advantages that because the two electrodes of the brush plating move relatively and the electroplating solution is in a flowing state, the problem of concentration polarization generated by electroplating is solved, relatively higher current density can be used, and the production efficiency of the powder is improved;
5. compared with the conventional brush plating, the method has no requirement on the stress and the surface quality of the plating layer, so that a larger current density can be adopted, the preparation speed of the amorphous alloy plating layer is improved, and the method is also beneficial to obtaining the amorphous alloy plating layer which is looser and has larger internal stress, so that the amorphous alloy plating layer is easier to mechanically strip;
6. the method does not need to consider the amorphous forming capability of the material, and can obtain amorphous alloy powder with different component compositions and proportions by adjusting the concentration proportion of each main component of the electroplating solution, so the method has wider applicability and stronger operability, and can meet the performance requirements of different occasions.
Detailed Description
The present invention is further illustrated by the following examples.
EXAMPLE 1 preparation of Ni-P amorphous alloy powder
The content of Ni in the amorphous alloy powder of the embodiment is 91.2wt%, and the content of P in the amorphous alloy powder is 8.8wt% of the composite coating.
The preparation process comprises the following steps:
(1) pretreatment of the surface of the metal substrate: selecting a No. 45 steel plate as a metal substrate, machining the surface of the plated substrate, and then cleaning the plated substrate in 20wt% sodium hydroxide solution for 10min to remove grease;
(2) the electroplating solution comprises the following components: 2mol/L of nickel sulfate, 0.7mol/L of boric acid, 0.6mol/L of sodium hypophosphite, 1.2g/L of tartaric acid and the balance of water;
(4) preparing an amorphous alloy coating: the pretreated plating piece is connected to the cathode of a plating bath, the anode adopts graphite and is stirred with electroplating solution, and the current density of the electrode is 0.5A/mm2The plating temperature is 60 ℃, and the pH value of the electroplating solution is 0.6 by titrating hydrochloric acid;
(5) stripping the amorphous alloy coating by adopting a rolling and rolling method;
(6) ball milling of amorphous alloy particles is carried out by adopting a planetary ball mill, amorphous alloy powder is filled with argon for protection, ball milling is carried out for 5 hours, and the ball-to-material ratio is 5: 1;
(7) sieving the amorphous alloy powder by adopting 200-mesh and 400-mesh sieves, wherein the powder with the size larger than 200 meshes accounts for 30 percent, the powder with the size of 200-mesh and 400-mesh accounts for 48 percent, and the powder with the size smaller than 400 meshes accounts for 22 percent.
EXAMPLE 2 preparation of Ni-Fe-P amorphous alloy powder
The Ni-Fe-P amorphous alloy powder of this example had the composition of Ni content 80.3wt%, Fe content 12.8wt%, and P content 5.1 wt%.
The preparation process comprises the following steps:
(1) pretreatment of the surface of the metal substrate: selecting a No. 45 steel plate as a metal substrate, machining the surface of the plated substrate, and then cleaning the plated substrate in 20wt% sodium hydroxide solution for 10min to remove grease;
(2) the preparation composition of the electroplating solution is as follows: 2.8mol/L of nickel sulfate, 0.3mol/L of ferrous chloride, 0.6mol/L of phosphoric acid, 0.4mol/L of phosphorous acid, 1g/L of potassium iodide and 1g/L of tartaric acid serving as a complexing agent;
(4) preparing an amorphous alloy coating: the pretreated metal substrate is connected to the cathode of an electroplating bath, graphite is adopted as the anode, the electroplating solution is mechanically stirred, and the current density of the electrode is 0.8A/mm2The plating temperature is 50 ℃,titrating hydrochloric acid to ensure that the pH value of the electroplating solution is 0.8;
(5) stripping the amorphous alloy plating layer: stripping the coating by adopting a scraping method;
(6) ball milling of amorphous alloy particles is carried out by adopting a planetary ball mill, and amorphous alloy powder is filled with argon for protection and ball milling for 3 hours, wherein the ball-to-material ratio is 3: 1;
(7) sieving the amorphous alloy powder by adopting 200-mesh and 400-mesh sieves, wherein the powder with the size larger than 200 meshes accounts for 36 percent, the powder with the size 200-400 meshes accounts for 49 percent, and the powder with the size smaller than 400 meshes accounts for 15 percent.
Claims (1)
1. A nickel-based amorphous alloy powder is characterized in that: the nickel-based amorphous alloy powder comprises 40-95 wt% of Ni, and alloy elements which are electrodeposited together with Ni and are the combination of one or more elements of P, Fe, Cr, Co, Mo, W and Re;
the nickel-based amorphous alloy powder is prepared by the following method:
(1) pretreating the plated surface of the metal substrate;
(2) the electroplating solution comprises the following components: 1-4.5mol/L of nickel salt, 0.2-1mol/L of acid, 0.5-5g/L of complexing agent, 0.2-2mol/L of alloying element additive and the balance of water;
the nickel salt is nickel sulfate or nickel chloride or a mixture of the nickel sulfate and the nickel chloride;
the acid is boric acid, or phosphoric acid, or carboxylic acid;
the complexing agent comprises tartaric acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and citrate;
in the alloy element additive, iron is added in the form of ferrous sulfate or ferrous chloride, chromium is added in the form of chromic anhydride, molybdenum is added in the form of sodium molybdate, cobalt is added in the form of cobalt sulfate, tungsten is added in the form of sodium tungstate, phosphorus is added in the form of phosphorous acid or hypophosphite, and Re is added in the form of Re soluble salt;
when the iron is added in the form of ferrous sulfate or ferrous chloride, a reducing agent is additionally added;
(3) preparing an amorphous alloy coating by adopting an electric brush plating method, wherein the parameters of the electroplating process are as follows: the anode is made of graphite, and the current density of the electrode is 0.4-1.5A/mm2Electrodes ofThe relative movement speed is 5-20m/min, the pH value of the electroplating solution is less than 1, and the plating temperature is 30-60 ℃;
(4) stripping the amorphous alloy coating by a mechanical method;
(5) ball milling of amorphous alloy particles;
(6) and screening the nickel-based amorphous alloy powder into nickel-based amorphous alloy powder with different thicknesses.
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Denomination of invention: A nickel based amorphous alloy powder and its production method Effective date of registration: 20230403 Granted publication date: 20200626 Pledgee: Penglai Minsheng Rural Bank Co.,Ltd. Pledgor: PENGLAI SUPERHARD COMPOUND MATERIAL Co.,Ltd. Registration number: Y2023980037259 |
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