CN109036753A - A kind of amorphous nano-crystalline composite magnetic powder core and preparation method thereof - Google Patents
A kind of amorphous nano-crystalline composite magnetic powder core and preparation method thereof Download PDFInfo
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- 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
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- H01F1/15366—Making agglomerates therefrom, e.g. by pressing using a binder
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- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
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- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
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Abstract
The invention discloses a kind of amorphous nano-crystalline composite magnetic powder cores and preparation method thereof to be prepared using iron-based amorphous nanometer crystalline magnetic powder, nanometer glass powder/micron order glass powder as primary raw material by discharge plasma sintering process.Amorphous nano-crystalline composite magnetic powder core magnetic conductivity with higher, higher consistency, lower magnetic loss and the lower coercivity, therefore the amorphous nano-crystalline composite magnetic powder core has very excellent soft magnetism and mechanical property, can be widely used for the manufacture of the equipment such as high power switching power supply, high-power inductance and high-efficiency energy-saving motor.
Description
Technical field
The invention belongs to powder core technical fields, are related to amorphous nano-crystalline composite magnetic powder core and preparation method thereof.
Background technique
With the high speed development of the technologies such as power electronics, electronic information and new energy, to the electricity of the elements such as inductance, transformer
Performance, reliability, energy saving and it is compact in size more stringent requirements are proposed, need constantly to be promoted as inductance, transformer etc.
The soft magnet performance of the powder core of element important component, including high magnetic permeability, high saturation magnetic flux amount, high working efficiency and low magnetic
Conductance.Currently, the powder core of research and development include pure iron powder core, it is iron Si-Al Magnetic Powder Core, permalloy powder core, FERRITE CORE, non-
Five major class such as brilliant nanocrystalline magnetic core.Compared to other four classes powder cores, amorphous nano-crystalline powder core have high saturation magnetic flux amount,
The advantages that low-loss, good high frequency characteristics, bias magnet properties and biggish power bearing ability.
The amorphous nano-crystalline powder core that current published powder core preparation process obtains, magnetic conductivity, coercivity, magnetic powder
The soft magnet performances such as core loss and mechanical property are difficult to combine.Application No. is the application documents of CN201310410905.1 to disclose
A kind of amorphous nano-crystalline composite magnetic powder core and preparation method thereof, the amorphous nano-crystalline composite magnetic powder core is mainly by Fe-based amorphous powder
End, iron based nano crystal powder, organic binder and insulating compound composition, although the composite magnetic powder core is with inorganic oxide, carbide
Mixture with nitride is insulating compound, and the soft magnet performance of powder core and mechanical property is made to be improved, but its magnetic
Conductance only has 60 or so, and compression strength is less than 500MPa, it can be seen that, the soft magnet performance and mechanical property of this composite magnetic powder core
It is still poor, it is difficult to meet the technical requirements as inductance, transformer element powder core.Application No. is 201510961792.3 Shens
Please file disclose a kind of preparation method of amorphous nanocrystalline soft magnetic powder core, pass through cure under pressure, inorganic binder (including silicon
Hydrochlorate, phosphate, sulfate and borate) solution impregnates, annealing, epoxy resin organic adhesive agent solution impregnate and solidify
Processing etc. obtains amorphous nanocrystalline soft magnetic powder core；The powder core obtained by the preparation method, density are about 5.5~5.8,
Far below the theoretical density of pure iron, it will lead to that magnetic conductivity is lower, and coercivity is higher, mechanical strength is poor.Application No. is
201210206560.3 application documents disclose a kind of preparation method of high-performance nano-crystal magnetic powder core, by Fe-based amorphous
Strip is successively heat-treated, is crushed, ball milling, screening, later mixes products therefrom with sodium silicate binder, repressed, move back
It is coated with to obtain high-performance nano-crystal magnetic powder core with insulating resin after fire processing, the powder core magnetic conductance obtained by this preparation method
Rate only has 60 or so, and magnetic core is damaged in 250~300mW/cm3, it can be seen that, the soft magnet performance and mechanical property of this powder core
It can be still poor, it is difficult to meet the technical requirements as inductance, transformer element powder core.
Therefore, the amorphous that the soft magnet performances such as exploitation magnetic conductivity, coercivity, magnetic powder core loss and mechanical property combine is received
Brilliant powder core of rice and preparation method thereof is the needs of the technologies such as power electronics, electronic information and new energy development.
Summary of the invention
The purpose of the present invention is intended in view of the deficiency of the prior art, provide a kind of amorphous nano-crystalline composite magnetic powder core
And preparation method thereof, it there is higher magnetic permcability, lower low-loss, is received compared with the amorphous of low-coercivity and higher mechanical strength to obtain
The brilliant composite magnetic powder core of rice, meets its technical requirements as inductance, transformer element powder core, and simplify preparation process.
The weight percent of amorphous nano-crystalline composite magnetic powder core provided by the invention, raw material components and each component is as follows:
Iron-based amorphous nanometer crystalline magnetic powder 98~99.8%,
Glass phase 0.2~2%；
It will be uniformly mixed to form mixture with glass phase after the heat treatment of iron-based amorphous nanometer crystalline magnetic powder vacuum, mixture is adopted
It is sintered to obtain with discharge plasma；
Or the raw material components of the composite magnetic powder core and the weight percent of each component it is as follows:
Iron-based amorphous nanometer crystalline magnetic powder 96.5~99.3%,
Glass phase 0.2~2%,
Organic binder 0.5~1.5%；
It will be mixed again with organic binder after mixing after the heat treatment of iron-based amorphous nanometer crystalline magnetic powder vacuum with glass phase
Mixture uniformly and after drying is formed, mixture is sintered to obtain using discharge plasma；
The glass phase is nanometer glass powder or micron order glass powder.
Above-mentioned amorphous nano-crystalline composite magnetic powder core, the Fe with partial size at 10~70 μm73.5Si13.5B9Nb3Cu amorphous nano-crystalline
Magnetic powder is major ingredient, is mixed by different-grain diameter magnetic powder and increases powder core compactness；With nanometer glass powder or micron order glass powder
As glass phase, not only increases the compactness of powder core by liquid-phase sintering while improving its resistivity to reduce loss, wherein 1
~30 μm of micron order glass powder liquefy during the sintering process filling powder core inside large scale hole, 50~300nm's receives
Meter level glass powder, which increases compactness simultaneously by liquid-phase sintering, can uniformly coat magnetic powder reduction loss.When further containing in powder core
When having the organic binder being formulated by silicone resin and ethyl orthosilicate 1:2 in mass ratio, heat resistanceheat resistant point during the sintering process
Capability improving is solved, good thermosetting is played the role of.
Invention further provides the preparation methods of above-mentioned amorphous nano-crystalline composite magnetic powder core, with the non-of further crystallization
Brilliant nanocrystalline magnetic and nanometer glass powder/micron order glass powder are raw material, by putting in 450~600 DEG C, 100~900MPa
Electro-plasma sintering can obtain high magnetic permeability, low magnetic loss, low-coercivity, high mechanical strength and good non-of frequency stability
Brilliant nanocomposite powder core.When further added in raw material by by silicone resin and ethyl orthosilicate 1:2 in mass ratio preparation
Made of organic binder when, heat resistanceheat resistant capacity of decomposition is promoted in discharge plasma sintering process, is played good thermosetting and is made
With.Component according to powder core is different, and the present invention provides the preparation methods of four kinds of amorphous nano-crystalline composite magnetic powder cores, below into
Row is discussed in detail.
When amorphous nano-crystalline composite magnetic powder core is made of iron-based amorphous nanometer crystalline magnetic powder and nanometer glass powder, the present invention
The preparation method of the first the amorphous nano-crystalline composite magnetic powder core provided is prepared according to the following steps:
(11) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By iron-based amorphous nanometer crystalline magnetic powder under vacuum conditions in 300~400 DEG C of 1~1.5h of heat treatment；
(12) nanometer glass powder is prepared
Ethyl orthosilicate, ethyl alcohol, nitric acid and acetic acid are mixed, is stirred at room temperature to the complete prehydrolysis of ethyl orthosilicate and is formed
The first mixed liquor containing pre-hydrolysate；By the first mixed liquor containing pre-hydrolysate and contain Li+Nitric acid solution, contain Ca2+'s
Nitric acid solution, H3BO3Aqueous solution contains Al3+Aqueous solution be uniformly mixed form the second mixed liquor, with aqueous ethanolamine or ammonium hydroxide
The pH to 0.5~2 of the second mixed liquor of gained is adjusted, it is transparent to being formed then at being stored at room temperature later in 60~80 DEG C of 3~5h of ageing
Vitreosol is dried to obtain xerogel by colloidal sol, and gained xerogel is obtained glass blank through 400~650 DEG C of 1~3h of heat treatment,
Gained glass blank obtains nanometer glass powder through ball milling, drying, sieving；The ethyl orthosilicate, Li+、Ca2+、H3BO3、
Al3+Molar ratio be 104.9:11.99:2:62.12:5；
(13) ingredient and mixing
The nanometer glass powder weight percent obtained by step (12) is 0.2~2%, step (11) through vacuum heat treatment
Iron-based amorphous nanometer crystalline magnetic powder weight percent be 98~99.8% ingredients, by the nanometer glass powder and through Vacuum Heat at
The iron-based amorphous nanometer crystalline magnetic powder of reason is uniformly mixed and obtains mixture；
(14) it is sintered
Mixture obtained by step (13) is sintered 2~4min in 450~600 DEG C, 100~900MPa discharge plasma,
Obtain amorphous nano-crystalline composite magnetic powder core.
The preparation method of above-mentioned amorphous nano-crystalline composite magnetic powder core, step (11) first by iron-based amorphous nanometer crystalline magnetic powder in
300~400 DEG C of 1~1.5h of vacuum heat treatment make the further nano-crystallization of part non crystalline structure, powder core can be effectively reduced in this way
Loss and coercivity；Vacuum degree will be 10 in treatment process-1It is more than Pa magnitude.
The preparation method of above-mentioned amorphous nano-crystalline composite magnetic powder core, step (12) is prepared by sol-gal process
LiBSiCaAl nanometer glass powder, this method are the realization methods that nanometer glass powder is simple and cost performance is high, pass through this side
The nanometer glass powder diameter that method obtains is mixed in 50~300nm, by it with major ingredient iron-based amorphous nanometer crystalline magnetic powder, Ke Yiti
The uniformity of high magnetic powder insulating wrapped, at the same it is finally obtained by Transient liquid phase sintering raising in discharge plasma sintering
The compactness of powder core simultaneously inhibits growing up for crystal grain, so that improving magnetic conductivity reduces coercivity.In this step, first by positive silicic acid second
The complete prehydrolysis of ester makes ethyl orthosilicate form the silica for having hydroxyl；It, can in order to accelerate ethyl orthosilicate complete hydrolysis
It is vigorously stirred so that ethyl orthosilicate, ethyl alcohol, nitric acid and acetic acid mixture are carried out at room temperature.After the complete prehydrolysis of ethyl orthosilicate
With contain Li+Nitric acid solution, contain Ca2+Nitric acid solution, H3BO3Aqueous solution, contain Al3+Aqueous solution mix and be adjusted to pH and be
0.5~2, heating is aged certain time later, then is stored at room temperature and to form vitreosol, the further drying of vitreosol, high temperature
Heat treatment obtains glass blank, and gained glass blank obtains LiBSiCaAl nanometers through wet ball grinding, drying, 500 meshes excessively again
Grade glass powder.In order to avoid introducing impurity, use solution for containing Li+Nitric acid solution, contain Ca2+Nitric acid solution, H3BO3Water
Solution contains Al3+Aqueous solution；It is described to contain Li+Nitric acid solution be by LiNO3Be dissolved in deionized water or by LiOH or
LiOH·H2O, which is dissolved in nitric acid, to be obtained, described to contain Ca2+Nitric acid solution be by Ca (NO3)2It is dissolved in deionized water or by Ca
(OH)2It is dissolved in nitric acid and obtaining, the H3BO3Aqueous solution be by H3BO3It is soluble in water to obtain, it is described to contain Al3+Aqueous solution be
By Al (NO3)3Or (Al (NO3)3)·9H2O is dissolved in deionized water or by Al (OH)3It is dissolved in nitric acid and obtaining.Above-mentioned nitric acid or
The dosage of deionized water is at least Li+、Ca2+、Al3+Corresponding alkali or salt and H3BO3Completely, the dosage of nitric acid can be with for dissolution
Slightly excessive (for example be Li+、Ca2+Or Al3+Twice of the amount of substance) so that the aobvious acidity of solution, facilitates subsequent reactions.
The preparation method of above-mentioned amorphous nano-crystalline composite magnetic powder core, the nanometer glass that step (13) obtains step (12)
Iron-based amorphous nanometer crystalline magnetic powder of the powder with step (11) through vacuum heat treatment is uniformly mixed to obtain mixture using wet ball grinding, has
Body is to be put into nanometer particle size glass and Fe-based amorphous nano-magnetic powder in ball milling filling, using dehydrated alcohol as ball-milling medium, and to
Leading to 5~10 minutes nitrogen in ball milling filling, 2~4h of ball milling, iron-based amorphous nanometer crystalline magnetic powder and glass phase are uniformly mixed later,
Vacuum drying oven drying is put into after finally taking out to get mixture is arrived.
The preparation method of above-mentioned amorphous nano-crystalline composite magnetic powder core, step (14) use 450~600 DEG C, 100~900MPa
Discharge plasma sintering process, the traditional powder core system combined compared to 0.5GPa~2.5GPa compression moulding with normal sintering
Standby technique can more improve the consistency of gained powder core to obtain bigger magnetic conductivity and mechanical strength.
When amorphous nano-crystalline composite magnetic powder core is by iron-based amorphous nanometer crystalline magnetic powder, nanometer glass powder and organic binder group
The preparation method of Cheng Shi, second of amorphous nano-crystalline composite magnetic powder core provided by the invention are prepared according to the following steps:
(21) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By iron-based amorphous nanometer crystalline magnetic powder under vacuum conditions in 300~400 DEG C of 1~1.5h of heat treatment；
(22) nanometer glass powder is prepared
Ethyl orthosilicate, ethyl alcohol, nitric acid and acetic acid are mixed, is stirred at room temperature to the complete prehydrolysis of ethyl orthosilicate and is formed
The first mixed liquor containing pre-hydrolysate；By the first mixed liquor containing pre-hydrolysate and contain Li+Nitric acid solution, contain Ca2+'s
Nitric acid solution, H3BO3Aqueous solution contains Al3+Aqueous solution be uniformly mixed form the second mixed liquor, with aqueous ethanolamine or ammonium hydroxide
The pH to 0.5~2 of the second mixed liquor of gained is adjusted, it is transparent to being formed then at being stored at room temperature later in 60~80 DEG C of 3~5h of ageing
Vitreosol is dried to obtain xerogel by colloidal sol, and gained xerogel is obtained glass blank through 400~650 DEG C of 1~3h of heat treatment,
Gained glass blank obtains nanometer glass powder through ball milling, drying, sieving；The ethyl orthosilicate, Li+、Ca2+、H3BO3、
Al3+Molar ratio be 104.9:11.99:2:62.12:5；
(23) ingredient and mixing
The nanometer glass powder weight percent obtained by step (22) is 0.2~2%, step (21) through vacuum heat treatment
Iron-based amorphous nanometer crystalline magnetic powder weight percent be 96.5~99.3%, organic binder weight percent is 0.5~1.5%
The nanometer glass powder is uniformly mixed to obtain the first mixing by ingredient with the iron-based amorphous nanometer crystalline magnetic powder through vacuum heat treatment
Material, obtains the second mixture, the organic binder is by silicon after organic binder is uniformly mixed and is dried with the first mixture
Ketone resin and ethyl orthosilicate 1:2 in mass ratio are formulated；
(24) it is sintered
By the second mixture obtained by step (23) in 450~600 DEG C, 100~900MPa discharge plasma sintering 2~
4min to get arrive amorphous nano-crystalline composite magnetic powder core.
The preparation method of second of amorphous nano-crystalline composite magnetic powder core and the first amorphous nano-crystalline composite magnetic powder core
Preparation method the difference is that, will be further uniformly mixed by silicone resin and ethyl orthosilicate 1:2 in mass ratio and obtained
Organic binder is added to by the mixing of the iron-based amorphous nanometer crystalline magnetic powder and LiBSiCaAl nanometer glass powder of vacuum heat treatment
In material, then it is sintered to obtain amorphous nano-crystalline composite magnetic powder core through discharge plasma.Silicone resin and ethyl orthosilicate press quality
Heat resistanceheat resistant capacity of decomposition in discharge plasma sintering process can be made to be promoted than the organic binder that 1:2 is mixed to get, played good
Good thermosetting effect.
When amorphous nano-crystalline composite magnetic powder core is made of iron-based amorphous nanometer crystalline magnetic powder and micron order glass powder, the present invention
The preparation method of the third amorphous nano-crystalline composite magnetic powder core provided is prepared according to the following steps:
(31) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By iron-based amorphous nanometer crystalline magnetic powder under vacuum conditions in 300~400 DEG C of 1~1.5h of heat treatment；
(32) micron order glass powder is prepared
By Li2O、B2O3、SiO2、CaO、Al2O3It measures and is mixed according to molar ratio 52.45:31.06:11.99:2:2.5
It is heated to 1110~1200 DEG C of 10~60min of heat preservation after even, then rapid quenching, quenches products therefrom through ball milling, drying, sieving
Obtain micron order glass powder；
(33) ingredient and mixing
The micron order glass powder weight percent obtained by step (32) is 0.2~2%, step (31) through vacuum heat treatment
Iron-based amorphous nanometer crystalline magnetic powder weight percent be 98~99.8% ingredients, by the micron order glass powder and through Vacuum Heat at
The iron-based amorphous nanometer crystalline magnetic powder of reason is uniformly mixed and obtains mixture；
(34) it is sintered
Gained mixture is sintered 2~4min in 450~600 DEG C, 100~900MPa discharge plasma to get amorphous is arrived
Nanocomposite powder core.
The preparation method of the third amorphous nano-crystalline composite magnetic powder core and the first amorphous nano-crystalline composite magnetic powder core
Preparation method the difference is that, glass phase is using the partial size obtained by rapid quenching method at 1~30 μm
LiBSiCaAl micron order glass powder, this method simple process, glass phase at low cost and preparing are with high purity, by itself and major ingredient
Iron-based amorphous nanometer crystalline magnetic powder mixes, in discharge plasma sintering inside micron order glass powder liquefaction filling powder core
Large scale hole simultaneously realizes part insulating wrapped magnetic powder, improves the compactness of powder core, so that improving magnetic conductivity reduces coercivity.
By Li in step (32)2O、B2O3、SiO2、CaO、Al2O3It is heated to 1110~1200 DEG C of 10~60min of heat preservation after mixing,
Then rapid quenching can quickly prepare the glass phase of purity is high in this way.What rapid quenching can be had disclosed using this field
Conventional means realize that the present invention is quenched using water-bath, put through directly taking out the reactant under high temperature from sintering furnace
Enter in deionized water.Quenching products therefrom obtains micron order glass through conventional wet ball grinding, drying, 100~200 meshes excessively
Powder.
When amorphous nano-crystalline composite magnetic powder core is by iron-based amorphous nanometer crystalline magnetic powder, micron order glass powder and organic binder group
The preparation method of Cheng Shi, the 4th kind of amorphous nano-crystalline composite magnetic powder core provided by the invention are prepared according to the following steps:
(41) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By iron-based amorphous nanometer crystalline magnetic powder under vacuum conditions in 300~400 DEG C of 1~1.5h of heat treatment；
(42) micron grain size glass is prepared
By Li2O、B2O3、SiO2、CaO、Al2O3It measures and is mixed according to molar ratio 52.45:31.06:11.99:2:2.5
It is heated to 1110~1200 DEG C of 10~60min of heat preservation after even, then rapid quenching, quenches products therefrom through ball milling, drying, sieving
Obtain micron order glass powder；
(43) ingredient and mixing
The micron order glass powder weight percent obtained by step (42) is 0.2~2%, step (41) through vacuum heat treatment
Iron-based amorphous nanometer crystalline magnetic powder weight percent be 96.5~99.3%, organic binder weight percent is 0.5~1.5%
The micron order glass powder is uniformly mixed to obtain third mixing with the iron-based amorphous nanometer crystalline magnetic powder through vacuum heat treatment by ingredient
Material, obtains the 4th mixture, the organic binder is by silicon after organic binder is uniformly mixed and is dried with third mixture
Ketone resin and ethyl orthosilicate 1:2 in mass ratio are formulated；
(44) it is sintered
By the 4th mixture obtained by step (43) in 450~600 DEG C, 100~900MPa discharge plasma sintering 2~
4min to get arrive amorphous nano-crystalline composite magnetic powder core.
The preparation method of 4th kind of amorphous nano-crystalline composite magnetic powder core and the third amorphous nano-crystalline composite magnetic powder core
Preparation method the difference is that, will be further uniformly mixed by silicone resin and ethyl orthosilicate 1:2 in mass ratio and obtained
Organic binder is added to by the mixing of the iron-based amorphous nanometer crystalline magnetic powder and LiBSiCaAl micron order glass powder of vacuum heat treatment
In material, then it is sintered to obtain amorphous nano-crystalline composite magnetic powder core through discharge plasma.Silicone resin and ethyl orthosilicate press quality
Heat resistanceheat resistant capacity of decomposition in discharge plasma sintering process can be made to be promoted than the organic binder that 1:2 is mixed to get, played good
Good thermosetting effect.
The amorphous nano-crystalline composite magnetic powder core obtained by above-mentioned four kinds of preparation methods, magnetic conductivity are up to 246, and Vickers is hard
Degree is about up to 7.6GPa, density about 6.8~7.3g/cm3, magnetic loss is down to 120W/m3(20mT, 1kHz), coercivity is down to 8A/
m；It can be seen that the consistency of the amorphous nano-crystalline composite magnetic powder core is greatly improved, to greatly improve powder core
Soft magnet performance and mechanical property.
Compared with prior art, the invention has the following advantages:
1, amorphous nano-crystalline composite magnetic powder core of the present invention, with Fe73.5Si13.5B9Nb3Cu amorphous nano-crystalline magnetic powder is major ingredient,
Using nanometer glass powder or micron order glass powder as glass phase, it is uniformly mixed with magnetic powder, the cause of powder core can be improved
Close property can increase the uniformity of magnetic powder insulating wrapped especially when using nanometer glass powder；When further containing in powder core
It is sintered in discharge plasma when the organic binder being formulated by silicone resin and ethyl orthosilicate 1:2 in mass ratio
Heat resistanceheat resistant capacity of decomposition is promoted in journey, plays the role of good thermosetting；
2, amorphous nano-crystalline composite magnetic powder core of the present invention, it is magnetic conductivity with higher, higher consistency, lower
Magnetic loss and lower coercivity, therefore the amorphous nano-crystalline composite magnetic powder core have very excellent soft magnetism and mechanical property
Can, it can be widely used for the manufacture of the equipment such as high power switching power supply, high-power inductance and high-efficiency energy-saving motor；
3, the preparation method of amorphous nano-crystalline composite magnetic powder core of the present invention, with iron-based amorphous nanometer crystalline magnetic powder, nanometer
Grade glass powder/micron order glass powder is primary raw material, is sintered by discharge plasma, and Transient liquid phase sintering may be implemented, mention
Height finally obtains the compactness of powder core, while crystal grain being inhibited further to grow up, thus help to improve the magnetic conductivity of powder core,
Its magnetic loss and coercivity are reduced, the comprehensive soft magnet performance and mechanical property for improving powder core makes suitable for promoting in the art
With；
4, the preparation method of amorphous nano-crystalline composite magnetic powder core of the present invention, with sol-gal process preparation
LiBSiCaAl nanometer glass powder is glass phase, and advantage, which specifically includes that, effectively realizes glass phase partial size from micron dimension to receiving
Rice magnitude transformation；It is more advantageous to the uniformity of magnetic powder insulating wrapped during the sintering process.
5, the preparation method of amorphous nano-crystalline composite magnetic powder core of the present invention, simple process, device therefor are conventional set
It is standby, it is convenient for industrialized production.
Detailed description of the invention
Fig. 1 is 13 gained amorphous nano-crystalline composite magnetic powder core scanning electron microscope (SEM) photograph of the embodiment of the present invention.
Specific embodiment
Clear, complete description is carried out below with reference to technical solution of the attached drawing to various embodiments of the present invention, it is clear that is retouched
Stating embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, originally
Field those of ordinary skill obtained all other embodiment without making creative work, belongs to this hair
Bright protected range.
Sintering furnace used in following embodiment is the discharge plasma sintering furnace of SPS-1050 model.
Examples 1 to 3
(11) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By Fe73.5Si13.5B9Nb3Cu iron-based amorphous nanometer crystalline magnetic powder is in 350 DEG C of vacuum heat treatment 1.5h, wherein vacuum degree
10-1It is more than Pa magnitude.
(12) nanometer glass powder is prepared
By ethyl orthosilicate, ethyl alcohol, nitric acid and acetic acid, 1:7:0.02:0.05 is mixed in molar ratio, and is acutely stirred in room temperature
About 0.5h is mixed to complete first mixed liquor of the prehydrolysis formation containing pre-hydrolysate of ethyl orthosilicate；By LiOHH2O is dissolved in
LiOH·H2The first solution is obtained in the nitric acid of the amount of twice of substance of O；By Ca (OH)2It is dissolved in Ca (OH)2The nitre of the amount of twice of substance
Acid obtains the second solution；By H3BO3It is dissolved in H3BO3The deionized water of the amount of twice of substance obtains third solution；By (Al
(NO3)3)·9H2O is dissolved in (Al (NO3)3)·9H2The deionized water of the amount of twice of substance of O, obtains the 4th solution；By above-mentioned first
Mixed liquor, the first solution, the second solution, third solution and the 4th solution are mixed and stirred for being formed uniformly the second mixed liquor, are used in combination
Aqueous ethanolamine adjusts the pH to 1.2 of the second mixed liquor of gained；Later in being aged 4h in 70 DEG C of water-baths, then at being stored at room temperature
Vitreosol is about formed for 24 hours, 80 DEG C of vitreosol drying is obtained into xerogel, gained xerogel is obtained through 450 DEG C of heat treatment 1h
Glass blank, it is to obtain nanometer glass powder that gained glass blank, which dries through ball milling, 80 DEG C, crosses 500 meshes,；The positive silicic acid second
Ester, Li+、Ca2+、H3BO3、Al3+Molar ratio be 104.9:11.99:2:62.12:5.
(13) ingredient and mixing
The nanometer glass powder and the iron-based amorphous nanometer crystalline magnetic of step (11) through vacuum heat treatment that step (12) is obtained
Powder using dehydrated alcohol as ball-milling medium, and leads to 5min nitrogen into ball grinder in being put into ball milling filling after ratio ingredient described in table 1
Gas, ball milling 3h later, then the taking-up of ball milling material is put into 110 DEG C of vacuum drying oven drying to get to mixture.
(14) it is sintered
Gained mixture is in discharge plasma sintering furnace, through 525 DEG C of sintered heat insulating 3min under 500Mpa pressure, i.e.,
Obtain amorphous nano-crystalline composite magnetic powder core.
1 amorphous nano-crystalline composite magnetic powder core component ratio (by weight percentage) of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Iron-based amorphous nanometer crystalline magnetic powder | 99.70% | 99.40% | 99.10% |
| Nanometer glass powder | 0.30% | 0.60% | 0.90% |
Embodiment 4
(11) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By Fe73.5Si13.5B9Nb3Cu iron-based amorphous nanometer crystalline magnetic powder is in 400 DEG C of vacuum heat treatment 1h, and wherein vacuum degree exists
10-1It is more than Pa magnitude.
(12) nanometer glass powder is prepared
By ethyl orthosilicate, ethyl alcohol, nitric acid and acetic acid, 1:7:0.02:0.05 is mixed in molar ratio, and is acutely stirred in room temperature
About 0.5h is mixed to complete first mixed liquor of the prehydrolysis formation containing pre-hydrolysate of ethyl orthosilicate；By LiOHH2O is dissolved in
LiOH·H2The first solution is obtained in the nitric acid of the amount of twice of substance of O；By Ca (OH)2It is dissolved in Ca (OH)2The nitre of the amount of twice of substance
Acid obtains the second solution；By H3BO3It is dissolved in H3BO3The deionized water of the amount of twice of substance obtains third solution；By (Al
(NO3)3)·9H2O is dissolved in (Al (NO3)3)·9H2The deionized water of the amount of twice of substance of O, obtains the 4th solution；By above-mentioned first
Mixed liquor, the first solution, the second solution, third solution and the 4th solution are mixed and stirred for being formed uniformly the second mixed liquor, are used in combination
Ammonium hydroxide adjusts the pH to 0.5 of the second mixed liquor of gained；Later in being aged 5h in 60 DEG C of water-baths, then at being stored at room temperature about shape for 24 hours
At vitreosol, 70 DEG C of vitreosol drying are obtained into xerogel, gained xerogel obtains glass billet through 400 DEG C of heat treatment 3h
Material, it is to obtain nanometer glass powder that gained glass blank, which dries through ball milling, 80 DEG C, crosses 500 meshes,；The ethyl orthosilicate, Li+、Ca2+、H3BO3、Al3+Molar ratio be 104.9:11.99:2:62.12:5.
(13) ingredient and mixing
By weight percentage, the nanometer glass powder 0.20% that step (12) is obtained and step (11) through Vacuum Heat at
It is put into after 99.80% ingredient of iron-based amorphous nanometer crystalline magnetic powder of reason during ball milling fills, using dehydrated alcohol as ball-milling medium, and to ball
Lead to 10min nitrogen in grinding jar, later ball milling 2h, then the taking-up of ball milling material is put into 110 DEG C of vacuum drying oven drying to get mixing is arrived
Material.
(14) it is sintered
Gained mixture is in discharge plasma sintering furnace, through 600 DEG C of sintered heat insulating 4min under 100Mpa pressure, i.e.,
Obtain amorphous nano-crystalline composite magnetic powder core.
Embodiment 5
(11) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By Fe73.5Si13.5B9Nb3Cu iron-based amorphous nanometer crystalline magnetic powder is in 300 DEG C of vacuum heat treatment 1.5h, wherein vacuum degree
10-1It is more than Pa magnitude.
(12) nanometer glass powder is prepared
By ethyl orthosilicate, ethyl alcohol, nitric acid and acetic acid, 1:7:0.02:0.05 is mixed in molar ratio, and is acutely stirred in room temperature
About 0.5h is mixed to complete first mixed liquor of the prehydrolysis formation containing pre-hydrolysate of ethyl orthosilicate；By LiOHH2O is dissolved in
LiOH·H2The first solution is obtained in the nitric acid of the amount of twice of substance of O；By Ca (OH)2It is dissolved in Ca (OH)2The nitre of the amount of twice of substance
Acid obtains the second solution；By H3BO3It is dissolved in H3BO3The deionized water of the amount of twice of substance obtains third solution；By (Al
(NO3)3)·9H2O is dissolved in (Al (NO3)3)·9H2The deionized water of the amount of twice of substance of O, obtains the 4th solution；By above-mentioned first
Mixed liquor, the first solution, the second solution, third solution and the 4th solution are mixed and stirred for being formed uniformly the second mixed liquor, are used in combination
Ammonium hydroxide adjusts the pH to 2 of the second mixed liquor of gained；Later in being aged 3h in 80 DEG C of water-baths, about formed for 24 hours then at being stored at room temperature
70 DEG C of vitreosol drying are obtained xerogel by vitreosol, and gained xerogel obtains glass blank through 650 DEG C of heat treatment 1h,
It is to obtain nanometer glass powder that gained glass blank, which dries through ball milling, 80 DEG C, crosses 500 meshes,；The ethyl orthosilicate, Li+、Ca2 +、H3BO3、Al3+Molar ratio be 104.9:11.99:2:62.12:5.
(13) ingredient and mixing
By weight percentage, the nanometer glass powder 2.0% that step (12) is obtained and step (11) through Vacuum Heat at
It is put into after 98.0% ingredient of iron-based amorphous nanometer crystalline magnetic powder of reason during ball milling fills, using dehydrated alcohol as ball-milling medium, and to ball
Lead to 5min nitrogen in grinding jar, later ball milling 4h, then the taking-up of ball milling material is put into 110 DEG C of vacuum drying oven drying to get mixing is arrived
Material.
(14) it is sintered
Gained mixture is in discharge plasma sintering furnace, through 450 DEG C of sintered heat insulating 2min under 900Mpa pressure, i.e.,
Obtain amorphous nano-crystalline composite magnetic powder core.
Embodiment 6~8
(31) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By Fe73.5Si13.5B9Nb3Cu iron-based amorphous nanometer crystalline magnetic powder is in 350 DEG C of vacuum heat treatment 1.5h, wherein vacuum degree
10-1It is more than Pa magnitude；
(32) micron order glass powder is prepared
By Li2O、B2O3、SiO2、CaO、Al2O3According to molar ratio 52.45:31.06:11.99:2:2.5 ingredient, and use
Wet ball grinding is uniformly mixed, and is dried after taking-up in 100 DEG C, is crossed 120 meshes；Powder after sieving is heated to 1150 DEG C of heat preservations about
Then 30min directly takes out in 1150 DEG C and is put into rapid quenching in deionized water, quenching products therefrom through ball milling, 80 DEG C drying,
It crosses 200 meshes and obtains micron order glass powder.
(33) ingredient and mixing
The micron order glass powder and the iron-based amorphous nanometer crystalline magnetic of step (31) through vacuum heat treatment that step (32) is obtained
Powder is put into ball milling filling in ratio described in table 2, using dehydrated alcohol as ball-milling medium, and leads to 5min nitrogen into ball grinder, it
Ball milling 3h afterwards, then the taking-up of ball milling material is put into 100 DEG C of vacuum drying oven drying to get mixture is arrived.
(34) it is sintered
Gained mixture is in discharge plasma sintering furnace, through 525 DEG C of sintered heat insulating 3min under 500Mpa pressure, i.e.,
Obtain amorphous nano-crystalline composite magnetic powder core.
2 amorphous nano-crystalline composite magnetic powder core component ratio (by weight percentage) of table
| Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Iron-based amorphous nanometer crystalline magnetic powder | 99.70% | 99.40% | 99.10% |
| Micron order glass powder | 0.30% | 0.60% | 0.90% |
Embodiment 9
(31) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By Fe73.5Si13.5B9Nb3Cu iron-based amorphous nanometer crystalline magnetic powder is in 400 DEG C of vacuum heat treatment 1h, and wherein vacuum degree exists
10-1It is more than Pa magnitude；
(32) micron order glass powder is prepared
By Li2O、B2O3、SiO2、CaO、Al2O3According to molar ratio 52.45:31.06:11.99:2:2.5 ingredient, and use
Wet ball grinding is uniformly mixed, and is dried after taking-up in 120 DEG C, is crossed 120 meshes；Powder after sieving is heated to 1110 DEG C of heat preservations about
Then 10min directly takes out in 1110 DEG C and is put into rapid quenching in deionized water, quenching products therefrom through ball milling, 80 DEG C drying,
It crosses 200 meshes and obtains micron order glass powder.
(33) ingredient and mixing
By weight percentage, the micron order glass powder 0.20% that step (32) is obtained and step (31) through Vacuum Heat at
It is put into after 99.80% ingredient of iron-based amorphous nanometer crystalline magnetic powder of reason during ball milling fills, using dehydrated alcohol as ball-milling medium, and to ball
Lead to 10min nitrogen in grinding jar, later ball milling 2h, then the taking-up of ball milling material is put into 120 DEG C of vacuum drying oven drying to get mixing is arrived
Material.
(34) gained mixture is in discharge plasma sintering furnace, through 500 DEG C of sintered heat insulatings under 600MPa pressure
3min to get arrive amorphous nano-crystalline composite magnetic powder core.
Embodiment 10
(31) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By Fe73.5Si13.5B9Nb3Cu iron-based amorphous nanometer crystalline magnetic powder is in 300 DEG C of vacuum heat treatment 1.5h, wherein vacuum degree
10-1It is more than Pa magnitude；
(32) micron order glass powder is prepared
By Li2O、B2O3、SiO2、CaO、Al2O3According to molar ratio 52.45:31.06:11.99:2:2.5 ingredient, and use
Wet ball grinding is uniformly mixed, and is dried after taking-up in 110 DEG C, is crossed 120 meshes；Powder after sieving is heated to 1200 DEG C of heat preservations about
Then 60min directly takes out in 1200 DEG C and is put into rapid quenching in deionized water, quenching products therefrom through ball milling, 80 DEG C drying,
It crosses 200 meshes and obtains micron order glass powder.
(33) ingredient and mixing
By weight percentage, the micron order glass powder 2.0% that step (32) is obtained and step (31) through Vacuum Heat at
It is put into after 98.0% ingredient of iron-based amorphous nanometer crystalline magnetic powder of reason during ball milling fills, using dehydrated alcohol as ball-milling medium, and to ball
Lead to 5min nitrogen in grinding jar, later ball milling 2h, then the taking-up of ball milling material is put into 110 DEG C of vacuum drying oven drying to get mixing is arrived
Material.
(34) it is sintered
Gained mixture is in discharge plasma sintering furnace, through 550 DEG C of sintered heat insulating 4min under 400MPa pressure, i.e.,
Obtain amorphous nano-crystalline composite magnetic powder core.
Embodiment 11~15
(21) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By Fe73.5Si13.5B9Nb3Cu iron-based amorphous nanometer crystalline magnetic powder is in 350 DEG C of vacuum heat treatment 1.5h, wherein vacuum degree
10-1It is more than Pa magnitude.
(22) nanometer glass powder is prepared
By ethyl orthosilicate, ethyl alcohol, nitric acid and acetic acid, 1:7:0.02:0.05 is mixed in molar ratio, and is acutely stirred in room temperature
About 0.5h is mixed to complete first mixed liquor of the prehydrolysis formation containing pre-hydrolysate of ethyl orthosilicate；By LiOHH2O is dissolved in
LiOH·H2The first solution is obtained in the nitric acid of the amount of twice of substance of O；By Ca (OH)2It is dissolved in Ca (OH)2The nitre of the amount of twice of substance
Acid obtains the second solution；By H3BO3It is dissolved in H3BO3The deionized water of the amount of twice of substance obtains third solution；By (Al
(NO3)3)·9H2O is dissolved in (Al (NO3)3)·9H2The deionized water of the amount of twice of substance of O, obtains the 4th solution；By above-mentioned first
Mixed liquor, the first solution, the second solution, third solution and the 4th solution are mixed and stirred for being formed uniformly the second mixed liquor, are used in combination
Aqueous ethanolamine adjusts the pH to 1.2 of the second mixed liquor of gained；Later in being aged 4h in 70 DEG C of water-baths, then at being stored at room temperature
Vitreosol is about formed for 24 hours, 80 DEG C of vitreosol drying is obtained into xerogel, gained xerogel is obtained through 450 DEG C of heat treatment 1h
Glass blank, it is to obtain nanometer glass powder that gained glass blank, which dries through ball milling, 80 DEG C, crosses 500 meshes,；The positive silicic acid second
Ester, Li+、Ca2+、H3BO3、Al3+Molar ratio be 104.9:11.99:2:62.12:5.
(23) ingredient and mixing
The nanometer glass powder and the iron-based amorphous nanometer crystalline magnetic of step (21) through vacuum heat treatment that step (22) is obtained
Powder using dehydrated alcohol as ball-milling medium, and leads to 5min nitrogen into ball grinder in being put into ball milling filling after ratio ingredient described in table 3
Gas, ball milling 3h later, then the taking-up of ball milling material is put into 110 DEG C of vacuum drying oven drying to get to the first mixture；It will be organic viscous
Knot agent is uniformly mixed with the first mixture and obtains the second mixture after 110 DEG C of vacuum drying oven drying；The organic binder
It is formulated by silicone resin and ethyl orthosilicate 1:2 in mass ratio；
(24) it is sintered
The second mixture of gained is in discharge plasma sintering furnace, through 525 DEG C of sintered heat insulatings under 500MPa pressure
3min to get arrive amorphous nano-crystalline composite magnetic powder core.
3 amorphous nano-crystalline composite magnetic powder core component ratio (by weight percentage) of table
| Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | |
| Iron-based amorphous nanometer crystalline magnetic powder | 99.3% | 98.70% | 98.41% | 98.11% | 96.5% |
| Nanometer glass powder | 0.2% | 0.30% | 0.59% | 0.89% | 2% |
| Organic binder | 0.5% | 1% | 1% | 1% | 1.5% |
Embodiment 16~20
(41) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By Fe73.5Si13.5B9Nb3Cu iron-based amorphous nanometer crystalline magnetic powder is in 350 DEG C of vacuum heat treatment 1.5h, wherein vacuum degree
10-1It is more than Pa magnitude；
(42) micron order glass powder is prepared
By Li2O、B2O3、SiO2、CaO、Al2O3According to molar ratio 52.45:31.06:11.99:2:2.5 ingredient, and use
Wet ball grinding is uniformly mixed, and is dried after taking-up in 110 DEG C, is crossed 120 meshes；Powder after sieving is heated to 1150 DEG C of heat preservations about
Then 30min directly takes out in 1150 DEG C and is put into rapid quenching in deionized water, quenching products therefrom through ball milling, 80 DEG C drying,
It crosses 200 meshes and obtains micron order glass powder.
(43) ingredient and mixing
The micron order glass powder and the iron-based amorphous nanometer crystalline magnetic of step (41) through vacuum heat treatment that step (42) is obtained
Powder using dehydrated alcohol as ball-milling medium, and leads to 5min nitrogen into ball grinder in being put into ball milling filling after ratio ingredient described in table 4
Gas, ball milling 3h later, then the taking-up of ball milling material is put into 110 DEG C of vacuum drying oven drying to get to third mixture；It will be organic viscous
Knot agent is uniformly mixed with third mixture and obtains the 4th mixture after 110 DEG C of vacuum drying oven drying；The organic binder
It is formulated by silicone resin and ethyl orthosilicate 1:2 in mass ratio；
(44) it is sintered
The 4th mixture of gained is in discharge plasma sintering furnace, through 525 DEG C of sintered heat insulatings under 500MPa pressure
3min to get arrive amorphous nano-crystalline composite magnetic powder core.
4 amorphous nano-crystalline composite magnetic powder core component ratio (by weight percentage) of table
| Embodiment 16 | Embodiment 17 | Embodiment 18 | Embodiment 19 | Embodiment 20 | |
| Iron-based amorphous nanometer crystalline magnetic powder | 99.3% | 98.70% | 98.41% | 98.11% | 96.5% |
| Micron order glass powder | 0.2% | 0.30% | 0.59% | 0.89% | 2% |
| Organic binder | 0.5% | 1% | 1% | 1% | 1.5% |
Pattern, soft magnetism and mechanical property point are carried out to the amorphous nano-crystalline composite magnetic powder core of above-mentioned section Example preparation
Analysis:
Electron microscope analysis is scanned to the amorphous nano-crystalline composite magnetic powder core that embodiment 13 is prepared, as a result such as Fig. 1 institute
Show, it can be seen from the figure that the amorphous nano-crystalline composite magnetic powder core compact structure being prepared by the method for the invention, while magnetic
Powder is uniformly coated by nanometer glass powder, so that magnetic conductivity and mechanical strength greatly improved, while be greatly reduced magnetic loss with
Coercivity.
Soft magnetism and mechanics property analysis are carried out to embodiment 1-3,6-8,12-14,17-19, analysis the results are shown in Table 5.
Table 5 analyzes result
As can be seen from Table 5, the amorphous nano-crystalline composite magnetic powder core that preparation method obtains through the invention generally has
Higher magnetic conductivity, higher consistency, lower coercivity and lower magnetic loss, therefore the amorphous nano-crystalline composite magnetic powder
Core has excellent soft magnet performance and mechanical property.Especially when glass phase is nanometer glass powder, it is exhausted that magnetic powder can be improved
The uniformity of edge cladding, while finally obtained powder core is improved by Transient liquid phase sintering in discharge plasma sintering
Compactness, to further improve the soft magnet performance and mechanical property of powder core.And it is pressed by silicone resin and ethyl orthosilicate
The addition of the organic binder of mass ratio 1:2 composition, heat resistanceheat resistant capacity of decomposition is promoted during the sintering process, is played good thermosetting and is made
With.Therefore, the amorphous nano being prepared as a raw material by iron-based amorphous nanometer crystalline magnetic powder, nanometer particle size glass and organic binder
The soft magnet performance and mechanical property of brilliant composite magnetic powder core are best.
Claims (10)
1. a kind of amorphous nano-crystalline composite magnetic powder core, it is characterised in that the raw material components of the composite magnetic powder core and the weight of each component
Percentage is as follows:
Iron-based amorphous nanometer crystalline magnetic powder 98~99.8%,
Glass phase 0.2~2%；
It will be uniformly mixed to form mixture with glass phase after the heat treatment of iron-based amorphous nanometer crystalline magnetic powder vacuum, mixture is used and is put
Electro-plasma is sintered to obtain；
Or the raw material components of the composite magnetic powder core and the weight percent of each component it is as follows:
Iron-based amorphous nanometer crystalline magnetic powder 96.5~99.3%,
Glass phase 0.2~2%,
Organic binder 0.5~1.5%；
It will be uniformly mixed again with organic binder after mixing after the heat treatment of iron-based amorphous nanometer crystalline magnetic powder vacuum with glass phase
And mixture is formed after drying, mixture is sintered to obtain using discharge plasma；
The glass phase is nanometer glass powder or micron order glass powder.
2. amorphous nano-crystalline composite magnetic powder core according to claim 1, it is characterised in that the iron-based amorphous nanometer crystalline magnetic powder
For Fe73.5Si13.5B9Nb3Cu amorphous nano-crystalline magnetic powder.
3. amorphous nano-crystalline composite magnetic powder core according to claim 1 or claim 2, it is characterised in that the grain of the nanometer glass powder
Diameter is 50~300nm；The partial size of the micron order glass powder is 1~30 μm.
4. amorphous nano-crystalline composite magnetic powder core according to claim 1 or claim 2, it is characterised in that the organic binder is by silicone
Resin and ethyl orthosilicate 1:2 in mass ratio are formulated.
5. a kind of preparation method of amorphous nano-crystalline composite magnetic powder core, it is characterised in that be prepared according to the following steps:
(11) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By iron-based amorphous nanometer crystalline magnetic powder under vacuum conditions in 300~400 DEG C of 1~1.5h of heat treatment；
(12) nanometer glass powder is prepared
Ethyl orthosilicate, ethyl alcohol, nitric acid and acetic acid are mixed, is stirred at room temperature to the complete prehydrolysis of ethyl orthosilicate and is formed containing pre-
First mixed liquor of hydrolysate；By the first mixed liquor containing pre-hydrolysate and contain Li+Nitric acid solution, contain Ca2+Nitric acid
Solution, H3BO3Aqueous solution contains Al3+Aqueous solution be uniformly mixed and form the second mixed liquor, adjusted with aqueous ethanolamine or ammonium hydroxide
The pH to 0.5~2 of the second mixed liquor of gained, it is transparent molten to being formed then at being stored at room temperature later in 60~80 DEG C of 3~5h of ageing
Vitreosol is dried to obtain xerogel by glue, gained xerogel is obtained glass blank through 400~650 DEG C of 1~3h of heat treatment, institute
It obtains glass blank and obtains nanometer glass powder through ball milling, drying, sieving；The ethyl orthosilicate, Li+、Ca2+、H3BO3、Al3+
Molar ratio be 104.9:11.99:2:62.12:5；
(13) ingredient and mixing
It is 0.2~2%, the iron of step (11) through vacuum heat treatment by the nanometer glass powder weight percent that step (12) obtains
Based amorphous nano magnetic powder weight percent is 98~99.8% ingredients, by the nanometer glass powder and through vacuum heat treatment
Iron-based amorphous nanometer crystalline magnetic powder is uniformly mixed and obtains mixture；
(14) it is sintered
By mixture obtained by step (13) in 450~600 DEG C, 100~900MPa discharge plasma be sintered 2~4min to get
To amorphous nano-crystalline composite magnetic powder core.
6. a kind of preparation method of amorphous nano-crystalline composite magnetic powder core, it is characterised in that be prepared according to the following steps:
(21) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By iron-based amorphous nanometer crystalline magnetic powder under vacuum conditions in 300~400 DEG C of 1~1.5h of heat treatment；
(22) nanometer glass powder is prepared
Ethyl orthosilicate, ethyl alcohol, nitric acid and acetic acid are mixed, is stirred at room temperature to the complete prehydrolysis of ethyl orthosilicate and is formed containing pre-
First mixed liquor of hydrolysate；By the first mixed liquor containing pre-hydrolysate and contain Li+Nitric acid solution, contain Ca2+Nitric acid
Solution, H3BO3Aqueous solution contains Al3+Aqueous solution be uniformly mixed and form the second mixed liquor, adjusted with aqueous ethanolamine or ammonium hydroxide
The pH to 0.5~2 of the second mixed liquor of gained, it is transparent molten to being formed then at being stored at room temperature later in 60~80 DEG C of 3~5h of ageing
Vitreosol is dried to obtain xerogel by glue, gained xerogel is obtained glass blank through 400~650 DEG C of 1~3h of heat treatment, institute
It obtains glass blank and obtains nanometer glass powder through ball milling, drying, sieving；The ethyl orthosilicate, Li+、Ca2+、H3BO3、Al3+
Molar ratio be 104.9:11.99:2:62.12:5；
(23) ingredient and mixing
It is 0.2~2%, the iron of step (21) through vacuum heat treatment by the nanometer glass powder weight percent that step (22) obtains
Based amorphous nano magnetic powder weight percent is 96.5~99.3%, organic binder weight percent is 0.5~1.5% to match
Material, the nanometer glass powder is uniformly mixed to obtain the first mixing with the iron-based amorphous nanometer crystalline magnetic powder through vacuum heat treatment
Material, obtains the second mixture, the organic binder is by silicon after organic binder is uniformly mixed and is dried with the first mixture
Ketone resin and ethyl orthosilicate 1:2 in mass ratio are formulated；
(24) it is sintered
Second mixture obtained by step (23) is sintered 2~4min in 450~600 DEG C, 100~900MPa discharge plasma,
Obtain amorphous nano-crystalline composite magnetic powder core.
7. according to the preparation method of the amorphous nano-crystalline powder core of claim 5 or 6, it is characterised in that described to contain Li+Nitric acid
Solution is by LiNO3It is dissolved in deionized water or by LiOH or LiOHH2O, which is dissolved in nitric acid, to be obtained, described to contain Ca2+Nitric acid
Solution is by Ca (NO3)2It is dissolved in deionized water or by Ca (OH)2It is dissolved in nitric acid and obtaining, the H3BO3Aqueous solution be by
H3BO3It is soluble in water to obtain, it is described to contain Al3+Aqueous solution be by Al (NO3)3Or (Al (NO3)3)·9H2O is dissolved in deionized water
In or by Al (OH)3It is dissolved in nitric acid and obtaining.
8. a kind of preparation method of amorphous nano-crystalline composite magnetic powder core, it is characterised in that be prepared according to the following steps:
(31) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By iron-based amorphous nanometer crystalline magnetic powder under vacuum conditions in 300~400 DEG C of 1~1.5h of heat treatment；
(32) micron order glass powder is prepared
By Li2O、B2O3、SiO2、CaO、Al2O3According to molar ratio 52.45:31.06:11.99:2:2.5 metering and after mixing
Be heated to 1110~1200 DEG C of 10~60min of heat preservation, then rapid quenching, quench products therefrom through ball milling, drying, be sieved to obtain the final product
To micron order glass powder；
(33) ingredient and mixing
It is 0.2~2%, the iron of step (31) through vacuum heat treatment by the micron order glass powder weight percent that step (32) obtains
Based amorphous nano magnetic powder weight percent is 98~99.8% ingredients, by the micron order glass powder and through vacuum heat treatment
Iron-based amorphous nanometer crystalline magnetic powder is uniformly mixed and obtains mixture；
(34) it is sintered
Gained mixture is sintered 2~4min in 450~600 DEG C, 100~900MPa discharge plasma to get amorphous nano is arrived
Brilliant composite magnetic powder core.
9. a kind of preparation method of amorphous nano-crystalline composite magnetic powder core, it is characterised in that be prepared according to the following steps:
(41) heat treatment of iron-based amorphous nanometer crystalline magnetic powder
By iron-based amorphous nanometer crystalline magnetic powder under vacuum conditions in 300~400 DEG C of 1~1.5h of heat treatment；
(42) micron grain size glass is prepared
By Li2O、B2O3、SiO2、CaO、Al2O3According to molar ratio 52.45:31.06:11.99:2:2.5 metering and after mixing
Be heated to 1110~1200 DEG C of 10~60min of heat preservation, then rapid quenching, quench products therefrom through ball milling, drying, be sieved to obtain the final product
To micron order glass powder；
(43) ingredient and mixing
It is 0.2~2%, the iron of step (41) through vacuum heat treatment by the micron order glass powder weight percent that step (42) obtains
Based amorphous nano magnetic powder weight percent is 96.5~99.3%, organic binder weight percent is 0.5~1.5% to match
The micron order glass powder is uniformly mixed to obtain third mixing with the iron-based amorphous nanometer crystalline magnetic powder through vacuum heat treatment by material
Material, obtains the 4th mixture, the organic binder is by silicon after organic binder is uniformly mixed and is dried with third mixture
Ketone resin and ethyl orthosilicate 1:2 in mass ratio are formulated；
(44) it is sintered
4th mixture obtained by step (43) is sintered 2~4min in 450~600 DEG C, 100~900MPa discharge plasma,
Obtain amorphous nano-crystalline composite magnetic powder core.
10. according to claim 5,6,8 or the preparation method of the 9 amorphous nano-crystalline composite magnetic powder cores, it is characterised in that described
Iron-based amorphous nanometer crystalline magnetic powder is Fe73.5Si13.5B9Nb3Cu amorphous nano-crystalline magnetic powder.
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| CN110838398A (en) * | 2019-11-15 | 2020-02-25 | 安徽大学 | Composite soft magnetic material and preparation method thereof |
| CN112359211A (en) * | 2020-11-16 | 2021-02-12 | 江苏集萃安泰创明先进能源材料研究院有限公司 | Method for recycling waste amorphous nanocrystalline iron core and amorphous nanocrystalline powder core |
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