CN102360665A - Soft magnetic composite material of glass insulating layer and preparation method thereof - Google Patents
Soft magnetic composite material of glass insulating layer and preparation method thereof Download PDFInfo
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Abstract
A soft magnetic composite material of a glass insulating layer and a preparation method thereof relate to a soft magnetic composite material and a preparation method thereof. The soft magnetic composite material of the glass insulating layer and the preparation method thereof disclosed by the invention solve technical problems that high-temperature annealing cannot be performed on existing soft magnetic composite materials to remove residual stress generated in the preparation process and to further improve magnetic performance of the soft magnetic composite material and magnetic performance cannot be kept steady all the time when the material emits heat in an environment with a great temperature difference or in long-term use process. The soft magnetic composite material of the glass insulating layer disclosed by the invention is formed by depositing amorphous substances on magnetic powder and then annealing after cold-pressing or hot-pressing. The soft magnetic composite material disclosed by the invention has an initial magnetic conductivity up to 200 or more, a maximum magnetic conductivity up to 900 or more, a saturated magnetization intensity up to 1.5 T, and a coercive force less than 250 A/m; and iron loss at 50 Hz and 1 T alternating current magnetic field can be less than 3 W/Kg.
Description
Technical field
The present invention relates to soft-magnetic composite material and preparation method thereof.
Background technology
Soft-magnetic composite material is meant between magnetic one type of soft magnetic material independent mutually and that couple together through insulating layer material.The outstanding advantage of this soft-magnetic composite material is to have low iron loss and three-dimensional isotropic nature under the AC magnetic field.Therefore can prepare the parts that a lot of conventional soft magnetic materials are difficult to realize, be applied in switching magnetic-resistance, resonant inductance, anti-lock brake sensor, electromagnetic actuator device, brshless DC motor, rotating machinery, fields such as low-frequency filter.If can the magnetic property of present soft-magnetic composite material further be improved, obtain bigger application prospect and create bigger economic benefit helping it.
The preparation technology of soft-magnetic composite material is normally to metal or alloy Magnaglo surface coated inorganic thing and organic insulating barrier; Or adopt Magnaglo matrix-high resistivity continuous fiber complex method to form the composite soft-magnetic powder, adopt the powder metallurgy compaction process to be prepared into closely knit block soft magnetic material then.According in the market with scientific research field in the research situation, the coating layer composition of soft-magnetic composite material roughly can be three types, (1) organic substance coating layer; (2) inorganic matter coating layer; (3) coating layer of organic substance and inorganic matter mixing.The heat resisting temperature of organic substance insulating barrier is low, and temperature stability is poor, and the soft-magnetic composite material of organic coating is not suitable for hot conditions.In addition; The soft-magnetic composite material that contains the organic substance coating layer in the preparation process, often impose severe pressure (being not less than 800MPa usually); This is in order to obtain bigger compacted density; It is very big that but the drawback of bringing is exactly the residual stress of material, so generally its saturation induction density and magnetic permeability are not high.Removing the most effective way of internal stress is that soft magnetic material is annealed, yet because the common non-refractory of organic substance, so be difficult to effectively remove its residual stress.The inorganic matter coating layer of soft-magnetic composite material generally adopts chemical method to realize, mostly coating is to contain the metallic compound of P or S, and the insulating properties of coating layer is undesirable, and it is serious to contain the coating layer environmental pollution of P or S.At present, there is the soft-magnetic composite material of a lot of inorganic coating layers to occur again, the inorganic insulation layer that mixes like coated Si O2, MgO or even SiO2, Al2O3, ZrO2, mica powder and water etc.Inorganic insulation layer generally has high-temperature stable, can high annealing to remove advantage such as residual stress.But present inorganic insulation layer also has shortcoming, and is bad like the associativity of iron and inorganic insulation layer, and the mechanical property of soft-magnetic composite material is relatively poor.The thermal coefficient of expansion of inorganic insulation layer and iron differs bigger, can in iron, produce internal stress when under high temperature or alternating temperature condition, using, and then its saturation induction density and magnetic permeability are descended, and the magnetic property of material has than great fluctuation process with temperature.These situation are all restricting the application of soft-magnetic composite material.
Consider the needs of soft-magnetic composite material in practical application; Improve the compacted density and the density of material; And effectively remove the residual stress in the preparation process; And can the bigger environment of the temperature difference or in long-time use because of the material adstante febre remains the stable of magnetic property, these are key technical problems that present soft-magnetic composite material need solve.
Summary of the invention
The present invention will solve existing soft-magnetic composite material can't carry out high annealing to remove the residual stress that the preparation process produces; And then can't improve the soft-magnetic composite material magnetic property; In addition can't the bigger environment of the temperature difference or in long-time use because of the material adstante febre remains the stable technical problem of magnetic property, developed a kind of with glass as soft-magnetic composite material of insulating barrier and preparation method thereof.This soft-magnetic composite material designability is strong, and is controlled like thickness of insulating layer, and thermal coefficient of expansion and softening point are adjustable, and can at high temperature anneal, to improve the magnetic property of soft-magnetic composite material.
Among the present invention the soft-magnetic composite material of glass dielectric layer is a deposited amorphous attitude material on magnetic, cold pressing then or hot-pressing processing after process through annealing in process; Amorphous substance is divided into two retes, is made up of the hydrolysate of alkoxide near the rete of magnetic, and another rete is made up of the mixture of the hydrolysate of the hydrolysate of alkoxide or alkoxide and inorganic salts, and said alkoxide is metal alkoxide or semimetal alkoxide.
The preparation method of the soft-magnetic composite material of glass dielectric layer is undertaken by following step among the present invention:
Step 1, magnetic, coupling agent and organic solvent mixed obtain mixture A, coupling agent and the magnetic mass fraction in mixture A is 0.01%～3%, and the volume ratio of organic solvent and magnetic is greater than 100; Stir with 120～300r/min speed under the room temperature; Add entry, the mass ratio of water and coupling agent is 1: 1～20, continues to stir 20～30min; Obtain mixture B, said water is deionized water or distilled water;
Step 3, the mixture of alkoxide or alkoxide and inorganic salts is dissolved in the solution B that is mixed with in the solvent (can dissolve the organic solvent of coupling agent, alkoxide and inorganic salts); In the solution B concentration of alkoxide less than used alkoxide in organic solvent saturation 1/10th; The mol ratio of inorganic salts and alkoxide is not more than 2, then solution B is added in the mixture C, under 60 ℃ of temperature, continues to stir 5～20min with 120～300r/min speed; Splash into acidic aqueous solution or alkaline aqueous solution with 0.5～1.5mL/min speed then; The dropping time is 8min, obtains mixture D, and said alkoxide is metal alkoxide and/or semimetal alkoxide;
The present invention adopts the glass gel as the Magnaglo that insulating barrier coats, and can or cold pressing the preparation soft-magnetic composite material through the high temperature hot pressed sintering.Owing to adopt unorganic glass as coating layer, therefore can under higher temperature, anneal with the soft-magnetic composite material of this Magnaglo preparation, make soft-magnetic composite material have the excellent magnetism ability.The initial permeability of soft-magnetic composite material can reach more than 200 among the present invention, and maximum permeability can reach more than 900, and saturation induction density can reach 1.5T, and coercive force is less than 250A/m, and the iron loss under the AC magnetic field of 50Hz, 1T can be less than 3W/Kg.Material can experience high temperature in preparation or annealing process; Therefore iron powder and coating layer to combine no longer be simple mechanical bond; But combination with certain intensity; Therefore the mechanical property of material also improves a lot, and this provides wide space for the application of soft-magnetic composite material in bigger field.
Description of drawings
Fig. 1 is the SEM photo of iron powder; Fig. 2 is that the soft-magnetic composite material multiplication factor of the glass dielectric layer of test one method preparation is 500 times a SEM photo; Fig. 3 is the SEM photo of soft-magnetic composite material of the glass dielectric layer of test one method preparation; Fig. 4 is a ferro element distribution photo, and Fig. 5 is a sodium element distribution photo; Fig. 6 is an element silicon distribution photo; Fig. 7 is the SEM photo at interface of glass coating layer and iron powder of the soft-magnetic composite material of test one preparation glass dielectric layer; Fig. 8 is the amorphous diffraction ring of glass coating layer of the soft-magnetic composite material of test one preparation glass dielectric layer; Fig. 9 is a metallograph horizontal when testing a hot pressing; Figure 10 is test metallograph longitudinally during one hot pressing; Figure 11 is iron loss figure under the soft-magnetic composite material different frequency of glass dielectric layer of test one method preparation, before ■ representes annealing among Figure 11, ● after the expression annealing; Figure 11 is iron loss figure under the soft-magnetic composite material different frequency of glass dielectric layer of test two methods preparation, before ■ representes annealing among Figure 12, ● after the expression annealing; Figure 13 is iron loss figure under the soft-magnetic composite material different frequency of glass dielectric layer of the tripartite method of test preparation, before ■ representes annealing among Figure 13, ● after the expression annealing; Figure 14 is iron loss figure under the soft-magnetic composite material different frequency of glass dielectric layer of the cubic method of test preparation, before ■ representes annealing among Figure 14, ● after the expression annealing.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: the soft-magnetic composite material of glass dielectric layer is a deposited amorphous attitude material on magnetic in this execution mode, cold pressing then or hot-pressing processing after process through annealing in process; Amorphous substance is divided into two retes, is made up of the hydrolysate of alkoxide near the rete of magnetic, and another rete is made up of the mixture of the hydrolysate of the hydrolysate of alkoxide or alkoxide and inorganic salts, and said alkoxide is metal alkoxide or semimetal alkoxide.
The initial permeability of soft-magnetic composite material can reach more than 200, and maximum permeability can reach more than 900, and saturation induction density can reach 1.5T, and coercive force is less than 250A/m, and the iron loss under the AC magnetic field of 50Hz, 1T can be less than 3W/Kg.
Embodiment two: the preparation method of the soft-magnetic composite material of glass dielectric layer is undertaken by following step in this execution mode:
One, magnetic, coupling agent and organic solvent mixing are obtained mixture A, coupling agent and the magnetic mass fraction in mixture A is 0.01%～3%, and the volume ratio of organic solvent and magnetic is greater than 100; Stir with 120～300r/min speed under the room temperature; Add entry, the mass ratio of water and coupling agent is 1: 1～20, continues to stir 20～30min; Obtain mixture B, said water is deionized water or distilled water;
Two, alkoxide is dissolved in the solution A that is mixed with in the organic solvent; In the solution A concentration of alkoxide less than used alkoxide in organic solvent saturation 1/10th, then solution A is added among the mixture B, again under 15 ℃～65 ℃ temperature with 120～300r/min speed continuous stirring, 5～20min; Drip acidic aqueous solution or alkaline aqueous solution with 0.5～1.5mL/min speed then; Obtain mixture C, the dropping time is 5～10min, and said alkoxide is metal alkoxide or semimetal alkoxide;
Three, the mixture with alkoxide or alkoxide and inorganic salts is dissolved in the solution B that is mixed with in the solvent; In the solution B concentration of alkoxide less than used alkoxide in organic solvent saturation 1/10th, the mol ratio of inorganic salts and alkoxide is not more than 2, then solution B is added in the mixture C; Under 60 ℃ of temperature, continue to stir 5～20min with 120～300r/min speed; Splash into acidic aqueous solution or alkaline aqueous solution with 0.5～1.5mL/min speed then, the dropping time is 8min, obtains mixture D; Said alkoxide is metal alkoxide and/or semimetal alkoxide (during mixture, various alkoxide are pressed arbitrarily than mixing);
Four, mixture D is filtered (filtering liquid) with filter paper, will filter the solid that obtains then and place 20～100 ℃ of down dry 20～200min, put into mould again, pressure sintering or cold-press method compacting are annealed, and obtain the soft-magnetic composite material of glass dielectric layer.
The initial permeability of soft-magnetic composite material can reach more than 200, and maximum permeability can reach more than 900, and saturation induction density can reach 1.5T, and coercive force is less than 250A/m, and the iron loss under the AC magnetic field of 50Hz, 1T can be less than 3W/Kg.
The hydrolysate of the alkoxide of step 2, through dry and behind certain high-temperature residence certain hour (greater than 450 ℃, 10min) at least can form glass state material.
The hydrolysate of the alkoxide of step 3 and the mixture of inorganic salts, through dry and behind certain high-temperature residence certain hour (greater than 450 ℃, 10min) at least can form glass state material.Inorganic salts are not essential, but contain a kind of alkoxide at least.
Glass dielectric layer in the soft-magnetic composite material of the present invention is a kind of amorphous substance, but possibly there is the crystalline state phase in wherein local microcosmos area.In its glass dielectric layer, as long as contain a kind of glass forming substance and a kind of glass adjustment thing in principle, intermediate is not essential; Perhaps contain a kind of intermediate and a kind of glass adjustment thing; Glass forming substance is not essential; Just can obtain the coating layer of glassy state with certain proportioning; This just forms the fundamental prerequisite of glassy state coating layer, can certainly select more than a kind of glass forming substance, glass adjustment thing and intermediate to dispose the coating layer of glassy state as required.For example: select SiO
2Make glass forming substance, Na
2O do glass adjustment thing can join SiO
2-Na
2O glass also can add intermediate A l again
2O
3Proportioning with certain obtains SiO
2-Al
2O
3-Na
2O glass; Select Al for another example
2O
3Make intermediate, select CaO and BaO to make glass adjustment thing and obtain Al with certain proportioning
2O
3-CaO-BaO glass.
(1) glass forming substance, i.e. network organizator refers to can form separately the material of glass network, like oxide S iO
2, B
2O
3, P
2O
5, GeO
2, Ae
2O
3Deng.
(2) glass adjustment thing refers to form glass separately, but the material that glass structure (network) is changed, like oxide Na
2O, K
2O, CaO, MgO, BaO, La
2O
3, ThO
2Deng.
(3) intermediate is claimed the network intermediate again, and performance is between forming between thing and the adjustment thing, like BeO, Al
2O
3, Ga
2O
3, TiO
2Deng.
Embodiment three: what this execution mode and embodiment two were different is: the said magnetic of step 1 is the powder that contains iron or nickel or cobalt with soft magnetic property, and crystal structure is crystalline state or amorphous state, and average grain diameter is 5～500 μ m.Other step is identical with embodiment two with parameter.
Embodiment four: what this execution mode and embodiment two were different is: the said magnetic of step 1 is Fe powder, Fe-Si-Al powder, Fe-Ni-Mo powder, Fe-Ni powder, Fe-Cu-Nb-Si-B powder, Fe
3O
4A kind of or wherein several kinds mixing in the powder.Other step is identical with embodiment two with parameter.
When magnetic is mixture in this execution mode, can be between each magnetic by any than mixing.
Embodiment five: what this execution mode was different with one of embodiment two to four is: the said coupling agent of step 1 is silane coupler, titanate coupling agent, aluminate coupling agent or aluminium titanium composite coupler.Other step is identical with one of embodiment two to four with parameter.
Embodiment six: what this execution mode was different with one of embodiment two to five is: the said organic solvent of step 1 is that organic solvent is the organic solvent that can dissolve coupling agent, alkoxide and inorganic salts, for example: ethanol or acetone.Other step and parameter are identical with one of embodiment two to five.
Embodiment seven: what this execution mode was different with one of embodiment two to six is: the described metal alkoxide of step 2 is NaOC
2H
5, KOC
2H
5, Ca (OC
2H
5)
2Or Si (OCH
3)
4The described semimetal alkoxide of step 2 is Si (OCH
3)
4Or H
3BO
3The described metal alkoxide of step 3 is NaOC
2H
5, KOC
2H
5, Ca (OC
2H
5)
2Or Si (OCH
3)
4The described semimetal alkoxide of step 3 is Si (OCH
3)
4Or H
3BO
3Other step is identical with one of embodiment two to six with parameter.
Embodiment eight: what this execution mode was different with one of embodiment two to seven is: the step 3 inorganic salts are NaNO
3Or Ca (NO
3)
24H
2O.Other step is identical with one of embodiment two to seven with parameter.
Embodiment nine: what this execution mode was different with one of embodiment two to eight is: required pressure was 500MPa～1200MPa when step 4 adopted the cold-press method compacting, and annealing temperature is lower than 5～50 ℃ of softening points, and annealing time is 30min～200min.Other step is identical with one of embodiment two to eight with parameter.
Embodiment ten: what this execution mode was different with one of embodiment two to nine is: required pressure was 50MPa～500MPa when step 4 adopted the pressure sintering compacting; Hot pressing temperature is controlled at 400 ℃～1000 ℃; Annealing temperature is lower than 10～100 ℃ of softening points, and annealing time is 30min～150min.Other step is identical with one of embodiment two to nine with parameter.
Adopt following verification experimental verification invention effect:
Test one: magnetic: straight iron powder, 250g, average grain diameter 88 μ m.Coupling agent: titanate coupling agent, 15g.Solvent: analyze absolute alcohol, 1000ml.The three mixes, and uses electric mixer to stir 30min with 200r/min, adds the 10ml deionized water, stirring at normal temperature 20min.
Weighing 25ml tetraethoxysilane (TEOS) is analyzed absolute alcohol with 400ml and is mixed, and pours in the mixture of above-mentioned iron powder and coupling agent.Continue to stir 5min down at 60 ℃.Slowly splash into pH value and be rare nitric acid of 4, the speed of splashing into is 1ml/min, continues 8min.
With 30ml tetraethoxysilane, 9.26gNaNO
3, 1.73gCa (NO
3)
24H
2O and 100ml analyze absolute alcohol and mix, and pour in the mixture of above-mentioned iron powder and coupling agent and colloidal sol.Continue to stir 5min down at 60 ℃.Slowly splash into pH value and be rare nitric acid of 4, the speed of splashing into is 1ml/min, continues 8min.
Said mixture is fallen liquid filtering through filter paper, and powder is placed 60 ℃ of dry 3h down.Just obtained coating the iron powder of amorphous substance layer.This iron powder is put into mould, be warming up to 700 ℃, pressurization 80MPa behind the insulation 1h, with the stove cooling, obtains the block of soft-magnetic composite material.
Soft-magnetic composite material can be at 600 ℃, and the 30min that anneals under the atmosphere of hydrogen is to eliminate residual stress.Magnetism testing sample external diameter 40mm, internal diameter 32mm, high 6mm.
By Fig. 1 and 2 contrast, explain that the surface that coats the back iron powder has formed one deck coating layer; Be evenly distributed and coated by Fig. 3,4,5 and 6 explanation iron powders, contain Na, Si element in the coating layer; Can know that by Fig. 7 and 8 being coated on iron powder material on every side is amorphous substance, i.e. glass; Fig. 9 and 10 can know that therefore the distortion situation of horizontal vertical both direction iron powder does not have significant change because in the hot pressing, glass has taken place softening, makes the distortion in hot pressing of iron powder very little.Figure 11 shows that the iron loss of soft-magnetic composite material increases along with the increase of frequency, and has the characteristic of low iron loss.
The static electromagnetic performance of table 1 soft-magnetic composite material
| SMC | μ i | μ m | B s(T) | B r(T) | H c(A/m) | ?ρ(μΩ·m) |
| Before the annealing | 210 | 953 | 1.56 | 0.23 | 245.2 | 36.1 |
| After the annealing | 262 | 1105 | 1.62 | 0.17 | 185.4 | 35.8 |
What table 1 was represented respectively is initial permeability, maximum permeability, saturation induction density, remanent magnetization, coercive force and dc resistivity.Show that it has good static-magnetic performance.
Test two: magnetic: high-purity nickel powder (Ni), average grain diameter 48 μ m, 250g.Coupling agent: silane coupler, 10g.Solvent: isopropyl alcohol, 800ml.The three mixes, and uses electric mixer to stir 30min with 200r/min, slowly adds 8ml distilled water, stirring at normal temperature 20min with buret.
Weighing 30ml propyl alcohol germanium salt (Ge (OC
3H
7)
4), mix with the 400ml isopropyl alcohol, pour in the mixture of above-mentioned nickel powder and coupling agent.Continue to stir 10min down at 30 ℃.Slowly splash into pH value and be 5 acetic acid, the speed of splashing into is 1ml/min, continues 10min.
With 30ml tetraethoxysilane, 9.26gH
3BO
3, 5.23g Ca (OC
2H
5)
2Mix with the 100ml isopropyl alcohol, pour in the mixture of above-mentioned iron powder and coupling agent and colloidal sol.Continue to stir 20min down at 30 ℃.Slowly splash into pH value and be 5 acetic acid, the speed of splashing into is 1ml/min, continues 8min.
Said mixture is fallen liquid filtering through filter paper, and powder is placed 80 ℃ of dry 3h down.Just obtained coating the nickel powder of amorphous substance layer.This nickel powder is put into mould, be warming up to 800 ℃, pressurization 50MPa behind the insulation 1h, with the stove cooling, obtains the block of soft-magnetic composite material.
Soft-magnetic composite material is at 650 ℃, vacuum (10
-1Pa) 30min that anneals under the atmosphere is to eliminate residual stress.Magnetism testing sample external diameter 40mm, internal diameter 32mm, high 6mm.
The static electromagnetic performance of table 2 soft-magnetic composite material
| SMC | μ i | μ m | B s(T) | B r(T) | H c(A/m) | ?ρ(μΩ·m) |
| Before the |
15 | 40 | 0.40 | 0.20 | 1500.3 | 40.1 |
| After the annealing | 17 | 45 | 0.45 | 0.19 | 1400.5 | 37.6 |
Test three
Magnetic: high-purity cobalt powder (Co), average grain diameter 95 μ m, 300g.Coupling agent: titanate coupling agent, 15g.Solvent: analyze absolute alcohol, 700ml.The three mixes, and uses electric mixer to stir 30min with 150r/min, slowly adds 8ml distilled water, stirring at normal temperature 15min with buret.
Weighing 25ml tetraethoxysilane (TEOS) is analyzed absolute alcohol with 400ml and is mixed, and pours in the mixture of above-mentioned cobalt powder and coupling agent.Continue to stir 5min down at 60 ℃.Slowly splash into pH value and be 5 aqueous acetic acid, the speed of splashing into is 1ml/min, continues 8min.
With 50ml tetraethoxysilane, 5.26gNaOC
2H
5, 3.24g KOC
2H
5, 3.13gH
3BO
3Analyze absolute alcohol with 200ml and mix, pour in the mixture of above-mentioned cobalt powder and coupling agent and colloidal sol.Continue to stir 20min down at 30 ℃.Slowly splash into pH value and be 5 aqueous acetic acid, the speed of splashing into is 1ml/min, continues 8min.
Said mixture is fallen liquid filtering through filter paper, and powder is placed 60 ℃ of dry 3h down.Just obtained coating the cobalt powder of amorphous substance layer.This cobalt powder is put into mould, pressurization 500MPa, pressurize 20min obtains the block of soft-magnetic composite material.
Soft-magnetic composite material is at 650 ℃, vacuum (10
-1Pa) 60min that anneals under the atmosphere is to eliminate residual stress.Magnetism testing sample external diameter 40mm, internal diameter 32mm, high 6mm.
The static electromagnetic performance of table 3 soft-magnetic composite material
| SMC | μ i | μ m | B s(T) | B r(T) | H c(A/m) | ρ(μΩ·m) |
| Before the annealing | - | 42 | 1.20 | 0.53 | 800.5 | 58.2 |
| After the annealing | - | 44 | 1.21 | 0.48 | 750.4 | 50.6 |
Test four
Magnetic: tri-iron tetroxide powder (Fe
3O
4), average grain diameter 81 μ m, 150g.Coupling agent: titanate coupling agent, 9g.Solvent: analyze absolute alcohol, 700ml.The three mixes, and uses electric mixer to stir 30min with 150r/min, slowly adds 5ml distilled water, stirring at normal temperature 15min with buret.
Weighing 25ml tetraethoxysilane (TEOS) is analyzed absolute alcohol with 400ml and is mixed, and pours in the mixture of above-mentioned tri-iron tetroxide powder and coupling agent.Continue to stir 5min down at 60 ℃.Slowly splash into pH value and be 5 aqueous solution of nitric acid, the speed of splashing into is 1ml/min, continues 8min.
With 40ml tetraethoxysilane, 5.51g NaNO3,2.14g KOC
2H
5, 3.13gH
3BO
3Analyze absolute alcohol with 200ml and mix, pour in the mixture of above-mentioned tri-iron tetroxide powder and coupling agent and colloidal sol.Continue to stir 20min down at 30 ℃.Slowly splash into pH value and be 5 aqueous acetic acid, the speed of splashing into is 1ml/min, continues 8min.
Said mixture is fallen liquid filtering through filter paper, and powder is placed 60 ℃ of dry 3h down.Just obtained coating the tri-iron tetroxide powder of amorphous substance layer.This tri-iron tetroxide powder is put into mould, pressurization 800MPa, pressurize 20min obtains the block of soft-magnetic composite material.
Soft-magnetic composite material is at 650 ℃, vacuum (10
-1Pa) 60min that anneals under the atmosphere is to eliminate residual stress.Magnetism testing sample external diameter 40mm, internal diameter 32mm, high 6mm.
The static electromagnetic performance of table 4 soft-magnetic composite material
| SMC | μ i | μ m | B s(T) | B r(T) | H c(A/m) | ?ρ(μΩ·m) |
| Before the |
20 | 100 | 1.00 | 0.55 | 600.1 | 101.1 |
| After the annealing | 22 | 105 | 1.01 | 0.53 | 560.4 | 99.5 |
Claims (10)
1. the soft-magnetic composite material of glass dielectric layer, the soft-magnetic composite material that it is characterized in that glass dielectric layer is a deposited amorphous attitude material on magnetic, cold pressing then or hot-pressing processing after process through annealing in process; Amorphous substance is divided into two retes, is made up of the hydrolysate of alkoxide near the rete of magnetic, and another rete is made up of the mixture of the hydrolysate of the hydrolysate of alkoxide or alkoxide and inorganic salts, and said alkoxide is metal alkoxide or semimetal alkoxide.
2. the preparation method of the soft-magnetic composite material of glass dielectric layer as claimed in claim 1 is characterized in that the preparation method of the soft-magnetic composite material of glass dielectric layer is undertaken by following step:
One, magnetic, coupling agent and organic solvent mixing are obtained mixture A, coupling agent and the magnetic mass fraction in mixture A is 0.01%～3%, and the volume ratio of organic solvent and magnetic is greater than 100; Stir with 120～300r/min speed under the room temperature; Add entry, the mass ratio of water and coupling agent is 1: 1～20, continues to stir 20～30min; Obtain mixture B, said water is deionized water or distilled water;
Two, alkoxide is dissolved in the solution A that is mixed with in the organic solvent; In the solution A concentration of alkoxide less than used alkoxide in organic solvent saturation 1/10th, then solution A is added among the mixture B, again under 15 ℃～65 ℃ temperature with 120～300r/min speed continuous stirring, 5～20min; Drip acidic aqueous solution or alkaline aqueous solution with 0.5～1.5mL/min speed then; Obtain mixture C, the dropping time is 5～10min, and said alkoxide is metal alkoxide or semimetal alkoxide;
Three, the mixture with alkoxide or alkoxide and inorganic salts is dissolved in the solution B that is mixed with in the solvent; In the solution B concentration of alkoxide less than used alkoxide in organic solvent saturation 1/10th; The mol ratio of inorganic salts and alkoxide is not more than 2, then solution B is added in the mixture C, under 60 ℃ of temperature, continues to stir 5～20min with 120～300r/min speed; Splash into acidic aqueous solution or alkaline aqueous solution with 0.5～1.5mL/min speed then; The dropping time is 8min, obtains mixture D, and said alkoxide is metal alkoxide and/or semimetal alkoxide;
Four, mixture D is filtered with filter paper, will filter the solid that obtains then and place 20～100 ℃ of down dry 20～200min, put into mould again, pressure sintering or cold-press method compacting are annealed, and obtain the soft-magnetic composite material of glass dielectric layer.
3. according to the preparation method of the soft-magnetic composite material of the said glass dielectric layer of claim 2, it is characterized in that the said magnetic of step 1 is the powder that contains iron or nickel or cobalt with soft magnetic property, crystal structure is crystalline state or amorphous state, and average grain diameter is 5～500 μ m.
4. according to the preparation method of the soft-magnetic composite material of the said glass dielectric layer of claim 2, it is characterized in that the said magnetic of step 1 is Fe powder, Fe-Si-Al powder, Fe-Ni-Mo powder, Fe-Ni powder, Fe-Cu-Nb-Si-B powder, Fe
3O
4A kind of or wherein several kinds mixing in the powder.
5. according to the preparation method of the soft-magnetic composite material of claim 2,3 or 4 said glass dielectric layers, it is characterized in that the said coupling agent of step 1 is silane coupler, titanate coupling agent, aluminate coupling agent or aluminium titanium composite coupler.
6. according to the preparation method of the soft-magnetic composite material of the said glass dielectric layer of claim 5, it is characterized in that the said organic solvent that can dissolve coupling agent, alkoxide and inorganic salts of step 1.
7. according to the preparation method of the soft-magnetic composite material of the said glass dielectric layer of claim 6, it is characterized in that the metal alkoxide described in step 2 and three is NaOC
2H
5, KOC
2H
5, Ca (OC
2H
5)
2Or Si (OCH
3)
4The semimetal alkoxide is Si (OCH
3)
4Or H
3BO
3
8. according to the preparation method of the soft-magnetic composite material of the said glass dielectric layer of claim 7, it is characterized in that the step 3 inorganic salts are NaNO
3Or Ca (NO
3)
24H
2O.
9. the preparation method of the soft-magnetic composite material of said glass dielectric layer according to Claim 8; Required pressure is 500MPa～1200MPa when it is characterized in that the compacting of step 4 employing cold-press method; Annealing temperature is lower than 5～50 ℃ of softening points, and annealing time is 30min～200min.
10. according to the preparation method of the soft-magnetic composite material of the said glass dielectric layer of claim 9; Required pressure is 50MPa～500MPa when it is characterized in that the compacting of step 4 employing pressure sintering; Hot pressing temperature is controlled at 400 ℃～1000 ℃; Annealing temperature is lower than 10～100 ℃ of softening points, and annealing time is 30min～150min.
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