CN102789862A - Sol-infiltrated glass-erogel-coated soft magnetic composite material and preparation method thereof - Google Patents

Sol-infiltrated glass-erogel-coated soft magnetic composite material and preparation method thereof Download PDF

Info

Publication number
CN102789862A
CN102789862A CN2012103189181A CN201210318918A CN102789862A CN 102789862 A CN102789862 A CN 102789862A CN 2012103189181 A CN2012103189181 A CN 2012103189181A CN 201210318918 A CN201210318918 A CN 201210318918A CN 102789862 A CN102789862 A CN 102789862A
Authority
CN
China
Prior art keywords
magnetic
glass
composite material
soft
obtains
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2012103189181A
Other languages
Chinese (zh)
Other versions
CN102789862B (en
Inventor
武高辉
丁伟
姜龙涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN201210318918.1A priority Critical patent/CN102789862B/en
Publication of CN102789862A publication Critical patent/CN102789862A/en
Application granted granted Critical
Publication of CN102789862B publication Critical patent/CN102789862B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Soft Magnetic Materials (AREA)
  • Glass Compositions (AREA)

Abstract

A sol-infiltrated glass-erogel-coated soft magnetic composite material and a preparation method thereof relate to a soft magnetic material and the preparation method of the soft magnetic material. Problems that coefficient of thermal expansion between an inorganic insulation layer and magnetic powder is large, and the coefficient of thermal expansion of the inorganic insulation layer itself can not change are solved. The sol-infiltrated glass-erogel-coated soft magnetic composite material is composed of the magnetic powder, a silicon dioxide layer coated on the magnetic powder, a glass xerogel layer and a glass sol infiltrated layer, wherein the glass xerogel layer and the glass sol infiltrated layer are coated outside the silicon dioxide layer. The preparation method includes: 1, preprocessing the magnetic powder; 2, coating the silicon dioxide layer on the surface of the magnetic powder; 3, preparing glass sol; 4, coating the glass xerogel layer outside the silicon dioxide layer; 5, preparing blanks of the soft magnetic composite material; 6, infiltrating the blanks by using the glass sol; and 7, preparing the soft magnetic composite material. The sol-infiltrated glass-erogel-coated soft magnetic composite material and the preparation method are applied to the fields of switch reluctance, resonant inductance, anti-lock brake sensors, electromagnetic driving devices, brushless direct current motors, rotating machinery and low frequency filters.

Description

Glass xerogel coating layer soft-magnetic composite material that colloidal sol soaks into and preparation method thereof
Technical field
The present invention relates to soft magnetic 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.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.Soft-magnetic composite material for existing organic substance coating layer; In its preparation process, need apply pressure greater than 800MPa; Reaching needed compacted density, but satisfy good saturation induction density and magnetic permeability again simultaneously, just need anneal and remove the residual stress of material the soft-magnetic composite material that contains the organic substance coating layer; Because the common non-refractory of organic substance coating layer, so be difficult to effectively remove its residual stress.For the soft-magnetic composite material of existing inorganic matter coating layer, the insulating properties of coating layer does not reach requirement, and the existing coating layer environmental pollution that contains P or S is serious, so SiO occurred using 2, MgO, SiO 2With aqueous mixtures, Al 2O 3Mix with water, ZrO 2Mix with water, the inorganic insulation layer of mica powder and aqueous mixtures preparation is as the inorganic matter coating layer, inorganic insulation layer generally has high-temperature stable, it has overcome the shortcoming of the common non-refractory of organic substance coating layer.But existing inorganic insulation layer also has shortcoming; The own thermal coefficient of expansion that the thermal coefficient of expansion of inorganic insulation layer and magnetic differs big and inorganic insulation layer can not change; Can in magnetic, produce thermal stress at the bigger environment of the temperature difference or in long-time use, cause the soft-magnetic composite material of inorganic matter coating layer can't have good magnetic property.These problems are all restricting the development and the application of soft-magnetic composite material.
Summary of the invention
The present invention will solve in the soft-magnetic composite material of existing inorganic matter coating layer; The thermal coefficient of expansion of inorganic insulation layer and magnetic differs thermal coefficient of expansion big and inorganic insulation layer itself can not be changed, and glass xerogel coating layer soft-magnetic composite material of colloidal sol infiltration and preparation method thereof is provided.
The glass xerogel coating layer soft-magnetic composite material that colloidal sol soaks into is made up of magnetic, the silicon dioxide layer that coats magnetic, glass xerogel layer and the glass colloidal sol soakage layer that is coated on outside the silicon dioxide layer; Wherein, magnetic is a kind of or wherein several kinds the combination in the metal powder with magnetic, the metal alloy powder with magnetic and the metallic compound powder with magnetic.
The preparation method of the glass xerogel coating layer soft-magnetic composite material that colloidal sol soaks into accomplishes according to the following steps:
One, magnetic is put into cleaning agent with the ultrasonic 10min ~ 20min of the frequency of 24KHz ~ 35KHz; Filtration obtains clean magnetic; In clean magnetic, add ethanol and oleic acid; To be 20% ~ 30% ammoniacal liquor be adjusted to 8.5～9.5 with the pH value of solution to the service quality percentage concentration, stirred 1 h ~ 2 hours with ultrasonic dispersion 1 h ~ of the frequency of 24KHz ~ 35KHz 2 hours or with the rotating speed of 600r/min ~ 1200r/min, obtains solidliquid mixture;
Wherein, The mass ratio of oleic acid and magnetic is (0.03 ~ 0.2): 1; The volume ratio of oleic acid and ethanol is 1: (40 ~ 75), magnetic are a kind of or wherein several kinds the combination in the metal powder with magnetic, the metal alloy powder with magnetic and the metallic compound powder with magnetic;
Two, in the solidliquid mixture that step 1 obtains, add ethanol, to use mass percentage concentration be 20% ~ 30% ammoniacal liquor is adjusted to 8.5～9.5 with the pH value of solution, the rotating speed with 600r/min ~ 1200r/min stir with the pH value be under 8.5～9.5 the condition; Divide the tetraethoxysilane that adds equivalent for 2 ~ 4 times, each 0.5 h ~ at interval 1.5 hours, the gross mass of the tetraethoxysilane of adding and the mass ratio of magnetic are (0.25 ~ 0.4): 1; After all adding, reacted 0.5 h ~ 1.5 hours, after reaction is accomplished; Leave standstill 10min～30min, outwell solution, the solid that obtains is cleaned; Filter, will clean the back solid and put into drying box, temperature is 40 ℃ ~ 80 ℃; Dry 20min ~ 360min screens dried solid with electromagnet, promptly obtain the magnetic of coated silica layer;
Wherein, the volume ratio of the solidliquid mixture that obtains of the ethanol of adding and step 1 is (2 ~ 4): 1;
Three, the organizator compound is dissolved in alcoholic solvent, obtains organizator solution; With a kind of in additive compound and the inorganic salts or wherein several kinds combination be dissolved in solvent, obtain solution of additive; Organizator solution is (0.2 ~ 2) by volume with solution of additive: 1 mixes, and under 15 ℃～65 ℃ temperature, with the mixing speed of 180r/min ~ 600r/min, continuous stirring 10min～120min obtains mixed solution; Adopt again the rate of addition of 0.5mL/min ~ 1.5mL/min drip acidic aqueous solution with the pH value of mixed solution be adjusted to 2 ~ 6 or the rate of addition dropping alkaline aqueous solution that adopts 0.5mL/min ~ 1.5mL/min the pH value of mixed solution is adjusted to 8 ~ 12, promptly obtain glass colloidal sol; Wherein, the organizator compound is boric acid, phosphoric acid, Ge (OC 3H 7) 4, Ti (OC 2H 5) 4, Al (OC 4H 9) 3, Si (OCH 3) 4And Si (OC 2H 5) 4In a kind of or wherein several kinds combination; Alcoholic solvent is a kind of or wherein several kinds the combination in methyl alcohol, ethanol, ethylene glycol and the propyl alcohol; Additive compound is for meeting chemical general formula M (OR) xCompound in a kind of or wherein several kinds combination, M is Si, Ti, Be, Mn, In, Ge, Al, Zr, Na, K, Li, Mg, Ca, Mg or Ba, R is C nH 2n+1And n is 1,2,3,4 or 5, and x is 1～5 and M (OR) xCompound be electric neutrality; Inorganic salts are NaNO 3Or Ca (NO 3) 24H 2The combination of one or both among the O; Solvent is a kind of or wherein several kinds the combination in methyl alcohol, ethanol, ethylene glycol, third alcohol and water; Acidic aqueous solution is a kind of or wherein several kinds the combination in aqueous hydrochloric acid solution, aqueous solution of nitric acid and the aqueous acetic acid; Alkaline aqueous solution is an ammoniacal liquor; The gross mass of organizator compound is (50g ~ 700g): 1L with the ratio of the volume of alcoholic solvent; A kind of in additive compound and the inorganic salts or wherein several kinds the ratio of gross mass and the volume of solvent of combination be (10g ~ 600g): 1L; The mass percent concentration of acidic aqueous solution is 1% ~ 20%; The mass percent concentration of alkaline aqueous solution is 10% ~ 30%;
In the magnetic of the coated silica layer that four, in step 2, obtains, drip the glass colloidal sol that obtains in the step 3, after the mixing, under 40 ℃ ~ 100 ℃, dry 60min ~ 500min promptly obtains outside silicon dioxide layer, coating the magnetic of glass xerogel layer;
Wherein, the quality of the magnetic of coated silica layer is (100g ~ 2000g): 1L with the ratio of the volume of glass colloidal sol;
Five, with the magnetic that outside silicon dioxide layer, coats the glass xerogel layer that obtains in the step 4, put into mould, at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min ~ 5min removes pressure, promptly obtains the blank of soft-magnetic composite material;
Six, in step 5, be loaded with in the mould of blank of soft-magnetic composite material, add the glass colloidal sol in the step 3, at room temperature; Apply the mechanical pressure of 0.1MPa ~ 10MPa; Constant voltage 1min ~ 60min removes pressure, under 20 ℃ ~ 80 ℃ of temperature; Dry 20min ~ 1000min obtains the blank of the soft-magnetic composite material of glass colloidal sol infiltration; The ratio of the quality of the blank of the soft-magnetic composite material that the volume that wherein, in mould, adds the glass colloidal sol in the step 3 and step 5 obtain is (0.02mL ~ 0.1mL): 1g;
Seven, the blank with the soft-magnetic composite material of the glass colloidal sol that obtains in step 6 infiltration is 10 in vacuum degree -1Under the condition of Pa, be warmed up to 500 ℃ ~ 1000 ℃ from room temperature with the heating rate of 1 ℃/min ~ 5 ℃/min, constant temperature 30min ~ 180min, the rate of temperature fall with 1 ℃/min ~ 5 ℃/min is cooled to room temperature afterwards, promptly accomplishes annealing, obtains soft-magnetic composite material.
The preparation method of the glass xerogel coating layer soft-magnetic composite material that colloidal sol soaks into can also accomplish according to the following steps: one, magnetic is put into cleaning agent with the ultrasonic 10min ~ 20min of the frequency of 24KHz ~ 35KHz; Filtration obtains clean magnetic; In clean magnetic, add ethanol and oleic acid; To be 20% ~ 30% ammoniacal liquor be adjusted to 8.5～9.5 with the pH value of solution to the service quality percentage concentration; Stir 1 h ~ 2 hours with ultrasonic dispersion 1 h ~ of the frequency of 24KHz ~ 35KHz 2 hours or with the rotating speed of 600r/min ~ 1200r/min, obtain solidliquid mixture;
Wherein, The mass ratio of oleic acid and magnetic is (0.03 ~ 0.2): 1; The volume ratio of oleic acid and ethanol is 1: (40 ~ 75), magnetic are a kind of or wherein several kinds the combination in the metal powder with magnetic, the metal alloy powder with magnetic and the metallic compound powder with magnetic;
Two, in the solidliquid mixture that step 1 obtains, add ethanol, to use mass percentage concentration be 20% ~ 30% ammoniacal liquor is adjusted to 8.5～9.5 with the pH value of solution, the rotating speed with 600r/min ~ 1200r/min stir with the pH value be under 8.5～9.5 the condition; Divide the tetraethoxysilane that adds equivalent for 2 ~ 4 times, each 0.5 h ~ at interval 1.5 hours, the gross mass of the tetraethoxysilane of adding and the mass ratio of magnetic are (0.25 ~ 0.4): 1; After all adding, reacted 0.5 h ~ 1.5 hours, after reaction finishes; In product, add oleic acid, the mass ratio that adds with magnetic be (0.25 ~ 0.6): to be 20% ~ 30% ammoniacal liquor be adjusted to 8.5～9.5 with the pH value of solution for 1 tetraethoxysilane, use mass percentage concentration; The rotating speed with 600r/min～1200r/min stir with the pH value be under 8.5～9.5 the condition, reacted 2 hours～4 hours, after reaction is accomplished; Leave standstill 10～30min, outwell solution, the solid that obtains is cleaned; Filter, will clean the back solid and put into drying box, temperature is 40 ℃ ~ 80 ℃; Dry 20min ~ 360min screens dried solid with electromagnet, promptly obtain the magnetic of coated silica layer;
Wherein, the volume ratio of the solidliquid mixture that the ethanol of adding and step 1 obtain is (2 ~ 4): 1, and the oleic acid of adding and the mass ratio of magnetic are (0.05 ~ 0.1): 1;
Three, the organizator compound is dissolved in alcoholic solvent, obtains organizator solution; With a kind of in additive compound and the inorganic salts or wherein several kinds combination be dissolved in solvent, obtain solution of additive; Organizator solution is (0.2 ~ 2) by volume with solution of additive: 1 mixes, and under 15 ℃～65 ℃ temperature, with the mixing speed of 180r/min ~ 600r/min, continuous stirring 10min～120min obtains mixed solution; Adopt again the rate of addition of 0.5mL/min～1.5mL/min drip acidic aqueous solution with the pH value of mixed solution be adjusted to 2 ~ 6 or the rate of addition dropping alkaline aqueous solution that adopts 0.5mL/min ~ 1.5mL/min the pH value of mixed solution is adjusted to 8～12, promptly obtain glass colloidal sol; Wherein, the organizator compound is boric acid, phosphoric acid, Ge (OC 3H 7) 4, Ti (OC 2H 5) 4, Al (OC 4H 9) 3, Si (OCH 3) 4And Si (OC 2H 5) 4In a kind of or wherein several kinds combination; Alcoholic solvent is a kind of or wherein several kinds the combination in methyl alcohol, ethanol, ethylene glycol and the propyl alcohol; Additive compound is for meeting chemical general formula M (OR) xCompound in a kind of or wherein several kinds combination, M is Si, Ti, Be, Mn, In, Ge, Al, Zr, Na, K, Li, Mg, Ca, Mg or Ba, R is C nH 2n+1And n is 1,2,3,4 or 5, and x is 1～5 and M (OR) xCompound be electric neutrality; Inorganic salts are NaNO 3Or Ca (NO 3) 24H 2The combination of one or both among the O; Solvent is a kind of or wherein several kinds the combination in methyl alcohol, ethanol, ethylene glycol, third alcohol and water; Acidic aqueous solution is a kind of or wherein several kinds the combination in aqueous hydrochloric acid solution, aqueous solution of nitric acid and the aqueous acetic acid; Alkaline aqueous solution is an ammoniacal liquor; The gross mass of organizator compound is (50g ~ 700g): 1L with the ratio of the volume of alcoholic solvent; A kind of in additive compound and the inorganic salts or wherein several kinds the ratio of gross mass and the volume of solvent of combination be (10g ~ 600g): 1L; The mass percent concentration of acidic aqueous solution is 1% ~ 20%; The mass percent concentration of alkaline aqueous solution is 10% ~ 30%;
In the magnetic of the coated silica layer that four, in step 2, obtains, drip the glass colloidal sol that obtains in the step 3, after the mixing, under 40 ℃ ~ 100 ℃, dry 60min ~ 500min promptly obtains outside silicon dioxide layer, coating the magnetic of glass xerogel layer;
Wherein, the quality of the magnetic of coated silica layer is (100g ~ 2000g): 1L with the ratio of the volume of glass colloidal sol;
Five, with the magnetic that outside silicon dioxide layer, coats the glass xerogel layer that obtains in the step 4, put into mould, at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min ~ 5min removes pressure, promptly obtains the blank of soft-magnetic composite material;
Six, in step 5, be loaded with in the mould of blank of soft-magnetic composite material, add the glass colloidal sol in the step 3, at room temperature; Apply the mechanical pressure of 0.1MPa ~ 10MPa; Constant voltage 1min ~ 60min removes pressure, under 20 ℃ ~ 80 ℃ of temperature; Dry 20min ~ 1000min obtains the blank of the soft-magnetic composite material of glass colloidal sol infiltration; The ratio of the quality of the blank of the soft-magnetic composite material that the volume that wherein, in mould, adds the glass colloidal sol in the step 3 and step 5 obtain is (0.02mL ~ 0.1mL): 1g;
Seven, the blank with the soft-magnetic composite material of the glass colloidal sol that obtains in step 6 infiltration is 10 in vacuum degree -1Under the condition of Pa, be warmed up to 500 ℃ ~ 1000 ℃ from room temperature with the heating rate of 1 ℃/min ~ 5 ℃/min, constant temperature 30min ~ 180min, the rate of temperature fall with 1 ℃/min ~ 5 ℃/min is cooled to room temperature afterwards, promptly accomplishes annealing, obtains soft-magnetic composite material.
Advantage of the present invention: the soft-magnetic composite material of the present invention's design has the following advantages:
One, the thermal coefficient of expansion of insulating barrier is adjustable; Controlled significantly change takes place in the thermal coefficient of expansion that can pass through the feasible glass xerogel layer that coats of proportioning of each composition in the adjusting glass; Can itself and magnetic be mated on thermal coefficient of expansion; The maximized thermal stress that in magnetic, produces when soft-magnetic composite material uses under temperature-fall period or the alternating temperature condition after annealing of reducing, and then improved the magnetic property of soft-magnetic composite material;
Two, under greater than glass xerogel layer softening temperature, anneal, can eliminate the internal stress in the soft-magnetic composite material effectively, improved the magnetic property of soft-magnetic composite material;
Three, the annealing temperature of soft-magnetic composite material is adjustable; Can be through regulating the proportioning of each composition in the glass; Make that the softening point temperature of glass xerogel layer is adjustable; And the annealing temperature of soft-magnetic composite material is again greater than the softening point temperature of glass xerogel layer, and then the annealing temperature of also having regulated soft-magnetic composite material accordingly.
Description of drawings
Fig. 1 is 200 times electron scanning micrograph of test one soft-magnetic composite material for preparing.
Embodiment
Below provide embodiment of the present invention and be further described, yet technical scheme of the present invention but is not limited to following cited embodiment.
Embodiment one: the glass xerogel coating layer soft-magnetic composite material that the colloidal sol that this execution mode provides soaks into is made up of magnetic, the silicon dioxide layer that coats magnetic, glass xerogel layer and the glass colloidal sol soakage layer that is coated on outside the silicon dioxide layer; Wherein, magnetic is a kind of or wherein several kinds the combination in the metal powder with magnetic, the metal alloy powder with magnetic and the metallic compound powder with magnetic.
The glass xerogel coating layer soft-magnetic composite material that the colloidal sol that this execution mode provides soaks into can be adjusted the composition and the proportioning of glass xerogel layer according to thermal coefficient of expansion.The thermal coefficient of expansion of two kinds of materials in a kind of material does not match, and when variations in temperature, is easy to produce internal stress at material internal, and then makes the magnetic property of soft-magnetic composite material descend.So in the selection of coating layer, will make its thermal coefficient of expansion as far as possible and the matched coefficients of thermal expansion of soft magnetism powder.With the straight iron powder is magnetic, and having coated the preparation soft-magnetic composite material that carries out hot pressing behind the glass colloidal sol is example.The thermal coefficient of expansion of pure iron is 12 * 10 -6/ K, the thermal coefficient of expansion of silicon dioxide is 5.5 * 10 -7/ K, both thermal coefficient of expansions differ very big, so select to significantly improve the component of the oxide of thermal expansion coefficient of glass as glass.With reference to Jie Mujinnafa or high bridge Itou Kentaro method thermal expansion coefficient of glass is designed.With high bridge Itou Kentaro method is example; Thermal expansion additive property coefficient with reference to its common oxide that provides (can be interpreted as simply that here thermal expansion additive property coefficient is big more; It can make the thermal coefficient of expansion increase of glass big more); The oxide that thermal expansion additive property coefficient is bigger has: I A family metal oxide, II A family metal oxide and PbO, and the additive property coefficient of I A family metal oxide is maximum, PbO takes second place.Can confirm SiO according to high bridge Itou Kentaro method 266%, CaO4%, Na 2The thermal expansion coefficient of glass that O30% forms is 12 * 10 -6The thermal coefficient of expansion of/K and pure iron is consistent.Can reach the purpose of the matched coefficients of thermal expansion that in the selection of coating layer, will make its thermal coefficient of expansion and soft magnetism powder.Add I A family metal oxide, II A family metal oxide or PbO and be the effective method of the thermal coefficient of expansion that improves the glass xerogel layer.
The glass xerogel coating layer soft-magnetic composite material that the colloidal sol that this execution mode provides soaks into is adjusted the composition and the proportioning of glass xerogel layer according to softening point.Because the glass of high softening-point is unfavorable for the densification of material, and the size of material density is directly connected to the magnetic property height of material; Though the glass of low softening point helps the densification of material,, causes material the material softening distortion when being carried out high annealing again easily.Therefore the glass xerogel layer of glass softening point temperature between 400 ℃ and 900 ℃ meets the demands.
The glass xerogel coating layer soft-magnetic composite material that the colloidal sol that this execution mode provides soaks into has the following advantages: the thermal coefficient of expansion of insulating barrier is adjustable; Controlled significantly change takes place in the thermal coefficient of expansion that can pass through the feasible glass xerogel layer that coats of proportioning of each composition in the adjusting glass; Can itself and magnetic be mated on thermal coefficient of expansion; The maximized thermal stress that in magnetic, produces when soft-magnetic composite material uses under temperature-fall period or the alternating temperature condition after annealing of reducing, and then improved the magnetic property of soft-magnetic composite material; Under greater than glass xerogel layer softening temperature, anneal, can eliminate the internal stress in the soft-magnetic composite material effectively, improved the magnetic property of soft-magnetic composite material; The annealing temperature of soft-magnetic composite material is adjustable; Can be through regulating the proportioning of each composition in the glass; Make that the softening point temperature of glass xerogel layer is adjustable; And the annealing temperature of soft-magnetic composite material is again greater than the softening point temperature of glass xerogel layer, and then the annealing temperature of also having regulated soft-magnetic composite material.
Embodiment two: the difference of this execution mode and embodiment one is: magnetic be Fe powder, Ni powder, Co powder, iron alloy powder, nickel alloy powder, cobalt alloy powder, oxides-containing iron powder, nickeliferous oxidate powder and contain a kind of in the cobalt/cobalt oxide powder or wherein several kinds combination and have magnetic.Other is identical with embodiment one.
The described iron alloy powder of this execution mode is the alloy powder that ferro element and one or more elements are formed; The mass fraction maximum that iron is shared, wherein iron alloy powder can be a kind of or wherein several kinds the combination in Fe-Si-Al powder, Fe-Ni-Mo powder, Fe-Ni powder, Fe-Cu-Nb-Si-B powder, Fe-Pt powder, Fe-Ni-Cr powder, Fe-Zn powder, La-Co-Fe powder, Pb-Fe powder, W-Ni-Fe powder and the Zr-Ni-Sn-Fe powder.
The described nickel alloy powder of this execution mode is the alloy powder that nickel element and one or more elements are formed, the mass fraction maximum that nickel is shared, and wherein nickel alloy powder can be 35%～90% permalloy powder for the shared mass fraction of nickel.
The described cobalt alloy powder of this execution mode is the alloy powder that cobalt and one or more elements are formed, the mass fraction maximum that cobalt is shared, and wherein the cobalt alloy powder can be the Fe-Co-V powder.
Embodiment three: the preparation method of the glass xerogel coating layer soft-magnetic composite material that the colloidal sol that this execution mode provides soaks into, specifically accomplish according to the following steps:
One, magnetic is put into cleaning agent with the ultrasonic 10min ~ 20min of the frequency of 24KHz ~ 35KHz; Filtration obtains clean magnetic; In clean magnetic, add ethanol and oleic acid; To be 20% ~ 30% ammoniacal liquor be adjusted to 8.5～9.5 with the pH value of solution to the service quality percentage concentration, stirred 1 h ~ 2 hours with ultrasonic dispersion 1 h ~ of the frequency of 24KHz ~ 35KHz 2 hours or with the rotating speed of 600r/min ~ 1200r/min, obtains solidliquid mixture;
Wherein, The mass ratio of oleic acid and magnetic is (0.03 ~ 0.2): 1; The volume ratio of oleic acid and ethanol is 1: (40 ~ 75), magnetic are a kind of or wherein several kinds the combination in the metal powder with magnetic, the metal alloy powder with magnetic and the metallic compound powder with magnetic;
Two, in the solidliquid mixture that step 1 obtains, add ethanol, to use mass percentage concentration be 20% ~ 30% ammoniacal liquor is adjusted to 8.5～9.5 with the pH value of solution, the rotating speed with 600r/min ~ 1200r/min stir with the pH value be under 8.5～9.5 the condition; Divide the tetraethoxysilane that adds equivalent for 2 ~ 4 times, each 0.5 h ~ at interval 1.5 hours, the gross mass of the tetraethoxysilane of adding and the mass ratio of magnetic are (0.25 ~ 0.4): 1; After all adding, reacted 0.5 h ~ 1.5 hours, after reaction is accomplished; Leave standstill 10min～30min, outwell solution, the solid that obtains is cleaned; Filter, will clean the back solid and put into drying box, temperature is 40 ℃ ~ 80 ℃; Dry 20min ~ 360min screens dried solid with electromagnet, promptly obtain the magnetic of coated silica layer;
Wherein, the volume ratio of the solidliquid mixture that obtains of the ethanol of adding and step 1 is (2 ~ 4): 1;
Three, the organizator compound is dissolved in alcoholic solvent, obtains organizator solution; With a kind of in additive compound and the inorganic salts or wherein several kinds combination be dissolved in solvent, obtain solution of additive; Organizator solution is (0.2 ~ 2) by volume with solution of additive: 1 mixes, and under 15 ℃～65 ℃ temperature, with the mixing speed of 180r/min ~ 600r/min, continuous stirring 10min～120min obtains mixed solution; Adopt again the rate of addition of 0.5mL/min ~ 1.5mL/min drip acidic aqueous solution with the pH value of mixed solution be adjusted to 2 ~ 6 or the rate of addition dropping alkaline aqueous solution that adopts 0.5mL/min ~ 1.5mL/min the pH value of mixed solution is adjusted to 8 ~ 12, promptly obtain glass colloidal sol; Wherein, the organizator compound is boric acid, phosphoric acid, Ge (OC 3H 7) 4, Ti (OC 2H 5) 4, Al (OC 4H 9) 3, Si (OCH 3) 4And Si (OC 2H 5) 4In a kind of or wherein several kinds combination; Alcoholic solvent is a kind of or wherein several kinds the combination in methyl alcohol, ethanol, ethylene glycol and the propyl alcohol; Additive compound is for meeting chemical general formula M (OR) xCompound in a kind of or wherein several kinds combination, M is Si, Ti, Be, Mn, In, Ge, Al, Zr, Na, K, Li, Mg, Ca, Mg or Ba, R is C nH 2n+1And n is 1,2,3,4 or 5, and x is 1～5 and M (OR) xCompound be electric neutrality; Inorganic salts are NaNO 3Or Ca (NO 3) 24H 2The combination of one or both among the O; Solvent is a kind of or wherein several kinds the combination in methyl alcohol, ethanol, ethylene glycol, third alcohol and water; Acidic aqueous solution is a kind of or wherein several kinds the combination in aqueous hydrochloric acid solution, aqueous solution of nitric acid and the aqueous acetic acid; Alkaline aqueous solution is an ammoniacal liquor; The gross mass of organizator compound is (50g ~ 700g): 1L with the ratio of the volume of alcoholic solvent; A kind of in additive compound and the inorganic salts or wherein several kinds the ratio of gross mass and the volume of solvent of combination be (10g ~ 600g): 1L; The mass percent concentration of acidic aqueous solution is 1% ~ 20%; The mass percent concentration of alkaline aqueous solution is 10% ~ 30%;
In the magnetic of the coated silica layer that four, in step 2, obtains, drip the glass colloidal sol that obtains in the step 3, after the mixing, under 40 ℃ ~ 100 ℃, dry 60min ~ 500min promptly obtains outside silicon dioxide layer, coating the magnetic of glass xerogel layer;
Wherein, the quality of the magnetic of coated silica layer is (100g ~ 2000g): 1L with the ratio of the volume of glass colloidal sol;
Five, with the magnetic that outside silicon dioxide layer, coats the glass xerogel layer that obtains in the step 4, put into mould, at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min ~ 5min removes pressure, promptly obtains the blank of soft-magnetic composite material;
Six, in step 5, be loaded with in the mould of blank of soft-magnetic composite material, add the glass colloidal sol in the step 3, at room temperature; Apply the mechanical pressure of 0.1MPa ~ 10MPa; Constant voltage 1min ~ 60min removes pressure, under 20 ℃ ~ 80 ℃ of temperature; Dry 20min ~ 1000min obtains the blank of the soft-magnetic composite material of glass colloidal sol infiltration; The ratio of the quality of the blank of the soft-magnetic composite material that the volume that wherein, in mould, adds the glass colloidal sol in the step 3 and step 5 obtain is (0.02mL ~ 0.1mL): 1g;
Seven, the blank with the soft-magnetic composite material of the glass colloidal sol that obtains in step 6 infiltration is 10 in vacuum degree -1Under the condition of Pa, be warmed up to 500 ℃ ~ 1000 ℃ from room temperature with the heating rate of 1 ℃/min ~ 5 ℃/min, constant temperature 30min ~ 180min, the rate of temperature fall with 1 ℃/min ~ 5 ℃/min is cooled to room temperature afterwards, promptly accomplishes annealing, obtains soft-magnetic composite material.
The thickness that outside magnetic, coats silicon dioxide layer that this execution mode step 2 obtains is 50nm ~ 150nm.
The described dried solid of this execution mode step 2 uses electromagnet to carry out method for screening: when iron powder is blown afloat with air blast; Utilize electromagnet to coating the active force of magnetic; To coat magnetic and carry out postsearch screening; The silica xerogel that does not have magnetic is blown out, and has reached the purpose of screening.
The glass xerogel coating layer soft-magnetic composite material that the colloidal sol of this execution mode preparation soaks into can be adjusted the composition and the proportioning of glass xerogel layer according to thermal coefficient of expansion.The thermal coefficient of expansion of two kinds of materials in a kind of material does not match, and when variations in temperature, is easy to produce internal stress at material internal, and then makes the magnetic property of soft-magnetic composite material descend.So in the selection of coating layer, will make its thermal coefficient of expansion as far as possible and the matched coefficients of thermal expansion of soft magnetism powder.With the straight iron powder is magnetic, and having coated the preparation soft-magnetic composite material that carries out hot pressing behind the glass colloidal sol is example.The thermal coefficient of expansion of pure iron is 12 * 10 -6/ K, the thermal coefficient of expansion of silicon dioxide is 5.5 * 10 -7/ K, both thermal coefficient of expansions differ very big, so select to significantly improve the component of the oxide of thermal expansion coefficient of glass as glass.With reference to Jie Mujinnafa or high bridge Itou Kentaro method thermal expansion coefficient of glass is designed.With high bridge Itou Kentaro method is example; Thermal expansion additive property coefficient with reference to its common oxide that provides (can be interpreted as simply that here thermal expansion additive property coefficient is big more; It can make the thermal coefficient of expansion increase of glass big more); The oxide that thermal expansion additive property coefficient is bigger has: I A family metal oxide, II A family metal oxide and PbO, and the additive property coefficient of I A family metal oxide is maximum, PbO takes second place.Can confirm SiO according to high bridge Itou Kentaro method 266%, CaO4%, Na 2The thermal expansion coefficient of glass that O30% forms is 12 * 10 -6The thermal coefficient of expansion of/K and pure iron is consistent.Can reach the purpose of the matched coefficients of thermal expansion that in the selection of coating layer, will make its thermal coefficient of expansion and soft magnetism powder.Add I A family metal oxide, II A family metal oxide or PbO and be the effective method of the thermal coefficient of expansion that improves the glass xerogel layer.
The glass xerogel coating layer soft-magnetic composite material that the colloidal sol of this execution mode preparation soaks into can be adjusted the composition and the proportioning of glass xerogel layer according to softening point.Because the glass of high softening-point is unfavorable for the densification of material, and the size of material density is directly connected to the magnetic property height of material; Though the glass of low softening point helps the densification of material,, causes material the material softening distortion when being carried out high annealing again easily.Therefore the glass xerogel layer of glass softening point temperature between 400 ℃ and 900 ℃ meets the demands.
The soft-magnetic composite material of this execution mode preparation has the following advantages: the thermal coefficient of expansion of insulating barrier is adjustable; Controlled significantly change takes place in the thermal coefficient of expansion that can pass through the feasible glass xerogel layer that coats of proportioning of each composition in the adjusting glass; Can itself and magnetic be mated on thermal coefficient of expansion; The maximized thermal stress that in magnetic, produces when soft-magnetic composite material uses under temperature-fall period or the alternating temperature condition after annealing of reducing, and then improved the magnetic property of soft-magnetic composite material; Under greater than glass xerogel layer softening temperature, anneal, can eliminate the internal stress in the soft-magnetic composite material effectively, improved the magnetic property of soft-magnetic composite material; The annealing temperature of soft-magnetic composite material is adjustable; Can be through regulating the proportioning of each composition in the glass; Make that the softening point temperature of glass xerogel layer is adjustable; And the annealing temperature of soft-magnetic composite material is again greater than the softening point temperature of glass xerogel layer, and then the annealing temperature of also having regulated soft-magnetic composite material.
Embodiment four: the difference of this execution mode and embodiment three is: the described magnetic of step 1 be Fe powder, Ni powder, Co powder, iron alloy powder, nickel alloy powder, cobalt alloy powder, oxides-containing iron powder, nickeliferous oxidate powder and contain a kind of in the cobalt/cobalt oxide powder or wherein several kinds combination and have magnetic.Other is identical with embodiment three
The described iron alloy powder of this execution mode is the alloy powder that ferro element and one or more elements are formed; The mass fraction maximum that iron is shared, wherein iron alloy powder can be a kind of or wherein several kinds the combination in Fe-Si-Al powder, Fe-Ni-Mo powder, Fe-Ni powder, Fe-Cu-Nb-Si-B powder, Fe-Pt powder, Fe-Ni-Cr powder, Fe-Zn powder, La-Co-Fe powder, Pb-Fe powder, W-Ni-Fe powder and the Zr-Ni-Sn-Fe powder.
The described nickel alloy powder of this execution mode is the alloy powder that nickel element and one or more elements are formed, the mass fraction maximum that nickel is shared, and wherein nickel alloy powder can be 35%～90% permalloy powder for the shared mass fraction of nickel.
The described cobalt alloy powder of this execution mode is the alloy powder that cobalt and one or more elements are formed, the mass fraction maximum that cobalt is shared, and wherein the cobalt alloy powder can be the Fe-Co-V powder.
Embodiment five: this execution mode and embodiment three or four difference are: the described cleaning agent of step 1 is acetone or concentration expressed in percentage by volume greater than 95% ethanol.Other is identical with embodiment three or four.
Embodiment six: the preparation method of the glass xerogel coating layer soft-magnetic composite material that the colloidal sol that this execution mode provides soaks into, specifically accomplish according to the following steps:
One, magnetic is put into cleaning agent with the ultrasonic 10min ~ 20min of the frequency of 24KHz ~ 35KHz; Filtration obtains clean magnetic; In clean magnetic, add ethanol and oleic acid; To be 20% ~ 30% ammoniacal liquor be adjusted to 8.5～9.5 with the pH value of solution to the service quality percentage concentration, stirred 1 h ~ 2 hours with ultrasonic dispersion 1 h ~ of the frequency of 24KHz ~ 35KHz 2 hours or with the rotating speed of 600r/min ~ 1200r/min, obtains solidliquid mixture;
Wherein, The mass ratio of oleic acid and magnetic is (0.03 ~ 0.2): 1; The volume ratio of oleic acid and ethanol is 1: (40 ~ 75), magnetic are a kind of or wherein several kinds the combination in the metal powder with magnetic, the metal alloy powder with magnetic and the metallic compound powder with magnetic;
Two, in the solidliquid mixture that step 1 obtains, add ethanol, to use mass percentage concentration be 20% ~ 30% ammoniacal liquor is adjusted to 8.5～9.5 with the pH value of solution, the rotating speed with 600r/min ~ 1200r/min stir with the pH value be under 8.5～9.5 the condition; Divide the tetraethoxysilane that adds equivalent for 2 ~ 4 times, each 0.5 h ~ at interval 1.5 hours, the gross mass of the tetraethoxysilane of adding and the mass ratio of magnetic are (0.25 ~ 0.4): 1; After all adding, reacted 0.5 h ~ 1.5 hours, after reaction finishes; In product, add oleic acid, the mass ratio that adds with magnetic be (0.25 ~ 0.6): to be 20% ~ 30% ammoniacal liquor be adjusted to 8.5～9.5 with the pH value of solution for 1 tetraethoxysilane, use mass percentage concentration; The rotating speed with 600r/min ~ 1200r/min stir with the pH value be under 8.5～9.5 the condition, reacted 2 hours～4 hours, after reaction is accomplished; Leave standstill 10～30min, outwell solution, the solid that obtains is cleaned; Filter, will clean the back solid and put into drying box, temperature is 40 ℃ ~ 80 ℃; Dry 20min ~ 360min screens dried solid with electromagnet, promptly obtain the magnetic of coated silica layer;
Wherein, the volume ratio of the solidliquid mixture that the ethanol of adding and step 1 obtain is (2 ~ 4): 1, and the oleic acid of adding and the mass ratio of magnetic are (0.05 ~ 0.1): 1;
Three, the organizator compound is dissolved in alcoholic solvent, obtains organizator solution; With a kind of in additive compound and the inorganic salts or wherein several kinds combination be dissolved in solvent, obtain solution of additive; Organizator solution is (0.2 ~ 2) by volume with solution of additive: 1 mixes, and under 15 ℃～65 ℃ temperature, with the mixing speed of 180r/min ~ 600r/min, continuous stirring 10min～120min obtains mixed solution; Adopt again the rate of addition of 0.5mL/min ~ 1.5mL/min drip acidic aqueous solution with the pH value of mixed solution be adjusted to 2 ~ 6 or the rate of addition dropping alkaline aqueous solution that adopts 0.5mL/min ~ 1.5mL/min the pH value of mixed solution is adjusted to 8 ~ 12, promptly obtain glass colloidal sol; Wherein, the organizator compound is boric acid, phosphoric acid, Ge (OC 3H 7) 4, Ti (OC 2H 5) 4, Al (OC 4H 9) 3, Si (OCH 3) 4And Si (OC 2H 5) 4In a kind of or wherein several kinds combination; Alcoholic solvent is a kind of or wherein several kinds the combination in methyl alcohol, ethanol, ethylene glycol and the propyl alcohol; Additive compound is for meeting chemical general formula M (OR) xCompound in a kind of or wherein several kinds combination, M is Si, Ti, Be, Mn, In, Ge, Al, Zr, Na, K, Li, Mg, Ca, Mg or Ba, R is C nH 2n+1And n is 1,2,3,4 or 5, and x is 1～5 and M (OR) xCompound be electric neutrality; Inorganic salts are NaNO 3Or Ca (NO 3) 24H 2The combination of one or both among the O; Solvent is a kind of or wherein several kinds the combination in methyl alcohol, ethanol, ethylene glycol, third alcohol and water; Acidic aqueous solution is a kind of or wherein several kinds the combination in aqueous hydrochloric acid solution, aqueous solution of nitric acid and the aqueous acetic acid; Alkaline aqueous solution is an ammoniacal liquor; The gross mass of organizator compound is (50g ~ 700g): 1L with the ratio of the volume of alcoholic solvent; A kind of in additive compound and the inorganic salts or wherein several kinds the ratio of gross mass and the volume of solvent of combination be (10g ~ 600g): 1L; The mass percent concentration of acidic aqueous solution is 1% ~ 20%; The mass percent concentration of alkaline aqueous solution is 10% ~ 30%;
In the magnetic of the coated silica layer that four, in step 2, obtains, drip the glass colloidal sol that obtains in the step 3, after the mixing, under 40 ℃ ~ 100 ℃, dry 60min ~ 500min promptly obtains outside silicon dioxide layer, coating the magnetic of glass xerogel layer;
Wherein, the quality of the magnetic of coated silica layer is (100g ~ 2000g): 1L with the ratio of the volume of glass colloidal sol;
Five, with the magnetic that outside silicon dioxide layer, coats the glass xerogel layer that obtains in the step 4, put into mould, at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min ~ 5min removes pressure, promptly obtains the blank of soft-magnetic composite material;
Six, in step 5, be loaded with in the mould of blank of soft-magnetic composite material, add the glass colloidal sol in the step 3, at room temperature; Apply the mechanical pressure of 0.1MPa ~ 10MPa; Constant voltage 1min ~ 60min removes pressure, under 20 ℃ ~ 80 ℃ of temperature; Dry 20min ~ 1000min obtains the blank of the soft-magnetic composite material of glass colloidal sol infiltration; The ratio of the quality of the blank of the soft-magnetic composite material that the volume that wherein, in mould, adds the glass colloidal sol in the step 3 and step 5 obtain is (0.02mL ~ 0.1mL): 1g;
Seven, the blank with the soft-magnetic composite material of the glass colloidal sol that obtains in step 6 infiltration is 10 in vacuum degree -1Under the condition of Pa, be warmed up to 500 ℃ ~ 1000 ℃ from room temperature with the heating rate of 1 ℃/min ~ 5 ℃/min, constant temperature 30min ~ 180min, the rate of temperature fall with 1 ℃/min ~ 5 ℃/min is cooled to room temperature afterwards, promptly accomplishes annealing, obtains soft-magnetic composite material.
The thickness at magnetic coated silica layer that this execution mode step 2 obtains is 150nm ~ 500nm.
The described dried solid of this execution mode step 2 uses electromagnet to carry out method for screening: when iron powder is blown afloat with air blast; Utilize electromagnet to coating the active force of magnetic; To coat magnetic and carry out postsearch screening; The silica xerogel that does not have magnetic is blown out, and has reached the purpose of screening.
The glass xerogel coating layer soft-magnetic composite material that the colloidal sol that this execution mode provides soaks into can be adjusted the composition and the proportioning of glass xerogel layer according to thermal coefficient of expansion.The thermal coefficient of expansion of two kinds of materials in a kind of material does not match, and when variations in temperature, is easy to produce internal stress at material internal, and then makes the magnetic property of soft-magnetic composite material descend.So in the selection of coating layer, will make its thermal coefficient of expansion as far as possible and the matched coefficients of thermal expansion of soft magnetism powder.With the straight iron powder is magnetic, and having coated the preparation soft-magnetic composite material that carries out hot pressing behind the glass colloidal sol is example.The thermal coefficient of expansion of pure iron is 12 * 10 -6/ K, the thermal coefficient of expansion of silicon dioxide is 5.5 * 10 -7/ K, both thermal coefficient of expansions differ very big, so when selecting the component of glass, should select those oxides that can significantly improve thermal expansion coefficient of glass, with reference to Jie Mujinnafa or high bridge Itou Kentaro method thermal expansion coefficient of glass are designed.With high bridge Itou Kentaro method is example; Thermal expansion additive property coefficient with reference to its common oxide that provides (can be interpreted as simply that here thermal expansion additive property coefficient is big more; It can make the thermal coefficient of expansion increase of glass big more); The oxide that thermal expansion additive property coefficient is bigger has: I A family metal oxide, II A family metal oxide and PbO, and the additive property coefficient of I A family metal oxide is maximum, PbO takes second place.Can estimate SiO according to high bridge Itou Kentaro method 266%, CaO4%, Na 2The thermal expansion coefficient of glass that O30% forms is 12 * 10 -6Thermal coefficient of expansion with pure iron about/K matees basically.So can design the soft-magnetic composite material of multiple coating glass xerogel layer.The common glass forming substance and the thermal coefficient of expansion of intermediate oxide are all quite low, and to add I A family, II A family oxide or PbO be effective method as improving its thermal coefficient of expansion.
The glass xerogel coating layer soft-magnetic composite material that the colloidal sol that this execution mode provides soaks into is adjusted the composition and the proportioning of glass xerogel layer according to softening point.Because the glass of high softening-point is unfavorable for the densification of material, and the size of material density is directly connected to the magnetic property height of material; Though the glass of low softening point helps the densification of material,, causes material the material softening distortion when being carried out high annealing again easily.Therefore the glass xerogel layer of glass softening point temperature between 400 ℃ and 900 ℃ meets the demands.
The soft-magnetic composite material of this execution mode preparation has the following advantages: the thermal coefficient of expansion of insulating barrier is adjustable; Controlled significantly change takes place in the thermal coefficient of expansion that can pass through the feasible glass xerogel layer that coats of proportioning of each composition in the adjusting glass; Can itself and magnetic be mated on thermal coefficient of expansion; The maximized thermal stress that in magnetic, produces when soft-magnetic composite material uses under temperature-fall period or the alternating temperature condition after annealing of reducing, and then improved the magnetic property of soft-magnetic composite material; Under greater than glass xerogel layer softening temperature, anneal, can eliminate the internal stress in the soft-magnetic composite material effectively, improved the magnetic property of soft-magnetic composite material; The annealing temperature of soft-magnetic composite material is adjustable; Can be through regulating the proportioning of each composition in the glass; Make that the softening point temperature of glass xerogel layer is adjustable; And the annealing temperature of soft-magnetic composite material is again greater than the softening point temperature of glass xerogel layer, and then the annealing temperature of also having regulated soft-magnetic composite material.
Embodiment seven: the difference of this execution mode and embodiment six is: the described magnetic of step 1 be Fe powder, Ni powder, Co powder, iron alloy powder, nickel alloy powder, cobalt alloy powder, oxides-containing iron powder, nickeliferous oxidate powder and contain a kind of in the cobalt/cobalt oxide powder or wherein several kinds combination and have magnetic.Other and embodiment six phase are together.
The described iron alloy powder of this execution mode is the alloy powder that ferro element and one or more elements are formed; The mass fraction maximum that iron is shared, wherein iron alloy powder can be a kind of or wherein several kinds the combination in Fe-Si-Al powder, Fe-Ni-Mo powder, Fe-Ni powder, Fe-Cu-Nb-Si-B powder, Fe-Pt powder, Fe-Ni-Cr powder, Fe-Zn powder, La-Co-Fe powder, Pb-Fe powder, W-Ni-Fe powder and the Zr-Ni-Sn-Fe powder.
The described nickel alloy powder of this execution mode is the alloy powder that nickel element and one or more elements are formed, the mass fraction maximum that nickel is shared, and wherein nickel alloy powder can be 35%～90% permalloy powder for the shared mass fraction of nickel.
The described cobalt alloy powder of this execution mode is the alloy powder that cobalt element and one or more elements are formed, the mass fraction maximum that cobalt is shared, and wherein the cobalt alloy powder can be the Fe-Co-V powder.
Embodiment eight: this execution mode and embodiment six or seven difference are: the described cleaning agent of step 1 is acetone or concentration expressed in percentage by volume greater than 95% ethanol.Other is identical with embodiment six or seven
Adopt following verification experimental verification effect of the present invention:
Test one: the preparation method of the glass xerogel coating layer soft-magnetic composite material that colloidal sol soaks into, specifically accomplish according to the following steps:
One, the ATOMET_1001HP water-atomized iron powder 150g with Quebec, CAN metal dust Co., Ltd puts into ethanol; With the ultrasonic 10min of the frequency of 30KHz; Filtration obtains iron powder, adds ethanol 660mL and oleic acid 10.72g (12mL) therein, and to be 25% ammoniacal liquor be adjusted to 9 with the pH value of solution to the service quality percentage concentration; Rotating speed with 800r/min stirred 1.5 hours, obtained solidliquid mixture;
Two, in the solidliquid mixture that step 1 obtains, add ethanol 2340mL, to use mass percentage concentration be 25% ammoniacal liquor is adjusted to 9 with the pH value of solution, stirs with the rotating speed of 800r/min, divides the tetraethoxysilane of 2 adding equivalent; Each 1 hour at interval, the gross mass of the tetraethoxysilane of adding was 44.64g (48mL), after all adding, reacted 2 hours; Reaction is left standstill 20min after accomplishing, and outwells solution, and the solid that obtains is cleaned; Filter, will clean the back solid and put into drying box, temperature is 60 ℃; Dry 300min screens dried solid with electromagnet, promptly obtain the iron powder of coated silica layer;
Three, in the tetraethoxysilane of 23.25g (25mL), add 5mL deionized water, 25mL ethanol, at room temperature,, stir 30min with the mixing speed of 300r/min, obtain organizator solution; To the mass percent concentration of 30mL is in the ethanolic solution of 10% caustic alcohol, adds the Ca (NO of 30mL ethanol, 2.5g 3) 24H 2O obtains solution of additive; Organizator solution is mixed with solution of additive, and to add mass percent concentration be 25% ammoniacal liquor that the pH value of solution is transferred to 9 with the rate of addition of 1mL/min, and with the mixing speed of 300r/min, stirring 180min promptly obtains glass colloidal sol again;
Four, the iron powder with the coated silica layer of 145g is deposited in the surface plate naturally; Evenly drip the glass colloidal sol of 75mL on the surface of the iron powder of coated silica layer; Put into drying baker,, promptly obtain outside silicon dioxide layer, coating the iron powder of glass xerogel layer at 60 ℃ of dry 240min;
Five, with the cladding iron powder that obtains in the step 4, put into mould, at room temperature, apply the mechanical pressure of 800MPa, constant voltage 2min removes pressure, promptly obtains the blank of 149g soft-magnetic composite material;
Six, in step 5, be loaded with in the mould of blank of soft-magnetic composite material, add the glass colloidal sol 6ml in the step 3, at room temperature; Apply the mechanical pressure of 1MPa, constant voltage 30min removes pressure; Under 60 ℃ of temperature, dry 60min obtains the blank of the soft-magnetic composite material of glass colloidal sol infiltration;
Seven, the blank with the soft-magnetic composite material that obtains in the step 6 is 10 in vacuum degree -1Under the condition of Pa, be warmed up to 700 ℃ from room temperature with the heating rate of 2 ℃/min, constant temperature 60min, the rate of temperature fall with 2 ℃/min is cooled to room temperature afterwards, promptly accomplishes annealing, obtains soft-magnetic composite material.
The soft-magnetic composite material that obtains is carried out sem observation; Obtain Fig. 1; Fig. 1 is 200 times electron scanning micrograph of test one soft-magnetic composite material for preparing; The part that from Fig. 1, can observe black crackle shape is an insulating barrier, and the white portion that is being coated by the black crackle is an iron powder, can show and prepare soft-magnetic composite material.
The electromagnetic performance and the mechanical property of this kind soft-magnetic composite material are as shown in table 1.
The electromagnetic performance and the mechanical performance index of the soft-magnetic composite material of table 1 test one preparation
In the table 1, μ mMaximum permeability for soft-magnetic composite material; B 5000The magnetic flux density value of soft-magnetic composite material when the expression magnetizing field is 5000A/m; Br representes residual magnetic flux density; Hc representes coercive force; W (50Hz) be soft-magnetic composite material at maximum magnetic field strength 1T, the iron loss value under the alternative frequency 50Hz; W (200Hz) be soft-magnetic composite material at maximum magnetic field strength 1T, the iron loss value under the alternative frequency 200Hz; TRS representes cross-breaking strength.
Test two: the preparation method of the glass xerogel coating layer soft-magnetic composite material that colloidal sol soaks into, specifically accomplish according to the following steps:
One, the ATOMET_1001HP water-atomized iron powder 150g with Quebec, CAN metal dust Co., Ltd puts into ethanol; With the ultrasonic 10min of the frequency of 30KHz; Filtration obtains iron powder, adds ethanol 660mL and oleic acid 10.72g (12mL) therein, and to be 25% ammoniacal liquor be adjusted to 9 with the pH value of solution to the service quality percentage concentration; Rotating speed with 800r/min stirred 1.5 hours, obtained solidliquid mixture;
Two, in the solidliquid mixture that step 1 obtains, add ethanol 2340mL, to use mass percentage concentration be 25% ammoniacal liquor is adjusted to 9 with the pH value of solution, stirs with the rotating speed of 800r/min, divides the tetraethoxysilane of 2 adding equivalent; Each 1 hour at interval, the gross mass of the tetraethoxysilane of adding was 44.64g (48mL), after all adding, reacted 2 hours; Reaction is left standstill 20min after accomplishing, and outwells solution, and the solid that obtains is cleaned; Filter, will clean the back solid and put into drying box, temperature is 60 ℃; Dry 300min screens dried solid with electromagnet, promptly obtain the iron powder of coated silica layer;
Three, in the tetraethoxysilane of 23.25g (25mL), add 5mL deionized water, 25mL ethanol, at room temperature,, stir 30min with the mixing speed of 300r/min, obtain organizator solution; To the mass percent concentration of 30mL is in the ethanolic solution of 10% caustic alcohol, and the mass percent concentration that adds 10mL is that the mass percent concentration of methanol solution, the 10mL of 5% calcium methoxide is 5% aluminium secondary butylate Al (OC 4H 9) 3Ethanolic solution, with the mixing speed of 400r/min, stir 30min, obtain solution of additive; Organizator solution is mixed with solution of additive, and to add mass percent concentration be 10% aqueous hydrochloric acid solution that the pH value of solution is adjusted to 4 with the rate of addition of 1mL/min, and with the mixing speed of 300r/min, stirring 120min promptly obtains glass colloidal sol again;
Four, the iron powder with the coated silica layer of 140g is deposited in the surface plate naturally; Evenly drip the glass colloidal sol of 80mL on the surface of the iron powder of coated silica layer; Put into drying baker,, promptly obtain outside silicon dioxide layer, coating the iron powder of glass xerogel layer at 70 ℃ of dry 300min;
Five, with the cladding iron powder that obtains in the step 4, put into mould, at room temperature, apply the mechanical pressure of 1000MPa, constant voltage 2.5min removes pressure, promptly obtains the blank of 146g soft-magnetic composite material;
Six, in step 5, be loaded with in the mould of blank of soft-magnetic composite material, add the glass colloidal sol 7ml in the step 3, at room temperature; Apply the mechanical pressure of 1.5MPa; Constant voltage 30min removes pressure, under 50 ℃ of temperature; Dry 100min obtains the blank of the soft-magnetic composite material of glass colloidal sol infiltration;
Seven, the blank with the soft-magnetic composite material that obtains in the step 6 is 10 in vacuum degree -1Under the condition of Pa, be warmed up to 750 ℃ from room temperature with the heating rate of 2 ℃/min, constant temperature 60min, the rate of temperature fall with 2 ℃/min is cooled to room temperature afterwards, promptly accomplishes annealing, obtains soft-magnetic composite material.The electromagnetic performance and the mechanical property of this kind soft-magnetic composite material are as shown in table 2.
The electromagnetic performance and the mechanical performance index of the soft-magnetic composite material of table 2 test two preparations
Figure BDA00002086144200161
In the table 2, μ mMaximum permeability for soft-magnetic composite material; B 5000The magnetic flux density value of soft-magnetic composite material when the expression magnetizing field is 5000A/m; Br representes residual magnetic flux density; Hc representes coercive force; W (50Hz) be soft-magnetic composite material at maximum magnetic field strength 1T, the iron loss value under the alternative frequency 50Hz; W (200Hz) be soft-magnetic composite material at maximum magnetic field strength 1T, the iron loss value under the alternative frequency 200Hz; TRS representes cross-breaking strength.
Test three: the preparation method of the glass xerogel coating layer soft-magnetic composite material that colloidal sol soaks into, specifically accomplish according to the following steps:
One, the reduced iron powder 150g that the Tianjin roc is reached chemical industry Co., Ltd puts into ethanol; With the ultrasonic 10min of the frequency of 30KHz; Filtration obtains iron powder, adds ethanol 660mL and oleic acid 10.72g (12mL) therein, and to be 25% ammoniacal liquor be adjusted to 9 with the pH value of solution to the service quality percentage concentration; Rotating speed with 700r/min stirred 1.5 hours, obtained solidliquid mixture;
Two, in the solidliquid mixture that step 1 obtains, add ethanol 2340mL, to use mass percentage concentration be 25% ammoniacal liquor is adjusted to 9 with the pH value of solution, stirs with the rotating speed of 700r/min; Divide the tetraethoxysilane that adds equivalent for 2 times, each 1 hour at interval, the gross mass of the tetraethoxysilane of adding was 44.64g (48mL); After all adding, reacted 2 hours, after reaction finishes; In product, add oleic acid 12.06g (13.5mL); Add tetraethoxysilane 69.75g (75mL), to use mass percentage concentration be 25% ammoniacal liquor is adjusted to 9 with the pH value of solution, stirs at the rotating speed with 700r/min; Reacted 2 hours, and promptly obtained solidliquid mixture at magnetic surface coated silica layer; Leave standstill 20min, outwell solution, the solid that obtains is cleaned, filter, will clean the back solid and put into drying box, temperature is 60 ℃, and dry 300min screens dried solid with electromagnet, promptly obtain the iron powder of coated silica layer;
Three, in the tetraethoxysilane of 23.25g (25mL), add 5mL deionized water, 25mL ethanol, at room temperature,, stir 30min with the mixing speed of 300r/min, obtain organizator solution; To the mass percent concentration of 30mL is in the ethanolic solution of 10% caustic alcohol, with the mixing speed of 400r/min, stirs 30min, obtains solution of additive; Organizator solution is mixed with solution of additive, with the mixing speed of 300r/min, stir 120min again, promptly obtain glass colloidal sol;
Four, the iron powder with the coated silica layer of 140g is deposited in the surface plate naturally; Evenly drip the glass colloidal sol of 90mL on the surface of the iron powder of coated silica layer; Put into drying baker,, promptly obtain outside silicon dioxide layer, coating the iron powder of glass xerogel layer at 70 ℃ of dry 120min;
Five, with the cladding iron powder that obtains in the step 4, put into mould, at room temperature, apply the mechanical pressure of 950MPa, constant voltage 2.5min removes pressure, promptly obtains the blank of 147g soft-magnetic composite material;
Six, in step 5, be loaded with in the mould of blank of soft-magnetic composite material, add the glass colloidal sol 7ml in the step 3, at room temperature; Apply the mechanical pressure of 1.5MPa; Constant voltage 40min removes pressure, under 60 ℃ of temperature; Dry 70min obtains the blank of the soft-magnetic composite material of glass colloidal sol infiltration;
Seven, the blank with the soft-magnetic composite material that obtains in the step 5 is 10 in vacuum degree -1Under the condition of Pa, be warmed up to 500 ℃ from room temperature with the heating rate of 2 ℃/min, constant temperature 60min, the rate of temperature fall with 2 ℃/min is cooled to room temperature afterwards, promptly accomplishes annealing, obtains soft-magnetic composite material.
The electromagnetic performance and the mechanical property of this kind soft-magnetic composite material are as shown in table 3.
The electromagnetic performance and the mechanical performance index of the soft-magnetic composite material of table 3 test three preparations
In the table 3, μ mMaximum permeability for soft-magnetic composite material; B 5000The magnetic flux density value of soft-magnetic composite material when the expression magnetizing field is 5000A/m; Br representes residual magnetic flux density; Hc representes coercive force; W (50Hz) be soft-magnetic composite material at maximum magnetic field strength 1T, the iron loss value under the alternative frequency 50Hz; W (200Hz) be soft-magnetic composite material at maximum magnetic field strength 1T, the iron loss value under the alternative frequency 200Hz; TRS representes cross-breaking strength.

Claims (8)

1. the glass xerogel coating layer soft-magnetic composite material that soaks into of colloidal sol, it is characterized in that soft-magnetic composite material by magnetic, coat magnetic silicon dioxide layer, be coated on silicon dioxide layer outer glass xerogel layer and glass colloidal sol soakage layer and form; Wherein, magnetic is a kind of or wherein several kinds the combination in the metal powder with magnetic, the metal alloy powder with magnetic and the metallic compound powder with magnetic.
2. the glass xerogel coating layer soft-magnetic composite material that colloidal sol according to claim 1 soaks into, it is characterized in that magnetic be iron powder, nickel powder, cobalt powder, iron alloy powder, nickel alloy powder, cobalt alloy powder, oxides-containing iron powder, nickeliferous oxidate powder and contain a kind of in the cobalt/cobalt oxide powder or wherein several kinds combination and have magnetic.
3. the preparation method of the glass xerogel coating layer soft-magnetic composite material that colloidal sol as claimed in claim 1 soaks into is characterized in that the preparation method of the glass xerogel coating layer soft-magnetic composite material that colloidal sol soaks into accomplishes according to the following steps:
One, magnetic is put into cleaning agent with the ultrasonic 10min ~ 20min of the frequency of 24KHz ~ 35KHz; Filtration obtains clean magnetic; In clean magnetic, add ethanol and oleic acid; To be 20% ~ 30% ammoniacal liquor be adjusted to 8.5～9.5 with the pH value of solution to the service quality percentage concentration, stirred 1 h ~ 2 hours with ultrasonic dispersion 1 h ~ of the frequency of 24KHz ~ 35KHz 2 hours or with the rotating speed of 600r/min ~ 1200r/min, obtains solidliquid mixture;
Wherein, The mass ratio of oleic acid and magnetic is (0.03 ~ 0.2): 1; The volume ratio of oleic acid and ethanol is 1: (40 ~ 75), magnetic are a kind of or wherein several kinds the combination in the metal powder with magnetic, the metal alloy powder with magnetic and the metallic compound powder with magnetic;
Two, in the solidliquid mixture that step 1 obtains, add ethanol, to use mass percentage concentration be 20% ~ 30% ammoniacal liquor is adjusted to 8.5～9.5 with the pH value of solution, the rotating speed with 600r/min ~ 1200r/min stir with the pH value be under 8.5～9.5 the condition; Divide the tetraethoxysilane that adds equivalent for 2 ~ 4 times, each 0.5 h ~ at interval 1.5 hours, the gross mass of the tetraethoxysilane of adding and the mass ratio of magnetic are (0.25 ~ 0.4): 1; After all adding, reacted 0.5 h ~ 1.5 hours, after reaction is accomplished; Leave standstill 10min～30min, outwell solution, the solid that obtains is cleaned; Filter, will clean the back solid and put into drying box, temperature is 40 ℃ ~ 80 ℃; Dry 20min ~ 360min screens dried solid with electromagnet, promptly obtain the magnetic of coated silica layer;
Wherein, the volume ratio of the solidliquid mixture that obtains of the ethanol of adding and step 1 is (2 ~ 4): 1;
Three, the organizator compound is dissolved in alcoholic solvent, obtains organizator solution; With a kind of in additive compound and the inorganic salts or wherein several kinds combination be dissolved in solvent, obtain solution of additive; Organizator solution is (0.2 ~ 2) by volume with solution of additive: 1 mixes, and under 15 ℃～65 ℃ temperature, with the mixing speed of 180r/min ~ 600r/min, continuous stirring 10min～120min obtains mixed solution; Adopt again the rate of addition of 0.5mL/min ~ 1.5mL/min drip acidic aqueous solution with the pH value of mixed solution be adjusted to 2 ~ 6 or the rate of addition dropping alkaline aqueous solution that adopts 0.5mL/min ~ 1.5mL/min the pH value of mixed solution is adjusted to 8 ~ 12, promptly obtain glass colloidal sol; Wherein, the organizator compound is boric acid, phosphoric acid, Ge (OC 3H 7) 4, Ti (OC 2H 5) 4, Al (OC 4H 9) 3, Si (OCH 3) 4And Si (OC 2H 5) 4In a kind of or wherein several kinds combination; Alcoholic solvent is a kind of or wherein several kinds the combination in methyl alcohol, ethanol, ethylene glycol and the propyl alcohol; Additive compound is for meeting chemical general formula M (OR) xCompound in a kind of or wherein several kinds combination, M is Si, Ti, Be, Mn, In, Ge, Al, Zr, Na, K, Li, Mg, Ca, Mg or Ba, R is C nH 2n+1And n is 1,2,3,4 or 5, and x is 1～5 and M (OR) xCompound be electric neutrality; Inorganic salts are NaNO 3Or Ca (NO 3) 24H 2The combination of one or both among the O; Solvent is a kind of or wherein several kinds the combination in methyl alcohol, ethanol, ethylene glycol, third alcohol and water; Acidic aqueous solution is a kind of or wherein several kinds the combination in aqueous hydrochloric acid solution, aqueous solution of nitric acid and the aqueous acetic acid; Alkaline aqueous solution is an ammoniacal liquor; The gross mass of organizator compound is (50g ~ 700g): 1L with the ratio of the volume of alcoholic solvent; A kind of in additive compound and the inorganic salts or wherein several kinds the ratio of gross mass and the volume of solvent of combination be (10g ~ 600g): 1L; The mass percent concentration of acidic aqueous solution is 1% ~ 20%; The mass percent concentration of alkaline aqueous solution is 10% ~ 30%;
In the magnetic of the coated silica layer that four, in step 2, obtains, drip the glass colloidal sol that obtains in the step 3, after the mixing, under 40 ℃ ~ 100 ℃, dry 60min ~ 500min promptly obtains outside silicon dioxide layer, coating the magnetic of glass xerogel layer;
Wherein, the quality of the magnetic of coated silica layer is (100g ~ 2000g): 1L with the ratio of the volume of glass colloidal sol;
Five, with the magnetic that outside silicon dioxide layer, coats the glass xerogel layer that obtains in the step 4, put into mould, at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min ~ 5min removes pressure, promptly obtains the blank of soft-magnetic composite material;
Six, in step 5, be loaded with in the mould of blank of soft-magnetic composite material, add the glass colloidal sol in the step 3, at room temperature; Apply the mechanical pressure of 0.1MPa ~ 10MPa; Constant voltage 1min ~ 60min removes pressure, under 20 ℃ ~ 80 ℃ of temperature; Dry 20min ~ 1000min obtains the blank of the soft-magnetic composite material of glass colloidal sol infiltration; The ratio of the quality of the blank of the soft-magnetic composite material that the volume that wherein, in mould, adds the glass colloidal sol in the step 3 and step 5 obtain is (0.02mL ~ 0.1mL): 1g;
Seven, the blank with the soft-magnetic composite material of the glass colloidal sol that obtains in step 6 infiltration is 10 in vacuum degree -1Under the condition of Pa, be warmed up to 500 ℃ ~ 1000 ℃ from room temperature with the heating rate of 1 ℃/min ~ 5 ℃/min, constant temperature 30min ~ 180min, the rate of temperature fall with 1 ℃/min ~ 5 ℃/min is cooled to room temperature afterwards, promptly accomplishes annealing, obtains soft-magnetic composite material.
4. the preparation method of the glass xerogel coating layer soft-magnetic composite material that colloidal sol according to claim 3 soaks into, it is characterized in that the described magnetic of step 1 be iron powder, nickel powder, cobalt powder, iron alloy powder, nickel alloy powder, cobalt alloy powder, oxides-containing iron powder, nickeliferous oxidate powder and contain a kind of in the cobalt/cobalt oxide powder or wherein several kinds combination and have magnetic.
5. the preparation method of the glass xerogel coating layer soft-magnetic composite material that colloidal sol according to claim 3 soaks into is characterized in that the described cleaning agent of step 1 is acetone or concentration expressed in percentage by volume greater than 95% ethanol.
6. the preparation method of the glass xerogel coating layer soft-magnetic composite material that colloidal sol as claimed in claim 1 soaks into is characterized in that the preparation method of soft-magnetic composite material accomplishes according to the following steps:
One, magnetic is put into cleaning agent with the ultrasonic 10min ~ 20min of the frequency of 24KHz ~ 35KHz; Filtration obtains clean magnetic; In clean magnetic, add ethanol and oleic acid; To be 20% ~ 30% ammoniacal liquor be adjusted to 8.5～9.5 with the pH value of solution to the service quality percentage concentration, stirred 1 h ~ 2 hours with ultrasonic dispersion 1 h ~ of the frequency of 24KHz ~ 35KHz 2 hours or with the rotating speed of 600r/min ~ 1200r/min, obtains solidliquid mixture;
Wherein, The mass ratio of oleic acid and magnetic is (0.03 ~ 0.2): 1; The volume ratio of oleic acid and ethanol is 1: (40 ~ 75), magnetic are a kind of or wherein several kinds the combination in the metal powder with magnetic, the metal alloy powder with magnetic and the metallic compound powder with magnetic;
Two, in the solidliquid mixture that step 1 obtains, add ethanol, to use mass percentage concentration be 20% ~ 30% ammoniacal liquor is adjusted to 8.5～9.5 with the pH value of solution, the rotating speed with 600r/min ~ 1200r/min stir with the pH value be under 8.5～9.5 the condition; Divide the tetraethoxysilane that adds equivalent for 2 ~ 4 times, each 0.5 h ~ at interval 1.5 hours, the gross mass of the tetraethoxysilane of adding and the mass ratio of magnetic are (0.25 ~ 0.4): 1; After all adding, reacted 0.5 h ~ 1.5 hours, after reaction finishes; In product, add oleic acid, the mass ratio that adds with magnetic be (0.25 ~ 0.6): to be 20% ~ 30% ammoniacal liquor be adjusted to 8.5～9.5 with the pH value of solution for 1 tetraethoxysilane, use mass percentage concentration; The rotating speed with 600r/min ~ 1200r/min stir with the pH value be under 8.5～9.5 the condition, reacted 2 hours～4 hours, after reaction is accomplished; Leave standstill 10～30min, outwell solution, the solid that obtains is cleaned; Filter, will clean the back solid and put into drying box, temperature is 40 ℃ ~ 80 ℃; Dry 20min ~ 360min screens dried solid with electromagnet, promptly obtain the magnetic of coated silica layer;
Wherein, the volume ratio of the solidliquid mixture that the ethanol of adding and step 1 obtain is (2 ~ 4): 1, and the oleic acid of adding and the mass ratio of magnetic are (0.05 ~ 0.1): 1;
Three, the organizator compound is dissolved in alcoholic solvent, obtains organizator solution; With a kind of in additive compound and the inorganic salts or wherein several kinds combination be dissolved in solvent, obtain solution of additive; Organizator solution is (0.2 ~ 2) by volume with solution of additive: 1 mixes, and under 15 ℃～65 ℃ temperature, with the mixing speed of 180r/min ~ 600r/min, continuous stirring 10min～120min obtains mixed solution; Adopt again the rate of addition of 0.5mL/min ~ 1.5mL/min drip acidic aqueous solution with the pH value of mixed solution be adjusted to 2 ~ 6 or the rate of addition dropping alkaline aqueous solution that adopts 0.5mL/min ~ 1.5mL/min the pH value of mixed solution is adjusted to 8 ~ 12, promptly obtain glass colloidal sol; Wherein, the organizator compound is boric acid, phosphoric acid, Ge (OC 3H 7) 4, Ti (OC 2H 5) 4, Al (OC 4H 9) 3, Si (OCH 3) 4And Si (OC 2H 5) 4In a kind of or wherein several kinds combination; Alcoholic solvent is a kind of or wherein several kinds the combination in methyl alcohol, ethanol, ethylene glycol and the propyl alcohol; Additive compound is for meeting chemical general formula M (OR) xCompound in a kind of or wherein several kinds combination, M is Si, Ti, Be, Mn, In, Ge, Al, Zr, Na, K, Li, Mg, Ca, Mg or Ba, R is C nH 2n+1And n is 1,2,3,4 or 5, and x is 1～5 and M (OR) xCompound be electric neutrality; Inorganic salts are NaNO 3Or Ca (NO 3) 24H 2The combination of one or both among the O; Solvent is a kind of or wherein several kinds the combination in methyl alcohol, ethanol, ethylene glycol, third alcohol and water; Acidic aqueous solution is a kind of or wherein several kinds the combination in aqueous hydrochloric acid solution, aqueous solution of nitric acid and the aqueous acetic acid; Alkaline aqueous solution is an ammoniacal liquor; The gross mass of organizator compound is (50g ~ 700g): 1L with the ratio of the volume of alcoholic solvent; A kind of in additive compound and the inorganic salts or wherein several kinds the ratio of gross mass and the volume of solvent of combination be (10g ~ 600g): 1L; The mass percent concentration of acidic aqueous solution is 1% ~ 20%; The mass percent concentration of alkaline aqueous solution is 10% ~ 30%;
In the magnetic of the coated silica layer that four, in step 2, obtains, drip the glass colloidal sol that obtains in the step 3, after the mixing, under 40 ℃ ~ 100 ℃, dry 60min ~ 500min promptly obtains outside silicon dioxide layer, coating the magnetic of glass xerogel layer;
Wherein, the quality of the magnetic of coated silica layer is (100g ~ 2000g): 1L with the ratio of the volume of glass colloidal sol;
Five, with the magnetic that outside silicon dioxide layer, coats the glass xerogel layer that obtains in the step 4, put into mould, at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min ~ 5min removes pressure, promptly obtains the blank of soft-magnetic composite material;
Six, in step 5, be loaded with in the mould of blank of soft-magnetic composite material, add the glass colloidal sol in the step 3, at room temperature; Apply the mechanical pressure of 0.1MPa ~ 10MPa; Constant voltage 1min ~ 60min removes pressure, under 20 ℃ ~ 80 ℃ of temperature; Dry 20min ~ 1000min obtains the blank of the soft-magnetic composite material of glass colloidal sol infiltration; The ratio of the quality of the blank of the soft-magnetic composite material that the volume that wherein, in mould, adds the glass colloidal sol in the step 3 and step 5 obtain is (0.02mL ~ 0.1mL): 1g;
Seven, the blank with the soft-magnetic composite material of the glass colloidal sol that obtains in step 6 infiltration is 10 in vacuum degree -1Under the condition of Pa, be warmed up to 500 ℃ ~ 1000 ℃ from room temperature with the heating rate of 1 ℃/min ~ 5 ℃/min, constant temperature 30min ~ 180min, the rate of temperature fall with 1 ℃/min ~ 5 ℃/min is cooled to room temperature afterwards, promptly accomplishes annealing, obtains soft-magnetic composite material.
7. the preparation method of the glass xerogel coating layer soft-magnetic composite material that colloidal sol according to claim 6 soaks into, it is characterized in that the described magnetic of step 1 be iron powder, nickel powder, cobalt powder, iron alloy powder, nickel alloy powder, cobalt alloy powder, oxides-containing iron powder, nickeliferous oxidate powder and contain a kind of in the cobalt/cobalt oxide powder or wherein several kinds combination and have magnetic.
8. the preparation method of the glass xerogel coating layer soft-magnetic composite material that colloidal sol according to claim 6 soaks into is characterized in that the described cleaning agent of step 1 is acetone or concentration expressed in percentage by volume greater than 95% ethanol.
CN201210318918.1A 2012-08-31 2012-08-31 Sol-infiltrated glass-erogel-coated soft magnetic composite material and preparation method thereof Active CN102789862B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210318918.1A CN102789862B (en) 2012-08-31 2012-08-31 Sol-infiltrated glass-erogel-coated soft magnetic composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210318918.1A CN102789862B (en) 2012-08-31 2012-08-31 Sol-infiltrated glass-erogel-coated soft magnetic composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN102789862A true CN102789862A (en) 2012-11-21
CN102789862B CN102789862B (en) 2014-11-12

Family

ID=47155242

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210318918.1A Active CN102789862B (en) 2012-08-31 2012-08-31 Sol-infiltrated glass-erogel-coated soft magnetic composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN102789862B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000030925A (en) * 1998-07-14 2000-01-28 Daido Steel Co Ltd Dust core and its manufacture
US6287703B1 (en) * 1997-12-24 2001-09-11 Kawasaki Steel Corporation Ultralow-iron-loss grain oriented silicon steel plate and process for producing the same
CN101127267A (en) * 2007-09-20 2008-02-20 安泰科技股份有限公司 Amorphous nano crystal soft magnet alloy strip with surface insulation coating and its preparation method
CN101694800A (en) * 2009-09-08 2010-04-14 清华大学 Compound soft magnetic material with operational performances of high-frequency and large power and process for preparing same
CN102360665A (en) * 2011-09-30 2012-02-22 哈尔滨工业大学 Soft magnetic composite material of glass insulating layer and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6287703B1 (en) * 1997-12-24 2001-09-11 Kawasaki Steel Corporation Ultralow-iron-loss grain oriented silicon steel plate and process for producing the same
JP2000030925A (en) * 1998-07-14 2000-01-28 Daido Steel Co Ltd Dust core and its manufacture
CN101127267A (en) * 2007-09-20 2008-02-20 安泰科技股份有限公司 Amorphous nano crystal soft magnet alloy strip with surface insulation coating and its preparation method
CN101694800A (en) * 2009-09-08 2010-04-14 清华大学 Compound soft magnetic material with operational performances of high-frequency and large power and process for preparing same
CN102360665A (en) * 2011-09-30 2012-02-22 哈尔滨工业大学 Soft magnetic composite material of glass insulating layer and preparation method thereof

Also Published As

Publication number Publication date
CN102789862B (en) 2014-11-12

Similar Documents

Publication Publication Date Title
CN102789861B (en) Preparation method of soft magnetic composite material of collosol infiltrating glass powder coating layer
Füzer et al. Innovative ferrite nanofibres reinforced soft magnetic composite with enhanced electrical resistivity
CN102820115B (en) Sol soaked glass wrapped layer soft magnetism composite material and preparation method thereof
Li et al. In-situ formation of Fe3O4 and ZrO2 coated Fe-based soft magnetic composites by hydrothermal method
CN103240411B (en) Production methods of inorganic-organic insulation layer soft magnetic composites
CN102360665B (en) Soft magnetic composite material of glass insulating layer and preparation method thereof
WO2010073590A1 (en) Composite soft magnetic material and method for producing same
CN103236332B (en) The preparation method of compound soft magnetic material
JP6255783B2 (en) COMPOSITE MAGNETIC MATERIAL, ITS MANUFACTURING METHOD, AND COMPOSITE MAGNETIC MATERIAL MATERIAL SET
CN102007550A (en) Method of producing composite magnetic material and composite magnetic material
US20150050178A1 (en) Soft Magnetic Composite Materials
CN102789859B (en) Soft magnetic composite material and preparation method thereof
JP2009158652A (en) Compound magnetic material and manufacturing method thereof
JP2008130780A (en) Rare-earth magnet
WO2007077689A1 (en) Soft magnetic material, dust magnetic core, process for producing soft magnetic material and process for producing dust magnetic core
CN102789863B (en) Preparation method of soft magnetic composite material taking glass powder as coating layer
CN106601417A (en) Core-shell-structured iron silicon soft magnetic composite iron core and preparation method therefor
CN104157389B (en) Preparing method of high-performance soft magnetism composite materials
CN110246675A (en) A kind of high saturation magnetic flux density, low-loss soft-magnetic composite material and preparation method thereof
JP2008130781A (en) Magnet, motor using magnet, and manufacturing method of magnet
JP2010236018A (en) High-strength low-core-loss composite soft magnetic material, method for manufacturing the same, and electromagnetic circuit parts
CN102789860B (en) Soft magnetic composite with glass xerogel serving as coating layer and method for preparing soft magnetic composite
CN110783091B (en) Preparation method of nanocrystalline FeSiBCr magnetic powder core
CN105359228A (en) Method for producing a permanent magnet, and permanent magnet and electrical machine having such a permanent magnet
CN102789862B (en) Sol-infiltrated glass-erogel-coated soft magnetic composite material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant