CN102820115B - Sol soaked glass wrapped layer soft magnetism composite material and preparation method thereof - Google Patents
Sol soaked glass wrapped layer soft magnetism composite material and preparation method thereof Download PDFInfo
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- CN102820115B CN102820115B CN201210318916.2A CN201210318916A CN102820115B CN 102820115 B CN102820115 B CN 102820115B CN 201210318916 A CN201210318916 A CN 201210318916A CN 102820115 B CN102820115 B CN 102820115B
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- 239000002131 composite material Substances 0.000 title claims abstract description 163
- 239000011521 glass Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 230000005389 magnetism Effects 0.000 title abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 37
- 230000008595 infiltration Effects 0.000 claims abstract description 25
- 238000001764 infiltration Methods 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims description 142
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 102
- 239000000203 mixture Substances 0.000 claims description 102
- 239000010410 layer Substances 0.000 claims description 91
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 70
- 239000002184 metal Substances 0.000 claims description 53
- 229910052751 metal Inorganic materials 0.000 claims description 53
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- 239000005642 Oleic acid Substances 0.000 claims description 43
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 43
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 43
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- 150000004703 alkoxides Chemical class 0.000 claims description 42
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 39
- 239000011247 coating layer Substances 0.000 claims description 37
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- 238000000137 annealing Methods 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- 235000012239 silicon dioxide Nutrition 0.000 claims description 23
- 238000005253 cladding Methods 0.000 claims description 16
- 229910000531 Co alloy Inorganic materials 0.000 claims description 13
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- 239000010941 cobalt Substances 0.000 claims description 13
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012459 cleaning agent Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229910000765 intermetallic Inorganic materials 0.000 claims description 10
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 10
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- 238000004140 cleaning Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 230000000717 retained effect Effects 0.000 claims description 8
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 claims description 7
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000000696 magnetic material Substances 0.000 abstract description 6
- 239000006247 magnetic powder Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 29
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- 229910004298 SiO 2 Inorganic materials 0.000 description 2
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- 238000012795 verification Methods 0.000 description 2
- JHLCADGWXYCDQA-UHFFFAOYSA-N calcium;ethanolate Chemical compound [Ca+2].CC[O-].CC[O-] JHLCADGWXYCDQA-UHFFFAOYSA-N 0.000 description 1
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- Soft Magnetic Materials (AREA)
Abstract
The invention discloses a sol soaked glass wrapped layer soft magnetism composite material and a preparation method thereof and relates to a soft magnetic material and a preparation method thereof. By means of the sol soaked glass wrapped layer soft magnetism composite material and the preparation method thereof, the problems that thermal expansion coefficients of inorganic insulating layers and magnetic powder are large in difference, and the thermal expansion coefficients of inorganic insulating layers are invariable are solved. The sol soaked glass wrapped layer soft magnetism composite material is composed of magnetic powder, a silica layer wrapped with magnetic powder, a glass layer wrapped outside the silica layer and a glass sol infiltration layer. The preparation method includes: 1, pretreating the magnetic powder; 2, wrapping the silica layer on the surface of the magnetic powder; 3, wrapping the glass layer outside the silica layer; 4, preparing a blank of soft magnetic composite materials; 5, performing infiltration on the blank of the soft magnetic composite materials through glass sol; and 6, preparing the soft magnetic materials.
Description
Technical field
The present invention relates to a kind of preparation method of soft magnetic material.
Background technology
Soft-magnetic composite material refers to a class soft magnetic material independently mutual between magnetic and that couple together by insulating layer material.The outstanding advantages of this soft-magnetic composite material is under AC magnetic field, to have low iron loss and Three-Dimensional Isotropic character.Therefore can prepare a lot of conventional soft magnetic materials and be difficult to the parts of realizing, be applied in switching magnetic-resistance, resonant inductance, anti-lock brake sensor, electromagnetic actuator device, brshless DC motor, rotating machinery, the 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 composite soft-magnetic powder, then adopt powder metallurgy compaction process to be prepared into closely knit block soft magnetic material.For the soft-magnetic composite material of existing Coated with Organic Matter layer, in its preparation process, need to apply the pressure that is greater than 800MPa, to reach needed compacted density, but meet again good saturation induction density and magnetic permeability simultaneously, just need to anneal and remove the residual stress of material the soft-magnetic composite material that contains Coated with Organic Matter layer, due to the common non-refractory of Coated with Organic Matter 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 existing coating layer environmental pollution containing P or S is serious, so there is using SiO
2, MgO, SiO
2with aqueous mixtures, Al
2o
3mix with water, ZrO
2the inorganic insulation layer of mix with water, preparing by mica powder and aqueous mixtures is as inorganic matter coating layer, and inorganic insulation layer generally has high-temperature stable, and it has overcome the shortcoming of the common non-refractory of Coated with Organic Matter 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 large and inorganic insulation layer can not change, can in magnetic, produce thermal stress at the larger environment of the temperature difference or in long-time use procedure, cause the soft-magnetic composite material of inorganic matter coating layer cannot there is good magnetic property.These problems are all restricting 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 large and inorganic insulation layer itself can not be changed, and the preparation method of the glass coating layer soft-magnetic composite material of colloidal sol infiltration is provided.
The glass coating layer soft-magnetic composite material that colloidal sol infiltrates is made up of the silicon dioxide layer of magnetic, coated magnetic, glassy layer, the glass colloidal sol infiltration layer being coated on outside silicon dioxide layer; Wherein, magnetic is a kind of in the magnetic metal powder of tool, the magnetic metal alloy powder of tool and the magnetic metallic compound powder of tool or wherein several combination.
One, magnetic is put into the frequency ultrasonic 10min～20min of cleaning agent with 24KHz～35KHz, filtration obtains clean magnetic, in clean magnetic, add ethanol and oleic acid, service quality percentage concentration is that 20%～30% ammoniacal liquor is adjusted to 8.5～9.5 by the pH value of solution, stir 1 hour～2 hours with the ultrasonic dispersion of frequency 1 hour～2 hours of 24KHz～35KHz 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 is a kind of in the magnetic metal powder of tool, the magnetic metal alloy powder of tool and the magnetic metallic compound powder of tool or wherein several combination;
Two, in the solidliquid mixture obtaining in step 1, add ethanol, the ammoniacal liquor that is 20%～30% by mass percentage concentration is adjusted to 8.5～9.5 by the pH value of solution, stirring taking the rotating speed of 600r/min～1200r/min with the pH value of solidliquid mixture under 8.5～9.5 condition, divide the tetraethoxysilane that adds equivalent for 2～4 times, every minor tick 0.5 hour～1.5 hours, the gross mass of the tetraethoxysilane adding and the mass ratio of magnetic are (0.25～0.4): 1, after all adding, react 0.5 hour～1.5 hours, obtain the solidliquid mixture at magnetic surface coated silica layer,
The volume ratio of the solidliquid mixture that the ethanol wherein, adding and step 1 obtain is (2～4): 1;
Three, in the solidliquid mixture obtaining in step 2, add oleic acid, tetraethoxysilane and the organic solution that is dissolved with metal alkoxide, the ammoniacal liquor that is 20%～30% by mass percentage concentration is adjusted to 8.5～9.5 by the pH value of solution, stirring taking the rotating speed of 600r/min～1200r/min with the pH value of solidliquid mixture under 8.5～9.5 condition, react 1 hour～6 hours, the solidliquid mixture obtaining is left standstill to 10min～30min, pouring soln is also retained solution for subsequent use, the solid obtaining is cleaned, filter, solid after cleaning is put into drying box, temperature is 40 DEG C～80 DEG C, dry 20min～360min, dried solid is screened with electromagnet, obtain the coated magnetic at silicon dioxide layer outer cladding glassy layer,
Wherein, the mass ratio of oleic acid and magnetic is (0.05～0.1): 1, the mass ratio of tetraethoxysilane and magnetic is (0.25～0.6): 1, the mass ratio of metal alkoxide and magnetic is (0.05～0.6): 1, and the mass percentage concentration of metal alkoxide in organic solution is 10%～20%;
Four, the coated magnetic obtaining in step 3 is put into mould, at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min～5min, removes pressure, obtains the blank of soft-magnetic composite material;
Five, in step 4, be loaded with in the mould of blank of soft-magnetic composite material, add and in step 3, retain solution for subsequent use, at room temperature, apply the mechanical pressure of 0.1MPa～10MPa, constant voltage 1min～60min, removes pressure, at 20 DEG C～80 DEG C of temperature, be dried 20min～1000min, obtain the blank of the soft-magnetic composite material of glass colloidal sol infiltration; Wherein, be (0.02mL～0.1mL): 1g to the ratio of the quality of the blank of the soft-magnetic composite material that adds in mould the volume of retaining solution for subsequent use in step 3 and step 4 to obtain;
Six, be 10 by the blank of the soft-magnetic composite material of the glass colloidal sol infiltration obtaining in step 5 in vacuum degree
-1under the condition of Pa, be warmed up to 500 DEG C～1000 DEG C with the heating rate of 1 DEG C/min～5 DEG C/min from room temperature, constant temperature 30min～180min, is cooled to room temperature with the rate of temperature fall of 1 DEG C/min～5 DEG C/min afterwards, completes annealing, obtains soft-magnetic composite material.
The preparation method of the glass coating layer soft-magnetic composite material that colloidal sol infiltrates can also complete according to the following steps:
One, magnetic is put into the frequency ultrasonic 10min～20min of cleaning agent with 24KHz～35KHz, filtration obtains clean magnetic, in clean magnetic, add ethanol and oleic acid, service quality percentage concentration is that 20%～30% ammoniacal liquor is adjusted to 8.5～9.5 by the pH value of solution, stir 1 hour～2 hours with the ultrasonic dispersion of frequency 1 hour～2 hours of 24KHz～35KHz 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 is a kind of in the magnetic metal powder of tool, the magnetic metal alloy powder of tool and the magnetic metallic compound powder of tool or wherein several combination;
Two, in the solidliquid mixture obtaining in step 1, add ethanol, the ammoniacal liquor that is 20%～30% by mass percentage concentration is adjusted to 8.5～9.5 by the pH value of solution, stirring taking the rotating speed of 600r/min～1200r/min with the pH value of solidliquid mixture under 8.5～9.5 condition, divide the tetraethoxysilane that adds equivalent for 2～4 times, every minor tick 0.5 hour～1.5 hours, the gross mass of the tetraethoxysilane adding and the mass ratio of magnetic are (0.25～0.4): 1, after all adding, react 0.5 hour～1.5 hours, after reaction finishes, in product, add oleic acid, adding with the mass ratio of magnetic is (0.25～0.6): 1 tetraethoxysilane, the ammoniacal liquor that is 20%～30% by mass percentage concentration is adjusted to 8.5～9.5 by the pH value of solution, stirring taking the rotating speed of 600r/min～1200r/min with the pH value of solidliquid mixture under 8.5～9.5 condition, react 2 hours～4 hours, obtain the solidliquid mixture at magnetic surface coated silica layer,
Wherein, the volume ratio of the solidliquid mixture that the ethanol adding and step 1 obtain is (2～4): 1, and the oleic acid adding and the mass ratio of magnetic are (0.05～0.1): 1;
Three, in the solidliquid mixture obtaining in step 2, add oleic acid, tetraethoxysilane and the organic solution that is dissolved with metal alkoxide, the ammoniacal liquor that is 20%～30% by mass percentage concentration is adjusted to 8.5～9.5 by the pH value of solution, stirring taking the rotating speed of 600r/min～1200r/min with the pH value of solidliquid mixture under 8.5～9.5 condition, react 1 hour～6 hours, the solidliquid mixture obtaining is left standstill to 10min～30min, pouring soln is also retained solution for subsequent use, the solid obtaining is cleaned, filter, solid after cleaning is put into drying box, temperature is 40 DEG C～80 DEG C, dry 20min～360min, dried solid is screened with electromagnet, obtain the coated magnetic at silicon dioxide layer outer cladding glassy layer,
Wherein, the mass ratio of oleic acid and magnetic is (0.05～0.1): 1, the mass ratio of tetraethoxysilane and magnetic is (0.25～0.6): 1, the mass ratio of metal alkoxide and magnetic is (0.05～0.6): 1, and the mass percentage concentration of metal alkoxide in organic solution is 10%～20%;
Four, the coated magnetic obtaining in step 3 is put into mould, at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min～5min, removes pressure, obtains the blank of soft-magnetic composite material;
Five, in step 4, be loaded with in the mould of blank of soft-magnetic composite material, add and in step 3, retain solution for subsequent use, at room temperature, apply the mechanical pressure of 0.1MPa～10MPa, constant voltage 1min～60min, removes pressure, at 20 DEG C～80 DEG C of temperature, be dried 20min～1000min, obtain the blank of the soft-magnetic composite material of glass colloidal sol infiltration; Wherein, be (0.02mL～0.1mL): 1g to the ratio of the quality of the blank of the soft-magnetic composite material that adds in mould the volume of retaining solution for subsequent use in step 3 and step 4 to obtain;
Six, be 10 by the blank of the soft-magnetic composite material of the glass colloidal sol infiltration obtaining in step 5 in vacuum degree
-1under the condition of Pa, be warmed up to 500 DEG C～1000 DEG C with the heating rate of 1 DEG C/min～5 DEG C/min from room temperature, constant temperature 30min～180min, is cooled to room temperature with the rate of temperature fall of 1 DEG C/min～5 DEG C/min afterwards, completes 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, can be by regulating the proportioning of each composition in glass to make the thermal coefficient of expansion of coated glassy layer that significantly controlled change occur, it can be mated on thermal coefficient of expansion with magnetic, the maximized thermal stress that produces in magnetic when soft-magnetic composite material uses under temperature-fall period or temperature match curing conditions after annealing of reducing, and then improved the magnetic property of soft-magnetic composite material;
Two, anneal being greater than under glassy layer softening temperature, can effectively eliminate the internal stress in soft-magnetic composite material, improved the magnetic property of soft-magnetic composite material;
Three, the annealing temperature of soft-magnetic composite material is adjustable, can be by regulating the proportioning of each composition in glass, make the softening point temperature of glassy layer adjustable, and the annealing temperature of soft-magnetic composite material is greater than the softening point temperature of glassy layer again, and then also regulate accordingly the annealing temperature of soft-magnetic composite material;
Four, because glass colloidal sol infiltrates to soft-magnetic composite material blank, filled the space between coated magnetic, reduced the porosity of soft-magnetic composite material, and then made the cross-breaking strength of soft-magnetic composite material reach 80MPa.
Brief description of the drawings
Fig. 1 is the electron scanning micrograph of 200 times of the soft-magnetic composite material of test one preparation
Embodiment
Below provide the specific embodiment of the present invention and be further described, but technical solution of the present invention is but not limited to following cited embodiment.
Embodiment one: the glass coating layer soft-magnetic composite material that the colloidal sol that present embodiment provides infiltrates is made up of the silicon dioxide layer of magnetic, coated magnetic, glassy layer, the glass colloidal sol infiltration layer being coated on outside silicon dioxide layer; Wherein, magnetic is a kind of in the magnetic metal powder of tool, the magnetic metal alloy powder of tool and the magnetic metallic compound powder of tool or wherein several combination.
The glass coating layer soft-magnetic composite material that colloidal sol that present embodiment provides infiltrates, can be according to thermal coefficient of expansion the composition to glassy layer and proportioning adjust.The thermal coefficient of expansion of two kinds of materials in a kind of material does not mate, and is easy to produce internal stress at material internal, and then the magnetic property of soft-magnetic composite material is declined in the time of variations in temperature.So will make its thermal coefficient of expansion as far as possible and the matched coefficients of thermal expansion of soft magnetism powder in the selection of coating layer.Taking straight iron powder as magnetic, being coated the soft-magnetic composite material of preparing that carries out hot pressing after 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, it is very large that both thermal coefficient of expansions differ, so select can significantly improve the oxide of thermal expansion coefficient of glass as the component of glass.With reference to Jie Mujinnafa or high bridge Itou Kentaro method, thermal expansion coefficient of glass is designed.Taking high bridge Itou Kentaro method as example, the thermal expansion additive property coefficient of the common oxide providing with reference to it (can simply be interpreted as that thermal expansion additive property coefficient is larger here, it can make the thermal coefficient of expansion increase of glass larger), the oxide that thermal expansion additive property coefficient is larger has: I A family metal oxide, II A family metal oxide and PbO, and the additive property coefficient maximum of I A family metal oxide, PbO takes second place.Can determine SiO according to high bridge Itou Kentaro method
266%, CaO4%, Na
2the thermal expansion coefficient of glass of O30% composition is 12 × 10
-6the thermal coefficient of expansion of/K and pure iron is consistent.Can reach the object of the matched coefficients of thermal expansion that will make its thermal coefficient of expansion and soft magnetism powder in the selection of coating layer.Adding I A family metal oxide, II A family metal oxide or PbO is the effective method of thermal coefficient of expansion that improves glassy layer.
The glass coating layer soft-magnetic composite material that the colloidal sol that present embodiment provides infiltrates, composition and proportioning according to softening point to glassy layer are adjusted.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; Although the glass of low softening point is conducive to the densification of material, in the time that being carried out to high annealing, easily causes again material material softening distortion.Therefore the glassy layer of glass softening point temperature between 400 DEG C and 900 DEG C meets the demands.
The glass coating layer soft-magnetic composite material that the colloidal sol that present embodiment provides infiltrates has the following advantages: the thermal coefficient of expansion of insulating barrier is adjustable, can be by regulating the proportioning of each composition in glass to make the thermal coefficient of expansion of coated glassy layer that significantly controlled change occur, it can be mated on thermal coefficient of expansion with magnetic, the maximized thermal stress that produces in magnetic when soft-magnetic composite material uses under temperature-fall period or temperature match curing conditions after annealing of reducing, and then improved the magnetic property of soft-magnetic composite material; Anneal being greater than under glassy layer softening temperature, can effectively eliminate the internal stress in soft-magnetic composite material, improved the magnetic property of soft-magnetic composite material; The annealing temperature of soft-magnetic composite material is adjustable, can be by regulating the proportioning of each composition in glass, make the softening point temperature of glassy layer adjustable, and the annealing temperature of soft-magnetic composite material is greater than the softening point temperature of glassy layer again, and then has also regulated the annealing temperature of soft-magnetic composite material; Because glass colloidal sol infiltrates to soft-magnetic composite material blank, fill the space between coated magnetic, reduce the porosity of soft-magnetic composite material, and then made the cross-breaking strength of soft-magnetic composite material reach 80MPa.
Embodiment two: the difference of present embodiment and embodiment one is: magnetic is Fe powder, Ni powder, Co powder, iron alloy powder, nickel alloy powder, cobalt alloy powder, oxides-containing iron powder, nickeliferous oxidate powder and containing a kind of in cobalt/cobalt oxide powder or wherein several combination and have magnetic.
Iron alloy powder described in present embodiment is the alloy powder of ferro element and one or more elements composition, the mass fraction maximum that iron is shared, wherein iron alloy powder can be a kind of 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 Zr-Ni-Sn-Fe powder or wherein several combination.
Nickel alloy powder described in present embodiment is the alloy powder of nickel element and one or more elements composition, the mass fraction maximum that nickel is shared, and wherein nickel alloy powder can be the permalloy powder that the shared mass fraction of nickel is 35%～90%.
Cobalt alloy powder described in present embodiment is the alloy powder of cobalt and one or more elements composition, the mass fraction maximum that cobalt is shared, and wherein cobalt alloy powder can be Fe-Co-V powder.
Embodiment three: the preparation method of the glass coating layer soft-magnetic composite material that the colloidal sol that present embodiment provides infiltrates, specifically completes according to the following steps:
One, magnetic is put into the frequency ultrasonic 10min～20min of cleaning agent with 24KHz～35KHz, filtration obtains clean magnetic, in clean magnetic, add ethanol and oleic acid, service quality percentage concentration is that 20%～30% ammoniacal liquor is adjusted to 8.5～9.5 by the pH value of solution, stir 1 hour～2 hours with the ultrasonic dispersion of frequency 1 hour～2 hours of 24KHz～35KHz 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 is a kind of in the magnetic metal powder of tool, the magnetic metal alloy powder of tool and the magnetic metallic compound powder of tool or wherein several combination;
Two, in the solidliquid mixture obtaining in step 1, add ethanol, the ammoniacal liquor that is 20%～30% by mass percentage concentration is adjusted to 8.5～9.5 by the pH value of solution, stirring taking the rotating speed of 600r/min～1200r/min with the pH value of solidliquid mixture under 8.5～9.5 condition, divide the tetraethoxysilane that adds equivalent for 2～4 times, every minor tick 0.5 hour～1.5 hours, the gross mass of the tetraethoxysilane adding and the mass ratio of magnetic are (0.25～0.4): 1, after all adding, react 0.5 hour～1.5 hours, obtain the solidliquid mixture at magnetic surface coated silica layer,
The volume ratio of the solidliquid mixture that the ethanol wherein, adding and step 1 obtain is (2～4): 1;
Three, in the solidliquid mixture obtaining in step 2, add oleic acid, tetraethoxysilane and the organic solution that is dissolved with metal alkoxide, the ammoniacal liquor that is 20%～30% by mass percentage concentration is adjusted to 8.5～9.5 by the pH value of solution, stirring taking the rotating speed of 600r/min～1200r/min with the pH value of solidliquid mixture under 8.5～9.5 condition, react 1 hour～6 hours, the solidliquid mixture obtaining is left standstill to 10min～30min, pouring soln is also retained solution for subsequent use, the solid obtaining is cleaned, filter, solid after cleaning is put into drying box, temperature is 40 DEG C～80 DEG C, dry 20min～360min, dried solid is screened with electromagnet, obtain the coated magnetic at silicon dioxide layer outer cladding glassy layer,
Wherein, the mass ratio of oleic acid and magnetic is (0.05～0.1): 1, the mass ratio of tetraethoxysilane and magnetic is (0.25～0.6): 1, the mass ratio of metal alkoxide and magnetic is (0.05～0.6): 1, and the mass percentage concentration of metal alkoxide in organic solution is 10%～20%;
Four, the coated magnetic obtaining in step 3 is put into mould, at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min～5min, removes pressure, obtains the blank of soft-magnetic composite material;
Five, in step 4, be loaded with in the mould of blank of soft-magnetic composite material, add and in step 3, retain solution for subsequent use, at room temperature, apply the mechanical pressure of 0.1MPa～10MPa, constant voltage 1min～60min, removes pressure, at 20 DEG C～80 DEG C of temperature, be dried 20min～1000min, obtain the blank of the soft-magnetic composite material of glass colloidal sol infiltration; Wherein, be (0.02mL～0.1mL): 1g to the ratio of the quality of the blank of the soft-magnetic composite material that adds in mould the volume of retaining solution for subsequent use in step 3 and step 4 to obtain;
Six, be 10 by the blank of the soft-magnetic composite material of the glass colloidal sol infiltration obtaining in step 5 in vacuum degree
-1under the condition of Pa, be warmed up to 500 DEG C～1000 DEG C with the heating rate of 1 DEG C/min～5 DEG C/min from room temperature, constant temperature 30min～180min, is cooled to room temperature with the rate of temperature fall of 1 DEG C/min～5 DEG C/min afterwards, completes annealing, obtains soft-magnetic composite material.
The thickness at magnetic outer cladding silicon dioxide layer that present embodiment step 2 obtains is 50nm～150nm.
Metal alkoxide described in present embodiment step 3, its kind is determined by the glass ingredient designing.As being coated the coated soda-lime glass in magnetic surface of silicon dioxide layer, metal alkoxide can be selected the alkoxide that contains sodium and calcium so.The difference of different metal alkoxide and the tetraethoxysilane concentration ratio in mixed liquor causes the difference of the composition of final glassy layer, simultaneously, the difference that difference also can cause composition proportion in final glass in the difference of reaction rate and reaction time, and concentration and the acid-base value of controlling reactant can regulate reaction rate and reaction time, thereby reach the object of controlling glassy layer composition.
The method that dried solid described in present embodiment step 3 screens with electromagnet is: when iron powder is blown afloat with air blast, utilize the active force of electromagnet to coated magnetic, to be coated magnetic and carry out postsearch screening, the magnetic glass xerogel of tool is not blown out, and has reached the object of screening.
The glass coating layer soft-magnetic composite material that colloidal sol prepared by present embodiment infiltrates, can be according to thermal coefficient of expansion the composition to glassy layer and proportioning adjust.The thermal coefficient of expansion of two kinds of materials in a kind of material does not mate, and is easy to produce internal stress at material internal, and then the magnetic property of soft-magnetic composite material is declined in the time of variations in temperature.So will make its thermal coefficient of expansion as far as possible and the matched coefficients of thermal expansion of soft magnetism powder in the selection of coating layer.Taking straight iron powder as magnetic, being coated the soft-magnetic composite material of preparing that carries out hot pressing after 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, it is very large that both thermal coefficient of expansions differ, so select can significantly improve the oxide of thermal expansion coefficient of glass as the component of glass.With reference to Jie Mujinnafa or high bridge Itou Kentaro method, thermal expansion coefficient of glass is designed.Taking high bridge Itou Kentaro method as example, the thermal expansion additive property coefficient of the common oxide providing with reference to it (can simply be interpreted as that thermal expansion additive property coefficient is larger here, it can make the thermal coefficient of expansion increase of glass larger), the oxide that thermal expansion additive property coefficient is larger has: I A family metal oxide, II A family metal oxide and PbO, and the additive property coefficient maximum of I A family metal oxide, PbO takes second place.Can determine SiO according to high bridge Itou Kentaro method
266%, CaO4%, Na
2the thermal expansion coefficient of glass of O30% composition is 12 × 10
-6the thermal coefficient of expansion of/K and pure iron is consistent.Can reach the object of the matched coefficients of thermal expansion that will make its thermal coefficient of expansion and soft magnetism powder in the selection of coating layer.Adding I A family metal oxide, II A family metal oxide or PbO is the effective method of thermal coefficient of expansion that improves glassy layer.
The glass coating layer soft-magnetic composite material that colloidal sol prepared by present embodiment infiltrates, can be according to softening point the composition to glassy layer and proportioning adjust.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; Although the glass of low softening point is conducive to the densification of material, in the time that being carried out to high annealing, easily causes again material material softening distortion.Therefore the glassy layer of glass softening point temperature between 400 DEG C and 900 DEG C meets the demands.
Soft-magnetic composite material prepared by present embodiment has the following advantages: the thermal coefficient of expansion of insulating barrier is adjustable, can be by regulating the proportioning of each composition in glass to make the thermal coefficient of expansion of coated glassy layer that significantly controlled change occur, it can be mated on thermal coefficient of expansion with magnetic, the maximized thermal stress that produces in magnetic when soft-magnetic composite material uses under temperature-fall period or temperature match curing conditions after annealing of reducing, and then improved the magnetic property of soft-magnetic composite material; Anneal being greater than under glassy layer softening temperature, can effectively eliminate the internal stress in soft-magnetic composite material, improved the magnetic property of soft-magnetic composite material; The annealing temperature of soft-magnetic composite material is adjustable, can be by regulating the proportioning of each composition in glass, make the softening point temperature of glassy layer adjustable, and the annealing temperature of soft-magnetic composite material is greater than the softening point temperature of glassy layer again, and then has also regulated the annealing temperature of soft-magnetic composite material; Because glass colloidal sol infiltrates to soft-magnetic composite material blank, fill the space between coated magnetic, reduce the porosity of soft-magnetic composite material, and then made the cross-breaking strength of soft-magnetic composite material reach 80MPa.
Embodiment four: the difference of present embodiment and embodiment three is: the magnetic described in step 1 is Fe powder, Ni powder, Co powder, iron alloy powder, nickel alloy powder, cobalt alloy powder, oxides-containing iron powder, nickeliferous oxidate powder and containing a kind of in cobalt/cobalt oxide powder or wherein several combination and have magnetic.
Iron alloy powder described in present embodiment is the alloy powder of ferro element and one or more elements composition, the mass fraction maximum that iron is shared, wherein iron alloy powder can be a kind of 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 Zr-Ni-Sn-Fe powder or wherein several combination.
Nickel alloy powder described in present embodiment is the alloy powder of nickel element and one or more elements composition, the mass fraction maximum that nickel is shared, and wherein nickel alloy powder can be the permalloy powder that the shared mass fraction of nickel is 35%～90%.
Cobalt alloy powder described in present embodiment is the alloy powder of cobalt and one or more elements composition, the mass fraction maximum that cobalt is shared, and wherein cobalt alloy powder can be Fe-Co-V powder.
Embodiment five: the difference of present embodiment and embodiment three or four is: the cleaning agent described in step 1 is the ethanol that acetone or concentration expressed in percentage by volume are greater than 95%.Other is identical with embodiment three or four.
Embodiment six: the difference of one of present embodiment and embodiment three to five is: the chemical formula of the metal alkoxide described in step 3 is M (OR)
x, wherein, M is a kind of or its kind of several combination in Ti, B, Be, Mn, In, Ge, Al, Zr, Na, K, Li, Mg, Ca or Ba, R is C
nh
2n+1and n be 1,2,3,4 or 5, x be 1～5 and metal alkoxide be electric neutrality; Be dissolved with organic solvent in the organic solution of metal alkoxide and be a kind of in methyl alcohol, ethanol, ethylene glycol and propyl alcohol or wherein several combination.
Metal alkoxide described in present embodiment is ZnO, Al
2o
3, K
2o, CaO, MgO, BaO, TiO
2, ZrO
2, Fe
2o
3, BeO, Li
2o, MnO, SrO, PbO, B
2o
3, In
2o
3, GeO
2and Ti
2the corresponding metal alkoxide of one in O, comprises NaOC
2h
5, KOC
2h
5, Ca (OC
2h
5)
2, Ge (OC
3h
7)
4, Ti (OC
2h
5)
4, In (OC
3h
7)
3, Al (OC
4h
9)
3, Zr (OC
5h
11)
4and Ta (OC
3h
7)
5.
Embodiment seven: the preparation method of the glass coating layer soft-magnetic composite material that the colloidal sol that present embodiment provides infiltrates, specifically completes according to the following steps:
One, magnetic is put into the frequency ultrasonic 10min～20min of cleaning agent with 24KHz～35KHz, filtration obtains clean magnetic, in clean magnetic, add ethanol and oleic acid, service quality percentage concentration is that 20%～30% ammoniacal liquor is adjusted to 8.5～9.5 by the pH value of solution, stir 1 hour～2 hours with the ultrasonic dispersion of frequency 1 hour～2 hours of 24KHz～35KHz 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 is a kind of in the magnetic metal powder of tool, the magnetic metal alloy powder of tool and the magnetic metallic compound powder of tool or wherein several combination;
Two, in the solidliquid mixture obtaining in step 1, add ethanol, the ammoniacal liquor that is 20%～30% by mass percentage concentration is adjusted to 8.5～9.5 by the pH value of solution, stirring taking the rotating speed of 600r/min～1200r/min with the pH value of solidliquid mixture under 8.5～9.5 condition, divide the tetraethoxysilane that adds equivalent for 2～4 times, every minor tick 0.5 hour～1.5 hours, the gross mass of the tetraethoxysilane adding and the mass ratio of magnetic are (0.25～0.4): 1, after all adding, react 0.5 hour～1.5 hours, after reaction finishes, in product, add oleic acid, adding with the mass ratio of magnetic is (0.25～0.6): 1 tetraethoxysilane, the ammoniacal liquor that is 20%～30% by mass percentage concentration is adjusted to 8.5～9.5 by the pH value of solution, stirring taking the rotating speed of 600r/min～1200r/min with the pH value of solidliquid mixture under 8.5～9.5 condition, react 2 hours～4 hours, obtain the solidliquid mixture at magnetic surface coated silica layer,
Wherein, the volume ratio of the solidliquid mixture that the ethanol adding and step 1 obtain is (2～4): 1, and the oleic acid adding and the mass ratio of magnetic are (0.05～0.1): 1;
Three, in the solidliquid mixture obtaining in step 2, add oleic acid, tetraethoxysilane and the organic solution that is dissolved with metal alkoxide, the ammoniacal liquor that is 20%～30% by mass percentage concentration is adjusted to 8.5～9.5 by the pH value of solution, stirring taking the rotating speed of 600r/min～1200r/min with the pH value of solidliquid mixture under 8.5～9.5 condition, react 1 hour～6 hours, the solidliquid mixture obtaining is left standstill to 10min～30min, pouring soln is also retained solution for subsequent use, the solid obtaining is cleaned, filter, solid after cleaning is put into drying box, temperature is 40 DEG C～80 DEG C, dry 20min～360min, dried solid is screened with electromagnet, obtain the coated magnetic at silicon dioxide layer outer cladding glassy layer,
Wherein, the mass ratio of oleic acid and magnetic is (0.05～0.1): 1, the mass ratio of tetraethoxysilane and magnetic is (0.25～0.6): 1, the mass ratio of metal alkoxide and magnetic is (0.05～0.6): 1, and the mass percentage concentration of metal alkoxide in organic solution is 10%～20%;
Four, the coated magnetic obtaining in step 3 is put into mould, at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min～5min, removes pressure, obtains the blank of soft-magnetic composite material;
Five, in step 4, be loaded with in the mould of blank of soft-magnetic composite material, add and in step 3, retain solution for subsequent use, at room temperature, apply the mechanical pressure of 0.1MPa～10MPa, constant voltage 1min～60min, removes pressure, at 20 DEG C～80 DEG C of temperature, be dried 20min～1000min, obtain the blank of the soft-magnetic composite material of glass colloidal sol infiltration; Wherein, be (0.02mL～0.1mL): 1g to the ratio of the quality of the blank of the soft-magnetic composite material that adds in mould the volume of retaining solution for subsequent use in step 3 and step 4 to obtain;
Six, be 10 by the blank of the soft-magnetic composite material of the glass colloidal sol infiltration obtaining in step 5 in vacuum degree
-1under the condition of Pa, be warmed up to 500 DEG C～1000 DEG C with the heating rate of 1 DEG C/min～5 DEG C/min from room temperature, constant temperature 30min～180min, is cooled to room temperature with the rate of temperature fall of 1 DEG C/min～5 DEG C/min afterwards, completes annealing, obtains soft-magnetic composite material.
The thickness at magnetic coated silica layer that present embodiment step 2 obtains is 150nm～500nm.
Metal alkoxide described in present embodiment step 3, its kind is determined by the glass ingredient designing.As being coated the coated soda-lime glass in magnetic surface of silicon dioxide layer, metal alkoxide can be selected the alkoxide that contains sodium and calcium so.The difference of different metal alkoxide and the tetraethoxysilane concentration ratio in mixed liquor causes the difference of the composition of final glassy layer, simultaneously, the difference that difference also can cause composition proportion in final glass in the difference of reaction rate and reaction time, and concentration and the acid-base value of controlling reactant can regulate reaction rate and reaction time, thereby reach the object of controlling glassy layer composition.
The method that dried solid described in present embodiment step 3 screens with electromagnet is: when iron powder is blown afloat with air blast, utilize the active force of electromagnet to coated magnetic, to be coated magnetic and carry out postsearch screening, the magnetic glass xerogel of tool is not blown out, and has reached the object of screening.
The glass coating layer soft-magnetic composite material that colloidal sol that present embodiment provides infiltrates, can be according to thermal coefficient of expansion the composition to glassy layer and proportioning adjust.The thermal coefficient of expansion of two kinds of materials in a kind of material does not mate, and is easy to produce internal stress at material internal, and then the magnetic property of soft-magnetic composite material is declined in the time of variations in temperature.So will make its thermal coefficient of expansion as far as possible and the matched coefficients of thermal expansion of soft magnetism powder in the selection of coating layer.Taking straight iron powder as magnetic, being coated the soft-magnetic composite material of preparing that carries out hot pressing after 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, it is very large that both thermal coefficient of expansions differ, so should select those oxides that can significantly improve thermal expansion coefficient of glass in the time selecting the component of glass, with reference to Jie Mujinnafa or high bridge Itou Kentaro method, thermal expansion coefficient of glass designed.Taking high bridge Itou Kentaro method as example, the thermal expansion additive property coefficient of the common oxide providing with reference to it (can simply be interpreted as that thermal expansion additive property coefficient is larger here, it can make the thermal coefficient of expansion increase of glass larger), the oxide that thermal expansion additive property coefficient is larger has: I A family metal oxide, II A family metal oxide and PbO, and the additive property coefficient maximum of I A family metal oxide, PbO takes second place.Can estimate SiO according to high bridge Itou Kentaro method
266%, CaO4%, Na
2the thermal expansion coefficient of glass of O30% composition is 12 × 10
-6the thermal coefficient of expansion of/K left and right and pure iron mates substantially.So can design the soft-magnetic composite material of multiple coated glassy layer.Common glass forming substance and the thermal coefficient of expansion of intermediate oxide are all quite low, and as improved its thermal coefficient of expansion, to add I A family, II A family oxide or PbO be effective method.
The glass coating layer soft-magnetic composite material that the colloidal sol that present embodiment provides infiltrates, composition and proportioning according to softening point to glassy layer are adjusted.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; Although the glass of low softening point is conducive to the densification of material, in the time that being carried out to high annealing, easily causes again material material softening distortion.Therefore the glassy layer of glass softening point temperature between 400 DEG C and 900 DEG C meets the demands.
Soft-magnetic composite material prepared by present embodiment has the following advantages: the thermal coefficient of expansion of insulating barrier is adjustable, can be by regulating the proportioning of each composition in glass to make the thermal coefficient of expansion of coated glassy layer that significantly controlled change occur, it can be mated on thermal coefficient of expansion with magnetic, the maximized thermal stress that produces in magnetic when soft-magnetic composite material uses under temperature-fall period or temperature match curing conditions after annealing of reducing, and then improved the magnetic property of soft-magnetic composite material; Anneal being greater than under glassy layer softening temperature, can effectively eliminate the internal stress in soft-magnetic composite material, improved the magnetic property of soft-magnetic composite material; The annealing temperature of soft-magnetic composite material is adjustable, can be by regulating the proportioning of each composition in glass, make the softening point temperature of glassy layer adjustable, and the annealing temperature of soft-magnetic composite material is greater than the softening point temperature of glassy layer again, and then has also regulated the annealing temperature of soft-magnetic composite material.
Embodiment eight: the difference of present embodiment and embodiment seven is: the magnetic described in step 1 is Fe powder, Ni powder, Co powder, iron alloy powder, nickel alloy powder, cobalt alloy powder, oxides-containing iron powder, nickeliferous oxidate powder and containing a kind of in cobalt/cobalt oxide powder or wherein several combination and have magnetic.
Iron alloy powder described in present embodiment is the alloy powder of ferro element and one or more elements composition, the mass fraction maximum that iron is shared, wherein iron alloy powder can be a kind of 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 Zr-Ni-Sn-Fe powder or wherein several combination.
Nickel alloy powder described in present embodiment is the alloy powder of nickel element and one or more elements composition, the mass fraction maximum that nickel is shared, and wherein nickel alloy powder can be the permalloy powder that the shared mass fraction of nickel is 35%～90%.
Cobalt alloy powder described in present embodiment is the alloy powder of cobalt element and one or more elements composition, the mass fraction maximum that cobalt is shared, and wherein cobalt alloy powder can be Fe-Co-V powder.
Embodiment nine: the difference of present embodiment and embodiment seven or eight is: the cleaning agent described in step 1 is the ethanol that acetone or concentration expressed in percentage by volume are greater than 95%.Other is identical with embodiment seven or eight.
Embodiment ten: the difference of one of present embodiment and embodiment seven to nine is: the chemical formula of the metal alkoxide described in step 3 is M (OR)
x, wherein, M is a kind of or its kind of several combination in Ti, B, Be, Mn, In, Ge, Al, Zr, Na, K, Li, Mg, Ca or Ba, R is C
nh
2n+1and n be 1,2,3,4 or 5, x be 1～5 and metal alkoxide be electric neutrality; Be dissolved with organic solvent in the organic solution of metal alkoxide and be a kind of in methyl alcohol, ethanol, ethylene glycol and propyl alcohol or wherein several combination.
Metal alkoxide described in present embodiment is ZnO, Al
2o
3, K
2o, CaO, MgO, BaO, TiO
2, ZrO
2, Fe
2o
3, BeO, Li
2o, MnO, SrO, PbO, B
2o
3, In
2o
3, GeO
2and Ti
2the corresponding metal alkoxide of one in O, comprises NaOC
2h
5, KOC
2h
5, Ca (OC
2h
5)
2, Ge (OC
3h
7)
4, Ti (OC
2h
5)
4, In (OC
3h
7)
3, Al (OC
4h
9)
3, Zr (OC
5h
11)
4and Ta (OC
3h
7)
5.
Adopt following verification experimental verification effect of the present invention:
Test one: the preparation method of the glass coating layer soft-magnetic composite material that colloidal sol infiltrates, specifically completes according to the following steps:
One, the ATOMET_1001HP water-atomized iron powder 150g of Canadian Quebec Metal Powder Company Ltd. is put into ethanol, with the ultrasonic 10min of frequency of 30KHz, filtration obtains iron powder, add therein ethanol 660mL and oleic acid 10.72g (12mL), service quality percentage concentration is that 25% ammoniacal liquor is adjusted to 9 by the pH value of solution, rotating speed with 800r/min stirs 1.5 hours, obtains solidliquid mixture;
Two, in the solidliquid mixture obtaining in step 1, add ethanol 2340mL, the ammoniacal liquor that is 25% by mass percentage concentration is adjusted to 9 by the pH value of solution, rotating speed with 800r/min stirs, by the tetraethoxysilane that adds equivalent for 2 times, every minor tick 1 hour, the gross mass of the tetraethoxysilane adding is 44.64g (48mL), after all adding, react 2 hours, obtain the solidliquid mixture at magnetic surface coated silica layer;
Three, in the solidliquid mixture obtaining in step 2, add oleic acid 12.95g (14.5mL) and tetraethoxysilane 61.38g (66mL), adding mass percentage concentration is the ethanolic solution 120mL of 15% caustic alcohol, the ammoniacal liquor that is 25% by mass percentage concentration is adjusted to 9 by the pH value of solution, rotating speed with 800r/min stirs, react 3 hours, the solidliquid mixture obtaining is left standstill to 30min, pouring soln is also retained solution for subsequent use, in the solid obtaining, add ionized water and ethanol to clean 2 times, filter, rear cleaning and solid are put into drying box, temperature is 60 DEG C, dry 240min, dried solid is screened with electromagnet, obtain the cladding iron powder at silicon dioxide layer outer cladding glassy layer,
Four, the cladding iron powder obtaining in step 3 is put into mould, at room temperature, the unidirectional mechanical pressure that applies 1000MPa, constant voltage 3min, removes pressure, obtains the blank of 130g soft-magnetic composite material;
Five, in step 4, be loaded with in the mould of blank of soft-magnetic composite material, add and in 10mL step 3, retain solution for subsequent use, at room temperature, apply the mechanical pressure of 1MPa, constant voltage 30min, removes pressure, under temperature 60 C, be dried 60min, obtain the blank of the soft-magnetic composite material of glass colloidal sol infiltration;
Six, be 10 by the blank of the soft-magnetic composite material of the glass colloidal sol infiltration obtaining in step 5 in vacuum degree
-1under the condition of Pa, be warmed up to 550 DEG C with the heating rate of 2 DEG C/min from room temperature, constant temperature 60min, is cooled to room temperature with the rate of temperature fall of 2 DEG C/min afterwards, completes annealing, obtains soft-magnetic composite material.
To obtain soft-magnetic composite material and carry out scanning electron microscope test, as shown in Figure 1, Fig. 1 is the electron scanning micrograph of 200 times of the soft-magnetic composite material of test one preparation, the part that can obtain black crackle shape from figure is insulating barrier, the white portion being coated by black crackle is iron powder, can show to have prepared soft-magnetic composite material.
Electromagnetic performance and the mechanical property of this kind of soft-magnetic composite material are as shown in table 1.
Table 1 is tested electromagnetic performance and the mechanical performance index of the soft-magnetic composite material of a preparation
In table 1, μ
mfor the maximum permeability of soft-magnetic composite material; B
5000represent the magnetic flux density value of soft-magnetic composite material when magnetizing field is 5000A/m; Br represents residual magnetic flux density; Hc represents coercive force; W (50Hz) be soft-magnetic composite material at maximum magnetic field strength 1T, the iron loss value under alternative frequency 50Hz; W (200Hz) be soft-magnetic composite material at maximum magnetic field strength 1T, the iron loss value under alternative frequency 200Hz; TRS represents cross-breaking strength.
Test two: the preparation method of the glass coating layer soft-magnetic composite material that colloidal sol infiltrates, specifically completes according to the following steps:
One, the ATOMET_1001HP water-atomized iron powder 150g of Canadian Quebec Metal Powder Company Ltd. is put into ethanol, with the ultrasonic 10min of frequency of 30KHz, filtration obtains iron powder, add therein ethanol 660mL and oleic acid 10.72g (12mL), service quality percentage concentration is that 25% ammoniacal liquor is adjusted to 9 by the pH value of solution, rotating speed with 900r/min stirs 1.5 hours, obtains solidliquid mixture;
Two, in the solidliquid mixture obtaining in step 1, add ethanol 2340mL, the ammoniacal liquor that is 25% by mass percentage concentration is adjusted to 9 by the pH value of solution, rotating speed with 900r/min stirs, by the tetraethoxysilane that adds equivalent for 2 times, every minor tick 1 hour, the gross mass of the tetraethoxysilane adding is 44.64g (48mL), after all adding, react 2 hours, obtain the solidliquid mixture at magnetic surface coated silica layer;
Three, in the solidliquid mixture obtaining in step 2, add oleic acid 12.95g (14.5mL) and tetraethoxysilane 61.38g (66mL), adding mass percentage concentration is the ethanolic solution 120mL of 15% caustic alcohol, mass percentage concentration is the ethanolic solution 60mL of 10% calcium ethoxide, the ammoniacal liquor that is 25% by mass percentage concentration is adjusted to 9 by the pH value of solution, rotating speed with 900r/min stirs, react 2.5 hours, the solidliquid mixture obtaining is left standstill to 30min, pouring soln is also retained solution for subsequent use, in the solid obtaining, add ionized water and ethanol to clean 2 times, filter, rear cleaning and solid are put into drying box, temperature is 60 DEG C, dry 240min, dried solid is screened with electromagnet, obtain the cladding iron powder at silicon dioxide layer outer cladding glassy layer,
Four, the cladding iron powder obtaining in step 3 is put into mould, at room temperature, the unidirectional mechanical pressure that applies 1000MPa, constant voltage 3min, removes pressure, obtains the blank of 135g soft-magnetic composite material;
Five, in step 4, be loaded with in the mould of blank of soft-magnetic composite material, add in the step 3 of 8mL and retain solution for subsequent use, at room temperature, apply the mechanical pressure of 1.5MPa, constant voltage 30min, removes pressure, under temperature 60 C, be dried 90min, obtain the blank of the soft-magnetic composite material of glass colloidal sol infiltration;
Six, be 10 by the blank of the soft-magnetic composite material of the glass colloidal sol infiltration obtaining in step 5 in vacuum degree
-1under the condition of Pa, be warmed up to 700 DEG C with the heating rate of 2 DEG C/min from room temperature, constant temperature 60min, is cooled to room temperature with the rate of temperature fall of 2 DEG C/min afterwards, completes annealing, obtains soft-magnetic composite material.
Electromagnetic performance and the mechanical property of this kind of soft-magnetic composite material are as shown in table 2.
Table 2 is tested electromagnetic performance and the mechanical performance index of the soft-magnetic composite material of two preparations
In table 2, μ
mfor the maximum permeability of soft-magnetic composite material; B
5000represent the magnetic flux density value of soft-magnetic composite material when magnetizing field is 5000A/m; Br represents residual magnetic flux density; Hc represents coercive force; W (50Hz) be soft-magnetic composite material at maximum magnetic field strength 1T, the iron loss value under alternative frequency 50Hz; W (200Hz) be soft-magnetic composite material at maximum magnetic field strength 1T, the iron loss value under alternative frequency 200Hz; TRS represents cross-breaking strength.
Test three: the preparation method of the glass coating layer soft-magnetic composite material that colloidal sol infiltrates, specifically completes according to the following steps:
One, the reduced iron powder 150g of Tianjin Peng Da chemical industry Co., Ltd is put into ethanol, with the ultrasonic 10min of frequency of 30KHz, filtration obtains iron powder, add therein ethanol 660mL and oleic acid 10.72g (12mL), service quality percentage concentration is that 25% ammoniacal liquor is adjusted to 9 by the pH value of solution, rotating speed with 700r/min stirs 1.5 hours, obtains solidliquid mixture;
Two, in the solidliquid mixture obtaining in step 1, add ethanol 2340mL, the ammoniacal liquor that is 25% by mass percentage concentration is adjusted to 9 by the pH value of solution, rotating speed with 700r/min stirs, by the tetraethoxysilane that adds equivalent for 2 times, every minor tick 1 hour, the gross mass of the tetraethoxysilane adding is 44.64g (48mL), after all adding, react 2 hours, after reaction finishes, in product, add oleic acid 12.06g (13.5mL), add tetraethoxysilane 69.75g (75mL), the ammoniacal liquor that is 25% by mass percentage concentration is adjusted to 9 by the pH value of solution, stir at the rotating speed with 700r/min, react 2 hours, obtain the solidliquid mixture at iron powder surface coated silica layer,
Three, in the solidliquid mixture obtaining in step 2, add oleic acid 12.95g (14.5mL) and tetraethoxysilane 61.38g (66mL), adding mass percentage concentration is 15% Ti (OC
2h
5)
4ethanolic solution 150mL, the ammoniacal liquor that is 25% by mass percentage concentration is adjusted to 9 by the pH value of solution, stirs with the rotating speed of 800r/min, react 3 hours, the solidliquid mixture obtaining is left standstill to 30min, outwell solution, in the solid obtaining, add ionized water and ethanol to clean 2 times, filter, rear cleaning and solid are put into drying box, and temperature is 60 DEG C, dry 240min, dried solid is screened with electromagnet, obtain the cladding iron powder at silicon dioxide layer outer cladding glassy layer;
Four, by the cladding iron powder obtaining in step 3 at room temperature, the unidirectional mechanical pressure that applies 800MPa, constant voltage 3min, removes pressure, obtains the blank of 125g soft-magnetic composite material;
Five, in step 4, be loaded with in the mould of blank of soft-magnetic composite material, add and in 7mL step 3, retain solution for subsequent use, at room temperature, apply the mechanical pressure of 1.5MPa, constant voltage 40min, removes pressure, under temperature 50 C, be dried 100min, obtain the blank of the soft-magnetic composite material of glass colloidal sol infiltration;
Six, be 10 by the blank of the soft-magnetic composite material obtaining in step 5 in vacuum degree
-1under the condition of Pa, be warmed up to 700 DEG C with the heating rate of 2 DEG C/min from room temperature, constant temperature 60min, is cooled to room temperature with the rate of temperature fall of 2 DEG C/min afterwards, completes annealing, obtains soft-magnetic composite material.
Electromagnetic performance and the mechanical property of this kind of soft-magnetic composite material are as shown in table 3.
Table 3 is tested electromagnetic performance and the mechanical performance index of the soft-magnetic composite material of three preparations
In table 3, μ
mrepresent the maximum permeability of soft-magnetic composite material; B
5000represent the magnetic flux density value of soft-magnetic composite material when magnetizing field is 5000A/m; Br represents residual magnetic flux density; Hc represents coercive force; W (50Hz) represents that soft-magnetic composite material is at maximum magnetic field strength 1T, the iron loss value under alternative frequency 50Hz; W (200Hz) represents that soft-magnetic composite material is at maximum magnetic field strength 1T, the iron loss value under alternative frequency 200Hz; TRS represents cross-breaking strength.
Claims (6)
1. the preparation method of the glass coating layer soft-magnetic composite material that colloidal sol infiltrates, is characterized in that the preparation method of the glass coating layer soft-magnetic composite material of colloidal sol infiltration completes according to the following steps:
One, magnetic is put into the frequency ultrasonic 10min～20min of cleaning agent with 24KHz～35KHz, filtration obtains clean magnetic, in clean magnetic, add ethanol and oleic acid, service quality percentage concentration is that 20%～30% ammoniacal liquor is adjusted to 8.5～9.5 by the pH value of solution, stir 1 hour～2 hours with the ultrasonic dispersion of frequency 1 hour～2 hours of 24KHz～35KHz 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 is a kind of in the magnetic metal powder of tool, the magnetic metal alloy powder of tool and the magnetic metallic compound powder of tool or wherein several combination;
Two, in the solidliquid mixture obtaining in step 1, add ethanol, the ammoniacal liquor that is 20%～30% by mass percentage concentration is adjusted to 8.5～9.5 by the pH value of solution, stirring taking the rotating speed of 600r/min～1200r/min with the pH value of solidliquid mixture under 8.5～9.5 condition, divide the tetraethoxysilane that adds equivalent for 2～4 times, every minor tick 0.5 hour～1.5 hours, the gross mass of the tetraethoxysilane adding and the mass ratio of magnetic are (0.25～0.4): 1, after all adding, react 0.5 hour～1.5 hours, obtain the solidliquid mixture at magnetic surface coated silica layer,
The volume ratio of the solidliquid mixture that the ethanol wherein, adding and step 1 obtain is (2～4): 1;
Three, in the solidliquid mixture obtaining in step 2, add oleic acid, tetraethoxysilane and the organic solution that is dissolved with metal alkoxide, the ammoniacal liquor that is 20%～30% by mass percentage concentration is adjusted to 8.5～9.5 by the pH value of solution, stirring taking the rotating speed of 600r/min～1200r/min with the pH value of solidliquid mixture under 8.5～9.5 condition, react 1 hour～6 hours, the solidliquid mixture obtaining is left standstill to 10min～30min, pouring soln is also retained solution for subsequent use, the solid obtaining is cleaned, filter, solid after cleaning is put into drying box, temperature is 40 DEG C～80 DEG C, dry 20min～360min, dried solid is screened with electromagnet, obtain the coated magnetic at silicon dioxide layer outer cladding glassy layer,
Wherein, the mass ratio of oleic acid and magnetic is (0.05～0.1): 1, the mass ratio of tetraethoxysilane and magnetic is (0.25～0.6): 1, the mass ratio of metal alkoxide and magnetic is (0.05～0.6): 1, and the mass percentage concentration of metal alkoxide in organic solution is 10%～20%; The chemical formula of described metal alkoxide is M (OR)
x, wherein, M is a kind of or its kind of several combination in Ti, B, Be, Mn, In, Ge, Al, Zr, Na, K, Li, Mg, Ca or Ba, R is C
nh
2n+1and n be 1,2,3,4 or 5, x be 1～5 and metal alkoxide be electric neutrality; Be dissolved with organic solvent in the organic solution of metal alkoxide and be a kind of in methyl alcohol, ethanol, ethylene glycol and propyl alcohol or wherein several combination;
Four, the coated magnetic obtaining in step 3 is put into mould, at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min～5min, removes pressure, obtains the blank of soft-magnetic composite material;
Five, in step 4, be loaded with in the mould of blank of soft-magnetic composite material, add and in step 3, retain solution for subsequent use, at room temperature, apply the mechanical pressure of 0.1MPa～10MPa, constant voltage 1min～60min, removes pressure, at 20 DEG C～80 DEG C of temperature, be dried 20min～1000min, obtain the blank of the soft-magnetic composite material of glass colloidal sol infiltration; Wherein, be (0.02mL～0.1mL): 1g to the ratio of the quality of the soft-magnetic composite material that adds in mould the volume of retaining solution for subsequent use in step 3 and step 4 to obtain;
Six, be 10 by the blank of the soft-magnetic composite material of the glass colloidal sol infiltration obtaining in step 5 in vacuum degree
-1under the condition of Pa, be warmed up to 500 DEG C～1000 DEG C with the heating rate of 1 DEG C/min～5 DEG C/min from room temperature, constant temperature 30min～180min, is cooled to room temperature with the rate of temperature fall of 1 DEG C/min～5 DEG C/min afterwards, completes annealing, obtains soft-magnetic composite material;
The glass coating layer soft-magnetic composite material that described colloidal sol infiltrates is made up of the silicon dioxide layer of magnetic, coated magnetic, glassy layer, the glass colloidal sol infiltration layer being coated on outside silicon dioxide layer; Wherein, magnetic is a kind of in the magnetic metal powder of tool, the magnetic metal alloy powder of tool and the magnetic metallic compound powder of tool or wherein several combination; Described magnetic is iron powder, nickel powder, cobalt powder, iron alloy powder, nickel alloy powder, cobalt alloy powder, oxides-containing iron powder, nickeliferous oxidate powder and containing a kind of in cobalt/cobalt oxide powder or wherein several combination and have magnetic.
2. the preparation method of the glass coating layer soft-magnetic composite material that colloidal sol according to claim 1 infiltrates, is characterized in that magnetic described in step 1 is iron powder, nickel powder, cobalt powder, iron alloy powder, nickel alloy powder, cobalt alloy powder, oxides-containing iron powder, nickeliferous oxidate powder and containing a kind of in cobalt/cobalt oxide powder or wherein several combination and have magnetic.
3. the preparation method of the glass coating layer soft-magnetic composite material that colloidal sol according to claim 1 infiltrates, is characterized in that the cleaning agent described in step 1 is the ethanol that acetone or concentration expressed in percentage by volume are greater than 95%.
4. the preparation method of the glass coating layer soft-magnetic composite material that colloidal sol infiltrates, is characterized in that the preparation method of soft-magnetic composite material completes according to the following steps:
One, magnetic is put into the frequency ultrasonic 10min～20min of cleaning agent with 24KHz～35KHz, filtration obtains clean magnetic, in clean magnetic, add ethanol and oleic acid, service quality percentage concentration is that 20%～30% ammoniacal liquor is adjusted to 8.5～9.5 by the pH value of solution, stir 1 hour～2 hours with the ultrasonic dispersion of frequency 1 hour～2 hours of 24KHz～35KHz 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 is a kind of in the magnetic metal powder of tool, the magnetic metal alloy powder of tool and the magnetic metallic compound powder of tool or wherein several combination;
Two, in the solidliquid mixture obtaining in step 1, add ethanol, the ammoniacal liquor that is 20%～30% by mass percentage concentration is adjusted to 8.5～9.5 by the pH value of solution, stirring taking the rotating speed of 600r/min～1200r/min with the pH value of solidliquid mixture under 8.5～9.5 condition, divide the tetraethoxysilane that adds equivalent for 2～4 times, every minor tick 0.5 hour～1.5 hours, the gross mass of the tetraethoxysilane adding and the mass ratio of magnetic are (0.25～0.4): 1, after all adding, react 0.5 hour～1.5 hours, after reaction finishes, in product, add oleic acid, adding with the mass ratio of magnetic is (0.25～0.6): 1 tetraethoxysilane, the ammoniacal liquor that is 20%～30% by mass percentage concentration is adjusted to 8.5～9.5 by the pH value of solution, stirring taking the rotating speed of 600r/min～1200r/min with the pH value of solidliquid mixture under 8.5～9.5 condition, react 2 hours～4 hours, obtain the solidliquid mixture at magnetic surface coated silica layer,
Wherein, the volume ratio of the solidliquid mixture that the ethanol adding and step 1 obtain is (2～4): 1, and the oleic acid adding and the mass ratio of magnetic are (0.05～0.1): 1;
Three, in the solidliquid mixture obtaining in step 2, add oleic acid, tetraethoxysilane and the organic solution that is dissolved with metal alkoxide, the ammoniacal liquor that is 20%～30% by mass percentage concentration is adjusted to 8.5～9.5 by the pH value of solution, stirring taking the rotating speed of 600r/min～1200r/min with the pH value of solidliquid mixture under 8.5～9.5 condition, react 1 hour～6 hours, the solidliquid mixture obtaining is left standstill to 10min～30min, pouring soln is also retained solution for subsequent use, the solid obtaining is cleaned, filter, solid after cleaning is put into drying box, temperature is 40 DEG C～80 DEG C, dry 20min～360min, dried solid is screened with electromagnet, obtain the coated magnetic at silicon dioxide layer outer cladding glassy layer,
Wherein, the mass ratio of oleic acid and magnetic is (0.05～0.1): 1, the mass ratio of tetraethoxysilane and magnetic is (0.25～0.6): 1, the mass ratio of metal alkoxide and magnetic is (0.05～0.6): 1, and the mass percentage concentration of metal alkoxide in organic solution is 10%～20%; The chemical formula of the metal alkoxide described in step 3 is M (OR)
x, wherein, M is a kind of or its kind of several combination in Ti, B, Be, Mn, In, Ge, Al, Zr, Na, K, Li, Mg, Ca or Ba, R is C
nh
2n+1and n be 1,2,3,4 or 5, x be 1～5 and metal alkoxide be electric neutrality; Be dissolved with organic solvent in the organic solution of metal alkoxide and be a kind of in methyl alcohol, ethanol, ethylene glycol and propyl alcohol or wherein several combination;
Four, the coated magnetic obtaining in step 3 is put into mould, at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min～5min, removes pressure, obtains the blank of soft-magnetic composite material;
Five, in step 4, be loaded with in the mould of blank of soft-magnetic composite material, add and in step 3, retain solution for subsequent use, at room temperature, apply the mechanical pressure of 0.1MPa～10MPa, constant voltage 1min～60min, removes pressure, at 20 DEG C～80 DEG C of temperature, be dried 20min～1000min, obtain the blank of the soft-magnetic composite material of glass colloidal sol infiltration; Wherein, be (0.02mL～0.1mL): 1g to the ratio of the quality of the blank of the soft-magnetic composite material that adds in mould the volume of retaining solution for subsequent use in step 3 and step 4 to obtain;
Six, be 10 by the blank of the soft-magnetic composite material of the glass colloidal sol infiltration obtaining in step 5 in vacuum degree
-1under the condition of Pa, be warmed up to 500 DEG C～1000 DEG C with the heating rate of 1 DEG C/min～5 DEG C/min from room temperature, constant temperature 30min～180min, is cooled to room temperature with the rate of temperature fall of 1 DEG C/min～5 DEG C/min afterwards, completes annealing, obtains soft-magnetic composite material;
The glass coating layer soft-magnetic composite material that described colloidal sol infiltrates is made up of the silicon dioxide layer of magnetic, coated magnetic, glassy layer, the glass colloidal sol infiltration layer being coated on outside silicon dioxide layer; Wherein, magnetic is a kind of in the magnetic metal powder of tool, the magnetic metal alloy powder of tool and the magnetic metallic compound powder of tool or wherein several combination; Described magnetic is iron powder, nickel powder, cobalt powder, iron alloy powder, nickel alloy powder, cobalt alloy powder, oxides-containing iron powder, nickeliferous oxidate powder and containing a kind of in cobalt/cobalt oxide powder or wherein several combination and have magnetic.
5. the preparation method of the glass coating layer soft-magnetic composite material that colloidal sol according to claim 4 infiltrates, is characterized in that magnetic described in step 1 is iron powder, nickel powder, cobalt powder, iron alloy powder, nickel alloy powder, cobalt alloy powder, oxides-containing iron powder, nickeliferous oxidate powder and containing a kind of in cobalt/cobalt oxide powder or wherein several combination and have magnetic.
6. the preparation method of the glass coating layer soft-magnetic composite material that colloidal sol according to claim 4 infiltrates, is characterized in that the cleaning agent described in step 1 is the ethanol that acetone or concentration expressed in percentage by volume are greater than 95%.
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