CN102789862B - 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 PDFInfo
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- CN102789862B CN102789862B CN201210318918.1A CN201210318918A CN102789862B CN 102789862 B CN102789862 B CN 102789862B CN 201210318918 A CN201210318918 A CN 201210318918A CN 102789862 B CN102789862 B CN 102789862B
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- 239000002131 composite material Substances 0.000 title claims abstract description 155
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000011521 glass Substances 0.000 claims abstract description 172
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 60
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 134
- 239000000843 powder Substances 0.000 claims description 128
- 239000010410 layer Substances 0.000 claims description 116
- 239000000243 solution Substances 0.000 claims description 82
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 72
- 239000000203 mixture Substances 0.000 claims description 55
- 230000000996 additive effect Effects 0.000 claims description 48
- 239000007864 aqueous solution Substances 0.000 claims description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- 239000000654 additive Substances 0.000 claims description 36
- 239000011247 coating layer Substances 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 36
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 29
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 28
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 28
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 28
- 239000005642 Oleic acid Substances 0.000 claims description 28
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000137 annealing Methods 0.000 claims description 28
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 28
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 28
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 20
- 238000005253 cladding Methods 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 230000002378 acidificating effect Effects 0.000 claims description 18
- 230000001476 alcoholic effect Effects 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 238000001764 infiltration Methods 0.000 claims description 17
- 230000008595 infiltration Effects 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- 229910000531 Co alloy Inorganic materials 0.000 claims description 11
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 11
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012459 cleaning agent Substances 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052774 Proactinium Inorganic materials 0.000 claims description 9
- 238000004140 cleaning 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
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910000765 intermetallic Inorganic materials 0.000 claims description 8
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 229910052790 beryllium Inorganic materials 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 claims description 5
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 claims description 5
- 238000009413 insulation Methods 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 6
- 239000000696 magnetic material Substances 0.000 abstract description 6
- 239000006247 magnetic powder Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 2
- 238000007781 pre-processing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 17
- 229910052742 iron Inorganic materials 0.000 description 16
- 229910044991 metal oxide Inorganic materials 0.000 description 13
- 150000004706 metal oxides Chemical class 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 239000011575 calcium Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 230000035882 stress Effects 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000000280 densification Methods 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 230000005389 magnetism Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000008646 thermal stress Effects 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 229910020598 Co Fe Inorganic materials 0.000 description 3
- 229910002519 Co-Fe Inorganic materials 0.000 description 3
- 229910020516 Co—V Inorganic materials 0.000 description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 3
- 229910003271 Ni-Fe Inorganic materials 0.000 description 3
- 229910003296 Ni-Mo Inorganic materials 0.000 description 3
- 229910018487 Ni—Cr Inorganic materials 0.000 description 3
- 229910002796 Si–Al Inorganic materials 0.000 description 3
- 229910008423 Si—B Inorganic materials 0.000 description 3
- 229910020900 Sn-Fe Inorganic materials 0.000 description 3
- 229910019314 Sn—Fe Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 229910000889 permalloy Inorganic materials 0.000 description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910002028 silica xerogel Inorganic materials 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- AMJQWGIYCROUQF-UHFFFAOYSA-N calcium;methanolate Chemical compound [Ca+2].[O-]C.[O-]C AMJQWGIYCROUQF-UHFFFAOYSA-N 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
Landscapes
- Soft Magnetic Materials (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a preparation method of a sol-infiltrated glass-erogel-coated soft magnetic composite material, and relates 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
Technical field
The present invention relates to soft magnetic material and preparation method thereof.
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 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 infiltrates is made up of magnetic, the silicon dioxide layer of coated magnetic, glass xerogel layer and the glass colloidal sol soakage 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 preparation method of the glass xerogel coating layer soft-magnetic composite material that colloidal sol infiltrates 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 pH value 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 having reacted, leave standstill 10min～30min, outwell solution, 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 magnetic of coated silica layer,
The volume ratio of the solidliquid mixture that the ethanol wherein, adding and step 1 obtain is (2～4): 1;
Three, organizator compound is dissolved in to alcoholic solvent, obtains organizator solution; By a kind of in additive compound and inorganic salts or wherein several combination be dissolved in solvent, obtain solution of additive; Be (0.2～2) by volume by organizator solution with solution of additive: 1 mixes, and at 15 DEG C～65 DEG C 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 to drip acidic aqueous solution the pH value of mixed solution is adjusted to 2～6 or adopt the rate of addition dropping alkaline aqueous solution of 0.5mL/min～1.5mL/min that the pH value of mixed solution is adjusted to 8～12, obtain glass colloidal sol; Wherein, 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 combination; Alcoholic solvent is a kind of in methyl alcohol, ethanol, ethylene glycol and propyl alcohol or wherein several combination; Additive compound is for meeting chemical general formula M (OR)
xcompound in a kind of or wherein several 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 be 1,2,3,4 or 5, x be 1～5 and M (OR)
xcompound be electric neutrality; Inorganic salts are NaNO
3or Ca (NO
3)
24H
2the combination of one or both in O; Solvent is a kind of in methyl alcohol, ethanol, ethylene glycol, the third alcohol and water or wherein several combination; Acidic aqueous solution is a kind of in aqueous hydrochloric acid solution, aqueous solution of nitric acid and aqueous acetic acid or wherein several combination; Alkaline aqueous solution is ammoniacal liquor; The gross mass of organizator compound is (50g～700g): 1L with the ratio of the volume of alcoholic solvent; The ratio of a kind of in additive compound and inorganic salts or the wherein gross mass of several combinations and the volume of solvent is (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%;
Four, in the magnetic of the coated silica layer obtaining in step 2, drip the glass colloidal sol obtaining in step 3, after mixing, at 40 DEG C～100 DEG C, dry 60min～500min, obtains the magnetic at silicon dioxide layer outer cladding 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, by the magnetic at silicon dioxide layer outer cladding glass xerogel layer obtaining in step 4, 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;
Six, in step 5, be loaded with in the mould of blank of soft-magnetic composite material, add the glass colloidal sol in step 3, 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; The ratio of the quality of the blank of the soft-magnetic composite material wherein, obtaining to the volume that adds the glass colloidal sol in step 3 in mould and step 5 is (0.02mL～0.1mL): 1g;
Seven, be 10 by the blank of the soft-magnetic composite material of the glass colloidal sol infiltration obtaining in step 6 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 xerogel 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 pH value 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 pH value under 8.5～9.5 condition, react 2 hours～4 hours, after having reacted, leave standstill 10～30min, outwell solution, 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 magnetic of 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, organizator compound is dissolved in to alcoholic solvent, obtains organizator solution; By a kind of in additive compound and inorganic salts or wherein several combination be dissolved in solvent, obtain solution of additive; Be (0.2～2) by volume by organizator solution with solution of additive: 1 mixes, and at 15 DEG C～65 DEG C 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 to drip acidic aqueous solution the pH value of mixed solution is adjusted to 2～6 or adopt the rate of addition dropping alkaline aqueous solution of 0.5mL/min～1.5mL/min that the pH value of mixed solution is adjusted to 8～12, obtain glass colloidal sol; Wherein, 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 combination; Alcoholic solvent is a kind of in methyl alcohol, ethanol, ethylene glycol and propyl alcohol or wherein several combination; Additive compound is for meeting chemical general formula M (OR)
xcompound in a kind of or wherein several 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 be 1,2,3,4 or 5, x be 1～5 and M (OR)
xcompound be electric neutrality; Inorganic salts are NaNO
3or Ca (NO
3)
24H
2the combination of one or both in O; Solvent is a kind of in methyl alcohol, ethanol, ethylene glycol, the third alcohol and water or wherein several combination; Acidic aqueous solution is a kind of in aqueous hydrochloric acid solution, aqueous solution of nitric acid and aqueous acetic acid or wherein several combination; Alkaline aqueous solution is ammoniacal liquor; The gross mass of organizator compound is (50g～700g): 1L with the ratio of the volume of alcoholic solvent; The ratio of a kind of in additive compound and inorganic salts or the wherein gross mass of several combinations and the volume of solvent is (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%;
Four, in the magnetic of the coated silica layer obtaining in step 2, drip the glass colloidal sol obtaining in step 3, after mixing, at 40 DEG C～100 DEG C, dry 60min～500min, obtains the magnetic at silicon dioxide layer outer cladding 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, by the magnetic at silicon dioxide layer outer cladding glass xerogel layer obtaining in step 4, 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;
Six, in step 5, be loaded with in the mould of blank of soft-magnetic composite material, add the glass colloidal sol in step 3, 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; The ratio of the quality of the blank of the soft-magnetic composite material wherein, obtaining to the volume that adds the glass colloidal sol in step 3 in mould and step 5 is (0.02mL～0.1mL): 1g;
Seven, be 10 by the blank of the soft-magnetic composite material of the glass colloidal sol infiltration obtaining in step 6 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 glass xerogel 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 glass xerogel 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 glass xerogel layer adjustable, and the annealing temperature of soft-magnetic composite material is greater than the softening point temperature of glass xerogel layer again, and then also regulate accordingly the annealing temperature of soft-magnetic composite material.
Brief description of the drawings
Fig. 1 is the electron scanning micrograph of 200 times of test one soft-magnetic composite material preparing.
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 xerogel coating layer soft-magnetic composite material that the colloidal sol that present embodiment provides infiltrates is made up of magnetic, the silicon dioxide layer of coated magnetic, glass xerogel layer and the glass colloidal sol soakage 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 xerogel 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 glass xerogel 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 glass xerogel layer.
The glass xerogel coating layer soft-magnetic composite material that the colloidal sol that present embodiment provides infiltrates, composition and proportioning according to softening point to glass xerogel 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 glass xerogel layer of glass softening point temperature between 400 DEG C and 900 DEG C meets the demands.
The glass xerogel 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 glass xerogel 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 glass xerogel 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 glass xerogel layer adjustable, and the annealing temperature of soft-magnetic composite material is greater than the softening point temperature of glass xerogel layer again, and then also regulate the annealing temperature of soft-magnetic composite material.
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.Other is identical with embodiment one.
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 xerogel 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 pH value 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 having reacted, leave standstill 10min～30min, outwell solution, 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 magnetic of coated silica layer,
The volume ratio of the solidliquid mixture that the ethanol wherein, adding and step 1 obtain is (2～4): 1;
Three, organizator compound is dissolved in to alcoholic solvent, obtains organizator solution; By a kind of in additive compound and inorganic salts or wherein several combination be dissolved in solvent, obtain solution of additive; Be (0.2～2) by volume by organizator solution with solution of additive: 1 mixes, and at 15 DEG C～65 DEG C 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 to drip acidic aqueous solution the pH value of mixed solution is adjusted to 2～6 or adopt the rate of addition dropping alkaline aqueous solution of 0.5mL/min～1.5mL/min that the pH value of mixed solution is adjusted to 8～12, obtain glass colloidal sol; Wherein, 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 combination; Alcoholic solvent is a kind of in methyl alcohol, ethanol, ethylene glycol and propyl alcohol or wherein several combination; Additive compound is for meeting chemical general formula M (OR)
xcompound in a kind of or wherein several 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 be 1,2,3,4 or 5, x be 1～5 and M (OR)
xcompound be electric neutrality; Inorganic salts are NaNO
3or Ca (NO
3)
24H
2the combination of one or both in O; Solvent is a kind of in methyl alcohol, ethanol, ethylene glycol, the third alcohol and water or wherein several combination; Acidic aqueous solution is a kind of in aqueous hydrochloric acid solution, aqueous solution of nitric acid and aqueous acetic acid or wherein several combination; Alkaline aqueous solution is ammoniacal liquor; The gross mass of organizator compound is (50g～700g): 1L with the ratio of the volume of alcoholic solvent; The ratio of a kind of in additive compound and inorganic salts or the wherein gross mass of several combinations and the volume of solvent is (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%;
Four, in the magnetic of the coated silica layer obtaining in step 2, drip the glass colloidal sol obtaining in step 3, after mixing, at 40 DEG C～100 DEG C, dry 60min～500min, obtains the magnetic at silicon dioxide layer outer cladding 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, by the magnetic at silicon dioxide layer outer cladding glass xerogel layer obtaining in step 4, 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;
Six, in step 5, be loaded with in the mould of blank of soft-magnetic composite material, add the glass colloidal sol in step 3, 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; The ratio of the quality of the blank of the soft-magnetic composite material wherein, obtaining to the volume that adds the glass colloidal sol in step 3 in mould and step 5 is (0.02mL～0.1mL): 1g;
Seven, be 10 by the blank of the soft-magnetic composite material of the glass colloidal sol infiltration obtaining in step 6 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.
The method that dried solid described in present embodiment step 2 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 silica xerogel of tool is not blown out, and has reached the object of screening.
The glass xerogel 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 glass xerogel 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 glass xerogel layer.
The glass xerogel coating layer soft-magnetic composite material that colloidal sol prepared by present embodiment infiltrates, can be according to softening point the composition to glass xerogel 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 glass xerogel 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 glass xerogel 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 glass xerogel 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 glass xerogel layer adjustable, and the annealing temperature of soft-magnetic composite material is greater than the softening point temperature of glass xerogel layer again, and then also regulate the annealing temperature of soft-magnetic composite material.
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.Other is identical with embodiment three
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 preparation method of the glass xerogel 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 pH value 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 pH value under 8.5～9.5 condition, react 2 hours～4 hours, after having reacted, leave standstill 10～30min, outwell solution, 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 magnetic of 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, organizator compound is dissolved in to alcoholic solvent, obtains organizator solution; By a kind of in additive compound and inorganic salts or wherein several combination be dissolved in solvent, obtain solution of additive; Be (0.2～2) by volume by organizator solution with solution of additive: 1 mixes, and at 15 DEG C～65 DEG C 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 to drip acidic aqueous solution the pH value of mixed solution is adjusted to 2～6 or adopt the rate of addition dropping alkaline aqueous solution of 0.5mL/min～1.5mL/min that the pH value of mixed solution is adjusted to 8～12, obtain glass colloidal sol; Wherein, 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 combination; Alcoholic solvent is a kind of in methyl alcohol, ethanol, ethylene glycol and propyl alcohol or wherein several combination; Additive compound is for meeting chemical general formula M (OR)
xcompound in a kind of or wherein several 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 be 1,2,3,4 or 5, x be 1～5 and M (OR)
xcompound be electric neutrality; Inorganic salts are NaNO
3or Ca (NO
3)
24H
2the combination of one or both in O; Solvent is a kind of in methyl alcohol, ethanol, ethylene glycol, the third alcohol and water or wherein several combination; Acidic aqueous solution is a kind of in aqueous hydrochloric acid solution, aqueous solution of nitric acid and aqueous acetic acid or wherein several combination; Alkaline aqueous solution is ammoniacal liquor; The gross mass of organizator compound is (50g～700g): 1L with the ratio of the volume of alcoholic solvent; The ratio of a kind of in additive compound and inorganic salts or the wherein gross mass of several combinations and the volume of solvent is (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%;
Four, in the magnetic of the coated silica layer obtaining in step 2, drip the glass colloidal sol obtaining in step 3, after mixing, at 40 DEG C～100 DEG C, dry 60min～500min, obtains the magnetic at silicon dioxide layer outer cladding 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, by the magnetic at silicon dioxide layer outer cladding glass xerogel layer obtaining in step 4, 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;
Six, in step 5, be loaded with in the mould of blank of soft-magnetic composite material, add the glass colloidal sol in step 3, 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; The ratio of the quality of the blank of the soft-magnetic composite material wherein, obtaining to the volume that adds the glass colloidal sol in step 3 in mould and step 5 is (0.02mL～0.1mL): 1g;
Seven, be 10 by the blank of the soft-magnetic composite material of the glass colloidal sol infiltration obtaining in step 6 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.
The method that dried solid described in present embodiment step 2 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 silica xerogel of tool is not blown out, and has reached the object of screening.
The glass xerogel 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 glass xerogel 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 glass xerogel 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 xerogel coating layer soft-magnetic composite material that the colloidal sol that present embodiment provides infiltrates, composition and proportioning according to softening point to glass xerogel 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 glass xerogel 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 glass xerogel 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 glass xerogel 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 glass xerogel layer adjustable, and the annealing temperature of soft-magnetic composite material is greater than the softening point temperature of glass xerogel layer again, and then also regulate the annealing temperature of soft-magnetic composite material.
Embodiment seven: the difference of present embodiment and embodiment six 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.Other is identical with embodiment six.
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 eight: the difference of present embodiment and embodiment six or seven 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 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 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, divide 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 having reacted, leave standstill 20min, outwell solution, the solid obtaining is cleaned, filter, solid after cleaning is put into drying box, temperature is 60 DEG C, dry 300min, dried solid is screened with electromagnet, 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, with the mixing speed of 300r/min, stir 30min, obtain organizator solution; In the ethanolic solution of the caustic alcohol that is 10% to the mass percent concentration of 30mL, add the Ca (NO of 30mL ethanol, 2.5g
3)
24H
2o, obtains solution of additive; Organizator solution is mixed with solution of additive, add mass percent concentration the pH value of solution to be adjusted to 9 as 25% ammoniacal liquor taking the rate of addition of 1mL/min, then with the mixing speed of 300r/min, stir 180min, obtain glass colloidal sol;
Four, by the iron powder natural packing of the coated silica layer of 145g in surface plate, drip the glass colloidal sol of 75mL at the surface uniform of the iron powder of coated silica layer, put into drying baker, at 60 DEG C of dry 240min, obtain the iron powder at silicon dioxide layer outer cladding glass xerogel layer;
Five, by the cladding iron powder obtaining in step 4, put into mould, at room temperature, apply the mechanical pressure of 800MPa, constant voltage 2min, removes pressure, 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 step 3, 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;
Seven, be 10 by the blank of the soft-magnetic composite material obtaining in step 6 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.
The soft-magnetic composite material obtaining is carried out to sem observation, obtain Fig. 1, Fig. 1 is the electron scanning micrograph of 200 times of test one soft-magnetic composite material preparing, the part that can observe black crackle shape from Fig. 1 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 xerogel 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, divide 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 having reacted, leave standstill 20min, outwell solution, the solid obtaining is cleaned, filter, solid after cleaning is put into drying box, temperature is 60 DEG C, dry 300min, dried solid is screened with electromagnet, 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, with the mixing speed of 300r/min, stir 30min, obtain organizator solution; In the ethanolic solution of the caustic alcohol that is 10% to the mass percent concentration of 30mL, the aluminium secondary butylate Al (OC that the methanol solution of the calcium methoxide that the mass percent concentration that adds 10mL is 5%, the mass percent concentration of 10mL are 5%
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, add mass percent concentration the pH value of solution to be adjusted to 4 as 10% aqueous hydrochloric acid solution taking the rate of addition of 1mL/min, then with the mixing speed of 300r/min, stir 120min, obtain glass colloidal sol;
Four, by the iron powder natural packing of the coated silica layer of 140g in surface plate, drip the glass colloidal sol of 80mL at the surface uniform of the iron powder of coated silica layer, put into drying baker, at 70 DEG C of dry 300min, obtain the iron powder at silicon dioxide layer outer cladding glass xerogel layer;
Five, by the cladding iron powder obtaining in step 4, put into mould, at room temperature, apply the mechanical pressure of 1000MPa, constant voltage 2.5min, removes pressure, 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 step 3, at room temperature, apply the mechanical pressure of 1.5MPa, constant voltage 30min, removes pressure, under temperature 50 C, be dried 100min, obtain the blank of the soft-magnetic composite material of glass colloidal sol infiltration;
Seven, be 10 by the blank of the soft-magnetic composite material obtaining in step 6 in vacuum degree
-1under the condition of Pa, be warmed up to 750 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 xerogel 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, divide 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 magnetic surface coated silica layer, leave standstill 20min, outwell solution, the solid obtaining is cleaned, filter, solid after cleaning is put into drying box, temperature is 60 DEG C, and dry 300min, screens dried solid with electromagnet, 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, with the mixing speed of 300r/min, stir 30min, obtain organizator solution; In the ethanolic solution of the caustic alcohol that is 10% to the mass percent concentration of 30mL, with the mixing speed of 400r/min, stir 30min, obtain solution of additive; Organizator solution is mixed with solution of additive, then with the mixing speed of 300r/min, stir 120min, obtain glass colloidal sol;
Four, by the iron powder natural packing of the coated silica layer of 140g in surface plate, drip the glass colloidal sol of 90mL at the surface uniform of the iron powder of coated silica layer, put into drying baker, at 70 DEG C of dry 120min, obtain the iron powder at silicon dioxide layer outer cladding glass xerogel layer;
Five, by the cladding iron powder obtaining in step 4, put into mould, at room temperature, apply the mechanical pressure of 950MPa, constant voltage 2.5min, removes pressure, 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 step 3, at room temperature, apply the mechanical pressure of 1.5MPa, constant voltage 40min, removes pressure, under temperature 60 C, be dried 70min, obtain the blank of the soft-magnetic composite material of glass colloidal sol infiltration;
Seven, 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 500 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
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.
Claims (6)
1. the preparation method of the glass xerogel coating layer soft-magnetic composite material that colloidal sol infiltrates, is characterized in that the preparation method of the glass xerogel 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);
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 pH value 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 having reacted, leave standstill 10min～30min, outwell solution, 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 magnetic of coated silica layer,
The volume ratio of the solidliquid mixture that the ethanol wherein, adding and step 1 obtain is (2～4): 1;
Three, organizator compound is dissolved in to alcoholic solvent, obtains organizator solution; By a kind of in additive compound and inorganic salts or wherein several combination be dissolved in solvent, obtain solution of additive; Be (0.2～2) by volume by organizator solution with solution of additive: 1 mixes, and at 15 DEG C～65 DEG C 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 to drip acidic aqueous solution the pH value of mixed solution is adjusted to 2～6 or adopt the rate of addition dropping alkaline aqueous solution of 0.5mL/min～1.5mL/min that the pH value of mixed solution is adjusted to 8～12, obtain glass colloidal sol; Wherein, 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 combination; Alcoholic solvent is a kind of in methyl alcohol, ethanol, ethylene glycol and propyl alcohol or wherein several combination; Additive compound is for meeting chemical general formula M (OR)
xcompound in a kind of or wherein several combination, M is Si, Ti, Be, Mn, In, Ge, Al, Zr, Na, K, Li, Ca, Mg or Ba, R is C
nh
2n+1and n be 1,2,3,4 or 5, x be 1～5 and M (OR)
xcompound be electric neutrality; Inorganic salts are NaNO
3or Ca (NO
3)
24H
2the combination of one or both in O; Solvent is a kind of in methyl alcohol, ethanol, ethylene glycol, the third alcohol and water or wherein several combination; Acidic aqueous solution is a kind of in aqueous hydrochloric acid solution, aqueous solution of nitric acid and aqueous acetic acid or wherein several combination; Alkaline aqueous solution is ammoniacal liquor; The gross mass of organizator compound is (50g～700g): 1L with the ratio of the volume of alcoholic solvent; The ratio of a kind of in additive compound and inorganic salts or the wherein gross mass of several combinations and the volume of solvent is (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%;
Four, in the magnetic of the coated silica layer obtaining in step 2, drip the glass colloidal sol obtaining in step 3, after mixing, at 40 DEG C～100 DEG C, dry 60min～500min, obtains the magnetic at silicon dioxide layer outer cladding 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, by the magnetic at silicon dioxide layer outer cladding glass xerogel layer obtaining in step 4, 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;
Six, in step 5, be loaded with in the mould of blank of soft-magnetic composite material, add the glass colloidal sol in step 3, 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; The ratio of the quality of the blank of the soft-magnetic composite material wherein, obtaining to the volume that adds the glass colloidal sol in step 3 in mould and step 5 is (0.02mL～0.1mL): 1g;
Seven, be 10 by the blank of the soft-magnetic composite material of the glass colloidal sol infiltration obtaining in step 6 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; Described soft-magnetic composite material is made up of magnetic, the silicon dioxide layer of coated magnetic, glass xerogel layer and the glass colloidal sol soakage 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.
2. the preparation method of the glass xerogel 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 xerogel 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 xerogel 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);
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 pH value 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 pH value under 8.5～9.5 condition, react 2 hours～4 hours, after having reacted, leave standstill 10～30min, outwell solution, 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 magnetic of 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, organizator compound is dissolved in to alcoholic solvent, obtains organizator solution; By a kind of in additive compound and inorganic salts or wherein several combination be dissolved in solvent, obtain solution of additive; Be (0.2～2) by volume by organizator solution with solution of additive: 1 mixes, and at 15 DEG C～65 DEG C 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 to drip acidic aqueous solution the pH value of mixed solution is adjusted to 2～6 or adopt the rate of addition dropping alkaline aqueous solution of 0.5mL/min～1.5mL/min that the pH value of mixed solution is adjusted to 8～12, obtain glass colloidal sol; Wherein, 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 combination; Alcoholic solvent is a kind of in methyl alcohol, ethanol, ethylene glycol and propyl alcohol or wherein several combination; Additive compound is for meeting chemical general formula M (OR)
xcompound in a kind of or wherein several combination, M is Si, Ti, Be, Mn, In, Ge, Al, Zr, Na, K, Li, Ca, Mg or Ba, R is C
nh
2n+1and n be 1,2,3,4 or 5, x be 1～5 and M (OR)
xcompound be electric neutrality; Inorganic salts are NaNO
3or Ca (NO
3)
24H
2the combination of one or both in O; Solvent is a kind of in methyl alcohol, ethanol, ethylene glycol, the third alcohol and water or wherein several combination; Acidic aqueous solution is a kind of in aqueous hydrochloric acid solution, aqueous solution of nitric acid and aqueous acetic acid or wherein several combination; Alkaline aqueous solution is ammoniacal liquor; The gross mass of organizator compound is (50g～700g): 1L with the ratio of the volume of alcoholic solvent; The ratio of a kind of in additive compound and inorganic salts or the wherein gross mass of several combinations and the volume of solvent is (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%;
Four, in the magnetic of the coated silica layer obtaining in step 2, drip the glass colloidal sol obtaining in step 3, after mixing, at 40 DEG C～100 DEG C, dry 60min～500min, obtains the magnetic at silicon dioxide layer outer cladding 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, by the magnetic at silicon dioxide layer outer cladding glass xerogel layer obtaining in step 4, 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;
Six, in step 5, be loaded with in the mould of blank of soft-magnetic composite material, add the glass colloidal sol in step 3, 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; The ratio of the quality of the blank of the soft-magnetic composite material wherein, obtaining to the volume that adds the glass colloidal sol in step 3 in mould and step 5 is (0.02mL～0.1mL): 1g;
Seven, be 10 by the blank of the soft-magnetic composite material of the glass colloidal sol infiltration obtaining in step 6 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; Described soft-magnetic composite material is made up of magnetic, the silicon dioxide layer of coated magnetic, glass xerogel layer and the glass colloidal sol soakage 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.
5. the preparation method of the glass xerogel 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 xerogel 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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