CN102789863B - Preparation method of soft magnetic composite material taking glass powder as coating layer - Google Patents
Preparation method of soft magnetic composite material taking glass powder as coating layer Download PDFInfo
- Publication number
- CN102789863B CN102789863B CN201210318920.9A CN201210318920A CN102789863B CN 102789863 B CN102789863 B CN 102789863B CN 201210318920 A CN201210318920 A CN 201210318920A CN 102789863 B CN102789863 B CN 102789863B
- Authority
- CN
- China
- Prior art keywords
- magnetic
- composite material
- soft
- powder
- glass dust
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Powder Metallurgy (AREA)
- Soft Magnetic Materials (AREA)
Abstract
The invention relates to a preparation method of the soft magnetic composite material taking glass powder as a coating layer, relating to the soft magnetic material and the preparation method thereof. In the invention, the problem that in the traditional soft magnetic composite material of an inorganic coating layer, excellent mechanical property of the soft magnetic composite material and excellent magnetic property of the soft magnetic composite material resulting from an annealing mean can not coexist, and the difference of coefficients of thermal expansion between an inorganic insulating layer and magnetic powder is greater is solved. The soft magnetic composite material taking the glass powder as the coating layer consists of the magnetic powder, a silicon dioxide layer coated by the magnetic powder and a glass powder layer coated outside the silicon dioxide layer. The preparation method comprises the following steps: firstly, pre-treating the magnetic powder; secondly, coating the silicon dioxide layer on the surface of the magnetic powder; thirdly, coating the glass powder layer outside the silicon dioxide layer; fourthly, preparing a blank material; and fifthly, annealing the blank material. The soft magnetic composite material taking the glass powder as the coating layer and the preparation method of the soft magnetic composite material are applied to the fields of switch magnetic resistance, resonance 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 associativity of magnetic and inorganic insulation layer is bad, the residual stress effectively removed in preparation process of method by annealing can cause the mechanical property of soft-magnetic composite material poor, and the cross-breaking strength of the coated soft-magnetic composite material of existing inorganic matter is less than 70MPa; Meanwhile, the thermal coefficient of expansion of inorganic insulation layer and magnetic differs larger, can in magnetic, produce thermal stress at the larger environment of the temperature difference or in long-time use procedure, causes the soft-magnetic composite material of inorganic matter coating layer cannot have 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, effectively remove by the method for annealing the thermal coefficient of expansion that the residual stress in preparation process causes again the cross-breaking strength of existing soft-magnetic composite material to be less than 70MPa and inorganic insulation layer and magnetic and differ larger problem, and soft-magnetic composite material using glass dust as coating layer and preparation method thereof is provided.
Soft-magnetic composite material using glass dust as coating layer is made up of magnetic, the silicon dioxide layer of coated magnetic and the glass frit 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 soft-magnetic composite material using glass dust as coating layer completes according to the following steps: one, magnetic is put into the frequency ultrasonic 10min～20min of cleaning agent with 24KHz～35KHz, filtration obtains magnetic, add therein 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, by 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, the solidliquid mixture that reaction is obtained leaves 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, in the magnetic of the coated silica layer three, obtaining in step 2, add glycerol, in batch mixer, be uniformly mixed mixing rate 15r/min～60r/min, incorporation time 20min～90min, in mixture, adding particle diameter is the glass dust of 10nm～500nm, continues to be uniformly mixed mixing rate 15r/min～60r/min in batch mixer, incorporation time 20min～90min, obtains the coated magnetic in silicon dioxide layer outer cladding glass frit layer, wherein, the mass ratio of glycerol and magnetic is (0.01～0.05): 1, and the mass ratio of glass dust and magnetic is (0.05～0.25): 1, four, by the coated magnetic obtaining in step 3 at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min～5min, removes pressure, obtains the blank of the soft-magnetic composite material using glass dust as coating layer, five, be 10 by the blank of the soft-magnetic composite material taking glass dust as coating layer obtaining in step 4 in vacuum degree
-1under the condition of Pa, heating rate with 1 DEG C/min～5 DEG C/min is warmed up to heat treatment temperature from room temperature, and 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, complete annealing, obtain the soft-magnetic composite material using glass dust as coating layer, wherein heat treatment temperature is 500 DEG C～1000 DEG C.
The preparation method of the soft-magnetic composite material using glass dust as coating layer completes according to the following steps: one, magnetic is put into the frequency ultrasonic 10min～20min of cleaning agent with 24KHz～35KHz, filtration obtains magnetic, add therein 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, by 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, the solidliquid mixture that reaction is obtained leaves 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, 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, in the magnetic of the coated silica layer three, obtaining in step 2, add glycerol, in batch mixer, be uniformly mixed mixing rate 15r/min～60r/min, incorporation time 20min～90min, in mixture, adding particle diameter is the glass dust of 10nm～500nm, continues to be uniformly mixed mixing rate 15r/min～60r/min in batch mixer, incorporation time 20min～90min, obtains the coated magnetic in silicon dioxide layer outer cladding glass frit layer, wherein, the mass ratio of glycerol and magnetic is (0.01～0.05): 1, and the mass ratio of glass dust and magnetic is (0.05～0.25): 1, four, by the coated magnetic obtaining in step 3 at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min～5min, removes pressure, obtains the blank of the soft-magnetic composite material using glass dust as coating layer, five, be 10 by the blank of the soft-magnetic composite material taking glass dust as coating layer obtaining in step 4 in vacuum degree
-1under the condition of Pa, heating rate with 1 DEG C/min～5 DEG C/min is warmed up to heat treatment temperature from room temperature, and 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, complete annealing, obtain the soft-magnetic composite material using glass dust as coating layer, wherein heat treatment temperature is 500 DEG C～1000 DEG C.
Advantage of the present invention: the soft-magnetic composite material using glass dust as coating layer 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 dust to make the thermal coefficient of expansion of coated glass frit 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 frit layer softening temperature, can effectively eliminate the internal stress in soft-magnetic composite material, improve the magnetic property of soft-magnetic composite material, simultaneously, material can experience the temperature that is greater than glass frit layer softening temperature in annealing process, and therefore the combination of magnetic and coating layer is no longer simple mechanical bond, but a kind of diffusion bond, therefore also improve the mechanical property of soft-magnetic composite material, made the cross-breaking strength of soft-magnetic composite material be greater than 90MPa.
Three, the annealing temperature of soft-magnetic composite material is adjustable, can be by regulating the proportioning of each composition in glass dust, make the softening point temperature of glass frit layer adjustable, and the annealing temperature of soft-magnetic composite material is greater than the softening point temperature of glass frit 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 iron powder in test one.
Fig. 2 is the electron scanning micrograph of 50000 times of glass dust in test one.
Fig. 3 is the electron scanning micrograph of 200 times at the coated magnetic of silicon dioxide layer outer cladding glass frit layer in test one.
Fig. 4 is the metallograph of the soft-magnetic composite material using glass dust as coating layer 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 soft-magnetic composite material using glass dust as coating layer that present embodiment provides is made up of magnetic, the silicon dioxide layer of coated magnetic and the glass frit 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 soft-magnetic composite material using glass dust as coating layer that present embodiment provides, can be according to thermal coefficient of expansion the composition to glass frit 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 dust 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 glass dust thermal coefficient of expansion as the component of glass dust.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 dust 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 glass dust thermal coefficient of expansion 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 frit layer.
The soft-magnetic composite material using glass dust as coating layer that present embodiment provides, composition and proportioning according to softening point to glass frit layer are adjusted.Because the glass dust 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 dust 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 frit layer of glass dust softening point temperature between 400 DEG C and 900 DEG C meets the demands.
The soft-magnetic composite material using glass dust as coating layer that present embodiment provides 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 dust to make the thermal coefficient of expansion of coated glass frit 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 frit layer softening temperature, can effectively eliminate the internal stress in soft-magnetic composite material, improve the magnetic property of soft-magnetic composite material, simultaneously, material can experience the temperature that is greater than glass frit layer softening temperature in annealing process, and therefore the combination of magnetic and coating layer is no longer simple mechanical bond, but a kind of diffusion bond, therefore also improve the mechanical property of soft-magnetic composite material, made the cross-breaking strength of soft-magnetic composite material be greater than 90MPa.The annealing temperature of soft-magnetic composite material is adjustable, can be by regulating the proportioning of each composition in glass dust, make the softening point temperature of glass frit layer adjustable, and the annealing temperature of soft-magnetic composite material is greater than the softening point temperature of glass frit layer again, and then has also regulated 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.
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 soft-magnetic composite material using glass dust as coating layer that present embodiment provides, 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 magnetic, add therein 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 the magnetic metal powder of tool, a kind of in 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, by 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, the solidliquid mixture that reaction is obtained leaves 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,
In the magnetic of the coated silica layer three, obtaining in step 2, add glycerol, in batch mixer, be uniformly mixed mixing rate 15r/min～60r/min, incorporation time 20min～90min, in mixture, adding particle diameter is the glass dust of 10nm～500nm, continues to be uniformly mixed mixing rate 15r/min～60r/min in batch mixer, incorporation time 20min～90min, obtains the coated magnetic in silicon dioxide layer outer cladding glass frit layer; Wherein, the mass ratio of glycerol and magnetic is (0.01～0.05): 1, and the mass ratio of glass dust and magnetic is (0.05～0.25): 1;
Four, by the coated magnetic obtaining in step 3 at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min～5min, removes pressure, obtains the blank of the soft-magnetic composite material using glass dust as coating layer;
Five, be 10 by the blank of the soft-magnetic composite material taking glass dust as coating layer obtaining in step 4 in vacuum degree
-1under the condition of Pa, heating rate with 1 DEG C/min～5 DEG C/min is warmed up to heat treatment temperature from room temperature, constant temperature 30min～180min, be cooled to room temperature with the rate of temperature fall of 1 DEG C/min～5 DEG C/min afterwards, complete annealing, obtain the soft-magnetic composite material using glass dust as coating layer, wherein heat treatment temperature is 500 DEG C～1000 DEG C.
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.
Soft-magnetic composite material using glass dust as coating layer prepared by present embodiment, can be according to thermal coefficient of expansion the composition to glass dust 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 dust 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 glass dust thermal coefficient of expansion as the component of glass dust.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 dust 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 glass dust thermal coefficient of expansion 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 frit layer.
Soft-magnetic composite material using glass dust as coating layer prepared by present embodiment, can be according to softening point the composition to glass frit layer and proportioning adjust.Because the glass dust 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 dust 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 frit layer of glass dust softening point temperature between 400 DEG C and 900 DEG C meets the demands.
Soft-magnetic composite material using glass dust as coating layer 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 dust to make the thermal coefficient of expansion of coated glass frit 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 frit layer softening temperature, can effectively eliminate the internal stress in soft-magnetic composite material, improve the magnetic property of soft-magnetic composite material, simultaneously, material can experience the temperature that is greater than glass frit layer softening temperature in annealing process, and therefore the combination of magnetic and coating layer is no longer simple mechanical bond, but a kind of diffusion bond, therefore also improve the mechanical property of soft-magnetic composite material, made the cross-breaking strength of soft-magnetic composite material be greater than 90MPa.The annealing temperature of soft-magnetic composite material is adjustable, can be by regulating the proportioning of each composition in glass dust, make the softening point temperature of glass frit layer adjustable, and the annealing temperature of soft-magnetic composite material is greater than the softening point temperature of glass frit layer again, and then has also regulated 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.
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, the permalloy powder that wherein 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: prepared by the sol-gal process of the glass dust described in step 3.
Embodiment seven: the preparation method of the soft-magnetic composite material using glass dust as coating layer that present embodiment provides, 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 magnetic, add therein 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, by 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, the solidliquid mixture that reaction is obtained leaves 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, 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,
In the magnetic of the coated silica layer three, obtaining in step 2, add glycerol, in batch mixer, be uniformly mixed mixing rate 15r/min～60r/min, incorporation time 20min～90min, in mixture, adding particle diameter is the glass dust of 10nm～500nm, continues to be uniformly mixed mixing rate 15r/min～60r/min in batch mixer, incorporation time 20min～90min, obtains the coated magnetic in silicon dioxide layer outer cladding glass frit layer; Wherein, the mass ratio of glycerol and magnetic is (0.01～0.05): 1, and the mass ratio of glass dust and magnetic is (0.05～0.25): 1;
Four, by the coated magnetic obtaining in step 3 at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min～5min, removes pressure, obtains the blank of the soft-magnetic composite material using glass dust as coating layer;
Five, be 10 by the blank of the soft-magnetic composite material taking glass dust as coating layer obtaining in step 4 in vacuum degree
-1under the condition of Pa, heating rate with 1 DEG C/min～5 DEG C/min is warmed up to heat treatment temperature from room temperature, and 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, complete annealing, obtain the soft-magnetic composite material using glass dust as coating layer;
Wherein heat treatment temperature is 500 DEG C～1000 DEG C.
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 soft-magnetic composite material using glass dust as coating layer that present embodiment provides, can be according to thermal coefficient of expansion the composition to glass frit 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 dust 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 glass dust thermal coefficient of expansion in the time selecting the component of glass dust, 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 dust 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 glass dust thermal coefficient of expansion 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 frit layer.Common glass dust formation 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 soft-magnetic composite material using glass dust as coating layer that present embodiment provides, composition and proportioning according to softening point to glass frit layer are adjusted.Because the glass dust 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 dust 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 frit layer of glass dust softening point temperature between 400 DEG C and 900 DEG C meets the demands.
Soft-magnetic composite material using glass dust as coating layer 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 dust to make the thermal coefficient of expansion of coated glass frit 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 frit layer softening temperature, can effectively eliminate the internal stress in soft-magnetic composite material, improve the magnetic property of soft-magnetic composite material, simultaneously, material can experience the temperature that is greater than glass frit layer softening temperature in annealing process, and therefore the combination of magnetic and coating layer is no longer simple mechanical bond, but a kind of diffusion bond, therefore also improve the mechanical property of soft-magnetic composite material, made the cross-breaking strength of soft-magnetic composite material be greater than 90MPa.The annealing temperature of soft-magnetic composite material is adjustable, can be by regulating the proportioning of each composition in glass dust, make the softening point temperature of glass frit layer adjustable, and the annealing temperature of soft-magnetic composite material is greater than the softening point temperature of glass frit 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, the permalloy powder that wherein 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: prepared by the sol-gal process of the glass dust described in step 3.
Adopt following verification experimental verification effect of the present invention:
Test one: the preparation method of the soft-magnetic composite material using glass dust as coating layer, 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 250mL 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 46.5g (50mL), after all adding, react 2 hours, the solidliquid mixture that reaction is obtained leaves standstill 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, temperature is 60 DEG C, dry 240min, dried solid is screened with electromagnet, obtain the magnetic of coated silica layer,
In the magnetic of the coated silica layer three, obtaining in step 2, add 4.5g glycerol, in V-type batch mixer, stir mixing speed 20r/min, duration 5min, in the mixture obtaining, adding particle diameter is the glass dust 15g of 10nm～300nm, continues to stir mixing speed 20r/min in V-type batch mixer, duration 30min, obtains the coated magnetic in silicon dioxide layer outer cladding glass frit layer; Wherein, glass dust is prepared with sol-gal process, and glass dust is pressed mass fraction by 30% Na
2o, 4% CaO and 66% SiO
2composition;
Four, by the cladding iron powder obtaining in step 3 at room temperature, apply the mechanical pressure of 1000MPa, constant voltage 3min, removes pressure, obtains the blank of the soft-magnetic composite material using glass dust as coating layer;
Five, be 10 by the blank of the soft-magnetic composite material taking glass dust as coating layer obtaining in step 4 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 the soft-magnetic composite material using glass dust as coating layer.
The iron powder of step 1 is carried out to scanning electron microscope test, and as shown in Figure 1, Fig. 1 is the electron scanning micrograph of 200 times of iron powder in test one; The glass dust of step 3 is carried out to scanning electron microscope test, and as shown in Figure 2, Fig. 2 is the electron scanning micrograph of 50000 times of glass dust in test one; The coated magnetic in silicon dioxide layer outer cladding glass frit layer that step 3 is obtained carries out scanning electron microscope test, as shown in Figure 3, Fig. 3 is the electron scanning micrograph of 200 times at the coated magnetic of silicon dioxide layer outer cladding glass frit layer in test one; From above-mentioned three figure, can draw, test is to be undertaken by described step, and has obtained the coated magnetic in silicon dioxide layer outer cladding glass frit layer.The soft-magnetic composite material using glass dust as coating layer that step 5 is prepared carries out Metallographic Analysis, as shown in Figure 4, Fig. 4 is the metallograph of the soft-magnetic composite material using glass dust as coating layer of test one preparation, from Fig. 4, the part that can obtain black crackle shape is insulating barrier, the white portion being coated by black crackle is iron powder, can show to have prepared the soft-magnetic composite material using glass dust as coating layer.
Electromagnetic performance and the mechanical property of the soft-magnetic composite material of this kind using glass dust as coating layer are as shown in table 1.
Table 1 is tested electromagnetic performance and the mechanical performance index of the soft-magnetic composite material using glass dust as coating layer 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 soft-magnetic composite material using glass dust as coating layer, 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 250mL 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 46.5g (50mL), after all adding, react 3 hours, the solidliquid mixture that reaction is obtained leaves standstill 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, temperature is 60 DEG C, dry 240min, dried solid is screened with electromagnet, obtain the magnetic of coated silica layer,
In the magnetic of the coated silica layer three, obtaining in step 2, add 4.5g glycerol, in V-type batch mixer, stir mixing speed 20r/min, duration 5min, in the mixture obtaining, adding particle diameter is the glass dust 15g of 10nm～300nm, continues to stir mixing speed 20r/min in V-type batch mixer, duration 30min, obtains the coated magnetic in silicon dioxide layer outer cladding glass frit layer; Wherein, glass dust is prepared with sol-gal process, and glass dust is pressed mass fraction by 25% Na
2o, 6% Al
2o
3with 69% SiO
2composition;
Four, by the cladding iron powder obtaining in step 3 at room temperature, apply the mechanical pressure of 1000MPa, constant voltage 3min, removes pressure, obtains the blank of the soft-magnetic composite material using glass dust as coating layer;
Five, be 10 by the blank of the soft-magnetic composite material taking glass dust as coating layer obtaining in step 4 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 the soft-magnetic composite material using glass dust as coating layer.
Electromagnetic performance and the mechanical property of the soft-magnetic composite material of this kind using glass dust as coating layer are as shown in table 2.
Table 2 is tested electromagnetic performance and the mechanical performance index of the soft-magnetic composite material using glass dust as coating layer 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 soft-magnetic composite material using glass dust as coating layer, 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 250mL 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 46.5g (50mL), after all adding, react 3 hours, after reaction finishes, in product, add oleic acid 12.00g (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, the solidliquid mixture that reaction is obtained leaves standstill 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, temperature is 60 DEG C, dry 240min, dried solid is screened with electromagnet, obtain the magnetic of coated silica layer,
In the magnetic of the coated silica layer three, obtaining in step 2, add 4.5g glycerol, in V-type batch mixer, stir mixing speed 20r/min, duration 5min, in the mixture obtaining, adding particle diameter is the glass dust 15g of 10nm～250nm, continues to stir mixing speed 20r/min in V-type batch mixer, duration 30min, obtains the coated magnetic in silicon dioxide layer outer cladding glass frit layer; Wherein, glass dust is prepared with sol-gal process, and glass dust is pressed mass fraction by 22% Na
2o, 4.5% Al
2o
3, 4.5% TiO
2with 69% SiO
2composition;
Four, by the cladding iron powder obtaining in step 3 at room temperature, apply the mechanical pressure of 900MPa, constant voltage 3min, removes pressure, obtains the blank of the soft-magnetic composite material using glass dust as coating layer;
Five, be 10 by the blank of the soft-magnetic composite material taking glass dust as coating layer obtaining in step 4 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 the soft-magnetic composite material using glass dust as coating layer.
Electromagnetic performance and the mechanical property of the soft-magnetic composite material of this kind using glass dust as coating layer are as shown in table 3.
Table 3 is tested electromagnetic performance and the mechanical performance index of the soft-magnetic composite material using glass dust as coating layer 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 (8)
1. the preparation method of the soft-magnetic composite material using glass dust as coating layer, is characterized in that the preparation method of the soft-magnetic composite material using glass dust as coating layer completes according to the following steps:
One, magnetic is put into the frequency ultrasonic 10min～20min of cleaning agent with 24KHz～35KHz, filtration obtains magnetic, add therein 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 the pH value of solidliquid mixture under 8.5～9.5 condition, by 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, the solidliquid mixture that reaction is obtained leaves 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, wherein, the volume ratio of the solidliquid mixture that the ethanol adding and step 1 obtain is (2～4): 1,
Three, in the magnetic of the coated silica layer obtaining in step 2, add glycerol, in batch mixer, be uniformly mixed, mixing rate 15r/min～60r/min, incorporation time 20min～90min, in mixture, adding particle diameter is the glass dust of 10nm～500nm, continue to be uniformly mixed in batch mixer, mixing rate 15r/min～60r/min, incorporation time 20min～90min, obtain the coated magnetic in silicon dioxide layer outer cladding glass frit layer, wherein, the mass ratio of glycerol and magnetic is (0.01～0.05): 1, the mass ratio of glass dust and magnetic is (0.05～0.25): 1,
Four, by the coated magnetic obtaining in step 3 at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min～5min, removes pressure, obtains the blank of the soft-magnetic composite material using glass dust as coating layer;
Five, be 10 by the blank of the soft-magnetic composite material taking glass dust as coating layer obtaining in step 4 in vacuum degree
-1under the condition of Pa, heating rate with 1 DEG C/min～5 DEG C/min is warmed up to heat treatment temperature from room temperature, constant temperature 30min～180min, be cooled to room temperature with the rate of temperature fall of 1 DEG C/min～5 DEG C/min afterwards, complete annealing, obtain the soft-magnetic composite material using glass dust as coating layer, wherein, heat treatment temperature is 500 DEG C～1000 DEG C; The described soft-magnetic composite material using glass dust as coating layer is made up of magnetic, the silicon dioxide layer of coated magnetic and the glass frit 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 soft-magnetic composite material using glass dust as coating layer according to claim 1, 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 soft-magnetic composite material using glass dust as coating layer according to claim 1, 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 soft-magnetic composite material using glass dust as coating layer according to claim 1, is characterized in that prepared by the glass dust sol-gal process described in step 3.
5. the preparation method of the soft-magnetic composite material using glass dust as coating layer, is characterized in that the preparation method of the soft-magnetic composite material using glass dust as coating layer completes according to the following steps:
One, magnetic is put into the frequency ultrasonic 10min～20min of cleaning agent with 24KHz～35KHz, filtration obtains magnetic, add therein 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 the pH value of solidliquid mixture under 8.5～9.5 condition, by 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, the solidliquid mixture that reaction is obtained leaves 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, wherein, the volume ratio of the solidliquid mixture that the ethanol adding and step 1 obtain is (2～4): 1, the oleic acid adding and the mass ratio of magnetic are (0.05～0.1): 1,
Three, in the magnetic of the coated silica layer obtaining in step 2, add glycerol, in batch mixer, be uniformly mixed, mixing rate 15r/min～60r/min, incorporation time 20min～90min, in mixture, adding particle diameter is the glass dust of 10nm～500nm, continue to be uniformly mixed in batch mixer, mixing rate 15r/min～60r/min, incorporation time 20min～90min, obtain the coated magnetic in silicon dioxide layer outer cladding glass frit layer, wherein, the mass ratio of glycerol and magnetic is (0.01～0.05): 1, the mass ratio of glass dust and magnetic is (0.05～0.25): 1,
Four, by the coated magnetic obtaining in step 3 at room temperature, apply the mechanical pressure of 600MPa～1500MPa, constant voltage 1min～5min, removes pressure, obtains the blank of the soft-magnetic composite material using glass dust as coating layer;
Five, be 10 by the blank of the soft-magnetic composite material taking glass dust as coating layer obtaining in step 4 in vacuum degree
-1under the condition of Pa, heating rate with 1 DEG C/min～5 DEG C/min is warmed up to heat treatment temperature from room temperature, constant temperature 30min～180min, be cooled to room temperature with the rate of temperature fall of 1 DEG C/min～5 DEG C/min afterwards, complete annealing, obtain the soft-magnetic composite material using glass dust as coating layer, wherein heat treatment temperature is 500 DEG C～1000 DEG C; The described soft-magnetic composite material using glass dust as coating layer is made up of magnetic, the silicon dioxide layer of coated magnetic and the glass frit 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.
6. the preparation method of the soft-magnetic composite material using glass dust as coating layer according to claim 5, 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.
7. the preparation method of the soft-magnetic composite material using glass dust as coating layer according to claim 5, 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%.
8. the preparation method of the soft-magnetic composite material using glass dust as coating layer according to claim 5, is characterized in that prepared by the glass dust sol-gal process described in step 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210318920.9A CN102789863B (en) | 2012-08-31 | 2012-08-31 | Preparation method of soft magnetic composite material taking glass powder as coating layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210318920.9A CN102789863B (en) | 2012-08-31 | 2012-08-31 | Preparation method of soft magnetic composite material taking glass powder as coating layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102789863A CN102789863A (en) | 2012-11-21 |
| CN102789863B true CN102789863B (en) | 2014-11-12 |
Family
ID=47155243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210318920.9A Active CN102789863B (en) | 2012-08-31 | 2012-08-31 | Preparation method of soft magnetic composite material taking glass powder as coating layer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102789863B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103177838B (en) * | 2012-12-30 | 2016-08-03 | 中南大学 | A kind of soft magnetic composite powder and preparation method thereof |
| JP6504287B1 (en) * | 2018-03-09 | 2019-04-24 | Tdk株式会社 | Soft magnetic metal powder, dust core and magnetic parts |
| CN113113324B (en) * | 2021-04-07 | 2024-02-06 | 捷捷半导体有限公司 | Passivation layer manufacturing method |
| CN113674983B (en) * | 2021-08-20 | 2023-06-23 | 合肥工业大学 | Preparation method of compact alumina coated soft magnetic powder core |
| CN113996781B (en) * | 2021-10-12 | 2023-10-13 | 内蒙金属材料研究所 | Soft magnetic composite material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163916C (en) * | 1997-12-24 | 2004-08-25 | 川崎制铁株式会社 | Ultralow-iron-loss grain oriented silicon steel plate and process for producing same |
| CN101127267A (en) * | 2007-09-20 | 2008-02-20 | 安泰科技股份有限公司 | Amorphous nano crystal soft magnet alloy strip with surface insulation coating and its preparation method |
| CN101694800B (en) * | 2009-09-08 | 2012-01-04 | 清华大学 | Compound soft magnetic material with operational performances of high-frequency and large power and process for preparing same |
| CN102360665B (en) * | 2011-09-30 | 2014-04-02 | 哈尔滨工业大学 | Soft magnetic composite material of glass insulating layer and preparation method thereof |
-
2012
- 2012-08-31 CN CN201210318920.9A patent/CN102789863B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102789863A (en) | 2012-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102789861B (en) | Preparation method of soft magnetic composite material of collosol infiltrating glass powder coating layer | |
| CN102789863B (en) | Preparation method of soft magnetic composite material taking glass powder as coating layer | |
| Füzer et al. | Innovative ferrite nanofibres reinforced soft magnetic composite with enhanced electrical resistivity | |
| CN102820115B (en) | Sol soaked glass wrapped layer soft magnetism composite material and preparation method thereof | |
| Zhou et al. | The core-shell structured Fe-based amorphous magnetic powder cores with excellent magnetic properties | |
| Hou et al. | An excellent soft magnetic Fe/Fe3O4-FeSiAl composite with high permeability and low core loss | |
| CN102142309B (en) | Block amorphous/ferrite soft magnetic composite material and preparation method thereof | |
| CN104550940B (en) | The method of a kind of soft magnetic ferrite cladding metallic magnetic powder and soft-magnetic composite material preparation method thereof | |
| CN102360665B (en) | Soft magnetic composite material of glass insulating layer and preparation method thereof | |
| CN103247402B (en) | A kind of preparation method of compound soft magnetic material | |
| CN103240411B (en) | Production methods of inorganic-organic insulation layer soft magnetic composites | |
| CN105355356A (en) | Dust core and method for manufacturing the same | |
| CN102264492A (en) | Composite soft magnetic material and method for producing same | |
| CN102789859B (en) | Soft magnetic composite material and preparation method thereof | |
| CN103890869A (en) | Core-shell structured nanoparticle having hard-soft magnetic heterostructure, magnet prepared with said nanoparticle, and preparing method thereof | |
| CN106601416B (en) | A kind of iron silicon soft magnetic composite powder of multi-layer core-shell structure and preparation method thereof | |
| CN110246675A (en) | A kind of high saturation magnetic flux density, low-loss soft-magnetic composite material and preparation method thereof | |
| CN103236332A (en) | Preparation method of composite soft magnetic material | |
| Yang et al. | Fe-6.5 wt% Si soft magnetic composites with significant improvement of magnetic properties by compositing nano-MnZn ferrites | |
| JP2016086124A (en) | Method for manufacturing soft magnetic material | |
| CN104157389B (en) | Preparing method of high-performance soft magnetism composite materials | |
| CN109887698A (en) | A kind of composite magnetic powder core and preparation method thereof | |
| JP6880472B1 (en) | How to make magnetic wedges, rotary electric machines, and magnetic wedges | |
| Zhu et al. | Highly efficient inorganic-coated FeSiAl/biotite soft magnetic composites | |
| CN109545494B (en) | A kind of preparation method of iron silica magnetic particle core material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |