CN106431380A - Method for preparing nano barium ferrite capable of being sintered under low temperature - Google Patents
Method for preparing nano barium ferrite capable of being sintered under low temperature Download PDFInfo
- Publication number
- CN106431380A CN106431380A CN201610809140.2A CN201610809140A CN106431380A CN 106431380 A CN106431380 A CN 106431380A CN 201610809140 A CN201610809140 A CN 201610809140A CN 106431380 A CN106431380 A CN 106431380A
- Authority
- CN
- China
- Prior art keywords
- barium ferrite
- sintering
- nano barium
- temperature
- distilled water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
- C04B35/2683—Other ferrites containing alkaline earth metals or lead
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3215—Barium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/781—Nanograined materials, i.e. having grain sizes below 100 nm
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/785—Submicron sized grains, i.e. from 0,1 to 1 micron
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Magnetic Ceramics (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a method for preparing barium ferrite capable of being sintered under low temperature. The method comprises the following steps: respectively weighing analytically-pure Ba(NO3)2, Fe(NO3)3, Fe(NO3)2, Cu (NO3)2 and Zn(NO3)2 according to a material mole ratio of Ba to Fe to Cu to Zn of 1 : (8-10) : (0.2-0.6) : (0.1-0.3); then dissolving the Ba(NO3)2, the the Fe(NO3)3, the Fe(NO3)2, the Cu (NO3)2 and the Zn(NO3)2 in distilled water, and uniformly stirring; preparing a sodium hydroxide solution and slowly titrating until the sodium hydroxide solution is subjected to complete precipitation; adjusting the pH value of the titrated mixed solution to be 9-11, and stirring and aging for 3-6 hours; transferring the solution into a high-pressure reaction kettle, adding distilled water into the high-pressure reaction kettle, enabling filling rate of the high-pressure reaction kettle to reach 70%-85%, and reacting; naturally cooling after reaction is completed, then taking out a product, washing the product with distilled water for 5-8 times, then washing the product with absolute ethyl alcohol for 1-3 times, then drying to obtain nano barium ferrite powder; molding and sintering the nano barium ferrite powder under low temperature to obtain the nano barium ferrite. The method is simple in process; the prepared product is uniform in particle diameter and high in dispersibility, can be sintered under low temperature, and can be widely applied to an LTCC low-temperature sintering technology.
Description
Technical field
The present invention relates to the preparation method of magnetic material, more particularly, to one kind prepare low temperature sintering nano barium ferrite
Method.
Background technology
Ferrite magnetic material mainly includes polycrystalline and the monocrystalline ferrite material of spinel-type, carbuncle type and Magnetoplumbate-type
Material, its resistivity is high, little, dielectric properties are lost and frequency characteristic is good, is the important magnetic functional material of a class, modern logical
The fields such as news, military affairs, electronics, information, chemical industry, biology, medical science all have a wide range of applications.Ferrite be widely used at present with
One of the absorbing material in stealthy field, and nano level ferrite be even more because its particle diameter less thus having more excellent property
Can, the existing method generally existing preparing nanometer ferrite complex process, and the size controlling of the product being prepared into is uneven
The problem of poor dispersion.
In recent years, steeply rise with various microelectronic component miniaturizations and demand, " high energy storage, low-loss, use frequency
Rate height, good stability " is increasingly becoming one of developing direction of Ferrite Material.Therefore, in Ferrite Material device preparation technology
In, how to improve the consistency of Ferrite Material, improve the uniformity of microstructure and component, and realize the integration knot of device
Structure, that is, magnetic media material can burn altogether with inner wire metal (Ag, Cu etc.), have highly important shadow to its performance and application
Ring.But Ferrite Material inner wire fusing point typically all relatively low (fusing point of such as Ag is 961 DEG C), accordingly, as magnetizing mediums
Ferrite Material must have relatively low sintering temperature.But the ferrite powder of conventional solid reaction method preparation, its sintering temperature
, typically more than 1200 DEG C, firing period is long, the easy segregation of material component in sintering process, and material internal crystal grain is easily extremely raw for degree
Long, thus deteriorating ferritic electromagnetic property, and production cost is high, energy consumption is greatly it is therefore necessary to manage to reduce its sintering temperature
And firing time, improve its performance.
Content of the invention
For solve above-mentioned technical problem, the present invention propose a kind of process is simple prepare low temperature sintering nanometer barium ferrum oxygen
The method of body, the particle size being not only prepared into is uniformly dispersed good, and realizes low-temperature sintering, can be widely applied to LTCC low
Warm sintering technology.
For reaching above-mentioned purpose, the present invention employs the following technical solutions：
The invention discloses a kind of method preparing low temperature sintering nano barium ferrite, comprise the following steps：
S1：According to Ba：Fe：Cu：Zn=1：(8～10)：(0.2～0.6)：The material mol ratio of (0.1～0.3) claims respectively
Take analytically pure Ba (NO3)2、Fe(NO3)3、Fe(NO3)2、Cu(NO3)2With Zn (NO3)2；
S2：The various raw materials weighing in step S1 are dissolved in distilled water in the lump, stir；
S3：Compound concentration is the sodium hydroxide solution of 1～2.5mol/L, is slowly titrated to the mixed liquor prepare in step S2
In until precipitation completely；
S4：The pH value of the mixed liquor after the titration in step S3 is adjusted to 9～11, then is stirred, and will stir
Solution after one-tenth is aged 3～6h；
S5：After solution in step S4 is transferred in autoclave, make to adding distilled water in autoclave
The filling rate of autoclave reaches 70%～85%, is reacted；
S6：Product is taken out, with distilled water wash 5～8 times, then with absolute ethanol washing 1 after natural cooling after the completion of reaction
Put into drying baker after～3 times to be dried, obtain nano barium ferrite powder；
S7：The nano barium ferrite powder that step S6 is obtained carries out molding, low-temperature sintering, obtains nano barium ferrite.
Preferably, the whipping step in step S2 and step S4 is all placed in being stirred on magnetic stirring apparatuss.
Preferably, the slow titration n (OH to solution for the sodium hydroxide solution in step S3-)/n(NO3 -)=2～5.
Preferably, in step S5 the reaction temperature in autoclave be 180 DEG C～240 DEG C, the response time be 2～
6h.
Preferably, in step S6, baking temperature is 60 DEG C～80 DEG C, and drying time is 2～3h.
Preferably, the low-temperature sintering in step S7 is specially and the nano barium ferrite after molding is placed in tunnel kiln
It is sintered, sintering temperature is 900 DEG C～950 DEG C.
Preferably, it is incubated 120min during the low-temperature sintering in step S7, sintering atmosphere is air.
Preferably, wherein Fe (NO3)2：Fe(NO3)3Molar ratio be less than 1.
Preferably, wherein Fe (NO3)2：Fe(NO3)3Molar ratio be 1：7.
Compared with prior art, the beneficial effects of the present invention is：The present invention prepares low temperature sintering nanometer barium ferrum
The method process is simple of oxysome, first, reached nano-scale, water using the superfines minimum grain size of hydro-thermal method preparation
Full-boiled process reacts in aqueous, and particle is not reunited, prepared magnetic powder good dispersion, good crystallinity, and particle diameter distribution is narrower, and product is pure
Degree is high；Second, by adding a certain amount of material containing Zn and Cu, the nano barium ferrite of Zn and Cu of its doping of Hydrothermal Synthesiss
Powder, the barium ferrite powder of the nano-scale being synthesized using hydro-thermal method after doping, it is possible to achieve low-temperature sintering densification, thus
The fine and close magnet of preparation, can be widely applied to LTCC (LTCC) low-temperature sintering technology, and then widely realizes
LTCC material technology.
In further scheme, mixture or ferric nitrate using ferrous nitrate and ferric nitrate are former as ferrum element
Material, wherein adopt ferrous nitrate and ferric nitrate mixture when, ferrous nitrate is less than 1 with the molar ratio of ferric nitrate, this mole
Ratio can also be 0, as adopts ferric nitrate as the raw material of ferrum element；When the molar ratio of ferrous nitrate and ferric nitrate is 1：
When 7, so that the consistency that the nano barium ferrite powder being obtained is carried out during low-temperature sintering improves further, and pcrmeability
Also improve further.
In further scheme, the hydro-thermal method that the present invention adopts, the reaction temperature in autoclave is 180 DEG C
～240 DEG C, the product crystallinity obtaining is more preferable.
Brief description
Fig. 1 is the XRD figure of the barium ferrite powder that the embodiment of the present invention 1 is obtained；
Fig. 2 is the SEM figure of the barium ferrite powder that the embodiment of the present invention 1 is obtained；
Fig. 3 a is the SEM figure through low sintering barium ferrite material that the embodiment of the present invention 1 is obtained；
Fig. 3 b is the SEM figure through low sintering barium ferrite material that the embodiment of the present invention 2 is obtained；
Fig. 3 c is the SEM figure through low sintering barium ferrite material that the embodiment of the present invention 3 is obtained；
Fig. 3 d is the SEM figure through low sintering barium ferrite material that comparative example 1 of the present invention is obtained；
Fig. 3 e is the SEM figure through low sintering barium ferrite material that comparative example 2 of the present invention is obtained；
Fig. 3 f is the SEM figure through low sintering barium ferrite material that comparative example 3 of the present invention is obtained.
Specific embodiment
Below against accompanying drawing and with reference to preferred embodiment the invention will be further described.
Embodiment of the invention discloses that a kind of method preparing low temperature sintering nano barium ferrite, walk including following
Suddenly：
S1：According to Ba：Fe：Cu：Zn=1：(8～10)：(0.2～0.6)：The material mol ratio of (0.1～0.3) claims respectively
Take analytically pure Ba (NO3)2、Fe(NO3)3、Fe(NO3)2、Cu(NO3)2With Zn (NO3)2, wherein Fe (NO3)2：Fe(NO3)3Rub
You are less than 1, further, Fe (NO by ratio3)2：Fe(NO3)3Molar ratio be 1：7；
S2：The various raw materials weighing in step S1 are dissolved in distilled water in the lump, stir；
S3：Compound concentration is the sodium hydroxide solution of 1～2.5mol/L, is slowly titrated to the mixed liquor prepare in step S2
In until precipitation completely；
S4：The pH value of the mixed liquor after the titration in step S3 is adjusted to 9～11, then is stirred, and will stir
Solution after one-tenth is aged 3～6h；
S5：After solution in step S4 is transferred in autoclave, make to adding distilled water in autoclave
The filling rate of autoclave reaches 70%～85%, is reacted；
S6：Product is taken out, with distilled water wash 5～8 times, then with absolute ethanol washing 1 after natural cooling after the completion of reaction
Put into drying baker after～3 times to be dried, obtain nano barium ferrite powder；
S7：The nano barium ferrite powder that step S6 is obtained carries out molding, low-temperature sintering, obtains nano barium ferrite.
In a further embodiment, the whipping step in step S2 and step S4 is all placed in carrying out on magnetic stirring apparatuss
Stirring；The slow titration n (OH to solution for the sodium hydroxide solution in step S3-)/n(NO3 -)=2～5；In high pressure in step S5
Reaction temperature in reactor is 180 DEG C～240 DEG C, and the response time is 2～6h；In step S6, baking temperature is 60 DEG C～80
DEG C, drying time is 2～3h；Low-temperature sintering in step S7 is specially and for the nano barium ferrite after molding to be placed on tunnel cave
It is sintered in stove, sintering temperature is 900 DEG C～950 DEG C；It is incubated 120min during low-temperature sintering in step S7, sinter gas
Atmosphere is air.
Reach nanoscale water according to described in the inventive method with the superfines minimum grain size of hydro-thermal method preparation
Flat；Hydro-thermal method is reacted in aqueous, and particle is not reunited, prepared magnetic powder good dispersion, good crystallinity, and particle diameter distribution is narrower,
Product purity is high.This is to carry out one of ferrite synthesis and the more active method of applied research at present.Further, the present invention
Pass through in method to add a certain amount of material containing Zn and Cu, the nano barium ferrite powder of Zn and Cu of its doping of Hydrothermal Synthesiss
Material, the barium ferrite powder of the nano-scale being synthesized using hydro-thermal method after doping, it is possible to achieve low-temperature sintering densification, thus make
Standby fine and close magnet, can be widely applied to LTCC (LTCC) low-temperature sintering technology, and then widely realizes
LTCC material technology；And existing unadulterated Barium hexaferrite, sintering temperature at least could sinter out more more than 1100 DEG C
Fine and close magnet.
Following sides preparing low temperature sintering nano barium ferrite to the present invention with comparative example in conjunction with specific embodiments
Method is further described.
Embodiment 1
A kind of method preparing low temperature sintering nano barium ferrite, specifically implements according to following steps：
S1：Weigh raw material, with analytically pure Ba (NO3)2、Fe(NO3)3、Cu(NO3)2With Zn (NO3)2(wherein Ba：Fe：Cu：
The mol ratio of Zn is 1：10：0.3：0.2) it is raw material, stoichiometrically mol ratio weighs these four raw materials；
S2：By weigh in step S1 four kinds of raw materials and be dissolved in distilled water, it is subsequently placed in and stirs all on magnetic stirring apparatuss
Even；
S3：Compound concentration is the sodium hydroxide solution of 1.5mol/L, is slowly titrated in the mixed liquor prepare in step S2
Until precipitation is complete；
S4：The pH value of the mixed liquor after titrating in step S3 is adjusted to 9, is placed in and is stirred on magnetic stirring apparatuss, and
The solution ageing 3h that stirring is completed；
S5：After solution in step S4 is transferred in autoclave, make to adding distilled water in autoclave
The filling rate of autoclave reaches 70%, then sets reaction temperature as 220 DEG C, and the response time is 2h, is reacted；
S6：Product is taken out, with distilled water wash 5 times, then with after absolute ethanol washing 1 time after natural cooling after the completion of reaction
Put into drying baker to be dried, baking temperature is 60 DEG C, drying time is 2h, that is, obtaining particle size is receiving of 50～200nm
Rice barium ferrite powder, the wherein XRD figure of nano barium ferrite powder, should as shown in figure 1, explanation generates Barium hexaferrite crystal
The SEM of nano barium ferrite powder schemes as shown in Fig. 2 its size is between 50～200nm.
S7：The nano barium ferrite powder that step S6 is obtained carries out molding, low-temperature sintering (900 DEG C), will be compressing
Nano barium ferrite afterwards is placed in tunnel kiln and is sintered, and sintering temperature is 900 DEG C, is incubated 120min, sintering atmosphere
For air, after terminating, cool to room temperature with the furnace, obtain the barium ferrite material of densified sintering product, its SEM figure is shown in Fig. 3 a, and surveys
The density of barium ferrite material after examination sintering and initial permeability μi(being shown in Table 1).
Embodiment 2
S1：Weigh raw material, with analytically pure Ba (NO3)2、Fe(NO3)3、Cu(NO3)2With Zn (NO3)2(wherein Ba：Fe：Cu：
The mol ratio of Zn is 1：8：0.3：0.2) it is raw material, stoichiometrically mol ratio weighs these four raw materials；
S2：By weigh in step S1 four kinds of raw materials and be dissolved in distilled water, it is subsequently placed in and stirs all on magnetic stirring apparatuss
Even；
S3：Compound concentration is the sodium hydroxide solution of 1.5mol/L, is slowly titrated in the mixed liquor prepare in step S2
Until precipitation is complete；
S4：The pH value of the mixed liquor after titrating in step S3 is adjusted to 10, is placed in and is stirred on magnetic stirring apparatuss, and
The solution ageing 6h that stirring is completed；
S5：After solution in step S4 is transferred in autoclave, make to adding distilled water in autoclave
The filling rate of autoclave reaches 75%, then sets reaction temperature as 220 DEG C, and the response time is 3h, is reacted；
S6：Product is taken out, with distilled water wash 8 times, then with after absolute ethanol washing 3 times after natural cooling after the completion of reaction
Put into drying baker to be dried, baking temperature is 70 DEG C, drying time is 3h, that is, obtain nano barium ferrite powder.
S7：The nano barium ferrite powder that step S6 is obtained carries out molding, low-temperature sintering (920 DEG C), will be compressing
Nano barium ferrite afterwards is placed in tunnel kiln and is sintered, and sintering temperature is 920 DEG C, is incubated 120min, sintering atmosphere
For air, after terminating, cool to room temperature with the furnace, obtain the barium ferrite material of densified sintering product, its SEM figure is shown in Fig. 3 b, and surveys
The density of barium ferrite material after examination sintering and initial permeability μi(being shown in Table 1).
Embodiment 3
S1：Weigh raw material, with analytically pure Ba (NO3)2、Fe(NO3)3、Fe(NO3)2、Cu(NO3)2With Zn (NO3)2(wherein
Fe(NO3)3：Fe(NO3)2Mol ratio be 7：1, Ba：Fe：Cu：The mol ratio of Zn is 1：8：0.3：0.2) it is raw material, by chemistry
Stoichiometric mole ratio weighs this five kinds of raw materials；
S2：By weigh in step S1 five kinds of raw materials and be dissolved in distilled water, it is subsequently placed in and stirs all on magnetic stirring apparatuss
Even；
S3：Compound concentration is the sodium hydroxide solution of 2.0mol/L, is slowly titrated in the mixed liquor prepare in step S2
Until precipitation is complete；
S4：The pH value of the mixed liquor after titrating in step S3 is adjusted to 9, is placed in and is stirred on magnetic stirring apparatuss, and
The solution ageing 4h that stirring is completed；
S5：After solution in step S4 is transferred in autoclave, make to adding distilled water in autoclave
The filling rate of autoclave reaches 80%, then sets reaction temperature as 250 DEG C, and the response time is 4h, is reacted；
S6：Product is taken out, with distilled water wash 6 times, then with after absolute ethanol washing 2 times after natural cooling after the completion of reaction
Put into drying baker to be dried, baking temperature is 60 DEG C, drying time is 2.5h, that is, obtain nano barium ferrite powder.
S7：The nano barium ferrite powder that step S6 is obtained carries out molding, low-temperature sintering (930 DEG C), will be compressing
Nano barium ferrite afterwards is placed in tunnel kiln and is sintered, and sintering temperature is 930 DEG C, is incubated 120min, sintering atmosphere
For air, after terminating, cool to room temperature with the furnace, obtain the barium ferrite material of densified sintering product, its SEM figure is shown in Fig. 3 c, and surveys
The density of barium ferrite material after examination sintering and initial permeability μi(being shown in Table 1).Add a small amount of Fe (II), sintering can be made
The sintered density of barium ferrite material afterwards is bigger, so that pcrmeability is bigger, but adds excessive Fe (II), Jiu Huisheng
Become more Fe2O3, arise that the more phenomenon of hole (see comparative example 3) after sintering, cause its density less than 4.0g/cm3.
Inventor confirms through many experiments, in composition of raw materials, Fe (NO3)2：Fe(NO3)3Mol ratio be favorably improved barium less than 1
The sintered density of Ferrite Material and raising pcrmeability, wherein Fe (NO3)2：Fe(NO3)3Mole be equal to 1：7 best results.
Comparative example 1
Specifically implement according to following steps：
S1：Weigh raw material, with analytically pure Ba (NO3)2、Fe(NO3)3、Cu(NO3)2With Zn (NO3)2(wherein Ba：Fe：Cu：
The mol ratio of Zn is 1：12：0.3：0.2) it is raw material, stoichiometrically mol ratio weighs these four raw materials；
S2：By weigh in step S1 four kinds of raw materials and be dissolved in distilled water, it is subsequently placed in and stirs all on magnetic stirring apparatuss
Even；
S3：Compound concentration is the sodium hydroxide solution of 1.5mol/L, is slowly titrated in the mixed liquor prepare in step S2
Until precipitation is complete；
S4：The pH value of the mixed liquor after titrating in step S3 is adjusted to 9, is placed in and is stirred on magnetic stirring apparatuss, and
The solution ageing 3h that stirring is completed；
S5：After solution in step S4 is transferred in autoclave, make to adding distilled water in autoclave
The filling rate of autoclave reaches 70%, then sets reaction temperature as 220 DEG C, and the response time is 2h, is reacted；
S6：Product is taken out, with distilled water wash 5 times, then with after absolute ethanol washing 1 time after natural cooling after the completion of reaction
Put into drying baker to be dried, baking temperature is 60 DEG C, drying time is 2h, that is, obtain nano barium ferrite powder.
S7：The nano barium ferrite powder that step S6 is obtained carries out molding, low-temperature sintering (920 DEG C), will be compressing
Nano barium ferrite afterwards is placed in tunnel kiln and is sintered, and sintering temperature is 920 DEG C, is incubated 120min, sintering atmosphere
For air, cool to room temperature with the furnace after terminating, obtain barium ferrite material, its SEM figure is shown in Fig. 3 d, and after testing sintering
The density of barium ferrite material and initial permeability μi(being shown in Table 1).
Comparative example 2
Specifically implement according to following steps：
S1：Weigh raw material, with analytically pure Ba (NO3)2、Fe(NO3)3、Cu(NO3)2With Zn (NO3)2(wherein Ba：Fe：Cu：
The mol ratio of Zn is 1：10：0.1：0.2) it is raw material, stoichiometrically mol ratio weighs these four raw materials；
S2：By weigh in step S1 four kinds of raw materials and be dissolved in distilled water, it is subsequently placed in and stirs all on magnetic stirring apparatuss
Even；
S3：Compound concentration is the sodium hydroxide solution of 1.5mol/L, is slowly titrated in the mixed liquor prepare in step S2
Until precipitation is complete；
S4：The pH value of the mixed liquor after titrating in step S3 is adjusted to 10, is placed in and is stirred on magnetic stirring apparatuss, and
The solution ageing 6h that stirring is completed；
S5：After solution in step S4 is transferred in autoclave, make to adding distilled water in autoclave
The filling rate of autoclave reaches 75%, then sets reaction temperature as 220 DEG C, and the response time is 3h, is reacted；
S6：Product is taken out, with distilled water wash 5 times, then with after absolute ethanol washing 1 time after natural cooling after the completion of reaction
Put into drying baker to be dried, baking temperature is 80 DEG C, drying time is 2h, that is, obtain nano barium ferrite powder.
S7：The nano barium ferrite powder that step S6 is obtained carries out molding, low-temperature sintering (920 DEG C), will be compressing
Nano barium ferrite afterwards is placed in tunnel kiln and is sintered, and sintering temperature is 920 DEG C, is incubated 120min, sintering atmosphere
For air, cool to room temperature with the furnace after terminating, obtain barium ferrite material, its SEM figure is shown in Fig. 3 d, and after testing sintering
The density of barium ferrite material and initial permeability μi(being shown in Table 1).Can be seen that the hole of this barium ferrite material from SEM in figure
More, sintering not fine and close, because its Cu content is less, cause it can not bake completely under low-temperature sintering so that sintered density relatively
Low, far below the density (4.6g/cm of Barium hexaferrite3).
Comparative example 3
Specifically implement according to following steps：
S1：Weigh raw material, with analytically pure Ba (NO3)2、Fe(NO3)3、Fe(NO3)2、Cu(NO3)2With Zn (NO3)2(wherein
Fe(NO3)3：Fe(NO3)2Mol ratio be 4：4, Ba：Fe：Cu：The mol ratio of Zn is 1：8：0.3：0.2) it is raw material, by chemistry
Stoichiometric mole ratio weighs this five kinds of raw materials；
S2：By weigh in step S1 five kinds of raw materials and be dissolved in distilled water, it is subsequently placed in and stirs all on magnetic stirring apparatuss
Even；
S3：Compound concentration is the sodium hydroxide solution of 2.0mol/L, is slowly titrated in the mixed liquor prepare in step S2
Until precipitation is complete；
S4：The pH value of the mixed liquor after titrating in step S3 is adjusted to 9, is placed in and is stirred on magnetic stirring apparatuss, and
The solution ageing 4h that stirring is completed；
S5：After solution in step S4 is transferred in autoclave, make to adding distilled water in autoclave
The filling rate of autoclave reaches 80%, then sets reaction temperature as 250 DEG C, and the response time is 4h, is reacted；
S6：Product is taken out, with distilled water wash 5 times, then with after absolute ethanol washing 1 time after natural cooling after the completion of reaction
Put into drying baker to be dried, baking temperature is 80 DEG C, drying time is 2h, that is, obtain nano barium ferrite powder.
S7：The nano barium ferrite powder that step S6 is obtained carries out molding, low-temperature sintering (920 DEG C), will be compressing
Nano barium ferrite afterwards is placed in tunnel kiln and is sintered, and sintering temperature is 920 DEG C, is incubated 120min, sintering atmosphere
For air, cool to room temperature with the furnace after terminating, obtain barium ferrite material, its SEM figure is shown in Fig. 3 f, and after testing sintering
The density of barium ferrite material and initial permeability μi(being shown in Table 1).
Low-temperature sintering processing technology comprises the steps of：Pre-sinter process is carried out to its each nano barium ferrite material, in 900
Carry out pre-burning below DEG C temperature；And sintering step, above-mentioned Preburning material is sintered under less than 950 DEG C of sintering temperature；Sintering
Finish, test the initial permeability of its Barium hexaferrite and the density of sintered magnet.
The formula of each embodiment of table 1 and each comparative example and test result
Final testing result：The magnetic permeability μ of barium ferrite materialiWithin 10.As can be seen from Table 1：Embodiment 1,
2nd, the 3 barium ferrite material densified sintering product being obtained, its sintered density is up to 4.6g/cm3More than, its initial permeability μiAbout 8～
Between 10；And the barium ferrite material that comparative example 1,2,3 is obtained does not cook, its sintered density is less than 4.0g/cm3, its initial magnetic
Conductance μiLess than 3.Can be seen that from the test result of embodiment and comparative example and received by the low temperature sintering of preparing of the present invention
The nano barium ferrite powder that the method for rice Barium hexaferrite is obtained can realize low-temperature sintering densification, thus preparing the magnetic of densification
Body, can be widely applied to LTCC low-temperature sintering technology, and the combustion knot density of the nano barium ferrite being obtained in comparative example is remote
Tie density less than the combustion of nano barium ferrite material, initial permeability is extremely low, does not bake it is impossible to realize low-temperature sintering, therefore
May not apply to LTCC low-temperature sintering technology.
Above content is to further describe it is impossible to assert with reference to specific preferred implementation is made for the present invention
Being embodied as of the present invention is confined to these explanations.For those skilled in the art, do not taking off
On the premise of present inventive concept, some equivalent substitutes or obvious modification can also be made, and performance or purposes are identical, all answer
When being considered as belonging to protection scope of the present invention.
Claims (9)
1. a kind of method preparing low temperature sintering nano barium ferrite is it is characterised in that comprise the following steps：
S1：According to Ba：Fe：Cu：Zn=1：(8～10)：(0.2～0.6)：The material mol ratio of (0.1～0.3) weighs point respectively
Analyse pure Ba (NO3)2、Fe(NO3)3、Fe(NO3)2、Cu(NO3)2With Zn (NO3)2；
S2：The various raw materials weighing in step S1 are dissolved in distilled water in the lump, stir；
S3：Compound concentration is the sodium hydroxide solution of 1～2.5mol/L, is slowly titrated to straight in the mixed liquor prepare in step S2
Complete to precipitating；
S4：The pH value of the mixed liquor after the titration in step S3 is adjusted to 9～11, then is stirred, and after the completion of stirring
Solution be aged 3～6h；
S5：After solution in step S4 is transferred in autoclave, make high pressure to adding distilled water in autoclave
The filling rate of reactor reaches 70%～85%, is reacted；
S6：Product is taken out, with distilled water wash 5～8 times, then with absolute ethanol washing 1～3 time after natural cooling after the completion of reaction
After put into drying baker and be dried, obtain nano barium ferrite powder；
S7：The nano barium ferrite powder that step S6 is obtained carries out molding, low-temperature sintering, obtains nano barium ferrite.
2. method according to claim 1 is it is characterised in that the whipping step in step S2 and step S4 is all placed in magnetic
It is stirred on power agitator.
3. method according to claim 1 is it is characterised in that slow titration sodium hydroxide solution is to solution in step S3
N (OH-)/n(NO3 -)=2～5.
4. method according to claim 1 it is characterised in that in step S5 the reaction temperature in autoclave be
180 DEG C～240 DEG C, the response time is 2～6h.
5. method according to claim 1 it is characterised in that in step S6 baking temperature be 60 DEG C～80 DEG C, when being dried
Between be 2～3h.
6. method according to claim 1 is it is characterised in that the low-temperature sintering in step S7 is specially receiving after molding
Rice Barium hexaferrite is placed in tunnel kiln and is sintered, and sintering temperature is 900 DEG C～950 DEG C.
7. method according to claim 1 is it is characterised in that be incubated 120min during low-temperature sintering in step S7,
Sintering atmosphere is air.
8. the method according to any one of claim 1 to 7 is it is characterised in that wherein Fe (NO3)2：Fe(NO3)3Mol ratio
Value is less than 1.
9. the method according to any one of claim 1 to 7 is it is characterised in that wherein Fe (NO3)2：Fe(NO3)3Mol ratio
It is worth for 1：7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610809140.2A CN106431380B (en) | 2016-09-05 | 2016-09-05 | A method of preparing low temperature sintering nano barium ferrite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610809140.2A CN106431380B (en) | 2016-09-05 | 2016-09-05 | A method of preparing low temperature sintering nano barium ferrite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106431380A true CN106431380A (en) | 2017-02-22 |
| CN106431380B CN106431380B (en) | 2019-09-13 |
Family
ID=58164255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610809140.2A Active CN106431380B (en) | 2016-09-05 | 2016-09-05 | A method of preparing low temperature sintering nano barium ferrite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106431380B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110342921A (en) * | 2019-06-11 | 2019-10-18 | 深圳顺络电子股份有限公司 | A kind of microwave ferrite material and preparation method thereof, lamination sheet type device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280373A (en) * | 2000-08-25 | 2001-01-17 | 清华大学 | Composition of high performance low-temperature sintered VHF laminated inductive material and its preparing method |
| CN1812019A (en) * | 2004-12-29 | 2006-08-02 | 巨东英 | Low-temperature sintering production technology for magnetic ferrite and inductive material |
| CN105502506A (en) * | 2014-10-15 | 2016-04-20 | 西安艾菲尔德复合材料科技有限公司 | Method utilizing hydrothermal method to prepare nano barium ferrite |
-
2016
- 2016-09-05 CN CN201610809140.2A patent/CN106431380B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280373A (en) * | 2000-08-25 | 2001-01-17 | 清华大学 | Composition of high performance low-temperature sintered VHF laminated inductive material and its preparing method |
| CN1812019A (en) * | 2004-12-29 | 2006-08-02 | 巨东英 | Low-temperature sintering production technology for magnetic ferrite and inductive material |
| CN105502506A (en) * | 2014-10-15 | 2016-04-20 | 西安艾菲尔德复合材料科技有限公司 | Method utilizing hydrothermal method to prepare nano barium ferrite |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110342921A (en) * | 2019-06-11 | 2019-10-18 | 深圳顺络电子股份有限公司 | A kind of microwave ferrite material and preparation method thereof, lamination sheet type device |
| CN110342921B (en) * | 2019-06-11 | 2021-11-12 | 深圳顺络电子股份有限公司 | Microwave ferrite material, preparation method thereof and laminated chip device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106431380B (en) | 2019-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1195705C (en) | Monocrystalline ferrite fines | |
| JP5105503B2 (en) | ε Iron oxide production method | |
| CN107151029B (en) | A kind of sol-gel self-combustion synthesis preparation process of tetra phase barium titanate powder | |
| CN108706637B (en) | A kind of preparation method of adjustable magnetic iron oxide mesomorphic material of uniform size | |
| CN101913854A (en) | Preparation method of nanometer strontium ferrite magnetic powder | |
| CN109052450B (en) | Preparation method of high-purity gadolinium oxide | |
| Xu et al. | Calcination induced phase transformation in MnZn ferrite powders | |
| CN112159219A (en) | Yttrium-doped nickel-zinc-cobalt ferrite and preparation method thereof | |
| JP6471015B2 (en) | Fe-Co alloy powder and antenna, inductor and EMI filter | |
| CN105016395A (en) | Nano ferrite material, and preparation method thereof | |
| CN107324406B (en) | A kind of composite modified strontium ferrite raw powder's production technology | |
| CN106431380A (en) | Method for preparing nano barium ferrite capable of being sintered under low temperature | |
| CN106830100B (en) | A kind of rodlike cobalt ferrite powder and preparation method thereof | |
| CN105254295B (en) | A kind of preparation method of neodymium-doped titanium acid barium nano-ceramic powder | |
| CN112126408A (en) | La-Al-TiN/h-BN nanosheet composite wave-absorbing material and preparation method thereof | |
| CN104326500B (en) | A kind of preparation method of fluffy state nano yttrium oxide powder | |
| CN109502643B (en) | Boron-magnesium co-doped VO2Powder and preparation method and application thereof | |
| CN108373327B (en) | Nickel-zinc-cerium ferrite soft magnetic material and preparation method thereof | |
| CN107903072B (en) | Method for preparing strontium barium niobate nano powder by two-step coprecipitation method | |
| CN115947387A (en) | B-site five-element high-entropy double perovskite structure oxide electrode material and preparation method thereof | |
| CN114085080B (en) | Rare earth doped tantalum titanate powder and preparation method thereof | |
| CN115246653A (en) | Nanometer dysprosium oxide and preparation method and application thereof | |
| JP6607751B2 (en) | Fe-Co alloy powder, manufacturing method thereof, antenna, inductor, and EMI filter | |
| CN110451575B (en) | Method for enhancing magnetic property of bismuth ferrite nanopowder based on size effect | |
| CN109762395A (en) | A kind of magnetic ink nano whiskers W-type ferrite magnetic paint and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |