CN106696410B - A kind of method that the tape casting prepares stratiform barium ferrite/RGO composite wave-suction materials - Google Patents

A kind of method that the tape casting prepares stratiform barium ferrite/RGO composite wave-suction materials Download PDF

Info

Publication number
CN106696410B
CN106696410B CN201611162399.9A CN201611162399A CN106696410B CN 106696410 B CN106696410 B CN 106696410B CN 201611162399 A CN201611162399 A CN 201611162399A CN 106696410 B CN106696410 B CN 106696410B
Authority
CN
China
Prior art keywords
powder
bafe
barium ferrite
composite wave
tape casting
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
Application number
CN201611162399.9A
Other languages
Chinese (zh)
Other versions
CN106696410A (en
Inventor
杨海波
韩宁
林营
刘潇
高淑雅
朱建锋
王芬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201611162399.9A priority Critical patent/CN106696410B/en
Publication of CN106696410A publication Critical patent/CN106696410A/en
Application granted granted Critical
Publication of CN106696410B publication Critical patent/CN106696410B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
    • B32B2307/102—Insulating

Landscapes

  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Soft Magnetic Materials (AREA)
  • Hard Magnetic Materials (AREA)

Abstract

A kind of method that the tape casting prepares stratiform barium ferrite/RGO composite wave-suction materials, prepares stratiform barium ferrite/RGO composite wave-suction materials, wherein BaFe by the tape casting12O19It is random powder BaFe12O19With the BaFe for having orientation12O19Powder is proportionally 90%~70%:10%~30% mixed powder, random point and the BaFe with orientation12O19Gross mass and the mass ratio of redox graphene be 5~7:0.1~0.5.Then it dries, organic matter is discharged.Present invention process is simple, at low cost, and obtained laminar composite thickness reaches micron dimension, and Coating combination is close, consistent internal structure, and has good electromagnetic wave absorption performance, has good application prospect in electromagnetic-wave absorbent field.

Description

A kind of method that the tape casting prepares stratiform barium ferrite/RGO composite wave-suction materials
Technical field
The invention belongs to materials science field, a kind of the tape casting is provided and prepares two layers of barium ferrite/RGO composite wave-suction materials Method belongs to MULTILAYER COMPOSITE absorbing material preparing technical field.
Background technology
With the development of science and technology, absorbing material plays more in modern national defense stealth technique and the pre- radiation protection field of life Carry out more important role.Realize good absorbing property, it is necessary to have two conditions：The electromagnetic wave that incidence comes is as more as possible Be not reflected into the inside of absorbing material；Electromagnetic wave into material internal will be absorbed as far as possible.Therefore, have The wave-absorber of multilayered structure is that the electromagnetic wave of space incident is as much as possible into suction wave material by the effect of impedance matching Expect and the absorption that is depleted.Traditional absorbing material is used primarily in military affairs, be difficult to meet simultaneously on wave absorbing efficiency it is thin, light, wide, Strong requirement, and preparation process is also more complicated.In the absorbing material of all multiple types, ferrite is that research application is relatively broad One kind.Ferrite BaFe12O19It is a kind of magnetic loss absorbing material, but density is bigger.Graphene is monoatomic thickness Carbon atomic layer has unique property, from quilt in 2004 as a kind of new carbon in terms of mechanics, quantum and electricity The research hotspot attached most importance to has been had become since it was found that.Graphene is a kind of absorbing material of typical dielectric loss type, and density is smaller, Make it that there is prodigious research potential in electromagnetic-wave absorbent field.Ferrite BaFe12O19It is a kind of magnetic loss absorbing material, But density is bigger.Ferrite BaFe12O19It is compound with graphene, it is expected to prepare that absorbing property is good, while the suction that proportion is lighter Wave material.
The tape casting moulding process is for the chemistry formings method such as EVD, CVD, and the prices of raw materials are cheap and cost of manufacture Low, obtained material structure is fine and close, high mechanical strength and defect are few, and it is compound that the laminations that different composition membrane materials are constituted can be made Material, to meet the property requirement to material.In addition to this, the tape casting is suitble to the base of mass production 0.4~1.0mm thickness Plate, and have the advantages that production efficiency height, good product consistency, performance are stablized, it is widely used in Japan and the United States, De Deng states. There is the BaFe being orientated using what molten-salt growth method synthesized12O19So that the advantage crystal face in crystal structure is collectively aligned, to strengthen It is each to performance on advantage crystal face, the spontaneous polarization strength and magnetic performance of bigger are obtained on a certain characteristic direction, promote it Use value, but granularity is big, is unfavorable for tape casting.
Invention content
The purpose of the present invention is to provide a kind of methods that the tape casting prepares stratiform barium ferrite/RGO composite wave-suction materials, should Equipment requirement is low, simple for process, and process condition is easy to control, and is conducive to tape casting.
For achieving the above object, the present invention adopts the following technical scheme that：
A kind of method that the tape casting prepares stratiform barium ferrite/RGO composite wave-suction materials, by absolute ethyl alcohol, butanone, three oleic acid Glyceride is uniformly mixed, and obtains mixed solvent, and polyvinyl butyral, dibutyl phthalate (DBP) and poly- second two is then added Alcohol is uniformly mixed, random BaFe is then added12O19Powder, the BaFe with orientation12O19Powder carries out after carrying out wet ball grinding First layer is cast；
Absolute ethyl alcohol, butanone, olein are uniformly mixed, mixed solvent is obtained, polyvinyl alcohol contracting is then added Butyraldehyde, dibutyl phthalate (DBP) and polyethylene glycol are uniformly mixed, and redox graphene is then added, and carry out wet ball grinding Second layer curtain coating is being carried out afterwards, is obtaining film；Film is dried, stratiform barium ferrite/RGO composite wave-suction materials are obtained；By quality percentage Number meter, random powder BaFe12O19And have orientation BaFe12O19Powder mass ratio be (70%~90%):(10%~ 30%)；Random powder and with being orientated BaFe12O19The gross mass of powder and the mass ratio of redox graphene be (5~ 7):(0.1~0.5).
The present invention further improve is, in the mixed solvent absolute ethyl alcohol, butanone, olein weight ratio (1 ~3):(2~3):(0.05~1.5).
The present invention further improve is, polyvinyl butyral, dibutyl phthalate (DBP) and polyethylene glycol matter Amount is than being 1:2.5:2.5；Mixed solvent, polyvinyl butyral, dibutyl phthalate (DBP) and polyethylene glycol gross mass with Random powder BaFe12O19And have orientation BaFe12O19Powder total mass ratio be 7:3, mixed solvent, polyvinyl butyral, The mass ratio of the gross mass and redox graphene of dibutyl phthalate (DBP) and polyethylene glycol is 15:1.
The present invention, which further improves, to be, in casting processes, film speed is 500~1200mm/min, per coating film Thickness is 200~250 μm.
The present invention, which further improves, to be, drying be in vacuum drying chamber dry 5 at 180~200 DEG C~ 10min。
The present invention, which further improves, to be, redox graphene is prepared by following procedure：
By natural flake graphite, the concentrated sulfuric acid of mass fraction 98%, sodium nitrate according to weight ratio (1~3):(95~ 100):(1.5~3.5), are put into ice water, and magnetic agitation is uniform；
Then 12~15g potassium permanganate is added, reacts 90min at 0 DEG C, is then heated to 35 DEG C and reacts 2h, then 80~100mL ultra-pure waters are added, temperature rises to 100 DEG C, and stops reaction after keeping the temperature 2h, and the quality of potassium permanganate is natural graphite The volume ratio of 4~12 times of quality, ultra-pure water and the concentrated sulfuric acid of mass fraction 98% is (1~1.5):1；
200mL ultra-pure waters are poured into the product of reaction again, and the hydrogen peroxide of 10mL mass fractions 30% is added, wait reacting molten Liquid cooling but after, product is subjected to centrifuge washing to neutrality with ultra-pure water, will be freeze-dried after the aqueous solution ultrasonic disperse 2h of product, Obtain the layered graphite oxide alkene powder of yellow；
Graphene oxide powder is dispersed in ethylene glycol, 1~2mgmL is made into-1Solution, then in homogeneous reactor In at 200 DEG C, reaction for 24 hours, obtains black product, it is washing, dry, obtain redox graphene.
The present invention, which further improves, is there is the BaFe being orientated12O19Powder is prepared by following procedure：
1) by BaCO3、Fe2O3It is uniform by ball milling mixing with NaCl, it then dries, cross 60 mesh sieve, obtain mixed powder A1；Wherein, BaCO3With Fe2O3Gross mass and NaCl mass ratio be 1:(1~2)；BaCO3With Fe2O3Amount press chemical general formula BaFe12O19In mol ratio；
2) by the obtained mixed powder A of step 1)1In 1000~1200 DEG C of 2~4h of pre-burning, washing obtains BaFe12O19 The precursor B of powder1；
3) by Fe2O3、BaCl2·2H2O and BaFe12O19The precursor B of powder1, it is uniformly mixed, obtains mixed slurry, so 60 mesh sieve is crossed after mixed slurry is dried afterwards, obtains mixed powder C1, then by mixed powder C1In 1000~1200 DEG C calcine 2~ 4h, washing obtain having the BaFe being orientated on (001) direction12O19Flaky powder.
The present invention, which further improves, to be, the rotating speed of ball milling is 500~600r/min in step 1), and dry temperature is 80~100 DEG C, the time is 4~8h；BaCl in step 3)2·2H2The quality of O is Fe2O32~3 times of quality, BaFe12O19Powder Precursor B1Quality be BaCl2·2H2O、Fe2O3And BaFe12O19The precursor B of powder1The 5%-15% of gross mass.
The present invention, which further improves, to be, random BaFe12O19Powder is prepared by following procedure：
According to chemical general formula BaFe12O19In mol ratio, by BaCO3And Fe2O3It is uniform by ball milling mixing, it is dry, Then 6~10h is calcined at 1000~1200 DEG C, obtains random BaFe12O19Powder.
Compared with prior art, the device have the advantages that：
Stratiform barium ferrite/RGO composite wave-suction materials are prepared using tape casting in the present invention.Present invention process is simple, at This is low, and obtained laminar composite thickness reaches micron dimension, and Coating combination is close, consistent internal structure, and has Good electromagnetic wave absorption performance has good application prospect in electromagnetic-wave absorbent field.The present invention will be by that will have orientation Powder is added to random powder BaFe according to a certain percentage12O19In, improve BaFe12O19Magnetic property, while being conducive to be cast Molding, improves the absorbing property of final product.When thickness is 2.5mm, absorption maximum can reach -27.1dB, and -10dB is below Absorption band width is 6.1GHz, which has good application prospect in electromagnetic-wave absorbent field.
Further, the BaFe for having and being preferably orientated is prepared using molten-salt growth method in the present invention12O19Powder, using hydro-thermal method Graphene is prepared, is conducive to improve the absorbing property of final material.
Further, it is prepared with the sheet BaFe being orientated using molten-salt growth method12O19Powder prepares graphite using hydro-thermal method Alkene, particle obtained are conducive to subsequent curtain coating.
Description of the drawings
Fig. 1 the tape castings of the present invention prepare stratiform BaFe12O19The SEM of/RGO composite wave-suction materials schemes.
Fig. 2 the tape castings of the present invention prepare stratiform BaFe12O19/ RGO composite wave-suction material thickness is the reflection loss of 2.0mm Figure.
Fig. 3 the tape castings of the present invention prepare stratiform BaFe12O19/ RGO composite wave-suction material thickness is the reflection loss of 2.5mm Figure.
Fig. 4 the tape castings of the present invention prepare stratiform BaFe12O19/ RGO composite wave-suction material thickness is the reflection loss of 3.0mm Figure.
Fig. 5 the tape castings of the present invention prepare stratiform BaFe12O19/ RGO composite wave-suction material thickness is the reflection loss of 3.5mm Figure.
Specific implementation mode
By specific embodiment, the present invention is described in detail below in conjunction with the accompanying drawings.
In the present invention compression moulding be specifically will the casting films that fold as in mold, hot pressing and pressurize one minute.
Embodiment 1
Step 1：By natural flake graphite, the concentrated sulfuric acid of mass fraction 98%, sodium nitrate according to weight ratio 1:95:1.5 It is put into ice water, magnetic agitation is uniform.
Then 12g potassium permanganate is slowly added in three times, temperature is controlled at 0 DEG C, reacts 90min.Be heated to 35 DEG C and 2h is reacted, 80mL ultra-pure waters are slowly added to, temperature rises to 100 DEG C, stops heating after keeping the temperature 2h.Wherein, the quality of potassium permanganate It is 4 times of natural flake graphite quality, the volume ratio of ultra-pure water and the concentrated sulfuric acid of mass fraction 98% is 1：1；
200mL ultra-pure waters are poured into the product of reaction again, and the hydrogen peroxide of 10mL mass fractions 30% is added.It waits reacting molten Liquid cooling but after, product is subjected to centrifuge washing to neutrality with ultra-pure water, will be freeze-dried after the aqueous solution ultrasonic disperse 2h of product The as layered graphite oxide alkene powder of yellow.Finally use hydro-thermal method redox graphene：Graphene oxide is dispersed in In ethylene glycol, it is made into 1mgmL-1Solution, 200 DEG C in homogeneous reactor, rotating speed be 10r/min under, reaction for 24 hours, obtain For several times, 60 DEG C in vacuum desiccator, dry 10h obtains redox graphene to black product centrifuge washing.
Step 2：Random powder BaFe is prepared by solid phase method12O19, prepared with the BaFe being orientated by molten-salt growth method12O19 Powder.According to chemical general formula BaFe12O19In mol ratio, it is 60g BaCO accurately to weigh total amount respectively with electronic balance3With Fe2O3, 60g NaCl are weighed, are then placed in the ball grinder of 200mL, abundant wet ball grinding 2h is uniformly mixed, then will mixing Slurry is placed in electric drying oven with forced convection dry.Wherein BaCO3With Fe2O3It is according to BaFe12O19In mol ratio carry out It weighs, BaCO3、Fe2O3Gross mass and NaCl mass ratio be 1:1.The mass ratio of material, ball, water used in ball milling is 1:2: 1, the rotating speed of ball mill is 500r/min, in 80 DEG C of dry 4h in electric drying oven with forced convection, 60 mesh sieve is crossed after dry, is mixed Close powder A1.By mixed powder A1It is placed in high temperature Muffle furnace in 1000 DEG C of pre-burning 2h, the pre-burning product that will be obtained, at 80 DEG C It is washed with ultra-pure water, until NaCl is washed clean, obtains BaFe12O19The precursor B of powder1。
A certain amount of Fe is accurately weighed respectively with electronic balance2O3、BaCl2·2H2O and BaFe12O19The precursor B of powder1, Wet ball grinding 2h is uniformly mixed, and then mixed slurry is placed in electric drying oven with forced convection and is dried in 80 DEG C of dry 4h, dry 60 mesh sieve is crossed afterwards, obtains mixed powder C1, by mixed powder C1It is placed in high temperature Muffle furnace and calcines 2h in 1000 DEG C, will obtain Calcined product, washed with ultra-pure water at 80 DEG C, until salt is washed clean, obtains having on (001) direction and be orientated BaFe12O19Powder.Wherein, BaCl2·2H2The quality of O is Fe2O32 times of quality, BaFe12O19The precursor B of powder1's Quality is BaCl2·2H2O、Fe2O3And BaFe12O19The precursor B of powder1The 5% of gross mass.
According to chemical general formula BaFe12O19In mol ratio, by BaCO3And Fe2O3It is uniform by ball milling mixing, it is dry, Then 10h is calcined at 1000 DEG C, obtains random BaFe12O19Powder.
Step 3：Stratiform BaFe is prepared by the tape casting12O19/ RGO composite materials.
By absolute ethyl alcohol, butanone, olein according to weight ratio 1:2:0.05, mixing carries out a ball milling, ball Time consuming is 4h, and polyvinyl butyral, polyethylene glycol and dibutyl phthalate (DBP), mass ratio 1 is then added:2.5: 2.5, secondary ball milling, Ball-milling Time 4h are carried out, solvent (refers to absolute ethyl alcohol, butanone, olein, polyvinyl alcohol contracting fourth Aldehyde, polyethylene glycol and dibutyl phthalate (DBP)) total amount be 21g, be eventually adding 8g fission BaFe at random12O19, 1g is in (001) There is the BaFe being orientated on direction12O19Powder carries out first layer curtain coating in the case where rotating speed is 250r/min after wet ball grinding 2h；
By absolute ethyl alcohol, butanone, olein according to weight ratio 1:2:0.05, mixing carries out a ball milling, ball Time consuming is 4h, and polyvinyl butyral, polyethylene glycol and dibutyl phthalate (DBP), mass ratio 1 is then added:2.5: 2.5, secondary ball milling, Ball-milling Time 4h are carried out, solvent (refers to absolute ethyl alcohol, butanone, olein, polyvinyl alcohol contracting fourth Aldehyde, polyethylene glycol and dibutyl phthalate (DBP)) total amount be 3g, be eventually adding the redox graphene of 0.2g, wet ball grinding Afterwards in BaFe12O19The second layer curtain coating for continuing RGO on the film of first layer curtain coating, obtains film, and when curtain coating, film speed is 500mm/min is 200 μm per coating film thickness.Film is put into vacuum drying chamber at 180 DEG C dry 5min, obtains stratiform BaFe12O19/ RGO composite wave-suction materials.
It will be seen from figure 1 that following one layer is RGO, above one layer be random powder and be orientated powder BaFe12O19It is mixed Object is closed, is tightly combined between layers.
Figure it is seen that thickness of composite material is 2mm, and in 10.9GHz, maximum reflection loss -15.5dB, -10dB Absorption band width below is 3.6GHz (9.8~12.2GHz) and (13.9~15.1GHz).
From figure 3, it can be seen that thickness of composite material is 2.5mm, and in 16.0GHz, maximum reflection loss -27.1dB, - 10dB absorption band width below is 6.1GHz (6.3~8.3GHz) and (13.5~17.6GHz).
From fig. 4, it can be seen that thickness of composite material is 3.0mm, and in 10.3GHz, maximum reflection loss -16.8dB, - 10dB absorption band width below is 5.0GHz (8.9~12.5GHz) and (14.0~15.4GHz).
From fig. 5, it can be seen that thickness of composite material is 3.5mm, and in 12.0GHz, maximum reflection loss -19.2dB, - 10dB absorption band width below is 5.8GHz (4.8~6.8GHz), (10.4~12.9GHz) and (13.9~15.2GHz).
Embodiment 2
Step 1：By natural flake graphite, the concentrated sulfuric acid of mass fraction 98%, sodium nitrate according to weight ratio 2:98:2, it puts Enter in ice water, magnetic agitation is uniform.Then 13g potassium permanganate is slowly added in three times, temperature is controlled at 0 DEG C, reacts 90min. It is heated to 35 DEG C and reacts 2h, be slowly added to 90mL ultra-pure waters, temperature rises to 100 DEG C, stops heating after keeping the temperature 2h.Wherein, The quality of potassium permanganate is 7 times of natural graphite quality, and the volume ratio of ultra-pure water and the concentrated sulfuric acid of mass fraction 98% is 1.5： 1；
200mL ultra-pure waters are poured into the product of reaction again, and the hydrogen peroxide of 10mL mass fractions 30% is added.It waits reacting molten Liquid cooling but after, product is subjected to centrifuge washing to neutrality with ultra-pure water, will be freeze-dried after the aqueous solution ultrasonic disperse 2h of product The as layered graphite oxide alkene powder of yellow.Finally use hydro-thermal method redox graphene.Graphene oxide is dispersed in In ethylene glycol, it is made into 1.5mgmL-1Solution, 200 DEG C in homogeneous reactor, rotating speed be 10r/min under, reaction for 24 hours, obtain For several times to black product centrifuge washing, 70 DEG C in vacuum desiccator, dry 9h obtains redox graphene.
Step 2：Random powder BaFe is prepared by solid phase method12O19, prepared with the BaFe being orientated by molten-salt growth method12O19 Powder.According to chemical general formula BaFe12O19In mol ratio, accurately weigh a certain amount of BaCO respectively with electronic balance3With Fe2O3, then NaCl is weighed, it is placed in the ball grinder of 200mL, abundant wet ball grinding 4h is uniformly mixed, and then puts mixed slurry It sets dry in electric drying oven with forced convection.Wherein BaCO3、Fe2O3Gross mass and NaCl mass ratio be 1:1.5, used in ball milling Material, ball, water mass ratio be 1:2:1, the rotating speed of ball mill is 550r/min, in 90 DEG C of dryings in electric drying oven with forced convection 6h crosses 60 mesh sieve, obtains mixed powder A after dry1.By mixed powder A1It is placed in high temperature Muffle furnace in 1100 DEG C of pre-burning 3h, The pre-burning product that will be obtained is washed at 90 DEG C with ultra-pure water, until NaCl is washed clean, obtains BaFe12O19Powder Precursor B1.A certain amount of Fe is accurately weighed respectively with electronic balance2O3、BaCl2·2H2O and BaFe12O19The precursor B of powder1, Wet ball grinding 4h is uniformly mixed, and then mixed slurry is placed in electric drying oven with forced convection and is dried in 90 DEG C of dry 6h, dry 60 mesh sieve is crossed afterwards, obtains mixed powder C1, by mixed powder C1It is placed in high temperature Muffle furnace and calcines 3h in 1100 DEG C, will obtain Calcined product, washed with ultra-pure water at 90 DEG C, until salt is washed clean, obtains having on (001) direction and be orientated BaFe12O19Powder.Wherein, BaCl2·2H2The quality of O is Fe2O33 times of quality, BaFe12O19The precursor B of powder1's Quality is BaCl2·2H2O、Fe2O3And BaFe12O19The precursor B of powder1The 10% of gross mass.
According to chemical general formula BaFe12O19In mol ratio, by BaCO3And Fe2O3It is uniform by ball milling mixing, it is dry, Then 6h is calcined at 1200 DEG C, obtains random BaFe12O19Powder.
Step 3：Stratiform BaFe is prepared by the tape casting12O19/ RGO composite materials.Absolute ethyl alcohol, butanone, three oleic acid are sweet Grease is according to weight ratio 2:2.5:1, mixing carry out a ball milling, Ball-milling Time 6h, then be added polyvinyl butyral, Polyethylene glycol and dibutyl phthalate (DBP), mass ratio 1:2.5:2.5, secondary ball milling is carried out, Ball-milling Time is 6h ball millings Time is 4h, and solvent (refers to absolute ethyl alcohol, butanone, olein, polyvinyl butyral, polyethylene glycol and O-phthalic Sour dibutylester) gross mass be 21g, be eventually adding 7.2g fission BaFe at random12O19, 1.8g is with the BaFe being orientated12O19Powder, In the case where rotating speed is 280r/min, first layer curtain coating is carried out after last wet ball grinding 3h；
By absolute ethyl alcohol, butanone, olein according to weight ratio 2:2.5:1, mixing carries out a ball milling, ball milling Time is 4h, and polyvinyl butyral, polyethylene glycol and dibutyl phthalate (DBP), mass ratio 1 is then added:2.5: 2.5, secondary ball milling, Ball-milling Time 4h are carried out, solvent (refers to absolute ethyl alcohol, butanone, olein, polyvinyl alcohol contracting fourth Aldehyde, polyethylene glycol and dibutyl phthalate (DBP)) gross mass be 3.75g, be eventually adding the redox graphene of 0.25g, it is wet Second layer curtain coating is carried out on film after method ball milling after first layer curtain coating, obtains film, when curtain coating, film speed is 800mm/min, It it is 230 μm per coating film thickness.Film is put into vacuum drying chamber at 190 DEG C dry 8min and obtains stratiform BaFe12O19/RGO Composite wave-suction material.
Embodiment 3
Step 1：By natural flake graphite, the concentrated sulfuric acid of mass fraction 98%, sodium nitrate according to weight ratio 3:100: 3.5, it is put into ice water, magnetic agitation is uniform.Then 15g potassium permanganate is slowly added in three times, temperature is controlled at 0 DEG C, reaction 90min.It is heated to 35 DEG C and reacts 2h, be slowly added to 100mL ultra-pure waters, temperature rises to 100 DEG C, stops adding after keeping the temperature 2h Heat.Wherein, the quality of potassium permanganate is 4~12 times of natural graphite quality, ultra-pure water and the concentrated sulfuric acid of mass fraction 98% Volume ratio is 1：1；
200mL ultra-pure waters are poured into the product of reaction again, and the hydrogen peroxide of 10mL mass fractions 30% is added.It waits reacting molten Liquid cooling but after, product is subjected to centrifuge washing to neutrality with ultra-pure water, will be freeze-dried after the aqueous solution ultrasonic disperse 2h of product The as layered graphite oxide alkene powder of yellow.Finally use hydro-thermal method redox graphene：Graphene oxide is dispersed in In ethylene glycol, it is made into 2mgmL-1Solution, 200 DEG C in homogeneous reactor, rotating speed be 10r/min under, reaction for 24 hours, obtain For several times, 80 DEG C in vacuum desiccator, dry 10h obtains redox graphene to black product centrifuge washing.
Step 2：Random powder BaFe is prepared by solid phase method12O19, prepared with the BaFe being orientated by molten-salt growth method12O19 Powder.According to chemical general formula BaFe12O19In mol ratio, accurately weigh a certain amount of BaCO respectively with electronic balance3With Fe2O3, then NaCl is weighed, it is then placed in the ball grinder of 200mL, abundant wet ball grinding 6h is uniformly mixed, then by mixture Slurry is placed in electric drying oven with forced convection dry.Wherein raw material BaCO3、Fe2O3Gross mass and NaCl mass ratio be 1:1:2, The mass ratio of material, ball, water used in ball milling is 1:2:1, the rotating speed of ball mill is 500~600r/min, in electric heating forced air drying In 100 DEG C of dry 8h in case, 60 mesh sieve is crossed after dry, obtains mixed powder A1.By mixed powder A1It is placed in high temperature Muffle furnace In 1200 DEG C of pre-burning 4h, the pre-burning product that will be obtained is washed at 100 DEG C with ultra-pure water, until NaCl is washed clean, is obtained To BaFe12O19The precursor B of powder1。
A certain amount of Fe is accurately weighed respectively with electronic balance2O3、BaCl2·2H2O and BaFe12O19The precursor B of powder1, Wet ball grinding 6h is uniformly mixed, and then mixed slurry is placed in electric drying oven with forced convection and is dried in 80~100 DEG C of dry 8h, 60 mesh sieve is crossed after drying, obtains mixed powder C1, by mixed powder C1It is placed in high temperature Muffle furnace and calcines 4h in 1200 DEG C, it will Obtained calcined product is washed at 100 DEG C with ultra-pure water, until salt is washed clean, obtains having on (001) direction The BaFe of orientation12O19Powder.Wherein, BaCl2·2H2The quality of O is Fe2O32 times of quality, BaFe12O19The presoma of powder B1Quality be BaCl2·2H2O、Fe2O3And BaFe12O19The precursor B of powder1The 15% of gross mass.
According to chemical general formula BaFe12O19In mol ratio, by BaCO3And Fe2O3It is uniform by ball milling mixing, it is dry, Then 8h is calcined at 1100 DEG C, obtains random BaFe12O19Powder.
Step 3：Stratiform BaFe is prepared by the tape casting12O19/ RGO composite materials.Absolute ethyl alcohol, butanone, three oleic acid are sweet Grease is according to weight ratio 3:3:1.5, mixing carry out a ball milling, Ball-milling Time 8h, then be added polyvinyl butyral, Polyethylene glycol and dibutyl phthalate (DBP), mass ratio 1:2.5:2.5, carry out secondary ball milling, Ball-milling Time 8h, solvent (referring to absolute ethyl alcohol, butanone, olein, polyvinyl butyral, polyethylene glycol and dibutyl phthalate (DBP)) total matter Amount is 21g, is eventually adding 6.3g fission BaFe at random12O19, 2.7g is with the BaFe being orientated12O19Powder is 240r/ in rotating speed Under min, first layer curtain coating is carried out after last wet ball grinding 4h,
By absolute ethyl alcohol, butanone, olein according to weight ratio 3:3:1.5 mixing carries out a ball milling, ball milling Time is 8h, and polyvinyl butyral, polyethylene glycol and dibutyl phthalate (DBP), mass ratio 1 is then added:2.5: 2.5, secondary ball milling, Ball-milling Time 8h are carried out, solvent (refers to absolute ethyl alcohol, butanone, olein, polyvinyl alcohol contracting fourth Aldehyde, polyethylene glycol and dibutyl phthalate (DBP)) gross mass be 1.5g, be eventually adding the redox graphene of 0.1g, wet method Second layer curtain coating is carried out on film after ball milling after first layer curtain coating, obtains film, when curtain coating, film speed is 1200mm/min, It it is 250 μm per coating film thickness.Film is put into vacuum drying chamber at 200 DEG C dry 10min and obtains stratiform BaFe12O19/ RGO composite wave-suction materials.
Ferrite BaFe12O19Absorbing material has the characteristics that absorption is strong, frequency band is wider and at low cost, but there is also density Greatly, the shortcomings of hot properties is poor, composite material research as Materials Science and Engineering field research hotspot, as graphene, Conduction high polymer, silicon carbide etc. form composite wave-suction material.Graphene has excellent electricity, thermodynamics and mechanical performance, close Degree is smaller, and dielectric loss is higher.The present invention uses tape casting, and it is equal that the dispersions such as solvent, dispersant, binder are added in powder Even stable slurry, is made forming method in homogeneous thickness on casting machine, this method have equipment is simple, can operate continuously, Production efficiency height, process stabilizing, the first-class series of advantages of body crack defects.Ferrite BaFe12O19It is compound with graphene, it is expected to Prepare that absorbing property is good, while the absorbing material that proportion is lighter.

Claims (9)

1. a kind of method that the tape casting prepares stratiform barium ferrite/RGO composite wave-suction materials, which is characterized in that
Absolute ethyl alcohol, butanone, olein are uniformly mixed, mixed solvent is obtained, then be added polyvinyl butyral, Dibutyl phthalate (DBP) and polyethylene glycol are uniformly mixed, random BaFe are then added12O19Powder, with orientation BaFe12O19Powder carries out first layer curtain coating after carrying out wet ball grinding；
Absolute ethyl alcohol, butanone, olein are uniformly mixed, mixed solvent is obtained, then be added polyvinyl butyral, Dibutyl phthalate (DBP) and polyethylene glycol are uniformly mixed, are then added redox graphene, carry out after wet ball grinding again into The row second layer is cast, and obtains film；Film is dried, stratiform barium ferrite/RGO composite wave-suction materials are obtained；By mass percentage, with Machine powder BaFe12O19And have orientation BaFe12O19Powder mass ratio be (70%~90%):(10%~30%)；Random powder Body and be orientated BaFe12O19The gross mass of powder and the mass ratio of redox graphene be (5~7):(0.1~ 0.5)。
2. the method that a kind of the tape casting according to claim 1 prepares stratiform barium ferrite/RGO composite wave-suction materials, special Sign is, in the mixed solvent absolute ethyl alcohol, butanone, olein weight ratio (1~3):(2~3):(0.05~1.5).
3. the method that a kind of the tape casting according to claim 1 prepares stratiform barium ferrite/RGO composite wave-suction materials, special Sign is that the mass ratio of polyvinyl butyral, dibutyl phthalate (DBP) and polyethylene glycol is 1:2.5:2.5 mixed solvent, The gross mass of polyvinyl butyral, dibutyl phthalate (DBP) and polyethylene glycol and random powder BaFe12O19And have orientation BaFe12O19Powder total mass ratio be 7:3, mixed solvent, polyvinyl butyral, dibutyl phthalate (DBP) and poly- second The gross mass of glycol and the mass ratio of redox graphene are 15:1.
4. the method that a kind of the tape casting according to claim 1 prepares stratiform barium ferrite/RGO composite wave-suction materials, special Sign is, in casting processes, film speed is 500~1200mm/min, is 200~250 μm per coating film thickness.
5. the method that a kind of the tape casting according to claim 1 prepares stratiform barium ferrite/RGO composite wave-suction materials, special Sign is that drying is to dry 5~10min at 180~200 DEG C in vacuum drying chamber.
6. the method that a kind of the tape casting according to claim 1 prepares stratiform barium ferrite/RGO composite wave-suction materials, special Sign is that redox graphene is prepared by following procedure：
By natural flake graphite, the concentrated sulfuric acid of mass fraction 98%, sodium nitrate according to weight ratio (1~3):(95~100): (1.5~3.5), are put into ice water, and magnetic agitation is uniform；
Then 12~15g potassium permanganate is added, reacts 90min at 0 DEG C, is then heated to 35 DEG C and reacts 2h, add 80~100mL ultra-pure waters, temperature rise to 100 DEG C, and stop reaction after keeping the temperature 2h, and the quality of potassium permanganate is natural graphite quality 4~12 times, the volume ratio of the concentrated sulfuric acid of ultra-pure water and mass fraction 98% is (1~1.5):1；
200mL ultra-pure waters are poured into the product of reaction again, and the hydrogen peroxide of 10mL mass fractions 30% is added, wait for that reaction solution is cold But after, product is subjected to centrifuge washing to neutrality with ultra-pure water, will be freeze-dried, obtain after the aqueous solution ultrasonic disperse 2h of product The layered graphite oxide alkene powder of yellow；
Graphene oxide powder is dispersed in ethylene glycol, 1~2mgmL is made into-1Solution, then in homogeneous reactor 200 DEG C of reactions for 24 hours, obtain black product, and washing, drying obtain redox graphene.
7. the method that a kind of the tape casting according to claim 1 prepares stratiform barium ferrite/RGO composite wave-suction materials, special Sign is there is the BaFe being orientated12O19Powder is prepared by following procedure：
1) by BaCO3、Fe2O3It is uniform by ball milling mixing with NaCl, it then dries, cross 60 mesh sieve, obtain mixed powder A1；Its In, BaCO3With Fe2O3Gross mass and NaCl mass ratio be 1:(1~2)；BaCO3With Fe2O3Amount press chemical general formula BaFe12O19In mol ratio；
2) by the obtained mixed powder A of step 1)1In 1000~1200 DEG C of 2~4h of pre-burning, washing obtains BaFe12O19Powder Precursor B1；
3) by Fe2O3、BaCl2·2H2O and BaFe12O19The precursor B of powder1, it is uniformly mixed, obtains mixed slurry, then will 60 mesh sieve is crossed after mixed slurry drying, obtains mixed powder C1, then by mixed powder C12~4h, water are calcined in 1000~1200 DEG C It washes, obtains that there is the BaFe being orientated on (001) direction12O19Flaky powder.
8. the method that a kind of the tape casting according to claim 7 prepares stratiform barium ferrite/RGO composite wave-suction materials, special Sign is that the rotating speed of ball milling is 500~600r/min in step 1), and dry temperature is 80~100 DEG C, and the time is 4~8h；Step It is rapid 3) in BaCl2·2H2The quality of O is Fe2O32~3 times of quality, BaFe12O19The precursor B of powder1Quality be BaCl2·2H2O、Fe2O3And BaFe12O19The precursor B of powder1The 5%-15% of gross mass.
9. the method that a kind of the tape casting according to claim 1 prepares stratiform barium ferrite/RGO composite wave-suction materials, special Sign is, random BaFe12O19Powder is prepared by following procedure：
According to chemical general formula BaFe12O19In mol ratio, by BaCO3And Fe2O3It is uniform by ball milling mixing, it is dry, then exist 6~10h is calcined at 1000~1200 DEG C, obtains random BaFe12O19Powder.
CN201611162399.9A 2016-12-15 2016-12-15 A kind of method that the tape casting prepares stratiform barium ferrite/RGO composite wave-suction materials Active CN106696410B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611162399.9A CN106696410B (en) 2016-12-15 2016-12-15 A kind of method that the tape casting prepares stratiform barium ferrite/RGO composite wave-suction materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611162399.9A CN106696410B (en) 2016-12-15 2016-12-15 A kind of method that the tape casting prepares stratiform barium ferrite/RGO composite wave-suction materials

Publications (2)

Publication Number Publication Date
CN106696410A CN106696410A (en) 2017-05-24
CN106696410B true CN106696410B (en) 2018-08-07

Family

ID=58937977

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611162399.9A Active CN106696410B (en) 2016-12-15 2016-12-15 A kind of method that the tape casting prepares stratiform barium ferrite/RGO composite wave-suction materials

Country Status (1)

Country Link
CN (1) CN106696410B (en)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100516140C (en) * 2007-05-18 2009-07-22 西安交通大学 Method for preparing strontium-barium titanate/polymide dielectric adjustable composite material thick film
CN102876288B (en) * 2012-10-29 2014-05-07 哈尔滨工业大学 Graphite/barium ferrite composite wave-absorbing material and preparation method thereof

Also Published As

Publication number Publication date
CN106696410A (en) 2017-05-24

Similar Documents

Publication Publication Date Title
CN109705808A (en) A kind of cobalt-nickel alloy with MOF structure-porous carbon composite wave-suction material and preparation method thereof
CN103304186B (en) Ferrite-base composite magnetic dielectric antenna substrate material and preparation method thereof
CN102964972B (en) Composite intensified heat dissipation coating containing graphene or graphene oxide and preparation method of coating
CN104193224B (en) A kind of microstrip antenna organic composite substrate material and preparation method thereof
CN109233740A (en) The method for preparing Fe/Co/C composite wave-suction material based on modified MOF materials pyrolysis
CN102275887A (en) Preparation method of high capacity high compacted density lithium iron phosphate material and product thereof
CN101531505B (en) Anti-radiation ceramics and preparation method thereof
CN108190876B (en) A kind of graphene composite absorber and preparation method thereof
WO2020113958A1 (en) Method for preparing high-performance iron oxide red/clay mineral hybrid pigment by mechanochemistry
CN110156453A (en) A kind of preparation method of high power rare earth yttrium iron garnet complex ferrite material
CN107934965A (en) A kind of Ti3C2‑Co(OH)(CO3)0.5The preparation method of nanocomposite
CN106673640A (en) Barium ferrite / zinc oxide composite wave-absorbing material and preparation method thereof
CN108409320A (en) A kind of double textural composite magnetic dielectric ceramic materials and preparation method
CN103588474B (en) Preparation method of magneto-electricity composite ceramic with coating structure
CN113121214B (en) Graphite tailing-based microwave dielectric ceramic material and preparation method thereof
CN106753238A (en) A kind of preparation method of lamination Wave suction composite material
CN106696410B (en) A kind of method that the tape casting prepares stratiform barium ferrite/RGO composite wave-suction materials
CN104439273B (en) Preparation method for FeCo/ZnO composite wave-absorbing material
CN104466167B (en) Method for preparing positive material LiNi1/3Co1/3Mn1/3O2 of lithium ion battery
Meng et al. Fabrication of core-shell Co@ HCN@ PANI composite material with enhanced electromagnetic wave absorption
CN106883825A (en) A kind of preparation method of stearic acid/modification infusorial earth composite phase-change energy storage material
CN114409391B (en) Preparation method of high-valence Ta-doped W-type barium ferrite wave-absorbing material
CN106587972A (en) Preparation method of Z-type ferrite plate-like powder
CN105948751A (en) Neodymium-doped strontium fluoride laser transparent ceramic and preparation method thereof
CN102910908B (en) Preparing process of double-perovskite Y2MNCoO6 dielectric ceramic

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant