CN106006751B - A kind of preparation method of the Ni-Zn ferrite nano materials of cation doping - Google Patents
A kind of preparation method of the Ni-Zn ferrite nano materials of cation doping Download PDFInfo
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- CN106006751B CN106006751B CN201610311768.XA CN201610311768A CN106006751B CN 106006751 B CN106006751 B CN 106006751B CN 201610311768 A CN201610311768 A CN 201610311768A CN 106006751 B CN106006751 B CN 106006751B
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- C01G49/00—Compounds of iron
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- C01G49/0063—Mixed oxides or hydroxides containing zinc
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- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
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Abstract
A kind of preparation method of the Ni-Zn ferrite nano materials of cation doping：1) Ni is pressedxZnyCo(1‑x‑y)Fe2O4Stoichiometric proportion, weighs nickel nitrate, zinc nitrate, cobalt nitrate and ferric nitrate, 0.75≤x+y≤0.95,0.4≤x≤0.6,0.15≤y≤0.4；Raw material is dissolved in distilled water, plus surfactant, mixed solution russet is obtained；2) sodium hydroxide solution in thermostatted water uniform stirring simultaneously, is added dropwise, adjusts pH of mixed=9~12, obtains precursors；3) normal temperature is aged, and obtains thick ageing liquid；4) brilliant magnificent liquid is obtained after crystallization；5) filter cake is vacuumized to obtain；6) ground after drying, obtain the Ni-Zn ferrite nano materials of cation doping.The Ni-Zn ferrite nano materials of cation doping of the present invention, particle is in spherical, 20~30nm of average grain diameter, has higher magnetic permcability and compared with low-k in 2 4GHz wave bands, traditional ferrite not good defect of wave-absorbing effect in the range of low frequency S-band is made up, ferritic absorbing property is improved.
Description
Technical field
The invention belongs to magnetic Nano material manufacture field, more particularly to a kind of Ni-Zn ferrite nano materials of cation doping
Preparation method.
Background technology
Nanometer spinel type nickel-zinc ferrite has dielectric loss and magnetic hystersis loss double grading as absorbing material, it
The attributes such as high resistivity, high magnetic permeability, low-dielectric loss, high-curie temperature and chemical stability, in many suction wave technology fields
Play key effect.It is mainly used in manufacture power switch, transformer, loading coil, radar equipment, stealth material, electronics
And microwave equipment.But due to single ferrite be difficult to meet wide absorption band, light weight, thickness of thin requirement, therefore in iron
Adulterate some additives composition composite absorber in oxysome micro mist, realizes to microwave absorption intensity, frequency bandwidth and electromagnetic parameter
Controllable adjustment.
Traditional dry method doping is difficult control due to doping, it is difficult to uniform mixing, is readily incorporated other impurities；And wet method
Doping avoids the defect of Traditional dopant method, dopant and ferrite is well mixed on atom or molecular scale, can be with
Accurate control doping, effectively improves the performance of nickel-zinc ferrite.
The existing method for preparing nanometer ferrite mainly has：Chemical coprecipitation, low-temperature solid phase reaction precursor process, from
Propagating combustion synthetic method, sol-gel process etc..But traditional synthetic method craft is complicated, environmental requirement is harsh and cost is very high,
It is unfavorable for industrialized production.The present invention uses hydrothermal synthesis method, in high temperature, high-pressure sealed environment, and reaction matchmaker is used as using water
Be situated between, add before the synthesis surfactant promote the uniform precursors of generation, reduce crystal surface can, make indissoluble or not
Molten substance dehydrates dissolving, is recrystallized.The nano-particle crystal grain prepared using hydrothermal synthesis method is tiny, and defect is few, crystallization
Well, lattice development is complete, and particle diameter distribution is narrower, and reunion degree is low.High temperature sintering is not needed in preparation process, it is to avoid crystal grain
Reunite, grow up, the formation of defect.This method is simple, cost is low, reaction condition is gently easily controlled.
At present, ferrite wave-absorbing material production cost is very high, is unfavorable for commercial introduction in daily life, inhales ripple scope main
8-18GHz frequency bands are concentrated on, it is bad in the absorbing property of low frequency S-band (2-4GHz), and the main source of electromagenetic wave radiation
One of the propagation of radio concentrate in the range of 2-6GHz.With in life electromagnetic radiation situation it is increasingly serious, prepare into
This low, technique is simple and has important value in the good ferrite of electromagnetic wave low frequency S-band (2-4GHz) absorbing property.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of preparation side of the Ni-Zn ferrite nano materials of cation doping
Method, realizes absorbing property of the ferrite in low-frequency band, is that a kind of method is simple, cost is low, reaction condition is easily-controllable, environmentally friendly section
Can, in the preparation method of the Ni-Zn ferrite nano materials of the good cation doping of low frequency S-band (2-4GHz) absorbing property.
The preparation method of the Ni-Zn ferrite nano materials of the cation doping of the present invention, comprises the following steps：
Step 1, dispensing：
(1) Ni is pressedxZnyCo(1-x-y)Fe2O4Stoichiometric proportion, weighs 4 kinds of raw materials respectively：Nickel nitrate (Ni (NO3)2·
6H2O), zinc nitrate (Zn (NO3)2·6H2O), cobalt nitrate (Co (NO3)2·6H2) and ferric nitrate (Fe (NO O3)3·9H2O), its
In, 0.75≤x+y≤0.95,0.4≤x≤0.6,0.15≤y≤0.4；
(2) by above-mentioned 4 kinds of raw materials, it is dissolved in distilled water, adds surfactant, after being uniformly dispersed, obtain bronzing
Mixed solution；Wherein, in mass ratio, 4 kinds of material qualities and: distilled water=(25~28): (150~200), 4 kinds of raw material matter
Amount and: surfactant=(25~28): (1~3)；
Step 2：Reaction of formation presoma；
Mixed solution russet is placed in four-hole boiling flask, in 30~50 DEG C of water bath with thermostatic control, turned with 150~270r/min
Fast continuous uniform stirring；1~3mol/L sodium hydroxide solution is added dropwise into four-hole boiling flask simultaneously, the pH=of mixed solution is adjusted
9~12；
Step 3, it is aged：
By precursors, in normal temperature 6~10h of static ageing, section top clear liquid is removed, the thick ageing of lower floor is obtained
Liquid；
Step 4, crystallization：
(1) by the thick ageing liquid of lower floor, concussion shakes up, and moves into the hydro-thermal reaction under high pressure with polytetrafluoroethyllining lining
Kettle；
(2) by hydro-thermal autoclave, at 160~220 DEG C, 6~12h of crystallization obtains crystallization liquid；
Step 5, suction filtration：
Crystallization liquid is cooled to room temperature, obtained solution is washed to neutrality, vacuum filtration, obtains filter cake；
Step 6, drying grinding：
(1) filter cake is obtained into dark brown block in 60~80 DEG C of drying；
(2) dark brown block is ground to powder, that is, obtains the Ni-Zn ferrite nano materials of cation doping.
In described step 1 (1), nickel nitrate, zinc nitrate, cobalt nitrate and ferric nitrate are that analysis is pure.
In described step 1 (2), surfactant is polyethylene glycol.
In described step 1 (2), it is set to be uniformly dispersed using ultrasonically treated.
In described step 2 (2), the speed that sodium hydroxide solution is added dropwise is 0.5~1 drop/sec.
In described step 4 (2), crystallization is carried out in cabinet-type electric furnace.
In described step 5, washed using distilled water and absolute ethyl alcohol.
In described step 6 (1), dried using air dry oven.
The preparation method of the Ni-Zn ferrite nano materials of the cation doping of the present invention, it is compared with prior art, of the invention
Advantage is：
The ferrite of the present invention is the Spinel nickel zinc Conjugate ferrite of pure phase, and sample particle is in spherical, average grain diameter
About 20~30nm, has higher magnetic conductivity and relatively low dielectric constant in 2-4GHz wave bands, compensate for traditional ferrite and exist
The not good defect of wave-absorbing effect in the range of low frequency S-band, improves ferritic absorbing property.In the base using hydrothermal synthesis method
On plinth, by the electromagnetic parameter of the first usually controlled materials itself of the Co that adulterates, the purpose for improving material electromagnetic performance is reached；Gentle
Under the conditions of, it is raw material using water miscible inorganic metal salt, reduces cost；It is stoichiometrically that the metal salt of doping is directly molten
Solution can accurately control doping into reactant solution, it is to avoid introduce other impurities；During crystallization, pass through control
Reaction temperature processed and time, regulate and control ferritic crystal formation and crystallite dimension, so as to synthesize the good nanometer nickel zinc of electromagnetic performance
Conjugate ferrite.Preparation method is simple, and cost is low, and reaction condition is easily-controllable, and environmental protection and energy saving, product particle size is tiny, and defect is few, crystallization
Well, reunion degree is low, it is adaptable to industrialized production.
Brief description of the drawings
The process chart of the preparation method of the Ni-Zn ferrite nano materials of the cation doping of Fig. 1 embodiment of the present invention；
The scanning electron microscopic picture of the Ni-Zn ferrite nano materials of cation doping prepared by Fig. 2 embodiment of the present invention 1；
The scanning electron microscopic picture of the Ni-Zn ferrite nano materials of cation doping prepared by Fig. 3 embodiment of the present invention 2；
The scanning electron microscopic picture of the Ni-Zn ferrite nano materials of cation doping prepared by Fig. 4 embodiment of the present invention 3；
The scanning electron microscopic picture of the Ni-Zn ferrite nano materials of cation doping prepared by Fig. 5 embodiment of the present invention 4；
The scanning electron microscopic picture of the Ni-Zn ferrite nano materials of cation doping prepared by Fig. 6 embodiment of the present invention 5；
The scanning electron microscopic picture of the Ni-Zn ferrite nano materials of cation doping prepared by Fig. 7 embodiment of the present invention 6；
The scanning electron microscopic picture of the Ni-Zn ferrite nano materials of cation doping prepared by Fig. 8 embodiment of the present invention 7；
The scanning electron microscopic picture of the Ni-Zn ferrite nano materials of cation doping prepared by Fig. 9 embodiment of the present invention 8.
Embodiment
The process chart of the preparation method of the Ni-Zn ferrite nano materials of the cation doping of following examples is shown in Fig. 1.
Embodiment 1
A kind of preparation method of the Ni-Zn ferrite nano materials of cation doping, comprises the following steps：
Step 1, dispensing：
(1) Ni is pressed0.5Zn0.4Co0.1Fe2O4Stoichiometric proportion, weighs 4 kinds of raw materials respectively：3.64g analyzes pure nickel nitrate (Ni
(NO3)2·6H2O), 2.97g analyzes pure zinc nitrate (Zn (NO3)2·6H2O), 0.73g analyzes pure cobalt nitrate (Co (NO3)2·
6H2) and 20.20g analyzes pure ferric nitrate (Fe (NO O3)3·9H2O)；
(2) by above-mentioned 4 kinds of raw materials, it is dissolved in 150mL distilled water, adds 2g polyethylene glycol, it is ultrasonically treated to disperse it
Uniformly, mixed solution russet is obtained；
Step 2：Reaction of formation presoma；
Mixed solution russet is placed in four-hole boiling flask, in 30 DEG C of water bath with thermostatic control, continued with 210r/min rotating speeds
Even stirring；3mol/L sodium hydroxide solution is added dropwise into four-hole boiling flask simultaneously, the pH=11 of mixed solution is adjusted；
Step 3, it is aged：
By precursors, in the static ageing 10h of normal temperature, section top clear liquid is removed, the thick ageing liquid of lower floor is obtained；
Step 4, crystallization：
(1) by the thick ageing liquid of lower floor, concussion shakes up, and moves into the hydro-thermal reaction under high pressure with polytetrafluoroethyllining lining
Kettle；
(2) by hydro-thermal autoclave, in 160 DEG C of cabinet-type electric furnace, crystallization 6h obtains crystallization liquid；
Step 5, suction filtration：
Crystallization liquid is cooled to room temperature, then with distilled water and absolute ethyl alcohol respectively washing 4 times, makes solution to neutrality, vacuum is taken out
Filter, obtains filter cake；
Step 6, drying grinding：
(1) filter cake is dried in 60 DEG C of drying baker, obtains dark brown block；
(2) dark brown block is ground to powder, that is, obtains the Ni-Zn ferrite nano materials of cation doping.
Ni manufactured in the present embodiment0.5Zn0.4Co0.1Fe2O4The Ni-Zn ferrite nano materials of cation doping, scanning electron microscopic picture
See accompanying drawing 2, its average grain diameter is 20-30nm, the nickel zinc Conjugate ferrite is 3.1, imaginary part in the magnetic conductivity real part of 3GHz Frequency points
For 3.0；Real part of permittivity is 7.2, and imaginary part is 0.16.
Embodiment 2
A kind of preparation method of the Ni-Zn ferrite nano materials of cation doping, comprises the following steps：
Step 1, dispensing：
(1) Ni is pressed0.6Zn0.15Co0.25Fe2O4Stoichiometric proportion, weighs 4 kinds of raw materials respectively：4.36g analyzes pure nickel nitrate
(Ni(NO3)2·6H2O), 1.12g analyzes pure zinc nitrate (Zn (NO3)2·6H2O), 1.82g analyzes pure cobalt nitrate (Co (NO3)2·
6H2) and 20.20g analyzes pure ferric nitrate (Fe (NO O3)3·9H2O)；
(2) by above-mentioned 4 kinds of raw materials, it is dissolved in 150mL distilled water, adds 2g polyethylene glycol, it is ultrasonically treated to disperse it
Uniformly, mixed solution russet is obtained；
Step 2：Reaction of formation presoma；
Mixed solution russet is placed in four-hole boiling flask, in 40 DEG C of water bath with thermostatic control, continued with 180r/min rotating speeds
Even stirring；2mol/L sodium hydroxide solution is added dropwise into four-hole boiling flask simultaneously, the pH=10 of mixed solution is adjusted；
Step 3, it is aged：
By precursors, in the static ageing 8h of normal temperature, section top clear liquid is removed, the thick ageing liquid of lower floor is obtained；
Step 4, crystallization：
(1) by the thick ageing liquid of lower floor, concussion shakes up, and moves into the hydro-thermal reaction under high pressure with polytetrafluoroethyllining lining
Kettle；
(2) by hydro-thermal autoclave, in 180 DEG C of cabinet-type electric furnace, crystallization 8h obtains crystallization liquid；
Step 5, suction filtration：
Crystallization liquid is cooled to room temperature, then with distilled water and absolute ethyl alcohol respectively washing 4 times, makes solution to neutrality, vacuum is taken out
Filter, obtains filter cake；
Step 6, drying grinding：
(1) filter cake is dried in 80 DEG C of drying baker, obtains dark brown block；
(2) dark brown block is ground to powder, that is, obtains the Ni-Zn ferrite nano materials of cation doping.
Ni manufactured in the present embodiment0.6Zn0.15Co0.25Fe2O4The Ni-Zn ferrite nano materials of cation doping, scanning electron microscope (SEM) photograph
Piece is shown in accompanying drawing 3, and its average grain diameter is 20-30nm, and the nickel zinc Conjugate ferrite is 3.4 in the magnetic conductivity real part of 3GHz Frequency points, empty
Portion is 3.2；Real part of permittivity is 7.5, and imaginary part is 0.17.
Embodiment 3
A kind of preparation method of the Ni-Zn ferrite nano materials of cation doping, comprises the following steps：
Step 1, dispensing：
(1) Ni is pressed0.4Zn0.4Co0.2Fe2O4Stoichiometric proportion, weighs 4 kinds of raw materials respectively：2.91g analyzes pure nickel nitrate (Ni
(NO3)2·6H2O), 2.97g analyzes pure zinc nitrate (Zn (NO3)2·6H2O), 1.46g analyzes pure cobalt nitrate (Co (NO3)2·
6H2) and 20.20g analyzes pure ferric nitrate (Fe (NO O3)3·9H2O)；
(2) by above-mentioned 4 kinds of raw materials, it is dissolved in 150mL distilled water, adds 2g polyethylene glycol, it is ultrasonically treated to disperse it
Uniformly, mixed solution russet is obtained；
Step 2：Reaction of formation presoma；
Mixed solution russet is placed in four-hole boiling flask, in 45 DEG C of water bath with thermostatic control, continued with 150r/min rotating speeds
Even stirring；1.5mol/L sodium hydroxide solution is added dropwise into four-hole boiling flask simultaneously, the pH=9 of mixed solution is adjusted；
Step 3, it is aged：
By precursors, in the static ageing 8h of normal temperature, section top clear liquid is removed, the thick ageing liquid of lower floor is obtained；
Step 4, crystallization：
(1) by the thick ageing liquid of lower floor, concussion shakes up, and moves into the hydro-thermal reaction under high pressure with polytetrafluoroethyllining lining
Kettle；
(2) by hydro-thermal autoclave, in 200 DEG C of cabinet-type electric furnace, crystallization 12h obtains crystallization liquid；
Step 5, suction filtration：
Crystallization liquid is cooled to room temperature, then with distilled water and absolute ethyl alcohol respectively washing 4 times, makes solution to neutrality, vacuum is taken out
Filter, obtains filter cake；
Step 6, drying grinding：
(1) filter cake is dried in 70 DEG C of drying baker, obtains dark brown block；
(2) dark brown block is ground to powder, that is, obtains the Ni-Zn ferrite nano materials of cation doping.
Ni manufactured in the present embodiment0.4Zn0.4Co0.2Fe2O4The Ni-Zn ferrite nano materials of cation doping, scanning electron microscopic picture
See accompanying drawing 4, its average grain diameter is 20-30nm, the nickel zinc Conjugate ferrite is 3.0, imaginary part in the magnetic conductivity real part of 3GHz Frequency points
For 2.8；Real part of permittivity is 7., and imaginary part is 0.15.
Embodiment 4
A kind of preparation method of the Ni-Zn ferrite nano materials of cation doping, comprises the following steps：
Step 1, dispensing：
(1) Ni is pressed.05Zn0.35Co0.15Fe2O4Stoichiometric proportion, weighs 4 kinds of raw materials respectively：3.64g analyzes pure nickel nitrate
(Ni(NO3)2·6H2O), 2.60g analyzes pure zinc nitrate (Zn (NO3)2·6H2O), 1.09g analyzes pure cobalt nitrate (Co (NO3)2·
6H2) and 20.20g analyzes pure ferric nitrate (Fe (NO O3)3·9H2O)；
(2) by above-mentioned 4 kinds of raw materials, it is dissolved in 150mL distilled water, adds 2g polyethylene glycol, it is ultrasonically treated to disperse it
Uniformly, mixed solution russet is obtained；
Step 2：Reaction of formation presoma；
Mixed solution russet is placed in four-hole boiling flask, in 35 DEG C of water bath with thermostatic control, continued with 240r/min rotating speeds
Even stirring；3mol/L sodium hydroxide solution is added dropwise into four-hole boiling flask simultaneously, the pH=12 of mixed solution is adjusted；
Step 3, it is aged：
By precursors, in the static ageing 6h of normal temperature, section top clear liquid is removed, the thick ageing liquid of lower floor is obtained；
Step 4, crystallization：
(1) by the thick ageing liquid of lower floor, concussion shakes up, and moves into the hydro-thermal reaction under high pressure with polytetrafluoroethyllining lining
Kettle；
(2) by hydro-thermal autoclave, in 220 DEG C of cabinet-type electric furnace, crystallization 10h obtains crystallization liquid；
Step 5, suction filtration：
Crystallization liquid is cooled to room temperature, then with distilled water and absolute ethyl alcohol respectively washing 4 times, makes solution to neutrality, vacuum is taken out
Filter, obtains filter cake；
Step 6, drying grinding：
(1) filter cake is dried in 80 DEG C of drying baker, obtains dark brown block；
(2) dark brown block is ground to powder, that is, obtains the Ni-Zn ferrite nano materials of cation doping.
Ni manufactured in the present embodiment0.5Zn0.35Co0.15Fe2O4The Ni-Zn ferrite nano materials of cation doping, scanning electron microscope (SEM) photograph
Piece is shown in accompanying drawing 5, and its average grain diameter is 20-30nm, and the nickel zinc Conjugate ferrite is 2.9 in the magnetic conductivity real part of 3GHz Frequency points, empty
Portion is 2.8；Real part of permittivity is 7.1, and imaginary part is 0.16.
Embodiment 5
A kind of preparation method of the Ni-Zn ferrite nano materials of cation doping, comprises the following steps：
Step 1, dispensing：
(1) Ni is pressed0.5Zn0.3Co0.2Fe2O4Stoichiometric proportion, weighs 4 kinds of raw materials respectively：3.64g analyzes pure nickel nitrate (Ni
(NO3)2·6H2O), 2.23g analyzes pure zinc nitrate (Zn (NO3)2·6H2O), 1.46g analyzes pure cobalt nitrate (Co (NO3)2·
6H2) and 20.20g analyzes pure ferric nitrate (Fe (NO O3)3·9H2O)；
(2) by above-mentioned 4 kinds of raw materials, it is dissolved in 150mL distilled water, adds 2g polyethylene glycol, it is ultrasonically treated to disperse it
Uniformly, mixed solution russet is obtained；
Step 2：(1) and (2) is carried out simultaneously, reaction of formation presoma；
Mixed solution russet is placed in four-hole boiling flask, in 50 DEG C of water bath with thermostatic control, continued with 180r/min rotating speeds
Even stirring；2.5mol/L sodium hydroxide solution is added dropwise into four-hole boiling flask simultaneously, the pH=11 of mixed solution is adjusted；
Step 3, it is aged：
By precursors, in the static ageing 7h of normal temperature, section top clear liquid is removed, the thick ageing liquid of lower floor is obtained；
Step 4, crystallization：
(1) by the thick ageing liquid of lower floor, concussion shakes up, and moves into the hydro-thermal reaction under high pressure with polytetrafluoroethyllining lining
Kettle；
(2) by hydro-thermal autoclave, in 190 DEG C of cabinet-type electric furnace, crystallization 9h obtains crystallization liquid；
Step 5, suction filtration：
Crystallization liquid is cooled to room temperature, then with distilled water and absolute ethyl alcohol respectively washing 4 times, makes solution to neutrality, vacuum is taken out
Filter, obtains filter cake；
Step 6, drying grinding：
(1) filter cake is dried in 80 DEG C of drying baker, obtains dark brown block；
(2) dark brown block is ground to powder, that is, obtains the Ni-Zn ferrite nano materials of cation doping.
Ni manufactured in the present embodiment0.5Zn0.3Co0.2Fe2O4The Ni-Zn ferrite nano materials of cation doping, scanning electron microscopic picture
See accompanying drawing 6, its average grain diameter is 20-30nm, the nickel zinc Conjugate ferrite is 3.1, imaginary part in the magnetic conductivity real part of 3GHz Frequency points
For 2.9；Real part of permittivity is 6.9, and imaginary part is 0.15.
Embodiment 6
A kind of preparation method of the Ni-Zn ferrite nano materials of cation doping, comprises the following steps：
Step 1, dispensing：
(1) Ni is pressed0.6Zn0.35Co0.05Fe2O4Stoichiometric proportion, weighs 4 kinds of raw materials respectively：4.36g analyzes pure nickel nitrate
(Ni(NO3)2·6H2O), 2.60g analyzes pure zinc nitrate (Zn (NO3)2·6H2O), 0.36g analyzes pure cobalt nitrate (Co (NO3)2·
6H2) and 20.20g analyzes pure ferric nitrate (Fe (NO O3)3·9H2O)；
(2) by above-mentioned 4 kinds of raw materials, it is dissolved in 150mL distilled water, adds 2g polyethylene glycol, it is ultrasonically treated to disperse it
Uniformly, mixed solution russet is obtained；
Step 2：Reaction of formation presoma；
Mixed solution russet is placed in four-hole boiling flask, in 40 DEG C of water bath with thermostatic control, continued with 270r/min rotating speeds
Even stirring；1mol/L sodium hydroxide solution is added dropwise into four-hole boiling flask simultaneously, the pH=10 of mixed solution is adjusted；
Step 3, it is aged：
By precursors, in the static ageing 9h of normal temperature, section top clear liquid is removed, the thick ageing liquid of lower floor is obtained；
Step 4, crystallization：
(1) by the thick ageing liquid of lower floor, concussion shakes up, and moves into the hydro-thermal reaction under high pressure with polytetrafluoroethyllining lining
Kettle；
(2) by hydro-thermal autoclave, in 180 DEG C of cabinet-type electric furnace, crystallization 7h obtains crystallization liquid；
Step 5, suction filtration：
Crystallization liquid is cooled to room temperature, then with distilled water and absolute ethyl alcohol respectively washing 4 times, makes solution to neutrality, vacuum is taken out
Filter, obtains filter cake；
Step 6, drying grinding：
(1) filter cake is dried in 70 DEG C of drying baker, obtains dark brown block；
(2) dark brown block is ground to powder, that is, obtains the Ni-Zn ferrite nano materials of cation doping.
Ni manufactured in the present embodiment0.6Zn0.35Co0.05Fe2O4The Ni-Zn ferrite nano materials of cation doping, scanning electron microscope (SEM) photograph
Piece is shown in accompanying drawing 7, and its average grain diameter is 20-30nm, and the nickel zinc Conjugate ferrite is 2.9 in the magnetic conductivity real part of 3GHz Frequency points, empty
Portion is 2.6；Real part of permittivity is 6.9, and imaginary part is 0.14.
Embodiment 7
A kind of preparation method of the Ni-Zn ferrite nano materials of cation doping, comprises the following steps：
Step 1, dispensing：
(1) Ni is pressed0.5Zn0.25Co0.25Fe2O4Stoichiometric proportion, weighs 4 kinds of raw materials respectively：3.64g analyzes pure nickel nitrate
(Ni(NO3)2·6H2O), 1.86g analyzes pure zinc nitrate (Zn (NO3)2·6H2O), 1.82g analyzes pure cobalt nitrate (Co (NO3)2·
6H2) and 20.20g analyzes pure ferric nitrate (Fe (NO O3)3·9H2O)；
(2) by above-mentioned 4 kinds of raw materials, it is dissolved in 150mL distilled water, adds 2g polyethylene glycol, it is ultrasonically treated to disperse it
Uniformly, mixed solution russet is obtained；
Step 2：Reaction of formation presoma；
Mixed solution russet is placed in four-hole boiling flask, in 45 DEG C of water bath with thermostatic control, continued with 210r/min rotating speeds
Even stirring；2mol/L sodium hydroxide solution is added dropwise into four-hole boiling flask simultaneously, the pH=9 of mixed solution is adjusted；
Step 3, it is aged：
By precursors, in the static ageing 7h of normal temperature, section top clear liquid is removed, the thick ageing liquid of lower floor is obtained；
Step 4, crystallization：
(1) by the thick ageing liquid of lower floor, concussion shakes up, and moves into the hydro-thermal reaction under high pressure with polytetrafluoroethyllining lining
Kettle；
(2) by hydro-thermal autoclave, in 210 DEG C of cabinet-type electric furnace, crystallization 12h obtains crystallization liquid；
Step 5, suction filtration：
Crystallization liquid is cooled to room temperature, then with distilled water and absolute ethyl alcohol respectively washing 4 times, makes solution to neutrality, vacuum is taken out
Filter, obtains filter cake；
Step 6, drying grinding：
(1) filter cake is dried in 60 DEG C of drying baker, obtains dark brown block；
(2) dark brown block is ground to powder, that is, obtains the Ni-Zn ferrite nano materials of cation doping.
Ni manufactured in the present embodiment0.5Zn0.25Co0.25Fe2O4The Ni-Zn ferrite nano materials of cation doping, scanning electron microscope (SEM) photograph
Piece is shown in accompanying drawing 8, and its average grain diameter is 20-30nm, and the nickel zinc Conjugate ferrite is 3.3 in the magnetic conductivity real part of 3GHz Frequency points, empty
Portion is 3.0；Real part of permittivity is 7.3, and imaginary part is 0.17.
Embodiment 8
A kind of preparation method of the Ni-Zn ferrite nano materials of cation doping, comprises the following steps：
Step 1, dispensing：
(1) Ni is pressed0.6Zn0.2Co0.2Fe2O4Stoichiometric proportion, weighs 4 kinds of raw materials respectively：4.36g analyzes pure nickel nitrate (Ni
(NO3)2·6H2O), 1.49g analyzes pure zinc nitrate (Zn (NO3)2·6H2O), 1.46g analyzes pure cobalt nitrate (Co (NO3)2·
6H2) and 20.20g analyzes pure ferric nitrate (Fe (NO O3)3·9H2O)；
(2) by above-mentioned 4 kinds of raw materials, it is dissolved in 150mL distilled water, adds 2g polyethylene glycol, it is ultrasonically treated to disperse it
Uniformly, mixed solution russet is obtained；
Step 2：Reaction of formation presoma；
Mixed solution russet is placed in four-hole boiling flask, in 40 DEG C of water bath with thermostatic control, continued with 150r/min rotating speeds
Even stirring；3mol/L sodium hydroxide solution is added dropwise into four-hole boiling flask simultaneously, the pH=12 of mixed solution is adjusted；
Step 3, it is aged：
By precursors, in the static ageing 6h of normal temperature, section top clear liquid is removed, the thick ageing liquid of lower floor is obtained；
Step 4, crystallization：
(1) by the thick ageing liquid of lower floor, concussion shakes up, and moves into the hydro-thermal reaction under high pressure with polytetrafluoroethyllining lining
Kettle；
(2) by hydro-thermal autoclave, in 170 DEG C of cabinet-type electric furnace, crystallization 11h obtains crystallization liquid；
Step 5, suction filtration：
Crystallization liquid is cooled to room temperature, then with distilled water and absolute ethyl alcohol respectively washing 4 times, makes solution to neutrality, vacuum is taken out
Filter, obtains filter cake；
Step 6, drying grinding：
(1) filter cake is dried in 80 DEG C of drying baker, obtains dark brown block；
(2) dark brown block is ground to powder, that is, obtains the Ni-Zn ferrite nano materials of cation doping.
Ni manufactured in the present embodiment0.6Zn0.2Co0.2Fe2O4The Ni-Zn ferrite nano materials of cation doping, scanning electron microscopic picture
See accompanying drawing 9, its average grain diameter is 20-30nm, the nickel zinc Conjugate ferrite is 3.2, imaginary part in the magnetic conductivity real part of 3GHz Frequency points
For 2.9；Real part of permittivity is 7.2, and imaginary part is 0.16.
Claims (4)
1. a kind of preparation method of the Ni-Zn ferrite nano materials of cation doping, it is characterised in that comprise the following steps:
Step 1, dispensing:
(1) Ni is pressedxZnyCo(1-x-y)Fe2O4Stoichiometric proportion, weighs 4 kinds of raw materials respectively:Nickel nitrate, zinc nitrate, cobalt nitrate and nitre
Sour iron, wherein, 0.75≤x+y≤0.95,0.4≤x≤0.6,0.15≤y≤0.4；Described nickel nitrate, zinc nitrate, cobalt nitrate
It is that analysis is pure with ferric nitrate；
(2) by above-mentioned 4 kinds of raw materials, it is dissolved in distilled water, adds surfactant, after being uniformly dispersed, obtains russet mixed
Close solution, wherein, in mass ratio, 4 kinds of material qualities and:Distilled water=(25~28):(150~200), 4 kinds of material qualities and:
Surfactant=(25~28):(1~3)；Described surfactant is polyethylene glycol；Described being uniformly dispersed is using super
Sonication makes it be uniformly dispersed；
Step 2, reaction of formation presoma：
Mixed solution russet is placed in four-hole boiling flask, in 30~50 DEG C of water bath with thermostatic control, held with 150~270r/min rotating speeds
Continuous uniform stirring；1~3mol/L sodium hydroxide solution is added dropwise into four-hole boiling flask simultaneously, the speed of sodium hydroxide solution is added dropwise
For 0.5~1 drop/sec, pH=9~12 of mixed solution are adjusted；
Step 3, it is aged：
By precursors, in normal temperature 6~10h of static ageing, section top clear liquid is removed, the thick ageing liquid of lower floor is obtained；
Step 4, crystallization：
(1) by the thick ageing liquid of lower floor, concussion shakes up, and moves into the hydro-thermal autoclave with polytetrafluoroethyllining lining；
(2) by hydro-thermal autoclave, at 160~220 DEG C, 6~12h of crystallization obtains crystallization liquid；
Step 5, suction filtration:Crystallization liquid is cooled to room temperature, obtained solution is washed to neutrality, vacuum filtration, obtains filter cake；
Step 6, drying grinding：
(1) filter cake is obtained into dark brown block in 60~80 DEG C of drying；
(2) dark brown block is ground to powder, that is, obtains the Ni-Zn ferrite nano materials of cation doping.
2. the preparation method of the Ni-Zn ferrite nano materials of cation doping according to claim 1, it is characterised in that described
In step 4 (2), crystallization is carried out in cabinet-type electric furnace.
3. the preparation method of the Ni-Zn ferrite nano materials of cation doping according to claim 1, it is characterised in that described
Step 5 in, washed using distilled water and absolute ethyl alcohol.
4. the preparation method of the Ni-Zn ferrite nano materials of cation doping according to claim 1, it is characterised in that described
Step 6 (1) in, dried using air dry oven.
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