CN103755336A - Preparation method of nanometer ferrite particles - Google Patents
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- CN103755336A CN103755336A CN201410058226.7A CN201410058226A CN103755336A CN 103755336 A CN103755336 A CN 103755336A CN 201410058226 A CN201410058226 A CN 201410058226A CN 103755336 A CN103755336 A CN 103755336A
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Abstract
The invention discloses a preparation method of nanometer ferrite particles. On the basis of the existing sol-gel technique, the method adopts an organic template to absorb sol to overcome the defects that segregation of microelements is easily generated during the drying process of common sol, so that the impurity phase is produced in the final product. The cracking and carbonizing of phenolic resin which is wrapped on the non-shaped ferrite particle surface and the crystal form conversion of the ferrite are simultaneously carried out, so the agglomeration and growth of the ferrite particles in the calcination process are prevented, and the nanometer ferrite particles with uniform particle size, large specific area and good magnetic performance can be obtained. The method has the advantages that the defects of multiple impurity phases, difficult control of particle size, poor magnetic performance and smaller specific area of the solid phase method are overcome, and the defects of easy agglomeration, nonuniform particle size and the like of the chemical precipitation method are also overcome.
Description
Technical field
The invention belongs to technical field of inorganic nonmetallic materials, be specifically related to a kind of preparation method of Nano-Ferrite Particle.
Background technology
Nano material refers to that characteristic dimension, at the material of the nano sized particles composition of nano level (being often referred to 1-100nm), has small-size effect, surface effects, quantum size effect and macro quanta tunnel effect etc.Ferrite is the widely used nonmetal magnetic material of a class.Nano-Ferrite Particle not only has specific physical and the chemical property that nano material is given, also there is special magnetic property, can make the material of the variforms such as nanometer magnetic film, nanometer magnet-wire, nano-magnetic powder and magnetic fluid, at traditional industries and high-technology field, have a wide range of applications as high voltage power transmission and transforming, communication, biomedicine, national defence etc.The purity of Nano-Ferrite Particle, specific surface area and magnetic property be its be widely used in magnetic recording media, magnetic fluid, absorbing material and in medical applications as the key of magnetic target pharmaceutical carrier, cellular segregation and magnetic control contrast medium etc.
The preparation method of nanometer ferrite powder has directly determined the performance of nanometer ferrite.The preparation method of nanometer ferrite is a lot of at present, mainly contains: coagulate-glue method of solid phase method, chemical coprecipitation, hydrothermal synthesis method and colloidal sol etc.Wherein, solid phase method output is high, and technique is simple, is the main method of suitability for industrialized production ferrite particle, but exist particle size large and uneven, easily produce the shortcomings such as impurity, particle magnetic property and specific surface area are lower.Chemical coprecipitation, due to advantages such as its technique are simple, not high to equipment, technical requirements, and products therefrom purity is higher, particle size is less, is widely used in recent years and prepares Nano-Ferrite Particle.But the standby magnetic-particle size distribution of this legal system is wider, to reunite serious, magnetic property is lower.Hydrothermal synthesis method gained Nano-Ferrite Particle have better crystallinity degree, particle diameter little, reunite low, without advantages such as pyroprocessing, but high to equipment requirements, the higher and more difficult batch production of cost.The prepared Nano-Ferrite Particle purity of sol-gel method is higher, and chemical constitution is evenly accurate.But dispersed for improving, usually add tensio-active agent, adopt the methods such as supercritical drying.Thereby exist cost higher, the shortcomings such as operational difficulty.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, and a kind of preparation method of Nano-Ferrite Particle is provided.
In order to achieve the above object, technical scheme provided by the invention is:
The preparation method of described Nano-Ferrite Particle comprises the steps:
(1) hybrid metal nitrate is dissolved in dehydrated alcohol, is mixed with hybrid metal nitrate-ethanolic soln; Citric acid is dissolved in dehydrated alcohol, is mixed with citric acid-ethanolic soln; Hybrid metal nitrate-ethanolic soln is mixed by the volume ratio of 1:1 with citric acid-ethanolic soln, make hybrid metal nitrate-citric acid ethanolic soln; Wherein, described hybrid metal nitrate is Fe (NO
3)
39H
2the mixture that the O transition metal nitrate different from one or both mixes according to the molar ratio that forms spinel type ferrite, the consisting of of described spinel type ferrite: M
xn
1-xfe
2o
4, M and N represent the transition-metal cation that different metal nitrates provides, 0≤x≤1; The add-on that described hybrid metal nitrate is dissolved in hybrid metal in dehydrated alcohol is: every 10g hybrid metal nitrate is dissolved in 50-300mL dehydrated alcohol; The add-on that described citric acid is dissolved in citric acid in dehydrated alcohol is: every 10g citric acid is dissolved in 50-300mL dehydrated alcohol;
(2) with ammoniacal liquor, regulating the pH value of hybrid metal nitrate-citric acid ethanolic soln is 0.5-6, is preferably 1-4, and concentrated this solution obtains the colloidal sol that viscosity is 0.005-0.03Pas;
(3) in colloidal sol, add absorbent cotton, after absorbent cotton adsorbs colloidal sol completely, absorbent cotton is dried, obtain xerogel-absorbent cotton;
(4) by xerogel-absorbent cotton in oxidizing atmosphere, temperature≤600 ℃, are preferably under ℃ condition of temperature≤500 and are incubated 0.5-6h, are preferably 2-4h, obtain amorphous ferrite powder;
(5) amorphous ferrite powder is ground to rear 600-900 mesh sieves of crossing, obtain the amorphous ferrite powder after grinding; Amorphous ferrite powder after grinding is added in dehydrated alcohol, after ultrasonic dispersion (general supersound process 1-3h), make ferrite particle-alcohol suspension; In ferrite particle-alcohol suspension, add resol, under 40-80 ℃ of conditions, stir, after ethanol evaporation and phenolic resin curing, obtain the coated amorphous Nano-Ferrite Particle of resol; Wherein, the amorphous ferrite powder after described grinding adds the add-on of amorphous ferrite powder in dehydrated alcohol to be: the amorphous ferrite powder after every 1g grinds adds 30-350mL, is preferably in 50-300mL dehydrated alcohol; Described resol adds the add-on of resol in ferrite particle-alcohol suspension to be: in every 100mL ferrite particle-alcohol suspension, add 5-140mL, be preferably 10-120mL resol;
(6) by the coated amorphous Nano-Ferrite Particle charing in inert atmosphere of resol, carbonization temperature is 500-1100 ℃, is preferably 600-1000 ℃, and carbonization time is 0.5-6h, be preferably 1-4h, obtain the coated nanometer spinel type ferrite particle of charcoal;
(7) the coated nanometer spinel type ferrite particle of charcoal is ground to rear 600-900 mesh sieves of crossing, obtain the Nano-Ferrite Particle after grinding; Nano-Ferrite Particle after grinding is carried out, after carbon removal processing, obtaining Nano-Ferrite Particle in acid.
In addition, the described transition metal of step (1) is copper, nickel, cobalt or zinc etc.
The described ammonia concn of step (2) is 1-12mol/L, is preferably 2-10mol/L.
The add-on of the described absorbent cotton of step (3) is: in every 100mL colloidal sol, add 1-10g, be preferably 2-8g absorbent cotton; After absorbent cotton adsorbs colloidal sol completely, absorbent cotton is dried under 60-100 ℃ of conditions.
The described oxidizing atmosphere of step (4) refers to air atmosphere.
The described inert atmosphere of step (6) is nitrogen atmosphere or argon atmospher.
The described acid of step (7) is that concentration of volume percent is 40-100%, preferred 60-100% perchloric acid, and the temperature that carbon removal is processed is 40-100 ℃, preferably 50-90 ℃.
The present invention, on the basis of existing sol-gel technique, prepares high purity, high-specific surface area and high magnetic characteristics Nano-Ferrite Particle by the coated recombining process of adsorb-charcoal of organic formwork.Organic formwork absorption has overcome the microcomponent segregation being prone in conventional colloidal sol drying process, occurs the shortcoming of a small amount of impurity phase in the finished product; The Phenolic resin pyrolysis Carbonization that is coated on amorphous iron oxysome particle surface is carried out with synchronizeing of ferrite crystal conversion, stoped the reunion of ferrite particle in calcination process to be grown up, be conducive to obtain particle diameter even, specific surface area is high, the Nano-Ferrite Particle of magnetic property excellence.
Preparation method of the present invention has overcome that the impurity phase that solid phase method is prone to is more, particle diameter is controlled difficulty, and the deficiency that magnetic property and specific surface area are less has also overcome the shortcomings such as the particle that chemical precipitation method exists is easily reunited, and granularity is inhomogeneous.The advantages such as the prepared nano magnetic particle of present method has that purity is high, particle diameter is even, the large and magnetic property excellence of specific surface area, and raw material sources enrich, and cheap, technique is simple, low for equipment requirements, is easy to mass production.The Nano-Ferrite Particle that adopts present method to prepare is expected to obtain in high-end fields such as high-density magnetic storage, photomagnetism, magnetic fluid, magnetic electric compound material, catalyzer application widely.
Accompanying drawing explanation
Fig. 1 is the TEM figure of gained Nano-Ferrite Particle in embodiment 1;
Fig. 2 is the magnetic hysteresis loop of gained Nano-Ferrite Particle in embodiment 1; Wherein, X-coordinate is magneticstrength H, and ordinate zou is magnetic induction density B.
Embodiment
Embodiment 1
Described Nano-Ferrite Particle CoFe
2o
4preparation method comprise the steps:
(1) by 30.9947g Fe (NO
3)
39H
2o and 11.1638g Co (NO
3)
26H
2o is dissolved in 300ml dehydrated alcohol, prepares hybrid metal nitrate-ethanolic soln; 24.1828g citric acid is dissolved in to 300ml ethanol, prepares citric acid-ethanolic soln.Under vigorous stirring, citric acid-ethanolic soln is under agitation added in hybrid metal nitrate-ethanolic soln, continue to stir 4h, prepare the ethanolic soln of hybrid metal nitrate-citric acid;
(2) under agitation, use the NH of 8mol/L
3h
2the pH value to 3.5 of O regulating step (1) gained solution, then concentrated this solution forms the colloidal sol with certain viscosity, should be positioned at 0.025Pas left and right under the viscosity room temperature of gained colloidal sol;
(3) in step (2) gained colloidal sol, add about 20g absorbent cotton to adsorb this colloidal sol, wait absorbent cotton completely by after colloidal sol absorption, move into interior 80 ℃ of baking oven and dry to constant weight, obtain xerogel-absorbent cotton;
(4) step (3) gained xerogel-absorbent cotton is put into box-type furnace, at 400 ℃, in air atmosphere, be incubated to absorbent cotton and burn (sample constant weight) completely, obtain amorphous CoFe
2o
4powder;
(5) by the amorphous CoFe of step (4) gained
2o
4powder porphyrize, crosses 800 mesh sieves.Amorphous CoFe after getting 3g and sieving
2o
4particle, adds 300ml dehydrated alcohol, and ultrasonic dispersion 2h, makes amorphous CoFe
2o
4uniform particles is dispersed in dehydrated alcohol, prepares ferrite particle-alcohol suspension.Get the resol of about 90ml, add in aforementioned suspension, ultrasonic dispersion 2h, is dispersed in the ethanolic soln of resol ferrite powder.Then 60 ℃ of mechanical stirring, make ethanol evaporation and make phenolic resin curing, obtain the coated amorphous nano Co Fe of resol
2o
4particle;
(6) by the coated amorphous nano Co Fe of step (5) gained resol
2o
4particle is placed in tube-type atmosphere furnace, under rare gas element (nitrogen or argon gas) protection, is incubated 2h charing at 800 ℃, obtains the coated nanometer spinel type CoFe of charcoal
2o
4particle;
(7) by the coated nanometer spinel type CoFe of step (6) gained charcoal
2o
4particle porphyrize is crossed 800 mesh sieves, and gained particle, at 80 ℃, is carried out to carbon removal processing in the perchloric acid solution that volume percent is 80%, can obtain high purity, high-specific surface area, high magnetic characteristics nano Co Fe
2o
4particle.
Gained nano Co Fe
2o
4xRD test result inclusion-free phase, particle diameter is 30 ± 10nm, specific surface area is 68.5m
2/ g; Saturation magnetization is 86.8emu/g, and residual magnetization is 41.1emu/g, and coercive force is 1176G, and squareness ratio is 0.47.Gained nano Co Fe
2o
4the TEM figure of particle is shown in Fig. 1, and magnetic hysteresis loop is shown in Fig. 2.
Embodiment 2
Described Nano-Ferrite Particle Ni
0.5zn
0.5fe
2o
4preparation method comprise the steps:
(1) by 10.1964g Fe (NO
3)
39H
2o, 1.8349g Ni (NO
3)
26H
2o and 1.8771g Zn (NO
3)
26H
2o is dissolved in 200ml dehydrated alcohol, prepares hybrid metal nitrate-ethanolic soln; 7.9555g citric acid is dissolved in to 200ml ethanol, prepares citric acid-ethanolic soln; Under vigorous stirring, citric acid-ethanolic soln is added in hybrid metal nitrate-ethanolic soln, continue to stir 4h, form the ethanolic soln of hybrid metal nitrate-citric acid;
(2) under agitation, use the NH of 6mol/L
3h
2the pH value to 3.5 of O regulating step (1) gained solution, then concentrated this solution forms the colloidal sol that viscosity is 0.015Pas;
(3) in step (2) gained colloidal sol, add about 15g absorbent cotton to adsorb this colloidal sol, wait absorbent cotton completely by after colloidal sol absorption, move into interior 80 ℃ of baking oven and dry to constant weight, obtain xerogel-absorbent cotton;
(4) step (3) gained xerogel-absorbent cotton sample is put into box-type furnace, at 400 ℃, in air atmosphere, be incubated to absorbent cotton and burn (sample constant weight) completely, obtain amorphous Ni
0.5zn
0.5fe
2o
4powder;
(5) by the amorphous Ni of step (4) gained
0.5zn
0.5fe
2o
4powder porphyrize, crosses 800 mesh sieves.Ni after getting 2g and sieving
0.5zn
0.5fe
2o
4particle, adds the dehydrated alcohol of 200ml to dilute, and ultrasonic dispersion 2h, is dispersed in ethanolic soln ferrite particle, prepares ferrite particle-alcohol suspension.Get the resol of about 60ml, add in aforementioned suspension, ultrasonic dispersion 2h, is dispersed in resol ethanolic soln ferrite powder.Then 60 ℃ of stirrings, make ethanol evaporation and make phenolic resin curing, obtain the coated amorphous nanometer Ni of resol
0.5zn
0.5fe
2o
4particle;
(6) by the coated amorphous nanometer Ni of step (5) gained resol
0.5zn
0.5fe
2o
4particle product is placed in tube-type atmosphere furnace, under rare gas element (nitrogen or argon gas) protection, is incubated 2h charing at 900 ℃, obtains the coated nanometer spinel type Ni of charcoal
0.5zn
0.5fe
2o
4particle;
(7) by the coated nanometer spinel type Ni of step (6) gained charcoal
0.5zn
0.5fe
2o
4particle porphyrize is crossed 800 mesh sieves, and gained particle, at 70 ℃, is carried out to carbon removal processing in the perchloric acid solution that volume percent is 70%, can obtain high purity, high-specific surface area, high magnetic characteristics nanometer Ni
0.5zn
0.5fe
2o
4particle.
Gained nanometer Ni
0.5zn
0.5fe
2o
4xRD test result inclusion-free phase, particle diameter is 50 ± 10nm, specific surface area can reach 95.8m
2/ g; Saturation magnetization is 66.8emu/g, residual magnetization 4.85emu/g, and coercive force is 56G, squareness ratio is 0.07.
Embodiment 3
Described Nano-Ferrite Particle NiFe
2o
4preparation method comprise the steps:
(1) by 31.0265g Fe (NO
3)
39H
2o and 11.1665g Ni (NO
3)
36H
2o is dissolved in 600ml dehydrated alcohol, prepares hybrid metal nitrate-ethanolic soln; 24.2076g citric acid is dissolved in 600ml dehydrated alcohol, prepares citric acid ethanol-solution; Under vigorous stirring, citric acid-ethanolic soln is added in hybrid metal nitrate-ethanolic soln, continue to stir 3h, obtain the ethanolic soln of hybrid metal nitrate-citric acid;
(2) under agitation, use the NH of 6mol/L
3h
2the pH value to 3.5 of O regulating step (1) gained solution, then concentrated this solution forms the colloidal sol that viscosity is 0.03Pas;
(3) in step (2) gained colloidal sol, add about 12g absorbent cotton to adsorb this colloidal sol, wait absorbent cotton completely by after colloidal sol absorption, move into interior 80 ℃ of baking oven and dry to constant weight, obtain xerogel-absorbent cotton;
(4) step (3) gained xerogel-absorbent cotton sample is put into box-type furnace, at 500 ℃, in air atmosphere, be incubated to absorbent cotton and burn (sample constant weight) completely, obtain amorphous NiFe
2o
4powder;
(5) by the amorphous NiFe of step (4) gained
2o
4powder porphyrize, crosses 900 mesh sieves.NiFe after getting 4g and sieving
2o
4particle, adds the dehydrated alcohol of 400ml, and ultrasonic dispersion 2h, is dispersed in dehydrated alcohol ferrite particle, prepares ferrite particle-alcohol suspension.Get the resol of about 150ml, add in aforementioned suspension, ultrasonic dispersion 2h, is dispersed in resol ethanolic soln ferrite powder.Then 60 ℃ of mechanical stirring, make ethanol evaporation and make phenolic resin curing, obtain the coated amorphous nano-Ni/Fe of resol
2o
4particle;
(6) by the coated amorphous nano-Ni/Fe of step (5) gained resol
2o
4particle product is placed in tube-type atmosphere furnace, under rare gas element (nitrogen or argon gas) protection, is incubated 2h charing at 900 ℃, obtains the coated nanometer spinel type rice NiFe of charcoal
2o
4particle;
(7) by the coated nanometer spinel type NiFe of step (6) gained charcoal
2o
4particle porphyrize is crossed 800 mesh sieves, and gained particle, at 90 ℃, is carried out to carbon removal processing in the perchloric acid solution that volume percent is 90%, can obtain high purity, high-specific surface area, high magnetic characteristics nano-Ni/Fe
2o
4particle.
Gained nano-Ni/Fe
2o
4xRD test result inclusion-free phase, particle diameter is 40 ± 5nm, specific surface area can reach 85.3m
2/ g; Saturation magnetization is 75.3emu/g, residual magnetization 7.85emu/g, and coercive force is 50G, squareness ratio is 0.10.
Claims (7)
1. a preparation method for Nano-Ferrite Particle, is characterized in that, described method comprises the steps:
(1) hybrid metal nitrate is dissolved in dehydrated alcohol, is mixed with hybrid metal nitrate-ethanolic soln; Citric acid is dissolved in dehydrated alcohol, is mixed with citric acid-ethanolic soln; Hybrid metal nitrate-ethanolic soln is mixed by the volume ratio of 1:1 with citric acid-ethanolic soln, make hybrid metal nitrate-citric acid ethanolic soln; Wherein, described hybrid metal nitrate is Fe (NO
3)
39H
2the mixture that the O transition metal nitrate different from one or both mixes according to the molar ratio that forms spinel type ferrite, the consisting of of described spinel type ferrite: M
xn
1-xfe
2o
4, M and N represent the transition-metal cation that different transition metal nitrates provide, 0≤x≤1; The add-on that described hybrid metal nitrate is dissolved in hybrid metal in dehydrated alcohol is: every 10g hybrid metal nitrate is dissolved in 50-300mL dehydrated alcohol; The add-on that described citric acid is dissolved in citric acid in dehydrated alcohol is: every 10g citric acid is dissolved in 50-300mL dehydrated alcohol;
(2) with ammoniacal liquor, regulating the pH value of hybrid metal nitrate-citric acid ethanolic soln is 0.5-6, and concentrated this solution obtains the colloidal sol that viscosity is 0.005-0.03Pas;
(3) in colloidal sol, add absorbent cotton, after absorbent cotton adsorbs colloidal sol completely, absorbent cotton is dried, obtain xerogel-absorbent cotton;
(4) by xerogel-absorbent cotton in oxidizing atmosphere, under ℃ condition of temperature≤600, be incubated 0.5-6h, obtain amorphous ferrite powder;
(5) amorphous ferrite powder is ground to rear 600-900 mesh sieves of crossing, obtain the amorphous ferrite powder after grinding; Amorphous ferrite powder after grinding is added in dehydrated alcohol, after ultrasonic dispersion, make ferrite particle-alcohol suspension; In ferrite particle-alcohol suspension, add resol, under 40-80 ℃ of conditions, stir, after ethanol evaporation and phenolic resin curing, obtain the coated amorphous Nano-Ferrite Particle of resol; Wherein, the amorphous ferrite powder after described grinding adds the add-on of amorphous ferrite powder in dehydrated alcohol to be: the amorphous ferrite powder after every 1g grinds adds in 30-350mL dehydrated alcohol; Described resol adds the add-on of resol in ferrite particle-alcohol suspension to be: in every 100mL ferrite particle-alcohol suspension, add 5-140mL resol;
(6) by the coated amorphous Nano-Ferrite Particle charing in inert atmosphere of resol, carbonization temperature is 500-1100 ℃, and carbonization time is 0.5-6h, obtains the coated nanometer spinel type ferrite particle of charcoal;
(7) the coated nanometer spinel type ferrite particle of charcoal is ground to rear 600-900 mesh sieves of crossing, obtain the Nano-Ferrite Particle after grinding; Nano-Ferrite Particle after grinding is carried out, after carbon removal processing, obtaining Nano-Ferrite Particle in acid.
2. the method for claim 1, is characterized in that, the described transition metal of step (1) is copper, nickel, cobalt or zinc.
3. the method for claim 1, is characterized in that, the described ammonia concn of step (2) is 1-12mol/L.
4. the method for claim 1, is characterized in that, the add-on of the described absorbent cotton of step (3) is: in every 100mL colloidal sol, add 1-10g absorbent cotton; After absorbent cotton adsorbs colloidal sol completely, absorbent cotton is dried under 60-100 ℃ of conditions.
5. the method for claim 1, is characterized in that, the described oxidizing atmosphere of step (4) refers to air atmosphere.
6. the method for claim 1, is characterized in that, the described inert atmosphere of step (6) is nitrogen atmosphere or argon atmospher.
7. the method for claim 1, is characterized in that, the described acid of step (7) is that concentration of volume percent is 40-100% perchloric acid, and the temperature that carbon removal is processed is 40-100 ℃.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016414A (en) * | 2014-06-23 | 2014-09-03 | 湖南大学 | Preparation method of ferrite nanowire |
| CN104496454A (en) * | 2015-01-19 | 2015-04-08 | 陈吉美 | Preparation method of nanometer ferrite particle |
| CN105753057A (en) * | 2016-01-21 | 2016-07-13 | 中国计量学院 | Soft magnetic nickel and zinc ferrite nanometer powder and method for preparing same |
| CN106145919A (en) * | 2016-07-05 | 2016-11-23 | 陕西科技大学 | A kind of preparation method of three-dimensional netted ferrite microwave absorbing material |
| CN108101114A (en) * | 2017-12-21 | 2018-06-01 | 湖南大学 | A kind of nanometer ferrite composite material of bivalve layer structure and preparation method thereof |
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| CN114014642A (en) * | 2021-10-09 | 2022-02-08 | 国家能源集团科学技术研究院有限公司 | Manganese-cobalt ferrite nano material and preparation method and application thereof |
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| CN104016414A (en) * | 2014-06-23 | 2014-09-03 | 湖南大学 | Preparation method of ferrite nanowire |
| CN104016414B (en) * | 2014-06-23 | 2015-11-18 | 湖南大学 | A kind of preparation method of ferrite nano line |
| CN104496454A (en) * | 2015-01-19 | 2015-04-08 | 陈吉美 | Preparation method of nanometer ferrite particle |
| CN104496454B (en) * | 2015-01-19 | 2016-02-03 | 陈吉美 | A kind of preparation method of Nano-Ferrite Particle |
| CN105753057A (en) * | 2016-01-21 | 2016-07-13 | 中国计量学院 | Soft magnetic nickel and zinc ferrite nanometer powder and method for preparing same |
| CN106145919A (en) * | 2016-07-05 | 2016-11-23 | 陕西科技大学 | A kind of preparation method of three-dimensional netted ferrite microwave absorbing material |
| CN108101114A (en) * | 2017-12-21 | 2018-06-01 | 湖南大学 | A kind of nanometer ferrite composite material of bivalve layer structure and preparation method thereof |
| CN108417821A (en) * | 2018-03-07 | 2018-08-17 | 浙江大学 | A kind of aluminium ion-seawater/aluminium composite battery and its application method |
| CN108417821B (en) * | 2018-03-07 | 2020-04-24 | 浙江大学 | Aluminum ion-seawater/aluminum composite battery and use method thereof |
| CN108617154A (en) * | 2018-04-16 | 2018-10-02 | 晋中学院 | A kind of porous carbon load nano nickel absorbing material and preparation method thereof |
| CN108617154B (en) * | 2018-04-16 | 2019-10-15 | 晋中学院 | A kind of porous carbon load nano nickel absorbing material and preparation method thereof |
| CN109295490A (en) * | 2018-11-26 | 2019-02-01 | 镇江市高等专科学校 | A kind of Ni ferrite electrophoresis suspensioning liquid and its preparation method and application |
| CN114014642A (en) * | 2021-10-09 | 2022-02-08 | 国家能源集团科学技术研究院有限公司 | Manganese-cobalt ferrite nano material and preparation method and application thereof |
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