CN103253713A - Method for preparing regular octahedral Fe3O4 particles - Google Patents

Method for preparing regular octahedral Fe3O4 particles Download PDF

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CN103253713A
CN103253713A CN2013101757584A CN201310175758A CN103253713A CN 103253713 A CN103253713 A CN 103253713A CN 2013101757584 A CN2013101757584 A CN 2013101757584A CN 201310175758 A CN201310175758 A CN 201310175758A CN 103253713 A CN103253713 A CN 103253713A
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贾识
宋廷廷
赵炳戈
高玉来
翟启杰
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University of Shanghai for Science and Technology
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Abstract

The invention provides a method for preparing regular octahedral Fe3O4 particles by using a dealloying method. The method is characterized by comprising the following steps: preparing an Al-Fe alloy thin belt by using an electric arc melting and high-vacuum single-roller rotary quenching device; then, placing a certain amount of the Al-Fe alloy thin belt into a NaOH solution (5 mol/L), heating a container from room temperature, and recording the reaction starting time; after the solution is heated to 90-100 DEG C, carrying out heat preservation on the solution; after the solution has no obviously visible bubbles, taking samples out of the solution, pouring out the solution, and simultaneously, recording the time; cleaning the samples subjected to the steps 3-5 times by using deionized water and anhydrous alcohol, placing the samples in an alcohol solution to carry out ultrasonic cleaning a period of time, and drying the samples in a drying oven to finally obtain Fe3O4 powder with a regular octahedral structure. Octahedron Fe3O4 obtained according to the invention is relatively high in saturation magnetization, residual magnetization and coercivity, and has a good engineering application prospect in the fields of magnetofluid, information storage and the like.

Description

The regular octahedra Fe of a kind of preparation 3O 4The method of particle
Technical field
The present invention relates to a kind of regular octahedral structure Fe 3O 4The preparation method, belong to Metallic Functional Materials, magneticsubstance preparation technology field.
Background technology
Z 250 (Fe 3O 4) as a kind of important spinels ferrite, it is one of soft magnetic material that is most widely used, be commonly used for magnetic fluid material, catalyzer etc., it also has good application prospects at biological technical field and medical field, therefore is subjected to researchist's extensive attention all the time.The submicron-scale and the nano-scale Fe that successfully prepare at present multiple pattern 3O 4, as octahedron, cubes, sphere and class sphere, nano wire, nanometer rod and nanometer sheet etc.Fe with other pattern 3O 4Compare octahedra Fe 3O 4In the higher saturation magnetization of maintenance, have higher residual magnetization and coercive force, can enough in fields such as magnetic fluid, information storage better application be arranged, thereby the Fe of octahedral structure 3O 4It is one of primary study object of researchist in recent years.
Former studies personnel utilize hydrothermal method to come synthesizing octahedral type Fe usually 3O 4It is solvent with water in the pressurized vessel of sealing that hydrothermal method refers to, temperature is from 100 ~ 400 ℃, pressure from greater than 0.1 MPa until tens under the condition of hundreds of MPa, make precursor (being raw material) reaction and crystallization.The octahedral crystal that Hydrothermal Preparation goes out, crystal grain is grown complete, seldom reunites between the particle, and this method raw material can obtain desirable stoichiometric composition material than horn of plenty; But its preparation process more complicated is had relatively high expectations to processing condition, generally need under High Temperature High Pressure, carry out, and prepared octahedra Fe 3O 4Particle size bigger and inhomogeneous usually.For example people such as Zhao is with (NH 4) 2Fe (SO 4) 26H 2O is raw material, adds additives such as Triton X-100 and NaOH simultaneously, in being full of the stainless steel autoclave of Ar protective atmosphere, being incubated 48 h by hydrothermal method under 200 ℃ high temperature and just having synthesized the octahedra Fe that average rib length is 4 μ m 3O 4People such as Jiao are by the synthetic octahedra Fe of similar method 3O 4Size also bigger, scope is 2.8 ~ 14.0 μ m.
Of the present invention is a kind of new octahedra Fe 3O 4Preparation method, i.e. removal alloying method.The octahedra Fe that this method has simple, the consuming time weak point of technical process, obtains 3O 4Less and the yield rate of size has overcome many shortcomings of hydrothermal method in the past than characteristics such as height, and being expected to substitute hydrothermal method becomes octahedra Fe 3O 4Main preparation methods.
The removal alloying method, also claim the selective corrosion method, refer under the electropotential between the alloy constituent element differs bigger situation, the active element of the electrochemical properties in the alloy under electrolytical effect optionally dissolving enter electrolytic solution and stay electrochemical properties than the corrosion process of stable element.Constituent element both can be a kind of element in the single phase solid solution alloy, can be again a certain phase in the polyphase alloy.All the time, the removal alloying method is mainly for the preparation of nano porous metal, and its object mostly is the single phase solid solution alloy of binary, by selecting suitable caustic solution, with wherein comparatively active dissolving metal, the atoms metal of remaining comparatively inertia is through the final nano-porous structure that forms co-continuous of the growth of reuniting.For example Meyerheim and Schofield etc. are with single-phase Cu-Pd alloy selective dissolution Cu and prepare nanoporous Pd(Nanoporous Palladium in acid solution, NPPd).Hayes etc. utilize Mn 0.7Cu 0.3Two phase alloys have made about tens nm in aperture as virgin alloy by galvanic corrosion and chemical corrosion method, the nanoporous Cu(Nanoporous Copper of thickness 300 μ m, NPC).But the removal alloying method also not merely is confined to prepare nano porous metal, also can be for the preparation of the metal oxide that has the special appearance property.As Qi etc. Al-Co, Al-Ti and Al-Mn alloy are placed on earlier and carry out removal alloying in the NaOH solution under the room temperature and handle, made the Co of nano-sheet respectively 3O 4, the cancellated TiO of three-dimensional co-continuous 2And the Mn of octahedral structure 3O 4, wherein as the Co of nanostructure 3O 4Very high catalytic activity is arranged aspect low temperature CO oxidation.These results show, handle by simple chemical corrosion, just can obtain the metal function oxide material of uniform special microscopic appearance.
The present invention is that virgin alloy, 95 ± 5 ℃ are that temperature of reaction, 5 mol/L NaOH are electrolyte solution with Al-15 at.%Fe alloy, and under heating condition, the removal alloying by two phase alloys has successfully prepared octahedra Fe 3O 4, concrete operational path has been proposed simultaneously.The present invention is raw materials used more easily to be obtained, and temperature of reaction reaches easily, and the used time is shorter, and the octahedra Fe for preparing 3O 4The particle shape rule, size is even, suitable batch production.The present patent application people adopts octahedron+Z 250+removal alloying (octahedron+Fe 3O 4+ dealloy) as keyword retrieval United States Patent (USP) digest (USPTO), European patent digest (EP-PCT), " Chinese patent Information Network " and " State Intellectual Property Office of the People's Republic of China's patent retrieval " are not found patent family.
Summary of the invention
The invention provides and a kind ofly can obtain regular octahedra Fe within a short period of time 3O 4The removal alloying preparation method.More particularly, the purpose of this invention is to provide that a kind of to place alkali lye after the heating to carry out chemical corrosion the Al-Fe alloy thin band be that removal alloying is handled, thereby obtain octahedra Fe 3O 4Method.Its concrete operations step is as follows:
1. take by weighing a certain amount of pure Al and pure Fe(at.%Fe＜80% by the proportioning of reserving in advance), confected materials is placed carry out arc melting in the high vacuum arc-melting furnace then, prepare the Al-Fe alloy pig with certain ingredients ratio;
2. place the lower end to have in the quartz glass tube of spout arc melting gained Al-Fe alloy pig, the single roller of the high vacuum of then quartz glass tube being packed into revolves the equipment of quenching, melt by induction melting, and by the draught head that quartz glass tube is interior and cavity is interior, the alloy of fusing is sprayed onto the copper roller surface of high speed rotating, gets rid of and make the Al-Fe alloy thin band;
3. it is long the Al-Fe alloy thin band to be cut into 2-4 cm, gets 3-5 bar strip;
4. prepare certain density alkaline solution, then strip is put into basic solution, and container is heated, the record reaction time opening;
5. be incubated after solution being heated to certain temperature;
6. the bubble situation of Al element and alkaline solution reaction in the observation container, when waiting not have obvious visible bubble in bubble, with sample by taking out writing time while in the solution;
7. will clean 3-5 time with deionized water and raw spirit respectively through the sample of said process;
8. put into the loft drier drying after sample being placed spirituous solution ultrasonic cleaning for some time, finally obtain having the Fe of regular octahedral structure 3O 4Powder.
Described Al-Fe alloy thin band is characterized in that Al wherein is amphoteric element, can be removed in alkali lye, thereby reach the purpose of removal alloying, and Fe wherein is for forming Fe 3O 4Bioelement, can be at OH -Effect under oxidized and finally form Fe 3O 4
Described alkaline solution is characterized in that and the Al element in the alloy system can be dissolved, and enough OH can be provided -Fe elemental oxygen is wherein changed into Fe 3O 4, and induce it to form octahedral structure, thus be generally strong alkali solution, such as solution such as sodium hydroxide, potassium hydroxide.
The mechanism of the inventive method is: utilize Al-Fe alloy removal alloying to prepare octahedra Fe 3O 4Relate to the dissolving of Al element and oxidation and the growth process of Fe atom, the OH in the basic solution -Can be adsorbed on Fe 3O 4Each surface, make them different and finally form octahedral structure in speeds of growth of different crystal faces.
Description of drawings
Fig. 1 be Al-15 at.%Fe virgin alloy strip and in 95 ± 5 ℃ 5 mol/L NaOH solution the XRD curve behind removal alloying 120 min.As seen Al-15 at.% Fe alloy thin band has been realized removal alloying process completely when 120 min, and has formed Fe 3O 4Crystal.
Fig. 2 is Al-15 at.% Fe alloy thin band gained Fe behind removal alloying 120 min in 95 ± 5 ℃ 5 mol/L NaOH solution 3O 4The SEM photo.As seen obtained the comparatively octahedra Fe of rule of shape this moment 3O 4, and granular size is more even, and the long mean sizes of its octahedra rib is 1093 ± 202 nm.
Fig. 3 is Al-15 at.% Fe alloy thin band octahedra Fe of gained behind removal alloying 120 min in 95 ± 5 ℃ 5 mol/L NaOH solution 3O 4Magnetic hysteresis loop.Octahedra Fe as can be seen therefrom 3O 4Not only keep higher saturation magnetization, also have higher residual magnetization and coercive force.
Embodiment
The present invention is described in detail below in conjunction with example:
Embodiment:Concrete steps are as follows:
1. take by weighing quantitative pure Al and pure Fe by atomic percent 85:15, and confected materials is placed copper crucible in the high vacuum arc-melting furnace, be evacuated to 3.0 * 10 -3Pa is above and feed the Ar protective atmosphere, carries out arc melting then, prepares Al-15 at.% Fe alloy pig;
2. place the lower end to have in the quartz glass tube of spout arc melting gained Al-15 at.% Fe alloy pig.The quartz glass tube single roller of high vacuum of packing into is revolved the equipment of quenching, be evacuated to 3.0 * 10 -3Pa is above and feed the Ar protective atmosphere, melt by induction melting, and by the draught head that quartz glass tube is interior and cavity is interior, the alloy that melts is sprayed onto the copper roller surface (linear velocity can reach 18.4 m/s) that rotating speed is 1600 rpm, get rid of and make Al-15 at.% Fe alloy thin band;
3. it is long Al-15 at.%Fe alloy thin band to be cut into 2-4 cm, gets 3-5 bar strip;
4. prepare 5 mol/L NaOH solution, strip is put into the NaOH solution that configures, container begins to heat from room temperature simultaneously, and the record reaction time opening;
5. container is heated to 95 ± 5 ℃ of insulations;
6. the bubble situation of alloy thin band Al element and NaOH solution reaction in the observation container when waiting not have obvious visible bubble in bubble, is taken out the solution bottom sample;
7. the product that makes is cleaned 3-5 time with deionized water and raw spirit respectively;
8. product is placed ultrasonic washing instrument sonic oscillation 20 min, take out and pour out spirituous solution then;
9. container is placed loft drier, under 40 ℃, carry out oven drying at low temperature, treat Fe 3O 4Take out and airtight preservation behind the powder finish-drying.
Fig. 1 in the present embodiment in the visible accompanying drawing of material phase analysis result of related Al-15 at.%Fe virgin alloy strip and removal alloying products obtained therefrom.Get Al-15 at.%Fe virgin alloy strip by sosoloid α-Al (Fe) and intermetallic compound Al according to Fig. 1 13Fe 4Two phase composites, only there is single face-centered cubic (f.c.c.) Fe in the removal alloying process through different time in NaOH solution in the product 3O 4, showing 120 min under the time, Al-15 at.%Fe has finished the removal alloying process, sosoloid α-Al (Fe) and intermetallic compound Al in the alloy 13Fe 4Al in the two-phase all is removed, and remaining Fe is then final oxidized and form Fe 3O 4
In the present embodiment behind NaOH solution removal alloying 120 min the Fe that obtains 3O 4Fig. 2 in the visible accompanying drawing of the structure and morphology of powder, prepared Fe as seen from Figure 2 3O 4Have octahedral structure, and this octahedral structure comparison rule and even, the long mean sizes of its octahedra rib is 1093 ± 202 nm, this is than the octahedra Fe that synthesizes by hydrothermal method 3O 4Size much smaller, and the preparation required time also shorten dramatically than hydrothermal method.
In the present embodiment behind NaOH solution removal alloying 120 min the octahedra Fe that obtains 3O 4Fig. 3 in the visible accompanying drawing of the magnetic hysteresis loop of powder can obtain this octahedron Fe from figure 3O 4Powder M sValue is 83.5 emu/g, M rValue is 7.9 emu/g, H cValue has then reached 179.3 Oe.Its M rThe value and H cValue is than other pattern Fe 3O 4Want high a lot, this further specifies the octahedra Fe by this method preparation 3O 4Can the better application prospect be arranged at some specific areas, as magnetic fluid, information storage etc.

Claims (1)

1. one kind prepares regular octahedra Fe 3O 4The method of particle is characterized in that this method has following steps:
A. take by weighing a certain amount of pure Al and pure Fe by the proportioning of reserving in advance, wherein Fe＜80 at.% place confected materials then and carry out arc melting in the high vacuum arc-melting furnace, prepare the Al-Fe alloy pig with certain ingredients ratio;
B. place the lower end to have in the quartz glass tube of spout arc melting gained Al-Fe alloy pig, the single roller of the high vacuum of then quartz glass tube being packed into revolves the equipment of quenching, melt by induction melting, and by the draught head that quartz glass tube is interior and cavity is interior, the alloy of fusing is sprayed onto the copper roller surface of high speed rotating, gets rid of and make the Al-Fe alloy thin band;
C. it is long the Al-Fe alloy thin band to be cut into 2-4 cm, gets 3-5 bar strip;
D. prepare 5 mol/L NaOH solution, strip is put into the NaOH solution that configures, container begins to heat from room temperature simultaneously, and the record reaction time opening;
E. container is heated to 95 ± 5 ℃ of insulations;
F. observe the bubble situation of Al element and NaOH solution reaction in the container, when waiting not have obvious visible bubble in bubble, with sample by taking out writing time while in the solution;
G. will clean 3-5 time with deionized water and raw spirit respectively through the sample of said process;
H. put into the loft drier drying after sample being placed spirituous solution ultrasonic cleaning for some time, finally obtain having the Fe of regular octahedral structure 3O 4Powder.
CN2013101757584A 2013-05-14 2013-05-14 Method for preparing regular octahedral Fe3O4 particles Pending CN103253713A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103771535A (en) * 2013-12-31 2014-05-07 惠州学院 Polyhedral nanometer ferroferric oxide and preparation method thereof
CN104628029A (en) * 2015-01-23 2015-05-20 济南大学 Method for preparing titanate, anatase TiO2 and AgCl/Ag/TiO2 composite material
CN105016397A (en) * 2015-07-10 2015-11-04 济南大学 Preparation method of nanometer metallic oxide in AB2O4 spinel structure
JP2018513087A (en) * 2015-03-18 2018-05-24 フィナジー リミテッド Metal oxide particles and method for producing the same
CN110482607A (en) * 2019-07-30 2019-11-22 中南大学 A kind of high grain boundary density MoO3Nanocrystalline and its preparation and the application in fragrant primary alconol catalysis oxidation

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103771535A (en) * 2013-12-31 2014-05-07 惠州学院 Polyhedral nanometer ferroferric oxide and preparation method thereof
CN103771535B (en) * 2013-12-31 2015-07-29 惠州学院 A kind of polyhedron nano ferriferrous oxide and preparation method thereof
CN104628029A (en) * 2015-01-23 2015-05-20 济南大学 Method for preparing titanate, anatase TiO2 and AgCl/Ag/TiO2 composite material
JP2018513087A (en) * 2015-03-18 2018-05-24 フィナジー リミテッド Metal oxide particles and method for producing the same
CN105016397A (en) * 2015-07-10 2015-11-04 济南大学 Preparation method of nanometer metallic oxide in AB2O4 spinel structure
CN105016397B (en) * 2015-07-10 2016-10-12 济南大学 A kind of AB2o4the preparation method of spinel structure nano-metal-oxide
CN110482607A (en) * 2019-07-30 2019-11-22 中南大学 A kind of high grain boundary density MoO3Nanocrystalline and its preparation and the application in fragrant primary alconol catalysis oxidation

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Application publication date: 20130821