CN100496820C - Process for preparing nano granule with high shape anisotropic property - Google Patents
Process for preparing nano granule with high shape anisotropic property Download PDFInfo
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- CN100496820C CN100496820C CNB2006101044695A CN200610104469A CN100496820C CN 100496820 C CN100496820 C CN 100496820C CN B2006101044695 A CNB2006101044695 A CN B2006101044695A CN 200610104469 A CN200610104469 A CN 200610104469A CN 100496820 C CN100496820 C CN 100496820C
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Abstract
The invention relates to a method for producing magnetic nanometer particles, with shape aeolotropism and magnetic crystal aeolotropism, or multi aeolotropism. Wherein, it can be used to prepare single-phase stack hexagonal (HCP) cobalt nanometer particles and binary or ternary alloy nanometer particles of iron, cobalt and nickel. The invention processes at 90-200Deg. C and more than one pressure reacts the metal salt or cobalt with water.
Description
Technical field
The present invention relates to the preparation method of magnetic function nano particle in the metal material, particularly preparation has shape anisotropy and magnetocrystalline anisotropy, the method for perhaps how anisotropic magnetic metal nano particle.The method of wood invention is particularly useful for making the binary or the ternary alloy nano particle of single-phase close heap hexagonal structure (HCP) cobalt nano-particle and iron, cobalt, the corresponding composition of nickel.
Background technology
Metal such as iron, nickel, cobalt and alloy have in fields such as magnetic recording material, high performance microwave absorber material, high-temperature alloy material, Hardmetal materials, anti-corrosive alloy material, catalytic material, diamond tool materials widely to be used.Compare with the coarse-grain micro mist, because big specific area, little size and its specific structure feature, nano level metallic particles shows excellent more performance, therefore, the metallic particles of nanometre grade cobalt, and binary and the preparation of ternary alloy three-partalloy and the extensive attention that performance study is subjected to people of nano level iron, cobalt, nickel.
At present the synthetic technology of nano particle mainly faces the problem of the following aspects: how can control the Size Distribution of particle, prepare that particle diameter is evenly distributed, the mono-dispersed nano particle; How in certain range scale, grain diameter to be controlled accurately, can prepare the single-size of different-grain diameter; How the crystallization degree of nano particle is controlled, prepared the nano particle of required crystal structure; How the pattern of nano particle is controlled, according to the nano particle of its performance demands being prepared different-shapes such as sphere, bar-shaped, sheet.The preparation method of cobalt nano-particle can be divided into physical method and chemical method.Physical method mainly contains vapour deposition process, evaporation-condensation method (containing plasma evaporation, laser evaporation and electron beam evaporation etc.).The shortcoming of physical method is the equipment that needs large-scale costliness, and prepared nanoparticle size is bigger than normal, and the size, the shape that are difficult to particle effectively control, and granular size, shape are inhomogeneous.Chemical method mainly contains: as liquid phase reduction, carbonyl salt thermal decomposition method, micro emulsion method, polyalcohol method etc.
People such as Victor F.Puntes (referring to Science, 2001,291:2115) utilize Co
2(CO)
8Decomposition in dichloro-benzenes is controlled the forming core and the growth rate of particle and is prevented intergranular reunion by adding oleic acid and TOPO surfactant, and successfully having prepared diameter is 4nm, the bar-shaped cobalt nano-particle of length between 25～75nm.People such as A.Paul Alivisatos (referring to J.Am.Chem.Soc., 2002,124:12874) reported that carbonyl salt thermal decomposition method prepares the cobalt nanometer sheet of HCP phase, its average diameter is about 50nm, and experimental technique is with Co
2(CO)
8Be dissolved in the organic solvent, it is decomposed under inert atmosphere protection, in course of reaction, add surfactant oleic acid, TDA, HDA, ODA, TBA, TOA, TOPO etc. simultaneously.Reaction raw materials has toxicity and costs an arm and a leg, and the course of reaction complexity is unsuitable for large-scale production.J.P Chen (J.Appl.Phys.1994,76 (10): 6316) use microemulsion method, utilize DDAB to make surfactant, toluene is made oil phase, uses sodium borohydride to make reducing agent reduction cobalt chloride, made particle diameter at 1.8nm to the spherical cobalt nano-particle between the 44nm.But the method easily produces the boride of cobalt, the preparation process complexity, and also the cobalt nano-particle of preparation at room temperature is in super-paramagnetic state.Z.L.Wang (J.Phys.Chem.B; 2005; 109:15309) grade utilizes microemulsion method at first to prepare the cobalt nano powder of particle diameter for 7nm, crystallization degree difference equally; this moment, its saturation magnetization had only 85 ± 5emu/g; then at particle surface parcel one deck laurate; under temperature is 275 ℃, the condition of nitrogen protection, heat-treat, make its saturation magnetization bring up to 145 ± 5emu/g.But the method technology is complicated more, and finally the obstruction temperature of gained cobalt nano-particle is 275K, still is super paramagnetic under the room temperature.People such as Q.Xie (Nanotechnology, 2005,16:2958) utilize hydro-thermal method, in the alcohol solution of water and ethanol volume ratio 1:2 mixing, add CoCl
2Solution, surfactant SDBS, NaH
2PO
2H
2The NaOH solution of O and 10M is put into the reactor of poly-tetrafluoro with mixed solution, 160 ℃ of reactions down, has made the wide 200～500nm of being, thick 50～80nm, long close heap hexagonal structure cobalt nanometer band for several microns.
C.P.Gibson is (referring to Science, 1995,267:1338) once utilized hydrazine hydrate to make reducing agent, under the superenergy action of ultrasonic waves, having made average diameter is the hexagon sheet cobalt nano-particle of 100nm, but the method needs high-octane ultrasonic unit, and that the inhomogeneous meeting of diverse location ultrasonic energy causes reacting in the solution is inhomogeneous, is not suitable for large-scale industrialization production.This in addition method can only be prepared face-centered cubic and close heap six sides' mixture, can't obtain the nano particle of single-phase close heap hexagonal structure.
Utilize simple chemical method, cheap synthetic synthesis technique with single-phase close heap hexagonal structure leaf shape cobalt nano-particle of high shape anisotropic property and magnetocrystalline anisotropy of one step of chemical reagent does not appear in the newspapers so far.
Summary of the invention
The invention provides a kind of method that is used to prepare the nano particle of single-phase close heap hexagonal structure cobalt, this method is also with preparation iron, cobalt, the binary of nickel or the nano particle of ternary alloy three-partalloy simultaneously.
The inventive method is that the aqueous solution with hydrazine hydrate and slaine reacts.
The way of the nano particle of the single-phase close heap hexagonal structure cobalt of the concrete preparation of the present invention is: the soluble-salt of dissolved cobalt or nickel in water, the aqueous solution at slaine adds the hydrazine hydrate that is at least 2 times of cobalt salt amounts, after stirring reaction system is heated to 90～200 ℃, and under greater than an atmospheric condition, react, after finishing, reaction carries out Separation of Solid and Liquid, after resulting solid cleaned with distilled water, carry out Separation of Solid and Liquid again, the gained solid is carried out the dry cobalt nano-particle that obtains single-phase close heap hexagonal structure of handling.
Used cobalt salt is the hydrochloride or the sulfate of cobalt in the method for the present invention; Can guarantee to react products therefrom when the hydrazine hydrate amount that is added is 10 times～80 times of cobalt salt amount is sheet; Only need lid with reactor screw to be placed on after adding hydrazine hydrate and add thermal response in the heating furnace, what the pressure that is produced in reactor by heating had been enough to guarantee to react normally carries out.Show best effect to be arranged when reaction temperature of the present invention is 180 ± 50 ℃ according to relevant test.
Method of the present invention adds an amount of strong alkali aqueous solution in aqueous metal salt, as the aqueous solution of NaOH or potassium hydroxide, can make the reaction acceleration.Test shows that the concentration of the NaOH water that is added in final mixed solution should be greater than 20mol/L.
When implementing method of the present invention, also can in aqueous metal salt, add the aqueous solution of softex kw, the concentration range of the softex kw that is added in final solution is 0.001～0.10mol/L.Adopt the dispersiveness that can improve particle after this measure, obtain more homodisperse nano particle.
The present invention is used to prepare iron, cobalt, the preparation method of the binary alloy nano particle of the corresponding composition of nickel is: by wanting the designing requirement amount that the soluble-salt of iron and cobalt or iron and nickel or cobalt and nickel is soluble in water, at the hydrazine hydrate of aqueous metal salt adding greater than slaine amount twice, after stirring reaction system is heated to 90～200 ℃, under greater than an atmospheric pressure, react, after finishing, reaction carries out Separation of Solid and Liquid, after resulting solid cleaned with distilled water, carry out Separation of Solid and Liquid again, the gained solid is carried out the drying processing obtain alloy nanoparticle.
The preparation method that the present invention is used for preparing the ternary alloy nano particle of iron, cobalt, the corresponding composition of nickel is: be dissolved in water by the soluble-salt of wanting the designing requirement amount with iron, cobalt and nickel, at the hydrazine hydrate of aqueous metal salt adding greater than slaine amount twice, after stirring reaction system is heated to 90～200 ℃, under the condition of doing greater than an atmosphere, react, after finishing, reaction carries out Separation of Solid and Liquid, after resulting solid cleaned with distilled water, carry out Separation of Solid and Liquid again, the gained solid is carried out the drying processing obtain alloy nanoparticle.
The invention has the advantages that:
1, provide a kind of aqueous solution reducing process simple to operate, cheap, good reproducibility to prepare the synthesis technique of cobalt nano-particle;
2, employed reducing agent is a hydrazine hydrate, and the reaction back generates nitrogen and hydrogen, and entire reaction is carried out thoroughly, product is pollution-free.It is a kind of method of synthetic cobalt nano-particle of environmental type;
3, can prepare the pure single-phase close heap hexagonal structure cobalt nano-particle of the sheet with strong magnetocrystalline anisotropy and high shape anisotropic property, also can prepare the binary or the ternary alloy nano particle of iron, cobalt, nickel simultaneously with method of the present invention;
4, prepared cobalt nano-particle adjustable size has magnetocrystalline anisotropy, shape anisotropy and also have anisotropy in the face of nanometer sheet, is a kind of cobalt nano-particle with multiple anisotropy characteristics.The sheet cobalt nano-particle of this many anisotropy, high saturation and magnetic intensity has very big using value aspect the exploitation of new and effective microwave absorbing material;
5, the good dispersion of prepared particle, uniform particles, tiny.
Description of drawings
Accompanying drawing 1 and accompanying drawing 2 are cobalt nano-particle stereoscan photographs of two kinds of different-grain diameters preparing of the present invention.Accompanying drawing 3 is the X ray diffracting spectrum of cobalt nano-particle, the sample of the corresponding embodiment one of 1# wherein, the sample of the corresponding embodiment two of 2#.
The specific embodiment
Embodiment one, when the preparation radial dimension is tens microns a leaf shape cobalt nanometer sheet, concrete technology is as follows:
1. measure the CoCl of 0.1mol/L
2Solution 20ml pours in the reactor, and softex kw (CTAB) the solution 2ml of measuring 0.1mol/L pours CoCl into
2In the solution, stir, obtain clear pink solution, drip the NaOH solution 0.8ml of 25mol/L in this solution, mix, obtain blue clear solution, add 2ml N at this moment
2H
4H
2O content is 85% hydrazine hydrate, stirs, the reactor lid of screwing on;
2. reactor being put into temperature and be 180 ℃ baking oven, be incubated after 1 hour and take out, open after being cooled to room temperature, is silver gray powder and colourless solution in the reactor;
3. the washing of cobalt nano-particle, drying.Use magnetic separation technique that colourless solution is outwelled, obtain the silver gray powder, in the silver gray powder, add the about 150ml of distilled water, shake evenly, magnetic separates once more, repeats 2～3 times after the pH value of solution value be neutrality, outwell distilled water this moment, powder is put into drying under reduced pressure case drying under reduced pressure, take out after several hours, can deposit in and wait until follow-up X-ray diffraction, ESEM sign and Magnetic Measurement in the air.
By the particle of present embodiment gained is radial dimension at tens microns leaf shape cobalt nano-particle, and referring to Fig. 1, it can also be seen that from figure: this sheet cobalt nano-particle also is anisotropic structure in its face.
Embodiment two, preparation radial dimension are when being the cobalt nanometer sheet of hundreds of nanometer, and concrete technology is as follows:
1. measure the CoCl of 0.1mol/L
2Solution 20ml pours in the reactor, measures N
2H
4H
2O content is that 85% hydrazine hydrate 2ml pours CoCl into
2Solution stirs, and covers the reactor lid;
2. reactor being put into temperature and be 180 ℃ baking oven, be incubated after 1 hour and take out, open after being cooled to room temperature, is black powder and colourless solution in the reactor;
3. the washing of cobalt nano-particle, drying.This step is identical with technology among the embodiment one.
By present embodiment gained particle is the sheet cobalt nano-particle of radial dimension in the hundreds of nanometer, referring to Fig. 2.
Embodiment three, preparation bianry alloy Fe
0.1Co
0.9The flake nano particle, concrete technology is as follows:
1. take by weighing the FeSO of 0.2mmol
47H
2The CoCl of O and 1.8mmol
26H
2O puts in the reactor, pours 20ml distilled water in reactor, stirs with glass bar it is dissolved fully, obtain clear solution, drip the NaOH solution 1.5ml of 25mol/L in this solution, mix, obtain blue clear solution, add 2ml N this moment
2H
4H
2O content is 85% hydrazine hydrate, stirs, the reactor lid of screwing on;
2. reactor being put into temperature and be 180 ℃ baking oven, be incubated after 2 hours and take out, open after being cooled to room temperature, is grey black powder and colourless solution in the reactor;
3.Fe0.1Co0.9 the washing of alloy nanoparticle, drying, these steps are identical with technology among the embodiment one.The preparation powder is the flake nano particle, and the coercivity of actual measurement material is 230Oe.
Embodiment four, preparation bianry alloy Fe
0.1Co
0.9The flake nano particle, its concrete technology is identical with embodiment three, but also is added with the CTAB solution that 2ml concentration is 0.1mol/L in reaction system.The present embodiment products therefrom is identical with embodiment three products therefroms, but after product put into water and disperse with ultrasonic wave, its sinking speed is starkly lower than the sinking speed of embodiment three products therefroms under similarity condition, and the dispersiveness of this explanation present embodiment product obviously is better than embodiment three products therefroms.
Embodiment five, preparation ternary alloy three-partalloy Fe
0.1(Co
0.5Ni
0.5)
0.9The flake nano particle, concrete technology is as follows:
1. take by weighing the FeSO of 0.2mmol
47H
2The CoCl of O, 0.9mmol
26H
2The NiCl of O and 0.9mmol
26H
2O puts in the reactor, pours 20ml distilled water in reactor, stirs with glass bar it is dissolved fully, obtains clear solution, drips the NaOH solution 0.8ml of 25mol/L in this solution, mixes adding 2mlN
2H
4H
2O content is 85% hydrazine hydrate, stirs, the reactor lid of screwing on;
2. reactor being put into temperature and be 160 ℃ baking oven, be incubated after 2 hours and take out, open after being cooled to room temperature, is grey black powder and colourless solution in the reactor;
3.Fe
0.1(Co
0.5Ni
0.5)
0.9The washing of alloy nanoparticle, drying, everything is identical with technology among the embodiment one.The preparation powder is the flake nano particle, and the coercivity of actual measurement material is 210Oe.
Embodiment six, preparation ternary alloy three-partalloy Fe
0.1(Co
0.5Ni
0.5)
0.9The flake nano particle, its concrete technology is identical with embodiment five, but also is added with the CTAB solution that 2ml concentration is 0.1mol/L in reaction system.The present embodiment products therefrom is identical with embodiment five products therefroms, but after product put into water and disperse with ultrasonic wave, its sinking speed is starkly lower than the sinking speed of embodiment five products therefroms under similarity condition, and the dispersiveness of this explanation present embodiment product obviously is better than embodiment five products therefroms.
Claims (5)
1, the method for preparing single-phase close heap hexagonal structure cobalt nano-particle, the aqueous solution with hydrazine hydrate and cobalt soluble-salt reacts, it is characterized in that adding at the aqueous solution of cobalt salt earlier the aqueous solution of softex kw, the concentration range of the softex kw that is added in final solution is 0.001～0.10mol/L, in cobalt salt solution, add the hydrazine hydrate that is at least 2 times of cobalt salt amounts again, after stirring reaction system is heated to 90～200 ℃, and under greater than an atmospheric condition, react, after finishing, reaction carries out Separation of Solid and Liquid, after resulting solid cleaned with distilled water, carry out Separation of Solid and Liquid again, the gained solid is carried out the dry cobalt nano-particle that obtains single-phase close heap hexagonal structure of handling.
2, the method for the single-phase close heap hexagonal structure cobalt nano-particle of preparation according to claim 1, it is characterized in that used cobalt salt is the hydrochloride or the sulfate of cobalt, the hydrazine hydrate amount that is added is 10 times～80 times of cobalt salt amount, adds behind the hydrazine hydrate lid with reactor and screws to be placed on and add thermal response in the heating furnace.
3, the method for the single-phase close heap hexagonal structure cobalt nano-particle of preparation according to claim 2 is characterized in that adding earlier strong alkali aqueous solution in cobalt saline solution, hydrazine hydrate is added again, and the concentration of alkali in final mixed solution should be greater than 20mol/L.
4, iron, cobalt, the preparation method of the binary alloy nano particle of nickel, it is characterized in that by wanting the designing requirement amount that the soluble-salt of iron and cobalt or iron and nickel or cobalt and nickel is soluble in water, add an amount of strong alkali aqueous solution, again at the hydrazine hydrate of aqueous metal salt adding greater than slaine amount twice, the softex kw that also has 0.10mol/L in the reaction system, after stirring reaction system is heated to 90～200 ℃, under greater than an atmospheric pressure, react, after finishing, reaction carries out Separation of Solid and Liquid, after resulting solid cleaned with distilled water, carry out Separation of Solid and Liquid again, the gained solid is carried out the drying processing obtain alloy nanoparticle.
5, iron, cobalt, the preparation method of the ternary alloy nano particle of nickel, it is characterized in that by wanting the designing requirement amount iron, the soluble-salt of cobalt and nickel is dissolved in the water, add an amount of strong alkali aqueous solution, again at the hydrazine hydrate of aqueous metal salt adding greater than slaine amount twice, the softex kw that also has 0.10mol/L in the reaction system, after stirring reaction system is heated to 90～200 ℃, under greater than an atmospheric pressure, react, after finishing, reaction carries out Separation of Solid and Liquid, after resulting solid cleaned with distilled water, carry out Separation of Solid and Liquid again, the gained solid is carried out the drying processing obtain alloy nanoparticle.
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| CN101698234B (en) * | 2009-10-21 | 2011-02-16 | 北京科技大学 | Chemical preparation method of metal cobalt nanowire |
| CN102601384B (en) * | 2012-03-31 | 2014-01-15 | 北京科技大学 | Chemical method for preparing cobalt nickel nanoscale alloy powder |
| CN102717091A (en) * | 2012-05-15 | 2012-10-10 | 同济大学 | Method for preparing NiCo nanometer material having hexagon sheet structure |
| CN102921960A (en) * | 2012-11-19 | 2013-02-13 | 扬州大学 | Preparation method of magnetic cobalt nanometer material |
| CN103042229B (en) * | 2012-12-26 | 2014-12-17 | 中北大学 | preparation method of branched magnetic metal cobalt micro-nano material |
| CN103774218B (en) * | 2014-02-13 | 2016-08-17 | 中国计量学院 | A kind of controllable method for preparing of cobalt nanodendrites |
| CN107008922B (en) * | 2017-04-20 | 2019-06-28 | 郑州航空工业管理学院 | A kind of magnetic metal Co nano-powder and preparation method thereof |
| CN108597834A (en) * | 2018-05-02 | 2018-09-28 | 徐靖才 | A kind of preparation method of induced by magnetic field overlength one-dimentional structure magnetic material |
| CN111482619B (en) * | 2020-06-19 | 2022-12-02 | 北京铁路信号有限公司 | Cobalt particle with multi-level lamellar structure, and preparation method and application thereof |
| CN113084183B (en) * | 2021-03-17 | 2022-03-15 | 电子科技大学 | Cunninghamia lanceolata leaf-shaped cobalt particles and method for preparing magnetic composite material by using same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4089676A (en) * | 1976-05-24 | 1978-05-16 | Williams Gold Refining Company Incorporated | Method for producing nickel metal powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4089676A (en) * | 1976-05-24 | 1978-05-16 | Williams Gold Refining Company Incorporated | Method for producing nickel metal powder |
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