CN100453219C - Nano-iron powder prepn. method - Google Patents
Nano-iron powder prepn. method Download PDFInfo
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- CN100453219C CN100453219C CNB2004100647516A CN200410064751A CN100453219C CN 100453219 C CN100453219 C CN 100453219C CN B2004100647516 A CNB2004100647516 A CN B2004100647516A CN 200410064751 A CN200410064751 A CN 200410064751A CN 100453219 C CN100453219 C CN 100453219C
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- nanometer iron
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Abstract
The present invention relates to a chemical preparation method for nanometer iron powder. The present invention is characterized in that molysite is dissolved in ethanol, water or the mixed solution of the ethanol and the water, and the mol concentration of iron ions is from 0.02 to 1.0 mol/L; NaOH and hydrazine hydrate solution are added, wherein the mol number of the NaOH is 15 to 50 times of that of the iron ions, the hydrazine content of the hydrazine hydrate solution is 8 to 30 times of the mol number of the iron ions, and the mass concentration of the hydrazine hydrate solution is 40 to 80%; after mother liquor is uniformly stirred, the heating and the refluxing of the mother liquor are carried out at the temperature of 80 to 120 DEG C until the mother liquor is colorless and transparent, and the nanometer iron powder is obtained; the size of the iron powder can be controlled by changing reaction solvent and regulating the concentration of alkali. The nanometer iron powder prepared by the present invention has high purity, and the grain diameter is from 10 nm to 250 nm; the further surface modification of the prepared nanometer iron powder can be carried out to obtain surface coated nanometer iron powder, and thereby, the magnetic property and the antioxidation property of the product are improved. Raw materials of the present invention are cheap and are obtained easily, a desired device is simple, the technology is convenient, the reaction can be finished in one step under ordinary pressure, and the reaction is safe and is controlled easily; the production rate achieves above 99%, the mother liquor can be repeatedly used, and the present invention is suitable for large scale industrial production.
Description
Technical field:
The invention belongs to the preparing technical field of metal nano material, particularly the liquid phase chemical preparation process of nanometer iron powder under the normal pressure.
Background technology:
Nanometer iron powder since its good magnetic, bigger surface area and high reactivity have a very wide range of applications in fields such as catalysis, magnetic recording and electronics.At present its main chemical preparation process has: thermal decomposition or ultrasonic decomposition ferrous metal organic compound method, borohydride reduction iron salt method, hydrogen reducing iron hydroxide or iron oxide process etc., but shortcoming such as these methods all exist apparatus expensive, operating procedure complexity to some extent, step is various, product purity is not high, productive rate is low.
" JACS " (Sonochemical Synthesis of Iron Colloids, Journal of AmericanChemistry Society, 11960-11961,1996,118,47) " sonochemical method synthesizes the iron colloid " literary composition was once reported and is adopted highdensity ultrasonic wave to decompose Fe (CO)
5Method prepare the iron colloid, but this method needs high-octane Vltrasonic device, and the carbonyls presoma that adopts has certain toxicity, is not suitable for large-scale industrial production.
U.S.'s " magnetics transactions " magazine (Fabrication and Magnetic Properties of Chains Composed ofSpherical Iron Particles, IEEE, Transanctions.Magnetics, 4481-4483,1996,32,5) " preparation and the magnetic property of the molecular chain structure of spherical abrasive grit " literary composition has reported that the method with the borohydride reduction ferrous salt prepares nanometer iron powder, but because the existence of side reaction, mixing in the products therefrom has a certain amount of boride.
U.S.'s " nanometer wall bulletin " magazine (Aqueous Chemical Route to Ferromagnetic 3-D Arrays of IronNanorods, Nano.Letters, 1393-1395,2002,2,12) method for preparing the iron nanometer rods with hydrogen reducing β-FeOOH reported in " the chemistry of aqueous solution legal system is equipped with the three-dimensional iron nanometer stick array of ferromagnetism " literary composition, this method step is more, operation is complicated, and needs special device with hydrogen reducing, and security is not high.
Chinese patent (Granted publication number: CN1101289C, the patent No.: ZL99110250.9) propose in the alcohol-water system under the condition of high voltage, to utilize the hydrazine hydrate reduction molysite to prepare the method for iron powder, owing to be reflected in the closed reaction kettle and carry out, the difficult control of reaction, and in the course of reaction because the generation of gaseous products, cause in the system pressure higher, require reactor to have certain resistance to pressure.
Summary of the invention:
The present invention propose a kind of under normal pressure the liquid phase chemical reduction method of simple and effective ground preparation nanometer iron powder.
The preparation method of nanometer iron powder of the present invention, it is characterized in that: molysite is dissolved in the mixed solution of ethanol, water or second alcohol and water, the molar concentration that makes iron ion is 0.02-1.0mol/L, adding molal quantity is that iron ion 15-50 NaOH and hydrazine content doubly is that iron ion molal quantity 8-30 mass concentration doubly is the hydrazine hydrate solution of 50-80%, after stirring, when 80-120 ℃ of heating was back to the mother liquor water white transparency, reaction can finish; Product promptly obtains the nanometer iron powder of grey black through magnetic separation, washing, vacuum drying.
Different according to the raw material proportioning of above-mentioned reaction and heating-up temperature, reaction generally can finish in 8-16h.
For the magnetic of improving iron powder and anti-oxidant, can also further carry out finishing to the nanometer iron powder for preparing:
Be 1-5% and cobalt salt with the above-mentioned nanometer iron powder for preparing in the ratio of polyvinylpyrrolidone and the amount of iron powder and the ratio of iron powder amount is the ratio of 5-30%, iron powder is joined in the ethanolic solution that contains polyvinylpyrrolidone 0.002-0.01mol/L and cobalt salt 0.01-0.06mol/L, be uniformly dispersed; Adding molal quantity is that cobalt ions 10-30 NaOH and hydrazine content doubly is that cobalt ions molal quantity 8-20 mass concentration doubly is the hydrazine hydrate solution of 50-80%, and 30-80 ℃ of water-bath is stirred to the mother liquor water white transparency, promptly obtains the nanometer iron powder that the surface coats the cobalt layer.
In precious metal ion and iron atom mol ratio is 1 ‰-1% ratio, and it is 1 * 10 that nanometer iron powder is joined concentration
-4-1 * 10
-3In the precious metal salt solution of mol/l,, or, promptly obtain the nanometer iron powder that the surface is coated with layer of precious metal with the electronic stirring 2-6h of the speed of 200-400r/min with the power ultrasonic 1-4h of 50-80W; Described noble metal comprises silver or palladium.
Nanometer iron powder is evenly spread in the aqueous solution of polyvinylpyrrolidone that amount is iron powder 1-5%, the admixture quality is an iron powder 0.5-2.0 ethyl orthosilicate doubly again, with ammoniacal liquor regulator solution pH value at 10.0-13.0, with the electronic stirring 12-36h of the speed of 200-400r/min, promptly obtain surperficial coated Si O under the room temperature
2Nanometer iron powder.
The present invention prepares on the basis of the method for iron powder at hydrazine hydrate reduction molysite under the existing condition of high voltage, reaction condition is improved,, strengthen the reproducibility of hydrazine hydrate by improving the concentration of alkali, make reaction be able to that next step is finished at normal pressure, productive rate is up to more than 99%; The present invention has overcome in the prior art reaction needed and has carried out in enclosed autoclave, shortcomings such as the difficult control of reaction, and equipment is simple, and technology is convenient, safety, reaction condition is easy to control; And can control the size of product by the means such as concentration that change reaction dissolvent, adjusting alkali; Can also further carry out finishing, obtain surface coated nanometer iron powder, thereby improve the magnetic property and the antioxygenic property of product the nanometer iron powder for preparing.
Raw material of the present invention is inexpensive, is easy to get, and reacts under normal pressure, is applicable to large-scale industrial production; The reacted mother liquor that contains alkali can reuse, and post processing is simple, and ambient influnence is little.
The specific embodiment:
Below be embodiments of the invention:
Embodiment 1: preparation iron nano powder in the alcohol solvent
With 4.0g FeCl
36H
2O is dissolved in the 20ml ethanol, adds the hydrazine hydrate solution of 15.0g NaOH and 10.0ml 80%, is stirred to evenly; Said mixture is added hot reflux 12h at 100 ℃, and mother liquor becomes colorless transparent, and reaction can finish; Product separates through magnetic, washing, and vacuum drying obtains dark gray powder.
Prove that through X-ray diffraction this dark gray powder is pure phase α-Fe; Transmission electron microscope characterizes sample and manifests the blockage shape, and particle size is even, and average-size is about 120nm.The product for preparing of present embodiment is pure phase α-Fe nano powder as can be known.
Get the mother liquor that separates behind the iron powder, after the acidifying, use SCN
-Colour developing, not seeing has Fe
3+Characteristic color, represent Fe in this mother liquor
3+Content be lower than 10
-5Mol/l illustrates to react and carries out very thoroughly that productive rate is up to more than 99%.
On the vibration magnetic determining device gained iron powder is carried out Magnetic Measurement, its coercivity is 198Oe, shows that this iron powder can be used as magnetic recording material.
Embodiment 2: preparation iron nano powder in the aqueous solvent
With 4.0g FeCl
36H
2O is dissolved in the 20ml water, adds the hydrazine hydrate solution of 20.0g NaOH and 20.0ml 80%, is stirred to evenly; Said mixture is added hot reflux 12h at 120 ℃, and mother liquor becomes colorless transparent, and reaction can finish.Product washs through separating, and vacuum drying obtains dark gray powder.
The X-ray diffraction style of product proves that this dark gray powder is pure phase α-Fe; Transmission electron microscope characterizes sample and manifests the blockage shape, and particle size is even, and size is about 250nm.What present embodiment prepared as can be known is the pure phase nanometer iron powder.
Get the mother liquor that separates behind the iron powder, after the acidifying, use SCN
-Colour developing, not seeing has Fe
3+Characteristic color, Fe in this mother liquor is described
3+Content be lower than 10
-5Mol/l shows to react and carries out very thoroughly that the productive rate of iron powder is more than 99%.
On the vibration magnetic determining device gained iron powder is carried out Magnetic Measurement, its coercivity is 150Oe, and is littler than the iron powder coercivity for preparing in the alcohol solvent.
In the present embodiment, if change reaction dissolvent into water by ethanol, strengthen the consumption of NaOH simultaneously, the size of gained iron powder increases, and coercivity descends, and explanation can be regulated the size and the magnetic property of product by the consumption that changes solvent and alkali.
Embodiment 3: preparation iron nano powder in the pure water mixed solvent
Get the mother liquor 15ml that contains alkali among the embodiment 1 behind the separated product, add 10ml water and 8.0g NaOH, obtain pure water mixed solution; Then, add 4.0g FeCl
24H
2The hydrazine hydrate solution of O and 20.0ml 50% stirs; Said mixture is added hot reflux 11h at 100 ℃, and mother liquor becomes colorless transparent, and reaction can finish.Product separates through magnetic, washing, and vacuum drying promptly obtains dark gray powder.
X-ray diffraction proves that products therefrom is pure phase α-Fe; Transmission electron microscope characterizes sample and manifests the blockage shape, and particle size is even, and average-size is about 180nm.Show that the dark gray powder that present embodiment prepares is a nanometer iron powder.
Get the mother liquor that separates behind the iron powder, after the acidifying, add the Phen colour developing, not seeing has Fe
2+Characteristic color, Fe in this mother liquor is described
2+Content be lower than 10
-5Mol/l shows to react and carries out very thoroughly that productive rate reaches more than 99%.
Utilized reaction mother liquor later among the embodiment 1 in the present embodiment, can save reaction raw materials, reduced production costs, and reduced influence environment.
Embodiment 4: the surface coats the preparation of the nanometer iron powder of cobalt
Get the iron powder 0.56g for preparing among the embodiment 1, behind the separating, washing, add 50ml and contain 0.02mol/l Co
2+In the ethanolic solution of 0.004mol/l polyvinylpyrrolidone, stir so that the speed of 300r/min is electronic; Add 1.0gNaOH and 1ml mass concentration again and be 80% hydrazine hydrate solution, 50 ℃ of water-baths continue to stir 40min, and solution becomes water white transparency, and reaction can finish.Product separates through magnetic, washing, 60 ℃ of following vacuum drying.
Comprised six side's phase cobalts and body-centered cubic two kinds of characteristic peaks of iron mutually in the x-ray diffraction pattern of product, transmission electron microscope characterizes average grain diameter and is about 130nm; Heat is analyzed and x-ray photoelectron spectroscopy the analysis showed that: cobalt is coated on the surface of iron.What present embodiment prepared as can be known is the nanometer iron powder that the surface coats cobalt.
Iron powder to surface cobalt-coating on the vibration magnetic determining device carries out Magnetic Measurement, and its coercivity is 298Oe, has improved about 50% before not coating.
Embodiment 5: the preparation of the nanometer iron powder of coated with silver on surface
Get the iron powder 0.056g for preparing among the embodiment 1, behind the separating, washing, inserting 50ml concentration is 1 * 10
-4In the liquor argenti nitratis ophthalmicus of mol/l, behind the power ultrasonic 2h with 60W, reaction can finish; Product washs through separating, and vacuum drying obtains black powder.
Adopt X-ray diffraction that product is carried out material phase analysis, only comprised the iron characteristic peak in its X-ray diffraction characteristic peak, this is because the silver content that is cladded is less, below the detectability of X-ray diffraction.Transmission electron microscope shows that product is the square shape, is of a size of 250-260nm.Heat is analyzed and x-ray photoelectron spectroscopy the analysis showed that: silver is coated on the surface of iron.What illustrate that present embodiment prepares is the nanometer iron powder of coated with silver on surface.
Iron powder to coated with silver on surface on the vibration magnetic determining device carries out Magnetic Measurement, and coercivity is 217Oe, has improved 9.6% than the iron powder before not coating.
The hot analysis result explanation of product: with respect to the iron powder that is not coated, the oxidized time of the iron powder of coated with silver on surface is delayed, and shows that coating palladium on the iron powder surface can play a protective role to iron powder, improves the non-oxidizability of iron powder.
Embodiment 6: the surface coats the preparation of the nanometer iron powder of palladium
Get the iron powder 0.056g for preparing among the embodiment 2, behind the separating, washing, inserting 50ml concentration is 2 * 10
-4In the palladium chloride solution of mol/l, behind the power ultrasonic 2h with 50W, reaction can finish; Product washs through separating, and vacuum drying obtains black powder.
Only comprised the iron characteristic peak in the X-ray diffraction characteristic peak of sample; Transmission electron microscope shows that product is the square shape, is of a size of 250-260nm.X-ray photoelectron spectroscopy the analysis showed that: palladium overlays on the surface of iron.What illustrate that present embodiment prepares is the rice iron powder that the surface coats palladium.
The hot analysis result of product shows that coating palladium on the iron powder surface can play a protective role to iron powder, delays the oxidation of iron powder.
Embodiment 7: surperficial coated Si O
2The preparation of nanometer iron powder
Get the iron powder 0.56g that embodiment 3 prepares, add and contain in the 50ml distilled water of 1.0g PVP,, obtain the dispersed system of grey black with the power ultrasonic 1.0h of 50W; Afterwards, adding 0.5ml mass concentration is 30% concentrated ammonia liquor, the 2ml ethyl orthosilicate, and continuous stirring 24h under the room temperature, reaction can finish.Product is through centrifugation, 60 ℃ of following vacuum drying.
According to the difference of reaction ratio, the time of stirring hydrolysis generally can be controlled in 12-36h.
Comprised pure phase α-Fe characteristic peak in the X-ray diffraction style of product; Transmission electron microscope characterizes the explanation products therefrom and presents tangible nucleocapsid structure, disperses better, and the thickness of clad is about 20nm.
Photoelectron spectroscopy the analysis showed that the iron particle surface is really by SiO
2Coat, that illustrate that present embodiment prepares is surperficial coated Si O
2Nanometer iron powder.
On the vibration magnetic determining device product is carried out Magnetic Measurement, coercivity still is 149.2Oe, and is suitable with the coercivity that does not coat preceding iron powder, and instruction card bread covers SiO
2Do not influence the magnetic of iron powder.
X-ray diffraction characterizes proof, places the surperficial coated Si O of 72h in air
2Iron powder still do not have oxidizedly, and the characteristic peak of the oxide of iron has appearred in the diffraction pattern of the iron powder that coats, illustrate iron powder surface coated Si O
2Can improve the antioxygenic property of iron powder.
Claims (4)
1, a kind of preparation method of nanometer iron powder, it is characterized in that: molysite is dissolved in the mixed solution of ethanol, water or second alcohol and water, the molar concentration that makes iron ion is 0.02-1.0mol/L, adding molal quantity is that iron ion 15-50 NaOH and hydrazine content doubly is that iron ion molal quantity 8-30 mass concentration doubly is the hydrazine hydrate solution of 50-80%, after stirring, be back to the mother liquor water white transparency 80-120 ℃ of heating; Product promptly obtains the nanometer iron powder of grey black through magnetic separation, washing, vacuum drying.
2, the preparation method of nanometer iron powder according to claim 1, be characterised in that ratio in polyvinylpyrrolidone and the amount of iron powder is 1-5% and cobalt salt and the ratio of iron powder amount is the ratio of 5-30%, to join in the ethanolic solution that contains polyvinylpyrrolidone 0.002-0.01mol/L and cobalt salt 0.01-0.06mol/L by the nanometer iron powder of claim 1 method preparation, be uniformly dispersed; Adding molal quantity is that cobalt ions 10-30 NaOH and hydrazine content doubly is that cobalt ions molal quantity 8-20 mass concentration doubly is the hydrazine hydrate solution of 50-80%, and 30-80 ℃ of water-bath is stirred to the mother liquor water white transparency, promptly obtains the nanometer iron powder that the surface coats the cobalt layer.
3, the preparation method of nanometer iron powder according to claim 1 is characterised in that in precious metal ion and iron atom mol ratio to be 1 ‰-1% ratio, and will join concentration by the nanometer iron powder of claim 1 method preparation is 1 * 10
-4-1 * 10
-3In the precious metal salt solution of mol/l,, or, promptly obtain the nanometer iron powder that the surface is coated with layer of precious metal with the electronic stirring 2-6h of the speed of 200-400r/min with the power ultrasonic 1-4h of 50-80W; Described noble metal comprises silver or palladium.
4, the preparation method of nanometer iron powder according to claim 1, be characterised in that and evenly spread to by the nanometer iron powder of claim 1 method preparation in the aqueous solution of polyvinylpyrrolidone that amount is iron powder 1-5%, the admixture quality is an iron powder 0.5-2.0 ethyl orthosilicate doubly, with ammoniacal liquor regulator solution pH value at 10.0-13.0, with the electronic stirring 12-36h of the speed of 200-400r/min, promptly obtain surperficial coated Si O under the room temperature
2Nanometer iron powder.
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Families Citing this family (13)
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| CN100406171C (en) * | 2006-04-07 | 2008-07-30 | 北京科技大学 | Process for preparing nano iron powder |
| CN100464908C (en) * | 2006-07-03 | 2009-03-04 | 南京大学 | Method for preparing nanometer zero-valent iron grain using improved liquid phase reduction method |
| CN100453220C (en) * | 2006-07-17 | 2009-01-21 | 南京大学 | Improved nanometer nulvalent iron particle and method for making same |
| CN100446900C (en) * | 2006-08-17 | 2008-12-31 | 王惠民 | Cutting production technology of metal nanometer powder zero boundry particle |
| CN101138792B (en) * | 2007-10-15 | 2010-11-10 | 吉林大学 | Novel process for preparing simple substance Fe nanometer particles at normal temperature and pressure in liquid phase original station |
| CN101386075B (en) * | 2008-10-23 | 2010-12-29 | 安徽工业大学 | Preparation method of nano ferrous powder |
| KR101576320B1 (en) * | 2008-10-24 | 2015-12-09 | 가부시키가이샤 닛신 세이훈 구루프혼샤 | Method for classifying powder |
| RU2565699C2 (en) * | 2009-10-27 | 2015-10-20 | Басф Се | Heat ageing-resistant polyamides |
| CN106493354B (en) * | 2016-10-24 | 2018-11-16 | 兰州大学 | The preparation method of the composite nano powder of oxide coated by zinc magnetic metal nano particle |
| CN108608004B (en) * | 2016-12-12 | 2021-11-02 | 昆明仁旺科技有限公司 | Preparation method of ultrathin palladium foil and palladium powder |
| CN107033386B (en) * | 2017-04-14 | 2019-06-14 | 长安大学 | Nanometer iron powder raising pitch is anti-aging or restores the application of road surface heavy metal ion |
| CN108018425A (en) * | 2017-12-08 | 2018-05-11 | 蒋央芳 | Preparation method of low-sulfur nano iron powder |
| CN113477937B (en) * | 2021-07-05 | 2023-04-07 | 扬州工业职业技术学院 | Method for green synthesis of composite nano iron particles and application thereof |
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| CN1280044A (en) * | 1999-07-08 | 2001-01-17 | 中国科学技术大学 | Chemicalpreparing method for nanometre metal iron powder |
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Patent Citations (6)
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| JPH06336601A (en) * | 1993-05-28 | 1994-12-06 | Sumitomo Metal Mining Co Ltd | Production of nickel powder |
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