CN1709799A - Method for preparing superfine/nano iron oxide/iron powder - Google Patents

Method for preparing superfine/nano iron oxide/iron powder Download PDF

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CN1709799A
CN1709799A CN 200410023302 CN200410023302A CN1709799A CN 1709799 A CN1709799 A CN 1709799A CN 200410023302 CN200410023302 CN 200410023302 CN 200410023302 A CN200410023302 A CN 200410023302A CN 1709799 A CN1709799 A CN 1709799A
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powder
ultra
fine
iron
nanometer
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CN1319864C (en
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范景莲
成会朝
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Central South University
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Central South University
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Abstract

The invention relates to the powder metallurgy domain, specially used in the preparation method of nano/superfine ferric oxide. Tts characteristic lies in: Uses Fe(NO)3 the crystal (Fe (NO3) 3 - 9H2O), the ferrous sulfate crystal (FecSO4 - 7H2O), the ferric chloride crystal (FeCl3 - 6H2O) as the raw material, which matches the density - 30wt% molysite solution; Joins the ammonia water and adjusts pH to 1.5-3; Then joins 0.1-1.0% surface active agent and 0.01-0.1% crystal grain inhibitor, vibrates 10 - 60min after the ultrasonic waving, obtains the transparent colloid; Then dry, then gets the superfine mix powder forerunner body; Under 350 - 700 DEG C temperatures for calcination, then obtains the nanometer / superfine ferric oxide powder. This invention preparation powder granularity is thin, which is smaller than 100nm, high purity which can reaches 99% - 99.5%, which is serviceable and makes the high performance magnetic powder and the absorbing material; The craft is simple, the process is easy to control, the powder output is high.

Description

A kind of ultra-fine/preparation method of nano-sized iron oxide/iron powder
Technical field:
The present invention relates to field of powder metallurgy, the method for the ultra-fine/nano-sized iron oxide that particularly adopts nanotechnology to prepare.
Background technology:
The PREPARATION OF NANO FERRIC OXIDE method can be divided into wet method (Wet Method) and dry method (Dry Method) generally.Wet method is many to be raw material with industrial green vitriol, industrial iron protochloride and iron nitrate, adopt preparations such as oxidation-precipitation method, hydrothermal method, force water solution, colloid chemistry method, its characteristics are exactly that raw material is easy to get and can directly uses (only need suitable purifying treatment), particle is controlled, but technological process is oversize, yields poorly down, and is strict to operating environment, the production cost height is difficult to be applied on the industrial production.Dry method is often with iron carbonyl (Fe (CO) 5) or ferrocene (FeCP 2) be raw material, adopt flame thermolysis, low-temperature plasma chemical Vapor deposition process (PCVP) or the preparation of LASER HEAT decomposition method, have advantages such as technical process weak point, good operational environment, quality product height, particle are ultra-fine evenly, good dispersity, but its technical difficulty is big simultaneously, structure and material to equipment require high, one-time investment is big, and is domestic very few to its research.
Summary of the invention:
The present invention fully utilizes the strong point of prior art, overcome its deficiency, adopt colloidal sol and drying process with atomizing technology to prepare crystallite or amorphous mixed powder presoma, powder is calcined, preparation purity height, grain-size or powder single particle granularity are the nanocrystalline ultra-fine croci of 15～30nm, the body of powder granularity is 1～1.5 μ m, by ball milling the granularity of body of powder is reduced to below the 100nm again, to satisfy the needs of electronics, Chemical Manufacture.
The present invention is for achieving the above object, and the scheme of employing is:
Adopt iron nitrate crystal (Fe (NO 3) 39H 2O), ferrous sulfate crystal (FeSO 47H 2O), iron(ic) chloride crystal (FeCl 36H 2O) be raw material, be mixed with the iron salt solutions of concentration for～30wt%;
Adding ammoniacal liquor adjusting pH in above-mentioned solution is 1.5～3; Add 0.1～1.0% tensio-active agent and 0.01～0.1% grain inhibitor again,, obtain transparent colloid through ultra-sonic oscillation 10～60min;
Then that transparent colloid is dry on spray-drier, make ultra-fine mixed powder presoma;
The ultra-fine mixed powder that spraying drying is obtained obtains nanometer/superfine iron oxide powder at 350～700 ℃ of temperature lower calcinations;
To carry out ball-milling technology through the powder that calcining obtains and handle, powder size is reduced to below the 100nm;
The ultrafine powder presoma that makes or brown iron oxide reduced under reducing atmosphere obtain superfine iron powder.
Tensio-active agent is polyoxyethylene glycol-400, polyoxyethylene glycol-1000, cetomacrogol 1000 0, N, dinethylformamide, ethylene glycol, urea, tartrate, the third three acid, dodecyl, sodium sulfonate, adjacent stupid dioctyl phthalate, dimethyl ester, Citrate trianion, phosphoric acid salt.
Grain inhibitor is SnCl 2, Cr2O 3
Advantage of the present invention and positively effect are embodied in:
(1) powder size of the present invention's preparation is thin, and less than 100nm, the purity height reaches 99%～99.5%, can be used as high performance magnetic powder and absorbing material.
(2) the present invention can prepare spherical powder or lamellar powder, and can control powder morphology.
(3) technology of the present invention is simple, and process is easy to control, and powder output is big, is fit to very much suitability for industrialized production.
(4) the present invention can make nanometer or ultra-fine serial brown iron oxide as Fe 3O 3, Fe 3O 4Powder.
(5) the prepared nano oxidized iron powder of the present invention can be carried out in a big way adjusting at aspect of performance, can prepare nonmagnetic to the very strong croci of magnetic.
Embodiment:
Example one:
Take by weighing 100gFe (NO 3) 39H 2O is dissolved in 500gH 2O;
Adding concentration is the ammoniacal liquor 120ml of 2.4wt%, is heated to 70 ℃ and makes it form Fe (OH) 3Colloid;
At Fe (OH) 3Add 0.5%N in the colloid, dinethylformamide, ultra-sonic oscillation 20min;
With colloid spraying drying in above-mentioned, obtain amorphous/crystallite nanometer mixed powder presoma;
With amorphous/crystallite nanometer mixed powder presoma, calcining temperature is 350 ℃ of calcinings, obtains ultra-fine/nanometer Fe 2O 3Powder;
To ultra-fine/nanometer Fe 2The O powder carries out ball milling, makes its granularity further refine to below the 100nm;
With powder presoma or Fe 2O 3Powder is at H 2Reduce under the atmosphere, reduction temperature is 500 ℃, further obtains ultra-fine Fe powder.
Example two:
(1) takes by weighing 100gFe (NO 3) 39H 2O and 50gFeS 47H 2O is dissolved in 600gH with it 2O;
(2) adding concentration is 2.4% ammoniacal liquor 300ml, and temperature is controlled at 40 ℃;
(3) add 0.5% polyoxyethylene glycol, 0.1% urea and 0.05%Cr 2O 3, through ultra-sonic oscillation 30min;
(4) the transparent colloid spraying drying be will obtain, amorphous or crystallite nanometer mixed powder presoma obtained;
(5) be 600 ℃ of O with the powder presoma in calcining temperature 2Calcine in the air atmosphere.Obtain ultra-fine/nanometer Fe 3O 4Powder;
(6) with powder presoma or nano level Fe 2O 3Powder is 400 ℃ in temperature, reduces in the hydrocarbon mixed gas, can further obtain ultra-fine Fe powder.

Claims (5)

1. the preparation method of ultra-fine/nano-sized iron oxide/iron powder is characterized in that: adopt iron nitrate crystal (Fe (NO 3) 39H 2O), ferrous sulfate crystal (FeSO 47H 2O), iron(ic) chloride crystal (FeCl 36H 2O) be raw material, be mixed with the iron salt solutions of concentration for～30wt%;
Adding ammoniacal liquor adjusting pH in above-mentioned solution is 1.5～3; Add 0.1～1.0% tensio-active agent and 0.01～0.1% grain inhibitor again,, obtain transparent colloid through ultra-sonic oscillation 10～60min;
Then that transparent colloid is dry on spray-drier, make ultra-fine mixed powder presoma;
The ultra-fine mixed powder that spraying drying is obtained obtains nanometer/superfine iron oxide powder at 350～700 ℃ of temperature lower calcinations;
To carry out ball-milling technology through the powder that calcining obtains and handle, powder size is reduced to below the 100nm;
The ultrafine powder presoma that makes or brown iron oxide reduced under reducing atmosphere obtain superfine iron powder.
As requested 1 described ultra-fine/preparation method of nano-sized iron oxide/iron powder, it is characterized in that: tensio-active agent is polyoxyethylene glycol-400, polyoxyethylene glycol-1000, cetomacrogol 1000 0, N, dinethylformamide, ethylene glycol, urea, tartrate, the third three acid, dodecyl, sodium sulfonate, adjacent stupid dioctyl phthalate, dimethyl ester, Citrate trianion, phosphoric acid salt.
As requested 1 described ultra-fine/preparation method of nano-sized iron oxide/iron powder, it is characterized in that: grain inhibitor is SnCl 2, Cr 2O 3
As requested 1 described ultra-fine/preparation method of nano-sized iron oxide/iron powder, it is characterized in that:
Take by weighing 100gFe (NO 3) 39H 2O is dissolved in 500gH 2O;
Adding concentration is the ammoniacal liquor 120ml of 2.4wt%, is heated to 70 ℃ and makes it form Fe (OH) 3Colloid;
At Fe (OH) 3Add 0.5%N in the colloid, dinethylformamide, ultra-sonic oscillation 20min;
With colloid spraying drying in above-mentioned, obtain amorphous/crystallite nanometer mixed powder presoma;
With amorphous/crystallite nanometer mixed powder presoma, calcining temperature is 350 ℃ of calcinings, obtains ultra-fine/nanometer Fe 2O 3Powder;
To ultra-fine/nanometer Fe 2The O powder carries out ball milling, makes its granularity further refine to below the 100nm;
With powder presoma or Fe 2O 3Powder is at H 2Reduce under the atmosphere, reduction temperature is 500 ℃, further obtains ultra-fine Fe powder.
As requested 1 described ultra-fine/preparation method of nano-sized iron oxide/iron powder, it is characterized in that:
(1) takes by weighing 100gFe (NO 3) 39H 2O and 50gFeS47H 2O is dissolved in 600gH with it 2O;
(2) adding concentration is 2.4% ammoniacal liquor 300ml, and temperature is controlled at 40 ℃;
(3) add 0.5% polyoxyethylene glycol, 0.1% urea and 0.05%Cr 2O 3, through ultra-sonic oscillation 30min;
(4) the transparent colloid spraying drying be will obtain, amorphous or crystallite nanometer mixed powder presoma obtained;
(5) be 600 ℃ of O with the powder presoma in calcining temperature 2Calcine in the air atmosphere.Obtain ultra-fine/nanometer Fe 3O 4Powder;
(6) with powder presoma or nano level Fe 2O 3Powder is 400 ℃ in temperature, reduces in the hydrocarbon mixed gas, can further obtain ultra-fine Fe powder.
CNB2004100233027A 2004-06-16 2004-06-16 Method for preparing superfine/nano iron oxide/iron powder Expired - Fee Related CN1319864C (en)

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CN100348501C (en) * 2006-01-10 2007-11-14 江苏天一超细金属粉末有限公司 Production and producer for nanometer ferric oxide
CN100406171C (en) * 2006-04-07 2008-07-30 北京科技大学 Process for preparing nano iron powder
CN100429152C (en) * 2006-11-21 2008-10-29 浙江大学 Process for preparing oxide nano sphere
CN101823767A (en) * 2010-05-17 2010-09-08 哈尔滨师范大学 Method for preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor
CN101664710B (en) * 2009-09-30 2011-02-16 南通宝聚颜料有限公司 Manufacturing method of ultra-fine iron oxide black
CN102470441A (en) * 2009-07-30 2012-05-23 国立大学法人京都大学 Metal nanoparticles, dispersion containing same, and process for production of same
CN102775739A (en) * 2012-08-17 2012-11-14 张宇 Composite wave-absorbing material adopting mesoporous silica foam material as matrix and preparation method of composite wave-absorbing material
CN103204547A (en) * 2012-01-16 2013-07-17 中国科学院化学研究所 Ferrum oxyhydroxide and ferrum oxide hierarchical nanostructured material, preparation methods and applications thereof
CN103833086A (en) * 2014-03-18 2014-06-04 济南大学 Preparation method of flaky iron trioxide
CN103898736A (en) * 2014-01-23 2014-07-02 上海嘉乐股份有限公司 Anti-radiation finishing processing method for fabric
CN103922421A (en) * 2014-05-13 2014-07-16 西北大学 Method for preparing alpha-Fe2O3
CN104058464A (en) * 2014-06-09 2014-09-24 青岛东方循环能源有限公司 Method for preparing nano ferric oxide
CN104839202A (en) * 2015-05-05 2015-08-19 贺州学院 Nanometer iron oxide composite triazophos type pesticide and preparation method thereof
CN107244698A (en) * 2017-06-17 2017-10-13 常州帝君金属构件厂 A kind of preparation method of iron oxide red
WO2018177177A1 (en) * 2017-03-31 2018-10-04 深圳光启高等理工研究院 Method for preparing wave-absorbing material, and wave-absorbing coating
CN111733430A (en) * 2020-07-31 2020-10-02 北京化工大学 Fe-Fe3O4 composite anode and method for preparing ferrate by electrolyzing same
CN114560505A (en) * 2022-03-03 2022-05-31 华鼎国联四川电池材料有限公司 Preparation method of lithium ion battery positive electrode additive and lithium supplementing method
WO2024021231A1 (en) * 2022-07-28 2024-02-01 广东邦普循环科技有限公司 Preparation method for high-capacity battery active material and use thereof

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CN1312224A (en) * 2000-10-16 2001-09-12 童忠良 Liquid phase synthesis process of producing nanometer iron oxide red
CN1386710A (en) * 2001-05-21 2002-12-25 邵建华 Process for preparing superfine iron oxide
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CN100348501C (en) * 2006-01-10 2007-11-14 江苏天一超细金属粉末有限公司 Production and producer for nanometer ferric oxide
CN100406171C (en) * 2006-04-07 2008-07-30 北京科技大学 Process for preparing nano iron powder
CN100429152C (en) * 2006-11-21 2008-10-29 浙江大学 Process for preparing oxide nano sphere
CN102470441A (en) * 2009-07-30 2012-05-23 国立大学法人京都大学 Metal nanoparticles, dispersion containing same, and process for production of same
CN102470441B (en) * 2009-07-30 2013-10-30 国立大学法人京都大学 Metal nanoparticles, dispersion containing same, and process for production of same
CN101664710B (en) * 2009-09-30 2011-02-16 南通宝聚颜料有限公司 Manufacturing method of ultra-fine iron oxide black
CN101823767A (en) * 2010-05-17 2010-09-08 哈尔滨师范大学 Method for preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor
CN103204547A (en) * 2012-01-16 2013-07-17 中国科学院化学研究所 Ferrum oxyhydroxide and ferrum oxide hierarchical nanostructured material, preparation methods and applications thereof
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CN103833086A (en) * 2014-03-18 2014-06-04 济南大学 Preparation method of flaky iron trioxide
CN103922421B (en) * 2014-05-13 2017-05-03 西北大学 Method for preparing alpha-Fe2O3
CN103922421A (en) * 2014-05-13 2014-07-16 西北大学 Method for preparing alpha-Fe2O3
CN104058464A (en) * 2014-06-09 2014-09-24 青岛东方循环能源有限公司 Method for preparing nano ferric oxide
CN104058464B (en) * 2014-06-09 2016-05-11 青岛东方循环能源有限公司 A kind of method of preparing nano-sized iron oxide
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CN111733430A (en) * 2020-07-31 2020-10-02 北京化工大学 Fe-Fe3O4 composite anode and method for preparing ferrate by electrolyzing same
CN111733430B (en) * 2020-07-31 2022-08-05 北京化工大学 Fe-Fe 3 O 4 Composite anode and method for preparing ferrate by electrolysis of composite anode
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