CN102180522A - Controllable preparation method of nano magnetic iron oxide with narrow particle size distribution - Google Patents
Controllable preparation method of nano magnetic iron oxide with narrow particle size distribution Download PDFInfo
- Publication number
- CN102180522A CN102180522A CN 201110075659 CN201110075659A CN102180522A CN 102180522 A CN102180522 A CN 102180522A CN 201110075659 CN201110075659 CN 201110075659 CN 201110075659 A CN201110075659 A CN 201110075659A CN 102180522 A CN102180522 A CN 102180522A
- Authority
- CN
- China
- Prior art keywords
- solution
- iron oxide
- size distribution
- coo
- magnetic iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention provides a controllable preparation method of nano magnetic iron oxide with narrow particle size distribution. By using the method, the nucleation process of the iron oxide can be controlled and the distribution of the prepared nano powder particle size is extremely narrow. The method comprises the following steps: carrying out ultrasound treatment in a high-concentration NaOH solution so as to form a Fe[CH3(CH2)7CH=CH(CH2)7COO]n micelle, thereby effectively protecting the aggregation and precipitation of Fe<2+>; adding hydrazine hydrate so as to inhibit oxidation of Fe<2+> and form extremely good dispersion under the condition of hydrothermal; and diluting the obtain transparent concentrated base solution so as to slowly form a Fe(OH)x[CH3(CH2)7CH=CH(CH2)7COO]2-x (x is larger than 0 and less than 2) gel micelle, then oxidizing and dehydrating so as to form FeO(OH)y[CH3(CH2)7CH-CH(CH2)7COO]1-y (y is more than 0 and less than 1), and finally sintering at the atmosphere of mixing Ar and H2 for removing surface organics and water, so as to form gamma-Fe2O3.
Description
[technical field]
The invention belongs to wet chemistry method and prepare the nano-powder technical field, be specifically related to a kind of preparation method of nano magnetic iron oxide.
[background technology]
Nano magnetic iron oxide (γ-Fe
2O
3) be important magneticsubstance, crossing aspects such as heat cure in the tumour of energy storage, electrochemical sensor, alternating magnetic field all has important use.The PREPARATION OF NANO FERRIC OXIDE method of having reported at present all can obtain nano particle, but still can not obtain satisfactory result aspect particle size and the nucleating growth controllability.As, Li Yuehuas etc. are with Fe
3O
4Be raw material, prepared γ-Fe by air oxidation process
2O
3, but its particle diameter is bigger, and distribution range is very wide, between 30-400nm.Chinese patent is announced CN100436334C number and has been reported that a kind of is the feedstock production magnetic Fe with converter slag
2O
3Method.By slag is ground, pickling is leached and is made FeSO
4Solution then with obtaining precipitation after the alkaline purification, adds crystal seed at last and forms γ-Fe through high temperature crystallization
2O
3Though method can obtain high-purity powder, but still owing to obtain by intermediate processing, nucleation process is uncontrollable, and the particle diameter of acquisition is bigger.In addition, also need to add crystal seed.
Reference:
Li Yuehua, etc. nanometer γ-Fe
2O
3The preparation of particle and magnetic behavior thereof, functional materials, 2007,38 (supplementary issue): 1981-1983.
Liu Chengjun, etc. a kind of preparation method who is used to make the high purity magnetic material nano ferric oxide, Chinese invention patent, CN100436334C, 2007.
[summary of the invention]
The preparation method who the purpose of this invention is to provide a kind of narrow size distribution nano-magnetic ferric oxide has solved nucleation and the uncontrollable problem of growth, and the nanoparticle size of preparation distributes very narrow.
To achieve these goals, the present invention adopts following technical scheme:
A kind of controllable method for preparing of narrow size distribution nano magnetic iron oxide may further comprise the steps:
1) with FeSO
47H
2O and NaOH are dissolved in respectively in the equal-volume distilled water, and it is 0.5～5 * 10 that the dissolving back forms concentration
-3The FeSO of mol/L
4Solution and concentration are the NaOH solution of 10～14mol/L;
2) FeSO that step 1 is disposed
4Solution is dissolved in the NaOH solution of step 1 configuration, and supersound process is up to obtaining transparent solution;
3) in the clear solution that step 2 obtains, add sodium oleate and form mixing solutions, control oleic acid root and FeSO
4Mol ratio be 0.83～1.5;
4) with the mixing solutions of step 3, ultra-sonic dispersion is to oleic acid root and Fe
2+Formed the grey micella;
5) add hydrazine hydrate in the mixing solutions that step 4 forms, the volume that adds hydrazine hydrate is to dispose FeSO in the step 1
42.5%～5% of solution and the used distilled water volume of NaOH solution sum; Supersound process forms the grey spherical particle to forming a large amount of grey micellas after the grey micella is reunited then;
6) solution that step 5 is obtained moves in the Teflon water heating kettle, and packing ratio is 20%～60%, is incubated 24～48 hours down at 140～180 ℃; The heating back forms clear solution;
7) clear solution that step 6 is obtained with distilled water diluting after, place the air at room temperature slow oxidation, generate colloid Fe (OH)
x[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
2-x, slow oxidation and dehydration generate FeO (OH) then
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y
8) FeO (OH) that step 7 is prepared
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-yAfter the centrifugal settling, vacuum-drying obtains nanometer Fe O (OH)
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-yPowder;
9) with the nanometer Fe O (OH) of step 8
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-yPowder calcination is removed the residual organic matter on surface, obtains γ-Fe
2O
3Powder;
0＜x＜2,0＜y＜1 wherein.
The frequency of supersound process described in ultra-sonic dispersion described in supersound process, the step 4 and the step 5 is 39.48～44.52kHz described in the step 2.
The time of ultra-sonic dispersion is 5 minutes in the step 4, and the time of supersound process is 30～60 minutes in the step 5.
Temperature rise rate when heating in the step 6 is 10 ℃/min.
Clear solution is 1: 20 with the Dilution ratio that distilled water diluting adopted in the step 7.
The clear solution that in the step 7 step 6 is obtained with distilled water diluting after, the time that places the air at room temperature slow oxidation is 24～48 hours.
Vacuum drying condition is in the step 8: 50 ℃ of temperature, 22～50 hours time.
The incinerating condition is in the step 9: at 95%Ar+5H
2Calcined 20～40 minutes in 480～500 ℃ in the % atmosphere.
Compared with prior art, the present invention has the following advantages: the nucleation process that the inventive method can controlled oxidation iron, the particle diameter of nanometer powder of preparation distributes very narrow, at 16nm between the 21nm.Form Fe[CH by supersound process in high density NaOH solution
3(CH
2)
7CH=CH (CH
2)
7COO]
nMicella, and then protect Fe effectively
2+Gathering and precipitation.Add hydrazine hydrate in the process and suppress Fe
2+Oxidation forms fabulous dispersion then under hydrothermal condition.The transparent concentrated alkali solution that obtains slowly forms Fe (OH) through the dilution back
x[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
2-x(0＜x＜2) gel strands, oxidation and dehydration form nanometer Fe O (OH) then
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1) is at last at Ar and H
2Mixed atmosphere under sintering remove surface organic matter and surface-moisture forms nanometer γ-Fe
2O
3
[description of drawings]
Fig. 1 is preparation technology's schema;
Fig. 2 is the X-ray diffraction spectrogram of embodiment 4 preparation powders;
Fig. 3 is the transmission electron microscope picture of embodiment 1 preparation powder;
Fig. 4 is the size distribution figure of embodiment 3 preparation powders.
[embodiment]
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
First part: the step that the inventive method is complete is described.
See also shown in Figure 1ly, the present invention mainly may further comprise the steps:
(1) with a certain amount of FeSO
47H
2O and NaOH are dissolved in respectively in isopyknic distilled water, and the dissolving back forms clear solution, FeSO in the solution
4Be respectively 0.5～5 * 10 with NaOH concentration
-3Mol/L and 10～14mol/L.
(2) FeSO that step 1 is disposed
4Solution is dissolved in the concentrated NaOH solution of step 1 configuration, and supersound process can not form precipitation up to obtaining transparent solution in this step.Supersound process is carried out (model: 5510J-MT, output rating: 135W, operating frequency: 39.48～44.52kHz) in the ultrasonic generator that U.S. Brason Ultrasonics Corporation produces.
(3) a certain amount of sodium oleate is added in the clear solution of step 2 acquisition control oleic acid root and FeSO
4Mol ratio be 0.83～1.5.
(4) with the mixing solutions of step 3, ultra-sonic dispersion is after 5 minutes, oleic acid root and Fe
2+Formed the grey micella.Supersound process is carried out (model: 5510J-MT, output rating: 135W, operating frequency: 39.48～44.52kHz) in the ultrasonic generator that U.S. Brason Ultrasonics Corporation produces.
(5) add hydrazine hydrate in step 4, the volume that adds hydrazine hydrate is to dispose FeSO in the step 1
42.5%～5% of solution and the used distilled water volume of NaOH solution sum; Supersound process is 30～60 minutes then, forms a large amount of grey micellas, forms the grey spherical particle after the grey micella is reunited.
(6) solution that step 5 is obtained moves into the Teflon water heating kettle, and packing ratio is 20%～60%, is incubated 24～48 hours down at 140～180 ℃, and temperature rise rate is 10 ℃/min.
(7) clear solution that step 6 is obtained with distilled water diluting after (ratio of dilution is 1: 20), place the air at room temperature slow oxidation, the time is 24～48 hours, generates colloid Fe (OH)
x[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
2-x(0＜x＜2), slow oxidation and dehydration generate FeO (OH) then
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1).
(8) FeO (OH) that step 7 is prepared
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-yAfter (0＜y＜1) centrifugal settling,, obtain nanometer Fe O (OH) 50 ℃ of following vacuum-dryings 22～50 hours
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-yPowder.
(9) with the nanometer Fe O (OH) of step 8
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-yPowder is at 95%Ar+5H
2After 20～40 minutes, remove the residual organic matter on surface in 480～500 ℃ of calcinings in the % atmosphere, obtain γ-Fe
2O
3Powder.
Second section:
Can control nucleation and process of growth fully by this method, and then the control reaction process.Reaction process can be write as:
Fe
2++x(OH)
-+(2-x)[CH
3(CH
2)
7CH＝CH(CH
2)
7COO]
-
Fe
2+(OH)
x[CH
3(CH
2)
7CH＝CH(CH
2)
7COO]
2-x
Fe
2+(OH)
x[CH
3(CH
2)
7CH＝CH(CH
2)
7COO]
2-x
Fe
3+O(OH)
y[CH
3(CH
2)
7CH＝CH(CH
2)
7COO]
1-y
Fe
3+O(OH)
y[CH
3(CH
2)
7CH＝CH(CH
2)
7COO]
1-y
(3)
Third part:
Enumerate various embodiment
Embodiment 1
(1) with a certain amount of FeSO
47H
2O and NaOH are dissolved in 50ml distilled water respectively, and the dissolving back forms clear solution, FeSO in the solution
4Be respectively 0.5 * 10 with NaOH concentration
-3Mol/L and 10mol/L.
(2) FeSO that step 1 is disposed
4Solution is dissolved in the NaOH solution of step 1 configuration, and supersound process can not form precipitation up to obtaining transparent solution in this step.Supersound process is carried out (model: 5510J-MT, output rating: 135W, operating frequency: 40kHz) in the ultrasonic generator that U.S. Brason Ultrasonics Corporation produces.
(3) a certain amount of sodium oleate is added in the clear solution of step 2 acquisition control oleic acid root and FeSO
4Mol ratio be 1.
(4) with the mixing solutions of step 3, ultra-sonic dispersion is after 5 minutes, oleic acid root and Fe
2+Formed micella.Supersound process is carried out (model: 5510J-MT, output rating: 135W, operating frequency: 40kHz) in the ultrasonic generator that U.S. Brason Ultrasonics Corporation produces.
(5) add hydrazine hydrate in the mixing solutions that step 4 forms, the volume that adds hydrazine hydrate is to dispose FeSO in the step 1
42.5% of solution and the used distilled water volume of NaOH solution sum, i.e. 2.5ml, supersound process is 30 minutes then, forms a large amount of grey micellas, and the grey micella back of reuniting forms the grey spherical particle.
(6) solution that step 5 is obtained moves into the Teflon water heating kettle, and packing ratio is 20%, is incubated 24 hours down at 140 ℃, and temperature rise rate is 10 ℃/min; The heating back forms clear solution;
(7) clear solution that step 6 is obtained with distilled water diluting after (ratio of dilution is 1: 20), place the air at room temperature slow oxidation, the time is 24 hours, generates colloid Fe (OH)
x[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
2-x(0＜x＜2), slow oxidation and dehydration generate FeO (OH) then
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1).
(8) FeO (OH) that step 7 is prepared
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-yAfter (0＜y＜1) centrifugal settling,, obtain nanometer Fe O (OH) 50 ℃ of following vacuum-dryings 22 hours
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1) powder.
(9) with the nanometer Fe O (OH) of step 8
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1) powder is at 95%Ar+5H
2After 20 minutes, remove the residual organic matter on surface in 480 ℃ of calcinings in the % atmosphere, obtaining the particle median size is γ-Fe of 16nm
2O
3Powder.
(1) with a certain amount of FeSO
47H
2O and NaOH are dissolved in 50ml distilled water respectively, and the dissolving back forms clear solution, FeSO in the solution
4Be respectively 5 * 10 with NaOH concentration
-3Mol/L and 14mol/L.
(2) FeSO that step 1 is disposed
4Solution is dissolved in the NaOH solution of step 1 configuration, and supersound process can not form precipitation up to obtaining transparent solution in this step.Supersound process is carried out (model: 5510J-MT, output rating: 135W, operating frequency: 42kHz) in the ultrasonic generator that U.S. Brason Ultrasonics Corporation produces.
(3) a certain amount of aqueous solution sodium oleate is added in the clear solution of step 2 acquisition control oleic acid root and FeSO
4Mol ratio be 1.5.
(4) with the mixing solutions of step 3, ultra-sonic dispersion is after 5 minutes, oleic acid root and Fe
2+Formed micella.Supersound process is carried out (model: 5510J-MT, output rating: 135W, operating frequency: 42kHz) in the ultrasonic generator that U.S. Brason Ultrasonics Corporation produces.
(5) add hydrazine hydrate in the mixing solutions that step 4 forms, the volume that adds hydrazine hydrate is to dispose FeSO in the step 1
45% of solution and the used distilled water volume of NaOH solution sum, i.e. 5ml, supersound process is 60 minutes then, forms a large amount of grey micellas, and the grey micella back of reuniting forms the grey spherical particle.
(6) solution that step 5 is obtained moves into the Teflon water heating kettle, and packing ratio is 60%, is incubated 48 hours down at 180 ℃, and temperature rise rate is 10 ℃/min; The heating back forms clear solution;
(7) clear solution that step 6 is obtained with distilled water diluting after (ratio of dilution is 1: 20), place the air at room temperature slow oxidation, the time is 48 hours, generates colloid Fe (OH)
x[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
2-x(0＜x＜2), slow oxidation and dehydration generate FeO (OH) then
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1).
(8) FeO (OH) that step 7 is prepared
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-yAfter (0＜y＜1) centrifugal settling,, obtain nanometer Fe O (OH) 50 ℃ of following vacuum-dryings 50 hours
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1) powder.
(9) with the nanometer Fe O (OH) of step 8
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1) powder is at 95%Ar+5H
2After 40 minutes, remove the residual organic matter on surface in 500 ℃ of calcinings in the % atmosphere, obtaining the particle median size is γ-Fe of 19nm
2O
3Powder.
Embodiment 3
(1) with a certain amount of FeSO
47H
2O and NaOH are dissolved in 50ml distilled water respectively, and the dissolving back forms clear solution, FeSO in the solution
4Be respectively 1.5 * 10 with NaOH concentration
-3Mol/L and 12mol/L.
(2) FeSO that step 1 is disposed
4Solution is dissolved in the NaOH solution of step 1 configuration, and supersound process can not form precipitation up to obtaining transparent solution in this step.Supersound process is carried out (model: 5510J-MT, output rating: 135W, operating frequency: 42kHz) in the ultrasonic generator that U.S. Brason Ultrasonics Corporation produces.
(3) a certain amount of sodium oleate is added in the clear solution of step 2 acquisition control oleic acid root and FeSO
4Mol ratio be 1.07.
(4) with the mixing solutions of step 3, ultra-sonic dispersion is after 5 minutes, oleic acid root and Fe
2+Formed micella.Supersound process is carried out (model: 5510J-MT, output rating: 135W, operating frequency: 42kHz) in the ultrasonic generator that U.S. Brason Ultrasonics Corporation produces.
(5) add hydrazine hydrate in the mixing solutions that step 4 forms, the volume that adds hydrazine hydrate is to dispose FeSO in the step 1
43% of solution and the used distilled water volume of NaOH solution sum, i.e. 3ml, supersound process is 60 minutes then, forms a large amount of grey micellas, and the grey micella back of reuniting forms the grey spherical particle.
(6) solution that step 5 is obtained moves into the Teflon water heating kettle, and packing ratio is 50%, is incubated 24 hours down at 160 ℃, and temperature rise rate is 10 ℃/min.The heating back forms clear solution;
(7) clear solution that step 6 is obtained with distilled water diluting after (ratio of dilution is 1: 20), place the air at room temperature slow oxidation, the time is 36 hours, generates colloid Fe (OH)
x[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
2-x(0＜x＜2), slow oxidation and dehydration generate FeO (OH) then
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1).
(8) FeO (OH) that step 7 is prepared
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-yAfter (0＜y＜1) centrifugal settling,, obtain nanometer Fe O (OH) 50 ℃ of following vacuum-dryings 26 hours
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1) powder.
(9) with the nanometer Fe O (OH) of step 8
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1) powder is at 95%Ar+5H
2After 30 minutes, remove the residual organic matter on surface in 500 ℃ of calcinings in the % atmosphere, obtaining the particle median size is γ-Fe of 18.5nm
2O
3Powder.
(1) with a certain amount of FeSO
47H
2O and NaOH are dissolved in 50ml distilled water respectively, and the dissolving back forms clear solution, FeSO in the solution
4Be respectively 3 * 10 with NaOH concentration
-3Mol/L and 13mol/L.
(2) FeSO that step 1 is disposed
4Solution is dissolved in the NaOH solution of step 1 configuration, and supersound process can not form precipitation up to obtaining transparent solution in this step.Supersound process is carried out (model: 5510J-MT, output rating: 135W, operating frequency: 44kHz) in the ultrasonic generator that U.S. Brason Ultrasonics Corporation produces.
(3) a certain amount of sodium oleate is added in the clear solution of step 2 acquisition control oleic acid root and FeSO
4Mol ratio be 1.17.
(4) with the mixing solutions of step 3, ultra-sonic dispersion formed the grey micella after 5 minutes, showed oleic acid root and Fe
2+Formed micella.Supersound process is carried out (model: 5510J-MT, output rating: 135W, operating frequency: 44kHz) in the ultrasonic generator that U.S. Brason Ultrasonics Corporation produces.
(5) add hydrazine hydrate in the mixing solutions that step 4 forms, the volume that adds hydrazine hydrate is to dispose FeSO in the step 1
42.5% of solution and the used distilled water volume of NaOH solution sum, i.e. 2.5ml, supersound process is 30 minutes then, forms a large amount of grey micellas, and the grey micella back of reuniting forms the grey spherical particle.
(6) solution that step 5 is obtained moves into the Teflon water heating kettle, and packing ratio is 60%, is incubated 20 hours down at 180 ℃, and temperature rise rate is 10 ℃/min; The heating back forms clear solution;
(7) clear solution that step 6 is obtained with distilled water diluting after (ratio of dilution is 1: 20), place the air at room temperature slow oxidation, the time is 24 hours, generates colloid Fe (OH)
x[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
2-x(0＜x＜2), slow oxidation and dehydration generate FeO (OH) then
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1).
(8) FeO (OH) that step 7 is prepared
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-yAfter (0＜y＜1) centrifugal settling,, obtain nanometer Fe O (OH) 50 ℃ of following vacuum-dryings 30 hours
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1) powder.
(9) with the nanometer Fe O (OH) of step 8
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1) powder is at 95%Ar+5H
2After 30 minutes, remove the residual organic matter on surface in 510 ℃ of calcinings in the % atmosphere, obtaining the particle median size is γ-Fe of 19.6nm
2O
3Powder.
Embodiment 5
(1) with a certain amount of FeSO
47H
2O and NaOH are dissolved in 50ml distilled water respectively, and the dissolving back forms clear solution, FeSO in the solution
4Be respectively 3.0 * 10 with NaOH concentration
-3Mol/L and 11.5mol/L.
(2) FeSO that step 1 is disposed
4Solution is dissolved in the NaOH solution of step 1 configuration, and supersound process can not form precipitation up to obtaining transparent solution in this step.Supersound process is carried out (model: 5510J-MT, output rating: 135W, operating frequency: 44.52kHz) in the ultrasonic generator that U.S. Brason Ultrasonics Corporation produces.
(3) a certain amount of sodium oleate is added in the clear solution of step 2 acquisition control oleic acid root and FeSO
4Mol ratio be 0.83.
(4) with the mixing solutions of step 3, ultra-sonic dispersion is after 5 minutes, oleic acid root and Fe
2+Formed micella.Supersound process is carried out (model: 5510J-MT, output rating: 135W, operating frequency: 44.52kHz) in the ultrasonic generator that U.S. Brason Ultrasonics Corporation produces.
(5) add hydrazine hydrate in the mixing solutions that step 4 forms, the volume that adds hydrazine hydrate is to dispose FeSO in the step 1
45% of solution and the used distilled water volume of NaOH solution sum, i.e. 5ml, supersound process is 55 minutes then, forms a large amount of grey micellas, and the grey micella back of reuniting forms the grey spherical particle.
(6) solution that step 5 is obtained moves into the Teflon water heating kettle, and packing ratio is 60%, is incubated 10 hours down at 180 ℃, and temperature rise rate is 10 ℃/min; The heating back forms clear solution.
(7) clear solution that step 6 is obtained with distilled water diluting after (ratio of dilution is 1: 20), place the air at room temperature slow oxidation, the time is 35 hours, generates colloid Fe (OH)
x[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
2-x(0＜x＜2), slow oxidation and dehydration generate FeO (OH) then
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1).
(8) FeO (OH) that step 7 is prepared
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-yAfter (0＜y＜1) centrifugal settling,, obtain nanometer Fe O (OH) 50 ℃ of following vacuum-dryings 24 hours
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1) powder.
(9) with the nanometer Fe O (OH) of step 8
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y(0＜y＜1) powder is at 95%Ar+5H
2After 30 minutes, remove the residual organic matter on surface in 505 ℃ of calcinings in the % atmosphere, obtaining particle diameter is γ-Fe of 21nm
2O
3Powder.
The 4th part:
See also shown in Figure 2ly, be the nanometer γ-Fe of embodiment 4 preparations
2O
3X ray diffracting spectrum, X ray test is the result show, the nano-powder perfect crystalline of preparation is the γ-Fe of cubic phase
2O
3See also shown in Figure 3ly, be the nanometer γ-Fe of embodiment 1 preparation
2O
3Transmission electron microscope picture, as can be seen from the figure, the nano particle diameter of the inventive method preparation distributes very narrow, between 16nm to 21nm.See also shown in Figure 4ly, be the nanometer γ-Fe of embodiment 3 preparations
2O
3Size distribution figure, size distribution is very narrow as can be seen, between 16.0nm to 20nm, mainly concentrates between the 17.0nm to 19.5nm.
Claims (8)
1. the controllable method for preparing of a narrow size distribution nano magnetic iron oxide is characterized in that, may further comprise the steps:
1) with FeSO
47H
2O and NaOH are dissolved in respectively in the equal-volume distilled water, and it is 0.5～5 * 10 that the dissolving back forms concentration
-3The FeSO of mol/L
4Solution and concentration are the NaOH solution of 10～14mol/L;
2) FeSO that step 1 is disposed
4Solution is dissolved in the NaOH solution of step 1 configuration, and supersound process is up to obtaining transparent solution;
3) in the clear solution that step 2 obtains, add sodium oleate and form mixing solutions, control oleic acid root and FeSO
4Mol ratio be 0.83～1.5;
4) with the mixing solutions of step 3, ultra-sonic dispersion is to oleic acid root and Fe
2+Formed the grey micella;
5) add hydrazine hydrate in the mixing solutions that step 4 forms, the volume that adds hydrazine hydrate is to dispose FeSO in the step 1
42.5%～5% of solution and the used distilled water volume of NaOH solution sum; Supersound process forms the grey spherical particle to forming a large amount of grey micellas after the grey micella is reunited then;
6) solution that step 5 is obtained moves in the Teflon water heating kettle, and packing ratio is 20%～60%, is incubated 24～48 hours down at 140～180 ℃; The heating back forms clear solution;
7) clear solution that step 6 is obtained with distilled water diluting after, place the air at room temperature slow oxidation, generate colloid Fe (OH)
x[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
2-x, slow oxidation and dehydration generate FeO (OH) then
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-y
8) FeO (OH) that step 7 is prepared
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-yAfter the centrifugal settling, vacuum-drying obtains nanometer Fe O (OH)
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-yPowder;
9) with the nanometer Fe O (OH) of step 8
y[CH
3(CH
2)
7CH=CH (CH
2)
7COO]
1-yPowder calcination is removed the residual organic matter on surface, obtains γ-Fe
2O
3Powder;
0＜x＜2,0＜y＜1 wherein.
2. a kind of according to claim 1 controllable method for preparing of narrow size distribution nano magnetic iron oxide, it is characterized in that: the frequency of supersound process described in ultra-sonic dispersion described in supersound process, the step 4 and the step 5 is 39.48～44.52kHz described in the step 2.
3. as the controllable method for preparing of a kind of narrow size distribution nano magnetic iron oxide as described in the claim 2, it is characterized in that: the time of ultra-sonic dispersion is 5 minutes in the step 4, and the time of supersound process is 30～60 minutes in the step 5.
4. a kind of according to claim 1 controllable method for preparing of narrow size distribution nano magnetic iron oxide is characterized in that: the temperature rise rate in the step 6 during heating is 10 ℃/min.
5. a kind of according to claim 1 controllable method for preparing of narrow size distribution nano magnetic iron oxide, it is characterized in that: clear solution is 1: 20 with the Dilution ratio that distilled water diluting adopted in the step 7.
6. a kind of according to claim 1 controllable method for preparing of narrow size distribution nano magnetic iron oxide is characterized in that: the clear solution that in the step 7 step 6 is obtained with distilled water diluting after, the time that places the air at room temperature slow oxidation is 24～48 hours.
7. a kind of according to claim 1 controllable method for preparing of narrow size distribution nano magnetic iron oxide is characterized in that, vacuum drying condition is in the step 8: 50 ℃ of temperature, 22～50 hours time.
8. a kind of according to claim 1 controllable method for preparing of narrow size distribution nano magnetic iron oxide is characterized in that, the incinerating condition is in the step 9: at 95%Ar+5H
2Calcined 20～40 minutes in 480～500 ℃ in the % atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110075659XA CN102180522B (en) | 2011-03-28 | 2011-03-28 | Controllable preparation method of nano magnetic iron oxide with narrow particle size distribution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110075659XA CN102180522B (en) | 2011-03-28 | 2011-03-28 | Controllable preparation method of nano magnetic iron oxide with narrow particle size distribution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102180522A true CN102180522A (en) | 2011-09-14 |
| CN102180522B CN102180522B (en) | 2012-11-28 |
Family
ID=44566849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110075659XA Expired - Fee Related CN102180522B (en) | 2011-03-28 | 2011-03-28 | Controllable preparation method of nano magnetic iron oxide with narrow particle size distribution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102180522B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103084147A (en) * | 2011-11-08 | 2013-05-08 | 纳科石油化工有限公司 | Iron oxide magnetic nano particle, preparation method and application method thereof in desulfurization |
| CN103204550A (en) * | 2013-04-12 | 2013-07-17 | 陕西科技大学 | Controllable preparation method of micron-order Fe2O3 |
| CN105749864A (en) * | 2016-04-13 | 2016-07-13 | 西安近代化学研究所 | Preparation method of high-specific-area magnetic adsorbent or magnetic catalyst support |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4512906A (en) * | 1981-10-16 | 1985-04-23 | Central Glass Company Limited | Wet process for preparing ferrites of magnetoplumbite structure in fine particle form |
| CN101003388A (en) * | 2006-12-30 | 2007-07-25 | 中国科学技术大学 | Method for preparing Nano cube of hematite |
| CN101269843A (en) * | 2008-05-06 | 2008-09-24 | 华东理工大学 | Method for preparing iron oxide nano-wire |
-
2011
- 2011-03-28 CN CN201110075659XA patent/CN102180522B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4512906A (en) * | 1981-10-16 | 1985-04-23 | Central Glass Company Limited | Wet process for preparing ferrites of magnetoplumbite structure in fine particle form |
| CN101003388A (en) * | 2006-12-30 | 2007-07-25 | 中国科学技术大学 | Method for preparing Nano cube of hematite |
| CN101269843A (en) * | 2008-05-06 | 2008-09-24 | 华东理工大学 | Method for preparing iron oxide nano-wire |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103084147A (en) * | 2011-11-08 | 2013-05-08 | 纳科石油化工有限公司 | Iron oxide magnetic nano particle, preparation method and application method thereof in desulfurization |
| CN103084147B (en) * | 2011-11-08 | 2015-02-25 | 纳科石油化工有限公司 | Iron oxide magnetic nano particle, preparation method and application method thereof in desulfurization |
| CN103204550A (en) * | 2013-04-12 | 2013-07-17 | 陕西科技大学 | Controllable preparation method of micron-order Fe2O3 |
| CN105749864A (en) * | 2016-04-13 | 2016-07-13 | 西安近代化学研究所 | Preparation method of high-specific-area magnetic adsorbent or magnetic catalyst support |
| CN105749864B (en) * | 2016-04-13 | 2018-10-12 | 西安近代化学研究所 | A kind of preparation method of high-specific surface area magnetic adsorbent or magnetic catalyst carrier |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102180522B (en) | 2012-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1333474C (en) | Preparation method of spinel lithium titanate nano tube/wire for lithium battery and capacitor | |
| CN101830516B (en) | Method for preparing nano ferroferric oxide particles | |
| CN101717122B (en) | Method for preparing ferroferric oxide nano-piece through microwave method | |
| Giannakoudakis et al. | Mechanochemical forces as a synthetic tool for zeroand one-dimensional titanium oxide-based nano-photocatalysts | |
| Zhang et al. | Facile hydrothermal synthesis and photocatalytic activity of rod-like nanosized silver tungstate | |
| Liu et al. | Ultrasonic-assisted ultra-rapid synthesis of monodisperse meso-SiO2@ Fe3O4 microspheres with enhanced mesoporous structure | |
| CN104609476B (en) | Method for using single-walled carbon nanotube as axis for preparation of coaxial composite nanowires | |
| Mandal et al. | Facile route to the synthesis of porous α-Fe2O3 nanorods | |
| CN107098341B (en) | The preparation method of the agent of graphene oxide Hydrothermal Template and its nanocomposite | |
| CN103447549A (en) | Preparation method of cobalt nanosphere | |
| Zhou et al. | Template-free synthesis and photocatalytic activity of hierarchical hollow ZnO microspheres composed of radially aligned nanorods | |
| CN102180522B (en) | Controllable preparation method of nano magnetic iron oxide with narrow particle size distribution | |
| Li et al. | TEA-assisted synthesis of single-crystalline Mn3O4 octahedrons and their magnetic properties | |
| Tang et al. | Synthesis of Micro–Nano-assembled manganese carbonate via aqueous precipitation assisted by ethanol | |
| Zhang et al. | Solvothermal synthesis of manganese sulfides and control of their phase and morphology | |
| CN103420428A (en) | Preparation method of magnesium ferrite nano-particles | |
| Tan et al. | Low-temperature synthesis of Li2TiO3 tritium breeder ceramic pebbles by water controlled-release solvothermal process | |
| CN103101964A (en) | Preparation method of zinc oxide nanoflower of spiauterite structure | |
| Chen et al. | Ionic liquid-assisted hydrothermal synthesis of β-MnO2 with hollow polyhedra morphology | |
| CN102962470A (en) | Method for preparing spherical ultrafine nickel powder at room temperature | |
| CN107935047A (en) | A kind of control synthetic method of different-shape and the nano-manganese dioxide of size | |
| Chen et al. | Review on the preparation and performance improvement methods of bismuth photocatalyst materials | |
| CN109616626B (en) | Low-temperature macro preparation method of carbon-coated ferroferric oxide nanocrystal | |
| CN103331452A (en) | Copper and carbon composite hollow sphere particle material and preparation method thereof | |
| CN102161500A (en) | Preparation method of cobalt-doped zinc oxide nano-material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Controllable preparation method of nano magnetic iron oxide with narrow particle size distribution Effective date of registration: 20130609 Granted publication date: 20121128 Pledgee: Xi'an hi tech Development Zone Guoxin micro credit Co., Ltd. Pledgor: Shaanxi Hongju Electronic Technology Co., Ltd. Registration number: 2013990000365 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20140306 Granted publication date: 20121128 Pledgee: Xi'an hi tech Development Zone Guoxin micro credit Co., Ltd. Pledgor: Shaanxi Hongju Electronic Technology Co., Ltd. Registration number: 2013990000365 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Controllable preparation method of nano magnetic iron oxide with narrow particle size distribution Effective date of registration: 20140404 Granted publication date: 20121128 Pledgee: Xi'an hi tech Development Zone Guoxin micro credit Co., Ltd. Pledgor: Shaanxi Hongju Electronic Technology Co., Ltd. Registration number: 2014990000235 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121128 Termination date: 20150328 |
|
| EXPY | Termination of patent right or utility model |