CN112723326B - Iron nitride nano powder and preparation method thereof - Google Patents

Iron nitride nano powder and preparation method thereof Download PDF

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CN112723326B
CN112723326B CN202011616861.4A CN202011616861A CN112723326B CN 112723326 B CN112723326 B CN 112723326B CN 202011616861 A CN202011616861 A CN 202011616861A CN 112723326 B CN112723326 B CN 112723326B
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iron nitride
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CN112723326A (en
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杨志平
许明亮
郭静
刘学千
李璇璇
赵金鑫
蒋丽涛
尤泳
王大伟
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Hebei Ledphor Optoelectronics Technology Co ltd
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    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
    • C01B21/0622—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with iron, cobalt or nickel
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Abstract

The invention provides an iron nitride nano powder and a preparation method thereof, wherein the powder mainly comprisesThe main phase is Fe4N, wherein the content of nitrogen is more than or equal to 4.9wt% and is more than or equal to 5.81wt%, and the particle size of the powder is less than 100 nm. The preparation method of the invention is that the specific iron powder is added with additive NH4And F, controlling the reaction atmosphere and the reaction process to sinter, and finally crushing and grading to obtain the product. The iron nitride prepared by the invention has the advantages of high purity, uniform particle size, good dispersibility, simple preparation method and process, easy operation and low cost, greatly improves the purity of the iron nitride powder, has controllable particle size, high yield and stable batch performance, and can be used for industrial large-scale production.

Description

Iron nitride nano powder and preparation method thereof
Technical Field
The invention relates to a nitride nano material, in particular to iron nitride nano powder and a preparation method thereof.
Background
The iron nitride has good hardness and corrosion resistance, and is a good magnetic material, and particularly, the nanoscale iron nitride is an ideal raw material for preparing magnetic liquid and magnetic devices. The ferro-magnetic nitride fluid is a novel functional material developed in recent decades, has the advantages of magnetism and fluidity and is not possessed by common solid magnetic materials, and is widely applied to the aspects of chemical industry, machinery, instruments, environmental protection, medical treatment and the like. In the field of catalysis, iron nitride is an effective catalyst for many reactions (for example, for the reactions of ammonia synthesis, fischer-tropsch synthesis, electrocatalytic oxidation-reduction and the like), wherein magnetohydrodynamic sealing, magnetohydrodynamic power generation and magnetohydrodynamic separation have very important significance for environmental protection and energy conservation, such as complete leakage-free dynamic non-contact sealing, magnetohydrodynamic power generation, magnetic printing, tilt sensors, damping devices, magnetohydrodynamic loudspeakers, novel lubricants, mineral separation, magnetic particle valves, magnetic ink and the like. And thus has received a great deal of attention.
At present, the main preparation methods of iron nitride powder are as follows: plasma methods, pyrolysis methods, chemical impregnation methods, chemical vapor deposition methods, physical vapor deposition methods, and the like. Chinese patent (publication number: CN101628712) discloses a method for preparing single-phase nano epsilon-Fe3N or gamma' -Fe4The method and the device adopt the technical scheme of vacuumizing, forced gas circulation, plasma evaporation powder preparation and powder modification. The product can be ensured to be high-purity single-phase nano iron nitride powder by accurate reaction atmosphere control. The method and the device disclosed by the above have certain defects, such as the need of special instruments and equipment, higher cost, small powder preparation amount, various and complex preparation steps, difficulty in conveying the nano powder by air flow, easiness in blocking pipelines and great influence on the purity of products by the equipment. In contrast, the nano iron powder adopts H2Reduction of NH3The direct nitridation preparation has the advantages of simple process and low cost, but NH in the prior art3The powder prepared by the direct nitridation method is easy to agglomerate, and is still not ideal in the aspects of dispersibility, purity, particle size uniformity and the like, so that the research on the preparation method of the iron nitride nano powder with simple process and good product properties is of great significance.
Disclosure of Invention
The invention aims to provide iron nitride nano powder and a preparation method thereof, and aims to solve the problems of low purity and complex process of the iron nitride nano powder prepared by the prior art.
The purpose of the invention is realized by the following technical scheme: the invention provides iron nitride nano powder, wherein the main phase of the powder is Fe4N, and 5.81wt% or more of nitrogen content 4.9wt% or more (Fe with purity of 100 wt%)4The theoretical N content of N is 5.9%) and the particle size of the powder is less than 100 nm.
Further, the content of nitrogen is more than or equal to 5.81wt% and more than or equal to 5.2 wt%, and the particle size of the powder is 45-55 nm.
A preparation method of iron nitride nano powder comprises the following steps:
a. weighing Fe powder and reaction additive NH4F, wherein NH is weighed4The total mass of F is 4-40% of the total mass of Fe powder;
b. b, fully mixing the raw materials weighed in the step a in a glove box for 15-25 minutes, and flatly paving the mixture in a molybdenum crucible;
c. putting the molybdenum crucible into a quartz sintering furnace, vacuumizing to 18-22 KPa, and circulating N2And H2Under the condition of mixed atmosphere, raising the temperature to 330-370 ℃ at the speed of 5-10 ℃/min, and then closing N2Introduction of NH3Heating to 450-600 ℃ at the speed of 2-7 ℃/min, and keeping the temperature for 2-5H, wherein H2And NH3The volume ratio of (A) to (B) is 1: 3-3: 1; then NH is turned off3And H2Introduction of N2And cooling to 180-220 ℃ at the speed of 3-7 ℃/min, then naturally cooling to room temperature to obtain a sintered product, and crushing and grading the product to obtain the iron nitride powder with the granularity of less than 100 nm.
In the step a, the purity of the Fe powder is 99.99wt%, and the particle size is 40-80 nm.
In step a, a reaction additive NH4The purity of F was 99.9%.
In step a, weighing NH4The total mass of the F is 12-40% of the total mass of the Fe powder.
In step c, N2Has a purity of 99.99%, H2Has a purity of 99.99%, N2And H2The volume ratio of (A) to (B) is 1:1, and the flow rate is controlled to be 0.8-2L/min.
In step c, H2And NH3Is 1: 3.
In the step c, the temperature of the heat preservation reaction is 500-550 ℃.
In steps a-c, the weighing, mixing and crushing of the materials are all carried out in a nitrogen glove box.
The iron nitride nano powder prepared by the invention has the advantages of high purity, less agglomeration, good dispersibility and powder granularity of less than 100 nm. The preparation method provided by the invention has the advantages of simple process and relatively high single-time yield, and is suitable for industrial production. By adding the additive which is easy to volatilize and decompose, the introduction of impurities can be effectively avoided, the full reaction is promoted, the self-sintering is prevented, and H2The Fe-based reducing agent can effectively destroy an oxidation film on the surface of Fe as a reducing atmosphere, and the obtained reduced iron has strong activity, promotes the nitridation reaction, and overcomes the defects of particle agglomeration and non-uniformity of a product obtained by a direct nitridation method.
The invention can obtain the powder material with high purity, less agglomeration, good dispersibility and powder granularity of less than 100 nanometers at lower cost by controlling the conditions of specific sintering atmosphere, flow, heating rate, heat preservation time and the like in sintering.
Drawings
FIG. 1 is Fe prepared in example 1 of the present invention4SEM image of N.
FIG. 2 shows Fe prepared in example 1 of the present invention4XRD pattern of N.
Detailed Description
Example 1
50g of metal Fe powder with the purity of 99.99wt% and the particle size of 50nm are weighed in a glove box, and 10g of reaction additive NH with the purity of 99.9% is weighed4F powder (additive A), mixed thoroughly for 20 minutes, and then spread in a molybdenum crucible. Putting the mixed materials into a quartz sintering furnace, vacuumizing to 20KPa, introducing nitrogen-hydrogen mixed gas with the volume ratio of 1:1, controlling the flow at 1.5L/min, heating to 350 ℃ at the speed of 5 ℃/min, and closing N2Introduction of NH3，H2And NH3The volume ratio is 1:3, the temperature is raised to 550 ℃ at the speed of 2 ℃/min, the temperature is kept for 3h, and then NH is closed3And H2Introduction of N2And cooling to 200 ℃ at a speed of 5 ℃/min, then naturally cooling to room temperature to obtain a sintered product, crushing and grading the product to obtain iron nitride below 100nm, and characterizing the iron nitride, as shown in fig. 1 and 2.
Reference ratio 1
The iron nitride powder obtained in example 1 of the "preparation method of nano iron nitride" (patent No. CN201410785030.8) was used as reference example 1. The preparation method comprises the following specific steps: weighing 0.025 mol of ferric nitrate and 0.0125 mol of glycine, dissolving the raw materials in distilled water to prepare a solution, and placing the solution on a temperature-controllable electric furnace for heating. The solution is subjected to a series of reactions such as volatilization, concentration, decomposition and the like to obtain nano iron oxide powder, and the nano iron oxide powder is reacted for 3 hours at the temperature of 600 ℃ in an ammonia atmosphere to obtain nano iron nitride powder.
Comparative example 1 and examples 2 to 10
Referring to the preparation method of example 1, the N content and the particle uniformity of the prepared iron nitride powder were measured by changing the addition amount of the reaction additive a under the same process conditions as in example 1, and the results are shown in table 1.
TABLE 1
Figure BDA0002872542980000031
As can be seen from Table 1, NH was added to the sintering mixture as an additive under otherwise unchanged process conditions4The uniformity of the particles is improved and then reduced when the addition amount of F is increased, the uniformity is best when the addition amount is 20 percent of that of the Fe powder, and the nitrogen content is close to that of pure-phase Fe4N。
Examples 11 to 15
Referring to the preparation method of example 1, the particle size of the raw iron powder was changed, and the other process conditions were the same as in example 1, and the N content and the particle morphology of the prepared iron nitride powder were measured, and the results are shown in table 2.
TABLE 2
Figure BDA0002872542980000041
As can be seen from table 2, the particle size of the raw iron powder directly affects the particle size of the product, and the particle size of the product can be adjusted by changing the particle size of the raw iron powder as needed.
Examples 16 to 29
With reference to the preparation process of example 1, the sintering temperature, H, was varied2And NH3The volume ratio and other process conditions were the same as in example 1, and the results of the tests on the N content and particle morphology of the prepared iron nitride powder are shown in table 3.
TABLE 3
Figure BDA0002872542980000042
Figure BDA0002872542980000051
As can be seen from Table 3, by varying the sintering temperature and H2And NH3The volume ratio is known, the nitrogen content is a trend that the nitrogen content is increased firstly and then reduced along with the increase of the sintering temperature, and the particles are agglomerated and the particle size of the particles is increased; when the sintering temperature is 550 ℃, the heat preservation time is 3H, H2And NH3The volume ratio is 1:3, the uniformity of the particles is best, the agglomeration is less, and the dispersibility is good.

Claims (7)

1. A preparation method of iron nitride nano powder is characterized by comprising the following steps:
a. weighing Fe powder and reaction additive NH4F, wherein NH is weighed4The total mass of F is 4-40% of the total mass of Fe powder; the purity of the Fe powder is 99.99wt%, and the particle size is 40-80 nm;
b. b, fully mixing the raw materials weighed in the step a in a glove box for 15-25 minutes, and flatly paving the mixture in a molybdenum crucible;
c. putting the molybdenum crucible into a quartz sintering furnace, vacuumizing to 18-22 KPa, and circulating N2And H2Under the condition of mixed atmosphere, raising the temperature to 330-370 ℃ at the speed of 5-10 ℃/min, and then closing N2Introduction of NH3Heating to 450-550 ℃ at the speed of 2-7 ℃/min, and preserving heat for 3H, wherein H2And NH3The volume ratio of (A) to (B) is 1:31: 1; then NH is turned off3And H2Introduction of N2And cooling to 180-220 ℃ at the speed of 3-7 ℃/min, then naturally cooling to room temperature to obtain a sintered product, and crushing and grading the product to obtain the iron nitride powder with the particle size of less than 100 nm.
2. The method for preparing iron nitride nanopowder of claim 1, wherein in step a, a reaction additive NH is added4The purity of F was 99.9%.
3. The method for preparing iron nitride nanopowder of claim 1, wherein in step a, the weighed NH is4The total mass of the F is 12-40% of the total mass of the Fe powder.
4. The method for preparing iron nitride nanopowder of claim 1, wherein in step c, N is2Has a purity of 99.99%, H2Has a purity of 99.99%, N2And H2The volume ratio of (A) to (B) is 1:1, and the flow rate is controlled to be 0.8-2L/min.
5. The method for preparing iron nitride nanopowder of claim 1, wherein in step c, H is2And NH3Is 1: 3.
6. The method for preparing iron nitride nano powder according to claim 1, wherein in the step c, the reaction temperature is kept at 500-550 ℃.
7. The method for preparing iron nitride nanopowder according to claim 1, wherein in steps a-c, the weighing, mixing and pulverization of the materials are all performed in a nitrogen glove box.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101628712A (en) * 2009-08-21 2010-01-20 东北大学 Method for preparing single phase nanometer epsilon-Fe3N or gamma'-Fe4N powder and device thereof
JP2014029896A (en) * 2012-07-31 2014-02-13 Hitachi Chemical Co Ltd Sintered magnet coating material
CN111206271A (en) * 2020-02-14 2020-05-29 山西大学 Preparation method, product and application of self-supporting metal doped iron nitride electrode

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101628712A (en) * 2009-08-21 2010-01-20 东北大学 Method for preparing single phase nanometer epsilon-Fe3N or gamma'-Fe4N powder and device thereof
JP2014029896A (en) * 2012-07-31 2014-02-13 Hitachi Chemical Co Ltd Sintered magnet coating material
CN111206271A (en) * 2020-02-14 2020-05-29 山西大学 Preparation method, product and application of self-supporting metal doped iron nitride electrode

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