CN103785847A - Method for preparing 1:12 type Nd-Fe(M)-N permanent magnet alloy powder through reduction diffusion method - Google Patents
Method for preparing 1:12 type Nd-Fe(M)-N permanent magnet alloy powder through reduction diffusion method Download PDFInfo
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- CN103785847A CN103785847A CN201410068201.5A CN201410068201A CN103785847A CN 103785847 A CN103785847 A CN 103785847A CN 201410068201 A CN201410068201 A CN 201410068201A CN 103785847 A CN103785847 A CN 103785847A
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Abstract
The invention discloses a method for preparing 1:12 type Nd-Fe(M)-N permanent magnet alloy powder through a reduction diffusion method. The method comprises the following steps that NdCl3, pure iron powder, M and Ca or CaH2 serve as raw materials, and vacuum dewatering processing is carried out on the NdCl3 at the temperature ranging from 250DEG C to 400DEG C; an reaction is carried out according to the reaction formula (1), vacuum drying is carried out to obtain Nd-Fe(M) alloy powder, a nitridation diffusion gas-solid reaction is carried out on the Nd-Fe(M) alloy powder under the condition of highly-pure nitrogen or NH4, or the condition of the highly-pure nitrogen and H2, or the condition of the NH4 and the H2, so that the Nd-Fe(M)-N permanent magnet alloy powder is obtained, and please see the reaction formula (1) in the specification. According to the method for preparing the 1:12 type Nd-Fe(M)-N permanent magnet alloy powder through the reduction diffusion method, the technology is simple, preparation is convenient, magnetism of the powder is high, and anisotropy performance is good.
Description
Technical field
The invention belongs to technical field of magnetic materials, be specifically related to a kind of reduction-diffusion process and manufacture the method for 1 ︰ 12 type Nd-Fe (M)-N permanent magnetic alloy powders.
Background technology
1 ﹕ 12 type Nd – Fe (M)-N are NdFe
12-Xm
xn
yinterstitial compound is the permanent-magnet material that a class has excellent properties, and aspect basic magnetic characteristic, its saturation magnetization is suitable with Nd-Fe-B system, and anisotropy field and Curie temperature are high than Nd-Fe-B.Because 1 ﹕ 12 type Nd – Fe (M)-N can decompose when higher than 700 ℃, therefore, be mainly used to manufacture bonded permanent magnet, the magnetic property of bonded permanent magnet depends primarily on the magnetic property of 1 ﹕ 12 type Nd – Fe (M)-N magnetics.The preparation method of current 1 ﹕ 12 type Nd – Fe (M)-N magnetic routines is ingot casting mechanical crushing methods.
Ingot casting mechanical crushing method: become Nd-Fe (M) alloy pig with Fe and magnesium-yttrium-transition metal M through vacuum metling with the rare earth metal Nd purifying through complicated technology, regrind into fine powder after mechanical disintegration, make Nd-Fe (M)-N magnetic after nitriding.
Given this,, for solving the extraction process of Traditional Method high pure rare earth metals complexity, reduce the volatilization loss of neodymium metal in manufacture process.The present invention adopts the NdCl with low melting point (700 ℃)
3for raw material, by metallothermic reduction and controlled Nd Fe (the M)-N alloy powder of diffusion-alloying method prepared sizes.
Summary of the invention
The object of the invention is to propose a kind of reduction-diffusion process and manufacture the method for 1 ︰ 12 type Nd-Fe (M)-N permanent magnetic alloy powders, solve the extraction process of Traditional Method high pure rare earth metals complexity, reduce the volatilization loss of neodymium metal in manufacture process.Employing has the NdCl of low melting point (700 ℃)
3for raw material, by metallothermic reduction and diffusion-alloying method, then high-pressure nitridation process, Nd – Fe (M)-N alloy powder that prepared sizes are controlled, its technique is simple, easy to prepare; Powder magnetic is high, and anisotropic properties is good.
In order to reach above-mentioned purpose of design, the technical solution used in the present invention is as follows:
A kind of reduction-diffusion process is manufactured the method for 1 ︰ 12 type Nd-Fe (M)-N permanent magnetic alloy powders, comprises the following steps:
A. raw material are selected: adopt NdCl
3for raw material, granularity is alloying element raw material at 300～800 object straight iron powders, and M is magnesium-yttrium-transition metal, and reducing agent is Ca or CaH
2, its granularity is at 3～5mm;
B. the pretreatment of raw material: NdCl
3through 250～400 ℃ of vacuum dehydration processing;
C. raw-material allocating into: according to fundamental reaction formula (1) and carry out the adjustment of raw-material calculating and the actual amount of allocating in conjunction with different reduction diffusion reaction conditions;
NdCl
3+Fe+M+Ca→NdFe(M)+CaCl
2 (1)
D. reduction diffusion reaction: mix after reactant ratio, carry out thermal reduction reaction and diffusion, reaction temperature is controlled at 760～860 ℃, obtains Nd-Fe (M) alloyed powder and accessory substance Ca Cl after having reacted
2, wash Chemical Decomposition, then obtain Nd-Fe (M) alloy powder through vacuum drying;
E.Nd-Fe (M) alloyed powder nitriding processing: Nd-Fe (M) alloyed powder is at High Purity Nitrogen or NH
4, or High Purity Nitrogen and H
2, or NH
4and H
2in, pressure is at 0.1～1.0Mpa, and temperature is in 400～500 ℃, and nitrogen treatment obtains anisotropy Nd-Fe (the M)-N permanent magnetic alloy powder of required composition and granularity requirements through nitriding diffusion gas-solid reaction in 1～10 hour.
Preferably, described M is Ti or Mo or W, and its granularity is at 300～800 orders.
Preferably, NdCl
3the amount of allocating into the chemical dose more required than basic chemical equation exceed 3-5wt%, chemical dose excess 5～20wt% that the amount of allocating into of reducing agent is more required than basic chemical equation.
More preferably, the scope that M replaces Fe amount is 1～2.
More preferably, the proportioning of High Purity Nitrogen and H2 or NH4 and H2 or NH4 and H2 is 7.5:2.5.
The beneficial effect that reduction-diffusion process of the present invention is manufactured the method for 1 ︰ 12 type Nd-Fe (M)-N permanent magnetic alloy powders is: owing to having adopted NdCl
3for raw material, extract neodymium metal by metallothermic reduction, save the extraction process of high pure rare earth metals complexity, reduction diffusion reaction temperature range is lower, has reduced the volatilization loss of neodymium metal, is also conducive to diffusion-alloying.Reduction reaction accessory substance Ca Cl
2water-soluble, therefore make the separation of product be easy to carry out.By reactant alloying element iron particle size is selected to control, again because solid-state diffusion reaction temperature is lower, can effectively control product NdFe
12-Xm
xalloy powder granularity, is conducive to the raising of powder magnetic after nitriding, obtain the anisotropic NdFe of high-performance
12-Xm
xn
ymagnet.The purification of rare earth Nd and completing in same course of reaction with the alloying of iron, has omitted the Mechanical Crushing operation of alloy in Traditional Method, and it is good that technique is simplified performance greatly.
The specific embodiment
Below optimum implementation of the present invention is described in further detail.
Embodiment 1
Raw material adopts NdCl
3, Fe powder (300 order) and Ti powder (300 order), calculate the chemical dose of required each reactant, NdCl by formula (1)
3the amount adding is 103% of chemical dose, and take metal Ca as reducing agent, its particle diameter is 3mm, addition metachemistry dosage 5%, NdCl
3through 250 ℃ of vacuum dehydration processing.Reduction diffusion reaction is under argon shield, and 760 ℃ are incubated 2 hours, and reaction block is put natural degradation in water, powder is leached to vacuum drying.The NH that alloyed powder is 1.0Mpa at pressure
4in atmosphere, process 1 hour the NdFe making for 500 ℃
11m
1n
yalloyed powder magnetic property is: Br=1.02T, Hci=480kA/M, (BH) m=170kJm
-3.
Embodiment 2
Raw material adopts NdCl
3, Fe powder (800 order) and Mo powder (800 order), calculate the chemical dose of required each reactant, NdCl by formula (1)
3the amount adding is 105% of chemical dose, with CaH
2for reducing agent, its particle diameter is 5mm, and addition is chemical dose 120%.NdCl
3through 400 ℃ of vacuum dehydration processing.Reduction diffusion reaction is under argon gas and protection, and in 860 ℃ of insulations 2 hours, reaction block was put natural degradation in water, powder is leached to vacuum drying.The NH that alloyed powder is 0.1Mpa at pressure
4and H
2(7.5:2.5) in mixed atmosphere, process 10 hours the NdFe making for 450 ℃
11mo
1n
yalloyed powder magnetic property is: Br=1.0T, Hci=400kA/M, (BH) m=160kJm
-3.
Embodiment 3
Raw material adopts NdCl
3, Fe powder (800 order) and W powder (800 order), calculate the chemical dose of required each reactant, NdCl by formula (1)
3the amount adding is 103% of chemical dose, and take metal Ca as reducing agent, its particle diameter is 3mm, addition metachemistry dosage 5%, NdCl
3through 250 ℃ of vacuum dehydration processing.Reduction diffusion reaction is under argon shield, and 760 ℃ are incubated 2 hours, and reaction block is put natural degradation in water, powder is leached to vacuum drying.The High Purity Nitrogen that alloyed powder is 10Mpa at pressure and H
2(7.5:2.5) in mixed atmosphere, process 10 hours the NdFe making for 450 ℃
11m
1n
yalloyed powder magnetic property is: Br=1.0T, Hci=400kA/M, (BH) m=160kJm
-3.
Embodiment 4
Raw material adopts NdCl
3, Fe powder (300 order) and W powder (300 order), calculate the chemical dose of required each reactant, NdCl by formula (1)
3the amount adding is 105% of chemical dose, with CaH
2for reducing agent, its particle diameter is 5mm, addition metachemistry dosage 20%, NdCl
3through 400 ℃ of vacuum dehydration processing.Reduction diffusion reaction is under argon shield, and 860 ℃ are incubated 2 hours, and reaction block is put natural degradation in water, powder is leached to vacuum drying.In the High Purity Nitrogen atmosphere that alloyed powder is 10Mpa at pressure, process 10 hours the NdFe making for 450 ℃
11m
1n
yalloyed powder magnetic property is: Br=1.02T, Hci=480kA/M, (BH) m=170kJm
-3.
Reaction equation (1) is:
NdCl
3+Fe+M+Ca→NdFe(M)+CaCl
2。
Above content is the further description of the present invention being done in conjunction with concrete preferred embodiment, and being convenient to these those skilled in the art can understand and apply the invention, and can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, can also make without departing from the inventive concept of the premise some simple deduction or replace, and needn't pass through performing creative labour.Therefore, those skilled in the art are according to announcement of the present invention, and the simple modifications that the present invention is made all should be within protection scope of the present invention.
Claims (5)
1. reduction-diffusion process is manufactured a method for 1 ︰ 12 type Nd-Fe (M)-N permanent magnetic alloy powders, it is characterized in that: comprise the following steps:
A. raw material are selected: adopt NdCl
3for raw material, granularity is alloying element raw material at 300～800 object straight iron powders, and M is magnesium-yttrium-transition metal, and reducing agent is Ca or CaH
2, its granularity is at 3～5mm;
B. the pretreatment of raw material: NdCl
3through 250～400 ℃ of vacuum dehydration processing;
C. raw-material allocating into: according to fundamental reaction formula (1) and carry out the adjustment of raw-material calculating and the actual amount of allocating in conjunction with different reduction diffusion reaction conditions;
NdCl
3+Fe+M+Ca→NdFe(M)+CaCl
2 (1)
D. reduction diffusion reaction: mix after reactant ratio, carry out thermal reduction reaction and diffusion, reaction temperature is controlled at 760～860 ℃, obtains Nd-Fe (M) alloyed powder and accessory substance CaCl after having reacted
2, wash Chemical Decomposition, then obtain Nd-Fe (M) alloy powder through vacuum drying;
E.Nd-Fe (M) alloyed powder nitriding processing: Nd-Fe (M) alloyed powder is at High Purity Nitrogen or NH
4, or High Purity Nitrogen and H
2, or NH
4and H
2in, pressure is at 0.1～1.0Mpa, and temperature is in 400～500 ℃, and nitrogen treatment obtains anisotropy Nd-Fe (the M)-N permanent magnetic alloy powder of required composition and granularity requirements through nitriding diffusion gas-solid reaction in 1～10 hour.
2. reduction-diffusion process according to claim 1 is manufactured the method for 1 ︰ 12 type Nd-Fe (M)-N permanent magnetic alloy powders, it is characterized in that: described M is Ti or Mo or W, and its granularity is at 300～800 orders.
3. reduction-diffusion process according to claim 1 is manufactured the method for 1 ︰ 12 type Nd-Fe (M)-N permanent magnetic alloy powders, it is characterized in that: NdCl
3the amount of allocating into the chemical dose more required than basic chemical equation exceed 3-5wt%, chemical dose excess 5～20wt% that the amount of allocating into of reducing agent is more required than basic chemical equation.
4. the method for manufacturing 1 ︰ 12 type Nd-Fe (M)-N permanent magnetic alloy powders according to the reduction-diffusion process described in claim 1 or 2 or 3, is characterized in that: M replaces the scope of Fe amount 1～2.
5. the method for manufacturing 1 ︰ 12 type Nd-Fe (M)-N permanent magnetic alloy powders according to the reduction-diffusion process described in claim 1 or 2 or 3, is characterized in that: High Purity Nitrogen and H
2, or NH
4and H
2proportioning be 7.5:2.5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105825989A (en) * | 2016-05-24 | 2016-08-03 | 郑精武 | Method for preparing N-containing rare earth-transition metal magnetic powder |
| CN111370194A (en) * | 2019-12-16 | 2020-07-03 | 横店集团东磁股份有限公司 | Preparation method of Fe-Si-Al soft magnetic powder |
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| JPH05226130A (en) * | 1992-02-07 | 1993-09-03 | Mitsubishi Materials Corp | Manufacture of smfen magnet powder |
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Cited By (3)
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|---|---|---|---|---|
| CN105825989A (en) * | 2016-05-24 | 2016-08-03 | 郑精武 | Method for preparing N-containing rare earth-transition metal magnetic powder |
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| CN111370194A (en) * | 2019-12-16 | 2020-07-03 | 横店集团东磁股份有限公司 | Preparation method of Fe-Si-Al soft magnetic powder |
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Application publication date: 20140514 |