CN101560628A - Rare-earth ferroalloy and preparation process thereof - Google Patents
Rare-earth ferroalloy and preparation process thereof Download PDFInfo
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Abstract
The invention relates to a rare-earth ferroalloy for producing a rare-earth permanent magnetism material with high performance and a preparation process thereof. The ferroalloy comprises the contents according to the weight percentage: 30-90 of neodymium or didymium rare earth, and the balance ferrum and less than 1 of unavoidable impurities, wherein the O content is less than or equal to 0.1, the C content is less than or equal to 0.1 and the N content is less than or equal to 0.05. The alloy is prepared by an electrolytic method of fluoride molten salt system oxide, and an electrolyte of the alloy comprises rare-earth fluoride and lithium fluoride.
Description
Technical field
The present invention relates to metal material field, belong to the rare earth pyrometallurgy.
Background technology
Rare earth is made various new function materials because high-performances such as its unique magnetic, light, electricity are widely used in, and is the basic raw material of preparation rare earth functional materials.For example:, in preparation process, need to add rare earth metals such as Nd, Pr, to obtain higher magnet coercive force and good temperature profile at the NdFeB permanent magnet material of rare earth permanent-magnetic material in occupation of extremely important position.Traditional NdFeB magnet directly adds above-mentioned single rare earth metal in preparation process, therefore, require smelting temperature higher, cause the rare earth metal scaling loss bigger, production cost increases, in addition, because smelting temperature is higher, causes the foreign matter content height, influences the performance of its derived product.And directly use Nd-Fe, Pr-Nd-Fe alloy can effectively avoid the problems referred to above, and electrolytic preparation Nd-Fe, Pr-Nd-Fe alloy electrolysis temperature are low, and various auxilliary material consumption are few, and foreign matter content is low.
European patent: EP0229516A1 adopts the electrolysis of fluorides method to prepare Dy-Fe, Nd-Dy-Fe alloy, used fluoride system is made of dysprosium fluoride, neodymium fluoride, lithium fluoride, barium fluoride, Calcium Fluoride (Fluorspan), oxide compound is dysprosium oxide, Neodymium trioxide, iron is the consumable negative electrode, but this method electrolyte system constituent element is more, complicated component, and alloying constituent is difficult to accurate control, only limit to laboratory study, do not carry out large-scale industrial production.
Chinese patent 02153736.4 has reported that a kind of fluoride system oxide electrolysis prepares the method for neodium iron intermediate alloy, its neodium iron intermediate alloy with solid pure iron or liquid norium or low eutectic composition is done negative electrode, plumbago crucible is an electrolyzer, and simultaneously as anode, with the susceptor of pure iron metallic crucible, at neodymium fluoride, praseodymium enriched substance 65～70%, BaF as neodymium-iron alloy
2In 10～20% and LiF10～25% molten salt electrolytes of forming, add praseodymium carbonate neodymium or Praseodymium trioxide neodymium raw material, obtain rich neodymium-iron alloy, cathode current density 2～17A/cm
2, 950～1050 ℃ of electrolysis temperatures, current efficiency is about 65%, rare earth metal yield about 90%.This method has following some deficiency: (1) does anode with graphite cuvette, and graphite cuvette consumption is very fast, can not continuous production, in addition, graphite cuvette is changed frequent, causes current efficiency and rare earth metal yield lower, the quality product fluctuation is bigger, and especially the carbon content in the product is higher; (2) the used crucible of this method hangs in the fused salt, realize that difficulty is bigger, and this patent does not provide implementation method yet; (3) this method is not suitable for large-scale industrial production.
Chinese patent 03805898.7 has reported that a kind of electrolysis of fluorides prepares the method for terbium iron, dysprosium iron and Tb-Dy-Fe alloy, its negative electrode is iron, graphite is as anode, its electrolyte weight percentage composition is by dysprosium fluoride and fluoridize the rare earth fluoride class 65～85% that at least one side of terbium forms, lithium fluoride 10～20 and barium fluoride 5～15%, electrolysis raw material are dysprosium fluoride or fluoridize terbium, and electrolysis obtains alloy, 900～970 ℃ of electrolysis temperatures, current efficiency about 70～80%.This method has following some deficiency: (1) its electrolysis raw material is a rare earth fluorine, and rare earth fluorine must be fluoridized by other compounds such as rare earth oxides and makes, obviously can increase cost (2) electrolysis rare earth fluorine than the direct electrolytic oxidation thing and can produce a large amount of fluorine-containing obnoxious flavoures, cause environmental pollution.
Summary of the invention
At above problem, the invention provides that a kind of foreign matter content is few, composition is even, cost is low and meet practical rare earth permanent-magnetic material and add with rare earth ferroalloy and preparation method capable of being industrialized thereof.
Rare earth ferroalloy provided by the invention is characterized in that:
1.a) in this rare earth ferroalloy, rare earth element is neodymium or praseodymium neodymium, content of rare earth is 30～90wt%, surplus is iron and inevitable impurity;
B) this alloy C content≤0.1wt%, O content≤0.1wt%, N content≤0.05wt%;
2.a) a kind of rare earth ferroalloy that is applied to Nd-Fe-Bo permanent magnet material, rare earth element is neodymium or praseodymium neodymium, content of rare earth is that 30～90wt% surplus is iron and inevitable impurity;
B) this alloy C content≤0.05wt%, O content≤0.05wt%, N content≤0.03wt%;
3. in this rare earth ferroalloy, content of rare earth is 60～90wt%, and neodymium content is 60～100wt% in the rare earth element.
4. this rare earth ferroalloy, C content≤0.03wt%.
The preparation method of rare earth ferroalloy provided by the invention is characterized in that:
1. adopt fused salt electrolysis process to prepare above-mentioned rare earth ferroalloy, do electrolyzer with graphite, graphite cake is an anode, and the pure iron rod is the consumable negative electrode, and the iron crucible is as the rare earth ferroalloy susceptor, at NdF
3-LiF or PrF
3-NdF
3-LiF or (PrNd) F
3In the fluoride molten salt electrolyte system of-LiF, be the electrolysis raw material, pass to the direct current electrolysis and obtain rare earth ferroalloy with the rare earth oxide.
2. according to the preparation method of 1 described rare earth ferroalloy,
A) the fused salt electrolysis temperature is between 900～1100 ℃;
B) anodic current density is 0.5～1.5A/cm
2, cathode current density is 5～15A/cm
2
C) current efficiency is greater than 75%, and the rare earth metal yield is greater than 95%.
3. according to the preparation method of 1 described rare earth ferroalloy, the electrolyte body of fused salt electrolysis is: neodymium fluoride is 35～90wt%, and praseodymium fluoride is 0～36wt%, lithium fluoride 5～40wt%.
4. according to the preparation method of 1 described rare earth ferroalloy, the content of Neodymium trioxide is 58～100wt% in the rare earth oxide of fused salt electrolysis, and Praseodymium trioxide content is 0～42wt%.
5. according to the preparation method of 1 described rare earth ferroalloy, the purity of described pure iron rod＞95% can be that diameter is that the pole or the cross section length of side of 30～100mm is the square rod of 30～100mm, or form by many.
6. according to the preparation method of 1 described rare earth ferroalloy, described graphite anode is made up of the polylith graphite cake.
7. adopt the smelting method for preparing rare earth ferroalloy, the raw material of use also contains at least a in the rare earth ferroalloy of metal praseodymium, neodymium metal, praseodymium neodymium, 1 described method preparation except iron.
Advantage of the present invention:
The advantage of rare earth ferroalloy disclosed by the invention is:
1. foreign matter content is low.Rare earth ferroalloy provided by the invention is because electrolysis temperature is low, and foreign matter content is few;
2. composition is even.Rare earth ferroalloy involved in the present invention is compared with the Nd-Fe-B series permanent magnetic material for preparing with rare earth elements such as pure praseodymium, neodymiums, and the Nd-Fe-B series permanent magnetic material composition of this alloy preparation is more even.As previously described, the homogeneity of composition to the performance of Nd-Fe-B series permanent magnetic material particularly coercive force play an important role, facts have proved, can prepare high performance Nd-Fe-B series magnet with alloy of the present invention, especially can improve the coercive force of magnet, can improve 5% at least.
The preparation method's of rare earth ferroalloy disclosed by the invention advantage is:
1. adopt Neodymium trioxide, Praseodymium trioxide as the electrolysis raw material, therefore, only produce the fluoro-gas of carbonic acid gas, carbon monoxide and minute quantity in the electrolytic process, environmental pollution is little;
2. adopt the pure iron rod to make the consumable negative electrode, neodymium that electrolysis is separated out and iron form low-melting neodymium-iron alloy, help reducing electrolysis temperature;
3. graphite anode is made up of the polylith graphite cake, and anode just can alternately be changed like this, and it is steady to help electrolysis temperature, and quality product is more stable, and current efficiency and rare earth metal yield are higher; The polylith graphite cake has reduced anodic current density as anode, has accelerated electrolytical speed of circulation, helps the dissolving of oxide compound, has reduced slag making, has improved metal yield and current efficiency and quality product;
4. cathode current density 5～15A/cm
2, electrolysis temperature is 900～1100 ℃, by controlling different electrolysis temperatures and different cathode current densities, can obtain the rare earth ferroalloy of different content of rare earth.
Description of drawings
Fig. 1 electrolysis rare earth ferroalloy equipment
1: conducting plates 2: positive plate 3: iron cathode 4: graphite cuvette 5: iron cover 6: thermal insulation layer 7: refractory brick 8: iron crucible 9: insulcrete
Embodiment
Below the invention will be further described with example.Protection domain of the present invention is not subjected to the restriction of these embodiment, and protection domain of the present invention is determined by claims.
The test of embodiment is carried out in the following manner among the present invention:
Metal detection adopts the ICP-MS test according to national standards such as GB/T18115.1-2006;
The detection of C is adopted high-frequency combustion-infrared method test according to GB/T12690.13-1990;
The detection of O is adopted noble gas pulse-infrared method test according to GB/T12690.4-2003;
The detection of N is adopted the test of rare gas element melting heat inducing defecation by enema and suppository according to GB/T 20124-2006.
Magnet performance detects according to GB/T 13560-2000 and GB/T 3217-1992, adopts the test of magnet performance tester.
The standard deviation S of chemical ingredients is calculated by following formula: S2=1/ (n-1) ∑ (Xi-X mean value) 2, and wherein Xi is the chemical ingredients of sample, X mean value is the average of the chemical composition of sample n point, n=10 among the present invention.
Electrolysis rare earth ferroalloy equipment used in the present invention as shown in Figure 1, the electrolyzer of this electrolysis rare earth ferroalloy equipment is a graphite cuvette 4, is surrounded by iron cover 5, thermal insulation layer 6, refractory brick 7 on the outer wall of graphite cuvette 4 successively; Be provided with insulcrete 9 in the middle of graphite cuvette 4 and the conducting plates 1; Middle part in graphite cuvette 4 is provided with iron cathode 1; In graphite cuvette 4, be provided with positive plate 2 around iron cathode 1; Positive plate 2 is connected with conducting plates 1; Center in the bottom of graphite cuvette 4 is provided with iron crucible 8, and relative with the iron cathode 1 on its top.During use, in the graphite cuvette 4 RF is housed
3-LiF fluoride molten salt electrolyte is equipped with rare earth ferroalloy in the iron crucible 8.
Adopt the circular graphitic cell of Φ 600mm, anode is made up of 4 graphite cakes, NdF in the ionogen
3Content is 65wt%, and LiF is 35wt%, and iron cathode is a Φ 55mm pure iron rod, average current intensity 2400A, and anodic current density is 0.5～0.8A/cm
2, cathode current density is 5～6A/cm
2, electrolysis temperature maintains 900～980 ℃.Every stove electrolysis 1 hour adds Neodymium trioxide 3.3kg, and continuous electrolysis 130 hours consumes Neodymium trioxide 425kg, consume neodymium fluoride 46kg, make NdFe alloy 421kg, average neodymium content is 90%, current efficiency is 75.3%, and the neodymium metal yield is 95.3%, and alloy analysis the results are shown in Table 1-1.
Add the alloy for preparing in the present embodiment to the neodymium iron boron principal constituent, adopt melt-spun → hydrogen fragmentation to prepare Sintered NdFeB magnet with airflow milling powder process → pressing under magnetic field → vacuum sintering technology, represent the homogeneity of chemical ingredients with standard deviation, analyze the standard deviation of Nd, Fe in the Sintered NdFeB magnet.For relatively, prepare Sintered NdFeB magnet with conventional method simultaneously, except Nd was interpolation separately, all the other items were all identical with the embodiment scheme.The Sintered NdFeB magnet of each scheme in the present embodiment with corresponding conventional method preparation compared, comprise the standard deviation and the magnet performance of chemical ingredients, the result sees Table 1-2 and 1-3 respectively.
Table 1-1 alloy component analysis result/wt%
| Nd | Fe | C | O | N |
| 90.0 | 9.6 | 0.045 | 0.036 | 0.01 |
The standard deviation of table 1-2 magnet composition
| Project | Nd | Fe |
| Add this alloy | 0.11 | 0.2 |
| Conventional method | 0.30 | 0.28 |
Table 1-3 magnet performance
| Project | Remanent magnetism Br (T) | HCJ Hcj (kA/m) | Maximum magnetic energy product (BH) max (kJ/m 3) |
| Add this alloy | 1.40 | 905 | 390 |
| Conventional method | 1.35 | 861 | 362 |
Adopt the circular graphitic cell of Φ 600mm, anode is made up of 4 graphite cakes, NdF in the ionogen
3Content is 75wt%, and LiF is 25wt%, and iron cathode is a Φ 55mm pure iron rod, average current intensity 2600A, and anodic current density is 0.6～0.9A/cm
2, cathode current density is 5～8A/cm
2, electrolysis temperature maintains 940～1020 ℃.About 1 hour of every stove electrolysis adds the about 3.6kg of Neodymium trioxide, and continuous electrolysis 160 hours consumes Neodymium trioxide 622kg, consume neodymium fluoride 55kg, make NdFe alloy 641kg, average neodymium content is 79.6%, current efficiency is 76%, and the neodymium metal yield is 95.8%, and alloy analysis the results are shown in Table 2-1.
Add the alloy for preparing in the present embodiment to the neodymium iron boron principal constituent, adopt melt-spun → hydrogen fragmentation to prepare Sintered NdFeB magnet with airflow milling powder process → pressing under magnetic field → vacuum sintering technology, represent the homogeneity of chemical ingredients with standard deviation, analyze the standard deviation of Nd, Fe in the Sintered NdFeB magnet.For relatively, prepare Sintered NdFeB magnet with conventional method simultaneously, except Nd was interpolation separately, all the other items were all identical with the embodiment scheme.The Sintered NdFeB magnet of each scheme in the present embodiment with corresponding conventional method preparation compared, comprise the standard deviation and the magnet performance of chemical ingredients, the result sees Table 2-2 and 2-3 respectively.
Table 2-1 alloy component analysis result/%
| Nd | Fe | C | O | N |
| 79.6 | 20.0 | 0.035 | 0.031 | 0.02 |
The standard deviation of table 2-2 magnet composition
| Project | Nd | Fe |
| Add this alloy | 0.15 | 0.2 |
| Conventional method | 0.32 | 0.27 |
Table 2-3 magnet performance
| Project | Remanent magnetism Br (T) | HCJ Hcj (kA/m) | Maximum magnetic energy product (BH) max (kJ/m 3) |
| Add this alloy | 1.39 | 900 | 384 |
| Conventional method | 1.35 | 855 | 360 |
Embodiment 3
Adopt the circular graphitic cell of Φ 600mm, anode is made up of 4 graphite cakes, NdF in the ionogen
3Content is 85wt%, and LiF is 15wt%, and iron cathode is a Φ 50mm pure iron rod, average current intensity 2800A, and anodic current density is 0.8～1.2A/cm
2, cathode current density is 7～11A/cm
2, electrolysis temperature maintains 980～1060 ℃.About 1 hour of every stove electrolysis adds the about 3.9kg of Neodymium trioxide, and continuous electrolysis 150 hours consumes Neodymium trioxide 584kg, consume neodymium fluoride 53kg, make NdFe alloy 726kg, average neodymium content is 71.2%, current efficiency is 76.2%, and the neodymium metal yield is 95.7%, and alloy analysis the results are shown in Table 3-1.
Add the alloy for preparing in the present embodiment to the neodymium iron boron principal constituent, adopt melt-spun → hydrogen fragmentation to prepare Sintered NdFeB magnet with airflow milling powder process → pressing under magnetic field → vacuum sintering technology, represent the homogeneity of chemical ingredients with standard deviation, analyze the standard deviation of Nd, Fe in the Sintered NdFeB magnet.For relatively, prepare Sintered NdFeB magnet with conventional method simultaneously, except Nd was interpolation separately, all the other items were all identical with the embodiment scheme.The Sintered NdFeB magnet of each scheme in the present embodiment with corresponding conventional method preparation compared, comprise the standard deviation and the magnet performance of chemical ingredients, the result sees Table 3-2 and 3-3 respectively.
Table 3-1 alloy component analysis result/%
| Nd | Fe | C | O | N |
| 71.2 | 28.4 | 0.069 | 0.036 | 0.02 |
The standard deviation of table 3-2 magnet composition
| Project | Nd | Fe |
| Add this alloy | 0.18 | 0.21 |
| Conventional method | 0.33 | 0.30 |
Table 3-3 magnet performance
| Project | Remanent magnetism Br (T) | HCJ Hcj (kA/m) | Maximum magnetic energy product (BH) max (kJ/m 3) |
| Add this alloy | 1.38 | 886 | 378 |
| Conventional method | 1.33 | 842 | 350 |
Embodiment 4
Adopt the circular graphitic cell of Φ 600mm, anode is made up of 4 graphite cakes, NdF in the ionogen
3Content is 90wt%, and LiF is 10wt%, and iron cathode is a Φ 40mm pure iron rod, and anodic current density is 1.0～1.5A/cm
2, average current intensity 3400A, cathode current density is 10～15A/cm
2, electrolysis temperature maintains 1020～1100 ℃.About 1 hour of every stove electrolysis adds the about 4.6kg of Neodymium trioxide, and continuous electrolysis 180 hours consumes Neodymium trioxide 837kg, consume neodymium fluoride 88kg, make NdFe alloy 1245kg, average neodymium content is 60%, current efficiency is 75.6%, and the neodymium metal yield is 95.5%, and alloy analysis the results are shown in Table 4-1.
Add the alloy for preparing in the present embodiment to the neodymium iron boron principal constituent, adopt melt-spun → hydrogen fragmentation to prepare Sintered NdFeB magnet with airflow milling powder process → pressing under magnetic field → vacuum sintering technology, represent the homogeneity of chemical ingredients with standard deviation, analyze the standard deviation of Nd, Fe in the Sintered NdFeB magnet.For relatively, prepare Sintered NdFeB magnet with conventional method simultaneously, except Nd was interpolation separately, all the other items were all identical with the embodiment scheme.The Sintered NdFeB magnet of each scheme in the present embodiment with corresponding conventional method preparation compared, comprise the standard deviation and the magnet performance of chemical ingredients, the result sees Table 4-2 and 4-3 respectively.
Table 4-1 alloy component analysis result/wt%
| Nd | Fe | C | O | N |
| 60.0 | 39.5 | 0.1 | 0.1 | 0.05 |
The standard deviation of table 4-2 magnet composition
| Project | Nd | Fe |
| Add this alloy | 0.20 | 0.22 |
| Conventional method | 0.40 | 0.30 |
Table 4-3 magnet performance
| Project | Remanent magnetism Br (T) | HCJ Hcj (kA/m) | Maximum magnetic energy product (BH) max (kJ/m 3) |
| Add this alloy | 1.38 | 880 | 375 |
| Conventional method | 1.33 | 838 | 350 |
Embodiment 5
Adopt the circular graphitic cell of Φ 600mm, anode is made up of 4 graphite cakes, NdF in the ionogen
3Content is 70wt%, PrF
3Be 20wt%, LiF is 10wt%, and iron cathode is a Φ 40mm pure iron rod, Nd in the rare earth oxide
2O
3Content is 78wt%, Pr
6O
11Be 22wt%, average current intensity 3300A, anodic current density is 1.0～1.5A/cm
2, cathode current density is 11～15A/cm
2, electrolysis temperature maintains 1020～1100 ℃.About 1 hour of every stove electrolysis adds mixed oxidization material 4.5kg, continuous electrolysis 130 hours, consume Praseodymium trioxide neodymium 590kg altogether, consume praseodymium fluoride neodymium 61kg, make PrNdFe alloy 724kg, current efficiency is 75.5%, and the rare earth metal yield is 95.6%, and alloy analysis the results are shown in Table 5-1.
Add the alloy for preparing in the present embodiment to the neodymium iron boron principal constituent, adopt melt-spun → hydrogen fragmentation to prepare Sintered NdFeB magnet with airflow milling powder process → pressing under magnetic field → vacuum sintering technology, represent the homogeneity of chemical ingredients with standard deviation, analyze the standard deviation of Pr, Nd, Fe in the Sintered NdFeB magnet.For relatively, prepare Sintered NdFeB magnet with conventional method simultaneously, except Pr, Nd were interpolation separately, all the other items were all identical with the embodiment scheme.The Sintered NdFeB magnet of each scheme in the present embodiment with corresponding conventional method preparation compared, comprise the standard deviation and the magnet performance of chemical ingredients, the result sees Table 5-2 and 5-3 respectively.
Table 5-1 alloy component analysis result/wt%
| Pr | Nd | Fe | C | O | N |
| 18.1 | 54.0 | 27.4 | 0.040 | 0.031 | 0.03 |
The standard deviation of table 5-2 magnet composition
| Project | Pr | Nd | Fe |
| Add this alloy | 0.12 | 0.13 | 0.2 |
| Conventional method | 0.22 | 0.28 | 0.27 |
Table 5-3 magnet performance
| Project | Remanent magnetism Br (T) | HCJ Hcj (kA/m) | Maximum magnetic energy product (BH) max (kJ/m3) |
| Add this alloy | 1.37 | 890 | 373 |
| Conventional method | 1.33 | 845 | 351 |
Adopt the circular graphitic cell of Φ 600mm, anode is made up of 4 graphite cakes, NdF in the ionogen
3Content is 50wt%, PrF
3Be 30wt%, LiF is 20wt%, and iron cathode is a Φ 55mm pure iron rod, Nd in the rare earth oxide
2O
3Content is 67wt%, Pr
6O
11Be 33wt%, average current intensity 2600A, anodic current density is 0.8～1.1A/cm
2, cathode current density is 5～9A/cm
2, electrolysis temperature maintains 940～1020 ℃.About 1 hour of every stove electrolysis adds Praseodymium trioxide neodymium 3.6kg, continuous electrolysis 120 hours, consume Praseodymium trioxide neodymium 434kg, consume praseodymium fluoride neodymium 39kg, make PrNdFe alloy 433kg, current efficiency is 76%, and the rare earth metal yield is 96.2%, and alloy analysis the results are shown in Table 6-1.
Add the alloy for preparing in the present embodiment to the neodymium iron boron principal constituent, adopt melt-spun → hydrogen fragmentation to prepare Sintered NdFeB magnet with airflow milling powder process → pressing under magnetic field → vacuum sintering technology, represent the homogeneity of chemical ingredients with standard deviation, analyze the standard deviation of Pr, Nd, Fe in the Sintered NdFeB magnet.For relatively, prepare Sintered NdFeB magnet with conventional method simultaneously, except Pr, Nd were interpolation separately, all the other items were all identical with the embodiment scheme.The Sintered NdFeB magnet of each scheme in the present embodiment with corresponding conventional method preparation compared, comprise the standard deviation and the magnet performance of chemical ingredients, the result sees Table 6-2 and 6-3 respectively.
Table 6-1 alloy component analysis result/wt%
| Pr | Nd | Fe | C | O | N |
| 29.0 | 59.3 | 11.3 | 0.036 | 0.024 | 0.021 |
The standard deviation of table 6-2 magnet composition
| Project | Pr | Nd | Fe |
| Add this alloy | 0.15 | 0.18 | 0.2 |
| Conventional method | 0.25 | 0.30 | 0.28 |
Table 6-3 magnet performance
| Project | Remanent magnetism Br (T) | HCJ Hcj (kA/m) | Maximum magnetic energy product (BH) max (kJ/m 3) |
| Add this alloy | 1.37 | 884 | 372 |
| Conventional method | 1.32 | 840 | 346 |
Embodiment 7
Adopt the circular graphitic cell of Φ 600mm, anode is made up of 4 graphite cakes, NdF in the ionogen
3Content is 65wt%, PrF
3Be 20wt%, LiF is 15wt%, and iron cathode is a Φ 50mm pure iron rod, Nd in the rare earth oxide
2O
3Content is 75wt%, Pr
6O
11Be 25wt%, average current intensity 2800A, anodic current density is 0.8～1.1A/cm
2, cathode current density is 8～11A/cm
2, electrolysis temperature maintains 980～1060 ℃.About 1 hour of every stove electrolysis adds Praseodymium trioxide neodymium 3.9kg, continuous electrolysis 140 hours, consume Praseodymium trioxide neodymium 542kg, consume praseodymium fluoride neodymium 51kg, make PrNdFe alloy 556kg, current efficiency is 75.3%, and the neodymium metal yield is 95.4%, and alloy analysis the results are shown in Table 7-1.
Add the alloy for preparing in the present embodiment to the neodymium iron boron principal constituent, adopt melt-spun → hydrogen fragmentation to prepare Sintered NdFeB magnet with airflow milling powder process → pressing under magnetic field → vacuum sintering technology, represent the homogeneity of chemical ingredients with standard deviation, analyze the standard deviation of Pr, Nd, Fe in the Sintered NdFeB magnet.For relatively, prepare Sintered NdFeB magnet with conventional method simultaneously, except Pr, Nd were interpolation separately, all the other items were all identical with the embodiment scheme.The Sintered NdFeB magnet of each scheme in the present embodiment with corresponding conventional method preparation compared, comprise the standard deviation and the magnet performance of chemical ingredients, the result sees Table 7-2 and 7-3 respectively.
Table 7-1 alloy component analysis result/wt%
| Pr | Nd | Fe | C | O | N |
| 21.7 | 63.8 | 14.1 | 0.033 | 0.035 | 0.044 |
The standard deviation of table 7-2 magnet composition
| Project | Pr | Nd | Fe |
| Add this alloy | 0.14 | 0.15 | 0.2 |
| Conventional method | 0.28 | 0.29 | 0.28 |
Table 7-3 magnet performance
| Project | Remanent magnetism Br (T) | HCJ Hcj (kA/m) | Maximum magnetic energy product (BH) max (kJ/m 3) |
| Add this alloy | 1.36 | 888 | 367 |
| Conventional method | 1.32 | 845 | 346 |
Embodiment 8
Adopt the circular graphitic cell of Φ 600mm, anode is made up of 4 graphite cakes, NdF in the ionogen
3Content is 54wt%, PrF
3Be 36wt%, LiF is 10wt%, and iron cathode is a Φ 55mm pure iron rod, Nd in the rare earth oxide
2O
3Content is 60wt%, Pr
6O
11Be 40wt%, average current intensity 3300A, anodic current density is 1.0～1.5A/cm
2, cathode current density is 11～15A/cm
2, electrolysis temperature maintains 1020～1100 ℃.About 1 hour of every stove electrolysis adds Praseodymium trioxide neodymium 4.5kg, continuous electrolysis 100 hours, consume Praseodymium trioxide neodymium 453kg altogether, consume praseodymium fluoride neodymium 49kg, make PrNdFe alloy 498kg, current efficiency is 75.4%, and the rare earth metal yield is 95.2%, and alloy analysis the results are shown in Table 8-1.
Add the alloy for preparing in the present embodiment to the neodymium iron boron principal constituent, adopt melt-spun → hydrogen fragmentation to prepare Sintered NdFeB magnet with airflow milling powder process → pressing under magnetic field → vacuum sintering technology, represent the homogeneity of chemical ingredients with standard deviation, analyze the standard deviation of Pr, Nd, Fe in the Sintered NdFeB magnet.For relatively, prepare Sintered NdFeB magnet with conventional method simultaneously, except Pr, Nd were interpolation separately, all the other items were all identical with the embodiment scheme.The Sintered NdFeB magnet of each scheme in the present embodiment with corresponding conventional method preparation compared, comprise the standard deviation and the magnet performance of chemical ingredients, the result sees Table 8-2 and 8-3 respectively.
Table 8-1 alloy component analysis result/%
| Pr | Nd | Fe | C | O | N |
| 32.2 | 48.3 | 19.1 | 0.047 | 0.039 | 0.046 |
The standard deviation of table 8-2 magnet composition
| Project | Pr | Nd | Fe |
| Add this alloy | 0.14 | 0.14 | 0.22 |
| Conventional method | 0.28 | 0.28 | 0.30 |
Table 8-3 magnet performance
| Project | Remanent magnetism Br (T) | HCJ Hcj (kA/m) | Maximum magnetic energy product (BH) max (kJ/m 3) |
| Add this alloy | 1.36 | 878 | 366 |
| Conventional method | 1.31 | 835 | 340 |
Embodiment 9
Adopt the circular graphitic cell of Φ 600mm, anode is made up of 4 graphite cakes, NdF in the ionogen
3Content is 35wt%, PrE
3Be 25wt%, LiF is 40wt%, and iron cathode is a Φ 50mm pure iron rod, Nd in the rare earth oxide
2O
3Content is 58wt%, Pr
6O
11Be 42wt%, average current intensity 3200A, anodic current density is 0.8～1.2A/cm
2, cathode current density is 8～10A/cm
2, electrolysis temperature maintains 900～980 ℃.About 1 hour of every stove electrolysis adds Praseodymium trioxide neodymium 4.4kg, continuous electrolysis 90 hours, consume Praseodymium trioxide neodymium 399kg altogether, consume praseodymium fluoride neodymium 38kg, make PrNdFe alloy 389kg, current efficiency is 75.5%, and the rare earth metal yield is 95.4%, and alloy analysis the results are shown in Table 9-1.
Add the alloy for preparing in the present embodiment to the neodymium iron boron principal constituent, adopt melt-spun → hydrogen fragmentation to prepare Sintered NdFeB magnet with airflow milling powder process → pressing under magnetic field → vacuum sintering technology, represent the homogeneity of chemical ingredients with standard deviation, analyze the standard deviation of Pr, Nd, Fe in the Sintered NdFeB magnet.For relatively, prepare Sintered NdFeB magnet with conventional method simultaneously, except Pr, Nd were interpolation separately, all the other items were all identical with the embodiment scheme.The Sintered NdFeB magnet of each scheme in the present embodiment with corresponding conventional method preparation compared, comprise the standard deviation and the magnet performance of chemical ingredients, the result sees Table 9-2 and 9-3 respectively.
Table 9-1 alloy component analysis result/%
| Pr | Nd | Fe | C | O | N |
| 36.0 | 54.0 | 9.4 | 0.048 | 0.033 | 0.023 |
The standard deviation of table 9-2 magnet composition
| Project | Pr | Nd | Fe |
| Add this alloy | 0.15 | 0.13 | 0.22 |
| Conventional method | 0.30 | 0.25 | 0.35 |
Table 9-3 magnet performance
| Project | Remanent magnetism Br (T) | HCJ Hcj (kA/m) | Maximum magnetic energy product (BH) max (kJ/m 3) |
| Add this alloy | 1.36 | 877 | 365 |
| Conventional method | 1.30 | 835 | 335 |
Embodiment 10
Adopt the circular graphitic cell of Φ 600mm, anode is made up of 4 graphite cakes, NdF in the ionogen
3Content is 75wt%, and LiF is 25wt%, and iron cathode is a Φ 55mm pure iron rod, average current intensity 2600A, and anodic current density is 0.6～0.9A/cm
2, cathode current density is 5～8A/cm
2, electrolysis temperature maintains 940～1020 ℃.About 1 hour of every stove electrolysis adds the about 3.6kg of Neodymium trioxide, and continuous electrolysis 160 hours consumes Neodymium trioxide 622kg, consumes neodymium fluoride 55kg, makes NdFe alloy 641kg, and average neodymium content is 79.6%, and current efficiency is 76%, and the neodymium metal yield is 95.8%.Utilize the NdFe alloy of above-mentioned preparation, add and join a certain amount of Fe, the NdFe alloy ingredient that is smelted into sees Table 10-1.
Add the alloy for preparing in the present embodiment to the neodymium iron boron principal constituent, adopt melt-spun → hydrogen fragmentation to prepare Sintered NdFeB magnet with airflow milling powder process → pressing under magnetic field → vacuum sintering technology, represent the homogeneity of chemical ingredients with standard deviation, analyze the standard deviation of Nd, Fe in the Sintered NdFeB magnet.For relatively, prepare Sintered NdFeB magnet with conventional method simultaneously, except Nd was interpolation separately, all the other items were all identical with the embodiment scheme.The Sintered NdFeB magnet of each scheme in the present embodiment with corresponding conventional method preparation compared, comprise the standard deviation and the magnet performance of chemical ingredients, the result sees Table 10-2 and 10-3 respectively.
Table 10-1 alloy component analysis result/%
| Nd | Fe | C | O | N |
| 30.0 | 69.2 | 0.033 | 0.031 | 0.01 |
The standard deviation of table 10-2 magnet composition
| Project | Nd | Fe |
| Add this alloy | 0.10 | 0.18 |
| Conventional method | 0.18 | 0.24 |
Table 10-3 magnet performance
| Project | Remanent magnetism Br (T) | HCJ Hcj (kA/m) | Maximum magnetic energy product (BH) max (kJ/m 3) |
| Add this alloy | 1.41 | 1000 | 394 |
| Conventional method | 1.35 | 950 | 360 |
Embodiment 11
Adopt the circular graphitic cell of Φ 600mm, anode is made up of 4 graphite cakes, NdF in the ionogen
3Content is 75wt%, and LiF is 25wt%, and iron cathode is a Φ 55mm pure iron rod, average current intensity 2600A, and anodic current density is 0.6～0.9A/cm
2, cathode current density is 5～8A/cm
2, electrolysis temperature maintains 940～1020 ℃.About 1 hour of every stove electrolysis adds the about 3.6kg of Neodymium trioxide, and continuous electrolysis 160 hours consumes Neodymium trioxide 622kg, consumes neodymium fluoride 55kg, makes NdFe alloy 641kg, and average neodymium content is 79.6%, and current efficiency is 76%, and the neodymium metal yield is 95.8%.Utilize the NdFe alloy of above-mentioned preparation, add and join a certain amount of Fe, the NdFe alloy ingredient that is smelted into sees Table 11-1.
Add the alloy for preparing in the present embodiment to the neodymium iron boron principal constituent, adopt melt-spun → hydrogen fragmentation to prepare Sintered NdFeB magnet with airflow milling powder process → pressing under magnetic field → vacuum sintering technology, represent the homogeneity of chemical ingredients with standard deviation, analyze the standard deviation of Nd, Fe in the Sintered NdFeB magnet.For relatively, prepare Sintered NdFeB magnet with conventional method simultaneously, except Nd was interpolation separately, all the other items were all identical with the embodiment scheme.The Sintered NdFeB magnet of each scheme in the present embodiment with corresponding conventional method preparation compared, comprise the standard deviation and the magnet performance of chemical ingredients, the result sees Table 11-2 and 11-3 respectively.
Table 11-1 alloy component analysis result/%
| Nd | Fe | C | O | N |
| 40.0 | 59.0 | 0.033 | 0.03 | 0.01 |
The standard deviation of table 11-2 magnet composition
| Project | Nd | Fe |
| Add this alloy | 0.13 | 0.19 |
| Conventional method | 0.20 | 0.25 |
Table 11-3 magnet performance
| Project | Remanent magnetism Br (T) | HCJ Hcj (kA/m) | Maximum magnetic energy product (BH) max (kJ/m 3) |
| Add this alloy | 1.40 | 1000 | 384 |
| Conventional method | 1.35 | 945 | 355 |
Embodiment 12
Adopt the circular graphitic cell of Φ 600mm, anode is made up of 4 graphite cakes, NdF in the ionogen
3Content is 75wt%, and LiF is 25wt%, and iron cathode is a Φ 55mm pure iron rod, average current intensity 2600A, and anodic current density is 0.6～0.9A/cm
2, cathode current density is 5～8A/cm
2, electrolysis temperature maintains 940～1020 ℃.About 1 hour of every stove electrolysis adds the about 3.6kg of Neodymium trioxide, and continuous electrolysis 160 hours consumes Neodymium trioxide 622kg, consumes neodymium fluoride 55kg, makes NdFe alloy 641kg, and average neodymium content is 79.6%, and current efficiency is 76%, and the neodymium metal yield is 95.8%.Utilize the NdFe alloy of above-mentioned preparation, add and join a certain amount of Fe, the NdFe alloy ingredient that is smelted into sees Table 12-1.
Add the alloy for preparing in the present embodiment to the neodymium iron boron principal constituent, adopt melt-spun → hydrogen fragmentation to prepare Sintered NdFeB magnet with airflow milling powder process → pressing under magnetic field → vacuum sintering technology, represent the homogeneity of chemical ingredients with standard deviation, analyze the standard deviation of Nd, Fe in the Sintered NdFeB magnet.For relatively, prepare Sintered NdFeB magnet with conventional method simultaneously, except Nd was interpolation separately, all the other items were all identical with the embodiment scheme.The Sintered NdFeB magnet of each scheme in the present embodiment with corresponding conventional method preparation compared, comprise the standard deviation and the magnet performance of chemical ingredients, the result sees Table 12-2 and 12-3 respectively.
Table 12-1 alloy component analysis result/%
| Nd | Fe | C | O | N |
| 50.0 | 49.0 | 0.032 | 0.031 | 0.01 |
The standard deviation of table 12-2 magnet composition
| Project | Nd | Fe |
| Add this alloy | 0.15 | 0.19 |
| Conventional method | 0.28 | 0.25 |
Table 12-3 magnet performance
| Project | Remanent magnetism Br (T) | HCJ Hcj (kA/m) | Maximum magnetic energy product (BH) max (kJ/m 3) |
| Add this alloy | 1.37 | 900 | 372 |
| Conventional method | 1.32 | 855 | 346 |
Claims (13)
1. rare earth ferroalloy is characterized in that:
A) rare earth element is neodymium or praseodymium neodymium, and content of rare earth is 30～90wt%, and surplus is iron and inevitable impurity;
B) this alloy C content≤0.1wt%, O content≤0.1wt%, N content≤0.05wt%;
2. rare earth ferroalloy that is applied to Nd-Fe-Bo permanent magnet material is characterized in that:
A) rare earth element is neodymium or praseodymium neodymium, and content of rare earth is 30～90wt%, and surplus is iron and inevitable impurity;
B) this alloy C content≤0.05wt%, O content≤0.05wt%, N content≤0.03wt%;
3. according to claim 1 or 2 described rare earth ferroalloys, it is characterized in that content of rare earth is 60～90wt%, neodymium content is 60～100wt% in the rare earth element.
4. a kind of rare earth ferroalloy according to claim 1 and 2 is characterized in that: C content≤0.03wt%.
5. a method for preparing claim 1 or 2 described rare earth ferroalloys is characterized in that doing electrolyzer with graphite, and graphite cake is an anode, and the pure iron rod is the consumable negative electrode, and the iron crucible is as the rare earth ferroalloy susceptor, at NdF
3-LiF or PrF
3-NdF
3-LiF or (PrNd) F
3In the fluoride molten salt electrolyte system of-LiF, be the electrolysis raw material, pass to the direct current electrolysis and obtain rare earth ferroalloy with the rare earth oxide.
6. the preparation method of rare earth ferroalloy according to claim 5 is characterized in that:
A) the fused salt electrolysis temperature is between 900～1100 ℃;
B) anodic current density is 0.5～1.5A/cm
2, cathode current density is 5～15A/cm
2
C) current efficiency is greater than 75%, and the rare earth metal yield is greater than 95%.
7. the preparation method of rare earth ferroalloy according to claim 5, it is characterized in that the electrolyte body of fused salt electrolysis is: neodymium fluoride is 35～90wt%, praseodymium fluoride is 0～36wt%, lithium fluoride 5～40wt%.
8. the preparation method of rare earth ferroalloy according to claim 5 is characterized in that the content of Neodymium trioxide in the rare earth oxide of fused salt electrolysis is 58～100wt%, and Praseodymium trioxide content is 0～42wt%.
9. the preparation method of rare earth ferroalloy according to claim 5 is characterized in that purity＞95% of described pure iron rod, can be that diameter is that the pole or the cross section length of side of 30～100mm is the square rod of 30～100mm, or form by many.
10. the preparation method of rare earth ferroalloy according to claim 5 is characterized in that described graphite anode is made up of the polylith graphite cake.
11. a method for preparing claim 1 or 2 described rare earth alloies is characterized in that selecting corresponding raw material according to the Pr in the composition of claim 1 or 2, Nd, Fe and content thereof, adopts the smelting method for preparing rare earth ferroalloy.
12. the preparation method of rare earth ferroalloy according to claim 11 is characterized in that employed raw material except iron, also contains at least a in the rare earth ferroalloy of the described method preparation of metal praseodymium, neodymium metal, praseodymium neodymium alloy, claim 5.
13. a rare earth permanent-magnetic material is characterized in that having used the described rare earth ferroalloy of claim 1～4.
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