CN101240394B - Rare earth alloy, preparation technique and application thereof - Google Patents
Rare earth alloy, preparation technique and application thereof Download PDFInfo
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Abstract
The invention relates to a light rare earth base heavy rare earth alloy, a preparation technology and application thereof. The alloy contains 1-40wt% heavy rare earth, and is prepared by oxide fused salt electrolysis process in fluoride molten salt. The electrolyte is composed of rare earth fluoride, lithium fluoride and magnesium fluoride, the compositions are: 65 to 87wt% of base fluoride in rare earth fluoride, 5 to 25wt% of heavy rear earth fluoride, 5-12wt% of lithium fluoride and 0.5 to 3wt% of magnesium fluoride. Since the electric efficiency is larger than 75%, the metal recovery rateis large than 90%, the preparation technology is especially suitable for industrialized mass production.
Description
Technical field:
The present invention relates to oxide electrolysis method preparation technology and application thereof in a kind of light rare earths based heavy rare earths alloy, the villiaumite system.Belong to the rare earth metallurgy field.
Technical background:
The electronic structure of rare earth element uniqueness, make it have characteristics such as excellent magnetic, light, electricity, be widely used in the preparation of functional materials, as needing to use a large amount of metal praseodymiums, neodymium, dysprosium, terbium etc. in the neodymium iron boron magnetic body, quick growth along with rare earth functional materials demands such as magneticsubstances, the rare earth metal price goes up significantly, and magnet producer faces huge cost pressure.In order to reduce cost, new prescription and new production method are constantly sought by neodymium iron boron enterprise and Metal Production enterprise, replace the pure metal raw material of above-mentioned costliness as adopting low, the low-melting praseodymium neodymium alloy of production cost, Dy-Fe alloy in recent years.The praseodymium neodymium alloy is directly to adopt the direct electrolysis production of praseodymium neodymium mixed oxide, has saved praseodymium neodymium extracting and separating operation, and cost reduces significantly; Dy-Fe alloy is directly to adopt dysprosium oxide electrolysis and meltability negative electrode iron to form alloy, and fusing point is reduced greatly.The appearance of this type of alloy greatly reduces the raw materials cost of neodymium iron boron magnetic body, has therefore obtained promoting rapidly, and nearly all neodymium iron boron magnetic body all adopts praseodymium neodymium alloy, Dy-Fe alloy now.At present, in order further to improve the performance of magneticsubstance, most of neodymium iron boron magnetic body not only contains light rare earths but also needs add a small amount of heavy rare earths, if energy direct production light rare earths based heavy rare earths alloy such as alloys such as praseodymium neodymium dysprosium, praseodymium neodymium terbium dysprosium, because the terbium dysprosium is also without extracting and separating, also produce dystectic heavy metal terbium, dysprosium etc. without the reduction distillation method, and directly adopt fused salt electrolysis process to produce low-melting alloy with light rare earths praseodymium neodymium etc., like this, production cost can reduce significantly, and energy consumption also reduces greatly.
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 uncontrollable, only limit to laboratory study, be unsuitable for large-scale industrial production.
Chinese patent CN1040399A has proposed a kind of preparation method and device of the Dy-Nd of production alloy, the oxide electrolysis of same employing villiaumite system, the villiaumite system is made up of dysprosium fluoride, neodymium fluoride, lithium fluoride, barium fluoride, add the oxidation material and continue electrolysis, having obtained dysprosium content is the neodymium-dysprosium alloy of 3～10wt%.But the dysprosium content range is on the low side in the neodymium-dysprosium alloy that this technology obtains, in the higher NdFeB material of dysprosium content requirement, can't use, carbon content more than its 0.1wt% is also higher simultaneously, can not prepare high performance neodymium iron boron magnetic body, has limited the large-scale promotion of this technology.
Chinese patent CN1025228C has proposed a kind of preparation method of rare earth alloy, this patent adopts the oxide electrolysis of villiaumite system, the villiaumite system is made up of matrix metal fluorochemical, heavy rare earth fluoride, lithium fluoride, Calcium Fluoride (Fluorspan), strengthened heavy rare earths ratio in ionogen, the oxidation material with respect to Chinese patent CN1040399A, obtained heavy rare earths content and reached as high as 35% neodymium and neodymium based heavy rare earths alloy, carbon content is controlled at below 0.05% simultaneously.But the described process current efficient fluctuation of this patent is bigger, and minimum current efficient is 20%, maximum current efficient＜75%, and metal yield＜90% has brought high energy consumption and expensive to suitability for industrialized production.
Summary of the invention:
At above problem, the present invention proposes a kind of light rare earths based heavy rare earths alloy and low-cost efficiently industrial preparation process thereof.
Compared with prior art, do not have barium fluoride and Calcium Fluoride (Fluorspan) in the electrolyte system of the present invention, this be because: the existence of barium fluoride and Calcium Fluoride (Fluorspan), can cause the accumulation of barium in the ionogen, calcium, ionogen viscosity increases thereupon, runs up to certain stage, can have a strong impact on the steady running of electrolytic process.Simultaneously, calcium has certain solid solubility in rare earth metal, and product purity is difficult to guarantee that alloy calcium contents of the present invention is less than 0.05wt%.
Maximum innovation part of the present invention is: electrolytical composition is different, promptly on rare earth fluoride and lithium fluoride basis, introduced the magnesium fluoride of low ratio, magnesium fluoride can increase the alternate interfacial tension of ionogen and rare earth alloy liquid two, make alloy and ionogen natural layering, reduce especially composition such as ionogen and Si, Ca of foreign matter content.In addition, through repeatedly experiment discovery, the introducing of low ratio magnesium fluoride, the bottom of electrolytic tank dry slag obviously reduces, ionogen viscosity degradation, good fluidity.Therefore the adding of magnesium fluoride can improve electrolytical electric conductivity, imitates thereby improve electricity.
The add-on of magnesium fluoride can not be too many, and this is because Mg
2+Theoretical electropotential than Ca
2+, Ba
2+Even most rare earth ions all will be just, other element ion is easier relatively in the fused salt electrolysis process separates out, in order to suppress separating out of magnesium ion, the concentration of rare earth fluorine must be higher than the concentration of magnesium fluoride far away, make it produce the intensive concentration polarization, the electropotential of rare earth ion is moved to positive dirction, alloying action between rare earth metal also can produce same effect simultaneously, these conditions all make the virtual electrode current potential of rare earth ion far just in magnesium ion, facts have proved, when magnesium ion just can not separated out less than 3% the time.
Through the test of many times checking, adopt the present invention to obtain that light rare earths based heavy rare earths alloying constituent is even, steady quality, heavy rare earths content reaches as high as 40wt%, nitrogen, calcium contents all are controlled in the 0.05wt%, this process current efficient＞75%, metal yield＞90%, electrolytic process is controlled easily, is suitable for large-scale industrial production.
Particular content of the present invention is:
1. method for preparing light rare earths based heavy rare earths alloy, this alloy contains the heavy rare earths of 1～40wt%, all the other be light rare earths and total amount less than the inevitable impurity of 1wt%, it is characterized in that the preparation method is:
A) ionogen is made of matrix light rare earth metal fluorochemical, heavy rare earth metal fluorochemical, lithium fluoride and magnesium fluoride, oxide compound is made of matrix light rare earth metal oxide compound and heavy rare earth metal oxide, wherein matrix light rare earth metal fluorochemical is 55～85wt%, heavy rare earth fluoride is 5～35wt%, lithium fluoride 5～12wt%, magnesium fluoride 0.5～3wt%;
B) the fused salt electrolysis temperature is between 1000～1200 ℃;
C) anodic current density is 0.5～1.2A/cm
2, cathode current density is 10～17A/cm
2。
Described light rare earths based heavy rare earths alloy is characterized in that: light rare earths is selected from one or more in lanthanum, cerium, praseodymium, neodymium, samarium, the europium formation group, and heavy rare earths is selected from one or more in yttrium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium formation group.
Described light rare earths based heavy rare earths alloy is characterized in that: light rare earths is selected from one or more in lanthanum, cerium, praseodymium, the neodymium formation group, and heavy rare earths is selected from one or more in terbium, gadolinium, dysprosium, holmium, the erbium formation group.
The preparation method of described light rare earths based heavy rare earths alloy is characterized in that, the oxide bulk of fused salt electrolysis is: matrix light rare earth metal oxide compound is 62～99wt%, and heavy rare earth metal oxide is: 1～38wt%.
The preparation method of described light rare earths based heavy rare earths alloy is characterized in that, when heavy rare-earth oxide by Ho
2O
3, Er
2O
3In one or both when constituting, electrolysis temperature is 1100～1200 ℃, cathode current density is 12～17A/cm
2
The preparation method of described light rare earths based heavy rare earths alloy is characterized in that, by the light rare earths based heavy rare earths alloy of this prepared, its impurity N content is less than 0.05wt%.
The preparation method of described light rare earths based heavy rare earths alloy is characterized in that, by the light rare earths based heavy rare earths alloy of this prepared, its impurity Ca content is less than 0.05wt%.
A kind of rare earth permanent-magnetic material is characterized in that using the rare earth alloy of the method preparation of having adopted described in this patent.
8, a kind of rare earth giant magnetostrictive material is characterized in that using the rare earth alloy of the method preparation of having adopted described in this patent.
Heavy rare earths content is in 1～40wt% in neodymium base that the present invention obtained and the Nd-Pr base heavy rare-earth alloy, and heavy rare earth element ratio control in ionogen and oxidation material all is lower than prior art, mainly considers the control of application and electrolytic process, and reason is:
The neodymium of the heavy rare earths content of (1) 1～40wt% and praseodymium meodymium-base alloy can satisfy the needs of existing neodymium-iron-boron magnetic material fully,
(2) heavy rare earths content is too high, causes alloy melting point to raise, and making alloy mobile variation on tungsten cathode of separating out in a large number attached to cathode surface, influences normally carrying out of electrolytic process, causes the decline of current efficiency and metal yield.Simultaneously, the heavy rare earth element ion that the standard potential of praseodymium, neodymium ion is addressed more than the present invention will just be to guarantee heavy rare earth element ratio in the alloy, in the electrolytic process in the oxidation material additional proportion of heavy rare-earth oxide must be lower than heavy rare earths content in the alloy.
The control of cathode current density, electrolysis temperature is extremely important, because cathode current density and electrolysis temperature influence the electrolyte circulation situation jointly, is arranging alloy in the speed of separating out of negative electrode and the relative proportion of dissolution rate, and the one-tenth of decision electrolytic production is grouped into.Cathode current density in the regulation electrolytic process of the present invention is controlled at 10～17A/cm
2, 1000～1200 ℃ of electrolysis temperatures, wherein 12～17A/cm
2, 1100～1200 ℃ for preparation is the optimum range of the rare earth alloy of main component with high-melting-point element Er, Ho, maximum value is less than prior art in this scope.Prior art thinks that the high cathode current density raises the cathode zone temperature, helps the alloy preparation, effectively reduces electrolysis temperature.But cathode current density is excessive, can increase cathodic polarization, promotes separating out of low electrode current potential neodymium, praseodymium, thereby reduces the ratio of heavy rare earth element in the alloy.Simultaneously big cathode current density makes that the probability of separating out of alkaline-earth metal increases in the ionogen, finally influences alloy purity.
Specific embodiment
Example one:
Ionogen ratio NdF
3: DyF
3: LiF: MgF
2=55: 35: 8: 2, the reinforced ratio of mixture was Nd
2O
3: Dy
2O
3=62: 38,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 10A/cm
2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 4.3kg.Obtain alloy 3.4kg, dysprosium content 40wt% in the alloy, current efficiency is 81%, yield 93%.Alloy component analysis the results are shown in following table:
Table 1 example 1 alloy component analysis is wt% as a result
| Nd | Dy | Impurity |
| 59.5 | 40 | Surplus |
Example two:
Ionogen ratio NdF
3: DyF
3: LiF: MgF
2=62: 32: 5: 1, the reinforced ratio of mixture was Nd
2O
3: Dy
2O
3=68: 32,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 15A/cm2, anodic current density 0.9A/cm
2, electrolysis time 1 hour, the mixture add-on is 4kg.Obtain alloy 3.2kg, Dy content 35wt% in the alloy, current efficiency is 76%, yield 93%.Alloy component analysis the results are shown in following table:
Table 2 example 2 alloy component analysis are wt% as a result
| Nd | Dy | Impurity |
| 64.5 | 35 | Surplus |
Example three:
Ionogen ratio NdF
3: DyF
3: LiF: MgF
2=70: 20: 9.5: 0.5, the reinforced ratio of mixture was Nd
2O
3: Dy
2O
3=83: 17,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 10A/cm
2, anodic current density 1.0A/cm
2, electrolysis time 1 hour, the mixture add-on is 4.2kg.Obtain alloy 3.3kg, dysprosium content 19wt% in the alloy, current efficiency is 81%, yield 93%.Alloy component analysis the results are shown in following table:
Table 3 example 3 alloy component analysis are wt% as a result
| Nd | Dy | Impurity |
| 80.6 | 19 | Surplus |
Example four:
Ionogen ratio NdF
3: DyF
3: LiF: MgF
2=70: 20: 9.5: 0.5, the reinforced ratio of mixture was Nd
2O
3: Dy
2O
3=87: 13,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 10A/cm
2, anodic current density 1.0A/cm
2, electrolysis time 1 hour, the mixture add-on is 3.6kg.Obtain alloy 2.9kg, dysprosium content 14.5wt% in the alloy, current efficiency is 81%, yield 93%.Alloy component analysis the results are shown in following table:
Table 4 example 4 alloy component analysis are wt% as a result
| Nd | Dy | Impurity |
| 85.1 | 14.5 | Surplus |
Example five:
Ionogen ratio NdF
3: DyF
3: LiF: MgF
2=85: 5: 9: 1, the reinforced ratio of mixture was Nd
2O
3: Dy
2O
3=95: 5,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 10A/cm
2, anodic current density 1.0A/cm
2, electrolysis time 1 hour, the mixture add-on is 4kg.Obtain alloy 3.2kg, dysprosium content 6.5wt% in the alloy, current efficiency is 81%, yield 93%.Alloy component analysis the results are shown in following table:
Table 5 example 5 alloy component analysis are wt% as a result
| Nd | Dy | Impurity |
| 93.1 | 6.5 | Surplus |
Example six:
Ionogen ratio NdF
3: LiF: MgF
2=85: 12: 3, the reinforced ratio of mixture was Nd
2O
3: Dy
2O
3=99: 1,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 10A/cm
2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 4.7kg.Obtain alloy 3.3kg, dysprosium content 1wt% in the alloy, current efficiency is 83%, yield 93%.Alloy component analysis the results are shown in following table:
Table 6 example 6 alloy component analysis are wt% as a result
| Nd | Dy | Impurity |
| 98.5 | 1 | Surplus |
Example seven:
Ionogen ratio NdF
3: TbF
3: LiF: MgF
2=60: 30: 8: 2, the reinforced ratio of mixture was Nd
2O
3: Tb
4O
7=62: 38,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 12A/cm
2, anodic current density 0.9A/cm
2, electrolysis time 1 hour, the mixture add-on is 3.1kg.Obtain alloy 2.6kg, terbium content 40wt% in the alloy, current efficiency is 72%, yield 93%.Alloy component analysis the results are shown in following table:
Table 7 example 7 alloy component analysis are wt% as a result
| Nd | Tb | Impurity |
| 59.5 | 40 | Surplus |
Example eight:
Ionogen ratio PrF
3: TbF
3: LiF: MgF
2=66: 28: 5.5: 0.5, the reinforced ratio of mixture was Pr
6O
11: Tb
4O
7=72: 28,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 15A/cm
2, anodic current density 1.1A/cm
2, electrolysis time 1 hour, the mixture add-on is 3.5kg.Obtain alloy 2.8kg, Tb content 30wt% in the alloy, current efficiency is 77%, yield 93%.Alloy component analysis the results are shown in following table:
Table 8 example 8 alloy component analysis are wt% as a result
| Pr | Tb | Impurity |
| 69.5 | 30 | Surplus |
Example nine:
Ionogen ratio NdF
3: TbF
3: LiF: MgF
2=77: 13: 8: 2, the reinforced ratio of mixture was Nd
2O
3: Tb
4O
7=88: 12,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 14A/cm
2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 3.9kg.Obtain alloy 3.1kg, Tb content 14.9wt% in the alloy, current efficiency is 81%, yield 93%.Alloy component analysis the results are shown in following table:
Table 9 example 9 alloy component analysis are wt% as a result
| Nd | Tb | Impurity |
| 84.6 | 14.9 | Surplus |
Example ten:
Ionogen ratio NdF
3: TbF
3: LiF: MgF
2=85: 5: 8: 2, the reinforced ratio of mixture was Nd
2O
3: Tb
4O
7=95: 5,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 14A/cm
2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 4kg.Obtain alloy 3.2kg, Tb content 6.6wt% in the alloy, current efficiency is 81%, yield 93%.Alloy component analysis the results are shown in following table:
Table 10 example 10 alloy component analysis are wt% as a result
| Nd | Tb | Impurity |
| 93 | 6.6 | Surplus |
Example 11:
Ionogen ratio PrF
3: LiF: MgF
2=85: 12: 3, the reinforced ratio of mixture was Pr
6O
11: Tb
4O
7=99: 1,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 13A/cm
2, anodic current density 1A/cm
2, electrolysis time 1 hour, the mixture add-on is 4kg.Obtain alloy 3.1kg, Tb content wt1% in the alloy, current efficiency is 80%, yield 92%.Alloy component analysis the results are shown in following table:
Table 11 example 11 alloy component analysis are wt% as a result
| Pr | Tb | Impurity |
| 98.5 | 1 | Surplus |
Example 12:
Ionogen ratio (Pr-Nd) F
3: DyF
3: LiF: MgF
2=60: 30: 8: 2, the reinforced ratio of mixture was (Pr-Nd)
2O
3: Dy
2O
3=62: 38,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 11A/cm
2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 4.3kg.Obtain alloy 3.4kg, dysprosium content 40wt% in the alloy, current efficiency is 81%, yield 93%.Alloy component analysis the results are shown in following table:
Table 12 example 12 alloy component analysis are wt% as a result
| Pr | Nd | Dy | Impurity |
| 15 | 44.6 | 40 | Surplus |
Example 13:
Ionogen ratio (Pr-Nd) F
3: DyF
3: LiF: MgF
2=62: 32: 5: 1, the reinforced ratio of mixture was (Pr-Nd)
2O
3: Dy
2O
3=68: 32,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 14A/cm2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 4kg.Obtain alloy 3.2kg, Dy content 35wt% in the alloy, current efficiency is 76%, yield 93%.Alloy component analysis the results are shown in following table:
Table 13 example 13 alloy component analysis are wt% as a result
| Pr | Nd | Dy | Impurity |
| 16.6 | 48 | 35 | Surplus |
Example 14:
Ionogen ratio (Pr-Nd) F
3: DyF
3: LiF: MgF
2=70: 20: 9.5: 0.5, the reinforced ratio of mixture was (Pr-Nd)
2O
3: Dy
2O
3=87: 13,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 10A/cm
2, anodic current density 1.1A/cm
2, electrolysis time 1 hour, the mixture add-on is 4.3kg.Obtain alloy 3.3kg, dysprosium content 14.5wt% in the alloy, current efficiency is 84%, yield 90%.Alloy component analysis the results are shown in following table:
Table 14 example 14 alloy component analysis are wt% as a result
| Pr | Nd | Dy | Impurity |
| 21.3 | 63.8 | 14.5 | Surplus |
Example 15:
Ionogen ratio (Pr-Nd) F
3: DyF
3: LiF: MgF
2=85: 5: 9.5: 0.5, the reinforced ratio of mixture was (Pr-Nd)
2O
3: Dy
2O
3=95: 5,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 10A/cm
2, anodic current density 1.1A/cm
2, electrolysis time 1 hour, the mixture add-on is 4.3kg.Obtain alloy 3.3kg, dysprosium content 6.7wt% in the alloy, current efficiency is 84%, yield 90%.Alloy component analysis the results are shown in following table:
Table 15 example 15 alloy component analysis are wt% as a result
| Pr | Nd | Dy | Impurity |
| 27.2 | 65.7 | 6.7 | Surplus |
Example 16:
Ionogen ratio (Pr-Nd) F
3: LiF: MgF
2=85: 12: 3, the compound additional proportion was (Pr-Nd)
2O
3: Dy
2O
3=99: 1,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 12A/cm
2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 4kg.Obtain alloy 3.3kg, dysprosium content 1wt% in the alloy, current efficiency is 83%, yield 95%.Alloy component analysis the results are shown in following table:
Table 16 example 16 alloy component analysis are wt% as a result
| Pr | Nd | Dy | Impurity |
| 24.9 | 73.8 | 1 | Surplus |
Example 17:
Ionogen ratio (Pr-Nd) F
3: TbF
3: LiF: MgF
2=60: 30: 8: 2, the reinforced ratio of mixture was (Pr-Nd)
2O
3: Tb
4O
7=62: 38,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 10A/cm
2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 3.6kg.Obtain alloy 2.9kg, Tb content 40wt% in the alloy, current efficiency is 81%, yield 93%.Alloy component analysis the results are shown in following table:
Table 17 example 17 alloy component analysis are wt% as a result
| Pr | Nd | Tb | Impurity |
| 15 | 44.6 | 40 | Surplus |
Example 18:
Ionogen ratio (Pr-Nd) F
3: TbF
3: LiF: MgF
2=62: 32: 5: 1, the reinforced ratio of mixture was (Pr-Nd)
2O
3: Tb
4O
7=78: 22,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 15A/cm2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 3.5kg.Obtain alloy 2.8kg, Tb content 25wt% in the alloy, current efficiency is 76%, yield 93%.Alloy component analysis the results are shown in following table:
Table 18 example 18 alloy component analysis are wt% as a result
| Pr | Nd | Tb | Impurity |
| 18.6 | 56 | 25 | Surplus |
Example 19:
Ionogen ratio (Pr-Nd) F
3: TbF
3: LiF: MgF
2=70: 20: 9.5: 0.5, the reinforced ratio of mixture was (Pr-Nd)
2O
3: Tb
4O
7=90: 10,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 10A/cm
2, anodic current density 1A/cm
2, electrolysis time 1 hour, the mixture add-on is 4.2kg.Obtain alloy 3.2kg, Tb content 12wt% in the alloy, current efficiency is 84%, yield 90%.Alloy component analysis the results are shown in following table:
Table 19 example 19 alloy component analysis are wt% as a result
| Pr | Nd | Tb | Impurity |
| 22.3 | 65.4 | 12 | Surplus |
Example 20:
Ionogen ratio (Pr-Nd) F
3: TbF
3: LiF: MgF
2=84: 6: 9.5: 0.5, the reinforced ratio of mixture was (Pr-Nd)
2O
3: Tb
4O
7=95: 5,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 10A/cm
2, anodic current density 1A/cm
2, electrolysis time 1 hour, the mixture add-on is 4.2kg.Obtain alloy 3.2kg, Tb content 6wt% in the alloy, current efficiency is 84%, yield 90%.Alloy component analysis the results are shown in following table:
Table 20 example 20 alloy component analysis are wt% as a result
| Pr | Nd | Tb | Impurity |
| 28.2 | 65.4 | 6 | Surplus |
Example 21:
Ionogen ratio (Pr-Nd) F
3: LiF: MgF
2=85: 12: 3, the mixture additional proportion was (Pr-Nd)
2O
3: Nd
2O
3=99: 1,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 13A/cm
2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 3.9kg.Obtain alloy 3.2kg, Tb content 1wt% in the alloy, current efficiency is 83%, yield 95%.Alloy component analysis the results are shown in following table:
Table 21 example 21 alloy component analysis are wt% as a result
| Pr | Nd | Tb | Impurity |
| 25.1 | 73.6 | 1 | Surplus |
Example 22:
Ionogen ratio (Pr-Nd) F
3: GdF
3: LiF: MgF
2=60: 30: 8: 2, the reinforced ratio of mixture was (Pr-Nd)
2O
3: Gd
2O
3=62: 38,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 10A/cm
2, anodic current density 0.9A/cm
2, electrolysis time 1 hour, the mixture add-on is 4.1kg.Obtain alloy 3.3kg, Gd content 40wt% in the alloy, current efficiency is 81%, yield 93%.Alloy component analysis the results are shown in following table:
Table 22 example 22 alloy component analysis are wt% as a result
| Pr | Nd | Gd | Impurity |
| 15 | 44.6 | 40 | Surplus |
Example 23:
Ionogen ratio (Pr-Nd) F
3: GdF
3: LiF: MgF
2=62: 32: 5: 1, the reinforced ratio of mixture was (Pr-Nd)
2O
3: Gd
2O
3=82: 18,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 13A/cm2, anodic current density 1.1A/cm
2, electrolysis time 1 hour, the mixture add-on is 3.8kg.Obtain alloy 3kg, Gd content 20wt% in the alloy, current efficiency is 76%, yield 93%.Alloy component analysis the results are shown in following table:
Table 23 example 23 alloy component analysis are wt% as a result
| Pr | Nd | Gd | Impurity |
| 19.9 | 59.8 | 20 | Surplus |
Example 24:
Ionogen ratio (Pr-Nd) F
3: GdF
3: LiF: MgF
2=72: 18: 9.5: 0.5, the reinforced ratio of mixture was (Pr-Nd)
2O
3: Gd
2O
3=90: 10,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 13A/cm
2, anodic current density 0.9A/cm
2, electrolysis time 1 hour, the mixture add-on is 4.3kg.Obtain alloy 3.3kg, Gd content 12wt% in the alloy, current efficiency is 84%, yield 90%.Alloy component analysis the results are shown in following table:
Table 24 example 24 alloy component analysis are wt% as a result
| Pr | Nd | Gd | Impurity |
| 22.3 | 65.4 | 12 | Surplus |
Example 25:
Ionogen ratio (Pr-Nd) F
3: LiF: MgF
2=85: 5: 7: 3, the mixture additional proportion was (Pr-Nd)
2O
3: Gd
2O
3=99: 1,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 12A/cm
2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 3.9kg.Obtain alloy 3.2kg, Gd content 1wt% in the alloy, current efficiency is 83%, yield 95%.Alloy component analysis the results are shown in following table:
Table 25 example 25 alloy component analysis are wt% as a result
| Pr | Nd | Gd | Impurity |
| 25.1 | 73.6 | 1 | Surplus |
Example 26:
Ionogen ratio (Pr-Nd) F
3: DyF
3: GdF
3: LiF: MgF
2=60: 20: 10: 8: 2, the reinforced ratio of mixture is (Pr-Nd)
2O
3: Dy
2O
3: Gd
2O
3=62: 25: 13,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 10A/cm
2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 4.1kg.Obtain alloy 3.3kg, dysprosium gadolinium total content 40wt% in the alloy, current efficiency is 81%, yield 93%.Alloy component analysis the results are shown in following table:
Table 26 example 26 alloy component analysis are wt% as a result
| Pr | Nd | Dy | Gd | Impurity |
| 15 | 44.6 | 27 | 13 | Surplus |
Example 27:
Ionogen ratio (Pr-Nd) F
3: DyF
3: GdF
3: LiF: MgF
2=62: 21: 11: 5: 1, the reinforced ratio of mixture is (Pr-Nd)
2O
3: Dy
2O
3: Gd
2O
3=82: 12: 6,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 15A/cm
2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 3.8kg.Obtain alloy 3kg, dysprosium gadolinium concentrations 20wt% in the alloy, current efficiency is 76%, yield 93%.Alloy component analysis the results are shown in following table:
Table 27 example 27 alloy component analysis are wt% as a result
| Pr | Nd | Dy | Gd | Impurity |
| 20 | 59.7 | 12 | 8 | Surplus |
Example 28:
Ionogen ratio (Pr-Nd) F
3: DyF
3: GdF
3: LiF: MgF
2=70: 12: 8: 8: 2, the reinforced ratio of mixture is (Pr-Nd)
2O
3: Dy
2O
3: Gd
2O
3=90: 6: 4,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 10A/cm
2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 4.3kg.Obtain alloy 3.3kg, dysprosium gadolinium concentrations 12wt% in the alloy, current efficiency is 84%, yield 90%.Alloy component analysis the results are shown in following table:
Table 28 example 28 alloy component analysis are wt% as a result
| Pr | Nd | Dy | Gd | Impurity |
| 22.3 | 65.4 | 8 | 4 | Surplus |
Example 29:
Ionogen ratio (Pr-Nd) F
3: LiF: MgF
2=85: 4: 1: 7: 3, the mixture additional proportion is (Pr-Nd)
2O
3: Dy
2O
3: Gd
2O
3=99: 0.8: 0.2,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 10A/cm
2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 3.9kg.Obtain alloy 3.2kg, dysprosium gadolinium concentrations 1wt% in the alloy, current efficiency is 83%, yield 95%.Alloy component analysis the results are shown in following table:
Table 29 example 29 alloy component analysis are wt% as a result
| Pr | Nd | Dy | Gd | Impurity |
| 25.1 | 73.6 | 0.8 | 0.2 | Surplus |
Example 30:
Ionogen ratio NdF
3: TbF
3: LiF: MgF
2=62: 32: 5: 1, the reinforced ratio of mixture was Nd
2O
3: Tb
4O
7=68: 32,1000～1020 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 15A/cm2, anodic current density 0.9A/cm
2, electrolysis time 1 hour, the mixture add-on is 4kg.Obtain alloy 3.2kg, terbium content 35wt% in the alloy, current efficiency is 76%, yield 93%.Alloy component analysis the results are shown in following table:
Table 30 example 30 alloy component analysis are wt% as a result
| Nd | Tb | Impurity |
| 64.5 | 35 | Surplus |
The example hentriaconta-:
Ionogen ratio (Pr-Nd) F
3: DyF
3: TbF
3: LiF: MgF
2=68wt%: 15wt%: 5%: 9wt%: 3wt%, the reinforced ratio of mixture is (Pr-Nd)
2O
3: Dy
2O
3: Tb
4O
7=76: 18: 6,1020～1050 ℃ of electrolysis temperatures: strength of current was 2200A, and cathode current density is 14A/cm
2, anodic current density 0.9A/cm
2, electrolysis time 1 hour, the mixture add-on is 4kg.Obtain alloy 3.1kg, dysprosium terbium total content 26.5wt% in the alloy, current efficiency is 77%, the rare earth metal yield is 91%.The alloying element analysis sees the following form.
Table 31 example 31 alloy component analysis are wt% as a result
| Pr | Nd | Dy | Tb | Impurity |
| 17.9 | 55.1 | 20 | 6.5 | Surplus |
Example 32:
Ionogen ratio (Pr-Nd) F
3: DyF
3: TbF
3: LiF: MgF
2=68wt%: 15wt%: 5%: 9wt%: 3wt%, the reinforced ratio of mixture is (Pr-Nd)
2O
3: Dy
2O
3: Tb
4O
7=88: 11: 1,1020～1050 ℃ of electrolysis temperatures: strength of current was 2200A, and cathode current density is 14A/cm
2, anodic current density 0.9A/cm
2, electrolysis time 1 hour, the mixture add-on is 3.9kg.Obtain alloy 3kg, dysprosium terbium total content 13.7wt% in the alloy, current efficiency is 77%, the rare earth metal yield is 91%.The alloying element analysis sees the following form.
Table 32 example 32 alloy component analysis are wt% as a result
| Pr | Nd | Dy | Tb | Impurity |
| 21.5 | 64.5 | 12 | 1.7 | Surplus |
Example 33:
Ionogen ratio (Pr-Nd) F
3: TbF
3: GdF
3: LiF: MgF
2=81: 5: 3: 9: 2, the reinforced ratio of mixture is (Pr-Nd)
2O
3: Tb
4O
7: Gd
2O
3=92: 5: 3,1060～1080 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 15A/cm
2, anodic current density 0.9A/cm
2, electrolysis time 1 hour, the mixture add-on is 3.7kg.Obtain alloy 2.9kg, terbium gadolinium total content 10wt% in the alloy, current efficiency is 76%, the rare earth metal yield is 91%.The alloying element analytical results sees the following form:
Table 33 example 33 alloy component analysis are wt% as a result
| Pr | Nd | Tb | Gd | Impurity |
| 22.4 | 67.2 | 6.3 | 3.7 | Surplus |
Example 34:
Ionogen ratio PrF
3: GdF
3: LiF: MgF
2=85: 5: 9.5: 0.5, continue to add Pr
6O
11, 1080～1100 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 13A/cm
2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 3.7kg.Obtain alloy 3kg, Gd content 1wt% in the alloy, current efficiency is 78%, the rare earth metal yield is 96%.The alloying element analytical results sees the following form:
Table 34 example 34 alloy component analysis are wt% as a result
| Pr | Gd | Impurity |
| 98.7 | 1 | Surplus |
Example 35:
Ionogen ratio CeF
3: LiF: MgF
2=85: 13: 2, the mixture additional proportion was CeO
2: Tb
4O
7=99: 1,1080～1100 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 13A/cm
2, anodic current density 0.8A/cm
2, electrolysis time 1 hour, the mixture add-on is 4.2kg.Obtain alloy 3.3kg, Tb content 1wt% in the alloy, current efficiency is 85%, metal gadolinium yield is 96%.The alloying element analytical results sees the following form:
Table 35 example 35 alloy component analysis are wt% as a result
| Ce | Tb | Impurity |
| 98.7 | 1 | Surplus |
Example 36:
Ionogen ratio (Pr-Nd) F
3: GdF
3: LiF: MgF
2=84: 5: 9: 2, the reinforced ratio of mixture was (Pr-Nd)
2O
3: Gd
2O
3=92: 8,1060～1080 ℃ of electrolysis temperatures, strength of current is 2200A, cathode current density is 14A/cm
2, anodic current density 0.9A/cm
2, electrolysis time 1 hour, the mixture add-on is 4.2kg.Obtain alloy 3.3kg, Ho content 10wt% in the alloy, current efficiency is 83%, metal gadolinium yield is 91%.The alloying element analytical results sees the following form:
Table 36 example 36 alloy component analysis are wt% as a result
| Pr | Nd | Gd | Impurity |
| 22.4 | 67.2 | 10 | Surplus |
Example 37:
Ionogen ratio (Pr-Nd) F
3: HoF
3: LiF: MgF
2=75: 18: 6: 1, the reinforced ratio of mixture was (Pr-Nd)
2O
3: Ho
2O
3=85: 15,1040～1060 ℃ of electrolysis temperatures: strength of current is 2200A, and cathode current density is 16A/cm
2, anodic current density 0.9A/cm
2, 1 hour continuous electrolysis time, the mixture add-on is 4.3kg.Obtain alloy 3.5kg, Ho content 22wt% in the alloy, current efficiency is 85.2%, metal gadolinium yield is 95%.The alloying element analysis sees the following form.
Table 37 example 37 alloy component analysis are wt% as a result
| Pr | Nd | Ho | Impurity |
| 19.4 | 58.1 | 22 | Surplus |
Example 38:
Ionogen ratio LaF
3: ErF
3: LiF: MgF
2=70wt%: 18wt%: 9wt%: 3wt%, the reinforced ratio of mixture is La
2O
3: Er
2O
3=80: 20,1020～1050 ℃ of electrolysis temperatures: strength of current is 2200A, and cathode current density is 17a/cm
2, anodic current density 1.1A/cm
2, electrolysis time 1 hour, the mixture add-on is 4.2kg.Obtain alloy 3.3kg, Er content 26wt% in the alloy, current efficiency is 83%, the rare earth metal yield is 91%.The alloying element analysis sees the following form.
Table 38 example 38 alloy component analysis are wt% as a result
| La | Er | Impurity |
| 73.6 | 26 | Surplus |
Claims (6)
1. method for preparing light rare earths based heavy rare earths alloy, this alloy contains the heavy rare earths of 1～40wt%, all the other be light rare earths and total amount less than the inevitable impurity of 1wt%, it is characterized in that the preparation method is:
A) ionogen is made of matrix light rare earth metal fluorochemical, heavy rare earth metal fluorochemical, lithium fluoride and magnesium fluoride, and the oxide system of fused salt electrolysis is made of matrix light rare earth metal oxide compound and heavy rare earth metal oxide; Wherein matrix light rare earth metal fluorochemical is 55～85wt%, the heavy rare earth metal fluorochemical is 5～35wt%, lithium fluoride 5～12wt%, magnesium fluoride 0.5～3wt%, matrix light rare earth metal oxide compound is 62～99wt% in the oxide system, and heavy rare earth metal oxide is: 1～38wt%;
B) the fused salt electrolysis temperature is between 1000～1200 ℃;
C) anodic current density is 0.5～1.2A/cm
2, cathode current density is 10～17A/cm
2
2. the method for preparing light rare earths based heavy rare earths alloy according to claim 1, it is characterized in that: described light rare earths is selected from one or more in lanthanum, cerium, praseodymium, neodymium, samarium, the europium formation group, and heavy rare earths is selected from one or more in gadolinium, yttrium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium formation group.
3. the method for preparing light rare earths based heavy rare earths alloy according to claim 1 is characterized in that: light rare earths is selected from one or more in lanthanum, cerium, praseodymium, the neodymium formation group, and heavy rare earths is selected from one or more in gadolinium, terbium, dysprosium, holmium, the erbium formation group.
4. the method for preparing light rare earths based heavy rare earths alloy according to claim 1 is characterized in that, when heavy rare-earth oxide by Ho
2O
3, Er
2O
3In one or both when constituting, electrolysis temperature is 1100～1200 ℃, cathode current density is 12～17A/cm
2
5. the method for preparing light rare earths based heavy rare earths alloy according to claim 1 is characterized in that, by the light rare earths based heavy rare earths alloy of this prepared, its impurity N content is less than 0.05wt%.
6. the method for preparing light rare earths based heavy rare earths alloy according to claim 1 is characterized in that, by the light rare earths based heavy rare earths alloy of this prepared, its impurity Ca content is less than 0.05wt%.
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| CN103276267B (en) * | 2013-03-07 | 2016-06-22 | 包头稀土研究院 | Rare earth zircaloy and rare earth magnesium zircaloy and preparation method thereof |
| CN103924266B (en) * | 2014-04-28 | 2017-12-01 | 包头稀土研究院 | A kind of method that co-electrodeposition method prepares rare earth gadpolinium alloy |
| CN105624737B (en) * | 2015-12-31 | 2017-09-29 | 包头稀土研究院 | A kind of method for preparing magnesium-rare earth and rare-earth yttrium neodymium magnesium alloy |
| CN105543900A (en) * | 2015-12-31 | 2016-05-04 | 包头稀土研究院 | Preparing method for rare earth holmium alloy and rare earth holmium alloy |
| CN105543901A (en) * | 2015-12-31 | 2016-05-04 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Preparation method for rare-earth erbium alloy and rare-earth erbium alloy |
| CN110964931A (en) * | 2019-12-31 | 2020-04-07 | 乌拉特前旗三才第一铁合金有限公司 | Method for producing light rare earth composite heavy rare earth silicon iron alloy |
| CN111440978A (en) * | 2020-03-24 | 2020-07-24 | 龙南龙钇重稀土科技股份有限公司 | Lanthanum-cerium-yttrium-magnesium intermediate alloy and preparation method thereof |
| CN112159993B (en) * | 2020-09-24 | 2022-03-29 | 江西江钨浩运科技有限公司 | Yttrium-containing mixed rare earth metal, rare earth hydrogen storage alloy and preparation method thereof |
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| CN1472366A (en) * | 2003-07-09 | 2004-02-04 | 北京科技大学 | Producing method for rare-earth aluminosilicate titanium alloy |
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| CN1064510A (en) * | 1992-03-18 | 1992-09-16 | 冶金工业部包头稀土研究院 | The preparation method of neodymium and Nd-Pr base heavy rare-earth alloy |
| CN1552935A (en) * | 2003-06-06 | 2004-12-08 | 陈春生 | Dysprosium alloy and preparing method thereof |
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