WO2008095448A1 - Alliage de terres rares, son procédé de préparation et son application - Google Patents

Alliage de terres rares, son procédé de préparation et son application Download PDF

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Publication number
WO2008095448A1
WO2008095448A1 PCT/CN2008/070287 CN2008070287W WO2008095448A1 WO 2008095448 A1 WO2008095448 A1 WO 2008095448A1 CN 2008070287 W CN2008070287 W CN 2008070287W WO 2008095448 A1 WO2008095448 A1 WO 2008095448A1
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Prior art keywords
rare earth
alloy
content
magnet
composition
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PCT/CN2008/070287
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English (en)
Chinese (zh)
Inventor
Hongwei Li
Shihong Yan
Zong'an Li
Dunbo Yu
Zhiqiang Wang
Kuoshe Li
Xiaowei Huang
Chunlei Zhao
Zhenhai Li
Zhijian Yu
Quanxia Hu
Jing Xu
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Grirem Advanced Materials Co., Ltd.
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Priority claimed from CN 200710063647 external-priority patent/CN101240393A/zh
Priority claimed from CN 200710063646 external-priority patent/CN101240392A/zh
Priority claimed from CN2007100636483A external-priority patent/CN101240394B/zh
Application filed by Grirem Advanced Materials Co., Ltd. filed Critical Grirem Advanced Materials Co., Ltd.
Publication of WO2008095448A1 publication Critical patent/WO2008095448A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/36—Alloys obtained by cathodic reduction of all their ions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B

Definitions

  • the present invention relates to a rare earth alloy, a preparation process and application thereof, and more particularly to a Nd-Fe-B permanent magnet material having excellent magnetic energy product and heat resistance.
  • rare earth elements make them excellent in magnetic, optical and electrical properties. It is widely used in the preparation of functional materials.
  • NdFeB magnets require the use of a large number of metals, ruthenium, osmium, iridium, etc.
  • the price of rare earth metals has risen sharply, and magnet manufacturers are facing huge cost pressures.
  • NdFeB companies and metal producers are constantly looking for new formulations and new production methods, such as the use of niobium alloys and niobium-iron alloys with low production costs and low melting points to replace the above-mentioned expensive pure metal materials.
  • Niobium alloy is directly produced by direct electrolysis of niobium mixed oxide, which eliminates the extraction and separation process of niobium, and the cost is greatly reduced.
  • the niobium-iron alloy is directly alloyed with oxidized tantalum electrolysis and fusible cathode iron, which greatly reduces the melting point. .
  • the appearance of such alloys has greatly reduced the raw material cost of NdFeB magnets, so it has been rapidly popularized.
  • Now almost all NdFeB magnets are made of bismuth alloy and bismuth iron alloy. At present, in order to further improve the performance of magnetic materials, most NdFeB magnets not only contain light rare earths but also need to add a small amount of heavy rare earth lanthanum.
  • the uniformity of the master alloy composition plays an important role in the properties of Nd-Fe-B permanent magnet materials, especially the coercivity.
  • the ideal microstructure of high performance Nd-Fe-B permanent magnet materials It is: (l) Nd 2 Fei 4 B grains are surrounded by a thin layer of Nd-rich phase with a thickness of about 2 nm, so that the grains and grains are isolated from each other, so that there is no magnetic exchange coupling between them; (2) The chemical composition and structure of Nd 2 Fe 14 B grains are uniform. The domain wall thickness of the Nd 2 Fe 14 B crystal is about 5.2 nm.
  • the magnetocrystalline anisotropy constant of the inhomogeneous region is lowered, which may become the nucleation center of the demagnetized domain, at a lower inverse.
  • the anti-magnetization domain is formed, which leads to the re-magnetization of the whole crystal grain, which reduces the coercive force of the magnet;
  • the fluoride system used consists of cesium fluoride, cesium fluoride, lithium fluoride, cesium fluoride and calcium fluoride.
  • the oxide is Cerium oxide, cerium oxide, and iron are consumable cathodes.
  • this method has many components in the electrolyte system, complex composition, and uncontrollable alloy composition. It is limited to laboratory research and is not suitable for large-scale industrial production.
  • Chinese patent CN1040399A proposes a preparation method and a device for producing a Dy-Nd alloy, which is also composed of a fluorine salt system oxide electrolysis, and the fluorine salt system is composed of barium fluoride, barium fluoride, lithium fluoride and barium fluoride.
  • the carbon content of the niobium alloy obtained by the process is relatively high, reaching 0.1 wt% or more, and the high-performance NdFeB magnet cannot be prepared, which limits the large-scale popularization of the process.
  • Chinese patent CN1025228C proposes a preparation method of rare earth alloy, which adopts fluorine salt system oxide electrolysis, and the fluorine salt system is composed of base metal fluoride, heavy rare earth fluoride, lithium fluoride and calcium fluoride, compared with Chinese patent.
  • CN1040399A increases the ratio of heavy rare earth in electrolyte and oxidized material, and obtains cerium and cerium-based heavy rare earth alloys with heavy rare earth content up to 35wt%, and the carbon content is controlled below 0.05wt%.
  • the current efficiency of the process described in this patent fluctuates greatly, the minimum current efficiency is 20%, the maximum current efficiency is ⁇ 75%, and the metal yield is ⁇ 90%, which brings high energy consumption and high cost to industrial production.
  • the above patents have an important issue that has been overlooked, namely the oxygen content of the alloy.
  • the oxygen content of the rare earth alloy will ultimately affect the performance of subsequent products.
  • the oxygen content is a very important indicator because the rare earth oxide and the oxyfluoride rare earth have a small vapor pressure, are not volatile, have a high melting point, cannot be melted at the melting temperature of the magnetic material master alloy, and have a density and a base metal or alloy. Similar, it cannot be separated from the matrix after it forms a solid state.
  • the oxygen content in the magnet is increased by 0.05 wt%, and the magnetic energy product is reduced by 30 to 100 kJ/m 3 .
  • the mixed rare earth alloy containing high melting point elements such as cerium and lanthanum is prepared by the prior art, the electrolysis process is unstable, the electric effect fluctuates greatly, the yield is low, and the alloy tends to contain a certain proportion of slag phase.
  • the slag phase is mainly composed of oxides and oxyfluorides, so that the oxygen content is inevitably increased. As described above, an excessively high oxygen content impairs the performance of the NdFeB magnet.
  • An object of the present invention is to provide a mixed rare earth alloy for magnetic material addition which has a low oxygen content, a low melting point, a small saturated vapor pressure, and a low cost. Particularly suitable for the preparation of high performance NdFeB magnets.
  • the present invention adopts the following technical solutions:
  • a rare earth alloy a) a composition formula represented by RR 2 M, said representative being at least one element selected from the group consisting of Tb and Dy, in an amount of 0.1 to 50% by weight, and M represents a transition metal Fe, Co, Cu , Zr, Ga, Al, Mn, Cr, Zn, One or more of Ge, Se, Mo, V, Ti, In, Sn, Sb, Pb, Hf, the content of M is 0 to 40 wt%, and R 2 is other rare earths other than Tb and Dy Element and unavoidable impurities, R 2 is the balance; b) The alloy has an oxygen content of ⁇ 0.3 wt%, a C content of ⁇ 0.04 wt%, and a N content of ⁇ 0.05 wt%; c) the alloy has a melting point of less than 1200 °C.
  • the composition formula is represented by ⁇ , the R1 represents at least one element selected from the group consisting of Tb and Dy, and the content is 0.1 to 30% by weight, and M represents a transition metal of Fe, Co, Cu, Zr, Ga, Al, Mn One or more of the group consisting of Cr, Zn, Ge, Se, Mo, V, Ti, In, Sn, Sb, Pb, and Hf, the content of M is 0 to 40 wt%, and R 2 is Tb and Other rare earth elements other than Dy and inevitable impurities, R 2 is the balance; b) The oxygen content of the alloy is ⁇ 0. 2 wt%, C content ⁇ 0. 03 wt%, N content ⁇ 0. 03 wt%; c) The melting point of the alloy is less than 1100 °C.
  • the rare earth alloy according to Item 1 or 2 wherein the content is from 1 to 20% by weight, and the M represents a transition metal of Fe, Co, Cu, Zr, Ga, Al, Mn, Cr, One or more of the group consisting of Zn, Ge, Se, Mo, V, Ti, and the one of the group consisting of Pr, Nd, La, Ce, Y, Ho, Gd, Er, and Lu Or several and inevitable impurities.
  • a rare earth alloy according to the item 1 or 2 which is at least one selected from the group consisting of Pr and Nd and an unavoidable impurity.
  • a rare earth alloy according to any one of 1 to 4 which has an oxygen content of ⁇ 0.1 wt%.
  • the corresponding fluoride containing R 2 , M, lithium fluoride and magnesium fluoride constitute an electrolyte or a fluoride containing R 2 , lithium fluoride and magnesium fluoride; and an oxide containing R 2 and M Raw material or containing R 2 oxide and metal M raw material; and tungsten, molybdenum inert cathode or M according to the composition formula of item 1 or 2 and its content selected iron or other M other than molybdenum and iron
  • a rare earth alloy according to item 1 or 2 as a neodymium iron boron permanent magnet material or a barium ferromagnetic stretching material.
  • a rare earth magnetostrictive material characterized by using the rare earth alloy according to items 1 to 10. The reason for limiting the composition of the present invention is described below:
  • the main component of the alloy of the invention is two elements, and the purpose of the addition is mainly to improve the performance of some aspects of the magnetic material.
  • the addition of Tb can improve the coercive force of the Nd-Fe-B magnet, but the addition thereof requires an appropriate amount, such as Tb in Nd. Adding too much to -Fe-B will greatly reduce the magnetic energy product, and too little will not work.
  • the melting point of both elements is higher than 1400 °C. Properly reducing the proportion of the above elements in the alloy can lower the melting point and melting temperature of the subsequent mother alloy and reduce the preparation cost. Therefore, Dy and Tb in the alloy of the present invention are controlled within 50% by weight.
  • Dy and Tb elements can be simultaneously present in the alloy, mainly because: on the one hand, the mixed rare earth containing lanthanum and cerium does not need to be separated in one step, thereby reducing the cost of raw materials, and on the other hand, lanthanum and cerium in rare earth ore.
  • the ratio is relatively stable, which provides a reliable guarantee for the melting of magnetic materials.
  • the magnetic material especially the Nd-Fe-B permanent magnet material, the rare earth metal and the alloy preparation method thereof are all an electrolytic process or a fluoride thermal reduction process, and the products of the two processes inevitably contain a certain amount of oxygen, According to the study by the inventors, the oxygen in the rare earth alloy exists mainly in three forms, one in the form of oxides, the other in the form of oxyfluorides, and the third in the form of free oxygen, if oxygen is the former two The existence of the form has a great influence on the magnetic properties of the magnetic material.
  • the rare earth oxide and the oxyfluoride rare earth have a small vapor pressure, are not volatile, have a high melting point, cannot be melted at the melting temperature of the magnetic material master alloy, and have a density similar to that of the base metal or alloy. It cannot be separated from the matrix after it forms a solid state. These characteristics make it impossible to remove once in the magnetic material addition alloy, and if the oxygen content is too high (>0.3 wt%), the coercive force and the magnetic energy product are lowered. Taking NdFeB permanent magnet as an example, the magnetic energy product is reduced by about 30 to 100 kJ/m 3 for every 0.05 wt% increase in oxygen content in the magnet. Therefore, the composition of the alloy of the present invention is designed to limit the content of oxyfluoride to within 0.3 wt%.
  • the other rare earth element of the alloy of the present invention is one or more selected from the group consisting of Pr, Nd, La, Ce, Y, Ho, Gd, Sm, Er, Lu, Tm, Yb, Eu, wherein La, Ce, Pr , Nd, Sm, Eu, Yb are all rare earth elements with a melting point below 1100 ° C.
  • Pr and Nd are important components in Nd-Fe-B permanent magnet materials.
  • the reason for the composition design is: On the one hand, it can greatly reduce the saturated vapor pressure of the main components in the alloy during smelting, reduce the volatilization loss, improve the product yield, and facilitate the accuracy of the control of the magnetic material composition.
  • the composition is designed to form a low melting point alloy with a melting point below 1200 ° C, which is much lower than the melting point of pure metal lanthanum (1409 ° C) and ⁇ (1364 ° C), Nd- at >1400 ° 0
  • the melting temperature of Fe-B master alloy the composition of the alloy is faster than the addition of pure metal lanthanum and cerium, and the yttrium-rich phase will have more abundant time to diffuse in the matrix, which will eventually make Nd-Fe-B permanent.
  • the yttrium-rich phase in the magnet is more uniformly dispersed and the composition segregation is smaller, and the rapid formation of the liquid phase also lowers the melting temperature of the Nd-Fe-B alloy.
  • Gd, Ho, Er, Y, Lu can play an important role in improving the coercivity of NdFeB alloys.
  • the Gd and Ho elements can also partially replace Pr and Nd in NdFeB.
  • the standard electrode potentials of Gd, Ho, Er, Y, and Lu are close to those of the main components of the alloy of the present invention, and are easily realized by the self-developed rare earth oxide molten salt electrolysis electrolysis method, which can greatly reduce the use of neodymium iron boron.
  • the cost of rare earth raw materials can also reduce the saturation vapor pressure of the rare earth elements near the melting temperature and the melting temperature of the NdFeB alloy to varying degrees.
  • the present invention increases the interfacial tension between the electrolyte and the rare earth alloy liquid by adding an appropriate proportion of magnesium fluoride to the electrolyte, improves the electrolyte conductivity, and improves the electrolyte fluidity. The proportion of the slag phase in the alloy is reduced, thereby achieving the purpose of reducing the oxygen content.
  • the composition is uniform.
  • the rare earth alloy according to the present invention is more Nb-Fe-B based on the Nd-Fe-B permanent magnet material prepared by using rare earth elements such as pure lanthanum, cerium, lanthanum and cerium. Evenly.
  • the uniformity of the composition plays an important role in the properties of the Nd-Fe-B permanent magnet material, especially the coercive force. It has been proved that the high performance Nd-Fe-B magnet can be prepared by using the alloy of the invention. In particular, the coercivity of the magnet can be increased by at least 5%. Therefore, the light rare earth based heavy rare earth alloy has strong practicability and good development prospects.
  • Metal detection is based on GB/T18115.1-2006 and other national standards, using ICP-MS testing;
  • the detection of C is based on GB/T12690.13-1990, using high frequency combustion-infrared method test;
  • the detection of 0 is based on GB/T12690.4-2003, using inert gas pulse-infrared method test;
  • N is based on GB/T 20124-2006, and is tested by inert gas fusion thermal conductivity method.
  • the performance of the magnet is tested according to GB/T 13560-2000 and GB/T 3217-1992, using a magnet performance tester.
  • the alloy composition of the solution is TbNdFe, and the specific preparation method is as follows: the reactor is graphite crucible, and the iron rod is used as a cathode.
  • the electrolyte is NdF 3 89 wt%, yttrium fluoride l wt%, LiF 9 wt% MgF 2 lwt%, DC electrolysis, anode current density 1.0 A/cm 2 , cathode current density 10 A/cm 2 , and electrolysis temperature maintained at 1000 ⁇ 1050 °C.
  • 0.03 kg of cerium oxide and 4.0 kg of cerium oxide were added, and electrolysis was carried out for about 1 hour to obtain 4.25 kg of TbNdFe alloy.
  • Table 1-1 The analysis results of main components, oxygen content and other impurities are shown in Table 1-1.
  • the alloy prepared in the present embodiment is added to the main component of the neodymium iron boron, and the sintered neodymium iron boron magnet is prepared by using the smelting crucible belt ⁇ hydrogen crushing and airflow milling powder ⁇ magnetic field forming ⁇ vacuum sintering process, and the chemical composition of the magnet sample is The performance of the magnet was analyzed, and the standard deviation was used to indicate the uniformity of the chemical composition. The method of sampling the chemical composition is: Take 10 points of analysis in the same magnet. For comparison, a sintered NdFeB magnet was prepared by a conventional method at the same time, except that the ruthenium was separately added, and the other matters were the same as those of the embodiment.
  • the alloy composition of the solution is DyTbNdFeCrV, and the specific preparation method is as follows:
  • the reactor is graphite crucible, and the &, V iron alloy rod is used as the cathode.
  • the alloy prepared in the present embodiment is added to the main component of the neodymium iron boron, and the sintered neodymium iron boron magnet is prepared by using the smelting crucible belt ⁇ hydrogen crushing and airflow milling powder ⁇ magnetic field forming ⁇ vacuum sintering process, and the chemical composition of the magnet sample is The performance of the magnet was analyzed, and the standard deviation was used to indicate the uniformity of the chemical composition.
  • the method of sampling the chemical composition is: Take 10 points of analysis in the same magnet.
  • a sintered NdFeB magnet was prepared by a conventional method at the same time, except that Dy, Tb, Cr, and V were separately added, and the other matters were the same as those in the embodiment.
  • the schemes in this example were compared with the corresponding conventionally prepared sintered NdFeB magnets, including the chemical composition standard deviation and the magnet properties. The results are shown in Tables 2-2 and 2-3, respectively.
  • Table 2-1 Alloy composition (wt%), melting point (°C)
  • the alloy composition of the solution is DyTbGdPrNd, and the specific preparation method is as follows: the reactor is graphite crucible, and the tungsten or molybdenum rod is used as the cathode.
  • the alloy prepared in the present embodiment is added to the main component of the neodymium iron boron, and the sintered neodymium iron boron magnet is prepared by using the smelting crucible belt ⁇ hydrogen crushing and airflow milling powder ⁇ magnetic field forming ⁇ vacuum sintering process, and the chemical composition of the magnet sample is The performance of the magnet was analyzed, and the standard deviation was used to indicate the uniformity of the chemical composition.
  • the method of sampling the chemical composition is: Take 10 points of analysis in the same magnet.
  • a sintered NdFeB magnet was prepared by a conventional method at the same time, except that Dy, Tb, and Gd were separately added, and the other matters were the same as those in the embodiment. Preparation of each embodiment in this embodiment and corresponding conventional methods The sintered NdFeB magnets were compared, including the standard deviation of the properties and chemical composition of the magnets. The results are shown in Tables 3-2 and 3-3, respectively.
  • the alloy composition of the solution is DyTbNd, and the specific preparation method is as follows: the reactor is graphite crucible, and the tungsten or molybdenum rod is used as the cathode.
  • the alloy prepared in the present embodiment is added to the main component of the neodymium iron boron, and the sintered neodymium iron boron magnet is prepared by using the smelting crucible belt ⁇ hydrogen crushing and airflow milling powder ⁇ magnetic field forming ⁇ vacuum sintering process, and the chemical composition of the magnet sample is The performance of the magnet was analyzed, and the standard deviation was used to indicate the uniformity of the chemical composition. The method of sampling the chemical composition is: Take 10 points of analysis in the same magnet. For comparison, a sintered NdFeB magnet was prepared by a conventional method at the same time, except that Dy, Tb, and Nd were separately added, and the other matters were the same as those in the embodiment.
  • the alloy composition of the solution is DyHoNdFeCuAl, and the specific preparation method is as follows: the reactor is graphite crucible, the tungsten rod or the molybdenum rod is used as the cathode.
  • the electrolyte is NdF 3 72.2 wt%, yttrium fluoride 18 wt%, LiF 9 wt%, MgF 2 0.8 wt%, DC direct current electrolysis, anode current density 1.0 A/cm 2 , cathode current density 12 A/cm 2 , and electrolysis temperature maintenance At 1050 ⁇ 1100 °C.
  • the alloy prepared in the present embodiment is added to the main component of the neodymium iron boron, and the sintered neodymium iron boron magnet is prepared by using the smelting crucible belt ⁇ hydrogen crushing and airflow milling powder ⁇ magnetic field forming ⁇ vacuum sintering process, and the chemical composition of the magnet sample is The performance of the magnet was analyzed, and the standard deviation was used to indicate the uniformity of the chemical composition. The chemical composition is sampled by: 10 points of analysis in the same magnet.
  • a sintered NdFeB magnet was prepared by a conventional method, and the other matters were the same as those of the embodiment except that Dy, Ho, Cu, and Al were separately added.
  • the schemes in this example were compared with the corresponding conventionally prepared sintered NdFeB magnets, including the standard deviations of the properties and chemical compositions of the magnets. The results are shown in Tables 4-2 and 4-3, respectively.
  • the alloy composition of the solution is DyNdFeCoAlZrCu, and the specific preparation method is as follows: the reactor is graphite crucible, and the iron rod is used as a cathode.
  • the electrolyte is NdF 3 89 wt%, DyF 3 l wt%, LiF 9 wt%, MgF 2 lwt% through DC electrolysis, anode current density 0.9 A/cm2, cathode current density 15 A/cm2, and electrolysis temperature maintained at 1000 ⁇ 1050° C.
  • 0.03 kg of cerium oxide and 3.72 kg of cerium oxide were added, and electrolysis was carried out for about 1 hour to prepare 4.25 kg of DyNdFe alloy.
  • the alloy prepared in the present embodiment is added to the main component of the neodymium iron boron, and the sintered neodymium iron boron magnet is prepared by using the smelting crucible belt ⁇ hydrogen crushing and airflow milling powder ⁇ magnetic field forming ⁇ vacuum sintering process, and the chemical composition of the magnet sample is The performance of the magnet was analyzed, and the standard deviation was used to indicate the uniformity of the chemical composition. The method of sampling the chemical composition is: Take 10 points of analysis in the same magnet. For comparison, a sintered NdFeB magnet was prepared by a conventional method at the same time, except that Dy, Co, Al, Zr, and Cu were separately added, and the other matters were the same as those in the embodiment.
  • the alloy composition of the solution is DyNdFeAl, and the specific preparation method is as follows: the reactor is graphite crucible, and the iron rod is used as a cathode.
  • the electrolyte is NdF 3 79 wt%, DyF 3 10 wt%, A1F 3 1 wt%, LiF 9 wt%, MgF 2 lwt%, DC direct current electrolysis, anode current density 1.0 A/cm 2 , cathode current density 10 A/cm 2
  • the electrolysis temperature is maintained at 1030 ⁇ 1080 °C.
  • the alloy prepared in the present embodiment is added to the main component of the neodymium iron boron, and the sintered neodymium iron boron magnet is prepared by using the smelting crucible belt ⁇ hydrogen crushing and airflow milling powder ⁇ magnetic field forming ⁇ vacuum sintering process, and the chemical composition of the magnet sample is The performance of the magnet was analyzed, and the standard deviation was used to indicate the uniformity of the chemical composition. The method of sampling the chemical composition is: Take 10 points of analysis in the same magnet. For comparison, sintered NdFeB magnets were prepared by a conventional method, and ruthenium, osmium, iron, and aluminum were separately added, and the rest of the matters were the same as those of the examples.
  • Example 8 Table 8-1 Alloy composition (wt%), melting point (°C)
  • Example 9 Table 9-1 Alloy composition (wt%), melting point (°C)
  • Example 11 Table 11-1 alloy composition (wt%), melting point (°C)
  • Example 12 Table 12-1 Alloy composition (wt%), melting point (°C)
  • Example 14 Table 14-1 Alloy composition (wt%), melting point (°C)
  • Example 15 Table 15-1 Alloy composition (wt%), melting point (°C)
  • Example 16 Table 16-1 Alloy composition (wt%), melting point (°C)
  • Example 17 Table 17-1 Alloy composition (wt%), melting point (°C)
  • Example 19 Table 19-1 Alloy composition (wt%), melting point (°C)
  • Example 20 Table 20-1 Alloy composition (wt%), melting point (°C)
  • Example 21 Table 21-1 Alloy composition (wt%), melting point (°C)
  • Example 22 Table 22-1 Alloy composition (wt%), melting point (°C)
  • Example 23 Table 23-1 alloy composition (wt%), melting point (°C)
  • Example 25 Table 25-1 Alloy composition (wt%), melting point (°C)
  • Example 26 Table 26-1 Alloy Composition (wt%)
  • Example 27 Table 27-1 alloy composition (wt%), melting point (°C)
  • Example 28 Table 28-1 Alloy composition (wt%), melting point (°C)
  • Example 29 Table 29-1 Alloy composition (wt%), melting point (°C)
  • Example 30 Table 30-1 Alloy composition (wt%), melting point (°C)
  • Example 31 Table 31-1 Alloy composition (wt%), melting point (°C)
  • Example 32 Table 32-1 Alloy composition (wt%), melting point (°C)
  • Example 33 Table 33-1 alloy composition (wt%), melting point (°C)
  • Example 34 Table 34-1 Alloy composition (wt%), melting point (°C)
  • Example 35 Table 35-1 Alloy composition (wt%), melting point (°C)
  • Example 36 Table 36-1 Alloy composition (wt%), melting point (°C)
  • Example 37 Table 37-1 alloy composition (wt%), melting point (°C)
  • Example 39 Table 39-1 Alloy composition (wt%), melting point (°C)
  • Example 40 Table 40-1 Alloy composition (wt%), melting point (°C)
  • Example 41 Table 41-1 Alloy composition (wt%), melting point (°C)
  • Example 42 Table 41-1 alloy composition (wt%), melting point (°C)
  • Example 43 Table 43-1 alloy composition (wt%), melting point (°C)
  • Example 44 Table 44-1 Alloy composition (wt%), melting point (°C)

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  • Hard Magnetic Materials (AREA)

Abstract

L'invention concerne un alliage de terres rares dont la composition est dénotée par R1R2M, R1 désignant un atome de Tb et/ou de Dy, la teneur en R1 étant comprise entre 0,1 et 50% en poids de l'alliage, M désignant un ou plusieurs métaux de transition sélectionnés parmi Fe, Co, Cu, Zr, Ga, Al, Mn, Cr, Zn, Ge, Se, Mo, V, Ti, In, Sn, Sb, Pb et Hf, la teneur en M étant comprise entre 0 et 40% en poids de l'alliage, R2 désignant les impuretés inévitables et les métaux du groupe des terres rares, excepté Tb et Dy, et le solde en poids de l'alliage étant constitué de R2. Par ailleurs, la teneur en oxygène est inférieure à 0,3% en poids de l'alliage, la teneur en carbone est inférieure à 0,04% en poids de l'alliage et la teneur en azote est inférieure à 0,05% en poids de l'alliage. L'alliage possède une température de fusion basse de 1200°C, une faible teneur en oxygène, une faible valeur de pression de vapeur saturante et un faible coût de fabrication. L'alliage pourrait être produit par procédé d'électrolyse en sels fondus d'oxyde. L'alliage convient à la préparation d'un matériau magnétique à hautes performances, en particulier un matériau magnétique permanent à base de Nd-Fe-B à hautes performances.
PCT/CN2008/070287 2007-02-07 2008-02-05 Alliage de terres rares, son procédé de préparation et son application WO2008095448A1 (fr)

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Application Number Priority Date Filing Date Title
CN200710063648.3 2007-02-07
CN 200710063647 CN101240393A (zh) 2007-02-07 2007-02-07 一种稀土合金、制备工艺及其应用
CN 200710063646 CN101240392A (zh) 2007-02-07 2007-02-07 一种稀土合金
CN2007100636483A CN101240394B (zh) 2007-02-07 2007-02-07 一种稀土合金、制备工艺及其应用
CN200710063647.9 2007-02-07
CN200710063646.4 2007-02-07

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CN108977855A (zh) * 2018-08-30 2018-12-11 李鹏 一种磁性材料的制备方法
CN113265684A (zh) * 2016-12-16 2021-08-17 包头稀土研究院 镨钕铁合金
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CN113430579A (zh) * 2016-12-16 2021-09-24 包头稀土研究院 镧铁合金的制备方法
CN113265684A (zh) * 2016-12-16 2021-08-17 包头稀土研究院 镨钕铁合金
CN113279018A (zh) * 2016-12-16 2021-08-20 包头稀土研究院 镨钕铁合金的制备方法
CN113279019A (zh) * 2016-12-16 2021-08-20 包头稀土研究院 镨铁合金
CN113279020A (zh) * 2016-12-16 2021-08-20 包头稀土研究院 镨铁合金的制备方法
CN113481545A (zh) * 2016-12-16 2021-10-08 包头稀土研究院 镧铁合金
CN113279018B (zh) * 2016-12-16 2023-01-03 包头稀土研究院 镨钕铁合金在稀土钢中的用途
CN113279020B (zh) * 2016-12-16 2023-04-25 包头稀土研究院 镨铁合金的制备方法
CN113279019B (zh) * 2016-12-16 2023-05-02 包头稀土研究院 镨铁合金
CN113481545B (zh) * 2016-12-16 2023-07-14 包头稀土研究院 镧铁合金
CN113871120A (zh) * 2017-12-26 2021-12-31 钢铁研究总院 一种混合稀土永磁材料及其制备方法
CN108977855A (zh) * 2018-08-30 2018-12-11 李鹏 一种磁性材料的制备方法
CN115389283A (zh) * 2022-06-24 2022-11-25 赣州艾科锐检测技术有限公司 一种稀土金属或合金检测中的内控样品及制备方法和应用

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