WO2021175174A1 - Method for preparing rare earth alloy spherical single crystal magnetic powder, and rare earth giant magnetostrictive material having <111> orientation - Google Patents

Method for preparing rare earth alloy spherical single crystal magnetic powder, and rare earth giant magnetostrictive material having <111> orientation Download PDF

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WO2021175174A1
WO2021175174A1 PCT/CN2021/078392 CN2021078392W WO2021175174A1 WO 2021175174 A1 WO2021175174 A1 WO 2021175174A1 CN 2021078392 W CN2021078392 W CN 2021078392W WO 2021175174 A1 WO2021175174 A1 WO 2021175174A1
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alloy
magnetic powder
single crystal
rare earth
spherical
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唐少龙
董大舜
钱进
黄业
都有为
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南京大学
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    • 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
    • H01F1/0555—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
    • H01F1/0558—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together bonded together
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B1/00—Single-crystal growth directly from the solid state
    • C30B1/02—Single-crystal growth directly from the solid state by thermal treatment, e.g. strain annealing
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/52—Alloys
    • 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
    • H01F1/0555—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
    • H01F1/0557—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together sintered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0266—Moulding; Pressing

Definitions

  • the present invention relates to a preparation method of rare earth super magnetostrictive material suitable for ⁇ 111> orientation and spherical single crystal magnetic powder, especially R-Fe-M alloy in the field of bonded rare earth super magnetostrictive material and sintered rare earth super magnetostrictive material Preparation method of spherical single crystal magnetic powder.
  • the rare earth-iron cubic Laves phase single crystal material exhibits a large magnetostrictive effect and has important applications in sonar, transducer and other fields.
  • the preparation process of the rare earth-iron cubic Laves phase single crystal material is complicated, the production cost is high, and it is difficult to prepare large-size single crystal materials with uniform composition and performance.
  • the magnetostrictive bulk material can be prepared by preparing rare earth-iron cubic Laves phase single crystal powder, using the single crystal powder as a raw material.
  • the single crystal powder can be oriented in a magnetic field and then pressed into a shape, and then annealed at a high temperature to prepare a sintered rare earth giant magnetostrictive material with a certain orientation.
  • single crystal powder with other materials, such as epoxy resin, to form a bonded rare earth giant magnetostrictive material, which exhibits magnetostrictive properties similar to bulk single crystal materials.
  • other materials such as epoxy resin
  • the magnetic single crystal magnetic powder can obtain a high degree of orientation, and the bonded magnetostrictive material will exhibit magnetostrictive properties similar to that of single crystal material. .
  • the current preparation method of rare earth-iron cubic Laves phase single crystal powder adopts the crushing method.
  • the preparation of single crystal particles by these two methods which are mainly manifested in the insufficient proportion of single crystal particles in the powder and irregular particle morphology.
  • the brittle magnetic intermetallic compound is easy to fracture along the intergranular when mechanically broken, there are still some particles that fracture along the intragranular, and it is difficult to obtain a high proportion of single crystal particles in the powder.
  • the particles of the mechanically crushed powder are mostly flakes with sharp diamond angles. It is difficult to obtain high density when mixed with other materials to prepare a giant magnetostrictive bonding material with a high degree of orientation. The reason is that when an external magnetic field is applied for orientation, the flake particles are greatly hindered by the surrounding powder and dispersant, and it is not easy to realize the rotational orientation of the particles. When the alloy particle density is high, it is difficult to obtain a high degree of orientation.
  • the rare earth-iron cubic Laves phase alloy spherical single crystal particles can easily realize the rotation orientation of the particles when a magnetic field is applied to obtain bonded rare earth giant magnetostrictive materials and sintered rare earth giant magnetostrictive materials with good orientation and high magnetic metal particle density.
  • the preparation of rare earth-iron cubic Laves phase alloy spherical single crystal magnetic powder is expected to develop bonded rare earth giant magnetostrictive materials and sintered rare earth giant magnetostrictive materials with high magnetostrictive effect.
  • the purpose of the present invention is to provide a method for preparing cubic Laves phase R-Fe-M alloy spherical single crystal magnetic powder, especially the preparation method of ⁇ 111> oriented rare earth giant magnetostrictive material and alloy spherical single crystal magnetic powder.
  • the method is to mix the R-Fe-M alloy spherical magnetic powder with an inert solid dispersant, so that the R-Fe-M alloy spherical magnetic powder is separated by the inert solid dispersant, and is below the melting point of the R-Fe-M alloy.
  • the technical scheme of the present invention is a preparation method of cubic Laves phase R-Fe-M alloy spherical single crystal magnetic powder, especially the preparation method of rare earth super magnetostrictive material and alloy spherical single crystal magnetic powder.
  • the preparation method of M alloy spherical single crystal magnetic powder includes the following steps:
  • R refers to rare earth elements, including one or more of terbium, dysprosium, samarium, praseodymium, neodymium, cerium, holmium, erbium, etc.
  • M refers to transition metal elements, For example, one or more of cobalt, manganese, aluminum, gallium, chromium, etc., and the rest is iron.
  • the R-Fe-M rare earth alloy is composed of 30-40% (atomic percentage) of R, 0-20% (atomic percentage) of M and the rest of Fe.
  • the step of preparing the R-Fe-M alloy spherical magnetic powder first obtain the R-Fe-M alloy by smelting or chemical reduction, and then use the atomization method, or plasma spheroidization method, or droplet spray method, or The electric spark method or the method in which the R-Fe-M alloy particles are separated by a solid dispersant and then annealed and spheroidized at a temperature higher than the melting point of the R-Fe-M alloy.
  • the size of the spherical particles of the R-Fe-M alloy is less than 1 mm, and the preferred size range is 10 ⁇ m to 300 ⁇ m.
  • the R-Fe-M alloy magnetic powder is separated with an inert solid dispersant.
  • the solid dispersant includes ceramic material powder (oxide ceramics, nitride ceramics, fluoride ceramics, and their composites and mixtures).
  • the step of mixing is to mechanically mix the R-Fe-M alloy magnetic powder and the solid dispersant, or stir and mix uniformly in an organic liquid, or achieve uniform mixing through the auxiliary dispersion of the dispersant.
  • the solid dispersant can be any size smaller than the size of the R-Fe-M alloy particles, and the preferred size range is 1 ⁇ -10 ⁇ m, and the morphology can be flake, spherical, linear, tubular or other shapes.
  • the mass ratio of the rare earth giant magnetostrictive alloy spherical magnetic powder to the solid dispersant should satisfy that the rare earth alloy spherical particles can be completely separated by the solid dispersant.
  • the requirements for annealing to achieve single crystallization of R-Fe-M alloy particles include: 1) Annealing the mixed powder of R-Fe-M alloy magnetic powder and solid dispersant in high vacuum or inert gas; 2) Annealing temperature is lower than R- For the melting point of the Fe-M alloy, the preferred annealing temperature is in the range of 50 to 200°C lower than the melting point of the R-Fe-M alloy, and the preferred annealing time is 1 to 4 hours.
  • the method of removing the solid dispersant to obtain R-Fe-M alloy spherical single crystal magnetic powder includes: 1) After soaking in liquid, ultrasonic cleaning, removing the solid dispersant, to obtain R-Fe-M alloy single crystal magnetic powder; 2) Separate ferromagnetic R-Fe-M alloy and non-magnetic solid dispersant by applying an external magnetic field to obtain R-Fe-M alloy spherical single crystal magnetic powder; 3) Use the difference in density between rare earth alloy magnetic powder and solid dispersant , Obtain the rare earth alloy cubic Laves phase spherical single crystal magnetic powder through the method of wind separation.
  • the size of the spherical single crystal particles of the rare earth giant magnetostrictive alloy is less than 1 mm.
  • the particle size of the preferred R-Fe-M alloy spherical single crystal magnetic powder is in the range of 10 ⁇ m to 300 ⁇ m.
  • the said ⁇ 111>-oriented rare-earth giant magnetostrictive material is processed with rare earth giant magnetostrictive alloy spherical single crystal magnetic powder as raw material (the magnetic powder is oriented and formed in a magnetic field). Is a common technique).
  • Rare earth elements hereinafter referred to as R
  • iron Fe
  • transition metal M
  • R Rare earth elements
  • Fe iron
  • M transition metal
  • the present invention separates the R-Fe-M alloy spherical magnetic powder with an inert solid dispersant, and anneals at a temperature lower than the melting point of the R-Fe-M alloy, and passes the R-Fe-M alloy and the solid dispersant.
  • the principle of preparing R-Fe-M alloy single crystal magnetic powder is clear, the process method for preparing R-Fe-M alloy single crystal magnetic powder is simple, and the production efficiency is high. Preparation method of Fe-M alloy single crystal magnetic powder.
  • the size of the prepared metal particles is less than 1 mm, and the size of the metal single crystal particles is preferably in the range of 10 ⁇ m to 300 ⁇ m.
  • R-Fe-M alloy spherical particles have high single crystallinity, and are especially used to prepare highly ⁇ 111>-oriented bonded rare-earth giant magnetostrictive materials and sintered rare-earth giant magnetostrictive materials. The orientation is particularly good, see the attached drawings.
  • the inventor of the present application found that: mixing the R-Fe-M alloy magnetic powder with an inert solid dispersant, the R-Fe-M alloy spherical magnetic powder is separated by the solid dispersant. Annealing at a temperature below the melting point of the R-Fe-M alloy, through the R-Fe-M alloy and the solid dispersant non-reaction and non-diffusion characteristics, the abnormality of the R-Fe-M cubic Laves phase grains at high temperature is utilized Growth ability to prepare spherical single crystal magnetic powder.
  • the preparation method of the R-Fe-M alloy spherical single crystal magnetic powder of the present invention will be described in detail.
  • the present invention first prepares R-Fe-M alloy spherical magnetic powder of required size.
  • the preparation of R-Fe-M alloy spherical magnetic powder is to first obtain R-Fe-M alloy through smelting or chemical reduction, and then through atomization method, plasma spheroidization method, or droplet spray method, or electric spark method, Or the R-Fe-M alloy particles are separated by a solid dispersant and then annealed and spheroidized at a temperature higher than the melting point of the R-Fe-M alloy.
  • the R-Fe-M alloy spherical magnetic powder is uniformly mixed with a solid dispersant of appropriate size and quantity to achieve the purpose of separating the R-Fe-M alloy spherical magnetic powder with the solid dispersant.
  • Mixing method 1) Use mechanical methods to mix uniformly; 2) Stir and mix uniformly in a liquid (such as alcohol, acetone, etc.); 3) Use dispersant to assist dispersion to achieve uniform mixing.
  • the uniformly mixed R-Fe-M alloy spherical magnetic powder/solid dispersant mixed powder is annealed in a high vacuum or an inert atmosphere at a temperature: lower than the melting point of the R-Fe-M alloy, and the preferred temperature is lower than R-Fe-
  • the melting point of M alloy is 50 ⁇ 200°C.
  • the solid dispersant in the annealed R-Fe-M alloy/solid dispersant is removed to obtain R-Fe-M alloy spherical single crystal magnetic powder.
  • the cleaning methods include: 1) After immersing in liquid (such as alcohol and other organic solvents, water), ultrasonic cleaning removes the solid dispersant to obtain R-Fe-M alloy spherical single crystal magnetic powder; 2) Separating R by applying a magnetic field -Fe-M alloy magnetic powder and solid dispersant to obtain R-Fe-M alloy spherical single crystal magnetic powder; 3) Using the difference in the density of metal and solid dispersant, the R-Fe-M alloy and solid dispersant are separated by wind separation The solid dispersant obtains R-Fe-M alloy spherical single crystal particles.
  • the size of the spherical single crystal particles prepared by the method for preparing the R-Fe-M alloy spherical single crystal magnetic powder of the present invention is less than 1 mm, and the preferred size is 10 ⁇ m to 300 ⁇ m.
  • the rare earth giant magnetostrictive alloy spherical single crystal magnetic powder prepared by the above method is used to prepare bonded rare earth giant magnetostrictive materials and sintered rare earth giant magnetostrictive materials with ⁇ 111> orientation.
  • TbFe 1.95 alloy (subscript is atomic ratio) is obtained by smelting method, and powder with a size of about 20 ⁇ m-100 ⁇ m is obtained as raw material by mechanical crushing. Take 50 grams of TbFe 1.95 alloy powder and Ca 6 Al 2 O 9 powder with a size of about 5 ⁇ m in a weight ratio of 1:3, and mix them evenly after mechanical stirring.
  • the mixed TbFe 1.95 alloy/Ca 6 Al 2 O 9 powder into the annealing furnace, evacuate to 1 ⁇ 10 -3 Pa, ventilate argon to 0.06 MPa, and heat the annealing furnace to 1240 °C at 20 ° /min ( Higher than the melting point temperature of TbFe 1.95 alloy), the temperature is rapidly reduced to 950°C after holding for 10 minutes, and the furnace is cooled to room temperature after holding for 2 hours.
  • TbFe 1.95 alloy/Ca 6 Al 2 O 9 mixed powder was soaked in alcohol , and TbFe 1.95 alloy magnetic powder was obtained by ultrasonic cleaning.
  • the particle size of the obtained TbFe 1.95 alloy magnetic powder is between 20 ⁇ m and 100 ⁇ m.
  • EBSD results show that the TbFe 1.95 alloy particles are single crystal particles. Single crystal particles are mixed with epoxy resin (50:50 by volume) and then solidified or oriented in a magnetic field.
  • XRD studies show that the crystal structure of TbFe 1.95 alloy is cubic laves phase. After comparison, it is found that the external magnetic field achieves a high degree of TbFe 1.95 alloy. ⁇ 111> Orientation. According to the preparation method of the present invention, it was confirmed that the Tb-Fe cubic laves phase single crystal spherical powder can be prepared.
  • Sm-Fe alloy cubic Laves phase spherical single crystal magnetic powder was prepared.
  • SmFe 1.85 alloy powder (subscript is atomic ratio) was prepared by atomization method, and powder with a size of 50 ⁇ m-100 ⁇ m was selected as the raw material. Take 100 grams of SmFe 1.85 alloy powder and CaO powder with a size of about 2 ⁇ m in a weight ratio of 1:2, and mix them evenly after mechanical stirring.
  • SmFe 1.85 alloy/CaO mixed powder was soaked in alcohol , and SmFe 1.85 alloy magnetic powder was obtained by ultrasonic cleaning. Scanning electron microscopy shows that the particles are spherical in size from 50 ⁇ m to 100 ⁇ m. XRD results confirmed that the crystal structure of SmFe 1.85 alloy is cubic laves phase. After the spherical powder and epoxy resin are uniformly mixed in a volume ratio of 50:50, they are cured and molded under a 1T magnetic field to obtain SmFe 1.85 /resin bonded magnetostrictive material.
  • Sm-Fe alloy cubic laves phase has a good ⁇ 111 >Orientation, indicating that Sm-Fe alloy particles have good single crystallinity. According to the preparation method of the present invention, it is confirmed that Sm-Fe cubic laves phase single crystal spherical powder can be prepared.
  • Tb 0.35 Dy 0.65 Fe 1.9 alloy cubic Laves phase spherical single crystal magnetic powder and ⁇ 111> oriented magnetostrictive material is obtained by smelting method, and the size is obtained by mechanical crushing Powder with a diameter of about 20 ⁇ m to 200 ⁇ m is used as a raw material.
  • Tb 0.35 Dy 0.65 Fe 1.9 alloy/CaO mixed powder was soaked in alcohol , and Tb 0.35 Dy 0.65 Fe 1.9 alloy magnetic powder was obtained by ultrasonic cleaning.
  • Figure 1 is a scanning electron micrograph of the obtained Tb 0.35 Dy 0.65 Fe 1.9 alloy magnetic powder. The size of the spherical particles is between 20 ⁇ m and 200 ⁇ m. ,
  • the EBSD picture of the Tb 0.35 Dy 0.65 Fe 1.9 alloy particles of the present invention can show that the particles are single crystals (not attached in the text). According to the preparation method of the present invention, it is confirmed that a spherical single crystal powder of Tb 0.35 Dy 0.65 Fe 1.9 cubic laves phase can be obtained.
  • Tb 0.35 Dy 0.65 Fe 1.9 cubic laves phase single crystal powder with spherical size distributed in 20 ⁇ m ⁇ 200 ⁇ m is uniformly mixed with epoxy resin in different volume ratios, and then cured and molded under a 1T magnetic field.
  • Figure 2 shows the magnetic field-oriented and non-oriented XRD After comparison, it can be seen that the cubic Laves phase of the Tb 0.35 Dy 0.65 Fe 1.9 alloy under an external magnetic field has achieved a good ⁇ 111> orientation, and a highly ⁇ 111> orientation of Tb 0.35 Dy 0.65 Fe 1.9 /resin bonded magneto-induced Stretching material.
  • Tb 0.35 Dy 0.65 Fe 1.9 cubic laves spherical single crystal powder with a size distribution of 20 ⁇ m ⁇ 200 ⁇ m is pressed into a mold after 1T magnetic field orientation, put into an annealing furnace, evacuated to 1 ⁇ 10 -3 Pa, press 20°C / The temperature is raised to 1180°C per minute for 2 hours, and the furnace is cooled to room temperature to obtain Tb 0.35 Dy 0.65 Fe 1.9 sintered magnetostrictive material with good ⁇ 111> orientation.
  • the sintered magnetostrictive material is at room temperature, the prestress is 8MP, and the magnetic field is 1kOe, the magnetostriction coefficient is 1080, and the saturation magnetostriction coefficient is above 1600.
  • Tb 0.32 Dy 0.68 Fe 1.95 alloy cubic Laves phase spherical single crystal magnetic powder and ⁇ 111> oriented bonded magnetostrictive material is prepared by atomization method, The particle size is about 30 ⁇ m to 100 ⁇ m. Take 100 grams of Tb 0.32 Dy 0.68 Fe 1.95 alloy powder and CaO powder with a size of about 5 ⁇ m in a weight ratio of 1:2, and mix them evenly after mechanical stirring.
  • Tb 0.32 Dy 0.68 Fe 1.95 alloy/CaO mixed powder was soaked in alcohol , and Tb 0.32 Dy 0.68 Fe 1.95 alloy magnetic powder was obtained by ultrasonic cleaning. Scanning electron microscopy shows that the particles are spherical in size from 30 ⁇ m to 100 ⁇ m, and the EBSD results indicate that the particles are single crystals. XRD results confirmed that the crystal structure of the Tb 0.32 Dy 0.68 Fe 1.95 alloy is cubic laves phase. Spherical single crystal powder and epoxy resin are uniformly mixed in a volume ratio of 69:31, and then cured under a 1T magnetic field to obtain Tb 0.32 Dy 0.68 Fe 1.95 /resin bonded magnetostrictive material.
  • the Tb 0.32 Dy 0.68 Fe 1.95 alloy in the bonded magnetostrictive material has a high ⁇ 111> orientation.
  • the prestress is 10MP
  • the magnetic field is 1kOe
  • the magnetostriction coefficient is 980
  • the saturation magnetostriction coefficient is 1600. above.
  • Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy cubic Laves phase spherical single crystal magnetic powder and ⁇ 111> oriented bonded magnetostrictive material is obtained by melting method (subscript is atomic ratio ), mechanical crushing to obtain powder with a size of 60 ⁇ m ⁇ 150 ⁇ m as a raw material. Take 100 grams of Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy powder and CaO powder with a size of about 5 ⁇ m in a weight ratio of 1:3, and mix them evenly after mechanical stirring.
  • Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy/CaO powder into the annealing furnace, vacuum to 1 ⁇ 10 -3 Pa, and argon to 0.1 MPa, and heat the annealing furnace to 1280 °C at 20 ° /min (Higher than the melting point temperature of Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy), after holding for 10 minutes, the temperature is rapidly reduced to 1050°C, and after holding for 2 hours, it is cooled to room temperature with the furnace.
  • Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy/CaO mixed powder was soaked in alcohol , and Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy magnetic powder was obtained by ultrasonic cleaning. Scanning electron microscopy showed that the particles were spherical in size from 60 ⁇ m to 150 ⁇ m, and the EBSD results showed that the particles were single crystals. XRD results confirmed that the crystal structure of the Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy is cubic laves phase.
  • Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 /resin-bonded magnetostrictive material Spherical single crystal powder and epoxy resin are uniformly mixed in a volume ratio of 65:35, then cured and molded under a 1T magnetic field to obtain Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 /resin-bonded magnetostrictive material.
  • the Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy in the bonded magnetostrictive material has a high ⁇ 111> orientation.
  • the prestress is 10MP
  • the magnetic field is 1kOe
  • the magnetostriction coefficient is 1000
  • the saturation magnetostriction coefficient Above 1700 the saturation magnetostriction coefficient Above 1700.
  • Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy cubic Laves phase spherical single crystal magnetic powder and ⁇ 111> orientation bonded magnetostrictive material Preparation of Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy cubic Laves phase spherical single crystal magnetic powder and ⁇ 111> orientation bonded magnetostrictive material.
  • Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy (subscript is atomic ratio ), mechanically crushed to obtain powder with a size of 50 ⁇ m ⁇ 120 ⁇ m as a raw material.
  • Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy/CaO powder into the annealing furnace, evacuating to 1 ⁇ 10 -3 Pa, venting argon to 0.1MPa, and heating the annealing furnace to 1260°C at 20 ° /min (Higher than the melting point temperature of Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy), the temperature is rapidly reduced to 1000 °C after holding for 10 minutes, and then cooled to room temperature with the furnace after holding for 2 hours.
  • Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy/CaO mixed powder was soaked in alcohol , and Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy magnetic powder was obtained by ultrasonic cleaning. Scanning electron microscopy showed that the particles were spherical in size from 50 ⁇ m to 120 ⁇ m, and the EBSD results showed that the particles were single crystals. XRD results confirmed that the crystal structure of the Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy is cubic laves phase.
  • Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 /resin bonded magnetostrictive material Spherical single crystal powder and epoxy resin are uniformly mixed in a volume ratio of 69:31, then cured and molded under a 1T magnetic field to obtain Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 /resin bonded magnetostrictive material.
  • the Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy in the bonded magnetostrictive material has a high ⁇ 111> orientation.
  • the prestress is 8MP
  • the magnetic field is 1kOe
  • the magnetostriction coefficient is 960
  • the saturation magnetostriction coefficient Above 1500 At room temperature, the prestress is 8MP, and the magnetic field is 1kOe, the magnetostriction coefficient is 960, and the saturation magnetostriction coefficient Above 1500.

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Abstract

The present invention provides a rare earth giant magnetostrictive material having <111> orientation and a method for preparing an alloy spherical single crystal magnetic powder. The method comprises the following steps: 1) preparing an R-Fe-M alloy spherical magnetic powder; 2) uniformly mixing the R-Fe-M alloy spherical magnetic powder with an inert solid dispersing agent, and annealing same at a temperature below the melting point of an R-Fe-M alloy, so as to obtain an R-Fe-M cubic Laves phase single crystal particle; and 3) removing the solid dispersing agent, so as to obtain an R-Fe-M cubic Laves phase spherical single crystal magnetic powder. In the present invention, the R-Fe-M alloy spherical magnetic powder is separated from the inert solid dispersing agent, and the spherical single crystal particle is prepared by means of the abnormal growth capability of an R-Fe-M cubic Laves phase crystal particle at the high temperature. The bonded rare earth giant magnetostrictive material having high degree of <111> orientation and the sintered rare earth giant magnetostrictive material are prepared.

Description

稀土合金球形单晶磁粉的制造方法及＜111＞取向稀土超磁致伸缩材料Method for manufacturing rare earth alloy spherical single crystal magnetic powder and <111> oriented rare earth giant magnetostrictive material 技术领域Technical field
本发明涉及适用于<111>取向的稀土超磁致伸缩材料及球形单晶磁粉的制备方法，尤其是粘结稀土超磁致伸缩材料和烧结稀土超磁致伸缩材料领域R-Fe-M合金球形单晶磁粉的制备方法。The present invention relates to a preparation method of rare earth super magnetostrictive material suitable for <111> orientation and spherical single crystal magnetic powder, especially R-Fe-M alloy in the field of bonded rare earth super magnetostrictive material and sintered rare earth super magnetostrictive material Preparation method of spherical single crystal magnetic powder.
背景技术Background technique
稀土-铁立方Laves相单晶材料表现出大的磁致伸缩效应，在声呐、换能器等领域都有重要应用。但稀土-铁立方Laves相单晶材料的制备工艺复杂，生产成本高，难以制备大尺寸成分和性能均一的单晶材料。作为一种替代方法，可以通过制备稀土-铁立方Laves相单晶粉末，用单晶粉末为原料制备磁致伸缩块体材料。可以将单晶粉末在磁场下取向后压制成型，高温退火制备具有一定取向的烧结稀土超磁致伸缩材料。也可以将单晶粉末与其他材料，比如环氧树脂，制成粘结稀土超磁致伸缩材料，表现出与大块单晶材料类似的磁致伸缩性能。比如，将铁磁单晶磁粉与环氧树脂混合后在磁场下成型，磁性单晶磁粉可获得高的取向度，该粘结磁致伸缩材料会表现出与单晶材料类似的磁致伸缩性能。The rare earth-iron cubic Laves phase single crystal material exhibits a large magnetostrictive effect and has important applications in sonar, transducer and other fields. However, the preparation process of the rare earth-iron cubic Laves phase single crystal material is complicated, the production cost is high, and it is difficult to prepare large-size single crystal materials with uniform composition and performance. As an alternative method, the magnetostrictive bulk material can be prepared by preparing rare earth-iron cubic Laves phase single crystal powder, using the single crystal powder as a raw material. The single crystal powder can be oriented in a magnetic field and then pressed into a shape, and then annealed at a high temperature to prepare a sintered rare earth giant magnetostrictive material with a certain orientation. It is also possible to combine single crystal powder with other materials, such as epoxy resin, to form a bonded rare earth giant magnetostrictive material, which exhibits magnetostrictive properties similar to bulk single crystal materials. For example, if ferromagnetic single crystal magnetic powder is mixed with epoxy resin and molded under a magnetic field, the magnetic single crystal magnetic powder can obtain a high degree of orientation, and the bonded magnetostrictive material will exhibit magnetostrictive properties similar to that of single crystal material. .
目前稀土-铁立方Laves相单晶粉末的制备方法采用的是破碎法。主要有两种方式：第一种，铸锭或速凝成晶片机械破碎(如专利CN200410037611.X)：将铸锭或速凝成晶片在高温退火，使晶粒长大，通过机械破碎的方法获得单晶颗粒，颗粒为不规则片状形貌；第二种是制备取向晶体或单晶，再破碎晶体获得单晶粉末(如美国专利US005792284A)。目前用这二种方式制备单晶颗粒仍存在不足，主要表现在粉末中单晶颗粒所占比例不够高和颗粒的形貌不规则。虽然脆性大的磁性金属间化合物在机械破碎时容易沿晶间断裂，但仍有部分颗粒会沿晶内断裂，要在粉末中获得高比例的单晶颗粒比较困难。另外，机械破碎后的粉末，颗粒形貌大多为片状，带有尖锐菱角，在与其他材料混合制备取向度高的超磁致伸缩粘结材料时难以获得高的密度。原因是，外加磁场取向时，片状颗粒受周围粉末和分散剂的阻碍作用比较大，不容易实现颗粒的转动取向，合金颗粒密度大时难以获得高的取向度。如果需要获得高得取向度，需要降低磁性颗粒的比例，如专利CN201210034284.7。降低磁性颗粒的比例会影响磁性颗粒间应变的传递，降低磁致伸缩的大小和能量转换效率。The current preparation method of rare earth-iron cubic Laves phase single crystal powder adopts the crushing method. There are two main methods: the first one is mechanical crushing of ingots or quick-setting wafers (such as patent CN200410037611.X): the ingots or rapid-setting wafers are annealed at high temperature to grow the crystal grains through mechanical crushing. Obtain single crystal particles, the particles have irregular flake morphology; the second is to prepare oriented crystals or single crystals, and then crush the crystals to obtain single crystal powders (for example, US Patent US005792284A). At present, there are still shortcomings in the preparation of single crystal particles by these two methods, which are mainly manifested in the insufficient proportion of single crystal particles in the powder and irregular particle morphology. Although the brittle magnetic intermetallic compound is easy to fracture along the intergranular when mechanically broken, there are still some particles that fracture along the intragranular, and it is difficult to obtain a high proportion of single crystal particles in the powder. In addition, the particles of the mechanically crushed powder are mostly flakes with sharp diamond angles. It is difficult to obtain high density when mixed with other materials to prepare a giant magnetostrictive bonding material with a high degree of orientation. The reason is that when an external magnetic field is applied for orientation, the flake particles are greatly hindered by the surrounding powder and dispersant, and it is not easy to realize the rotational orientation of the particles. When the alloy particle density is high, it is difficult to obtain a high degree of orientation. If you need to obtain a high degree of orientation, you need to reduce the proportion of magnetic particles, such as the patent CN201210034284.7. Reducing the ratio of magnetic particles will affect the strain transfer between magnetic particles, reducing the size of magnetostriction and energy conversion efficiency.
稀土-铁立方Laves相合金球形单晶颗粒，容易实现外加磁场时颗粒的转动取向，获得取向度好、磁性金属颗粒密度高的粘结稀土超磁致伸缩材料和烧结稀土超磁致伸缩材料。制备稀土-铁立方Laves相合金球形单晶磁粉，有望发展具有高磁致伸缩效应的粘结稀土超磁致伸缩材料和烧结稀土超磁致伸缩材料。The rare earth-iron cubic Laves phase alloy spherical single crystal particles can easily realize the rotation orientation of the particles when a magnetic field is applied to obtain bonded rare earth giant magnetostrictive materials and sintered rare earth giant magnetostrictive materials with good orientation and high magnetic metal particle density. The preparation of rare earth-iron cubic Laves phase alloy spherical single crystal magnetic powder is expected to develop bonded rare earth giant magnetostrictive materials and sintered rare earth giant magnetostrictive materials with high magnetostrictive effect.
发明内容Summary of the invention
本发明的目的在于，提出一种立方Laves相R-Fe-M合金球形单晶磁粉的制备方法，尤其是<111>取向有稀土超磁致伸缩材料及合金球形单晶磁粉的制备方法，该方法是通过将R-Fe-M合金球形磁粉与惰性的固体分散剂混合，让R-Fe-M合金球形磁粉被惰性固体分散剂隔开，在低于R-Fe-M合金熔点以下某一温度退火，通过R-Fe-M合金与固体分散剂不反应、不扩散的特性，利用高温下R-Fe-M立方Laves相晶粒的异常长大能力制备R-Fe-M立方Laves相球形单晶颗粒。The purpose of the present invention is to provide a method for preparing cubic Laves phase R-Fe-M alloy spherical single crystal magnetic powder, especially the preparation method of <111> oriented rare earth giant magnetostrictive material and alloy spherical single crystal magnetic powder. The method is to mix the R-Fe-M alloy spherical magnetic powder with an inert solid dispersant, so that the R-Fe-M alloy spherical magnetic powder is separated by the inert solid dispersant, and is below the melting point of the R-Fe-M alloy. Temperature annealing, through the R-Fe-M alloy and solid dispersant non-reaction, non-diffusion characteristics, the use of R-Fe-M cubic Laves phase crystal grain abnormal growth ability at high temperature to prepare R-Fe-M cubic Laves phase spherical Single crystal particles.
本发明的技术方案是，一种立方Laves相R-Fe-M合金球形单晶磁粉的制备方法，尤其是稀土超磁致伸缩材料及合金球形单晶磁粉的制备方法，所述R-Fe-M合金球形单晶磁粉制备方法的包括以下步骤：The technical scheme of the present invention is a preparation method of cubic Laves phase R-Fe-M alloy spherical single crystal magnetic powder, especially the preparation method of rare earth super magnetostrictive material and alloy spherical single crystal magnetic powder. The preparation method of M alloy spherical single crystal magnetic powder includes the following steps:
(1)制备R-Fe-M合金球形磁粉；(1) Preparation of R-Fe-M alloy spherical magnetic powder;
(2)单晶化处理：将R-Fe-M合金球形磁粉与惰性固体分散剂均匀混合后，在R-Fe-M合金熔点以下温度退火处理后获得具有立方Laves相结构的R-Fe-M单晶颗粒；(2) Single crystalization treatment: After uniformly mixing R-Fe-M alloy spherical magnetic powder and inert solid dispersant, annealed at a temperature below the melting point of R-Fe-M alloy to obtain R-Fe- with cubic Laves phase structure M single crystal particles;
(3)除掉固体分散剂，获得R-Fe-M立方Laves相球形单晶磁粉。(3) Remove the solid dispersant to obtain R-Fe-M cubic Laves phase spherical single crystal magnetic powder.
本发明所述的R-Fe-M合金,R是指稀土元素，包括铽、镝、钐、镨、钕、铈、钬、铒等中的一种或几种，M是指过渡金属元素，如钴、锰、铝、镓、铬等中的一种或几种，其余为铁。In the R-Fe-M alloy of the present invention, R refers to rare earth elements, including one or more of terbium, dysprosium, samarium, praseodymium, neodymium, cerium, holmium, erbium, etc., and M refers to transition metal elements, For example, one or more of cobalt, manganese, aluminum, gallium, chromium, etc., and the rest is iron.
R-Fe-M稀土合金由30～40％(原子百分比)的R，0～20％(原子百分比)的M和其余Fe所组成。The R-Fe-M rare earth alloy is composed of 30-40% (atomic percentage) of R, 0-20% (atomic percentage) of M and the rest of Fe.
所述制备R-Fe-M合金球形磁粉的步骤：先通过熔炼或化学还原的方法获得R-Fe-M合金，后通过雾化法、或等离子体球化法、或液滴喷射法、或电火花法、或用固体分散剂将R-Fe-M合金颗粒隔开后在高于R-Fe-M合金熔点以上温度退火球化的方法。The step of preparing the R-Fe-M alloy spherical magnetic powder: first obtain the R-Fe-M alloy by smelting or chemical reduction, and then use the atomization method, or plasma spheroidization method, or droplet spray method, or The electric spark method or the method in which the R-Fe-M alloy particles are separated by a solid dispersant and then annealed and spheroidized at a temperature higher than the melting point of the R-Fe-M alloy.
所述R-Fe-M合金球形颗粒尺寸小于1mm，优选的尺寸范围在10μm～300μm。The size of the spherical particles of the R-Fe-M alloy is less than 1 mm, and the preferred size range is 10 μm to 300 μm.
将R-Fe-M合金磁粉用惰性的固体分散剂隔开，固体分散剂包括陶瓷材料粉末(氧化物 陶瓷、氮化物陶瓷、氟化物陶瓷以及它们的复合物和混合物)。混料的步骤是将所述的R-Fe-M合金磁粉与固体分散剂经过机械混合，或在有机液体中搅拌均匀混合，或通过分散剂辅助分散实现均匀混合。The R-Fe-M alloy magnetic powder is separated with an inert solid dispersant. The solid dispersant includes ceramic material powder (oxide ceramics, nitride ceramics, fluoride ceramics, and their composites and mixtures). The step of mixing is to mechanically mix the R-Fe-M alloy magnetic powder and the solid dispersant, or stir and mix uniformly in an organic liquid, or achieve uniform mixing through the auxiliary dispersion of the dispersant.
所述固体分散剂可以是小于R-Fe-M合金颗粒尺寸的任意大小的尺寸，优选的尺寸范围为1μ～10μm，形貌可以是片状、球状、线状、管状或其他形状。The solid dispersant can be any size smaller than the size of the R-Fe-M alloy particles, and the preferred size range is 1 μ-10 μm, and the morphology can be flake, spherical, linear, tubular or other shapes.
所述稀土超磁致伸缩合金球形磁粉与固体分散剂的质量比应满足稀土合金球形颗粒能被固体分散剂完全隔离开。The mass ratio of the rare earth giant magnetostrictive alloy spherical magnetic powder to the solid dispersant should satisfy that the rare earth alloy spherical particles can be completely separated by the solid dispersant.
退火处理实现R-Fe-M合金颗粒单晶化的要求包括：1)在高真空或惰性气体中退火R-Fe-M合金磁粉与固体分散剂的混合粉末；2)退火温度低于R-Fe-M合金的熔点，优选的退火温度是在低于R-Fe-M合金熔点的50～200℃范围，优选的退火时间在1～4小时。The requirements for annealing to achieve single crystallization of R-Fe-M alloy particles include: 1) Annealing the mixed powder of R-Fe-M alloy magnetic powder and solid dispersant in high vacuum or inert gas; 2) Annealing temperature is lower than R- For the melting point of the Fe-M alloy, the preferred annealing temperature is in the range of 50 to 200°C lower than the melting point of the R-Fe-M alloy, and the preferred annealing time is 1 to 4 hours.
除掉固体分散剂获得R-Fe-M合金球形单晶磁粉的方法包括：1)在液体中浸泡后，超声清洗，除掉固体分散剂，获得R-Fe-M合金单晶磁粉；2)采用外加磁场的方法，分离铁磁性的R-Fe-M合金和非磁性的固体分散剂，获得R-Fe-M合金球形单晶磁粉；3)利用稀土合金磁粉与固体分散剂的密度的差异，通过风力分选的方法获得稀土合金立方Laves相球形单晶磁粉。The method of removing the solid dispersant to obtain R-Fe-M alloy spherical single crystal magnetic powder includes: 1) After soaking in liquid, ultrasonic cleaning, removing the solid dispersant, to obtain R-Fe-M alloy single crystal magnetic powder; 2) Separate ferromagnetic R-Fe-M alloy and non-magnetic solid dispersant by applying an external magnetic field to obtain R-Fe-M alloy spherical single crystal magnetic powder; 3) Use the difference in density between rare earth alloy magnetic powder and solid dispersant , Obtain the rare earth alloy cubic Laves phase spherical single crystal magnetic powder through the method of wind separation.
所述稀土超磁致伸缩合金球形单晶颗粒的尺寸小于1mm。优选的R-Fe-M合金球形单晶磁粉的颗粒尺寸在10μm～300μm的范围。The size of the spherical single crystal particles of the rare earth giant magnetostrictive alloy is less than 1 mm. The particle size of the preferred R-Fe-M alloy spherical single crystal magnetic powder is in the range of 10 μm to 300 μm.
所述的<111>取向的稀土超磁致伸缩材料是以稀土超磁致伸缩合金球形单晶磁粉为原料加工而成( 磁粉在磁场中取向成型
Figure PCTCN2021078392-appb-000001
为常用技术)。稀土类元素(以下简称R)、铁(Fe)和过渡金属(M)为成分的R-Fe-M立方Laves相球形单晶磁粉的制备成粉未,利用R-Fe-M立方Laves相单晶的磁各向异性和球形粉末磁场下容易取向的特性，制备具有高度<111>取向的粘结稀土超磁致伸缩材料和烧结稀土超磁致伸缩材料。以此原料特别能形成<111>取向的稀土超磁致伸缩材料。 The said <111>-oriented rare-earth giant magnetostrictive material is processed with rare earth giant magnetostrictive alloy spherical single crystal magnetic powder as raw material (the magnetic powder is oriented and formed in a magnetic field).
Figure PCTCN2021078392-appb-000001
Is a common technique). Rare earth elements (hereinafter referred to as R), iron (Fe), and transition metal (M) are composed of R-Fe-M cubic Laves phase spherical single crystal magnetic powder prepared into powder, using R-Fe-M cubic Laves phase single The magnetic anisotropy of the crystal and the characteristics of easy orientation of the spherical powder under the magnetic field, the preparation of bonded rare earth super magnetostrictive materials and sintered rare earth super magnetostrictive materials with high <111> orientation. This raw material can particularly form <111>-oriented rare earth giant magnetostrictive materials.
有益效果：本发明将R-Fe-M合金球形磁粉用惰性的固体分散剂隔开，在低于R-Fe-M合金熔点以下某一温度退火，通过R-Fe-M合金与固体分散剂不反应、不扩散的特性，利用高温下R-Fe-M立方Laves相晶粒的异常长大能力制备单晶颗粒。根据本发明，制备R-Fe-M合金单晶磁粉的原理清晰，制备R-Fe-M合金单晶磁粉的工艺方法简单，生产效率高，是一种简单易行、可规模化生产R-Fe-M合金单晶磁粉的制备方法。制备的金属颗粒尺寸小于1mm，优选金属单晶颗粒的尺寸在10μm～300μm的范围。R-Fe-M合金球形颗粒单晶度高，特别用 于制备高度<111>取向的粘结稀土超磁致伸缩材料和烧结稀土超磁致伸缩材料，取向特别好，参见附图。Beneficial effects: The present invention separates the R-Fe-M alloy spherical magnetic powder with an inert solid dispersant, and anneals at a temperature lower than the melting point of the R-Fe-M alloy, and passes the R-Fe-M alloy and the solid dispersant. Non-reaction, non-diffusion characteristics, using the abnormal growth ability of R-Fe-M cubic Laves phase crystal grains at high temperature to prepare single crystal particles. According to the present invention, the principle of preparing R-Fe-M alloy single crystal magnetic powder is clear, the process method for preparing R-Fe-M alloy single crystal magnetic powder is simple, and the production efficiency is high. Preparation method of Fe-M alloy single crystal magnetic powder. The size of the prepared metal particles is less than 1 mm, and the size of the metal single crystal particles is preferably in the range of 10 μm to 300 μm. R-Fe-M alloy spherical particles have high single crystallinity, and are especially used to prepare highly <111>-oriented bonded rare-earth giant magnetostrictive materials and sintered rare-earth giant magnetostrictive materials. The orientation is particularly good, see the attached drawings.
附图说明Description of the drawings
图1通过本发明的制备方法获得的Tb 0.35Dy 0.65Fe 1.9立方Laves相球形单晶磁粉的扫描电镜图片； Figure 1 SEM picture of Tb 0.35 Dy 0.65 Fe 1.9 cubic Laves phase spherical single crystal magnetic powder obtained by the preparation method of the present invention;
图2未磁场取向的Tb 0.35Dy 0.65Fe 1.9合金(TDF)球形粉末的x射线衍射图谱和磁场取向后不同Tb 0.35Dy 0.65Fe 1.9合金球形粉末体积含量的粘结磁致伸缩材料的x射线衍射图谱。 Figure 2 X-ray diffraction pattern of Tb 0.35 Dy 0.65 Fe 1.9 alloy (TDF) spherical powder without magnetic field orientation and X-ray diffraction of bonded magnetostrictive material with different volume content of Tb 0.35 Dy 0.65 Fe 1.9 alloy spherical powder after magnetic field orientation Atlas.
具体实施方式Detailed ways
如上所述，本申请的发明人发现：将R-Fe-M合金磁粉与惰性的固体分散剂混合，使R-Fe-M合金球形磁粉被固体分散剂隔开。在低于R-Fe-M合金熔点以下某一温度退火，通过R-Fe-M合金与固体分散剂不反应、不扩散的特性，利用高温下R-Fe-M立方Laves相晶粒的异常长大能力制备球形单晶磁粉。以下，对本发明的R-Fe-M合金球形单晶磁粉的制备方法进行详细的说明。As mentioned above, the inventor of the present application found that: mixing the R-Fe-M alloy magnetic powder with an inert solid dispersant, the R-Fe-M alloy spherical magnetic powder is separated by the solid dispersant. Annealing at a temperature below the melting point of the R-Fe-M alloy, through the R-Fe-M alloy and the solid dispersant non-reaction and non-diffusion characteristics, the abnormality of the R-Fe-M cubic Laves phase grains at high temperature is utilized Growth ability to prepare spherical single crystal magnetic powder. Hereinafter, the preparation method of the R-Fe-M alloy spherical single crystal magnetic powder of the present invention will be described in detail.
本发明首先将制备所需尺寸的R-Fe-M合金球形磁粉。制备R-Fe-M合金球形磁粉是先通过熔炼或化学还原的方法获得R-Fe-M合金，后通过雾化法、或等离子体球化法、或液滴喷射法、或电火花法、或用固体分散剂将R-Fe-M合金颗粒隔开后在高于R-Fe-M合金熔点以上温度退火球化的方法。The present invention first prepares R-Fe-M alloy spherical magnetic powder of required size. The preparation of R-Fe-M alloy spherical magnetic powder is to first obtain R-Fe-M alloy through smelting or chemical reduction, and then through atomization method, plasma spheroidization method, or droplet spray method, or electric spark method, Or the R-Fe-M alloy particles are separated by a solid dispersant and then annealed and spheroidized at a temperature higher than the melting point of the R-Fe-M alloy.
将R-Fe-M合金球形磁粉与适当尺寸和数量的固体分散剂均匀混合，以达到用固体分散剂隔开R-Fe-M合金球形磁粉的目的。混合方法：1)采取机械方法均匀混合；2)在液体(如：酒精、丙酮等)中搅拌均匀混合；3)通过分散剂辅助分散实现均匀混合。The R-Fe-M alloy spherical magnetic powder is uniformly mixed with a solid dispersant of appropriate size and quantity to achieve the purpose of separating the R-Fe-M alloy spherical magnetic powder with the solid dispersant. Mixing method: 1) Use mechanical methods to mix uniformly; 2) Stir and mix uniformly in a liquid (such as alcohol, acetone, etc.); 3) Use dispersant to assist dispersion to achieve uniform mixing.
将混合均匀的R-Fe-M合金球形磁粉/固体分散剂混合粉末在高真空或惰性气氛中退火，温度：低于R-Fe-M合金的熔点，优选的温度为低于R-Fe-M合金熔点50～200℃。The uniformly mixed R-Fe-M alloy spherical magnetic powder/solid dispersant mixed powder is annealed in a high vacuum or an inert atmosphere at a temperature: lower than the melting point of the R-Fe-M alloy, and the preferred temperature is lower than R-Fe- The melting point of M alloy is 50～200℃.
将退火处理的R-Fe-M合金/固体分散剂中的固体分散剂除掉，获得R-Fe-M合金球形单晶磁粉。清洗方法包括：1)在液体(如：酒精等有机溶剂、水)中浸泡后，超声清洗除掉固体分散剂，获得R-Fe-M合金球形单晶磁粉；2)外加磁场的方法分离R-Fe-M合金磁粉和固体分散剂，获得R-Fe-M合金球形单晶磁粉；3)利用金属与固体分散剂的密度的差异，通过风力分选的方法分离R-Fe-M合金与固体分散剂获得R-Fe-M合金球形单晶颗粒。The solid dispersant in the annealed R-Fe-M alloy/solid dispersant is removed to obtain R-Fe-M alloy spherical single crystal magnetic powder. The cleaning methods include: 1) After immersing in liquid (such as alcohol and other organic solvents, water), ultrasonic cleaning removes the solid dispersant to obtain R-Fe-M alloy spherical single crystal magnetic powder; 2) Separating R by applying a magnetic field -Fe-M alloy magnetic powder and solid dispersant to obtain R-Fe-M alloy spherical single crystal magnetic powder; 3) Using the difference in the density of metal and solid dispersant, the R-Fe-M alloy and solid dispersant are separated by wind separation The solid dispersant obtains R-Fe-M alloy spherical single crystal particles.
本发明的R-Fe-M合金球形单晶磁粉的制备方法制备的球形单晶颗粒的尺寸小于1mm，优选的尺寸为10μm～300μm。The size of the spherical single crystal particles prepared by the method for preparing the R-Fe-M alloy spherical single crystal magnetic powder of the present invention is less than 1 mm, and the preferred size is 10 μm to 300 μm.
采用上述方法制备的稀土超磁致伸缩合金球形单晶磁粉制备具有<111>取向的粘结稀土超磁致伸缩材料和烧结稀土超磁致伸缩材料。The rare earth giant magnetostrictive alloy spherical single crystal magnetic powder prepared by the above method is used to prepare bonded rare earth giant magnetostrictive materials and sintered rare earth giant magnetostrictive materials with <111> orientation.
实施例1Example 1
Tb-Fe合金立方Laves相球形单晶磁粉的制备Preparation of Tb-Fe Alloy Cubic Laves Phase Spherical Single Crystal Magnetic Powder
通过熔炼方法获得TbFe 1.95合金(下标为原子比),机械破碎得到尺寸为20μm～100μm左右的粉末作为原料。取50克TbFe 1.95合金粉末与尺寸为5μm左右的Ca 6Al 2O 9粉末按重量比为1:3配比，机械搅拌后均匀混合。 TbFe 1.95 alloy (subscript is atomic ratio) is obtained by smelting method, and powder with a size of about 20μm-100μm is obtained as raw material by mechanical crushing. Take 50 grams of TbFe 1.95 alloy powder and Ca 6 Al 2 O 9 powder with a size of about 5 μm in a weight ratio of 1:3, and mix them evenly after mechanical stirring.
将混合好的TbFe 1.95合金/Ca 6Al 2O 9粉放进退火炉中，抽真空到1×10 -3Pa,通氩气到0.06MPa，将退火炉按20 °/分钟加热到1240℃(高于TbFe 1.95合金熔点温度)，保温10分钟后快速降温至950℃，保温2小时后随炉冷却到室温。 Put the mixed TbFe 1.95 alloy/Ca 6 Al 2 O 9 powder into the annealing furnace, evacuate to 1×10 -3 Pa, ventilate argon to 0.06 MPa, and heat the annealing furnace to 1240 ℃ at 20 ° /min ( Higher than the melting point temperature of TbFe 1.95 alloy), the temperature is rapidly reduced to 950°C after holding for 10 minutes, and the furnace is cooled to room temperature after holding for 2 hours.
用酒精浸泡TbFe 1.95合金/Ca 6Al 2O 9混合粉末，通过超声清洗得到TbFe 1.95合金磁粉。得到的TbFe 1.95合金磁粉颗粒尺寸在20μm～100μm。EBSD结果表明，TbFe 1.95合金颗粒为单晶颗粒。将单晶颗粒与环氧树脂(按体积比50:50)混合后固化或磁场取向固化，XRD研究表明TbFe 1.95合金的晶体结构为立方laves相，对比后发现外加磁场实现了TbFe 1.95合金高度的<111>取向。根据本发明的制备方法，确认能够制备Tb-Fe立方laves相单晶球形粉末。 The TbFe 1.95 alloy/Ca 6 Al 2 O 9 mixed powder was soaked in alcohol , and TbFe 1.95 alloy magnetic powder was obtained by ultrasonic cleaning. The particle size of the obtained TbFe 1.95 alloy magnetic powder is between 20 μm and 100 μm. EBSD results show that the TbFe 1.95 alloy particles are single crystal particles. Single crystal particles are mixed with epoxy resin (50:50 by volume) and then solidified or oriented in a magnetic field. XRD studies show that the crystal structure of TbFe 1.95 alloy is cubic laves phase. After comparison, it is found that the external magnetic field achieves a high degree of TbFe 1.95 alloy. <111> Orientation. According to the preparation method of the present invention, it was confirmed that the Tb-Fe cubic laves phase single crystal spherical powder can be prepared.
实施例2Example 2
Sm-Fe合金立方Laves相球形单晶磁粉的制备，通过雾化方法制备SmFe 1.85合金粉(下标为原子比),选取尺寸为50μm～100μm的粉末作为原料。取100克SmFe 1.85合金粉末与尺寸为2μm左右的CaO粉末按重量比为1:2配比，机械搅拌后均匀混合。 Sm-Fe alloy cubic Laves phase spherical single crystal magnetic powder was prepared. SmFe 1.85 alloy powder (subscript is atomic ratio) was prepared by atomization method, and powder with a size of 50μm-100μm was selected as the raw material. Take 100 grams of SmFe 1.85 alloy powder and CaO powder with a size of about 2 μm in a weight ratio of 1:2, and mix them evenly after mechanical stirring.
将混合好的SmFe 1.85合金/CaO粉放进退火炉中，抽真空到1×10 -3Pa,通氩气到0.1MPa，将退火炉按20 °/分钟加热到860℃，保温4小时后随炉冷却到室温。 Put the mixed SmFe 1.85 alloy/CaO powder into the annealing furnace, vacuum to 1×10 -3 Pa, and argon to 0.1MPa. Heat the annealing furnace to 860°C at 20 ° /min, and keep it warm for 4 hours. The furnace is cooled to room temperature.
用酒精浸泡SmFe 1.85合金/CaO混合粉末，通过超声清洗得到SmFe 1.85合金磁粉。扫描电子显微镜表明颗粒尺寸在50μm～100μm，为球形。XRD结果证实SmFe 1.85合金的晶体结构为立方laves相。将球形粉末与环氧树脂按体积比为50:50均匀混合后，在1T磁场下固化成型，获得SmFe 1.85/树脂粘结磁致伸缩材料，发现Sm-Fe合金立方laves相具有良好的<111>取向，表明Sm-Fe合金颗粒具有好的单晶性。根据本发明的制备方法，确认能够制备Sm-Fe立方laves相单晶球形粉末。 SmFe 1.85 alloy/CaO mixed powder was soaked in alcohol , and SmFe 1.85 alloy magnetic powder was obtained by ultrasonic cleaning. Scanning electron microscopy shows that the particles are spherical in size from 50 μm to 100 μm. XRD results confirmed that the crystal structure of SmFe 1.85 alloy is cubic laves phase. After the spherical powder and epoxy resin are uniformly mixed in a volume ratio of 50:50, they are cured and molded under a 1T magnetic field to obtain SmFe 1.85 /resin bonded magnetostrictive material. It is found that the Sm-Fe alloy cubic laves phase has a good <111 >Orientation, indicating that Sm-Fe alloy particles have good single crystallinity. According to the preparation method of the present invention, it is confirmed that Sm-Fe cubic laves phase single crystal spherical powder can be prepared.
实施例3Example 3
Tb 0.35Dy 0.65Fe 1.9合金立方Laves相球形单晶磁粉的制备及<111>取向的磁致伸缩材料，通过熔炼方法获得Tb 0.35Dy 0.65Fe 1.9合金(下标为原子比),机械破碎得到尺寸为20μm～200μm左右的粉末作为原料。取200克Tb 0.35Dy 0.65Fe 1.9合金粉末与尺寸为2μm左右的CaO粉末按重量比为1:3配比，机械搅拌均匀混合。 Preparation of Tb 0.35 Dy 0.65 Fe 1.9 alloy cubic Laves phase spherical single crystal magnetic powder and <111> oriented magnetostrictive material. Tb 0.35 Dy 0.65 Fe 1.9 alloy (subscript is atomic ratio) is obtained by smelting method, and the size is obtained by mechanical crushing Powder with a diameter of about 20 μm to 200 μm is used as a raw material. Take 200 grams of Tb 0.35 Dy 0.65 Fe 1.9 alloy powder and CaO powder with a size of about 2 μm in a weight ratio of 1:3, and mechanically stir and mix them evenly.
将混合好的Tb 0.35Dy 0.65Fe 1.9合金/CaO粉放进退火炉中，抽真空到1×10 -3Pa,通氩气到0.06MPa，将退火炉按20 °/分钟加热到1290℃(高于Tb 0.35Dy 0.65Fe 1.9合金熔点温度)，保温10分钟后快速降温至1100℃，保温2小时后随炉冷却到室温。 The mixed Tb 0.35 Dy 0.65 Fe 1.9 alloy / CaO powder into the annealing furnace, evacuated to 1 × 10 -3 Pa, argon gas to 0.06MPa, the annealing furnace by 20 ° / min was heated to 1290 deg.] C (high At Tb 0.35 Dy 0.65 Fe 1.9 alloy melting point temperature), the temperature is quickly reduced to 1100 ℃ after 10 minutes of holding, and then cooled to room temperature in the furnace after holding for 2 hours.
用酒精浸泡Tb 0.35Dy 0.65Fe 1.9合金/CaO混合粉末，通过超声清洗得到Tb 0.35Dy 0.65Fe 1.9合金磁粉。图1为得到的Tb 0.35Dy 0.65Fe 1.9合金磁粉的扫描电子显微镜照片，球形颗粒的尺寸在20μm～200μm。、 Tb 0.35 Dy 0.65 Fe 1.9 alloy/CaO mixed powder was soaked in alcohol , and Tb 0.35 Dy 0.65 Fe 1.9 alloy magnetic powder was obtained by ultrasonic cleaning. Figure 1 is a scanning electron micrograph of the obtained Tb 0.35 Dy 0.65 Fe 1.9 alloy magnetic powder. The size of the spherical particles is between 20 μm and 200 μm. ,
本发明Tb 0.35Dy 0.65Fe 1.9合金颗粒的EBSD图片能说明颗粒为单晶(文中未附)。根据本发明的制备方法，确认能够得到Tb 0.35Dy 0.65Fe 1.9立方laves相球形单晶粉末。 The EBSD picture of the Tb 0.35 Dy 0.65 Fe 1.9 alloy particles of the present invention can show that the particles are single crystals (not attached in the text). According to the preparation method of the present invention, it is confirmed that a spherical single crystal powder of Tb 0.35 Dy 0.65 Fe 1.9 cubic laves phase can be obtained.
将球形尺寸分布在20μm～200μm的Tb 0.35Dy 0.65Fe 1.9立方laves相单晶粉末与环氧树脂按不同体积比均匀混合后，在1T磁场下固化成型，图2是磁场取向和未取向的XRD，对比后可以看到,外加磁场下Tb 0.35Dy 0.65Fe 1.9合金立方Laves相实现了很好的<111>取向，获得了高度<111>取向的Tb 0.35Dy 0.65Fe 1.9/树脂粘结磁致伸缩材料。当Tb 0.35Dy 0.65Fe 1.9合金立方laves相单晶粉末与环氧树脂体积比为55:45时，该粘结磁致伸缩材料在室温，预应力为10MP,磁场为1kOe时，磁致伸缩系数为880，饱和磁致伸缩系数在1500以上。 Tb 0.35 Dy 0.65 Fe 1.9 cubic laves phase single crystal powder with spherical size distributed in 20μm～200μm is uniformly mixed with epoxy resin in different volume ratios, and then cured and molded under a 1T magnetic field. Figure 2 shows the magnetic field-oriented and non-oriented XRD After comparison, it can be seen that the cubic Laves phase of the Tb 0.35 Dy 0.65 Fe 1.9 alloy under an external magnetic field has achieved a good <111> orientation, and a highly <111> orientation of Tb 0.35 Dy 0.65 Fe 1.9 /resin bonded magneto-induced Stretching material. When the volume ratio of Tb 0.35 Dy 0.65 Fe 1.9 alloy cubic laves phase single crystal powder to epoxy resin is 55:45, the bonded magnetostrictive material is at room temperature, the prestress is 10MP, and the magnetic field is 1kOe, the magnetostriction coefficient It is 880, and the saturation magnetostriction coefficient is above 1500.
将尺寸分布在20μm～200μm的Tb 0.35Dy 0.65Fe 1.9立方laves相球形单晶粉末在模具中1T磁场取向后压制成型,放入退火炉里，抽真空到1×10 -3Pa，按20℃/每分钟升温到1180℃保温2小时，随炉冷却到室温，获得了具有良好<111>取向的Tb 0.35Dy 0.65Fe 1.9烧结磁致伸缩材料。该烧结磁致伸缩材料在室温，预应力为8MP,磁场为1kOe时，磁致伸缩系数为1080，饱和磁致伸缩系数在1600以上。 Tb 0.35 Dy 0.65 Fe 1.9 cubic laves spherical single crystal powder with a size distribution of 20μm～200μm is pressed into a mold after 1T magnetic field orientation, put into an annealing furnace, evacuated to 1×10 -3 Pa, press 20℃ / The temperature is raised to 1180°C per minute for 2 hours, and the furnace is cooled to room temperature to obtain Tb 0.35 Dy 0.65 Fe 1.9 sintered magnetostrictive material with good <111> orientation. When the sintered magnetostrictive material is at room temperature, the prestress is 8MP, and the magnetic field is 1kOe, the magnetostriction coefficient is 1080, and the saturation magnetostriction coefficient is above 1600.
实施例4Example 4
Tb 0.32Dy 0.68Fe 1.95合金立方Laves相球形单晶磁粉的制备及<111>取向的粘结磁致伸缩材料，通过雾化方法制备了Tb 0.32Dy 0.68Fe 1.95合金(下标为原子比),颗粒尺寸为30μm～100μm左右。取100克Tb 0.32Dy 0.68Fe 1.95合金粉末与尺寸为5μm左右的CaO粉末按重量比为1:2配比，机械搅拌后均匀混合。 Preparation of Tb 0.32 Dy 0.68 Fe 1.95 alloy cubic Laves phase spherical single crystal magnetic powder and <111> oriented bonded magnetostrictive material. Tb 0.32 Dy 0.68 Fe 1.95 alloy (subscript is atomic ratio) is prepared by atomization method, The particle size is about 30 μm to 100 μm. Take 100 grams of Tb 0.32 Dy 0.68 Fe 1.95 alloy powder and CaO powder with a size of about 5 μm in a weight ratio of 1:2, and mix them evenly after mechanical stirring.
将混合好的Tb 0.32Dy 0.68Fe 1.95合金/CaO粉放进退火炉中，抽真空到1×10 -3Pa,通氩气到0.06MPa，将退火炉按20 °/分钟加热到1150℃，保温1小时后随炉冷却到室温。 Put the mixed Tb 0.32 Dy 0.68 Fe 1.95 alloy/CaO powder into the annealing furnace, evacuating to 1×10 -3 Pa, argon gas to 0.06 MPa, heating the annealing furnace to 1150 ℃ at 20 ° /min, and keep it warm. After 1 hour, the furnace was cooled to room temperature.
用酒精浸泡Tb 0.32Dy 0.68Fe 1.95合金/CaO混合粉末，通过超声清洗得到Tb 0.32Dy 0.68Fe 1.95合金磁粉。扫描电子显微镜表明颗粒尺寸在30μm～100μm，为球形，EBSD结果表明颗粒为单晶体。XRD结果证实Tb 0.32Dy 0.68Fe 1.95合金的晶体结构为立方laves相。球形单晶粉末与环氧树脂按体积比为69:31均匀混合后，在1T磁场下固化成型，获得Tb 0.32Dy 0.68Fe 1.95/树脂粘结磁致伸缩材料。该粘结磁致伸缩材料中Tb 0.32Dy 0.68Fe 1.95合金具有高度的<111>取向，在室温，预应力为10MP,磁场为1kOe时，磁致伸缩系数为980，饱和磁致伸缩系数在1600以上。 Tb 0.32 Dy 0.68 Fe 1.95 alloy/CaO mixed powder was soaked in alcohol , and Tb 0.32 Dy 0.68 Fe 1.95 alloy magnetic powder was obtained by ultrasonic cleaning. Scanning electron microscopy shows that the particles are spherical in size from 30 μm to 100 μm, and the EBSD results indicate that the particles are single crystals. XRD results confirmed that the crystal structure of the Tb 0.32 Dy 0.68 Fe 1.95 alloy is cubic laves phase. Spherical single crystal powder and epoxy resin are uniformly mixed in a volume ratio of 69:31, and then cured under a 1T magnetic field to obtain Tb 0.32 Dy 0.68 Fe 1.95 /resin bonded magnetostrictive material. The Tb 0.32 Dy 0.68 Fe 1.95 alloy in the bonded magnetostrictive material has a high <111> orientation. At room temperature, the prestress is 10MP, and the magnetic field is 1kOe, the magnetostriction coefficient is 980, and the saturation magnetostriction coefficient is 1600. above.
实施例5Example 5
Tb 0.5Dy 0.5Fe 1.9Mn 0.5合金立方Laves相球形单晶磁粉的制备及<111>取向的粘结磁致伸缩材料，通过熔炼方法获得Tb 0.5Dy 0.5Fe 1.9Mn 0.5合金(下标为原子比),机械破碎得到尺寸为60μm～150μm的粉末作为原料。取100克Tb 0.5Dy 0.5Fe 1.9Mn 0.5合金粉末与尺寸为5μm左右的CaO粉末按重量比为1:3配比，机械搅拌后均匀混合。 Preparation of Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy cubic Laves phase spherical single crystal magnetic powder and <111> oriented bonded magnetostrictive material. Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy is obtained by melting method (subscript is atomic ratio ), mechanical crushing to obtain powder with a size of 60μm～150μm as a raw material. Take 100 grams of Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy powder and CaO powder with a size of about 5 μm in a weight ratio of 1:3, and mix them evenly after mechanical stirring.
将混合好的Tb 0.5Dy 0.5Fe 1.9Mn 0.5合金/CaO粉放进退火炉中，抽真空到1×10 -3Pa,通氩气到0.1MPa，将退火炉按20 °/分钟加热到1280℃(高于Tb 0.5Dy 0.5Fe 1.9Mn 0.5合金熔点温度)，保温10分钟后快速降温至1050℃，保温2小时后随炉冷却到室温。 Put the mixed Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy/CaO powder into the annealing furnace, vacuum to 1×10 -3 Pa, and argon to 0.1 MPa, and heat the annealing furnace to 1280 ℃ at 20 ° /min (Higher than the melting point temperature of Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy), after holding for 10 minutes, the temperature is rapidly reduced to 1050°C, and after holding for 2 hours, it is cooled to room temperature with the furnace.
用酒精浸泡Tb 0.5Dy 0.5Fe 1.9Mn 0.5合金/CaO混合粉末，通过超声清洗得到Tb 0.5Dy 0.5Fe 1.9Mn 0.5合金磁粉。扫描电子显微镜表明颗粒尺寸在60μm～150μm，为球形，EBSD结果表明颗粒为单晶体。XRD结果证实Tb 0.5Dy 0.5Fe 1.9Mn 0.5合金的晶体结构为立方laves相。球形单晶粉末与环氧树脂按体积比为65:35均匀混合后，在1T磁场下固化成型，获得Tb 0.5Dy 0.5Fe 1.9Mn 0.5/树脂粘结磁致伸缩材料。该粘结磁致伸缩材料中Tb 0.5Dy 0.5Fe 1.9Mn 0.5合金具有高度的<111>取向，在室温，预应力为10MP，磁场为1kOe时，磁致伸缩系数为1000，饱和磁致伸缩系数在1700以上。 Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy/CaO mixed powder was soaked in alcohol , and Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy magnetic powder was obtained by ultrasonic cleaning. Scanning electron microscopy showed that the particles were spherical in size from 60μm to 150μm, and the EBSD results showed that the particles were single crystals. XRD results confirmed that the crystal structure of the Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy is cubic laves phase. Spherical single crystal powder and epoxy resin are uniformly mixed in a volume ratio of 65:35, then cured and molded under a 1T magnetic field to obtain Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 /resin-bonded magnetostrictive material. The Tb 0.5 Dy 0.5 Fe 1.9 Mn 0.5 alloy in the bonded magnetostrictive material has a high <111> orientation. At room temperature, the prestress is 10MP, and the magnetic field is 1kOe, the magnetostriction coefficient is 1000, and the saturation magnetostriction coefficient Above 1700.
实施例6Example 6
Tb 0.3Pr 0.15Dy 0.55Fe 1.9合金立方Laves相球形单晶磁粉的制备及<111>取向的粘结磁致伸缩材料，通过熔炼方法获得Tb 0.3Pr 0.15Dy 0.55Fe 1.9合金(下标为原子比),机械破碎得到尺寸为50μm～120μm的粉末作为原料。取100克Tb 0.3Pr 0.15Dy 0.55Fe 1.9合金粉末与尺寸为2μm左右的CaO粉末按重量比为1:3配比，机械搅拌后均匀混合。 Preparation of Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy cubic Laves phase spherical single crystal magnetic powder and <111> orientation bonded magnetostrictive material. Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy (subscript is atomic ratio ), mechanically crushed to obtain powder with a size of 50μm～120μm as a raw material. Take 100 grams of Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy powder and CaO powder with a size of about 2 μm in a weight ratio of 1:3, and mix them evenly after mechanical stirring.
将混合好的Tb 0.3Pr 0.15Dy 0.55Fe 1.9合金/CaO粉放进退火炉中，抽真空到1×10 -3Pa,通氩气到 0.1MPa，将退火炉按20 °/分钟加热到1260℃(高于Tb 0.3Pr 0.15Dy 0.55Fe 1.9合金熔点温度)，保温10分钟后快速降温至1000℃，保温2小时后随炉冷却到室温。 Put the mixed Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy/CaO powder into the annealing furnace, evacuating to 1×10 -3 Pa, venting argon to 0.1MPa, and heating the annealing furnace to 1260°C at 20 ° /min (Higher than the melting point temperature of Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy), the temperature is rapidly reduced to 1000 ℃ after holding for 10 minutes, and then cooled to room temperature with the furnace after holding for 2 hours.
用酒精浸泡Tb 0.3Pr 0.15Dy 0.55Fe 1.9合金/CaO混合粉末，通过超声清洗得到Tb 0.3Pr 0.15Dy 0.55Fe 1.9合金磁粉。扫描电子显微镜表明颗粒尺寸在50μm～120μm，为球形，EBSD结果表明颗粒为单晶体。XRD结果证实Tb 0.3Pr 0.15Dy 0.55Fe 1.9合金的晶体结构为立方laves相。球形单晶粉末与环氧树脂按体积比为69:31均匀混合后，在1T磁场下固化成型，获得Tb 0.3Pr 0.15Dy 0.55Fe 1.9/树脂粘结磁致伸缩材料。该粘结磁致伸缩材料中Tb 0.3Pr 0.15Dy 0.55Fe 1.9合金具有高度的<111>取向，在室温，预应力为8MP，磁场为1kOe时，磁致伸缩系数为960，饱和磁致伸缩系数在1500以上。 Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy/CaO mixed powder was soaked in alcohol , and Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy magnetic powder was obtained by ultrasonic cleaning. Scanning electron microscopy showed that the particles were spherical in size from 50 μm to 120 μm, and the EBSD results showed that the particles were single crystals. XRD results confirmed that the crystal structure of the Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy is cubic laves phase. Spherical single crystal powder and epoxy resin are uniformly mixed in a volume ratio of 69:31, then cured and molded under a 1T magnetic field to obtain Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 /resin bonded magnetostrictive material. The Tb 0.3 Pr 0.15 Dy 0.55 Fe 1.9 alloy in the bonded magnetostrictive material has a high <111> orientation. At room temperature, the prestress is 8MP, and the magnetic field is 1kOe, the magnetostriction coefficient is 960, and the saturation magnetostriction coefficient Above 1500.
以上所述仅为本发明的优选实施例，并不用于限制本发明，对于本领域的技术人员来说，凡在本发明的精神和原则之内，所作的任何修改、改进，均应包括在本发明的保护范围之内。The above descriptions are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, any modification and improvement made within the spirit and principle of the present invention should be included in Within the protection scope of the present invention.

Claims (9)

  1. 稀土超磁致伸缩合金球形单晶磁粉的制备方法，其特征在于，包括以下步骤：The preparation method of rare earth giant magnetostrictive alloy spherical single crystal magnetic powder is characterized in that it comprises the following steps:
    (1)制备R-Fe-M合金球形磁粉；(1) Preparation of R-Fe-M alloy spherical magnetic powder;
    (2)将R-Fe-M合金球形磁粉与惰性固体分散剂均匀混合后，在R-Fe-M合金熔点以下温度退火处理获得具有立方Laves相结构的R-Fe-M合金单晶颗粒；(2) After uniformly mixing R-Fe-M alloy spherical magnetic powder and inert solid dispersant, annealing at a temperature below the melting point of R-Fe-M alloy to obtain R-Fe-M alloy single crystal particles with cubic Laves phase structure;
    (3)除掉固体分散剂，获得R-Fe-M立方Laves相球形单晶磁粉；(3) Remove the solid dispersant to obtain R-Fe-M cubic Laves phase spherical single crystal magnetic powder;
    所述的R-Fe-M稀土合金,R是指稀土元素，包括铽、镝、钐、镨、钕、铈、钬、铒中的一种或几种，M是指过渡金属元素，即钴、锰、铝、镓或铬中的一种或几种，其余为铁；R-Fe-M稀土合金，由30～40％原子百分比的R，0～20％原子百分比的M和其余Fe所组成；In the R-Fe-M rare earth alloy, R refers to rare earth elements, including one or more of terbium, dysprosium, samarium, praseodymium, neodymium, cerium, holmium, and erbium, and M refers to transition metal elements, namely cobalt One or more of, manganese, aluminum, gallium or chromium, and the rest is iron; R-Fe-M rare earth alloy, composed of 30-40% atomic percentage of R, 0-20% atomic percentage of M and the rest of Fe composition;
    所述R-Fe-M合金球形颗粒尺寸小于1mm。The size of the spherical particles of the R-Fe-M alloy is less than 1 mm.
  2. 根据权利要求1所述的稀土超磁致伸缩球形单晶磁粉的制备方法，其特征在于：The method for preparing rare earth giant magnetostrictive spherical single crystal magnetic powder according to claim 1, characterized in that:
    准备所述制备R-Fe-M合金球形磁粉的步骤：先通过熔炼或化学还原的方法获得R-Fe-M合金，后通过雾化法、或等离子体球化法、或液滴喷射法、或电火花法、或用固体分散剂将R-Fe-M合金颗粒隔开后在高于R-Fe-M合金熔点以上温度退火球化的方法。The step of preparing the R-Fe-M alloy spherical magnetic powder: first obtain the R-Fe-M alloy by smelting or chemical reduction, and then use the atomization method, or plasma spheroidization method, or droplet spray method, Or the electric spark method, or the method in which the R-Fe-M alloy particles are separated by a solid dispersant and then annealed and spheroidized at a temperature higher than the melting point of the R-Fe-M alloy.
  3. 根据权利要求1所述的制备R-Fe-M合金球形磁粉，其特征在于：R-Fe-M合金球形颗粒尺寸在10微米～300微米。The preparation of R-Fe-M alloy spherical magnetic powder according to claim 1, wherein the size of the spherical particles of the R-Fe-M alloy is 10 micrometers to 300 micrometers.
  4. 根据权利要求1所述的稀土超磁致伸缩球形单晶磁粉的制备方法，其特征在于：将R-Fe-M合金磁粉用惰性的固体分散剂隔开，固体分散剂包括陶瓷材料粉末，包括氧化物陶瓷、氮化物陶瓷、氟化物陶瓷以及它们的复合物和混合物；混料的步骤是将所述的R-Fe-M合金磁粉与固体分散剂经过机械混合，在有机液体中搅拌均匀混合或通过分散剂辅助分散实现均匀混合。The method for preparing rare earth giant magnetostrictive spherical single crystal magnetic powder according to claim 1, wherein the R-Fe-M alloy magnetic powder is separated by an inert solid dispersant, and the solid dispersant includes ceramic material powder, including Oxide ceramics, nitride ceramics, fluoride ceramics, and their composites and mixtures; the mixing step is to mechanically mix the R-Fe-M alloy magnetic powder and the solid dispersant, and mix them evenly in the organic liquid. Or through dispersing agent assisted dispersion to achieve uniform mixing.
  5. 根据权利要求4所述的稀土超磁致伸缩球形单晶磁粉的制备方法，其特征在于：所述固体分散剂是小于R-Fe-M合金颗粒尺寸的任意大小的尺寸，尺寸范围为1微米～10微米，形貌是片状、球状、线状、管状；所述稀土超磁致伸缩合金球形磁粉与固体分散剂的质量比应满足稀土合金球形颗粒能被固体分散剂完全隔离开。The method for preparing rare earth giant magnetostrictive spherical single crystal magnetic powder according to claim 4, wherein the solid dispersant is any size smaller than the size of the R-Fe-M alloy particles, and the size range is 1 micron The morphology is flaky, spherical, linear and tubular; the mass ratio of the rare earth giant magnetostrictive alloy spherical magnetic powder to the solid dispersant should satisfy that the rare earth alloy spherical particles can be completely separated by the solid dispersant.
  6. 根据权利要求1中所述的稀土超磁致伸缩合金球形单晶磁粉的制备方法，其特征在于：退火处理实现R-Fe-M合金颗粒单晶化的要求包括：1)在高真空或惰性气体中退火R-Fe-M合金磁粉与固体分散剂的混合粉末；2)退火温度低于R-Fe-M合金的熔点。The method for preparing rare earth giant magnetostrictive alloy spherical single crystal magnetic powder according to claim 1, characterized in that the annealing treatment to achieve single crystalization of R-Fe-M alloy particles includes: 1) In high vacuum or inert Annealing the mixed powder of R-Fe-M alloy magnetic powder and solid dispersant in gas; 2) The annealing temperature is lower than the melting point of the R-Fe-M alloy.
  7. 根据权利要求1中所述的稀土超磁致伸缩合金球形单晶磁粉的制备方法，其特征在于： 除掉固体分散剂获得R-Fe-M合金球形单晶磁粉的方法包括：1)在液体中浸泡后，超声清洗，除掉固体分散剂，获得R-Fe-M合金球形单晶磁粉；2)采用外加磁场的方法，分离铁磁性的R-Fe-M合金和非磁性的固体分散剂，获得R-Fe-M合金球形单晶磁粉；3)利用稀土合金磁粉与固体分散剂的密度的差异，通过风力分选的方法获得R-Fe-M立方Laves相球形单晶磁粉。The method for preparing rare earth giant magnetostrictive alloy spherical single crystal magnetic powder according to claim 1, characterized in that: the method for obtaining R-Fe-M alloy spherical single crystal magnetic powder by removing the solid dispersant comprises: 1) in liquid After soaking in the medium, ultrasonic cleaning, remove the solid dispersant, obtain R-Fe-M alloy spherical single crystal magnetic powder; 2) Use the method of applying a magnetic field to separate the ferromagnetic R-Fe-M alloy and the non-magnetic solid dispersant , Obtain the R-Fe-M alloy spherical single crystal magnetic powder; 3) use the difference of the density of the rare earth alloy magnetic powder and the solid dispersant to obtain the R-Fe-M cubic Laves phase spherical single crystal magnetic powder by the method of wind separation.
  8. 根据权利要求1至7任一项所述的方法得到的<111>取向的稀土超磁致伸缩材料，其特征在于：所述稀土超磁致伸缩合金球形单晶颗粒的尺寸小于1mm；优选的R-Fe-M合金球形单晶磁粉的颗粒尺寸在10微米～300微米的范围；稀土超磁致伸缩材料以所述的稀土超磁致伸缩合金球形单晶磁粉为原料制备而成。The <111>-oriented rare earth giant magnetostrictive material obtained by the method according to any one of claims 1 to 7, characterized in that: the size of the spherical single crystal particles of the rare earth giant magnetostrictive alloy is less than 1 mm; preferably The particle size of the R-Fe-M alloy spherical single crystal magnetic powder is in the range of 10 micrometers to 300 micrometers; the rare earth giant magnetostrictive material is prepared by using the rare earth giant magnetostrictive alloy spherical single crystal magnetic powder as a raw material.
  9. 根据权利要求8所述的<111>取向的稀土超磁致伸缩材料，其特征在于：所述稀土超磁致伸缩合金球形单晶颗粒的尺寸在10微米～300微米的范围。The <111>-oriented rare earth giant magnetostrictive material according to claim 8, wherein the size of the spherical single crystal particles of the rare earth giant magnetostrictive alloy is in the range of 10 micrometers to 300 micrometers.
PCT/CN2021/078392 2020-03-04 2021-03-01 Method for preparing rare earth alloy spherical single crystal magnetic powder, and rare earth giant magnetostrictive material having &lt;111&gt; orientation WO2021175174A1 (en)

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