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WO2018188675A1 - 高温度稳定性永磁材料及其应用 - Google Patents

高温度稳定性永磁材料及其应用 Download PDF

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Publication number
WO2018188675A1
WO2018188675A1 PCT/CN2018/086056 CN2018086056W WO2018188675A1 WO 2018188675 A1 WO2018188675 A1 WO 2018188675A1 CN 2018086056 W CN2018086056 W CN 2018086056W WO 2018188675 A1 WO2018188675 A1 WO 2018188675A1
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Prior art keywords
permanent magnet
magnet material
temperature
temperature coefficient
phase
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English (en)
French (fr)
Inventor
刘雷
刘壮
闫阿儒
张鑫
孙颖莉
李东
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • H01F1/0557—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
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
    • 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
    • H01F7/00—Magnets
    • H01F7/02—Permanent magnets [PM]
    • H01F7/0205—Magnetic circuits with PM in general
    • H01F7/021—Construction of PM

Definitions

  • the invention relates to the field of magnetic materials, in particular to a permanent magnet material with high temperature stability and its application.
  • AlNiCo magnetic steel has a remanence temperature coefficient of about -0.02%/°C and a coercivity temperature coefficient of about -0.03%/°C, it is easily affected by low coercive force ( ⁇ 2kOe) and low magnetic energy product ( ⁇ 10MGOe). Vibration, magnetic field, radiation and other interferences cannot meet the long-term use of the device.
  • the present invention aims to disclose a novel high temperature stability magnet, which guarantees low surplus.
  • the magnetic temperature coefficient ⁇ Cobalt magnet steel has a high magnetic energy product and a low absolute value of the remanence temperature coefficient, which improves the coercive force temperature stability of the magnet.
  • the present invention provides a high temperature stability permanent magnet material and its use, which has a high temperature stability over a certain temperature range.
  • a high temperature stability permanent magnet material comprising a ferromagnetic phase and a magnetic phase having a spin phase transition, the ferromagnetic phase and the magnetic phase having the spin phase transition being isolated from each other .
  • the absolute value of the ferromagnetic phase saturation magnetization temperature coefficient is less than 0.02% / °C.
  • the microstructure has a size of from 5 nm to 800 nm in at least one dimension.
  • the isolating phase of the ferromagnetic phase and the magnetic phase having a spin phase change is either a package isolation or a layer spacer isolation.
  • the direction of easy magnetization of the magnetic phase having a spin phase change is shifted from the easy base to the easy axis.
  • the ferromagnetic phase is a SmHRECo-based compound, and the Sm moiety is substituted by a combination of HRE or HRE with other elements, and the magnetic phase having a spin phase transition is an RCo 5 compound, RCo 5 a derivative compound, a R 2 Co 17 compound or a derivative compound of R 2 Co 17 ;
  • HRE is selected from one or more of Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu;
  • R is selected from one or more of the group consisting of Pr, Nd, Dy, Tb, and Ho.
  • the permanent magnet material is a samarium cobalt-based permanent magnet
  • the samarium-cobalt-based permanent magnet includes a ferromagnetic phase (SmHRER) 2 (CoM) 17- based compound, and a magnetic phase (SmHRER) (CoM) 5 -based compound having a spin phase transformation, and a microscopic of the samarium-cobalt-based permanent magnet
  • the (SmHRER) (CoM) 5 line compound encapsulates the (SmHRER) 2 (CoM) 17 line compound;
  • HRE is selected from one or more of Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; R is selected from one or more of Pr, Nd, Dy, Tb and Ho, M is selected One or more of Fe, Cu, Zr, Ni, Ti, Nb, Mo, Hf, and W, and the SmHRER has at least three elements.
  • the samarium-cobalt-based permanent magnet has a mass percentage of R of 8% to 20%; and a mass percentage of HRE of 8% to 18%.
  • the Tb, Dy, and/or Ho simultaneously calculate the mass percentage of the R as R.
  • the spin phase transition temperature of the (SmHRER)(CoM) 5 compound increases, the coercive force maximum point and the coercivity minimum point temperature
  • the temperature range corresponding to the absolute value of the coercive force temperature coefficient is less than 0.03%/°C.
  • the temperature range of the saturation magnetization temperature coefficient of the ferromagnetic phase (SmHRER) 2 (CoM) 17- based compound is less than 0.02%/° C.
  • the permanent magnet material has an absolute value of the remanence temperature coefficient of less than 0.02%/° C. in a temperature range of 2K to 600K, and an absolute value of the coercive force temperature coefficient is less than 0.03%/° C.
  • the invention relates to the application of the high temperature stability permanent magnet material in a temperature changing environment.
  • the invention obtains a low coercivity temperature coefficient by a permanent magnet material comprising a ferromagnetic phase and a magnetic phase having a spin phase transition, so that the acquisition of the low coercivity temperature coefficient is more purposeful, regular and versatile;
  • the invention utilizes the antiferromagnetic coupling property of the heavy rare earth element and the transition metal to adjust the remanence temperature coefficient of the magnet, and solves the technical problem that the low coercivity temperature coefficient and the low remanence temperature coefficient are difficult to obtain at the same time in the prior art.
  • the invention can adjust the temperature range of the low coercivity temperature coefficient temperature interval and the low remanence temperature coefficient of the permanent magnet material by adjusting the components, thereby satisfying the application of the permanent magnet material in different demand fields.
  • Example 1 is a transmission electron micrograph of a samarium-cobalt-based permanent magnet obtained in Example 3 of the present invention
  • FIG. 2 is a test chart of AC magnetic susceptibility of the samarium-cobalt-based permanent magnets obtained in Examples 1 to 4 of the present invention, and the test conditions are: an AC field of 5 Oe, a frequency of 1000 Hz;
  • FIG. 3 is a graph showing changes in coercivity of a samarium-cobalt-based permanent magnet obtained in Examples 1 to 4 according to the present invention.
  • FIG. 5 is a graph showing changes in residual magnetization with temperature of samarium-cobalt-based permanent magnets obtained in Examples 1 to 4 of the present invention.
  • Example 6 is a demagnetization curve of a samarium-cobalt-based permanent magnet prepared in Example 1 of the present invention at a temperature range of 100 ° C at room temperature;
  • Fig. 7 is a graph showing the demagnetization curve of a samarium-cobalt-based permanent magnet obtained in Example 4 of the present invention at a temperature of 100 ° C in a room temperature zone.
  • Fig. 8 is a graph showing the AC magnetic susceptibility test of the samarium-cobalt-based permanent magnet produced in the comparative example, the change of coercive force with temperature, the saturation magnetization and the change of remanence with temperature.
  • ⁇ (T 0 -T 1 ) ⁇ [B r (T 0 )-B r (T 1 )]/[B r (T 0 ) ⁇ (T 0 -T 1 )] ⁇ 100%
  • B r (T 0 ) and B r (T 1 ) are the remanence values at temperatures of T 0 and T 1 , respectively.
  • ⁇ (T 0 -T 1 ) ⁇ [H cj (T 0 )-H cj (T 1 )]/[H cj (T 0 ) ⁇ (T 0 -T 1 )] ⁇ 100%
  • H cj (T 0 ) and H cj (T 1 ) are coercive force values at temperatures of T 0 and T 1 , respectively.
  • the inventors have found through a large number of experiments that the maximum or minimum value of the coercive force occurs in the vicinity of the spin phase transition temperature of the magnetic phase having a spin phase transition, and therefore, the temperature range around the maximum value or the minimum value The absolute value of the internal coercivity temperature coefficient is very low.
  • the magnetic phase with spin phase change means that some magnetic alloy phases change with the change of temperature, and the easy magnetization axis changes, including: easy axial easy surface transformation, easy to face easy axis transformation and other easy magnetization axis transformation Phenomenon, that is, spin reorientation occurs; the temperature point at which the easy magnetization axis changes is the spin reorientation transition temperature, that is, the spin phase transition temperature; and the temperature range near the maximum or minimum value is the low coercivity Temperature range of the temperature coefficient of force.
  • the present invention provides a high temperature stable permanent magnet material whose microstructure includes a ferromagnetic phase and a magnetic phase having a spin phase transition, and the ferromagnetic phase and the magnetic phase having a spin phase transition are isolated from each other.
  • the absolute value of the ferromagnetic phase saturation magnetization temperature coefficient is less than 0.02% / °C.
  • the size of the microstructure is from 5 nm to 800 nm in at least one dimension.
  • the saturation magnetization temperature coefficient has an absolute value of less than 0.01% / °C.
  • the ferromagnetic phase in the present invention means a magnetic phase having uniaxial anisotropy.
  • the magnetic phase having a spin phase transition may be an RCo 5 alloy, a derivative alloy of RCo 5 , a R 2 Co 17 compound or a derivative compound of R 2 Co 17 ; wherein R is selected from Pr One or more of Nd, Dy, Tb and Ho.
  • the derivative compound means that one or more elemental parts constituting the alloy are substituted by other elements, and in some embodiments, R may be partially substituted by Sm or a combination of Sm and HRE, and Co may be substituted by M part.
  • HRE is selected from one or more of Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu
  • M is selected from one of Fe, Cu, Zr, Ni, Ti, Nb, Mo, Hf and W
  • a plurality of, for example, Sm 1-x Dy x Co 5 (0 ⁇ x ⁇ 1) is a derivative compound of RCo 5 .
  • the ferromagnetic phase is generally an SmCo-based compound, and the Sm moiety is substituted by a combination of HRE or HRE with other elements (for example, an R element different from the HRE element), preferably Sm 2 Co 17 , SmCo
  • the Sm moiety in 5 or SmCo 7 is substituted with the obtained compound by HRE and R.
  • Co can also be replaced by an M moiety.
  • R and HRE in the ferromagnetic phase contain different elements, that is, Sm in the ferromagnetic phase is substituted with at least two element portions selected from the HRE and R to form a ternary component or more.
  • the R, M and HRE in the ferromagnetic phase may be the same or different in the magnetic phase of the spin phase transition, and are preferably the same respectively.
  • the spin phase transition temperature is also different.
  • DyCo 5 alloy turns from easy surface to easy axis in 370K easy magnetization direction
  • 370K is the spin phase transition temperature of DyCo 5 alloy
  • TbCo 5 alloy turns from easy surface to easy axis in 410K easy magnetization direction
  • 410K is TbCo 5
  • the spin phase transition temperature of the alloy Therefore, the desired spin phase transition temperature can be obtained by the selection of the magnetic phase having a spin phase transition, thereby obtaining the desired low coercivity temperature coefficient interval.
  • the temperature range of the low remanence temperature coefficient can be obtained by controlling the content of the heavy rare earth.
  • the high temperature stability permanent magnet material of the present invention has a low coercivity temperature coefficient in a temperature range of 10K to 600K (preferably an absolute value of less than 0.3%/°C, more preferably an absolute value of less than 0.03%/°C). And a low remanence temperature coefficient (preferably an absolute value of less than 0.03 / ° C, more preferably an absolute value of less than 0.02 / ° C). Since permanent magnet materials are mainly used in the fields of electronic and electrical appliances, automotive industry, microwave communication and inertial instrumentation, the low coercivity temperature coefficient and the low remanence temperature coefficient can be adjusted to meet the requirements of different fields of use through composition and process control.
  • the permanent magnet material When the temperature coefficient of low coercivity and low remanence temperature coefficient are in the temperature range of 100K to 600K, the permanent magnet material has better magnetic properties and higher practical application value.
  • the isolation of the ferromagnetic phase and the magnetic phase having a spin phase transition includes a package isolation and a layer spacer isolation.
  • a magnetic phase having a spin phase transition may be wrapped with a ferromagnetic phase, or a ferromagnetic phase may be wrapped with a magnetic phase having a spin phase transition, and may also be a ferromagnetic phase and a magnetic phase layer having a spin phase transition. staggered.
  • the isolation method is related to the specific preparation method of the permanent magnet material.
  • the preparation method of the high temperature stability permanent magnet material of the invention is preferably powder metallurgy method, sputtering method, electroplating method and diffusion method. .
  • the permanent magnet materials obtained by the sputtering method and the diffusion method are generally separated by a layer interval, and the permanent magnet materials obtained by the powder metallurgy method and the electroplating method are generally in a package isolation manner.
  • the high temperature stable permanent magnet material of the present invention is a samarium cobalt based permanent magnet.
  • the samarium-cobalt-based permanent magnet is mainly composed of an Sm element, a Co element, an HRE element, an R element, and an M element, wherein the HRE is selected from one or more of Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
  • R is selected from one or more of Pr, Nd, Dy, Tb, and Ho
  • M is selected from one or more of Fe, Cu, Zr, Ni, Ti, Nb, Mo, Hf, and W
  • the SmHRER has at least three elements; and in the samarium-cobalt-based permanent magnet, the ferromagnetic phase is a (SmHRER) 2 (CoM) 17- series compound, and the magnetic phase having a spin phase transition is a (SmHRER) (CoM) 5 compound.
  • (SmHRER) (CoM) 5 line compound also known as cell wall phase
  • encapsulates the (SmHRER) 2 (CoM) 17 line compound also known as intracellular phase).
  • (SmHRER) 2 (CoM) 17- based compound and (SmHRER) (CoM) 5 -based compound represent a series of compounds containing Sm element, Co element, HRE element, R element and M element, and are not limited.
  • the ratio of Sm, HRE to R is 1:1:1, or the ratio of Co to M is 1:1.
  • HRE and R may each include at least one of Dy, Tb, and Ho, and the contents of Dy, Tb, and Ho in R and HRE are repeatedly calculated, and when the HRE includes at least one of Tb, Dy, and Ho At the same time, the Tb, Dy and/or Ho simultaneously calculate the mass percentage of the R as R.
  • the mass percentage of R is the mass percentage of the Tb, Dy, and/or Ho + the mass percentage of other elements.
  • the samarium-cobalt-based permanent magnet of the present invention cannot be equivalent to the so-called samarium-cobalt-based permanent magnet.
  • the (SmHRER) (CoM) 5 -based compound has a spin. Phase change magnetic phase.
  • the mass percentage of R is 8% to 20%, and the mass percentage of HRE is 8. % ⁇ 18%.
  • the temperature range of the spin phase transition temperature and the low coercivity temperature coefficient of the spin-phase-changing (SmHRER) (CoM) 5 compound can be adjusted by adjusting the type and content of the R element.
  • the type and/or content of the R element changes, the spin phase transition temperature of the corresponding (SmHRER) (CoM) 5 compound also changes, and the corresponding low coercivity temperature coefficient
  • the temperature range will also change.
  • the spin phase transition temperature of the (SmHRER) (CoM) 5 compound increases as the R content increases, and the coercive force
  • the temperature range of the low remanence temperature coefficient can be achieved by controlling the type and content of heavy rare earth HRE elements.
  • the temperature range in which the saturation magnetization temperature coefficient has an absolute value of less than 0.02%/° C. moves to a high temperature, thereby causing low remanence.
  • the temperature coefficient temperature range moves toward high temperature.
  • the magnetic phase with spin phase change changes with temperature, its easy magnetization axis changes.
  • the easy magnetization direction of the magnetic phase with spin phase change is easy.
  • the base surface is turned to the easy axis.
  • permanent magnets conforming to the magnetic phase transition law such as the above-described samarium-cobalt-based permanent magnets.
  • the invention obtains a low coercivity temperature coefficient by a permanent magnet material comprising a ferromagnetic phase and a magnetic phase having a spin phase transition, so that the acquisition of the low coercivity temperature coefficient is more purposeful, regular and versatile, and the solution is solved.
  • the technical problem that the low coercivity temperature coefficient is difficult to obtain in the prior art at the same time, the invention utilizes the antiferromagnetic coupling property of the heavy rare earth element and the transition metal to adjust the remanence temperature coefficient of the magnet, thereby solving the low in the prior art.
  • the technical problem that the coercivity temperature coefficient and the low remanence temperature coefficient are difficult to obtain at the same time.
  • the invention can adjust the temperature range of the low coercivity temperature coefficient temperature interval and the low remanence temperature coefficient of the permanent magnet material by adjusting the components, thereby satisfying the application of the permanent magnet material in different demand fields.
  • the permanent magnet material has high temperature stability in a certain temperature range (temperature interval of low coercivity temperature coefficient), that is, the magnetic property does not decrease with an increase in temperature, and therefore, has a high practical value. Value.
  • the spin phase transition temperature of the magnetic phase with spin phase transformation determines the temperature range of the low coercivity temperature coefficient to some extent. Therefore, the temperature range with low coercivity temperature coefficient can be adjusted by adjusting the spin phase. Change the temperature to adjust; to meet the application of permanent magnet materials in different aspects.
  • the high temperature stability permanent magnet material of the invention maintains the magnetic properties substantially unchanged in a certain temperature range, and therefore has a high application value in a variable temperature environment.
  • the samarium-cobalt-based permanent magnets whose constituent elements are Sm, Co, Fe, Cu, Zr, Gd, Dy are prepared, wherein the mass percentage of each element is: Sm 12.90%, Co 50.61%, Fe 13.80%, Cu 6.28% , Zr 2.82%, Gd 10.79%, Dy 2.79%.
  • HRE is a combination of Gd and Dy, the mass percentage is 13.58%, and Dy is also R, and the content of R is 2.79%.
  • the specific preparation method is as follows:
  • the magnet powder obtained in the step S200 is molded under a nitrogen gas in a magnetic field of 2T strength, and then held under cold isostatic pressing at 200 MPa for 60 s to obtain a magnet body.
  • step S400 The magnet body obtained in step S300 is placed in a vacuum sintering furnace, vacuumed to below 4 mPa, and sintered under an argon atmosphere, wherein the specific sintering process is: first heating to 1200 ° C to 1215 ° C, at this temperature Sintering for 30min; cooling to 1160 ° C ⁇ 1190 ° C, solid solution at this temperature for 3h, then air or water cooled to room temperature; then heated to 830 ° C, at this temperature isothermal aging for 12h, then at 0.7 ° C / min speed After cooling to 400 ° C for 3 h, it was rapidly cooled to room temperature to obtain a samarium cobalt-based permanent magnet.
  • the specific sintering process is: first heating to 1200 ° C to 1215 ° C, at this temperature Sintering for 30min; cooling to 1160 ° C ⁇ 1190 ° C, solid solution at this temperature for 3h, then air or water cooled to room temperature; then
  • the microstructure of the obtained samarium-cobalt-based permanent magnet is: a SmHRER) (CoM) 5- series compound and a (SmHRER) 2 (CoM) 17- series compound, wherein (SmHRER) (CoM)
  • the 5th compound is a cell wall phase
  • the (SmHRER) 2 (CoM) 17 compound is an intracellular phase
  • the (SmHRER) 2 (CoM) 17 system has a rhombohedral structure and a (SmHRER) (CoM) 5 compound.
  • the crystal form is a hexagonal structure
  • Cu element is enriched in a cell wall phase (SmHRER) (CoM) 5 compound.
  • the samarium cobalt-based permanent magnet obtained in this example was subjected to an AC magnetic susceptibility test and a magnetic property test.
  • Figure 2 shows the AC susceptibility test results. It can be seen that the spin phase transition temperature of the (SmHRER) (CoM) 5 compound in this sample is about 18K;
  • Figure 3 is the curve of coercivity with temperature. It can be seen that The coercive force decreases as the temperature increases.
  • Fig. 4 and Fig. 5 are the curves of saturation magnetization and remanence with temperature, respectively. It can be seen that the saturation magnetization and remanence change with temperature are the same, and both increase first and decrease.
  • Figure 6 is a demagnetization curve from room temperature to 100 °C.
  • the absolute value of the remanence temperature coefficient of the magnet is less than 0.01%/°C and the temperature coefficient of coercivity is -0.2655%/°C in the temperature range from room temperature to 100 °C.
  • Table 1 shows the saturation magnetization, remanence, coercive force, and the saturation magnetization temperature coefficient, remanence temperature coefficient and coercive temperature coefficient of the samarium-cobalt-based permanent magnet obtained in Example 1 at different temperatures.
  • the samarium-cobalt-based permanent magnets whose constituent elements are Sm, Co, Fe, Cu, Zr, Dy, Gd are prepared, wherein the mass percentage of each element is: Sm 12.89%, Co 50.57%, Fe 13.79, Cu 6.28%, Zr 2.82%, Gd 8.09%, Dy 5.57%.
  • HRE is a combination of Gd and Dy, the mass percentage is 13.66%, and Dy is also R, and the content of R is 5.57%.
  • the specific preparation method is the same as in the first embodiment.
  • the microstructure of the samarium-cobalt-based permanent magnet obtained in this example is a cell complex formed by a (SmHRER) (CoM) 5- series compound and a (SmHRER) 2 (CoM) 17- series compound; wherein, (SmHRER) (CoM) 5
  • the compound is a cell wall phase
  • the (SmHRER) 2 (CoM) 17 compound is an intracellular phase
  • the (SmHRER) 2 (CoM) 17 compound has a rhombohedral structure and a (SmHRER) (CoM) 5 compound.
  • the crystal form is a hexagonal structure.
  • Example 2 The samarium cobalt-based permanent magnet obtained in Example 2 was subjected to an AC magnetic susceptibility test and a magnetic property test.
  • Figure 2 shows the AC susceptibility test results. It can be seen that the spin phase transition temperature of the (SmHRER) (CoM) 5 compound in this sample is about 80K;
  • Figure 3 shows the curve of coercivity with temperature. It can be seen that The coercive force decreases with increasing temperature, and the temperature coefficient of coercivity in the temperature range of 150 to 300 K is significantly lower than that of Example 1.
  • Fig. 4 and Fig. 5 are the curves of saturation magnetization and remanence with temperature, respectively.
  • the samarium-cobalt-based permanent magnets whose constituent elements are Sm, Co, Fe, Cu, Zr, Dy, Gd are prepared, wherein the mass percentage of each element is: Sm 12.88%, Co 50.52%, Fe 13.78, Cu 6 .27%, Zr2.81%, Gd5.39%, Dy8.35%.
  • HRE is a combination of Gd and Dy, the mass percentage is 13.74%, and Dy is also R, and the content of R is 8.35%.
  • the specific preparation method is the same as in the first embodiment.
  • the microstructure of the samarium-cobalt-based permanent magnet obtained in this example is a cell complex formed by a (SmHRER) (CoM) 5- series compound and a (SmHRER) 2 (CoM) 17- series compound; wherein, (SmHRER) (CoM) 5
  • the compound is a cell wall phase
  • the (SmHRER) 2 (CoM) 17 compound is an intracellular phase
  • the (SmHRER) 2 (CoM) 17 compound has a rhombohedral structure and a (SmHRER) (CoM) 5 compound.
  • the crystal form is a hexagonal structure.
  • the samarium cobalt-based permanent magnet obtained in this example was subjected to an AC magnetic susceptibility test and a magnetic property test.
  • Figure 2 shows the AC susceptibility test results. It can be seen that the spin phase transition temperature of the (SmHRER) (CoM) 5 compound in this sample is about 122K;
  • Figure 3 is the curve of coercivity with temperature.
  • Fig. 4 and Fig. 5 are the curves of saturation magnetization and remanence with temperature, respectively. It can be seen that the saturation magnetization and remanence change with temperature are the same, and both increase first and decrease, between 300 and 400K. Remanence is very low with temperature.
  • Table 3 shows the saturation magnetization, remanence, coercive force, and the saturation magnetization temperature coefficient, remanence temperature coefficient and coercive temperature coefficient of the samarium-cobalt-based permanent magnet obtained in Example 3 at different temperatures.
  • the samarium-cobalt-based permanent magnets whose constituent elements are Sm, Co, Fe, Cu, Zr, Dy, Gd are prepared, wherein the mass percentage of each element is: Sm 12.87%, Co 50.48%, Fe 13.76, Cu 6.26%, Zr was 2.81%, Gd was 2.69%, and Dy was 11.13%.
  • HRE is a combination of Gd and Dy, the mass percentage is 13.82%, and Dy is also R, and the content of R is 11.13%.
  • the specific preparation method is the same as in the first embodiment.
  • the samarium-cobalt-based permanent magnet obtained in this example was analyzed by a transmission electron microscope, and the results are shown in Fig. 1.
  • (a) is a transmission electron micrograph when the observation surface is perpendicular to the orientation axis
  • (b) is an observation surface and an orientation axis. Transmission electron micrographs in parallel. As can be seen from Fig.
  • the microstructure of the samarium-cobalt-based permanent magnet obtained in the present example is: a (SmHRER) (CoM) 5- series compound and a (SmHRER) 2 (CoM) 17- series compound formed into a cell complex;
  • (SmHRER (CoM) The 5- series compound is a cell wall phase
  • the (SmHRER) 2 (CoM) 17- series compound is an intracellular phase
  • the (SmHRER) 2 (CoM) 17- series compound has a rhombohedral structure
  • the crystal form of the 5- based compound is a hexagonal structure.
  • the samarium cobalt-based permanent magnet obtained in this example was subjected to an AC magnetic susceptibility test and a magnetic property test.
  • Figure 2 shows the AC susceptibility test results. It can be seen that the spin phase transition temperature of the (SmHRER) (CoM) 5 compound in this sample is about 163K;
  • Figure 3 shows the coercivity versus temperature curve.
  • the coercive force increases with the increase of temperature, that is, the temperature coefficient of positive coercivity is exhibited, and at 100K (minimum value of coercive force) or 350K ( In the vicinity of the maximum value of the coercive force, the absolute value of the coercive temperature coefficient is small, and the absolute value of the coercive temperature coefficient is less than 0.01%/°C.
  • Fig. 4 and Fig. 5 are the curves of saturation magnetization and remanence with temperature. It can be seen that the saturation magnetization and remanence change with temperature are the same, and both increase first and decrease, between 300 and 400K. Magnetic changes very slowly with temperature.
  • the absolute value of the remanence temperature coefficient is less than 0.01%/° C.
  • the absolute value of the coercive temperature coefficient is also less than 0.01%/° C.
  • Figure 6 is a demagnetization curve from room temperature to 100 °C. It can be seen that the absolute value of the remanence temperature coefficient of the magnet is less than 0.01%/°C in the temperature range from room temperature to 100 °C, and the absolute value of the coercivity temperature coefficient is also less than 0.01%/ °C.
  • Table 4 shows the saturation magnetization, remanence, coercive force, and the saturation magnetization temperature coefficient, remanence temperature coefficient and coercive temperature coefficient of the samarium-cobalt-based permanent magnet obtained in Example 4 at different temperatures.
  • Example 3 the absolute value of the remanence temperature coefficient is less than 0.01%/°C in the temperature range from room temperature to 100° C., but the coercive force of Example 3 is compared with Example 1.
  • the absolute value of the temperature coefficient is increased by two orders of magnitude.
  • a (Sm 0.5 Gd 0.5 )Co 5 permanent magnet material was prepared as a ferromagnetic phase, and DyCo 5 was selected as a magnetic phase having a spin phase transition.
  • DyCo 5 film was prepared by magnetron sputtering, and so on, a multilayer of (Sm 0.5 Gd 0.5 )Co 5 film and DyCo 5 film were isolated. a film in which each film has a thickness of between 5 and 800 nm.
  • the absolute value of the residual magnetic temperature coefficient of the permanent magnet material in the temperature range of (350K-400K) is less than 0.01%/K, and the absolute value of the coercive temperature coefficient is less than 0.03%/K.
  • the samarium-cobalt-based permanent magnets whose constituent elements are Sm, Co, Fe, Cu, Zr, Nd are prepared, wherein the mass percentage of each element is: Sm 13.06%, Co 51.23%, Fe 13.97%, Cu 6.36%, Zr 2.85%, Nd 12.53%.
  • the specific preparation method is as follows:
  • the magnet powder obtained in the step S200 is molded under a nitrogen gas in a magnetic field of 2T strength, and then held under cold isostatic pressing at 200 MPa for 60 s to obtain a magnet body.
  • step S400 The magnet body obtained in step S300 is placed in a vacuum sintering furnace, vacuumed to below 4 mPa, and sintered under an argon atmosphere, wherein the specific sintering process is: first heating to 1200 ° C to 1215 ° C, at this temperature Sintering for 30min; cooling to 1160 ° C ⁇ 1190 ° C, solid solution at this temperature for 3h, then air or water cooled to room temperature; then heated to 830 ° C, at this temperature isothermal aging for 12h, then at 0.7 ° C / min speed After cooling to 400 ° C for 3 h, it was rapidly cooled to room temperature to obtain a samarium cobalt-based permanent magnet.
  • the specific sintering process is: first heating to 1200 ° C to 1215 ° C, at this temperature Sintering for 30min; cooling to 1160 ° C ⁇ 1190 ° C, solid solution at this temperature for 3h, then air or water cooled to room temperature; then
  • the microstructure of the obtained samarium-cobalt-based permanent magnet is a cell complex formed of a (SmR) (CoM) 5 -based compound and a (SmR) 2 (CoM) 17- based compound, wherein (SmR) ( The CoM) 5- based compound is a cell wall phase, the (SmR) 2 (CoM) 17- based compound is an intracellular phase, and the (SmR) 2 (CoM) 17- based compound has a rhombohedral structure, and (SmR) (CoM) 5
  • the crystal of the compound is a hexagonal structure, and the Cu element is concentrated in the cell wall phase (SmR) (CoM) 5 compound.
  • FIG. 8 is a graph showing the AC magnetic susceptibility test of the samarium-cobalt-based permanent magnet prepared in the comparative example, the change of coercive force with temperature, the saturation magnetization and the change of remanence with temperature; it can be seen that the sample (SmR)
  • the (CoM) 5 series compound has a spin phase transition temperature of about 39K; the saturation magnetization and remanence have the same change with temperature, and all decrease with increasing temperature, and the saturation magnetization temperature coefficient and remanence temperature coefficient are both It is about -0.03 ⁇ -0.05%/°C; the curve of coercivity with temperature shows that in the temperature range of 50K ⁇ 200K, the coercive force increases with the increase of temperature, that is, it shows positive correction.
  • Coercivity temperature coefficient and in the vicinity of 50K (minimum value of coercive force) or 200K (maximum value of coercive force), the absolute value of the coercive temperature coefficient is small, and the coercive temperature coefficient is absolutely The value is less than 0.01% / °C.

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Abstract

一种高温度稳定性永磁材料及其应用，所述永磁材料的微观结构包括强磁性相和具有自旋相变的磁性相，所述强磁性相和所述具有自旋相变的磁性相相互隔离，且所述强磁性相饱和磁化强度温度系数绝对值小于0.02％/℃。通过包含强磁性相和具有自旋相变的磁性相的永磁材料来获得正矫顽力温度系数，使低矫顽力温度系数的获得更具有目的性、规律性和通用性；同时，利用重稀土元素与过渡金属的反铁磁性耦合特性来调节磁体的剩磁温度系数，解决了现有技术中低矫顽力温度系数系数和低剩磁温度系数难以同时获得的技术难题。另外，可以通过调节成分和工艺来调整永磁材料低矫顽力温度系数温度区间和低剩磁温度系数的温度区间，从而满足永磁材料在不同需求领域的应用。

Description

高温度稳定性永磁材料及其应用 技术领域
本发明涉及磁性材料领域，特别是涉及一种高温度稳定性的永磁材料及其应用。
背景技术
随着永磁材料在电子电器行业、汽车行业、微波通讯及航天航空等领域的广泛应用，实际需求中对永磁材料不断提出新的要求。例如惯性仪器仪表、行波管、传感器等特种领域在不同的环境领域应用，永磁材料随温度的微弱波动直接影响着仪器仪表的精度，给航天、航空、国防领域带来不可估量的风险。迫切需求具有更高温度稳定性的磁体。
在惯性仪器仪表、行波管、传感器等特种领域，目前一般应用铝镍钴磁钢或低剩磁温度系数钐钴磁钢。铝镍钴磁钢虽然剩磁温度系数约-0.02％/℃，矫顽力温度系数约-0.03％/℃，但因矫顽力低(＜2kOe)、磁能积低(～10MGOe)，容易受振动、磁场、辐射等干扰，不能满足器件的长期使用。低剩磁温度系数钐钴磁钢，虽然矫顽力较高(＞15kOe)，磁能积高(＞15MGOe)，剩磁温度系数绝对值小于0.01％/℃，但是矫顽力温度系数较高(～0.3％/℃)，导致磁体在不同温度下的不可逆磁损和可逆磁损差异较大，影响仪器仪表的长期稳定使用。迫切需求开发出更高温度稳定性的磁体。
一般地，惯性仪器仪表、行波管、传感器等特种领域的使用温度在-40℃至100℃区间，为此开发相应温度区间高稳定性磁体需求迫切。借鉴传统低剩磁温度系数钐钴磁体和具有正温度系数的永磁材料及其应用(专利号：201410663449.6)的领域背景，本发明目的在于公开一种新型高温度稳定性磁体，在保证低剩磁温度系数钐钴磁钢磁能积高、剩磁温度系数绝对值低的基础上，提高磁体的矫顽力温度稳定性。
发明内容
本发明提供了一种高温度稳定性永磁材料及其应用，该永磁材料在一定的 温度区间内具有较高的温度稳定性。
为达到上述目的，本发明采用如下技术方案：
一种高温度稳定性永磁材料，所述永磁材料的微观结构包括强磁性相和具有自旋相变的磁性相，所述强磁性相和所述具有自旋相变的磁性相相互隔离。且所述强磁性相饱和磁化强度温度系数绝对值小于0.02％/℃。
在其中一个实施例中，所述微观结构的尺寸至少在一个维度上为5nm～800nm。
在其中一个实施例中，所述强磁性相和所述具有自旋相变的磁性相的隔离方式为包裹隔离或层间隔隔离。
在其中一个实施例中，随着温度升高，所述具有自旋相变的磁性相的易磁化方向由易基面转向易轴。
在其中一个实施例中，所述强磁性相为SmHRECo系化合物，且Sm部分被HRE或HRE与其他元素的组合取代，所述具有自旋相变的磁性相为RCo 5系化合物、RCo 5的衍生化合物、R 2Co 17系化合物或R 2Co 17的衍生化合物；
其中，HRE选自Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu中的一种或多种；
其中，R选自Pr、Nd、Dy、Tb和Ho中的一种或多种。
在其中一个实施例中，所述永磁材料为钐钴基永磁体；
所述钐钴基永磁体包括强磁性相(SmHRER) 2(CoM) 17系化合物，以及具有自旋相变的磁性相(SmHRER)(CoM) 5系化合物，所述钐钴基永磁体的微观结构中，所述(SmHRER)(CoM) 5系化合物包裹所述(SmHRER) 2(CoM) 17系化合物；
其中，HRE选自Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu中的一种或多种；R选自Pr、Nd、Dy、Tb和Ho中的一种或多种，M选自Fe、Cu、Zr、Ni、Ti、Nb、Mo、Hf和W中的一种或多种，且所述SmHRER至少具有三种元素。
在其中一个实施例中，所述钐钴基永磁体中，R的质量百分含量为8％～20％；HRE的质量百分含量为8％～18％。
在其中一个实施例中，当所述HRE包括Tb、Dy及Ho中的至少一种时，所述Tb、Dy和/或Ho同时作为R计算所述R的质量百分含量。
在其中一个实施例中，随着R含量的增加，所述(SmHRER)(CoM) 5系化合物的自旋相变温度升高，矫顽力极大值点和矫顽力极小值点温度向高温移动， 对应矫顽力温度系数绝对值小于0.03％/℃的温度区间也向高温移动。
在其中一个实施例中，随着HRE含量的增加，所述强磁性相(SmHRER) 2(CoM) 17系化合物的饱和磁化强度温度系数绝对值小于0.02％/℃的温度区间向高温移动。
在其中一个实施例中，所述永磁材料在2K～600K的温度范围内剩磁温度系数绝对值小于0.02％/℃，且矫顽力温度系数绝对值小于0.03％/℃。
一种所述的高温度稳定性永磁材料在变温环境下的应用。
本发明的有益效果如下：
本发明通过包含强磁性相和具有自旋相变的磁性相的永磁材料来获得低矫顽力温度系数，使低矫顽力温度系数的获得更具有目的性、规律性和通用性；同时，本发明利用重稀土元素与过渡金属的反铁磁性耦合特性来调节磁体的剩磁温度系数，解决了现有技术中低矫顽力温度系数和低剩磁温度系数难以同时获得的技术难题。另外，本发明可以通过调节成分来调整永磁材料低矫顽力温度系数温度区间和低剩磁温度系数的温度区间，从而满足永磁材料在不同需求领域的应用。
附图说明
图1为本发明实施例3制得的钐钴基永磁体的透射电镜图；
图2为本发明实施例1～4制得的钐钴基永磁体的交流磁化率测试图，测试条件为：交流场5Oe，频率1000Hz；
图3为本发明实施例1～4制得的钐钴基永磁体的矫顽力随温度的变化图；
图4为本发明实施例1～4制得的钐钴基永磁体的饱和磁化强度随温度的变化图；
图5为本发明实施例1～4制得的钐钴基永磁体的剩磁随温度的变化图；
图6为本发明实施例1制得的钐钴基永磁体在室温带100℃温度区间的退磁曲线图；
图7为本发明实施例4制得的钐钴基永磁体在室温带100℃温度区间的退磁曲线图。
图8为对比实施例制得的钐钴基永磁体的交流磁化率测试图、矫顽力随温度的变化图、饱和磁化强度和剩磁随温度的变化图。
具体实施方式
为了更好地说明本发明，以下结合附图对本发明的具体实施方式进行详细说明。本领域技术人员应当理解，所举实施例只用于解释本发明，并非用于限制本发明的范围。
在现有技术中，利用反铁磁性耦合机理获得低剩磁温度系数磁性材料和外加补偿片是一种惯用方法。但是同时实现低矫顽力温度系数一般无法通过特定的规律获得。我们前期专利(专利号：201410663449.6)报道了具有正矫顽力温度系数的永磁材料，仅报道了获得正矫顽力温度系数永磁材料的技术方案。而一般技术应用领域要求剩磁温度系数和矫顽力温度系数都尽量低的永磁材料，现有技术无法更好的满足实际需求。
其中，剩磁温度系数的表达式为：
α(T 0-T 1)＝{[B r(T 0)-B r(T 1)]/[B r(T 0)×(T 0-T 1)]}×100％
上述公式中，B r(T 0)和B r(T 1)分别为T 0和T 1温度下的剩磁值。
其中，矫顽力温度系数的表达式为：
β(T 0-T 1)＝{[H cj(T 0)-H cj(T 1)]/[H cj(T 0)×(T 0-T 1)]}×100％
上述公式中，H cj(T 0)和H cj(T 1)分别为T 0和T 1温度下的矫顽力值。
发明人通过大量实验发现，在具有自旋相变的磁性相的自旋相变温度附近出现矫顽力的极大值或者极小值，因此，在极大值或极小值附近的温度区间内矫顽力温度系数绝对值很低。其中，具有自旋相变的磁性相是指某些磁性合金相随着温度的变化，易磁化轴会发生改变，包括：易轴向易面转变，易面向易轴转变等易磁化轴的转变现象，即发生自旋再取向；易磁化轴发生转变的温度点即为自旋再取向转变温度，即自旋相变温度；而极大值或极小值附近的温度区间即为低矫顽力温度系数的温度区间。
根据上述原理，本发明提供了一种高温度稳定性永磁材料，其微观结构包括强磁性相和具有自旋相变的磁性相，且强磁性相和具有自旋相变的磁性相相 互隔离，且所述强磁性相饱和磁化强度温度系数绝对值小于0.02％/℃。较佳地，微观结构的尺寸至少在一个维度上为5nm～800nm。
在更有选的实施例中，所述饱和磁化强度温度系数绝对值小于0.01％/℃。
需要说明的是，本发明中的强磁性相是指具有单轴各向异性的磁性相。
本发明的永磁材料中，具有自旋相变的磁性相可以为RCo 5系合金、RCo 5的衍生合金、R 2Co 17系化合物或R 2Co 17的衍生化合物；其中，R选自Pr、Nd、Dy、Tb和Ho中的一种或多种。其中，衍生化合物是指构成合金的一种或多种元素部分被其他元素取代，在一些实施例中，R可以被Sm或Sm与HRE的组合所部分取代，Co可以被M部分取代。HRE选自Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu中的一种或多种，M选自Fe、Cu、Zr、Ni、Ti、Nb、Mo、Hf和W中的一种或多种，例如，Sm 1-xDy xCo 5(0＜x＜1)即为RCo 5的衍生化合物。
本发明的永磁材料中，强磁性相一般为SmCo系化合物，且Sm部分被HRE或HRE与其他元素(例如与HRE元素不同的R元素)的组合取代，优选为使Sm 2Co 17、SmCo 5或SmCo 7中的Sm部分被HRE和R取代得到的化合物。在一些实施例中，Co还可以被M部分取代。优选的，强磁性相中的R与HRE含有不同元素，即强磁性相中Sm被选自所述HRE和R的至少两种元素部分取代，形成三元以上组成成分。
强磁性相中的R、M和HRE与自旋相变的磁性相中R、M和HRE可以相同或不同，优选是分别相同的。一般情况下，具有自旋相变的磁性相不同时，自旋相变温度也不同。例如，DyCo 5合金在370K易磁化方向由易面转向易轴，370K即为DyCo 5合金的自旋相变温度；TbCo 5合金在410K易磁化方向由易面转向易轴，410K即为TbCo 5合金的自旋相变温度。因此，可通过具有自旋相变的磁性相的选择，来得到所需的自旋相变温度，进而得到所需的低矫顽力温度系数区间。申请人通过大量实验发现，重稀土元素HRE含量越高，低剩磁温度系数温度区间向高温移动，因此，可通过控制重稀土的含量来得到所需的低剩磁温度系数温度区间。
较佳地，本发明的高温度稳定性永磁材料在10K～600K的温度范围内具有低矫顽力温度系数(优选为绝对值小于0.3％/℃，更优选为绝对值小于0.03％/℃)和低剩磁温度系数(优选为绝对值小于0.03/℃，更优选为绝对值小于0.02/℃)。 由于永磁材料主要用于电子电器行业、汽车行业、微波通讯及惯性仪器仪表等领域，低矫顽力温度系数和低剩磁温度系数可以通过成分和工艺调控满足不同领域使用条件的要求。
当100K～600K温度范围内具有低矫顽力温度系数和低剩磁温度系数时，该永磁材料具有较佳的磁性能和较高的实际应用价值。
本发明的高温度稳定性永磁材料中，强磁性相和具有自旋相变的磁性相的隔离方式包括包裹隔离和层间隔隔离。例如，可以为具有自旋相变的磁性相包裹强磁性相，也可为强磁性相包裹具有自旋相变的磁性相，还可为强磁性相与具有自旋相变的磁性相层层交错。其中，隔离方式与永磁材料的具体制备方法相关，为了形成两相隔离的结构，本发明的高温度稳定性永磁材料的制备方法优选为粉末冶金法、溅射法、电镀法和扩散法。通过溅射法和扩散法得到的永磁材料一般为层间隔隔离方式，而通过粉末冶金法和电镀法得到的永磁材料一般为包裹隔离方式。
较佳地，本发明的高温度稳定性永磁材料为钐钴基永磁体。该钐钴基永磁体主要由Sm元素、Co元素、HRE元素、R元素和M元素组成，其中，HRE选自Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu中的一种或多种，R选自Pr、Nd、Dy、Tb和Ho中的一种或多种，M选自Fe、Cu、Zr、Ni、Ti、Nb、Mo、Hf和W中的一种或多种，且SmHRER至少具有三种元素；且该钐钴基永磁体中，强磁性相为(SmHRER) 2(CoM) 17系化合物，具有自旋相变的磁性相为(SmHRER)(CoM) 5系化合物，其中，(SmHRER)(CoM) 5系化合物(又称胞壁相)包裹所述(SmHRER) 2(CoM) 17系化合物(又称胞内相)。可以理解，上述(SmHRER) 2(CoM) 17系化合物和(SmHRER)(CoM) 5系化合物代表的均是含有Sm元素、Co元素、HRE元素、R元素和M元素的一系列化合物，并非限定Sm、HRE与R的比例为1∶1∶1，或者Co与M的比例为1∶1。
HRE和R均可以包括Dy、Tb和Ho中的至少一种，且Dy、Tb和Ho在R与HRE中的含量是重复计算的，当所述HRE包括Tb、Dy及Ho中的至少一种时，所述Tb、Dy和/或Ho同时作为R计算所述R的质量百分含量。
例如，当HRE含有Dy、Tb和Ho中的至少一种时，R的质量百分含量为所述Tb、Dy和/或Ho的质量百分含量+其他元素的质量百分含量。需要说明的 是，本发明的钐钴基永磁体不能等同于通常所说的钐钴基永磁体，本发明中的钐钴基永磁体中，(SmHRER)(CoM) 5系化合物为具有自旋相变的磁性相。
为了保证具有低矫顽力温度系数和低的剩磁温度系数，较佳地，上述钐钴基永磁体中，R的质量百分含量为8％～20％，HRE的质量百分含量为8％～18％。
本发明的钐钴基永磁体中，具有自旋相变的(SmHRER)(CoM) 5系化合物的自旋相变温度和低矫顽力温度系数的温度区间可通过调节R元素的种类及含量来进行调控，当R元素的种类和/或其含量发生变化时，相应的(SmHRER)(CoM) 5系化合物的自旋相变温度也会发生变化，而其对应的低矫顽力温度系数的温度区间也会随之发生变化。作为一种可实施方式，当R的质量百分含量为8％～20％时，随着R含量的增加，(SmHRER)(CoM) 5系化合物的自旋相变温度升高，矫顽力温度系数绝对值小于0.03％/℃的温度区间向高温移动。而低剩磁温度系数的温度区间可以通过控制重稀土HRE元素的种类及含量实现。作为一种可行实施方式，当HRE的质量百分含量为8％～18％，随HRE含量增加，饱和磁化强度温度系数绝对值小于0.02％/℃的温度区间向高温移动，从而使低剩磁温度系数温度区间向高温移动。
由于具有自旋相变的磁性相随着温度的变化，其易磁化轴会发生改变，作为一种可实施方式，随着温度升高，具有自旋相变的磁性相的易磁化方向由易基面转向易轴。符合该磁性相变规律的永磁体有多种，如上述的钐钴基永磁体。
本发明通过包含强磁性相和具有自旋相变的磁性相的永磁材料来获得低矫顽力温度系数，使低矫顽力温度系数的获得更具有目的性、规律性和通用性，解决了现有技术中低矫顽力温度系数难以获得的技术难题，同时，本发明利用重稀土元素与过渡金属的反铁磁性耦合特性来调节磁体的剩磁温度系数，解决了现有技术中低矫顽力温度系数和低剩磁温度系数难以同时获得的技术难题。另外，本发明可以通过调节成分来调整永磁材料低矫顽力温度系数温度区间和低剩磁温度系数的温度区间，从而满足永磁材料在不同需求领域的应用。
该永磁材料在一定的温度区间(低矫顽力温度系数的温度区间)内具有较高的温度稳定性，即磁性能不会随着温度的升高而降低，因此，具有很高的实际应用价值。同时，具有自旋相变的磁性相的自旋相变温度在一定程度上决定了低矫顽力温度系数的温度区间，因此，具有低矫顽力温度系数的温度区间可 通过调节自旋相变温度来进行调整；从而满足永磁材料在不同方面的应用。
本发明的高温度稳定性永磁材料，在一定温度区间内保持磁性能基本不变，因此，在变温环境下具有较高的应用价值。
为了更好地理解本发明，下面通过具体的实施例对本发明进一步说明。
实施例1
制备组成元素为Sm、Co、Fe、Cu、Zr、Gd、Dy的钐钴基永磁体，其中，各元素的质量百分含量为：Sm 12.90％，Co 50.61％，Fe 13.80％，Cu 6.28％，Zr 2.82％，Gd 10.79％，Dy 2.79％。其中HRE为Gd与Dy的组合，质量百分含量为13.58％，且Dy同时为R，R的含量为2.79％。
具体制备方法如下：
S100：按照上述成分配比称取含有Sm、Co、Fe、Cu、Zr、Gd、Dy单质元素的原料；
S200：将称好的原料置于感应熔炼炉中进行熔炼，得到合金铸锭；然后将得到的合金铸锭进行粗破碎，再经气流磨或球磨后制得磁体粉末。
S300：将步骤S200得到的磁体粉末于氮气保护下，在强度为2T的磁场中成型，再于200MPa下经冷等静压保压60s，得到磁体坯体。
S400：将步骤S300中得到的磁体坯体装入真空烧结炉，抽真空至4mPa以下，氩气气氛下进行烧结，其中，具体烧结过程为：先加热至1200℃～1215℃，在此温度下烧结30min；降温至1160℃～1190℃，在此温度下固熔3h，然后风冷或水冷至室温；再加热到830℃，在此温度下等温时效12h，然后以0.7℃/min的速度降温至400℃，保温3h后快速冷却至室温，得到钐钴基永磁体。
该实施例中，得到的钐钴基永磁体的微观结构为：SmHRER)(CoM) 5系化合物和(SmHRER) 2(CoM) 17系化合物形成的胞状复合体，其中，(SmHRER)(CoM) 5系化合物为胞壁相，(SmHRER) 2(CoM) 17系化合物为胞内相，(SmHRER) 2(CoM) 17系化合物的结晶状为菱方结构，(SmHRER)(CoM) 5系化合物的结晶状为六方结构，且Cu元素富集在胞壁相(SmHRER)(CoM) 5系化合物中。
对该实施例得到的钐钴基永磁体进行交流磁化率测试和磁性能测试。图2为交流磁化率测试结果，可以看出该样品中(SmHRER)(CoM) 5系化合物的自旋相变温度约为18K；图3为矫顽力随温度的变化曲线，可以看出，矫顽力随温度 升高而降低。图4和图5分别为饱和磁化强度和剩磁随温度的变化曲线，可以看出，饱和磁化强度和剩磁随温度的变化规律相同，都是先升高而降低。图6为室温至100℃的退磁曲线图，可以看出，在室温至100℃温度区间，磁体剩磁温度系数绝对值小于0.01％/℃，矫顽力温度系数为-0.2655％/℃。表1为不同温度下实施例1得到的钐钴基永磁体的饱和磁化强度、剩磁、矫顽力，以及对应温度区间的饱和磁化强度温度系数、剩磁温度系数和矫顽力温度系数。
表1
Figure PCTCN2018086056-appb-000001
实施例2
制备组成元素为Sm、Co、Fe、Cu、Zr、Dy、Gd的钐钴基永磁体，其中，各元素的质量百分含量为：Sm 12.89％，Co 50.57％，Fe 13.79，Cu 6.28％，Zr 2.82％，Gd 8.09％，Dy 5.57％。其中HRE为Gd与Dy的组合，质量百分含量为13.66％，且Dy同时为R，R的含量为5.57％。
具体制备方法同实施例1。
本实施例得到的钐钴基永磁体的微观结构为：(SmHRER)(CoM) 5系化合物和(SmHRER) 2(CoM) 17系化合物形成的胞状复合体；其中，(SmHRER)(CoM) 5系化合物为胞壁相，(SmHRER) 2(CoM) 17系化合物为胞内相，(SmHRER) 2(CoM) 17系化合物的结晶状为菱方结构，(SmHRER)(CoM) 5系化合物的结晶状为六方结构。
对该实施例2得到的钐钴基永磁体进行交流磁化率测试和磁性能测试。图2为交流磁化率测试结果，可以看出该样品中(SmHRER)(CoM) 5系化合物的自旋相变温度约为80K；图3为矫顽力随温度的变化曲线，可以看出，矫顽力随温度升高而降低，其中在150～300K温度范围的矫顽力温度系数较实施例1明显降低。图4和图5分别为饱和磁化强度和剩磁随温度的变化曲线，可以看出，饱和磁化强度和剩磁随温度的变化规律相同，都是先升高而降低，在300～400K之间剩磁随温度变化很低。表2为不同温度下实施例2得到的钐钴基永磁体的饱和磁化强度、剩磁、矫顽力，以及对应温度区间的饱和磁化强度温度系数、剩磁温度系数和矫顽力温度系数。
表2
Figure PCTCN2018086056-appb-000002
Figure PCTCN2018086056-appb-000003
实施例3
制备组成元素为Sm、Co、Fe、Cu、Zr、Dy、Gd的钐钴基永磁体，其中，各元素的质量百分含量为：Sm12.88％，Co50.52％，Fe13.78，Cu6.27％，Zr2.81％，Gd5.39％，Dy8.35％。其中HRE为Gd与Dy的组合，质量百分含量为13.74％，且Dy同时为R，R的含量为8.35％。
具体制备方法同实施例1。
本实施例得到的钐钴基永磁体的微观结构为：(SmHRER)(CoM) 5系化合物和(SmHRER) 2(CoM) 17系化合物形成的胞状复合体；其中，(SmHRER)(CoM) 5系化合物为胞壁相，(SmHRER) 2(CoM) 17系化合物为胞内相，(SmHRER) 2(CoM) 17系化合物的结晶状为菱方结构，(SmHRER)(CoM) 5系化合物的结晶状为六方结构。
对该实施例得到的钐钴基永磁体进行交流磁化率测试和磁性能测试。图2为交流磁化率测试结果，可以看出该样品中(SmHRER)(CoM) 5系化合物的自旋相变温度约为122K；图3为矫顽力随温度的变化曲线，可以看出，在(100K～200K)的温度区间内，矫顽力随着温度的升高而增大，即表现出正矫顽力温度系数，而在100K(矫顽力的极小值点)或者200K(矫顽力的极大值点)附近，其矫顽力温度系数的绝对值很小，矫顽力温度系数绝对值小于0.01％/℃。图4和图5分别为饱和磁化强度和剩磁随温度的变化曲线，可以看出，饱和磁化强度和剩磁随温度的变化规律相同，都是先升高而降低，在300～400K之间剩磁随温度变化很低。剩磁温度系数绝对值小于0.01％/℃的温度区间并不和矫顽力温度系数绝对值小于0.01的温度区间重合。表3为不同温度下实施例3得到的钐钴基永磁体的饱和磁化强度、剩磁、矫顽力，以及对应温度区间的饱和磁化强度温度系数、剩磁温度系数和矫顽力温度系数。
表3
Figure PCTCN2018086056-appb-000004
实施例4
制备组成元素为Sm、Co、Fe、Cu、Zr、Dy、Gd的钐钴基永磁体，其中，各元素的质量百分含量为：Sm 12.87％，Co 50.48％，Fe 13.76，Cu 6.26％，Zr 2.81％，Gd 2.69％，Dy 11.13％。其中HRE为Gd与Dy的组合，质量百分含量为13.82％，且Dy同时为R，R的含量为11.13％。
具体制备方法同实施例1。
对该实施例得到的钐钴基永磁体采用透射电镜进行分析，结果如图1所示，其中(a)为观察面与取向轴垂直时的透射电镜图，(b)为观察面与取向轴平行时的透射电镜图。由图1可知，本实施例得到的钐钴基永磁体的微观结构为： (SmHRER)(CoM) 5系化合物和(SmHRER) 2(CoM) 17系化合物形成的胞状复合体；其中，(SmHRER)(CoM) 5系化合物为胞壁相，(SmHRER) 2(CoM) 17系化合物为胞内相，(SmHRER) 2(CoM) 17系化合物的结晶状为菱方结构，(SmHRER)(CoM) 5系化合物的结晶状为六方结构。
对该实施例得到的钐钴基永磁体进行交流磁化率测试和磁性能测试。图2为交流磁化率测试结果，可以看出该样品中(SmHRER)(CoM) 5系化合物的自旋相变温度约为163K；图3为矫顽力随温度的变化曲线，可以看出，在(100K～350K)的温度区间内，矫顽力随着温度的升高而增大，即表现出正矫顽力温度系数，而在100K(矫顽力的极小值点)或者350K(矫顽力的极大值点)附近，其矫顽力温度系数的绝对值很小，矫顽力温度系数绝对值小于0.01％/℃。图4和图5为饱和磁化强度和剩磁随温度的变化曲线，可以看出，饱和磁化强度和剩磁随温度的变化规律相同，都是先升高而降低，在300～400K之间剩磁随温度变化很低。在300～400K的温度区间，剩磁温度系数绝对值小于0.01％/℃，并且矫顽力温度系数绝对值也小于0.01％/℃。图6为室温至100℃的退磁曲线图，可以看出，在室温至100℃温度区间，磁体剩磁温度系数的绝对值小于0.01％/℃，矫顽力温度系数绝对值也小于0.01％/℃。表4为不同温度下实施例4得到的钐钴基永磁体的饱和磁化强度、剩磁、矫顽力，以及对应温度区间的饱和磁化强度温度系数、剩磁温度系数和矫顽力温度系数。
表4
Figure PCTCN2018086056-appb-000005
Figure PCTCN2018086056-appb-000006
表5：实施例1～4中的样品的组分含量(TM＝Co 0.695Fe 0.2Cu 0.08Zr 0.025)
Figure PCTCN2018086056-appb-000007
表6
编号 剩磁温度系数(％/℃) 矫顽力温度系数(％/℃)
实施例1 -0.0014 -0.2655
实施例3 0.0000 0.0018
通过表6可以看到，实施例3、实施例1在室温至100℃温度区间，剩磁温度系数绝对值都小于0.01％/℃，但与实施例1相比较，实施例3的矫顽力温度系数绝对值提高了两个数量级。
实施例5
制备(Sm 0.5Gd 0.5)Co 5永磁材料作为强磁性相，以DyCo 5选为具有自旋相变的磁性相。通过磁控溅射制备一层(Sm 0.5Gd 0.5)Co 5永磁材料膜一层DyCo 5膜，以此类推，制备出(Sm 0.5Gd 0.5)Co 5膜与DyCo 5膜相互隔离的多层膜，其中，每层膜的厚度在5-800nm之间。这种永磁材料在(350K-400K)的温度区间内剩磁温度系数绝对值小于0.01％/K，矫顽力温度系数绝对值小于0.03％/K。
对比实施例
制备组成元素为Sm、Co、Fe、Cu、Zr、Nd的钐钴基永磁体，其中，各元素的质量百分含量为：Sm 13.06％，Co 51.23％，Fe 13.97％，Cu 6.36％，Zr 2.85％，Nd 12.53％。
具体制备方法如下：
S100：按照上述成分配比称取含有Sm、Co、Fe、Cu、Zr、Nd单质元素的原料；
S200：将称好的原料置于感应熔炼炉中进行熔炼，得到合金铸锭；然后将得到的合金铸锭进行粗破碎，再经气流磨或球磨后制得磁体粉末。
S300：将步骤S200得到的磁体粉末于氮气保护下，在强度为2T的磁场中成型，再于200MPa下经冷等静压保压60s，得到磁体坯体。
S400：将步骤S300中得到的磁体坯体装入真空烧结炉，抽真空至4mPa以下，氩气气氛下进行烧结，其中，具体烧结过程为：先加热至1200℃～1215℃，在此温度下烧结30min；降温至1160℃～1190℃，在此温度下固熔3h，然后风冷或水冷至室温；再加热到830℃，在此温度下等温时效12h，然后以0.7℃/min的速度降温至400℃，保温3h后快速冷却至室温，得到钐钴基永磁体。
该对比实施例中，得到的钐钴基永磁体的微观结构为：(SmR)(CoM) 5系化合物和(SmR) 2(CoM) 17系化合物形成的胞状复合体，其中，(SmR)(CoM) 5系化合物为胞壁相，(SmR) 2(CoM) 17系化合物为胞内相，(SmR) 2(CoM) 17系化合物的结晶状为菱方结构，(SmR)(CoM) 5系化合物的结晶状为六方结构，且Cu元素富集在胞壁相(SmR)(CoM) 5系化合物中。
对该对比实施例得到的钐钴基永磁体进行交流磁化率测试和磁性能测试。图8为对比实施例制得的钐钴基永磁体的交流磁化率测试图、矫顽力随温度的变化图、饱和磁化强度和剩磁随温度的变化图；可以看出该样品中(SmR)(CoM) 5系化合物的自旋相变温度约为39K；饱和磁化强度和剩磁随温度的变化规律相同，都是随温度升高而降低，饱和磁化强度温度系数和剩磁温度系数均约为-0.03～-0.05％/℃；矫顽力随温度的变化曲线可以看出，在50K～200K的温度范围内，矫顽力随着温度的升高而增大，即表现出正矫顽力温度系数，而在50K(矫顽力的极小值点)或者200K(矫顽力的极大值点)附近，其矫顽力温度系数的 绝对值很小，矫顽力温度系数绝对值小于0.01％/℃。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (12)

  1. 一种高温度稳定性永磁材料，其特征在于，所述永磁材料的微观结构包括强磁性相和具有自旋相变的磁性相，所述强磁性相和所述具有自旋相变的磁性相相互隔离，且所述强磁性相饱和磁化强度温度系数绝对值小于0.02％/℃。
  2. 根据权利要求1所述的高温度稳定性永磁材料，其特征在于，所述微观结构的尺寸至少在一个维度上为5nm～800nm。
  3. 根据权利要求1或2所述的高温度稳定性永磁材料，其特征在于，所述强磁性相和所述具有自旋相变的磁性相的隔离方式为包裹隔离或层间隔隔离。
  4. 根据权利要求1所述的高温度稳定性永磁材料，其特征在于，随着温度升高，所述具有自旋相变的磁性相的易磁化方向由易基面转向易轴。
  5. 根据权利要求1所述的高温度稳定性永磁材料，其特征在于，所述强磁性相为SmCo系化合物，且Sm部分被HRE或HRE与其他元素的组合取代，所述具有自旋相变的磁性相为RCo 5系化合物、RCo 5的衍生化合物、R 2Co 17系化合物或R 2Co 17的衍生化合物；
    其中，HRE选自Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu中的一种或多种；
    其中，R选自Pr、Nd、Dy、Tb和Ho中的一种或多种。
  6. 根据权利要求1所述的高温度稳定性永磁材料，其特征在于，所述永磁材料为钐钴基永磁体；
    所述钐钴基永磁体包括强磁性相(SmHRER) 2(CoM) 17系化合物，以及具有自旋相变的磁性相(SmHRER)(CoM) 5系化合物，所述钐钴基永磁体的微观结构中，所述(SmHRER)(CoM) 5系化合物包裹所述(SmHRER) 2(CoM) 17系化合物；
    其中，HRE选自Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu中的一种或多种；R选自Pr、Nd、Dy、Tb和Ho中的一种或多种，M选自Fe、Cu、Zr、Ni、Ti、Nb、Mo、Hf和W中的一种或多种，且所述SmHRER至少具有三种元素。
  7. 根据权利要求6所述的高温度稳定性永磁材料，其特征在于，所述钐钴基永磁体中，R的质量百分含量为8％～20％；HRE的质量百分含量为8％～18％。
  8. 根据权利要求7所述的高温度稳定性永磁材料，其特征在于，当所述HRE包括Tb、Dy及Ho中的至少一种时，所述Tb、Dy和/或Ho同时作为R计算所述R的质量百分含量。
  9. 根据权利要求7所述的高温度稳定性永磁材料，其特征在于，
    随着R含量的增加，所述(SmHRER)(CoM) 5系化合物的自旋相变温度升高， 矫顽力极大值点和矫顽力极小值点温度向高温移动，对应矫顽力温度系数绝对值小于0.03％/℃的温度区间也向高温移动。
  10. 根据权利要求7所述的高温度稳定性永磁材料，其特征在于，
    随着HRE含量的增加，所述强磁性相(SmHRER) 2(CoM) 17系化合物的饱和磁化强度温度系数绝对值小于0.02％/℃的温度区间向高温移动。
  11. 根据权利要求1所述的高温度稳定性永磁材料，其特征在于，所述永磁材料在2K～600K的温度范围内剩磁温度系数绝对值小于0.02％/℃，且矫顽力温度系数绝对值小于0.03％/℃。
  12. 一种如权利要求1～11任一项所述的高温度稳定性永磁材料在变温环境下的应用。
PCT/CN2018/086056 2017-04-14 2018-05-08 高温度稳定性永磁材料及其应用 Ceased WO2018188675A1 (zh)

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