CN115925407A - Rare earth element doped Z-type ferrite material and preparation method thereof - Google Patents
Rare earth element doped Z-type ferrite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a rare earth element doped Z-type ferrite material and a preparation method thereof, wherein the metal elements of the Z-type ferrite material comprise iron, cobalt, alkaline earth metals and rare earth metals, and the alkaline earth metals comprise barium and/or strontium; the structure of the Z-type ferrite material is a hexagonal crystal system. The Z-type ferrite material improves the crystal structure in the material in a rare earth metal doping mode, the magnetic property of the material is obviously improved, and the material has high saturation magnetization; according to the preparation method, the prepared gel is subjected to self-propagating combustion reaction to generate precursor powder, then the precursor powder and the rare earth metal source are subjected to wet ball milling, and the rare earth metal is doped through calcination, so that the precursor powder can be prepared in advance, the time is saved, and the production efficiency is improved. The ferrite generated by the preparation method has uniform particle size and good crystallinity; the preparation method has the advantages of low production cost, simple process flow, low equipment requirement and better industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of magnetic material preparation, and relates to a Z-type ferrite material doped with rare earth elements and a preparation method thereof.
Background
With the rapid development of mobile communication devices and smart wearable devices, communication technologies and materials required for the same have attracted extensive attention. In wireless communication devices, antennas play an important role as components for transmitting and receiving electromagnetic waves. At present, spinel ferrite materials can only work in a frequency band range of about 100MHz, and can generate serious eddy current loss and skin effect under high frequency. However, the planar hexaferrite has higher magnetocrystalline anisotropy and thus higher resonant frequency than the spinel-type ferrite, and the Z-type hexaferrite has relatively high magnetic permeability, thus becoming an important soft magnetic ferrite material for the uhf-band antenna application.
Common preparation methods for the Z-type ferrite include a chemical coprecipitation method, a sol-gel method, a hydrothermal method, a solid-phase reaction method, a salt dissolving method and the like; the sol-gel method belongs to one of wet chemical synthesis methods, and has the advantages of low reaction temperature, high system activity, good controllability of chemical proportion, high purity of prepared samples, easiness in laboratory preparation and the like, however, the time required by the whole sol-gel process is long, and the problem of abnormal growth of particle size exists. The final product generated by the solid phase method is easy to introduce impurities, the component control is not accurate, and the formed powder particles are thick and the appearance is difficult to control.
CN 112851326A discloses a Co 2 The Z-type ferrite material and the preparation method thereof comprise the following steps: mixing a Ba source, a Sr source, a Co source and a Fe source according to a ratio and performing ball milling; sintering the ball-milled material for the first time at 1200-1300 ℃; granulating the material obtained by the first sintering, pressing and molding, and then sintering for the second time at 1000-1150 ℃ to obtain Co 2 A Z-type ferrite material. The method regulates and controls the crystal phase and the grain diameter of the ferrite material by sintering twice and controlling the sintering temperature, but the method still has the defects of a solid phase reaction method, inaccurate component control, multiple sintering steps and higher energy consumption.
Meanwhile, the performance of a simple ferrite material is often poor, and the ferrite material is usually required to be modified, and selectable methods include doping, compounding and the like. CN 07428556A discloses Mo-doped Co for ultrahigh frequency 2 A Z-type ferrite composite material, the hexaferrite composition having the formula: (Ba) z Sr (3-z) )Co (2+x) Mo x Fe (y-2x) O 41 Wherein x is 0.01 to 0.20, y is 20 to 24, and z is 0 to 3; the preparation method of the hexaferrite composition comprises the following steps: providing hexaferrite phase precursor compounds comprising Fe, ba, co and Mo, calcining the precursor compounds in air to form a material comprising a Z-type hexaferrite phase; the magnetic permeability and the permittivity of the material can be improved by doping molybdenum, so that the material is suitable for high-frequency application, but the material is prepared by adopting a solid-phase sintering method, and the content of each element is difficult to accurately control.
In summary, for the modification of the Z-type ferrite material, a suitable improvement mode and improved raw materials are needed, so as to develop the Z-type ferrite material with better performance, and at the same time, the preparation method is simplified, the preparation time is shortened, and the efficiency is improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a rare earth element doped Z-type ferrite material and a preparation method thereof, the Z-type ferrite material improves the crystal structure in the Z-type ferrite material in a rare earth metal doping mode, the magnetic property and the saturation magnetization intensity of the material are improved, the prepared gel is further subjected to self-propagating combustion reaction to prepare precursor powder, and then the rare earth metal doping is completed through calcination, so that the precursor powder can be prepared in advance, the time is saved, the operation steps are simple and reasonable, and the production efficiency is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a rare earth element doped Z-type ferrite material, wherein the metal element composition of the Z-type ferrite material comprises iron, cobalt, alkaline earth metals and rare earth metals, and the alkaline earth metals comprise barium and/or strontium; the structure of the Z-type ferrite material is a hexagonal crystal system.
According to the invention, according to the performance and the application of the Z-type ferrite material, the modification is carried out in a rare earth metal doping mode, and the rare earth metal ions replace iron ions in the crystal lattice of the Z-type ferrite, so that the magnetic performance is improved.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferred embodiment of the present invention, the rare earth metal comprises any one or a combination of at least two of gadolinium, terbium, dysprosium, or holmium, and typical but non-limiting examples of such combinations are: combinations of gadolinium and terbium, terbium and dysprosium, gadolinium, terbium and holmium, gadolinium, terbium, dysprosium and holmium, and the like.
Preferably, the Z-type ferrite material has a chemical formula of Ba 3 Co 2 Fe 24-x R x O 41 And/or Sr 3 Co 2 Fe 24-x R x O 41 Wherein x is not less than 0.01<0.5, for example 0.01, 0.05, 0.1, 0.2, 0.3, 0.4 or 0.5, etc., but is not limited to the recited values, which are not limitingOther values not listed within the range are equally applicable; r is rare earth metal.
In another aspect, the present invention provides a method for preparing a rare earth element doped Z-type ferrite material, comprising the steps of:
(1) Mixing an iron source, a cobalt source, an alkaline earth metal source, a complexing agent and water according to the element composition of the Z-type ferrite, adding a pH regulator, heating and stirring to obtain wet gel, and drying to obtain dry gel;
(2) Heating the xerogel obtained in the step (1) to raise the temperature, and carrying out self-propagating combustion reaction to obtain fluffy powder;
(3) And (3) performing wet ball milling on the fluffy powder obtained in the step (2) and a rare earth metal source, drying and calcining to obtain the rare earth element doped Z-type ferrite material.
According to the invention, the prepared gel is subjected to self-propagating combustion reaction, and the generated precursor powder has extremely small particle size, is easy to store, has high chemical activity and is beneficial to subsequent metal element doping.
As a preferable technical scheme of the invention, the iron source, the cobalt source and the alkaline earth metal source in the step (1) comprise nitrates of corresponding metals.
Preferably, the alkaline earth metal source comprises barium nitrate and/or strontium nitrate.
Preferably, the molar ratio of each element in the iron source, the cobalt source and the alkaline earth metal source in the step (1) is the same as that of each element in the chemical formula of the Z-type ferrite material.
Preferably, the complexing agent of step (1) comprises citric acid and/or ethylenediaminetetraacetic acid.
As a preferable technical scheme of the invention, the iron source, the cobalt source and the alkaline earth metal source in the step (1) are dissolved in water firstly, stirred to obtain a transparent solution, and then the complexing agent is added into the transparent solution.
Preferably, in step (1), the molar ratio of the complexing agent to the sum of the metal ions is (2 to 3) from 1, for example 2.
Preferably, in the complexing agent in the step (1), the molar ratio of the citric acid to the ethylenediamine tetraacetic acid is 1 (0.5-0.9), such as 1.
Preferably, the molar ratio of citric acid, ethylenediaminetetraacetic acid and the sum of metal ions is 1.5.
As a preferable technical scheme of the invention, the pH regulator in the step (1) comprises ammonia water.
Preferably, after the addition of the pH adjusting agent in step (1), the pH is adjusted to 6.0 to 8.0, for example 6.0, 6.5, 7.0, 7.5 or 8.0, but not limited to the values listed, and other values not listed within this range are equally applicable.
Preferably, the heating temperature in step (1) is 60 to 90 ℃, such as 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the heating time in step (1) is 5 to 8 hours, such as 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, or 8 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the stirring rate in step (1) is 20 to 60r/min, such as 20r/min, 30r/min, 40r/min, 50r/min or 60r/min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the drying temperature in step (1) is 80 to 120 ℃, for example 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 100 ℃.
Preferably, the drying time in step (1) is 8 to 15 hours, such as 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or 15 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the xerogel of step (1) is uniform and stable.
Preferably, the temperature of the self-propagating combustion reaction in step (2) is 180 to 220 ℃, such as 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃ or 220 ℃, but not limited to the recited values, and other values not recited in the range of the values are equally applicable, preferably 200 ℃.
Preferably, the time for the self-propagating combustion reaction in step (2) is 20-60 min, such as 20min, 30min, 40min, 50min or 60min, but is not limited to the recited values, and other unrecited values in the range of the recited values are also applicable.
Preferably, the components of the fluffy powder of step (2) comprise metal oxides and carbon nitrogen oxides.
In the invention, the xerogel prepared by the sol-gel method mainly comprises a complex of metal ions, and the self-propagating combustion reaction mainly comprises an oxidation-reduction combustion reaction to generate fluffy black powder, wherein the composition mainly comprises metal oxide and carbon oxynitride.
As a preferable technical scheme of the invention, the rare earth metal source in the step (3) comprises nitrate of rare earth metal.
Preferably, the nitrate of a rare earth metal comprises any one of gadolinium nitrate, terbium nitrate, dysprosium nitrate or holmium nitrate, or a combination of at least two of these, typical but non-limiting examples being: a combination of gadolinium nitrate and terbium nitrate, a combination of terbium nitrate and dysprosium nitrate, a combination of gadolinium nitrate, terbium nitrate and holmium nitrate, and the like.
Preferably, the ratio of the molar amount of the rare earth element in the rare earth metal source in the step (3) to the molar amount of each metal element in the fluffy powder satisfies the molar ratio of the corresponding elements in the chemical formula of the Z-type ferrite material.
Preferably, the wet ball milling time in step (3) is 5 to 8 hours, such as 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours or 8 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the rotation speed of the wet ball milling in the step (3) is 400 to 600r/min, such as 400r/min, 450r/min, 500r/min, 550r/min or 600r/min, but not limited to the recited values, and other non-recited values in the range of the values are also applicable.
As a preferred embodiment of the present invention, the drying temperature in the step (3) is 80 to 120 ℃, for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the drying time in step (3) is 8 to 15 hours, such as 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or 15 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the temperature increase rate of the calcination in step (3) is 3-5 deg.C/min, such as 3 deg.C/min, 3.5 deg.C/min, 4 deg.C/min, 4.5 deg.C/min, or 5 deg.C/min, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the temperature raising process in the calcining in the step (3) is divided into two sections, wherein the temperature is raised to the first-section calcining temperature, and then the temperature is raised to the second-section calcining temperature.
Preferably, the one-stage calcination is carried out at a temperature of 400 to 500 ℃, e.g., 400 ℃, 420 ℃, 440 ℃, 450 ℃, 460 ℃, 480 ℃ or 500 ℃ and the like, and the holding time is 1.5 to 2.5 hours, e.g., 1.5 hours, 1.6 hours, 1.8 hours, 2 hours, 2.25 hours or 2.5 hours and the like, but is not limited to the recited values, and other unrecited values within the respective value ranges are also applicable.
Preferably, the two-stage calcination temperature is 1250-1300 ℃, such as 1250 ℃, 1260 ℃, 1270 ℃, 1280 ℃, 1290 ℃, 1300 ℃ or the like; the holding time is 3 to 5 hours, for example 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours, but is not limited to the recited values, and other values not recited in the respective numerical ranges are also applicable.
Preferably, the temperature reduction rate after the calcination in step (3) is 4 to 6 ℃/min, such as 4 ℃/min, 4.5 ℃/min, 5 ℃/min, 5.5 ℃/min, or 6 ℃/min, but not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the temperature is reduced to room temperature after the calcination in the step (3).
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Dissolving an iron source, a cobalt source and an alkaline earth metal source in water according to the element composition of the Z-type ferrite, wherein the iron source, the cobalt source and the alkaline earth metal source comprise nitrates of corresponding metals, stirring to obtain a transparent solution, adding a complexing agent into the transparent solution, wherein the complexing agent comprises citric acid and/or ethylene diamine tetraacetic acid, the molar ratio of the complexing agent to the sum of metal ions is (2-3) to 1, the molar ratio of the citric acid to the ethylene diamine tetraacetic acid is (0.5-0.9), adding a pH regulator to regulate the pH value to 6.0-8.0, wherein the pH regulator comprises ammonia water, heating and stirring to obtain wet gel, wherein the heating temperature is 60-90 ℃, and the heating time is 5-8 hours; drying to obtain uniform and stable xerogel, wherein the drying temperature is 80-120 ℃, and the drying time is 8-15 h;
(2) Heating the xerogel obtained in the step (1) to raise the temperature, and carrying out self-propagating combustion reaction at the temperature of 180-220 ℃, and keeping the temperature for 20-60 min to obtain fluffy powder, wherein the components of the fluffy powder comprise metal oxide and carbon oxynitride;
(3) And (3) performing wet ball milling on the fluffy powder obtained in the step (2) and a rare earth metal source, wherein the rare earth metal source comprises nitrate of rare earth metal, the time of the wet ball milling is 5-8 h, the rotating speed of the wet ball milling is 400-600 r/min, the drying and calcining are performed, the drying temperature is 80-120 ℃, the time is 8-15 h, the temperature rising rate of the calcining is 3-5 ℃/min, the temperature rising process is divided into two sections, the temperature is firstly increased to 400-500 ℃, the temperature is kept for 1.5-2.5 h, then the temperature is increased to 1250-1300 ℃, the temperature is kept for 3-5 h, the temperature reducing rate after the calcining is 4-6 ℃/min, and the rare earth element doped Z-type ferrite material is obtained after the temperature is reduced to the room temperature.
Compared with the prior art, the invention has the following beneficial effects:
(1) The Z-type ferrite material improves the crystal structure in the Z-type ferrite material in a rare earth metal doping mode, the magnetic property of the material is obviously improved, and the material has high saturation magnetization;
(2) According to the preparation method, the prepared gel is subjected to self-propagating combustion reaction to generate precursor powder, then the precursor powder is subjected to wet ball milling with a rare earth metal source, and the doping of rare earth metal is completed through calcination, so that the precursor powder can be prepared in advance, the time is saved, and the production efficiency is improved;
(3) The preparation method disclosed by the invention is low in production cost, simple in process flow, low in equipment requirement and good in industrial application prospect.
Drawings
FIG. 1 is a magnetic property curve of a rare earth element doped Z-type ferrite material provided in example 1 of the present invention;
fig. 2 is an XRD pattern of rare earth element doped Z-type ferrite materials provided in examples 1-5 of the present invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The invention provides a Z-type ferrite material doped with rare earth elements and a preparation method thereof, wherein the metal elements of the Z-type ferrite material comprise iron, cobalt, alkaline earth metals and rare earth metals, and the alkaline earth metals comprise barium and/or strontium; the organization structure of the Z-type ferrite material is a hexagonal crystal system;
the preparation method comprises the following steps:
(1) Mixing an iron source, a cobalt source and an alkaline earth metal source which form the Z-type ferrite with a complexing agent and water, adding a pH regulator, heating and stirring to obtain wet gel, and drying to obtain dry gel;
(2) Drying the xerogel obtained in the step (1), heating the dried xerogel, and carrying out self-propagating combustion reaction to obtain fluffy powder;
(3) And (3) performing wet ball milling on the fluffy powder obtained in the step (2) and a rare earth metal source, drying and calcining to obtain the rare earth element doped Z-type ferrite material.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a rare earth element doped Z-type ferrite material and a preparation method thereof, wherein the metal elements of the Z-type ferrite material comprise iron, cobalt, alkaline earth metal barium and rare earth metal gadolinium; the structure of the Z-type ferrite material is a hexagonal crystal system.
The chemical formula of the Z-type ferrite material is Ba 3 Co 2 Fe 23.9 Gd 0.1 O 41 。
The preparation method comprises the following steps:
(1) Dissolving ferric nitrate, cobalt nitrate and barium nitrate in water, weighing according to the stoichiometric ratio of each element in the chemical formula of the Z-type ferrite material, stirring to obtain a yellow transparent solution, adding a complexing agent into the transparent solution, wherein the complexing agent comprises citric acid and ethylenediamine tetraacetic acid, the molar ratio of the total of the citric acid, the ethylenediamine tetraacetic acid and metal ions is 1.1; drying to obtain uniform and stable xerogel, wherein the drying temperature is 100 ℃, and the drying time is 12h;
(2) Heating the xerogel obtained in the step (1) to raise the temperature, and carrying out self-propagating combustion reaction at the temperature of 200 ℃, and keeping the temperature for 30min to obtain black fluffy powder;
(3) And (3) performing wet ball milling on the fluffy powder obtained in the step (2) and a rare earth metal source, wherein the rare earth metal source is gadolinium nitrate, the time of the wet ball milling is 6h, the rotation speed of the wet ball milling is 500r/min, the drying and calcining are performed, the drying temperature is 100 ℃, the time is 12h, the heating rate of the calcining is 5 ℃/min, the temperature is firstly increased to 450 ℃, the temperature is kept for 2h, then the temperature is continuously increased to 1250 ℃, the temperature is kept for 5h, the cooling rate after the calcining is 5 ℃/min, and the temperature is reduced to the room temperature to obtain the rare earth element gadolinium-doped Z-type ferrite material.
In this example, the prepared Z-type ferrite material was subjected to magnetic property test using a Vibrating Sample Magnetometer (VSM), and the magnetic property curve thereof is shown in fig. 1; as can be seen from FIG. 1, the maximum saturation magnetization of the Z-type ferrite material is 42.65emu/g.
Example 2:
the embodiment provides a rare earth element doped Z-type ferrite material and a preparation method thereof, wherein the metal elements of the Z-type ferrite material comprise iron, cobalt, alkaline earth metal barium and rare earth metal gadolinium; the organizational structure of the Z-type ferrite material is a hexagonal crystal system.
The chemical formula of the Z-type ferrite material is Ba 3 Co 2 Fe 23.8 Gd 0.2 O 41 。
The preparation method comprises the following steps:
(1) Dissolving ferric nitrate, cobalt nitrate and barium nitrate in water, weighing according to the stoichiometric ratio of each element in the chemical formula of the Z-type ferrite material, stirring to obtain a yellow transparent solution, adding a complexing agent into the transparent solution, wherein the complexing agent comprises citric acid and ethylene diamine tetraacetic acid, the molar ratio of the total of the citric acid, the ethylene diamine tetraacetic acid and metal ions is 1.1; drying to obtain uniform and stable xerogel, wherein the drying temperature is 90 ℃ and the drying time is 14h;
(2) Heating the xerogel obtained in the step (1) to raise the temperature, and carrying out self-propagating combustion reaction at 180 ℃, and keeping the temperature for 60min to obtain black fluffy powder;
(3) And (3) performing wet ball milling on the fluffy powder obtained in the step (2) and a rare earth metal source, wherein the rare earth metal source is gadolinium nitrate, the time of the wet ball milling is 7 hours, the rotation speed of the wet ball milling is 450r/min, the drying and calcining are performed, the drying temperature is 80 ℃, the time is 15 hours, the heating rate of the calcining is 4 ℃/min, the temperature is firstly increased to 450 ℃, the heat is preserved for 2 hours, then the temperature is continuously increased to 1280 ℃, the heat is preserved for 4 hours, the cooling rate after the calcining is 6 ℃/min, and the temperature is reduced to the room temperature to obtain the rare earth element gadolinium-doped Z-type ferrite material.
In this example, the prepared Z-type ferrite material was subjected to magnetic property test using a vibrating sample magnetometer, and the maximum saturation magnetization of the Z-type ferrite material was 43.47emu/g.
Example 3:
the embodiment provides a rare earth element doped Z-type ferrite material and a preparation method thereof, wherein the metal elements of the Z-type ferrite material comprise iron, cobalt, alkaline earth metal barium and rare earth metal gadolinium; the organizational structure of the Z-type ferrite material is a hexagonal crystal system.
The chemical formula of the Z-type ferrite material is Ba 3 Co 2 Fe 23.7 Gd 0.3 O 41 。
The preparation method comprises the following steps:
(1) Dissolving ferric nitrate, cobalt nitrate and barium nitrate in water, weighing according to the stoichiometric ratio of each element in the chemical formula of the Z-type ferrite material, stirring to obtain a yellow transparent solution, adding a complexing agent into the transparent solution, wherein the complexing agent comprises citric acid and ethylene diamine tetraacetic acid, the molar ratio of the total of the citric acid, the ethylene diamine tetraacetic acid and metal ions is 1.8; drying to obtain uniform and stable xerogel, wherein the drying temperature is 110 ℃, and the drying time is 10 hours;
(2) Heating the xerogel obtained in the step (1) to raise the temperature, and carrying out self-propagating combustion reaction at 210 ℃, and keeping the temperature for 25min to obtain black fluffy powder;
(3) And (3) performing wet ball milling on the fluffy powder obtained in the step (2) and a rare earth metal source, wherein the rare earth metal source is gadolinium nitrate, the time of the wet ball milling is 5h, the rotation speed of the wet ball milling is 600r/min, the drying and calcining are performed, the drying temperature is 120 ℃, the time is 8h, the heating rate of the calcining is 3 ℃/min, the temperature is firstly increased to 450 ℃, the temperature is kept for 2h, then the temperature is continuously increased to 1300 ℃, the temperature is kept for 3h, the cooling rate after the calcining is 4 ℃/min, and the temperature is reduced to room temperature to obtain the rare earth element gadolinium-doped Z-type ferrite material.
In this example, the prepared Z-type ferrite material was subjected to magnetic property test using a vibrating sample magnetometer, and the maximum saturation magnetization of the Z-type ferrite material was 42.45emu/g.
Example 4:
the embodiment provides a rare earth element doped Z-type ferrite material and a preparation method thereof, wherein the metal elements of the Z-type ferrite material comprise iron, cobalt, alkaline earth metal barium and rare earth metal terbium; the organizational structure of the Z-type ferrite material is a hexagonal crystal system.
The chemical formula of the Z-type ferrite material is Ba 3 Co 2 Fe 23.6 Tb 0.4 O 41 。
The preparation method comprises the following steps:
(1) Dissolving ferric nitrate, cobalt nitrate and barium nitrate in water, weighing according to the stoichiometric ratio of each element in the chemical formula of the Z-type ferrite material, stirring to obtain a yellow transparent solution, adding a complexing agent into the transparent solution, wherein the complexing agent comprises citric acid and ethylene diamine tetraacetic acid, the molar ratio of the total of the citric acid, the ethylene diamine tetraacetic acid and metal ions is (2.0); drying to obtain uniform and stable xerogel, wherein the drying temperature is 120 ℃, and the drying time is 9h;
(2) Heating the xerogel obtained in the step (1) to raise the temperature, and carrying out a self-propagating combustion reaction at 220 ℃, and keeping the temperature for 20min to obtain black fluffy powder;
(3) And (3) performing wet ball milling on the fluffy powder obtained in the step (2) and a rare earth metal source, wherein the rare earth metal source is terbium nitrate, the wet ball milling time is 8h, the rotation speed of the wet ball milling is 400r/min, drying and calcining are performed, the drying temperature is 110 ℃, the time is 10h, the temperature rising rate of the calcining is 4.5 ℃/min, the temperature is firstly increased to 450 ℃, the temperature is kept for 2h, then the temperature is continuously increased to 1260 ℃, the temperature is kept for 3.5h, the temperature reduction rate after the calcining is 5.5 ℃/min, and the temperature is reduced to the room temperature to obtain the rare earth element europium-doped Z-type ferrite material.
In the embodiment, the prepared Z-type ferrite material is subjected to magnetic property test by using a vibration sample magnetometer, and the maximum saturation magnetization of the Z-type ferrite material is 41.86emu/g.
Example 5:
the embodiment provides a rare earth element doped Z-type ferrite material and a preparation method thereof, wherein the metal elements of the Z-type ferrite material comprise iron, cobalt, alkaline earth metal barium and rare earth metal dysprosium; the organizational structure of the Z-type ferrite material is a hexagonal crystal system.
The chemical formula of the Z-type ferrite material is Ba 3 Co 2 Fe 23.5 Dy 0.5 O 41 。
The preparation method comprises the following steps:
(1) Dissolving ferric nitrate, cobalt nitrate and barium nitrate in water, weighing according to the stoichiometric ratio of each element in the chemical formula of the Z-type ferrite material, stirring to obtain a yellow transparent solution, adding a complexing agent into the transparent solution, wherein the complexing agent comprises citric acid and ethylene diamine tetraacetic acid, the molar ratio of the total of the citric acid, the ethylene diamine tetraacetic acid and metal ions is 1.2; drying to obtain uniform and stable dry gel, wherein the drying temperature is 180 ℃ and the drying time is 15h;
(2) Heating the xerogel obtained in the step (1) to raise the temperature, and carrying out self-propagating combustion reaction at 190 ℃, and keeping the temperature for 35min to obtain black fluffy powder;
(3) And (3) performing wet ball milling on the fluffy powder obtained in the step (2) and a rare earth metal source, wherein the rare earth metal source is dysprosium nitrate, the time of the wet ball milling is 6.5h, the rotation speed of the wet ball milling is 550r/min, the drying is performed at 90 ℃ for 14h, the heating rate of the calcining is 3.5 ℃/min, the temperature is firstly increased to 450 ℃ and is kept for 2h, then the temperature is continuously increased to 1270 ℃ and is kept for 4.5h, the cooling rate after the calcining is 4.5 ℃/min, and the temperature is reduced to room temperature to obtain the rare earth element dysprosium-doped Z-type ferrite material.
In this example, the prepared Z-type ferrite material was subjected to magnetic property test using a vibrating sample magnetometer, and the maximum saturation magnetization of the Z-type ferrite material was 40.13emu/g.
The Z-type ferrite materials obtained in examples 1 to 5 were subjected to XRD test, and XRD patterns thereof are shown in FIG. 2, which indicates that Z-type hexaferrite materials were generated, as compared with Z-type ferrite materials (PDF # 19-0047) which were not rare earth-doped.
Comparative example 1:
the present comparative example provides a Z-type ferrite material and a preparation method thereof, wherein the metallic element composition of the Z-type ferrite material includes iron, cobalt, and alkaline earth barium, and the microstructure of the Z-type ferrite material is a hexagonal system.
The chemical formula of the Z-type ferrite material is Ba 3 Co 2 Fe 24 O 41 。
The preparation is as described in example 1, with the only difference that: the raw materials for wet ball milling in step (3) do not include a rare earth metal source.
In the comparative example, the Z-type ferrite material is not doped with rare earth metal, iron ions are not replaced by rare earth ions in the corresponding crystal structure, the magnetic moment is smaller than that of a crystal replaced by the rare earth ions, the magnetization performance is weaker at the moment, and the maximum saturation magnetization is only 35.20emu/g through tests.
It can be seen from the above examples and comparative examples that the Z-type ferrite material of the present invention has improved crystal structure inside the Z-type ferrite material in a rare earth metal doping manner, the magnetic performance of the material is significantly improved, and the material has high saturation magnetization; the preparation method comprises the steps of generating precursor powder by utilizing self-propagating combustion reaction of the prepared gel, carrying out wet ball milling on the precursor powder and a rare earth metal source, and completing doping of rare earth metal by calcining, wherein the precursor powder can be prepared in advance, so that the time is saved, and the production efficiency is improved; the preparation method has the advantages of low production cost, simple process flow, low equipment requirement and better industrial application prospect.
The present invention is illustrated by the above examples, but the present invention is not limited to the above detailed products and methods, i.e., it is not meant to imply that the present invention must rely on the above detailed products and methods for its implementation. It will be apparent to those skilled in the art that any modifications to the present invention, equivalents of the method of the present invention and additions of ancillary steps, selection of specific means, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A rare earth element doped Z-type ferrite material is characterized in that the metal element composition of the Z-type ferrite material comprises iron, cobalt, alkaline earth metals and rare earth metals, wherein the alkaline earth metals comprise barium and/or strontium; the structure of the Z-type ferrite material is a hexagonal crystal system.
2. The Z-type ferrite material of claim 1, wherein the rare earth metal comprises any one of gadolinium, terbium, dysprosium, or holmium, or a combination of at least two thereof;
preferably, the Z-type ferrite material has a chemical formula of Ba 3 Co 2 Fe 24-x R x O 41 And/or Sr 3 Co 2 Fe 24-x R x O 41 Wherein x is not less than 0.01<0.5, R is rare earth metal.
3. The method of preparing a Z-type ferrite material according to claim 1 or 2, characterized in that it comprises the steps of:
(1) Mixing an iron source, a cobalt source, an alkaline earth metal source, a complexing agent and water according to the element composition of the Z-type ferrite, adding a pH regulator, heating and stirring to obtain wet gel, and drying to obtain dry gel;
(2) Heating the xerogel obtained in the step (1) to raise the temperature, and carrying out self-propagating combustion reaction to obtain fluffy powder;
(3) And (3) performing wet ball milling on the fluffy powder obtained in the step (2) and a rare earth metal source, drying and calcining to obtain the rare earth element doped Z-type ferrite material.
4. The method according to claim 3, wherein the iron source, cobalt source, alkaline earth metal source of step (1) comprise nitrates of the respective metals;
preferably, the alkaline earth metal source comprises barium nitrate and/or strontium nitrate;
preferably, the molar ratio of each element in the iron source, the cobalt source and the alkaline earth metal source in the step (1) is the same as that of each element in the chemical formula of the Z-type ferrite material;
preferably, the complexing agent of step (1) comprises citric acid and/or ethylenediaminetetraacetic acid.
5. The preparation method according to claim 3 or 4, characterized in that the iron source, the cobalt source and the alkaline earth metal source in the step (1) are dissolved in water, stirred to obtain a transparent solution, and then the complexing agent is added into the transparent solution;
preferably, the molar ratio of the complexing agent to the total of the metal ions in the step (1) is (2-3): 1;
preferably, in the complexing agent in the step (1), the molar ratio of the citric acid to the ethylenediamine tetraacetic acid is 1 (0.5-0.9), and preferably 1 (0.7-0.75).
6. The production method according to any one of claims 3 to 5, wherein the pH adjusting agent of step (1) comprises aqueous ammonia;
preferably, after the pH regulator is added in the step (1), the pH value is regulated to 6.0-8.0;
preferably, the heating temperature in the step (1) is 60-90 ℃;
preferably, the heating time in the step (1) is 5-8 h;
preferably, the stirring speed of the step (1) is 20-60 r/min;
preferably, the drying temperature in the step (1) is 80-120 ℃, and preferably 100 ℃;
preferably, the drying time in the step (2) is 8-15 h;
preferably, the xerogel of step (1) is uniform and stable.
7. The method according to any one of claims 3 to 6, wherein the temperature of the self-propagating combustion reaction in step (2) is 180 to 220 ℃, preferably 200 ℃;
preferably, the time of the self-propagating combustion reaction in the step (2) is 20-60 min;
preferably, the components of the fluffy powder of step (2) comprise metal oxides and carbon nitrogen oxides.
8. The production method according to any one of claims 3 to 7, wherein the rare earth metal source of step (3) comprises a nitrate of a rare earth metal;
preferably, the nitrate of the rare earth metal comprises any one of gadolinium nitrate, terbium nitrate, dysprosium nitrate or holmium nitrate or a combination of at least two of the two;
preferably, the ratio of the molar amount of the rare earth element in the rare earth metal source in the step (3) to the molar amount of each metal element in the fluffy powder satisfies the molar ratio of the corresponding elements in the chemical formula of the Z-type ferrite material;
preferably, the time of the wet ball milling in the step (3) is 5 to 8 hours;
preferably, the rotation speed of the wet ball milling in the step (3) is 400-600 r/min.
9. The method according to any one of claims 3 to 8, wherein the drying temperature in step (3) is 80 to 120 ℃;
preferably, the drying time in the step (3) is 8-15 h;
preferably, the heating rate of the calcination in the step (3) is 3-5 ℃/min;
preferably, the temperature rise process in the calcination in the step (3) is divided into two sections, wherein the temperature rise is carried out to a first-section calcination temperature, and then is carried out to a second-section calcination temperature;
preferably, the primary calcining temperature is 400-500 ℃, and the heat preservation time is 1.5-2.5 h;
preferably, the second-stage calcination temperature is 1250-1300 ℃, and the heat preservation time is 3-5 h;
preferably, the temperature reduction rate after the calcination in the step (3) is 4-6 ℃/min;
preferably, the temperature is reduced to room temperature after the calcination in the step (3).
10. The method according to any one of claims 3 to 9, characterized in that it comprises the following steps:
(1) Dissolving an iron source, a cobalt source and an alkaline earth metal source in water according to the element composition of the Z-type ferrite, wherein the iron source, the cobalt source and the alkaline earth metal source comprise nitrates of corresponding metals, stirring to obtain a transparent solution, adding a complexing agent into the transparent solution, wherein the complexing agent comprises citric acid and/or ethylene diamine tetraacetic acid, the molar ratio of the complexing agent to the sum of metal ions is (2-3) to 1, the molar ratio of the citric acid to the ethylene diamine tetraacetic acid is (0.5-0.9), adding a pH regulator to regulate the pH value to 6.0-8.0, wherein the pH regulator comprises ammonia water, heating and stirring to obtain wet gel, wherein the heating temperature is 60-90 ℃, and the heating time is 5-8 hours; drying to obtain uniform and stable dry gel, wherein the drying temperature is 80-120 ℃, and the drying time is 8-15 h;
(2) Heating the xerogel obtained in the step (1) to raise the temperature, and carrying out self-propagating combustion reaction at the temperature of 180-220 ℃, and keeping the temperature for 20-60 min to obtain fluffy powder, wherein the components of the fluffy powder comprise metal oxide and carbon oxynitride;
(3) And (3) performing wet ball milling on the fluffy powder obtained in the step (2) and a rare earth metal source, wherein the rare earth metal source comprises nitrate of rare earth metal, the time of the wet ball milling is 5-8 h, the rotating speed of the wet ball milling is 400-600 r/min, the drying and calcining are performed, the drying temperature is 80-120 ℃, the time is 8-15 h, the temperature rising rate of the calcining is 3-5 ℃/min, the temperature rising process is divided into two sections, the temperature is firstly increased to 400-500 ℃, the temperature is kept for 1.5-2.5 h, then the temperature is increased to 1250-1300 ℃, the temperature is kept for 3-5 h, the temperature reducing rate after the calcining is 4-6 ℃/min, and the rare earth element doped Z-type ferrite material is obtained after the temperature is reduced to the room temperature.
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