阅读说明：本技术 一种掺杂TmIG铁氧体晶体材料、其制备方法及应用 (TmIG-doped ferrite crystal material, and preparation method and application thereof ) 是由 吴少凡 李艳 王帅华 徐刘伟 于 2020-06-16 设计创作，主要内容包括：本发明提供一种掺杂TmIG铁氧体晶体材料,化学式为Tm<Sub>3-x</Sub>Ce<Sub>x</Sub>Fe<Sub>5-y</Sub>Cr<Sub>y</Sub>O<Sub>12</Sub>；其中,0≤x≤0.12,0≤y≤0.3；Ce<Sup>3+</Sup>取代晶体材料中Tm<Sup>3+</Sup>的格位,Cr<Sup>3+</Sup>取代晶体材料中Fe<Sup>3+</Sup>的格位。并公开了该晶体材料的制备方法。该制备方法工艺简单,生产周期短,反应过程易于控制,产品的综合磁性能良好,饱和磁化强度相对较高,适合工厂化大批量生产。(The invention provides a TmIG-doped ferrite crystal material with a chemical formula of Tm 3‑x Ce x Fe 5‑y Cr y O 12 (ii) a Wherein x is more than or equal to 0 and less than or equal to 0.12, and y is more than or equal to 0 and less than or equal to 0.3; ce 3+ Substitution of Tm in crystalline materials 3+ Lattice site of (2), Cr 3+ Substitution of Fe in crystalline materials 3+ The lattice site of (1). And discloses a preparation method of the crystal material. The preparation method has the advantages of simple process, short production period, easily controlled reaction process, good comprehensive magnetic property of the product, relatively high saturation magnetization intensity and suitability for industrial mass production.)

1. A TmIG-doped ferrite crystal material is characterized by having a chemical formula

Tm_3-xCe_xFe_5-yCr_yO₁₂

Wherein x is more than or equal to 0 and less than or equal to 0.12, and y is more than or equal to 0 and less than or equal to 0.3;

Ce³⁺substitution of Tm in crystals³⁺Lattice site of (2), Cr³⁺By substitution of Fe in the crystal³⁺The lattice site of (1).

2. The doped TmIG ferrite crystal material of claim 1,

preferably, the average grain diameter of the doped TmIG ferrite crystal material is 40-60 nm;

preferably, the saturation magnetization of the doped TmIG ferrite crystal material is 16-19 emu/g.

3. A method for producing a TmIG ferrite crystal doped with a dopant as claimed in any one of claims 1 to 2, comprising at least the steps of:

obtaining a mixed solution containing a Tm source, a Ce source, a Fe source and a Cr source, adding citric acid, adjusting the pH to 1-3, and reacting to obtain sol; and drying, grinding and sintering the sol to obtain the doped TmIG ferrite material.

4. The method of claim 3,

the Tm source is selected from Tm: (NO₃)₃、Tm₂O₃At least one of;

the Fe source is selected from Fe (NO)₃)₃、Fe₂O₃At least one of;

the Ce source is selected from Ce (NO)₃)₃、CeO₂At least one of;

the Cr source is selected from Cr (NO)₃)₃、Cr₂O₃At least one of (1).

5. The method according to claim 3, wherein the molar ratio of the Tm element, the Ce element, the Fe element, and the Cr element in the mixed solution is:

Tm：Ce：Fe：Cr＝3-x：x：5-y：y

wherein x is more than or equal to 0 and less than or equal to 0.12, and y is more than or equal to 0 and less than or equal to 0.3.

6. The method of claim 3, wherein the reaction conditions are:

the reaction temperature is 70-90 ℃, and the reaction time is 2-4 h.

7. The method of claim 3, wherein pre-sintering is performed prior to said sintering.

8. The method according to claim 7, characterized in that the conditions of the pre-sintering are:

raising the temperature to a pre-sintering temperature of 300-350 ℃ at a heating rate of 1-4 ℃/min, and keeping the temperature for 30-60 min.

9. The method according to claim 7, characterized in that the conditions of the sintering are: raising the temperature from the pre-sintering temperature to 1150-1250 ℃ at a temperature raising speed of 1-4 ℃/min, and preserving the heat for 2-4 hours.

10. Use of any one of the doped TmIG ferrite crystal material according to any one of claims 1 to 2, the doped TmIG ferrite crystal material prepared by the method according to any one of claims 3 to 9 in a magneto-optical isolator.

Technical Field

The invention belongs to the technical field of microwave ferrite crystal material preparation, and particularly relates to a TmIG-doped ferrite crystal material and a preparation method thereof.

Background

Ferrite microwave devices (such as electric tuning filters, limiters, phase shifters, circulators, etc.) have the advantages of high bearing power, low loss, etc., and have long played an important role in military and civil aspects such as phased array radar, electronic countermeasure, high-energy physical particle accelerators, mobile communication, artificial satellites, televisions, etc. With the development of ferrite microwave devices toward high frequency, light weight, etc., more new requirements such as saturation magnetization meeting specific requirements, high temperature stability, etc., are provided for ferrites applied thereto to obtain better communication quality and lower production cost.

The garnet type ferrite is one of ferrite structures having superior dielectric characteristics, a narrow resonance line width, a large faraday rotation angle, and small light absorption. The magnetic material has small magnetic loss and excellent adaptability, so that the magnetic material is applied to various fields of national defense, satellite communication and the like, and becomes an important ferrimagnetic material in the current physical material research.

Therefore, the TmIG ferrite material with simple development components, low cost and excellent performance has wide prospect for meeting the requirements of the current market.

Disclosure of Invention

As one aspect of the present application, there is provided a TmIG-doped ferrite crystal material characterized by the chemical formula Tm_3-xCe_xFe_5-yCr_yO₁₂

Wherein x is more than or equal to 0 and less than or equal to 0.12, and y is more than or equal to 0 and less than or equal to 0.3;

Ce³⁺substitution of Tm in crystalline materials³⁺Lattice site of (2), Cr³⁺Substitution of Fe in crystalline materials³⁺The lattice site of (1).

Alternatively, the upper limit of x is selected from 0.02, 0.04, 0.06, 0.08, 0.1 or 0.12; the lower limit is selected from 0, 0.02, 0.04, 0.06, 0.08 or 0.1.

Alternatively, the upper limit of y is selected from 0.05, 0.1, 0.15, 0.2, 0.25, or 0.3; the lower limit is selected from 0, 0.05, 0.1, 0.15, 0.2 or 0.25.

Optionally, the doped TmIG ferrite crystal material has an average particle size of 40-60 nm.

Optionally, the saturation magnetization of the doped TmIG ferrite crystal material is 16-19 emu/g.

Optionally, the doped TmIG ferrite crystal material has an average particle size of 40-50 nm.

Optionally, the saturation magnetization of the doped TmIG ferrite crystal material is 17-19 emu/g.

According to another aspect of the present application, there is provided a method for preparing the above-mentioned doped TmIG ferrite crystal material, characterized by comprising at least the steps of:

obtaining a mixed solution containing a Tm source, a Ce source, a Fe source and a Cr source, adding citric acid, adjusting the pH value to 1-3, reacting to obtain sol, drying, grinding and sintering to obtain the TmIG-doped ferrite material.

Alternatively, ammonia is used to adjust the pH to 2.

Optionally, the Tm source is selected from Tm (NO)₃)₃、Tm₂O₃At least one of;

optionally, the Fe source is selected from Fe (NO)₃)₃、Fe₂O₃At least one of;

optionally, the Ce source is selected from Ce (NO)₃)₃、CeO₂At least one of;

optionally, the source of Cr is selected from Cr (NO)₃)₃、Cr₂O₃At least one of (1).

Optionally, the molar ratio of the Tm element, the Ce element, the Fe element, and the Cr element in the mixed solution is:

Tm：Ce：Fe：Cr＝3-x：x：5-y：y

wherein x is more than or equal to 0 and less than or equal to 0.12, and y is more than or equal to 0 and less than or equal to 0.3.

Optionally, the reaction conditions are:

the reaction temperature is 70-90 ℃, and the reaction time is 2-4 h;

alternatively, the reaction temperature is 80 ℃ and the reaction time is 3 h.

Optionally, pre-sintering is performed prior to said sintering.

Optionally, the conditions of the pre-sintering are:

raising the temperature to a pre-sintering temperature of 300-350 ℃ at a heating rate of 1-4 ℃/min, and keeping the temperature for 30-60 min.

Optionally, the conditions of the sintering are: raising the temperature from the pre-sintering temperature to 1150-1250 ℃ at a temperature raising speed of 1-4 ℃/min, and preserving the heat for 2-4 hours.

The invention provides a preparation method of a TmIG-doped ferrite crystal material, which is characterized by comprising the following steps of:

1) selecting Tm (NO) as raw material₃)₃·6H₂O、Fe(NO₃)₃·9H₂O, citric acid, Ce (NO)₃)₃·6H₂Taking O as raw material, proportioning according to chemical formula, accurately weighing each raw material component, and firstly, Tm (NO)₃)₃·6H₂O、Fe(NO₃)₃·9H₂O、Ce(NO₃)₃·6H₂Diluting O in deionized water, adding citric acid into the mixed solution, and mechanically stirring uniformly to obtain a mixed solution;

2) adjusting the pH value: by NH₃·H₂Adjusting the pH value by O, and adjusting the pH value of the mother liquor to 2;

3) gelling: heating in 80 deg.C constant temperature water bath, evaporating water to make the mixed solution form sol, and further forming gel;

4) and (3) drying: putting the gel into a drying oven, and drying for 24h at 90 ℃;

5) grinding: grinding the dried gel precursor, and sieving with a 180-mesh sieve to obtain fine powder;

6) and (3) sintering: heating from room temperature to 350 deg.C at a heating rate of 3 deg.C/min, and holding for 30 min. Then the temperature rising speed of 3 ℃/min is increased from 350 to 1200 ℃, the heat preservation time is 3 hours, and then the temperature is reduced to the room temperature at 3 ℃/min.

According to a further aspect of the present application there is provided the use of the above-described doped TmIG ferrite material, the doped TmIG ferrite material prepared according to the above-described method, in a magneto-optical isolator.

Benefits of the present application include, but are not limited to:

the method has the advantages of simple process, short production period and easy control of the reaction process. The adjustment and control of the average particle size of the TmIG nano particles can be realized by adjusting various parameters of the sol-gel process, and the prepared nano particles have better particle size distribution, namely the nano particles with better particle size uniformity, and the prepared nano particles have good comprehensive magnetic property.

Drawings

FIG. 1 shows a flow chart of a sol-gel process for preparing a doped TmIG ferrite crystal material according to example 2.

FIG. 2 shows a graph of the saturation magnetization for various amounts of doped TmIG ferrite crystal materials (samples 1#, 2#, 4#, 9 #).

FIG. 3 shows XRD patterns of powders of doped TmIG ferrite material (samples 1#, 2#, 4#, 9#) with different doping levels.

FIG. 4 shows Tm of example 1₃Fe₅O₁₂SEM image of (d).

FIG. 5 shows Tm of example 4_2.96Ce_0.04Fe₅O₁₂SEM image of (d).

Detailed Description

The present invention will be described in more detail with reference to the following embodiments and the accompanying drawings, but the present invention is not limited to the following embodiments.

Unless otherwise specified, all materials and reagents used in the present application were purchased commercially and used as received without treatment, and the equipment used was the manufacturer's recommended protocol and parameters.

In the examples of the present application, the analysis method is as follows:

XRD of the crystalline material sample powder was measured by Miniflex600 under the conditions of an angle range of 10-80 °, an angular interval of 0.02 °, and a step scan at a scan speed of: 10 °/min.

The saturation magnetization of the crystal material sample is tested by an MPMS (SQUID) XL-7 superconducting interference Quantum instrument of Quantum Design company in the United states, and the testing conditions are in a range of room temperature and plus or minus 2T.

The appearance of the crystal material sample is transmitted by a Japanese Hitachi cold field S4800, the voltage is 10.0KV, the working distance is 9.6mm, the multiple is 5000 times, and the scale is 10 um.

The particle size distribution of the crystal material sample is calculated by the Sherle formula