阅读说明：本技术 一种电磁性能不合格的石榴石微波多晶铁氧体材料的处理方法 (Processing method of garnet microwave polycrystalline ferrite material with unqualified electromagnetic performance ) 是由 杨菲 任仕晶 廖杨 谢斌 何强 罗建成 于 2021-08-23 设计创作，主要内容包括：本发明公开了一种电磁性能不合格的石榴石微波多晶铁氧体材料的处理方法,属于磁性材料技术领域,经过配方计算后,在电磁性能不合格的粉料中加入质量比例不低于20%的氧化物原材料,然后依次通过一次球磨、预烧、二次球磨、造粒、成型、烧结,得到电磁性能合格的材料；本发明的方法能够将电磁性能不合格的材料制备成性能达标并可继续使用的材料,节约制造成本的同时,可以很好地保护环境。(The invention discloses a processing method of garnet microwave polycrystalline ferrite materials with unqualified electromagnetic properties, which belongs to the technical field of magnetic materials, wherein oxide raw materials with the mass proportion not less than 20 percent are added into powder with unqualified electromagnetic properties after formula calculation, and then the materials with qualified electromagnetic properties are obtained by sequentially carrying out primary ball milling, presintering, secondary ball milling, granulation, molding and sintering; the method can prepare the material with unqualified electromagnetic property into the material with qualified performance and capable of being used continuously, saves the manufacturing cost and can well protect the environment.)

1. A processing method of garnet microwave polycrystalline ferrite materials with unqualified electromagnetic properties is characterized by comprising the following steps: after the formula calculation, adding an oxide raw material with the mass ratio not less than 20% into the powder with unqualified electromagnetic performance, and then sequentially performing primary ball milling, presintering, secondary ball milling, granulation, molding and sintering to obtain the material with qualified electromagnetic performance.

2. The method of claim 1, wherein the garnet microwave polycrystalline ferrite material with unqualified electromagnetic properties comprises the following steps: the purity of the oxide raw material is analytically pure or higher.

3. The method of claim 1, wherein the garnet microwave polycrystalline ferrite material with unqualified electromagnetic properties comprises the following steps: the element composition of the oxide raw material is the same as that of the powder with unqualified electromagnetic performance, or elements which are not contained in the powder with unqualified electromagnetic performance are additionally added into the oxide raw material.

Technical Field

The invention relates to the technical field of magnetic materials, in particular to a processing method of garnet microwave polycrystalline ferrite materials with unqualified electromagnetic properties.

Background

The microwave ferrite material is a key core functional material of a ferrite device and determines the power capacity, temperature performance, insertion loss and the like of the device. Garnet microwavePolycrystalline ferrite material (R)₃Fe₅O₁₂) Has very narrow ferromagnetic resonance line width Delta H and low dielectric loss tan delta_εAnd small magnetocrystalline anisotropy, which currently dominates microwave ferrite device applications.

The electromagnetic properties of the microwave ferrite material mainly comprise intrinsic properties and extrinsic properties, the saturation magnetization intensity 4 π Ms and the Curie temperature Tc are intrinsic parameters of the material, and depend on the number and distribution of magnetic cations on each sub-lattice of the material, and the dielectric loss tan δ_εFerromagnetic resonance deltaH and the like are not only related to chemical components and crystal structures thereof, but also have close relationship with density, grain size, porosity and distribution of the density, the grain size, the porosity and the porosity in grains and among grains, and are structure sensitive quantities of material microstructures; and the value determines the loss of the device. Therefore, in practical applications, the saturation magnetization of 4 π Ms and the dielectric loss of tan δ are mainly used for the formulation-specific materials_εAnd judging whether the material performance is qualified or not by ferromagnetic resonance delta H.

At present, a preparation method of garnet microwave polycrystalline ferrite materials generally comprises the steps of primary ball milling → presintering → secondary ball milling → granulating → molding → sintering → testing and the like, wherein for powder subjected to secondary ball milling, because the powder cannot be directly subjected to performance judgment, for the powder subjected to secondary ball milling, a part of powder samples need to be selected for performance testing after molding and sintering, and if the performance is not qualified, the batch of powder is judged to be unqualified, that is, if the test is not qualified, the batch of powder is judged to be waste.

At present, the waste materials with unqualified electromagnetic performance can cause the performance of devices to be over-limit, so the current treatment method can only carry out scrap treatment. The scrapped powder cannot be recycled, and the powder containing various metal oxides cannot be discharged and buried, so that the powder can only be stored in a warehouse of a manufacturer, and the cost and pressure of the manufacturer are increased.

Namely, as an electronic functional material, the microwave polycrystalline ferrite material has no maintainability, cannot be used as a material with unqualified performance, and is only scrapped. The microwave ferrite material is composed of various oxides, and the scrapped powder cannot be recycled, so that the cost pressure and the environmental protection pressure are caused.

Disclosure of Invention

The invention aims to provide a processing method of garnet microwave polycrystalline ferrite materials with unqualified electromagnetic properties so as to solve the problems.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a processing method of garnet microwave polycrystalline ferrite materials with unqualified electromagnetic properties comprises the steps of adding oxide raw materials with the mass proportion of not less than 20wt% into powder with unqualified electromagnetic properties after formula calculation, and then sequentially carrying out primary ball milling, presintering, secondary ball milling, granulation, molding and sintering to obtain the materials with qualified electromagnetic properties.

The formula calculation process comprises the following steps: the required mass of each element is calculated according to the formula molecular formula, the content of the element substituted in the waste is calculated according to the unqualified waste molecular formula and the mass ratio, and the difference between the unqualified waste molecular formula and the unqualified waste molecular formula is the mass of each element in the newly added raw material. For example, Y_2.8Ca_0.2Sn_0.2Fe_4.8-δO₁₂In the molecular formula, the mass of required Y, Ca, Sn and Fe is calculated, then Y, Fe mass substituted by 70wt% of waste is calculated, and the rest is the raw material which needs to be newly added.

The inventor proves through a large number of experiments that: the performance transformation of unqualified powder can be completed by adding new raw materials and starting preparation to obtain qualified materials; except that if the added oxide feed does not change the formula (i.e., the same as the off-spec powder formulation), a higher proportion of fresh feed material needs to be added, thereby diluting the waste to some extent.

Regarding the proportion of the newly added oxide, the higher the proportion of the newly added oxide, the better improvement is certainly achieved, and the inventors have proved through a large number of experiments that the addition proportion reaches 20%, and the problem of "scrap repair" can be basically solved.

As a preferred technical scheme: the purity of the oxide raw material is analytically pure or higher.

As a preferred technical scheme: the element composition of the oxide raw material is the same as that of the powder with unqualified electromagnetic performance, or elements which are not contained in the powder with unqualified electromagnetic performance are additionally added into the oxide raw material.

That is, the formula of the oxide starting material added must cover all elements in the "off-magnetic performance frit" formula, i.e., the type of element in the new formula is greater than or equal to all elements in the "off-magnetic performance frit" formula.

Compared with the prior art, the invention has the advantages that: the invention solves the difficult problem that the garnet ferrite material can not be maintained, adds a proper amount of raw material oxide which is the same as or different from the waste material into the waste material (semi-finished powder with unqualified performance), and prepares the material with unqualified electromagnetic performance into the material with qualified performance and capable of being continuously used by an oxide wet process, thereby saving the manufacturing cost, including saving the material cost, the labor cost, the equipment use cost and the fertilizer storage cost of the original scrapping treatment mode, and also protecting the environment well.

Detailed Description

The invention will be further illustrated with reference to example 1.

Example 1

Has a chemical formula of Y₃Fe_5-δO₁₂(delta is the iron deficiency, delta is more than or equal to 0.02 and less than or equal to 0.2) the electromagnetic performance test results of the garnet microwave polycrystalline ferrite material are shown in Table 1, the material with unqualified electromagnetic performance is judged, and the semi-finished powder is treated as an unqualified semi-finished product.

TABLE 1Y₃Fe_5-δO₁₂Electromagnetic property of material

The unqualified semi-finished product is subjected to maintenance treatment according to the following method:

according to the same formula Y as "waste₃Fe_5-δO₁₂(delta is the iron deficiency, delta is more than or equal to 0.02 and less than or equal to 0.2), 50 weight percent of waste is weighed, and analytically pure Y₂O₃22.95 wt.% raw material, analytically pure Fe₂O₃27.05wt% of raw materials, then carrying out primary wet ball milling on the waste materials and other raw materials for 4 hours, uniformly mixing, and drying; presintering at 1250 ℃, and preserving heat for 5 hours; carrying out secondary wet ball milling for 6 hours, drying, adding 9wt% of polyvinyl alcohol for granulation, sintering at 1430 ℃ after molding, and preserving heat for 6 hours; and finally, performing performance parameter testing. The tested performance is shown in Table 2, and the electromagnetic performance of the material treated by the maintenance meets the corresponding requirement, and the material is qualified powder.

TABLE 2 electromagnetic Properties of the "repaired" Material

Example 2

Has a chemical formula of Y₃Fe_5-δO₁₂(delta is the iron deficiency, delta is more than or equal to 0.02 and less than or equal to 0.2) the electromagnetic performance test results of the garnet microwave polycrystalline ferrite material are shown in Table 1, the material with unqualified electromagnetic performance is judged, and the semi-finished powder is treated as an unqualified semi-finished product.

It is subjected to a "repair" treatment according to the following method:

according to formula Y different from "waste_2.8Ca_0.2Sn_0.2Fe_4.8-δO₁₂(delta is the iron deficiency, delta is more than or equal to 0.02 and less than or equal to 0.2), 80 weight percent of waste is weighed, and analytically pure Y₂O₃Raw material 5.24wt%, analytically pure Fe₂O₃Raw material 7.95wt%, analytically pure CaCO₃Raw material 2.73wt%, analytically pure SnO₂4.08wt% of raw materials, then carrying out primary wet ball milling on the waste materials and the weighed raw materials for 4 hours, uniformly mixing the mixture and drying the mixture; presintering at 1220 ℃, and preserving heat for 5 hours; then the mixture is dried after being ball milled for 6 hours by a secondary wet method, and 9 weight percent of the mixture is addedGranulating polyvinyl alcohol, sintering at 1420 ℃ after molding, and preserving heat for 6 hours; and finally, performing performance parameter testing. The tested performance is shown in Table 3, and the electromagnetic performance of the material treated by the maintenance meets the corresponding requirement, and the material is qualified powder.

TABLE 3 electromagnetic Properties of the "repaired" Material

Example 3

Has a chemical formula of Y₃Fe_5-δO₁₂(delta is the iron deficiency, delta is more than or equal to 0.02 and less than or equal to 0.2) the electromagnetic performance test results of the garnet microwave polycrystalline ferrite material are shown in Table 1, the material with unqualified electromagnetic performance is judged, and the semi-finished powder is treated as an unqualified semi-finished product.

It is subjected to a "repair" treatment according to the following method:

according to formula Y different from "waste_2.8Ca_0.2Sn_0.2Fe_4.8-δO₁₂(delta is the iron deficiency, delta is more than or equal to 0.02 and less than or equal to 0.2), 85wt% of waste is weighed, and analytically pure Y₂O₃Raw material 2.92 wt%, analytically pure Fe₂O₃Raw material 5.24wt%, analytically pure CaCO₃Raw material 2.74wt%, analytically pure SnO₂4.1wt% of raw materials, then carrying out primary wet ball milling on the waste and the weighed raw materials for 4 hours, uniformly mixing, and drying; presintering at 1220 ℃, and preserving heat for 5 hours; carrying out secondary wet ball milling for 6 hours, drying, adding 9wt% of polyvinyl alcohol for granulation, sintering at 1420 ℃ after molding, and keeping the temperature for 6 hours; and finally, performing performance parameter testing.

The tested performance is shown in table 4, and the material treated by the maintenance process has improved electromagnetic performance due to less new raw materials, but the electromagnetic performance still does not meet the corresponding requirements, and the material is unqualified powder.

TABLE 4 electromagnetic Properties of the "repaired" Material

Example 4

Has a chemical formula of Y_2.5Gd_0.5Al_0.12Fe_4.88-δO₁₂(delta is the iron deficiency, delta is more than or equal to 0.02 and less than or equal to 0.2) the electromagnetic performance test results of the garnet microwave polycrystalline ferrite material are shown in Table 5, the material with unqualified electromagnetic performance is judged, and the semi-finished powder is treated as an unqualified semi-finished product.

TABLE 5Y_2.5Gd_0.5Al_0.12Fe_4.88-δO₁₂Electromagnetic property of material

The unqualified semi-finished product is subjected to maintenance treatment according to the following method:

according to formula Y different from "waste_2.5Gd_0.5In_0.15Al_0.18Fe_4.67-δO₁₂(delta is the iron deficiency, delta is more than or equal to 0.02 and less than or equal to 0.2), 60 weight percent of waste is weighed, and analytically pure Y₂O₃14.37wt% raw material, analytically pure Fe₂O₃Raw material 17.23wt%, analytically pure Gd₂O₃Raw material 4.62 wt%, analytically pure In₂O₃Raw material 2.69 wt%, analytically pure Al (OH)₃1.09 wt% of raw materials, then carrying out primary wet ball milling on the waste and other raw materials for 4 hours, uniformly mixing, and drying; presintering at 1250 ℃, and preserving heat for 5 hours; then carrying out secondary wet ball milling for 6 hours, drying, adding 9wt% of polyvinyl alcohol for granulation, sintering at 1440 ℃ after molding, and keeping the temperature for 6 hours; and finally, performing performance parameter testing. The tested performance is shown in Table 6, and the electromagnetic performance of the material treated by the maintenance meets the corresponding requirement, and the material is qualified powder.

TABLE 6 electromagnetic Properties of the "repaired" Material

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.