CN112441830B - High-quality-factor yttrium-doped zirconia microwave dielectric ceramic material and preparation method thereof - Google Patents
High-quality-factor yttrium-doped zirconia microwave dielectric ceramic material and preparation method thereof Download PDFInfo
- Publication number
- CN112441830B CN112441830B CN201910815108.9A CN201910815108A CN112441830B CN 112441830 B CN112441830 B CN 112441830B CN 201910815108 A CN201910815108 A CN 201910815108A CN 112441830 B CN112441830 B CN 112441830B
- Authority
- CN
- China
- Prior art keywords
- yttrium
- powder
- doped zirconia
- ceramic material
- microwave dielectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to a high-quality-factor yttrium-doped zirconia microwave dielectric ceramic material and a preparation method thereof2‑x mol%Y2O3‑y wt%Al2O3‑z wt%SiO2X is more than or equal to 1.5 and less than or equal to 2.0, y is more than or equal to 0.04 and less than or equal to 0.06, and z is more than or equal to 0.001 and less than or equal to 0.002; wherein x mol% is Y2O3Y wt% is Al2O3Z wt% is SiO2The mass percentage of (A) is as follows.
Description
Technical Field
The invention relates to a high-quality-factor yttrium oxide doped zirconia microwave dielectric ceramic material and a preparation method thereof, belonging to the field of electronic component materials.
Background
The microwave dielectric ceramic material with the dielectric constant of about 30 can adapt to the development of L, S, C wave band and even X wave band communication technology, can meet the requirements of small size, light weight, integration, high reliability and low cost, and is an electronic ceramic material with important application value. Meanwhile, the microwave dielectric ceramic material also has a high quality factor, because the microwave device made of the high quality factor ceramic has lower loss and is beneficial to the precise frequency selection of the device[1]. Therefore, the dielectric constant is about 30 in the microwave frequency band, and the microwave dielectric ceramic material with high quality factor has important research value and wide application potential.
Yttria-doped tetragonal phase ZrO2The ceramic material is a typical microwave dielectric ceramic material with a dielectric constant of about 30. Undoped zirconia in generalThe material is a monoclinic phase, and can be converted into tetragonal zirconia when the sintering temperature is higher than 1170 ℃, and the volume shrinkage is accompanied by 7-9%; in the temperature reduction process, part of tetragonal phase can be converted into monoclinic phase at the temperature of 950 ℃, and the ceramic product is cracked along with 3-4% of volume expansion[2]. The addition of a proper amount of yttrium oxide can prevent the phase transformation of the zirconia ceramic in the cooling process, realize the stabilization of tetragonal phase, effectively solve the cracking problem of the ceramic and greatly improve the yield of the ceramic.
However, most of the commercial powder is based on optical or mechanical properties, the doping amount of yttrium oxide is generally higher (not less than 3 mol%), and the quality factor is generally about 200-[3]. According to Li and the like[3]Report, Y3+Non-equivalent substitution of Zr4+The ions will create oxygen vacancies. In fact, too many oxygen vacancies will further generate weakly bound electrons and holes with equivalent positive charges[3]The conductivity of the ceramic is increased, and further the conductivity loss of the ceramic is increased, so that the quality factor is greatly reduced. According to Li et al, a 6 mol% yttria doped zirconia ceramic has a Q f value of only about 200 GHz. Therefore, according to the mechanism of the non-equivalent ions, the proper reduction of the doping amount of yttrium is expected to significantly improve the Q f value of the ceramic[4]. At the same time, Y3+Average ionic polarizability with respect to Zr4 +Lower, properly reducing the yttrium doping amount is expected to improve the dielectric constant of the ceramic[5]. According to Li and other reports, the dielectric constant of the zirconia ceramic doped with 12 mol% of yttrium oxide is about 19, and the dielectric constant of the ceramic can be improved by about 15% by properly reducing the doping amount of yttrium oxide to 6 mol%. The dielectric constant of the existing yttrium-doped zirconia ceramics at the present stage is generally 18-28, but the Qxf value is only about 500GHz (@10GHz), and the application requirements of microwave devices can not be met completely.
Reference documents:
[1]M.T.Sebastian,Elsevier,UK Oxford,2008；
[2] hu xu, master academic paper, university of chinese academy of sciences, 2018;
[3] li, et al, rare metal materials and engineering, 36:623-626, 2007;
[4]A.Templeton et al.,J.Am.Ceram.Soc.,83:95-100,2000；
[5]R.Shannon,J.Appl.Phys.,73:348-366,1993.。
disclosure of Invention
In view of the defects of the microwave dielectric property of the existing yttrium-doped zirconia ceramic, the invention aims to provide an yttrium-doped zirconia microwave dielectric ceramic material with a high Q f value and a preparation method thereof.
In one aspect, the invention provides a yttrium (yttrium oxide) doped zirconia microwave dielectric ceramic material with a high quality factor, wherein the yttrium doped zirconia microwave dielectric ceramic material has a tetragonal phase structure and has a chemical composition of ZrO2-x mol％Y2O3-y wt％Al2O3-z wt％SiO2X is more than or equal to 1.5 and less than or equal to 2.0, y is more than or equal to 0.04 and less than or equal to 0.06, and z is more than or equal to 0.001 and less than or equal to 0.002; wherein x mol% is Y2O3Y wt% is Al2O3Z wt% is SiO2The mass percentage of (A) is as follows.
In the present disclosure, a substantial improvement in ceramic quality factor is achieved by appropriately reducing the amount of yttria substitution. Specifically, pure zirconia powder is directly introduced into yttria-doped zirconia powder with a molar content of 3mol% or more (for example, 3-5 mol%) to reduce the content of yttria, so that the content of oxygen vacancies and weakly bound electrons generated by non-equivalent substitution can be effectively reduced, and the quality factor of the yttria-doped zirconia ceramic is improved. At the same time, the lower yttrium content reduces the Y with lower average ionic polarizability3+The content can effectively improve the dielectric constant of the ceramic, and is expected to be applied to microwave devices such as radio frequency identification and the like.
Preferably, the Q multiplied by f value of the yttrium-doped zirconia microwave dielectric ceramic material at 5GHz is 5000-10000 GHz, the dielectric constant is 28-35, and the frequency temperature coefficient is near-100 ppm/DEG C.
In a second aspect, the invention provides a preparation method of the yttrium-doped zirconia microwave dielectric ceramic material with high quality factor, which comprises the following steps:
(1) selecting yttrium-doped zirconia powder, alumina powder and silica powder as raw materials, weighing and mixing according to the chemical composition of the yttrium-doped zirconia microwave dielectric ceramic material to obtain the raw material powder, wherein the molar content of yttrium oxide in the yttrium-doped zirconia powder is generally not less than 3mol%, and preferably 3-5 mol%;
(2) pressing and molding the obtained raw material powder to obtain a blank;
(3) and sintering the obtained blank in an air atmosphere at 1250-1350 ℃ for 2-4 hours to obtain the yttrium-doped zirconia microwave dielectric ceramic material.
Preferably, the particle size of the yttrium-doped zirconia powder is 20-80 nm; the particle size of the zirconia powder is 20-40 nm; the particle size of the alumina powder is 20-80 nm; the particle size of the silicon oxide powder is 20-80 nm.
Preferably, the mixing mode is ball milling mixing, the rotating speed of the ball milling mixing is 270-360 r/min, and the time is 24-48 hours.
Preferably, the raw material powder is sieved by a 100-mesh sieve before compression molding.
Preferably, the compression molding mode is dry compression molding or/and cold isostatic pressing, and preferably, the dry compression molding is firstly carried out, and then the cold isostatic pressing is carried out.
Preferably, the pressure of the dry pressing is 5-10 MPa; the pressure of the cold isostatic pressing is 180-200 MPa.
In a third aspect, the invention provides a method for adjusting the quality factor of an yttrium-doped zirconia microwave dielectric ceramic material, which selects yttrium-doped zirconia powder, alumina powder and silica powder as raw materials, and controls the molar ratio of yttrium oxide in the final powder to be 1.5-2.0 mol% so that the Qxf value of the yttrium-doped zirconia microwave dielectric ceramic material near 5GHz is 5000-10000 GHz; the molar content of yttrium oxide in the yttrium-doped zirconia powder is generally not less than 3 mol%. According to the basic principle of non-equivalent ion substitution, 1) according to the Clausius-Morse equation, the change rule of the dielectric constant can be clearly clarified from the change rule of parameters such as the ion polarizability of the unit cell after ion substitution, unit cell parameters and the like; 2) according to the displacement mechanism of replacing high valence ions by low valence ions, the theory points out that the reduction of the content of the low valence ions, namely the reduction of the content of yttrium can effectively reduce the content of oxygen vacancies and weakly bound electrons in the ceramic, further reduce the conductive loss of the ceramic and achieve the purpose of reducing the loss of the ceramic.
In the present disclosure, according to Y3+Substituted for Zr4+For the modulation mechanism of the quality factor, the doping amount of 3mol percent or even higher yttrium oxide in the existing yttrium-doped zirconia ceramic is reduced to 1.5-2 mol percent. In the method, the substitution amount of not less than 1.5 mol% can maintain the tetragonal phase structure of the ceramic, and the substitution amount is adjusted between 1.5 mol% and 2 mol%, so that the problem of low Q x f value caused by excessive substitution of non-equivalent ions can be solved, and the dielectric constant of the ceramic can be improved. Compared with the existing high yttrium-doped zirconia ceramic with the quality factor of only about 500GHz, the low yttrium-doped zirconia ceramic material with the Q multiplied by f value of about 5000-10000 GHz and the higher dielectric constant can be provided by the invention, and can be widely applied to the modern wireless communication industry.
Compared with the prior art, the invention has the following characteristics:
(1) the ceramic sintering process is simple. The cold isostatic pressing treatment which is simple and easy to operate is adopted to obtain a compact green body, the pre-sintering step is not needed, the direct sintering is carried out, and the sintering process is simple;
(2) compared with the existing high-yttrium-content zirconia ceramic material, the yttrium-doped zirconia ceramic has higher quality factor and dielectric constant. The microwave dielectric ceramic material provided by the invention has a Qxf value of 5000-10000 GHz (@5GHz), a relative dielectric constant of 28-35, a frequency temperature coefficient of about-100 ppm/DEG C, stable performance and capability of providing a storage material for the application requirements of modern microwave devices;
(3) the formula of the microwave dielectric ceramic material does not contain Pb, Cd and other volatile or heavy metals, and is an environment-friendly microwave dielectric ceramic material;
(4) the method of the invention has sufficient raw material supply and low price, and makes low cost of the high-performance microwave ceramic possible;
(5) in the invention, a planetary ball milling mode is adopted, and pure zirconia and zirconia with high yttrium content are mixed to realize the aim of reducing the yttrium content of the ceramic. The method is suitable for batch production, and the obtained ceramic material has stable performance.
Drawings
FIG. 1 shows a cross-sectional profile of the 1.75 mol% yttrium-doped zirconia ceramic prepared in example 1 after sintering at 1275 ℃, which shows that the cross-sectional profile is dense, the grain size is about 300nm, and no significant pores are present;
figure 2 shows the XRD phase results after 1275 deg.c sintering of the 1.75 mol% yttrium doped zirconia ceramic prepared in example 1, showing tetragonal phase.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the disclosure, aiming at the problems of low dielectric constant and high loss of the high yttrium doped zirconia ceramic, according to the basic principle of non-equivalent ion substitution, 1) according to the Clausius-Morse equation, the change rule of the dielectric constant can be clearly clarified from the change rule of parameters such as the ionic polarizability of unit cells after ion substitution, unit cell parameters and the like; 2) according to the displacement mechanism of replacing high valence ions by low valence ions, the theory points out that the reduction of the content of the low valence ions, namely the reduction of the content of yttrium can effectively reduce the content of oxygen vacancies and weakly bound electrons in the ceramic, further reduce the conductive loss of the ceramic and achieve the purpose of reducing the loss of the ceramic. Specifically, the microwave dielectric property of the yttrium-doped zirconia ceramic is regulated and controlled by controlling the content of yttrium oxide. The chemical composition of the obtained yttrium-doped zirconia microwave dielectric ceramic material with high quality factor can be ZrO2-x mol％Y2O3-y wt％Al2O3-z wt％SiO2Wherein x is a molar ratio, x is more than or equal to 1.5 and less than or equal to 2, y and z are mass percent, y is more than or equal to 0.04 and less than or equal to 0.06, and z is more than or equal to 0.001 and less than or equal to 0.002.
In the invention, the yttrium-doped zirconia microwave dielectric ceramic with high quality factor belongs to non-zero yttrium doping amount, and the final phase of the sintered ceramic can be a single tetragonal phase. By lowering Y3+The content (the yttrium content is within the range of 1.5 mol% to x mol% to 2.0 mol%), theoretically, the quantity of weakly bound electrons and oxygen vacancies generated by substitution of non-equivalent ions can be effectively reduced, the experimental observation shows that the conductivity loss is reduced, and the quality factor of the ceramic is improved. Furthermore, the lower average ionic polarizability Y is reduced3 +Experiments prove that the dielectric constant of the ceramic is effectively improved.
In the embodiment of the invention, the zirconium oxide powder is directly added into the yttrium-doped zirconium oxide ceramic, so that the reduction of the yttrium content in the ceramic is adjusted, and the performance is greatly improved. The preparation method of the yttrium-doped zirconia microwave dielectric ceramic material with high quality factor provided by the invention is exemplarily described as follows.
And (4) batching. The raw material is selected from yttrium-doped zirconia powder, a small amount of alumina powder and a small amount of silicon dioxide powder. The raw materials are all powder with nano grain diameter. Preferably, the particle size of the yttrium-doped zirconia and zirconia powder is maintained at about 20 to 80 nm. The molar content of yttrium oxide in the yttrium-doped zirconia powder is not less than 3mol%, preferably 3-5 mol%. Wherein the zirconia powder is further selected from monoclinic phase zirconia nano powder. Preferably, the particle diameters of the alumina powder and the silica powder are maintained at about 20 to 80 nm. ZrO according to chemical composition2-x mol％Y2O3-y wt％Al2O3-z wt％SiO2The raw materials are selected from yttrium-doped zirconia nano powder, pure zirconia nano powder and alumina and silicon dioxide nano powder, and the quality of each raw material is determined according to a chemical general formula to obtain mixed powder.
And (4) mixing. And further uniformly mixing the obtained mixed powder to obtain raw material powder. Wherein, the mixing mode can be ball milling mixing. Preferably, after ball milling and mixing, drying and sieving are carried out. The sieving can be 100 mesh sieving. The ball milling process is as follows: taking zirconium dioxide balls as a ball milling medium, and mixing the materials according to the following ratio: grinding balls: and ball-milling the alcohol according to the mass ratio of 1:5:1.5 to obtain a ball-milled material which is uniformly mixed. The rotation speed of ball milling and mixing can be 270-360 r/min, and the time can be 24-48 hours. As an example, the mixed powder is ball-milled to obtain a ball abrasive; and drying and sieving by a 100-mesh sieve to obtain dry raw material powder.
And (5) pressing and forming. And directly pressing and molding the obtained raw material powder to obtain a blank. The compression molding mode can be compression molding (dry compression molding) or/and cold isostatic pressing. Further, it is preferable to perform press molding first and then perform isostatic press molding. The pressure for compression molding is 5-10 MPa, and the time can be 1-2 minutes. And (3) carrying out cold isostatic pressing at the pressure of 180-200 MPa for 3-5 minutes to obtain a blank with low porosity.
And (5) sintering. And (3) placing the blank into a crucible, and sintering the blank for 2-4 hours at 1250-1350 ℃ in an air atmosphere to obtain the yttrium-doped zirconia microwave dielectric ceramic with high quality factor. The phase of the ceramic end product is tetragonal.
In the disclosure, the Q x f value of the yttrium-doped zirconia microwave dielectric ceramic material in the vicinity of 5GHz is 5000-10000 GHz, the dielectric constant is about 28-35, and the temperature coefficient of the resonance frequency is about-100 ppm/DEG C. The obtained microwave has excellent dielectric property, high dielectric constant and low loss, and can provide a new high-performance reserve ceramic material for modern microwave wireless communication systems (such as radio frequency identification technology (RFID)).
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Examples 1 to 3:
the invention provides a high-quality-factor yttrium-doped zirconia microwave dielectric ceramic material and a preparation method thereof, wherein the chemical composition of the material is ZrO2-x mol％Y2O3-y wt％Al2O3-z wt％SiO2Wherein x is a molar ratio, x is more than or equal to 1.5 and less than or equal to 2, y andz is mass percent, y is more than or equal to 0.04 and less than or equal to 0.06, and z is more than or equal to 0.001 and less than or equal to 0.002. The raw materials are selected from 3mol% yttrium-doped zirconia nano powder (20-80nm), zirconia nano powder (20-40nm), alumina powder and silicon dioxide powder (20-80 nm). Table 1 shows the mass percentage of each raw material in the embodiment in the total amount of the raw materials, the raw materials are weighed and subjected to ball milling and mixing treatment, and the ball milling rotation speed is 270-.
The method comprises the following steps:
(1) preparing materials: according to the chemical formula ZrO2-x mol％Y2O3-y wt％Al2O3-z wt％SiO2The raw materials are selected from 3mol% yttrium-doped zirconia nano powder, alumina nano powder and silicon dioxide nano powder, and various raw materials are accurately weighed according to the mass in the table 1 in the embodiment;
(2) ball milling: ball-milling the mixture obtained in the step (1), taking zirconium dioxide balls as ball-milling media, and mixing the materials: grinding balls: ball milling with alcohol in the mass ratio of 1:5:1.5 to obtain a ball milling material which is uniformly mixed, so as to obtain a ball milling material (namely mixed powder);
(3) drying and sieving: drying the ball-milled material obtained in the step (2) and sieving the dried ball-milled material with a 100-mesh sieve to obtain dried raw material powder;
(4) compression molding: putting the dried pre-sintering powder (raw material powder) obtained in the step (3) into a forming die for dry pressing forming to obtain a cylindrical green body with the diameter of 15mm and the thickness of about 7 mm;
(5) cold isostatic pressing: carrying out cold isostatic pressing treatment on the green body obtained in the step (4) at 200MPa for 5-10 minutes;
(6) and (3) sintering: and (4) placing the green body obtained in the step (5) in a crucible, and sintering for 3-5 hours at 1250-1350 ℃ in an air atmosphere to obtain the final microwave dielectric ceramic material.
Table 1 shows the preparation process of the microwave dielectric ceramic material in the examples:
. Wherein the total zirconia mass comprises: the mass of the zirconia powder + the mass of the zirconia in the yttrium-doped zirconia powder.
Table 2 shows the microwave dielectric properties of the microwave dielectric ceramic materials obtained in examples 1 to 3:
| numbering | Dielectric constant (. epsilon.)r) | Q×f(GHz) | τf(ppm/℃) |
| Example 1 | 32.9 | 5500 | -109 |
| Example 2 | 34.5 | 6200 | -102 |
| Example 3 | 34.6 | 7500 | -88 |
。
As can be seen from Table 2, compared with the existing yttrium-doped zirconia ceramic, the microwave dielectric ceramic material prepared by the detection example has a higher Q f value, a higher dielectric constant and a negative temperature coefficient of resonance frequency.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. The yttrium-doped zirconia microwave dielectric ceramic material with the high quality factor is characterized by having a tetragonal phase structure and a chemical composition of ZrO2-x mol% Y2O3-y wt%Al2O3-z wt%SiO2X is more than or equal to 1.5 and less than or equal to 2.0, y is more than or equal to 0.04 and less than or equal to 0.06, and z is more than or equal to 0.001 and less than or equal to 0.002; wherein the total mass of the powder is 100g, and x mol% is Y2O3Y wt% is Al2O3Z wt% is SiO2The balance being ZrO2(ii) a The Q multiplied by f value of the yttrium-doped zirconia microwave dielectric ceramic material at 5GHz is 5000-10000 GHz, the dielectric constant is 28-35, and the frequency temperature coefficient is near-100 ppm/DEG C.
2. The preparation method of the high-quality-factor yttrium-doped zirconia microwave dielectric ceramic material according to claim 1, comprising the following steps:
(1) selecting yttrium-doped zirconia powder, alumina powder and silicon dioxide powder as raw materials, weighing and mixing according to the chemical composition of the yttrium-doped zirconia microwave dielectric ceramic material to obtain raw material powder, wherein the molar content of yttrium oxide in the yttrium-doped zirconia powder is not lower than 3 mol%;
(2) pressing and molding the obtained raw material powder to obtain a blank;
(3) and sintering the obtained blank in an air atmosphere at 1250-1350 ℃ for 2-4 hours to obtain the yttrium-doped zirconia microwave dielectric ceramic material.
3. The preparation method according to claim 2, wherein the molar content of yttrium oxide in the yttrium-doped zirconia powder is 3-5 mol%.
4. The preparation method according to claim 2, wherein the yttrium-doped zirconia powder has a particle size of 20 to 80 nm; the particle size of the zirconia powder is 20-40 nm; the particle size of the alumina powder is 20-80 nm; the particle size of the silicon dioxide powder is 20-80 nm.
5. The preparation method of claim 2, wherein the mixing is ball milling, and the rotation speed of the ball milling is 270-360 r/min for 24-48 hours.
6. The production method according to claim 2, wherein the raw material powder is passed through a 100-mesh sieve before compression molding.
7. The method according to claim 2, wherein the compression molding is dry compression molding or/and cold isostatic pressing.
8. The method of claim 7, wherein the press-molding is performed by dry press-molding and then isostatic cool press-molding.
9. The production method according to claim 7 or 8, wherein the pressure of the dry-pressing is 5 to 10 MPa; the pressure of the cold isostatic pressing is 180-200 MPa.
10. A method for adjusting the quality factor of a yttrium-doped zirconia microwave dielectric ceramic material is characterized in that yttrium-doped zirconia powder, alumina powder and silica powder are selected as raw materials, and the Qxf value of the yttrium-doped zirconia microwave dielectric ceramic material near 5GHz is controllable between 5000 and 10000GHz by controlling the molar content of yttrium oxide in the raw materials to be between 1.5 and 2.0 mol%; the molar content of yttrium oxide in the yttrium-doped zirconia powder is not less than 3 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910815108.9A CN112441830B (en) | 2019-08-30 | 2019-08-30 | High-quality-factor yttrium-doped zirconia microwave dielectric ceramic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910815108.9A CN112441830B (en) | 2019-08-30 | 2019-08-30 | High-quality-factor yttrium-doped zirconia microwave dielectric ceramic material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112441830A CN112441830A (en) | 2021-03-05 |
| CN112441830B true CN112441830B (en) | 2021-12-07 |
Family
ID=74735104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910815108.9A Active CN112441830B (en) | 2019-08-30 | 2019-08-30 | High-quality-factor yttrium-doped zirconia microwave dielectric ceramic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112441830B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114349500A (en) * | 2022-01-21 | 2022-04-15 | 中国科学院上海硅酸盐研究所 | Medium-wave infrared transparent zirconia ceramic material and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63236212A (en) * | 1987-03-24 | 1988-10-03 | 沖電気工業株式会社 | Dielectric ceramic composition |
| CN1132730A (en) * | 1995-04-05 | 1996-10-09 | 中国科学院兰州化学物理研究所 | Sintering method of tetragonal zircite ceramic |
| CN103269999A (en) * | 2010-12-22 | 2013-08-28 | 京瓷株式会社 | DIELECTRIC CERAMIC AND DIELECTRIC FILTER PROVIDED WITH SAMe |
| CN104961461A (en) * | 2015-06-08 | 2015-10-07 | 南充三环电子有限公司 | Preparation method for zirconia ceramic rear cover of mobile phone |
| CN105198423A (en) * | 2015-08-18 | 2015-12-30 | 电子科技大学 | Sr-La-Al-based microwave dielectric ceramic material and preparation method thereof |
| CN105948723A (en) * | 2016-06-30 | 2016-09-21 | 华中科技大学 | Aluminum oxide microwave dielectric ceramic and preparation method thereof |
| CN107445612A (en) * | 2017-06-28 | 2017-12-08 | 瑞声科技(新加坡)有限公司 | Zirconia ceramics and preparation method thereof |
| CN109650871A (en) * | 2019-01-29 | 2019-04-19 | 电子科技大学 | A kind of ZnAl2O4Ceramic systems material and preparation method thereof |
-
2019
- 2019-08-30 CN CN201910815108.9A patent/CN112441830B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63236212A (en) * | 1987-03-24 | 1988-10-03 | 沖電気工業株式会社 | Dielectric ceramic composition |
| CN1132730A (en) * | 1995-04-05 | 1996-10-09 | 中国科学院兰州化学物理研究所 | Sintering method of tetragonal zircite ceramic |
| CN103269999A (en) * | 2010-12-22 | 2013-08-28 | 京瓷株式会社 | DIELECTRIC CERAMIC AND DIELECTRIC FILTER PROVIDED WITH SAMe |
| CN104961461A (en) * | 2015-06-08 | 2015-10-07 | 南充三环电子有限公司 | Preparation method for zirconia ceramic rear cover of mobile phone |
| CN105198423A (en) * | 2015-08-18 | 2015-12-30 | 电子科技大学 | Sr-La-Al-based microwave dielectric ceramic material and preparation method thereof |
| CN105948723A (en) * | 2016-06-30 | 2016-09-21 | 华中科技大学 | Aluminum oxide microwave dielectric ceramic and preparation method thereof |
| CN107445612A (en) * | 2017-06-28 | 2017-12-08 | 瑞声科技(新加坡)有限公司 | Zirconia ceramics and preparation method thereof |
| CN109650871A (en) * | 2019-01-29 | 2019-04-19 | 电子科技大学 | A kind of ZnAl2O4Ceramic systems material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "氧化钇含量对氧化锆陶瓷微波介电性能的影响";李鹏等;《稀有金属材料与工程》;20070930;第36卷;第623-626页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112441830A (en) | 2021-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2019113973A1 (en) | Dielectric ceramic material and preparation method therefor | |
| CN111592348A (en) | Low-dielectric-constant microwave dielectric ceramic with excellent temperature stability and preparation method thereof | |
| CN112851344B (en) | Microwave dielectric ceramic with medium dielectric constant and preparation method thereof | |
| CN107188557B (en) | Microwave dielectric ceramic material and preparation method thereof | |
| CN113943162B (en) | alpha-SiAlON high-entropy transparent ceramic material and preparation method thereof | |
| CN109336592B (en) | Zirconia ceramic bone implantation prosthesis and preparation method thereof | |
| WO2019169868A1 (en) | Fluorescent ceramic and preparation method therefor | |
| CN112321299A (en) | Ultra-low-loss yttrium aluminum garnet microwave dielectric ceramic material and preparation method thereof | |
| CN111285673A (en) | High-dielectric-constant microwave ferrite material, preparation method and microwave communication device | |
| Jin et al. | Microwave dielectric properties of pure YAG transparent ceramics | |
| Sayyadi-Shahraki et al. | Microwave dielectric properties of Li 2 ZnTi 3 O 8 ceramics prepared by reaction-sintering process | |
| CN104860672A (en) | High dielectric microwave ceramic dielectric material and preparation method thereof | |
| Jung et al. | Two-step sintering behavior of titanium-doped Y2O3 ceramics with monodispersed sub-micrometer powder | |
| CN111116193B (en) | Microwave ferrite material and preparation method and device thereof | |
| CN112441830B (en) | High-quality-factor yttrium-doped zirconia microwave dielectric ceramic material and preparation method thereof | |
| CN109111229A (en) | A kind of high temperature sintering microwave dielectric ceramic materials and preparation method thereof | |
| CN114163231B (en) | Lead-free pulse dielectric medium energy storage composite ceramic material and preparation method and application thereof | |
| Vozdecky et al. | Properties of tape-cast Y-substituted strontium titanate for planar anode substrates in SOFC applications | |
| CN111470864A (en) | Silicon-based temperature-stable microwave dielectric ceramic material and preparation method thereof | |
| CN111410526A (en) | Perovskite-doped barium stannate material and preparation method and application thereof | |
| Zhou et al. | Structure and microwave dielectric characteristics of lithium-excess Ca0. 6Nd0. 8/3TiO3/(Li0. 5Nd0. 5) TiO3 ceramics | |
| Qi et al. | Effects of Bi2O3–ZnO–B2O3–SiO2 glass addition on the sintering and microwave dielectric properties of ZnZrNb2O8 ceramics for LTCC applications | |
| Esposito et al. | Reactive sintering of YAG-based materials using micrometer-sized powders | |
| CN105218096B (en) | A kind of transparent YAG microwave dielectric ceramic materials of high Q and its application | |
| CN112390637A (en) | High dielectric constant microwave ferrite material without yttrium formula and preparation method and device thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |