CN110668817A - Sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature and preparation method thereof - Google Patents

Sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature and preparation method thereof Download PDF

Info

Publication number
CN110668817A
CN110668817A CN201911052052.2A CN201911052052A CN110668817A CN 110668817 A CN110668817 A CN 110668817A CN 201911052052 A CN201911052052 A CN 201911052052A CN 110668817 A CN110668817 A CN 110668817A
Authority
CN
China
Prior art keywords
ceramic material
moo
microwave dielectric
dielectric ceramic
based composite
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.)
Pending
Application number
CN201911052052.2A
Other languages
Chinese (zh)
Inventor
周迪
郝澍钊
郭欢欢
吴芳芳
李文艺
李睿韬
任佳佳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Jiaotong University
Original Assignee
Xian Jiaotong University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Xian Jiaotong University filed Critical Xian Jiaotong University
Priority to CN201911052052.2A priority Critical patent/CN110668817A/en
Publication of CN110668817A publication Critical patent/CN110668817A/en
Pending legal-status Critical Current

Links

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
    • C04B35/495—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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • 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
    • 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
    • C04B35/64—Burning or sintering processes
    • 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
    • C04B2235/3201—Alkali metal oxides 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3256—Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
    • 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
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Insulating Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention discloses an ultralow temperature sintered sodium-based composite microwave dielectric ceramic material and a preparation method thereof, wherein the composition expression of the ceramic material is x (Na)0.5Bi0.5)MoO4－(1‑x)Na2MoO4Wherein x is more than or equal to 0.6 and less than or equal to 0.8, the ceramic material can be obtained by sintering at low temperature, can be applied to LTCC technology, and has the advantages of simple preparation method, low cost and higher safety performance.

Description

Sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature and preparation method thereof
Technical Field
The invention belongs to the technical field of electronic ceramics, relates to a microwave dielectric ceramic material and a preparation method thereof, and particularly relates to an ultralow-temperature sintered sodium-based composite microwave dielectric ceramic material and a preparation method thereof.
Background
Rapid wireless communication field in recent yearsThe development of microwave technology equipment puts higher requirements on performance and size, high integration, microminiaturization and wider development towards civil use, and the series of actual requirements enable large-scale research work on dielectric materials to be started internationally. With the wide application of Low Temperature Co-fired Ceramics (LTCC) technology in recent years, high dielectric constant (epsilon) is sought, prepared and researchedr>10) Low loss (Qf)>5000GHz), low temperature coefficient of resonance frequency (TCF is approximately equal to 0 ppm/DEG C), lower sintering temperature (lower than the melting point of common metals such as Ag, Cu, Au and Al), low cost (no or little precious metal), and environmental protection (at least no lead, no or little toxic raw materials) become the hot point of research of people.
Since the seventies of the last century, the development of microwave dielectric ceramics has been going on for nearly forty years, and according to the incomplete statistics in the literature, at least hundreds of systems and tens of thousands of ceramics with good microwave dielectric properties have been developed so far. However, the higher sintering temperature (not less than 1000 ℃) is a common property of most microwave dielectric ceramics. For example, the following systems of comparative interest, Al, having a low dielectric constant2O3-TiO2、BaO-(Mg,Zn)O-(Ta,Nb)2O5、Li2O-Nb2O5-TiO2、Ba2Ti9O20And A (B)1B2)O3A composite perovskite structure system. In order to make it applicable to the LTCC field, the sintering temperature is first lowered. The commonly used methods for lowering the sintering temperature of ceramics can be classified into three categories: 1. the method for optimizing the raw material powder is that the particle size of the required powder is reduced (less than 500nm) by a physical or chemical preparation method, and then the uniform powder is sintered; 2. addition of sintering aids, e.g. low-melting oxides (MoO)3、Bi2O3、V2O5、B2O3Etc.) or a low softening point glass phase. 3. The sintering process is improved, and a novel sintering mode is adopted to enable the ceramic to be quickly and compactly formed. Disadvantage of the first methodThe points are that: the preparation difficulty of the powder with small particle size is higher, a high-energy ball milling mode is generally adopted in a physical method, and the mode of hydrothermal, sol-gel and the like is commonly used in a chemical method to obtain the fine powder with uniform particle size distribution, so that the method has high cost and lower efficiency. The second method has the disadvantages that: the introduced sintering aid can cause the internal impurity phase of the ceramic to further deteriorate the microwave dielectric property of the ceramic, but the method has the most wide application in consideration of low cost and simple preparation. The third method has disadvantages in that: the novel sintering modes such as microwave sintering, point ion spark sintering and the like are basically based on experimental conditions, so that the method is difficult to convert into industrial production in a large quantity, and the limitation of the method is increased due to high manufacturing cost. In recent decades, a more effective research approach has been found, namely, the research of intrinsic low-temperature sintering temperature (C)<900 deg.c) and such material systems are generally referred to as low-fire ceramic systems.
Theoretically, the sintering temperature of oxide ceramics should be between 80% and 95% of its melting point. Considering that various atomic bonds and ionic bonds in the ceramic become extremely active when the temperature is close to the melting point, the energy flows among various particles more easily, and the particles react with each other more quickly, so that the ceramic is formed more easily. Therefore, the melting point of the oxide in the starting material also determines the sintering temperature of the ceramic to some extent. The following are melting point data for several common low melting point oxides: TeO2(733℃)、MoO3(795℃)、Bi2O3(817℃)、B2O3(450℃)、V2O5(690 ℃) and Na2CO3(851 ℃), and the like. In the above oxide system, BaTe4O9The ceramic, which has attracted the attention of researchers since being reported, has a sintering temperature of about 550 ℃, a dielectric constant of 17.5, a Qf value of 54700GHz, and a TCF of-90 ppm/c, and does not react or diffuse with Al electrodes. However TeO2The price is high and the toxicity is high, and the disadvantages determine that the method is difficult to be applied to mass production.
In summary, with the urgent demands for miniaturization, integration and high frequency of microwave communication devices from the rapid development in the field of wireless communication, the research and development of microwave dielectric ceramic materials with intrinsically low sintering temperatures are always the current research focus and emphasis. The ultra-low temperature sintering microwave dielectric ceramic material rich in low melting point oxide is a novel research hotspot promoted in the field of LTCC, and the development of the series of ceramics fundamentally solves the bottleneck of reducing the sintering temperature of the microwave dielectric ceramic material, and simultaneously can introduce an Al electrode into the LTCC process, which undoubtedly is a great revolution on the LTCC process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an ultralow-temperature sintered sodium-based composite microwave dielectric ceramic material and a preparation method thereof.
In order to achieve the purpose, the composition expression of the ultralow-temperature sintered sodium-based composite microwave dielectric ceramic material is x (Na)0.5Bi0.5)MoO4－(1-x)Na2MoO4Wherein x is more than or equal to 0.6 and less than or equal to 0.8.
The ceramic material is composed of Na+And Bi3+The ion jointly occupies A site and Mo6+The ions occupying the B position (Na)0.5Bi0.5)MoO4With Na+Ions occupy A site, Mo6+Na having ions occupying the B position2MoO4And (4) forming.
The microwave dielectric constant epsilon of the ceramic materialr16.2 to 25.1, a temperature coefficient TCF of resonance frequency of-20 ppm/DEG C to +15 ppm/DEG C, and a high quality factor Qf of 9100GHz to 10280 GHz.
The preparation method of the sodium-based composite microwave dielectric ceramic material sintered at the ultralow temperature comprises the following steps of:
1) expressed as x (Na) according to the composition expression0.5Bi0.5)MoO4－(1-x)Na2MoO4Weighing Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying and sieving in sequence, pressing into blocks, and then preserving heat at 480-500 ℃ to obtain sample baked blocks;
3) crushing, ball-milling and drying the sample baked block obtained in the step 2), and then preserving heat at 480-500 ℃ to obtain a secondary sample baked block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then performing compression molding, and then sintering at 540-620 ℃ to obtain the ultralow-temperature sintering composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 4-6 h.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 120-150 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 4-6 h;
the heat preservation time in the step 3) is 4-6 h;
the sintering time in the step 4) is 2-4 h.
The invention has the following beneficial effects:
the sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature and the preparation method thereof use low-melting-point oxide Bi during specific operation2O3And MoO3And Na2CO3As a main element, the sodium-based composite microwave dielectric ceramic material can be sintered at low temperature. The invention is based on the principles of crystal chemistry and dielectric correlation, and uses ABO4Based on the structure of tetragonal scheelite, adopts Na in a two-phase composite form+、Bi3+The combined ions occupy the A site and Na+The ions occupy the A position independently, and high-valence Mo is used6+The ions occupy the B site, and on the premise of no addition of a sintering aid, a novel compact functional ceramic with good microwave dielectric property is sintered at a lower temperature range (540-620 ℃), and the ceramic material can be used as a dielectric material for a chip microwave dielectric resonator, a chip microwave dielectric filter, a low temperature co-fired ceramic system (LTCC), a dielectric microwave antenna and the like.
Detailed Description
The present invention is described in further detail below with reference to examples:
example one
The composition expression of the sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature is x (Na)0.5Bi0.5)MoO4－(1-x)Na2MoO4Wherein x is 0.6.
The preparation method of the sodium-based composite microwave dielectric ceramic material sintered at the ultralow temperature comprises the following steps of:
1) expressed as x (Na) according to the composition expression0.5Bi0.5)MoO4－(1-x)Na2MoO4Weighing Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying and sieving in sequence, pressing into blocks, and then preserving heat at 480 ℃ to obtain sample baked blocks;
3) crushing, ball-milling and drying the sample baked block obtained in the step 2), and then preserving heat at 480 ℃ to obtain a secondary sample baked block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then performing compression molding, and then sintering at 540-580 ℃ to obtain the ultralow-temperature sintering composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 6 hours.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 120 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 4 hours;
the heat preservation time in the step 3) is 4 hours;
the sintering time in the step 4) is 4 h.
The performance of the group of ceramic materials reaches the following indexes:
sintering the mixture into porcelain in air at 560-600 ℃, and obtaining the dielectric property epsilon under microwaver16.2(8.7GHz), quality factor Q1100, Qf 9100GHz, and temperature coefficient of resonance frequency TCF-20 ppm/deg.c (25-85 deg.c) under microwave.
Example two
The composition expression of the sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature is x (Na)0.5Bi0.5)MoO4－(1-x)Na2MoO4Wherein x is 0.7.
The preparation method of the sodium-based composite microwave dielectric ceramic material sintered at the ultralow temperature comprises the following steps of:
1) expressed as x (Na) according to the composition expression0.5Bi0.5)MoO4－(1-x)Na2MoO4Weighing Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying and sieving in sequence, pressing into blocks, and then preserving heat at 480 ℃ to obtain sample baked blocks;
3) crushing, ball-milling and drying the sample baked block obtained in the step 2), and then preserving heat at 480 ℃ to obtain a secondary sample baked block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then performing compression molding, and then sintering at 560-600 ℃ to obtain the ultralow-temperature sintering composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 4 h.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 120-150 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 4 hours;
the heat preservation time in the step 3) is 4 hours;
the sintering time in the step 4) is 3 h.
The performance of the group of ceramic materials reaches the following indexes:
sintering the mixture into porcelain in air at 560-600 ℃, and obtaining the dielectric property epsilon under microwaver20.7(7.9GHz), 1240 for the quality factor Q, 9700GHz for Qf, and-6 ppm/deg.c (25-85 deg.c) for the temperature coefficient of resonance frequency TCF under microwave.
EXAMPLE III
The composition expression of the sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature is x (Na)0.5Bi0.5)MoO4－(1-x)Na2MoO4Wherein x is 0.7.
The preparation method of the sodium-based composite microwave dielectric ceramic material sintered at the ultralow temperature comprises the following steps of:
1) expressed as x (Na) according to the composition expression0.5Bi0.5)MoO4－(1-x)Na2MoO4Weighing Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball milling, drying, sieving, pressing into block, and feeding at 500 deg.CCarrying out heat preservation to obtain a sample burning block;
3) crushing, ball-milling and drying the sample fired block obtained in the step 2), and then carrying out heat preservation at 500 ℃ to obtain a secondary sample fired block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then performing compression molding, and then sintering at 580-620 ℃ to obtain the ultralow-temperature sintering composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 6 hours.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 150 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 6 hours;
the heat preservation time in the step 3) is 6 hours;
the sintering time in the step 4) is 2 h.
The performance of the group of ceramic materials reaches the following indexes:
sintering the ceramic in air at 580-620 ℃ to form the dielectric property epsilon under microwaver25.3(7.4GHz), 1420, 10280GHz, and +15 ppm/deg.c (25-85 deg.c) of temperature coefficient of resonance frequency TCF under microwave.
Example four
The composition expression of the sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature is x (Na)0.5Bi0.5)MoO4－(1-x)Na2MoO4Wherein x is 0.6.
The preparation method of the sodium-based composite microwave dielectric ceramic material sintered at the ultralow temperature comprises the following steps of:
1) expressed as x (Na) according to the composition expression0.5Bi0.5)MoO4－(1-x)Na2MoO4Weighing Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying and sieving in sequence, pressing into blocks, and then preserving heat at 480 ℃ to obtain sample baked blocks;
3) crushing, ball-milling and drying the sample baked block obtained in the step 2), and then preserving heat at 480 ℃ to obtain a secondary sample baked block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then performing compression molding, and then sintering at 540 ℃ to obtain the ultralow-temperature sintered composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 4 h.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 120 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 4 hours;
the heat preservation time in the step 3) is 4 hours;
the sintering time in the step 4) is 2 h.
EXAMPLE five
The composition expression of the sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature is x (Na)0.5Bi0.5)MoO4－(1-x)Na2MoO4Wherein x is 0.8.
The preparation method of the sodium-based composite microwave dielectric ceramic material sintered at the ultralow temperature comprises the following steps of:
1) expressed as x (Na) according to the composition expression0.5Bi0.5)MoO4－(1-x)Na2MoO4Weighing Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying and sieving in sequence, pressing into blocks, and then preserving heat at 500 ℃ to obtain sample burning blocks;
3) crushing, ball-milling and drying the sample fired block obtained in the step 2), and then carrying out heat preservation at 500 ℃ to obtain a secondary sample fired block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then performing compression molding, and then sintering at 620 ℃ to obtain the ultralow-temperature sintered composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 6 hours.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 150 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 6 hours;
the heat preservation time in the step 3) is 6 hours;
the sintering time in the step 4) is 4 h.
EXAMPLE six
The composition expression of the sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature is x (Na)0.5Bi0.5)MoO4－(1-x)Na2MoO4Wherein x is 0.7.
The preparation method of the sodium-based composite microwave dielectric ceramic material sintered at the ultralow temperature comprises the following steps of:
1) expressed as x (Na) according to the composition expression0.5Bi0.5)MoO4－(1-x)Na2MoO4Weighing Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying and sieving in sequence, pressing into blocks, and then preserving heat at 490 ℃ to obtain sample burning blocks;
3) crushing, ball-milling and drying the sample fired block obtained in the step 2), and then carrying out heat preservation at 490 ℃ to obtain a secondary sample fired block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then performing compression molding, and then sintering at 580 ℃ to obtain the ultralow-temperature sintered composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 5 h.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 135 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 5 hours;
the heat preservation time in the step 3) is 5 hours;
the sintering time in the step 4) is 3 h.
EXAMPLE seven
The composition expression of the sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature is x (Na)0.5Bi0.5)MoO4－(1-x)Na2MoO4Wherein x is 0.8.
The preparation method of the sodium-based composite microwave dielectric ceramic material sintered at the ultralow temperature comprises the following steps of:
1) expressed as x (Na) according to the composition expression0.5Bi0.5)MoO4－(1-x)Na2MoO4Weighing Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying and sieving in sequence, pressing into blocks, and then preserving heat at 485 ℃ to obtain sample burning blocks;
3) crushing, ball-milling and drying the sample fired block obtained in the step 2), and then carrying out heat preservation at 485 ℃ to obtain a secondary sample fired block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then performing compression molding, and then sintering at 600 ℃ to obtain the ultralow-temperature sintered composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 4.5 h.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 125 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 4.5 h;
the heat preservation time in the step 3) is 4.5 h;
the sintering time in the step 4) is 2.5 h.
Example eight
The composition expression of the sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature is x (Na)0.5Bi0.5)MoO4－(1-x)Na2MoO4Wherein x is 0.65.
The preparation method of the sodium-based composite microwave dielectric ceramic material sintered at the ultralow temperature comprises the following steps of:
1) expressed as x (Na) according to the composition expression0.5Bi0.5)MoO4－(1-x)Na2MoO4Weighing Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying, sieving, pressing into blocks, and keeping the temperature at 495 ℃ to obtain a sample baked block;
3) crushing, ball-milling and drying the sample baked block obtained in the step 2), and then preserving heat at 495 ℃ to obtain a secondary sample baked block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then performing compression molding, and then sintering at 610 ℃ to obtain the ultralow-temperature sintered composite microwave dielectric ceramic material.
The ball milling time in the step 2), the step 3) and the step 4) is 5.5 h.
The temperature in the drying process in the step 2), the step 3) and the step 4) is 140 ℃.
The screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
The sintering in step 4) is performed in an air atmosphere.
The pressing in the step 4) is formed into a cylindrical shape.
The heat preservation time in the step 2) is 5.5 h;
the heat preservation time in the step 3) is 5.5 h;
the sintering time in the step 4) is 3.5 h.
The ceramic material is composed of Na+And Bi3+The ion jointly occupies A site and Mo6+The ions occupying the B position (Na)0.5Bi0.5)MoO4With Na+Ions occupy A site, Mo6+Na having ions occupying the B position2MoO4Composition is carried out; the microwave dielectric constant epsilon of the ceramic materialr16.2 to 25.1, a temperature coefficient TCF of resonance frequency of-20 ppm/DEG C to +15 ppm/DEG C, and a high quality factor Qf of 9100GHz to 10280 GHz.
The invention adopts a simple and effective solid-phase reaction sintering method, firstly, initial oxides and carbonates are mixed, raw materials are uniformly mixed through primary ball milling, the raw materials are subjected to primary reaction through a heat-preservation sintering process, the particle size of reactants is refined through secondary ball milling, the phase of a sample is uniformly dispersed through secondary heat-preservation sintering, the particle size is refined through a third ball milling method, and finally, a green blank is pressed, and a ceramic sample is prepared through a sintering process by using a high-temperature muffle furnace. By the simple and effective preparation method, the dielectric constant of the obtained ceramic sample is changed between 16.2 and 25.3 along with the components, Qf is distributed between 9100GHz and 10200GHz, the temperature coefficient of resonance frequency is adjustable between-20 and +15 ppm/DEG C, and the sintering temperature is 540-620 ℃, so that the ceramic sample is suitable for the requirements of LTCC technology and the application range of the LTCC technology is expanded.

Claims (10)

1. The sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature is characterized in that the composition expression of the ceramic material is x (Na)0.5Bi0.5)MoO4－(1-x)Na2MoO4Wherein x is more than or equal to 0.6 and less than or equal to 0.8.
2. The ultra-low temperature sintered sodium-based composite microwave dielectric ceramic material of claim 1, wherein the ceramic material is composed of Na+And Bi3+The ion jointly occupies A site and Mo6+The ions occupying the B position (Na)0.5Bi0.5)MoO4With Na+Ions occupy A site, Mo6+Na having ions occupying the B position2MoO4And (4) forming.
3. The ultra-low temperature sintered sodium-based composite microwave dielectric ceramic material as claimed in claim 1, wherein the ceramic material has a microwave dielectric constant ∈r16.2 to 25.1, a temperature coefficient TCF of resonance frequency of-20 ppm/DEG C to +15 ppm/DEG C, and a high quality factor Qf of 9100GHz to 10280 GHz.
4. The preparation method of the ultralow-temperature sintered sodium-based composite microwave dielectric ceramic material as claimed in claim 1, is characterized by comprising the following steps:
1) expressed as x (Na) according to the composition expression0.5Bi0.5)MoO4－(1-x)Na2MoO4Weighing Na2CO3、Bi2O3And MoO3；
2) Mixing Na2CO3、Bi2O3And MoO3Mixing, ball-milling, drying and sieving in sequence, pressing into blocks, and then preserving heat at 480-500 ℃ to obtain sample baked blocks;
3) crushing, ball-milling and drying the sample baked block obtained in the step 2), and then preserving heat at 480-500 ℃ to obtain a secondary sample baked block;
4) and 3) sequentially crushing, ball-milling, drying, granulating and sieving the secondary sample fired block obtained in the step 3), then performing compression molding, and then sintering at 540-620 ℃ to obtain the ultralow-temperature sintering composite microwave dielectric ceramic material.
5. The preparation method of the ultralow-temperature sintered sodium-based composite microwave dielectric ceramic material as claimed in claim 4, wherein the ball milling time in the steps 2), 3) and 4) is 4-6 h.
6. The preparation method of the ultralow-temperature sintered sodium-based composite microwave dielectric ceramic material as claimed in claim 4, wherein the temperature in the drying process in the steps 2), 3) and 4) is 120-150 ℃.
7. The preparation method of the ultralow-temperature sintered sodium-based composite microwave dielectric ceramic material as claimed in claim 4, wherein the screen used in the sieving in the step 2) is 200 meshes; the screen used in the sieving in the step 4) is a double-layer screen with 60 meshes and 120 meshes.
8. The preparation method of the ultra-low temperature sintered sodium-based composite microwave dielectric ceramic material as claimed in claim 4, wherein the sintering in the step 4) is performed in an air atmosphere.
9. The preparation method of the ultra-low temperature sintered sodium-based composite microwave dielectric ceramic material as claimed in claim 4, wherein the pressing in the step 4) is performed to press the ceramic material into a cylindrical shape.
10. The preparation method of the ultra-low temperature sintered sodium-based composite microwave dielectric ceramic material as claimed in claim 4,
the heat preservation time in the step 2) is 4-6 h;
the heat preservation time in the step 3) is 4-6 h;
the sintering time in the step 4) is 2-4 h.
CN201911052052.2A 2019-10-31 2019-10-31 Sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature and preparation method thereof Pending CN110668817A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911052052.2A CN110668817A (en) 2019-10-31 2019-10-31 Sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911052052.2A CN110668817A (en) 2019-10-31 2019-10-31 Sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature and preparation method thereof

Publications (1)

Publication Number Publication Date
CN110668817A true CN110668817A (en) 2020-01-10

Family

ID=69085219

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911052052.2A Pending CN110668817A (en) 2019-10-31 2019-10-31 Sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110668817A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113087525A (en) * 2021-03-31 2021-07-09 中国振华集团云科电子有限公司 Molybdate-based composite microwave dielectric ceramic material and preparation method thereof
CN113816736A (en) * 2021-11-11 2021-12-21 中国振华集团云科电子有限公司 Ultralow-temperature-sintered low-dielectric-loss LTCC material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002220279A (en) * 2001-01-24 2002-08-09 Sumitomo Special Metals Co Ltd Dielectric ceramic composition for microwave
CN101805186A (en) * 2010-03-24 2010-08-18 桂林理工大学 Microwave dielectric ceramic material with ultra-low sintering temperature and method for preparing same
CN103232241A (en) * 2013-04-22 2013-08-07 西安交通大学 Ultralow-temperature-sintered composite microwave dielectric ceramic material and preparation method thereof
CN107216150A (en) * 2017-06-30 2017-09-29 武汉工程大学 A kind of low-temperature co-burning ceramic material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002220279A (en) * 2001-01-24 2002-08-09 Sumitomo Special Metals Co Ltd Dielectric ceramic composition for microwave
CN101805186A (en) * 2010-03-24 2010-08-18 桂林理工大学 Microwave dielectric ceramic material with ultra-low sintering temperature and method for preparing same
CN103232241A (en) * 2013-04-22 2013-08-07 西安交通大学 Ultralow-temperature-sintered composite microwave dielectric ceramic material and preparation method thereof
CN107216150A (en) * 2017-06-30 2017-09-29 武汉工程大学 A kind of low-temperature co-burning ceramic material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GAOQUN ZHANG, ET AL.: "Ultra-low Sintering Temperature Microwave Dielectric Ceramics Based on Na2O-MoO3 Binary System", 《JOURNAL OF THE AMERICAN CERAMIC SOCIETY》 *
GAOQUN ZHANG, ET AL.: "Ultra-low temperature sintering and microwave dielectric properties of a novel temperature stable Na2Mo2O7-Na0.5Bi0.5MoO4 ceramic", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113087525A (en) * 2021-03-31 2021-07-09 中国振华集团云科电子有限公司 Molybdate-based composite microwave dielectric ceramic material and preparation method thereof
CN113087525B (en) * 2021-03-31 2023-04-18 中国振华集团云科电子有限公司 Molybdate-based composite microwave dielectric ceramic material and preparation method thereof
CN113816736A (en) * 2021-11-11 2021-12-21 中国振华集团云科电子有限公司 Ultralow-temperature-sintered low-dielectric-loss LTCC material and preparation method thereof
CN113816736B (en) * 2021-11-11 2023-02-17 中国振华集团云科电子有限公司 Ultralow-temperature-sintered low-dielectric-loss LTCC material and preparation method thereof

Similar Documents

Publication Publication Date Title
US10899669B2 (en) Boron aluminum silicate mineral material, low temperature co-fired ceramic composite material, low temperature co-fired ceramic, composite substrate and preparation methods thereof
CN108358632B (en) Ultralow-temperature sintered high-Q x f-value microwave dielectric material and preparation method thereof
US7241712B2 (en) Low-temperature sintered barium titanate microwave dielectric ceramic material
CN114349493B (en) Copper ion doped calcium silicate microwave dielectric ceramic and preparation method thereof
CN104003722A (en) Ultralow-dielectric constant microwave dielectric ceramic Li3AlV2O8 capable of being sintered at low temperature and preparation method thereof
CN110668817A (en) Sodium-based composite microwave dielectric ceramic material sintered at ultralow temperature and preparation method thereof
CN111995383A (en) Mg2-xMxSiO4-CaTiO3Composite microwave dielectric ceramic and preparation method thereof
CN115536390B (en) Transparent dielectric energy storage ceramic material and preparation method and application thereof
CN101913858B (en) Li2O-ZnO-TiO2 microwave medium ceramic material and preparation method thereof
CN103496981B (en) Low-temperature sintering temperature-stable microwave dielectric ceramic Bi14W2O27 and preparation method thereof
CN103232241B (en) Ultralow-temperature-sintered composite microwave dielectric ceramic material and preparation method thereof
CN103496973A (en) Low temperature sintered microwave dielectric ceramic BiTiNbO6 and preparation method thereof
CN110698193A (en) High-quality-factor K20 composite microwave dielectric ceramic material and preparation method thereof
CN110668818B (en) Ultralow temperature sintered composite microwave dielectric ceramic material and preparation method thereof
CN111320473B (en) Low-sintering microwave dielectric ceramic material and preparation method thereof
CN103319177B (en) Microwave dielectric ceramic Ba3WTiO8 with low-temperature sintering characteristic and preparation method thereof
CN107935584A (en) A kind of microwave dielectric ceramic materials for LTCC and preparation method thereof
CN109437901B (en) Microwave dielectric ceramic with perovskite structure and preparation method thereof
CN110950656A (en) Composite microwave dielectric ceramic and preparation method thereof
CN103496969B (en) Low-temperature sintering temperature-stable microwave dielectric ceramic Bi14WO24 and preparation method thereof
CN110372370A (en) A kind of microwave-medium ceramics and preparation method thereof
CN102173782B (en) Molybdenum-based and titanium-based temperature stabilized microwave dielectric ceramic material and preparation method thereof
CN104003721A (en) Microwave dielectric ceramic Li2W2Zn3O10 capable of being sintered at low temperature and preparation method thereof
CN103496986B (en) Low temperature sintered microwave dielectric ceramic BiCa9V7O28 and preparation method thereof
CN1974478A (en) Environment friendly ku band microwave dielectric ceramic

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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200110