CN106938924B - Microwave composite ceramic with small dielectric constant and high Q value and preparation method thereof - Google Patents

Microwave composite ceramic with small dielectric constant and high Q value and preparation method thereof Download PDF

Info

Publication number
CN106938924B
CN106938924B CN201710057174.5A CN201710057174A CN106938924B CN 106938924 B CN106938924 B CN 106938924B CN 201710057174 A CN201710057174 A CN 201710057174A CN 106938924 B CN106938924 B CN 106938924B
Authority
CN
China
Prior art keywords
sio
tio
dielectric constant
zno
mgo
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
Application number
CN201710057174.5A
Other languages
Chinese (zh)
Other versions
CN106938924A (en
Inventor
石锋
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.)
Shandong University of Science and Technology
Original Assignee
Shandong University of Science and Technology
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 Shandong University of Science and Technology filed Critical Shandong University of Science and Technology
Priority to CN201710057174.5A priority Critical patent/CN106938924B/en
Publication of CN106938924A publication Critical patent/CN106938924A/en
Application granted granted Critical
Publication of CN106938924B publication Critical patent/CN106938924B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C04B35/16—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 silicates other than clay
    • 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
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium 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
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • 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
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • 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
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (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 provides a microwave composite ceramic with small dielectric constant and high Q value and a preparation method thereof, and the microwave composite ceramic with small dielectric constant and high Q valueThe chemical expression of the synthetic ceramic is (1-z) [ (Mg)xZny)SiO2+x+y]‑zTiO2Wherein x is more than or equal to 0.65 and less than or equal to 0.95; y is more than or equal to 1.0 and less than or equal to 1.22; x + y is more than or equal to 1.75 and less than or equal to 1.95; z is more than or equal to 0.1 and less than or equal to 0.25; with MgO, ZnO, SiO2And TiO2As raw materials, according to MgO: ZnO: SiO 22：TiO2X (1-z): y (1-z): (1-z): z molar ratio. The ceramic has the advantages of low sintering temperature, small dielectric constant, high quality factor, small temperature coefficient of resonant frequency, continuous adjustment and capability of being used for microwave substrate materials and microwave packaging ceramics.

Description

Microwave composite ceramic with small dielectric constant and high Q value and preparation method thereof
Technical Field
The invention relates to the field of electronic materials, in particular to a microwave composite ceramic with small dielectric constant and high Q value and a preparation method thereof.
Background
The microwave dielectric ceramic refers to an information functional ceramic material which is suitable for a microwave frequency band (300 MHz-3000 GHz) and has low loss and stable temperature, is widely applied to resonators, filters, capacitors, oscillators, duplexers, dielectric waveguides, substrates, antennas and the like, is a key material of modern microwave communication technologies such as mobile communication, satellite communication, Global Positioning System (GPS), military radar, Wireless Local Area Network (WLAN), internet of things (IOT) and the like, and has important significance for miniaturization of microwave components and improving selectivity of the components. With the rapid development of microwave communication technology in recent years, microwave dielectric ceramics become a hot point of domestic and foreign research, and increasingly receive high attention from various countries. The dielectric properties of the microwave dielectric ceramic mainly comprise three parameters: dielectric constantrDielectric loss tan (quality factor Q1/tan) and resonant frequency temperature coefficient τf. The high-performance microwave dielectric ceramic is different from general functional ceramic, and it has need of meeting the requirements of large relative dielectric constant, high quality factor, resonant frequency temp. coefficient close to 0 and adjustable.
At present, modern communication is developing towards higher frequency, and the requirements for electronic components and corresponding electronic materials in the microwave high-frequency band, especially in the millimeter wave field, are increasing, especially for microwave packaging materials and microwave substrate materials, so that the development of microwave ceramics with small dielectric constant and high Q value applied to the millimeter wave frequency band has the greatest market potential.
Disclosure of Invention
One of the purposes of the invention is to provide a microwave composite ceramic with small dielectric constant and high Q value, which can be used as microwave packaging and microwave substrate materials in the millimeter wave field; the other purpose is to provide a preparation method of the microwave composite ceramic with small dielectric constant and high Q value.
One of the objects of the invention can be achieved by the following technical measures:
the chemical expression of the microwave composite ceramic with small dielectric constant and high Q value is (1-z) [ (Mg)xZny)SiO2+x+y]-zTiO2Wherein x is more than or equal to 0.65 and less than or equal to 0.95; y is more than or equal to 1.0 and less than or equal to 1.22; x + y is more than or equal to 1.75 and less than or equal to 1.95; z is more than or equal to 0.1 and less than or equal to 0.25; with MgO, ZnO, SiO2And TiO2As raw materials, according to MgO: ZnO: SiO 22：TiO2X (1-z): y (1-z): (1-z): z molar ratio.
One of the objects of the invention can also be achieved by the following technical measures:
further, the raw materials are MgO, ZnO and SiO2And TiO2And TiO2According to MgO: ZnO: SiO 22：TiO2X (1- (0.14-0.22)), (0.14-0.22) and are mixed according to a molar ratio.
Further, the microwave composite ceramic with small dielectric constant and high Q value according to claim 1, wherein the raw material is MgO, ZnO, SiO2And TiO2According to MgO: ZnO: SiO 22：TiO20.84x 0.84y 0.84:0.16 by mol ratio.
Further, the microwave composite ceramic with small dielectric constant and high Q value according to claim 1, wherein the raw material is MgO, ZnO, SiO2And TiO2According to MgO: ZnO: SiO 22：TiO2(1-z) (0.7 to 0.9) and (1-z) (1.05 to 1.15) wherein: z is mixed according to a molar ratio.
Further, the microwave composite ceramic with small dielectric constant and high Q value according to claim 1, wherein the raw material is MgO, ZnO, SiO2And TiO2According to MgO: ZnO: SiO 22：TiO20.8(1-z):1.1(1-z): z is mixed according to a molar ratio.
Further, the small dielectric constant high Q microwave composite ceramic according to claim 1, characterized in thatThe raw materials are MgO, ZnO and SiO2And TiO2According to MgO: ZnO: SiO 22：TiO20.672:0.924: 0.84:0.16 mol ratio and mixing.
The second purpose of the invention can be realized by the following technical measures:
the preparation method for preparing the microwave composite ceramic with small dielectric constant and high Q value by using the raw materials comprises the following steps:
step 1, weighing raw materials according to a raw material ratio;
step 2, putting the raw materials obtained in the step 1 into a ball mill, adding deionized water and zirconia balls, carrying out ball milling for 2-8 hours, drying the ball-milled raw materials, and sieving to obtain powder with uniform particles;
step 3, heating the powder material treated in the step 2 to 1050-1150 ℃, and preserving heat for 2-8 hours to obtain a pre-sintered material;
step 4, putting the pre-sintered material treated in the step 3 into a ball mill, adding deionized water and zirconia balls, carrying out ball milling for 2-12 hours, and finally drying the ball-milled raw materials;
step 5, adding the pre-sintered material dried in the step 4 into a polyvinyl alcohol (PVA) solution, granulating, and pressing into a green body by using a powder tablet press;
and 6, firing the blank in air at 1250-1400 ℃ for 2-12 hours to obtain the product.
The second object of the present invention can also be achieved by the following technical measures:
further, the ball milling time in the step 2 is 6 hours; the temperature rise in the step 3 is 1100 ℃, and the temperature is kept for 4 hours; the ball milling time in the step 4 is 6 hours; the green body described in step 6 was fired at 1300 ℃ for 6 hours.
Furthermore, the preparation method of the microwave composite ceramic with small dielectric constant and high Q value also comprises the step of testing the microwave dielectric property of the product by a network analyzer after the step 6, wherein the tested microwave dielectric property comprises the dielectric constantrQuality factor Qf and resonant frequency temperature coefficient tauf。
Hair brushA microwave composite ceramic with small dielectric constant and high Q value in the middle and a preparation method thereof belong to the technical field of electronic materials, and the ceramic is (Mg)xZny)SiO2+x+yIs a main crystal phase material and is made of TiO2And adjusting the temperature coefficient. High-purity ZnO, basic magnesium carbonate and SiO2And TiO2The raw materials are subjected to ball milling, drying, sieving, polyvinyl alcohol PVA granulation, molding and degumming treatment, and then are sintered in air at 1250-1400 ℃ for 2-12 hours. The microwave ceramic material prepared by the invention has small dielectric constantr(10-16), high Q value (Qf is 60000-85000), and nearly zero and adjustable frequency temperature coefficient (20 ppm/DEG C. is less than or equal to tau)f≤10ppm/℃).
Drawings
FIG. 1 is a flow chart of an embodiment of the method for preparing a microwave composite ceramic with small dielectric constant and high Q value.
Detailed Description
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below. The formulations mentioned in the following examples are non-limiting embodiments and are only used for illustrating the present invention, and those skilled in the art can select the formulations according to the concept and material selection ratio of the present invention.
Referring to fig. 1:
in step 101, MgO, ZnO, SiO2And TiO2According to the following formula of MgO: ZnO: SiO 22：TiO2X (1-z): y (1-z): (1-z): and weighing the raw materials according to the molar ratio of z.
In step 102, putting the raw materials in the step 101 into a ball mill, adding deionized water and zirconia balls, and carrying out ball milling for 2-8 hours; and drying the ball-milled raw materials at 110 ℃, and sieving the raw materials by a 40-mesh sieve to obtain powder with uniform particles.
And 103, pre-burning the sieved powder in the step 102 at 1050-1150 ℃, and preserving heat for 2-6 hours at the temperature.
In step 104, putting the pre-sintered material in step 103 into a ball milling tank, adding deionized water and zirconia balls, and carrying out ball milling for 2-12 hours; and drying the ball-milled raw materials at 110 ℃.
In step 105, adding a polyvinyl alcohol PVA solution as an adhesive for granulation after drying, sieving by a 80-mesh sieve after drying to obtain powder with uniform granules, and pressing into a green body by a powder tablet press.
And 106, firing the blank in the air at 1250-1400 ℃ for 2-12 hours to prepare the low-temperature sintered microwave composite ceramic with the small dielectric constant.
At step 107, the article is tested for microwave dielectric properties by a network analyzer. The microwave dielectric properties tested include dielectric constantrDielectric loss tan (quality factor Q1/tan) and resonant frequency temperature coefficient τf。
The ceramic has the advantages of low sintering temperature, small dielectric constant, high quality factor, small temperature coefficient of resonant frequency, continuous adjustment and capability of being used for microwave substrate materials and microwave packaging ceramics. The invention has simple process and no pollution in the process, and is a promising microwave dielectric material with small dielectric constant.
The following are several specific application examples of the present invention.
Example 1:
the chemical expression of the microwave composite ceramic with small dielectric constant and high Q value is [ (Mg)0.95Zn)SiO3.95]0.75-(TiO2)0.25The preparation method comprises the following steps:
the method for preparing the microwave composite ceramic with small dielectric constant and high Q value by using the raw materials comprises the following steps:
step 1, high-purity MgO, ZnO and SiO2And TiO2According to MgO: ZnO: SiO 22：TiO20.7125: 0.75: 0.75: weighing raw materials in a ratio of 0.25.
Step 2, putting the raw materials obtained in the step 1 into a planetary ball mill, adding deionized water and zirconia balls, carrying out ball milling for 8 hours, drying the ball-milled raw materials in an electric heating blowing type drying box at 110 ℃, and sieving the dried powder with a 40-mesh sieve to obtain powder with uniform particles;
step 3, heating the powder material treated in the step 2 to 1150 ℃, and preserving heat for 2 hours to obtain a pre-sintering material;
step 4, putting the pre-sintered material treated in the step 3 into a ball mill, adding deionized water and zirconia balls into a polyurethane ball mill, carrying out ball milling for 12 hours, and finally drying the ball-milled raw materials at 110 ℃;
step 5, adding the pre-sintered material dried in the step 4 into a polyvinyl alcohol (PVA) solution, granulating, pressing into a green body by using a powder tablet press, and pressing into a cylindrical green body with a certain size;
and 6, firing the blank in air at 1400 ℃ for 12 hours to obtain the product. After being cooled with the furnace, the dielectric property is testedr＝10；Qf＝85000，τf＝-20ppm/℃。
Example 2:
the chemical expression of the microwave composite ceramic with small dielectric constant and high Q value is [ (Mg)0.65Zn1.22)SiO3.87]0.9-(TiO2)0.10The preparation method comprises the following steps:
the method for preparing the microwave composite ceramic with small dielectric constant and high Q value by using the raw materials comprises the following steps:
step 1, high-purity MgO, ZnO and SiO2And TiO2According to MgO: ZnO: SiO 22：TiO20.585: 1.098: 0.9: weighing raw materials in a ratio of 0.1.
Step 2, putting the raw materials obtained in the step 1 into a planetary ball mill, adding deionized water and zirconia balls, carrying out ball milling for 2 hours, drying the ball-milled raw materials in an electric heating blowing type drying box at 110 ℃, and sieving the dried powder with a 40-mesh sieve to obtain powder with uniform particles;
step 3, heating the powder material treated in the step 2 to 1050 ℃, and preserving the heat for 8 hours to obtain a pre-sintered material;
step 4, putting the pre-sintered material treated in the step 3 into a ball mill, adding deionized water and zirconia balls into a polyurethane ball mill, carrying out ball milling for 2 hours, and finally drying the ball-milled raw materials at 110 ℃;
step 5, adding the pre-sintered material dried in the step 4 into a polyvinyl alcohol (PVA) solution, granulating, pressing into a green body by using a powder tablet press, and pressing into a cylindrical green body with a certain size;
and 6, firing the blank in air at 1250 ℃ for 2 hours to obtain the product. After being cooled with the furnace, the dielectric property is testedr＝16；Qf＝60000，τf＝10ppm/℃。
Example 3:
the chemical expression of the microwave composite ceramic with small dielectric constant and high Q value is [ (Mg)0.7Zn1.15)SiO3.85]0.86-(TiO2)0.14The preparation method comprises the following steps:
the method for preparing the microwave composite ceramic with small dielectric constant and high Q value by using the raw materials comprises the following steps:
step 1, high-purity MgO, ZnO and SiO2And TiO2According to MgO: ZnO: SiO 22：TiO20.602: 0.989: 0.86: weighing raw materials in a ratio of 0.14.
Step 2, putting the raw materials obtained in the step 1 into a planetary ball mill, adding deionized water and zirconia balls, carrying out ball milling for 6 hours, drying the ball-milled raw materials in an electric heating blowing type drying box at 110 ℃, and sieving the dried powder with a 40-mesh sieve to obtain powder with uniform particles;
step 3, heating the powder material treated in the step 2 to 1130 ℃, and preserving heat for 2 hours to obtain a pre-sintering material;
step 4, putting the pre-sintered material treated in the step 3 into a ball mill, adding deionized water and zirconia balls into a polyurethane ball mill, carrying out ball milling for 6 hours, and finally drying the ball-milled raw materials at 110 ℃;
step 5, adding the pre-sintered material dried in the step 4 into a polyvinyl alcohol (PVA) solution, granulating, pressing into a green body by using a powder tablet press, and pressing into a cylindrical green body with a certain size;
and 6, firing the blank in air at 1360 ℃ for 4 hours to obtain the product. After cooling down with the furnace, the test showsElectrical property ofr＝10.8；Qf＝83855，τf＝-3.1ppm/℃。
Example 4:
the chemical expression of the microwave composite ceramic with small dielectric constant and high Q value is [ (Mg)0.9Zn1.05)SiO3.95]0.78-(TiO2)0.22The preparation method comprises the following steps:
the method for preparing the microwave composite ceramic with small dielectric constant and high Q value by using the raw materials comprises the following steps:
step 1, high-purity MgO, ZnO and SiO2And TiO2According to MgO: ZnO: SiO 22：TiO20.702: 0.819: 0.78: weighing raw materials in a ratio of 0.22.
Step 2, putting the raw materials obtained in the step 1 into a planetary ball mill, adding deionized water and zirconia balls, carrying out ball milling for 4 hours, drying the ball-milled raw materials in an electric heating blowing type drying box at 110 ℃, and sieving the dried powder with a 40-mesh sieve to obtain powder with uniform particles;
step 3, heating the powder material treated in the step 2 to 1100 ℃, and preserving the heat for 4 hours to obtain a pre-sintered material;
step 4, putting the pre-sintered material treated in the step 3 into a ball mill, adding deionized water and zirconia balls into a polyurethane ball mill, carrying out ball milling for 6 hours, and finally drying the ball-milled raw materials at 110 ℃;
step 5, adding the pre-sintered material dried in the step 4 into a polyvinyl alcohol (PVA) solution, granulating, pressing into a green body by using a powder tablet press, and pressing into a cylindrical green body with a certain size;
and 6, firing the blank in air at 1360 ℃ for 4 hours to obtain the product. After being cooled with the furnace, the dielectric property is testedr＝15.3；Qf＝75660，τf＝-18.5ppm/℃。
Example 5:
the chemical expression of the microwave composite ceramic with small dielectric constant and high Q value is [ (Mg)0.8Zn1.1)SiO3.9]0.84-(TiO2)0.16Preparation thereofThe method comprises the following steps:
the method for preparing the microwave composite ceramic with small dielectric constant and high Q value by using the raw materials comprises the following steps:
step 1, high-purity MgO, ZnO and SiO2And TiO2According to MgO: ZnO: SiO 22：TiO20.672:0.924: 0.84: weighing raw materials in a ratio of 0.16.
Step 2, putting the raw materials obtained in the step 1 into a planetary ball mill, adding deionized water and zirconia balls, carrying out ball milling for 8 hours, drying the ball-milled raw materials in an electric heating blowing type drying box at 110 ℃, and sieving the dried powder with a 40-mesh sieve to obtain powder with uniform particles;
step 3, heating the powder material treated in the step 2 to 1080 ℃, and preserving the heat for 4 hours to obtain a pre-sintered material;
step 4, putting the pre-sintered material treated in the step 3 into a ball mill, adding deionized water and zirconia balls into a polyurethane ball mill, carrying out ball milling for 12 hours, and finally drying the ball-milled raw materials at 110 ℃;
step 5, adding the pre-sintered material dried in the step 4 into a polyvinyl alcohol (PVA) solution, granulating, pressing into a green body by using a powder tablet press, and pressing into a cylindrical green body with a certain size;
and 6, firing the blank body in air at 1280 ℃ for 4 hours to obtain the product. After being cooled with the furnace, the dielectric property is testedr＝14.2；Qf＝60590，τf＝9.1ppm/℃。
The above description is only for the specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed in the present invention should be covered within the protection scope of the present invention.

Claims (9)

1. The microwave composite ceramic with small dielectric constant and high Q value is characterized in that the chemical expression of the microwave composite ceramic with small dielectric constant and high Q value is (1-z) [ (Mg)xZny)SiO2+x+y]-zTiO2Wherein x is more than or equal to 0.65 and less than or equal to 0.95; y is more than or equal to 1.0 and less than or equal to 1.22; x + y is more than or equal to 1.75 and less than or equal to 1.95; z is more than or equal to 0.1 and less than or equal to 0.25; with MgO, ZnO, SiO2And TiO2As raw materials, according to MgO: ZnO: SiO 22：TiO2X (1-z): y (1-z): (1-z): z molar ratio.
2. The microwave composite ceramic with small dielectric constant and high Q value as claimed in claim 1, wherein said raw material is MgO, ZnO, SiO2And TiO2According to MgO: ZnO: SiO 22：TiO2X (1- (0.14-0.22)), (0.14-0.22) and are mixed according to a molar ratio.
3. The microwave composite ceramic with small dielectric constant and high Q value as claimed in claim 1, wherein said raw material is MgO, ZnO, SiO2And TiO2According to MgO: ZnO: SiO 22：TiO20.84x 0.84y 0.84:0.16 by mol ratio.
4. The microwave composite ceramic with small dielectric constant and high Q value as claimed in claim 1, wherein said raw material is MgO, ZnO, SiO2And TiO2According to MgO: ZnO: SiO 22：TiO2(1-z) (0.7 to 0.9) and (1-z) (1.05 to 1.15) wherein: z is mixed according to a molar ratio.
5. The microwave composite ceramic with small dielectric constant and high Q value as claimed in claim 1, wherein said raw material is MgO, ZnO, SiO2And TiO2According to MgO: ZnO: SiO 22：TiO20.8(1-z):1.1(1-z): z is mixed according to a molar ratio.
6. The microwave composite ceramic with small dielectric constant and high Q value as claimed in claim 1, wherein said raw material is MgO, ZnO, SiO2And TiO2According to MgO: ZnO: SiO 22：TiO2＝0.672:0.924:0.84:0.16 mol ratio and mixing.
7. The preparation method of the microwave composite ceramic with small dielectric constant and high Q value as claimed in any one of claims 1 to 6, characterized in that the preparation method comprises the following steps:
step 1, weighing raw materials according to a raw material ratio;
step 2, putting the raw materials obtained in the step 1 into a ball mill, adding deionized water and zirconia balls, carrying out ball milling for 2-8 hours, drying the ball-milled raw materials, and sieving to obtain powder with uniform particles;
step 3, heating the powder material treated in the step 2 to 1050-1150 ℃, and preserving heat for 2-8 hours to obtain a pre-sintered material;
step 4, putting the pre-sintered material treated in the step 3 into a ball mill, adding deionized water and zirconia balls, carrying out ball milling for 2-12 hours, and finally drying the ball-milled raw materials;
step 5, adding the pre-sintered material dried in the step 4 into a polyvinyl alcohol (PVA) solution, granulating, and pressing into a green body by using a powder tablet press;
and 6, firing the blank in air at 1250-1400 ℃ for 2-12 hours to obtain the product.
8. The method for preparing a microwave composite ceramic with small dielectric constant and high Q value as claimed in claim 7, wherein the ball milling time in step 2 is 6 hours; the temperature rise in the step 3 is 1100 ℃, and the temperature is kept for 4 hours; the ball milling time in the step 4 is 6 hours; the green body described in step 6 was fired at 1300 ℃ for 6 hours.
9. The method of claim 7, further comprising, after step 6, testing the microwave dielectric properties of the article with a network analyzer, wherein the tested microwave dielectric properties comprise dielectric constantrQuality factor Qf and resonant frequency temperature coefficient tauf。
CN201710057174.5A 2017-01-23 2017-01-23 Microwave composite ceramic with small dielectric constant and high Q value and preparation method thereof Active CN106938924B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710057174.5A CN106938924B (en) 2017-01-23 2017-01-23 Microwave composite ceramic with small dielectric constant and high Q value and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710057174.5A CN106938924B (en) 2017-01-23 2017-01-23 Microwave composite ceramic with small dielectric constant and high Q value and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106938924A CN106938924A (en) 2017-07-11
CN106938924B true CN106938924B (en) 2020-11-03

Family

ID=59469217

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710057174.5A Active CN106938924B (en) 2017-01-23 2017-01-23 Microwave composite ceramic with small dielectric constant and high Q value and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106938924B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107619275A (en) * 2017-10-12 2018-01-23 南京彼奥电子科技有限公司 A kind of medium with low dielectric constant ceramics and preparation method thereof
CN115536373B (en) * 2022-10-28 2023-04-25 杭州电子科技大学 High-entropy microwave dielectric ceramic material and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101172848A (en) * 2007-10-19 2008-05-07 浙江大学 Low dielectric constant and low temperature sintering microwave ceramic medium and its preparing process

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101172848A (en) * 2007-10-19 2008-05-07 浙江大学 Low dielectric constant and low temperature sintering microwave ceramic medium and its preparing process

Also Published As

Publication number Publication date
CN106938924A (en) 2017-07-11

Similar Documents

Publication Publication Date Title
CN110092655B (en) Barium samarium-titanium series low-loss microwave dielectric ceramic and preparation method thereof
CN110066169B (en) Silica-based low-dielectric-constant microwave dielectric ceramic and preparation method thereof
CN104844193A (en) Lithium-magnesium-titanium-based microwave dielectric ceramic with high Q value and low temperature sintering realization method thereof
CN104692795A (en) Ultra-low-loss lithium magnesium titanate microwave dielectric ceramic material and preparation method thereof
CN105036741A (en) Microwave dielectric ceramic material high in quality factor and preparation method thereof
CN108147809B (en) Medium-low temperature sintered barium-titanium series microwave dielectric material and preparation method thereof
CN106938924B (en) Microwave composite ceramic with small dielectric constant and high Q value and preparation method thereof
CN102674828A (en) Low-dielectric-loss temperature stabilization type microwave dielectric ceramic material and preparation method thereof
CN106866143B (en) Microwave complex phase ceramic AWO4-TiO2 and preparation method thereof
CN101967058A (en) High Q value microwave medium ceramic and preparation method thereof
CN104876542A (en) MgO-B2O3 binary system low-temperature-sintered microwave dielectric ceramic and preparation method thereof
CN107382314A (en) A kind of microwave-medium ceramics of barium base complex perovskite structure
CN106699164B (en) Microwave ceramics SrO-ZnO (MgO)-TiO2And preparation method
CN105174956A (en) High-quality-factor microwave dielectric ceramic used in X-band and preparation method thereof
CN108751983A (en) Microwave ceramics medium and preparation method thereof for high-frequency ceramic capacitor
CN111960821B (en) Microwave dielectric ceramic material and preparation method and application thereof
CN106904965B (en) Microwave complex phase ceramic KNaWO4-TiO2And method for preparing the same
CN106587968A (en) Microwave dielectric ceramic material with low dielectric constant and preparation method thereof
CN106830934B (en) Microwave complex phase ceramic KxNayMoO4-TiO2And preparation method
CN107445618A (en) A kind of microwave dielectric material and preparation method thereof
CN106904971B (en) Intermediate microwave composite ceramic LaGaO3-TiO2And method for preparing the same
CN106830909B (en) Microwave complex phase ceramic BAl2SiO6-TiO2And method for preparing the same
CN110627480A (en) MgO-Al2O3-GeO2Preparation method of ternary system microwave dielectric material
CN111302795A (en) Lithium-magnesium-niobium-aluminum-tungsten microwave dielectric ceramic and preparation method thereof
CN104310994A (en) Method for replacing A-site Mg<2+> by using Mn<2+> of Li2MgTi3O8 series microwave dielectric ceramic to increase Q value

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