CN109987930B - Low-temperature sintering microwave dielectric material - Google Patents

Low-temperature sintering microwave dielectric material Download PDF

Info

Publication number
CN109987930B
CN109987930B CN201910337373.0A CN201910337373A CN109987930B CN 109987930 B CN109987930 B CN 109987930B CN 201910337373 A CN201910337373 A CN 201910337373A CN 109987930 B CN109987930 B CN 109987930B
Authority
CN
China
Prior art keywords
sio
mgo
cao
microwave dielectric
dielectric material
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
CN201910337373.0A
Other languages
Chinese (zh)
Other versions
CN109987930A (en
Inventor
宋蓓蓓
程华容
齐世顺
杨魁勇
吴爱忠
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.)
BEIJING YUANLIU HONGYUAN ELECTRONIC TECHNOLOGY CO LTD
Original Assignee
BEIJING YUANLIU HONGYUAN ELECTRONIC TECHNOLOGY CO LTD
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 BEIJING YUANLIU HONGYUAN ELECTRONIC TECHNOLOGY CO LTD filed Critical BEIJING YUANLIU HONGYUAN ELECTRONIC TECHNOLOGY CO LTD
Priority to CN201910337373.0A priority Critical patent/CN109987930B/en
Publication of CN109987930A publication Critical patent/CN109987930A/en
Application granted granted Critical
Publication of CN109987930B publication Critical patent/CN109987930B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • 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
    • C04B35/22—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 rich in calcium oxide, e.g. wollastonite
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62675—Thermal treatment of powders or mixtures thereof other than sintering characterised by the treatment temperature
    • 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
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium 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
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C04B2235/3248—Zirconates or hafnates, e.g. zircon
    • C04B2235/3249—Zirconates or hafnates, e.g. zircon containing also titanium oxide or titanates, e.g. lead zirconate titanate (PZT)
    • 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
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, 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
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • 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
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • 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
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
    • C04B2235/3445—Magnesium silicates, e.g. forsterite
    • 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
    • C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
    • C04B2235/365—Borosilicate glass

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Insulating Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention discloses a low-temperature sintering microwave dielectric material, which comprises the following components: main material, auxiliary material, modified additive and sintering aid, wherein the main material is CaO-MgO-SiO2The auxiliary material is Sr (Zr)xTi1‑x)O3Wherein x is more than or equal to 0.05 and less than or equal to 0.4, and the modified additive is MnO, CoO or CeO2、Nb2O5At least one of, the sintering aid comprises LMZBS and/or lbssca. Wherein the sintering aid LMZBS is Li2O、MgO、ZnO、B2O3And SiO2The sintering aid LBSBA consists of Li2O、B2O3、SiO2CaO and Al2O3Composition is carried out; the microwave dielectric material is obtained by mixing the main material, the auxiliary material, the modified additive and the sintering aid, ball-milling, drying and sieving. By adopting the technical scheme of the invention, the prepared microwave dielectric material has a stable temperature coefficient of C0G capacity, the sintering temperature is as low as 830 ℃, the composition and preparation process are simple, the cost of raw materials is low, and the microwave dielectric material is green and environment-friendly.

Description

Low-temperature sintering microwave dielectric material
Technical Field
The invention relates to the technical field of dielectric ceramic materials, in particular to a low-temperature sintered microwave dielectric material.
Background
With the rapid development of the mobile internet technology and the rapid popularization of intelligent terminals, the existing fourth-generation mobile communication technology (4G) cannot meet the requirements of people on efficient and accurate confidence transfer. The fifth generation mobile communication technology (5G) is generated by depending on a 4G good technical framework. The millimeter wave band with the extremely large width is adopted, kilomega-level data transmission rate per second, zero time delay and high-reliability use experience can be provided for a user, and the application of scenes such as car networking, smart homes, mobile terminals, virtual reality, ultra-clear videos and cloud storage can be met.
The most remarkable characteristics of the 5G era are high speed and high capacity, and higher frequency bands must be used, and the ultrahigh frequency band (300 MHz-3 GHz) used before 4G, and 5G mainly develops to ultrahigh frequency and even higher frequency bands. The microwave dielectric ceramic Material (MWDC) is ceramic which is applied to a microwave frequency band (300 MHz-3000 GHz) circuit as a dielectric material and completes one or more functions. The grounded microwave dielectric ceramic is mainly used for microwave capacitors, resonators, oscillators, filters and the like in the fields of mobile communication base stations, satellite communication and the like; the dielectric constant is small, and the delay of signals can be effectively reduced when the dielectric material is used as a substrate and a package.
For radio frequency, microwave multilayer ceramic capacitors, the following properties are also required: high voltage resistance, large current, high power, ultrahigh Q value, stable temperature coefficient, ultralow equivalent series resistance ESR and the like. The loss of the capacitor is composed of metal loss and dielectric loss. Below 30MHz, the dielectric loss of the ceramic is dominant; above 30MHz, metal losses dominate. Since it is necessary to reduce metal loss in order to obtain a lower ESR at a high frequency, Ag having a lower sheet resistance is now used as an internal electrode, and the sintering temperature of the ceramic must be reduced to a temperature lower than the melting point of Ag because of its low melting point (961 ℃).
The main material CaO-MgO-SiO used in the invention2Sintered into porcelain at about 1350 ℃ and has a dielectric constant epsilonrAbout 8, and an internal temperature coefficient of 108 to 120 ppm/DEG C in a range of-55 to 125 ℃. In order to reduce CaO-MgO-SiO2Sintering temperature of ceramic and adjustment of CaO-MgO-SiO2The temperature coefficient of the ceramic is about 0 ppm/DEG C, and a glass auxiliary agent and a negative temperature coefficient component are added. SrTiO3The dielectric ceramic material has the characteristics of small high-frequency loss, small electrostriction and negative capacity temperature coefficient (-2500 ppm/DEG C), but has low breakdown strength and low pressure resistance; SrZrO3The material has the characteristics of stable system, high breakdown strength, small leakage density and the like; SrZrO3Can be mixed with SrTiO3Form solid solution, combine the advantages of the two, can be used as a negative temperature coefficient addition component, and keep good microwave characteristics.
Disclosure of Invention
Aiming at least one of the problems, the invention provides a low-temperature sintering microwave dielectric material which is prepared from CaO-MgO-SiO2Based on microwave dielectric ceramic, through adding Sr (Zr) as auxiliary materialxTi1-x)O3Adjusting the temperature coefficient to a proper range, reducing the sintering temperature to 830 ℃ by using a sintering aid, and then, selectively adding a modifying additive to fine-tune the temperature coefficient of capacity and the dielectric property.
In order to achieve the above object, the present invention provides a low temperature sintering microwave dielectric material, comprising: the main material comprises CaO-MgO-SiO, a secondary material, a modified additive and a sintering aid2The auxiliary material is Sr (Zr)xTi1-x)O3Wherein x is more than or equal to 0.05 and less than or equal to 0.4, and the modified additive is MnO, CoO or CeO2、Nb2O5The sintering aid comprises LMZBS and/or LBSCA, and the LMZBS is made of Li2O、MgO、ZnO、B2O3And SiO2The sintering aid LBSBCA consists of Li2O、B2O3、SiO2CaO and Al2O3Composition is carried out; the microwave dielectric material comprises 68.35-84.84 wt% of a main material, 7.5-15.71 wt% of an auxiliary material, 0.2-9.25 wt% of a modifying additive and 2-15 wt% of a sintering aid, wherein the LMZBS is 0-15 wt% and the LBSCA is 0-8 wt%, and the main material, the auxiliary material, the modifying additive and the sintering aid are mixed, subjected to ball milling, drying and sieving to obtain the microwave dielectric material.
In the above technical solution, preferably, the main material CaO-MgO-SiO2Made of CaO, MgO, SiO2The precursor is prepared by uniformly mixing the raw materials through ball milling, drying, sieving and calcining for 2-5 hours at 1070-1170 ℃ and is prepared by using CaO, MgO and SiO2The total amount of CaO is 25 to 31 mol%, MgO is 23 to 25 mol%, and SiO is 100 mol%246 to 50 mol%.
In the above technical solution, preferably, the precursor of CaO is CaO, Ca (OH)2、CaCO3One or more of; the precursor of MgO is MgO, Mg (OH)2、MgCO3And one or more of basic magnesium carbonate; the SiO2The precursor of (A) is SiO2、H2SiO3One or two of them.
In the above technical solution, preferably, the auxiliary material Sr (Zr)xTi1-x)O3From SrO, ZrO2And TiO2Ball-milling and mixing uniformly, drying, sieving, and calcining at 1050-1170 ℃ for 3-5 hours to obtain the catalyst.
In the above technical solution, preferably, the precursor of SrO is SrO, Sr (OH)2、SrCO3One or more of; the ZrO2The precursor of (A) is ZrO2、Zr(OH)4、Zr3CO8And zirconium basic carbonate.
In the above technical solution, preferably, the composition of the modifying additive relative to the whole microwave dielectric material is MnO 0-1 wt%, CoO 0-1.5 wt%, and CeO20 to 2 wt% and Nb2O50 to 8 wt%.
In the above technical solution, preferably, the constituent materials of the modification additive and the sintering aid are in the form of oxides, hydroxides, carbonates, or a mixture thereof.
Compared with the prior art, the invention has the beneficial effects that: the microwave dielectric material obtained by the invention can be sintered at the temperature as low as 830 ℃, meets the C0G characteristic and has good microwave performance; the dielectric ceramic prepared by the invention has the advantages of simple preparation process, low raw material cost and environmental protection, and can be used for manufacturing microwave devices such as MLCC (multilayer ceramic capacitor), microwave antenna and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention is described in further detail below:
the invention provides a low-temperature sintering microwave dielectric material, which comprises: a main material,The auxiliary material, the modified additive and the sintering aid, the main material is CaO-MgO-SiO2The auxiliary material is Sr (Zr)xTi1-x)O3Wherein x is more than or equal to 0.05 and less than or equal to 0.4, and the modified additive is MnO, CoO or CeO2、Nb2O5At least one of the sintering aids comprises LMZBS and/or LBSCA, and the sintering aid LMZBS is formed by Li2O、MgO、ZnO、B2O3And SiO2The sintering aid LBSBA consists of Li2O、B2O3、SiO2CaO and Al2O3Composition is carried out; the microwave dielectric material comprises 68.35-84.84 wt% of main materials, 7.5-15.71 wt% of auxiliary materials, 0.2-9.25 wt% of modified additives and 2-15 wt% of sintering aids, wherein the LMZBS is 0-15 wt% and the LBSCA is 0-8 wt%, and the main materials, the auxiliary materials, the modified additives and the sintering aids are mixed, subjected to ball milling, drying and sieving to obtain the microwave dielectric material.
In the above embodiment, preferably, the main material CaO-MgO-SiO2Made of CaO, MgO, SiO2The precursor is prepared by uniformly mixing the raw materials through ball milling, drying, sieving and calcining for 2-5 hours at 1070-1170 ℃ and is prepared by using CaO, MgO and SiO2The total amount of CaO is 25 to 31 mol%, MgO is 23 to 25 mol%, and SiO is 100 mol%246 to 50 mol%.
In the above embodiment, preferably, the precursor of CaO is CaO, Ca (OH)2、CaCO3One or more of; the precursor of MgO is MgO, Mg (OH)2、MgCO3And one or more of basic magnesium carbonate; SiO 22The precursor of (A) is SiO2、H2SiO3One or two of them.
In the above embodiment, preferably, the sub-material Sr (Zr)xTi1-x)O3From SrO, ZrO2And TiO2Ball-milling and mixing uniformly, drying, sieving, and calcining at 1050-1170 ℃ for 3-5 hours to obtain the catalyst.
In the above embodiment, preferably, the precursor of SrO is SrO, Sr (OH)2、SrCO3One or more of; ZrO (ZrO)2The precursor of (A) is ZrO2、Zr(OH)4、Zr3CO8And zirconium basic carbonate.
In the above embodiment, preferably, the composition of the modifying additive relative to the whole microwave dielectric material is MnO 0-1 wt%, CoO 0-1.5 wt%, CeO20 to 2 wt% and Nb2O50 to 8 wt%.
In the above embodiments, it is preferable that the constituent materials of the modification additive and the sintering aid are in the form of oxides, hydroxides, carbonates, or mixtures thereof.
Specifically, the preparation of each component and the preparation of the microwave dielectric material in the above examples are as follows:
(1) main material CaO-MgO-SiO2Preparation of
CaCO with purity of more than 99 percent3、Mg(OH)2、SiO2The raw material comprises 25 to 31 mol% of CaO, 23 to 25 mol% of MgO, and SiO2After 46-50 mol% of ingredients are added, deionized water and grinding media are added, and the mixture is subjected to ball milling, drying and sieving and then calcined at 1070-1170 ℃ for 2-5 hours to obtain the catalyst.
(2) Auxiliary material Sr (Zr)xTi1-x)O3Preparation of
SrCO with the purity of more than 99 percent3、ZrO2And TiO2The preparation method comprises the following steps of proportioning according to the following table 1, adding deionized water and a grinding medium, carrying out ball milling, drying and sieving, and calcining at 1050-1170 ℃ for 3-5 hours to obtain the catalyst.
TABLE 1 auxiliary materials Sr (Zr)xTi1-x)O3Formulation design of
Figure BDA0002039594810000041
Figure BDA0002039594810000051
(3) Preparation of sintering aid
Preparation of LMZBS frit: according to Li2CO3 30mol％、Mg(OH)2 20mol％、ZnO 10mol％、H3BO325 mol% and SiO2Weighing 15 mol% of raw materials, adding zirconia balls and a proper amount of deionized water, ball-milling for 6h, drying at 80 ℃, sieving with a 100-mesh sieve, and calcining at 550-690 ℃ for 3 h.
Preparation of LBSCA frit: according to Li2CO3 50mol％、H3BO3 30mol％、SiO210mol％、CaCO35 mol% and Al2O3Weighing 5 mol% of raw materials, adding zirconia balls and a proper amount of deionized water, ball-milling for 6h, drying at 80 ℃, sieving with a 100-mesh sieve, and calcining at 550-650 ℃ for 3 h.
(4) Preparation and dielectric property of microwave dielectric material
Preparing a microwave dielectric ceramic material: the formula of the low-temperature sintered C0G microwave dielectric material is shown in Table 2, sintering aids and modified additives are added into main materials and auxiliary materials according to a designed proportion, zirconia balls are added for ball milling, the ball milling time is 5 hours, the materials are dried for 6 hours at 120 ℃ and are sieved by a 100-mesh sieve to obtain the low-temperature sintered C0G microwave dielectric material.
And (3) testing dielectric properties: adding a microwave medium material into 6.5 wt% of PVA (polyvinyl alcohol) aqueous solution for bonding and granulation; respectively pressing the wafer and the cylindrical blank under the pressures of 4MPa and 6MPa, removing the glue from the blank, wherein the glue removing temperature is 540 ℃, the heating rate is 3 ℃/min, preserving the heat for 2 hours, and removing the adhesive; and sintering the blank after the binder removal at 830-970 ℃, preserving the heat for 2-5 hours, and naturally cooling to room temperature along with the furnace to obtain the microwave dielectric ceramic material.
After the two surfaces of the fired wafer are coated with silver paste and silver electrodes are fired, the room temperature electrical properties of the capacitor are tested, and the results are shown in table 3: the relative dielectric constant is 8.30-11.30, and the loss tangent is less than 3 multiplied by 10-4Insulation resistivity>1×1012Omega cm, and the temperature coefficient of capacitance of C0G is satisfied within the range of-55 to 125 ℃.
The diameter of the cylindrical sample is 8.4 +/-0.5 mm, the thickness of the cylindrical sample is 5.0 +/-1.0 mm, and the Q.f value of the cylindrical sample is 19100-49300 GHz.
Table 2 recipe ingredients and content composition (wt%)
Figure BDA0002039594810000061
TABLE 3 Performance parameters of the products obtained with the above formulation
Figure BDA0002039594810000062
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A low temperature sintered microwave dielectric material comprising: the main material, the auxiliary material, the modified additive and the sintering aid are characterized in that:
the main material is CaO-MgO-SiO2The auxiliary material is Sr (Zr)xTi1-x)O3Wherein x is more than or equal to 0.05 and less than or equal to 0.4, and the modified additive is MnO, CoO or CeO2、Nb2O5The sintering aid comprises LMZBS and/or LBSCA, and the LMZBS is made of Li2O、MgO、ZnO、B2O3And SiO2The sintering aid LBSBCA consists of Li2O、B2O3、SiO2CaO and Al2O3Composition is carried out;
wherein the main material is 68.35-84.84 wt%, the auxiliary material is 7.5-15.71 wt%, the modifying additive is 0.2-9.25 wt%, and the total amount of the sintering aid is 2-15 wt%, wherein the LMZBS is 0-15 wt%, and the LBSCA is 0-8 wt%;
mixing the main material, the auxiliary material, the modified additive and the sintering aid, and performing ball milling, drying and sieving to obtain a microwave medium material;
the main material CaO-MgO-SiO2Composed of CaO, MgO, SiO2The precursor is prepared by uniformly mixing the raw materials through ball milling, drying, sieving and calcining for 2-5 hours at 1070-1170 ℃ and is prepared by using CaO, MgO and SiO2The total amount of CaO is 25 to 31 mol%, MgO is 23 to 25 mol%, and SiO is 100 mol%246 to 50 mol%.
2. A low-temperature sintered microwave dielectric material as claimed in claim 1, wherein:
the precursor of CaO is CaO, Ca (OH)2、CaCO3One or more of;
the precursor of MgO is MgO, Mg (OH)2、MgCO3And one or more of basic magnesium carbonate;
the SiO2The precursor of (A) is SiO2、H2SiO3One or two of them.
3. The low-temperature-sintered microwave dielectric material as claimed in claim 1, wherein the sub-material Sr (Zr)xTi1-x)O3From SrO, ZrO2And TiO2Ball-milling and mixing uniformly, drying, sieving, and calcining at 1050-1170 ℃ for 3-5 hours to obtain the catalyst.
4. A low-temperature sintered microwave dielectric material as claimed in claim 3, wherein:
the precursor of SrO is SrO, Sr (OH)2、SrCO3One or more of;
the ZrO2The precursor of (A) is ZrO2、Zr(OH)4、Zr3CO8And zirconium basic carbonate.
5. The low-temperature sintered microwave dielectric material as claimed in claim 1, wherein the composition of the modifying additive relative to the whole microwave dielectric material is MnO 0-1 wt%, CoO 0-1.5 wt%, CeO20 to 2 wt% and Nb2O50 to 8 wt%.
6. The low-temperature sintering microwave dielectric material as claimed in claim 1, wherein the modifying additive and the sintering aid are in the form of oxide, hydroxide, carbonate or their mixture.
CN201910337373.0A 2019-04-25 2019-04-25 Low-temperature sintering microwave dielectric material Active CN109987930B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910337373.0A CN109987930B (en) 2019-04-25 2019-04-25 Low-temperature sintering microwave dielectric material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910337373.0A CN109987930B (en) 2019-04-25 2019-04-25 Low-temperature sintering microwave dielectric material

Publications (2)

Publication Number Publication Date
CN109987930A CN109987930A (en) 2019-07-09
CN109987930B true CN109987930B (en) 2021-12-24

Family

ID=67132981

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910337373.0A Active CN109987930B (en) 2019-04-25 2019-04-25 Low-temperature sintering microwave dielectric material

Country Status (1)

Country Link
CN (1) CN109987930B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111908494B (en) * 2020-08-17 2022-03-18 浙江钙科机械设备有限公司 Low-energy-consumption calcium carbonate suspension calcination process
CN113754419A (en) * 2021-08-11 2021-12-07 桂林理工大学 Preparation and application of silicon-based low-dielectric high-quality-factor microwave dielectric ceramic capable of being sintered at low temperature

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102898126A (en) * 2012-10-25 2013-01-30 北京元六鸿远电子技术有限公司 CaMgSi2O6 system microwave dielectric material and preparation method of CaMgSi2O6 system microwave dielectric material
CN104341144A (en) * 2013-08-01 2015-02-11 北京元六鸿远电子技术有限公司 Low-temperature sintering microwave medium material with C0G characteristics and preparing method thereof
CN107522481A (en) * 2016-06-22 2017-12-29 华新科技股份有限公司 Low-temperature co-fired microwave dielectric ceramic materials and its preparation method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI592384B (en) * 2016-05-17 2017-07-21 Low temperature co-fired microwave dielectric ceramic material and its preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102898126A (en) * 2012-10-25 2013-01-30 北京元六鸿远电子技术有限公司 CaMgSi2O6 system microwave dielectric material and preparation method of CaMgSi2O6 system microwave dielectric material
CN104341144A (en) * 2013-08-01 2015-02-11 北京元六鸿远电子技术有限公司 Low-temperature sintering microwave medium material with C0G characteristics and preparing method thereof
CN107522481A (en) * 2016-06-22 2017-12-29 华新科技股份有限公司 Low-temperature co-fired microwave dielectric ceramic materials and its preparation method

Also Published As

Publication number Publication date
CN109987930A (en) 2019-07-09

Similar Documents

Publication Publication Date Title
US8183171B2 (en) Dielectric ceramic composition
CN106587987B (en) The preparation method of C0G microwave dielectric material and preparation method and ceramic material
CN106699150B (en) Low Jie C0G microwave dielectric material of a kind of low-temperature sintering and preparation method thereof
CN113582683B (en) BaTiO for X8R MLCC 3 Preparation method of base ceramic material
CN109987930B (en) Low-temperature sintering microwave dielectric material
CN104341144B (en) Low-temperature sintering C0G characteristic microwave dielectric material and preparation method thereof
CN106631002A (en) Dielectric material for Mg-Zn-Ti-based radio-frequency MLCC (multi-layer ceramic capacitor) and preparation method of dielectric material
CN100494118C (en) Electronic ceramic material with superhigh temperature stability and its preparation method
KR102106974B1 (en) Method for manufacturing dielectirc ceramic composition using rare earth glass frit
CN111320473A (en) Low-sintering microwave dielectric ceramic material and preparation method thereof
RU2410358C1 (en) Low-temperature glass-ceramic material
KR100444225B1 (en) Dielectric ceramic composition, ceramic capacitor using the same and process of producing thereof
KR100444221B1 (en) Dielectric ceramic composition, ceramic capacitor using the same and process of producing thereof
CN114093668A (en) Medium-dielectric-constant low-temperature co-fired dielectric ceramic for multilayer ceramic capacitor and preparation method thereof
CN111943673A (en) Low-temperature sintered BNT microwave dielectric material and preparation method thereof
JP2000264721A (en) Dielectric porcelain composition
CN115010488B (en) Low-firing low-dielectric high-Q high-stability microwave porcelain for capacitor
JP2021153105A (en) Laminate electronic part
CN104310999A (en) Preparation method of low-temperature sintered X8R type ceramic capacitor medium
CN109650886A (en) A kind of Ba-Mg-Ta system LTCC material and preparation method thereof
CN115159977B (en) Wide-temperature low-loss dielectric ceramic material and preparation method thereof
KR100452817B1 (en) Dielectric ceramic composition, ceramic capacitor using the same and process of producing thereof
CN110171965B (en) NPO capacitor dielectric material and preparation method thereof
KR100444220B1 (en) Dielectric ceramic composition, ceramic capacitor using the same and process of producing thereof
JP2010235325A (en) Dielectric ceramic composition

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