CN109987930A - Low-temperature sintering microwave medium material - Google Patents

Low-temperature sintering microwave medium material Download PDF

Info

Publication number
CN109987930A
CN109987930A CN201910337373.0A CN201910337373A CN109987930A CN 109987930 A CN109987930 A CN 109987930A CN 201910337373 A CN201910337373 A CN 201910337373A CN 109987930 A CN109987930 A CN 109987930A
Authority
CN
China
Prior art keywords
sio
mgo
cao
low
sintering aid
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.)
Granted
Application number
CN201910337373.0A
Other languages
Chinese (zh)
Other versions
CN109987930B (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 Yuan Six Hongyuan Electronic Polytron Technologies Inc
Original Assignee
Beijing Yuan Six Hongyuan Electronic Polytron Technologies Inc
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 Yuan Six Hongyuan Electronic Polytron Technologies Inc filed Critical Beijing Yuan Six Hongyuan Electronic Polytron Technologies Inc
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

Abstract

The invention discloses a kind of low-temperature sintering microwave medium materials, comprising: major ingredient, secondary material, modified additive and sintering aid, major ingredient CaO-MgO-SiO2, pair material is Sr (ZrxTi1‑x)O3, wherein 0.05≤x≤0.4, modified additive MnO, CoO, CeO2、Nb2O5At least one of, sintering aid includes LMZBS and/or LBSCA.Wherein, sintering aid LMZBS is by Li2O、MgO、ZnO、B2O3And SiO2Composition, sintering aid LBSCA is by Li2O、B2O3、SiO2, CaO and Al2O3Composition；Major ingredient, secondary material, modified additive and sintering aid mixing obtain microwave dielectric material after ball milling, drying, sieving.According to the technical solution of the present invention, microwave dielectric material, which is made, has stable C0G temperature coefficient of capacity, and sintering temperature, most down to 830 DEG C, composition and preparation process are simple, and raw material cost is low, environmentally protective.

Description

Low-temperature sintering microwave medium material
Technical field
The present invention relates to dielectric ceramic material technical field more particularly to a kind of low-temperature sintering microwave medium materials.
Background technique
With quick universal, the existing forth generation mobile communication of the high speed development and intelligent terminal of development of Mobile Internet technology Technology (4G) has been unable to satisfy demand of the people to efficient, accurate confidence transmitting.4G good technique framework is relied on, the 5th generation moved Dynamic mechanics of communication (5G) comes into being.It takes the millimere-wave band for possessing very big width, and gigabit grade per second can be provided for user Message transmission rate, zero time delay and highly reliable usage experience can meet such as car networking, smart home, mobile terminal, virtual existing The utilization of the scenes such as real, super clear video, cloud storage.
5G epoch most significant feature is exactly high speed, Gao Rong, must just use higher frequency range, spy is used before 4G High band (300MHz~3GHz), 5G are then main toward the even higher frequency range development of ultra-high frequency.Microwave dielectric ceramic materials (MWDC) refer to applied to dielectric material is used as in microwave frequency band (300MHz~3000GHz) circuit, complete one or more kinds of The ceramics of function.And ground connects microwave-medium ceramics mainly in the fields such as mobile communication base station, satellite communication microwave capacitors, resonance Device, oscillator and filter etc.；Lesser dielectric constant can effectively reduce the delay of signal when being used as substrate and encapsulation.
For radio frequency, microwave multilayer ceramic capacitor, also require have following performance: high voltage, high current, big function Rate, ultrahigh Q-value, stable temperature coefficient, ultra-low equivalent series resistance ESR etc..The loss of capacitor is by metal loss and Jie Two parts composition is lost in matter.In 30MHz hereinafter, the dielectric loss of ceramics is occupied an leading position；In 30MHz or more, metal loss is accounted for Leading position.In order to obtain lower ESR under high frequency, it is necessary to reduce metal loss, therefore now begin to lower using sheet resistance Ag does internal electrode, since the fusing point of Ag is low (961 DEG C), must be requested that ceramic sintering temperature is reduced to Ag fusing point or less.
Major ingredient CaO-MgO-SiO used in the present invention2About 1350 DEG C sinter porcelain, permittivity ε intorAbout 8, -55~ 125 DEG C of range content amount temperature coefficients are 108~120ppm/ DEG C.In order to reduce CaO-MgO-SiO2Ceramics sintering temperature and Adjust CaO-MgO-SiO2The temperature coefficient of ceramics is to 0ppm/ DEG C or so, it is necessary to pass through addition glass agent and negative temperature coefficient Ingredient.SrTiO3Small with high-frequency loss, electrostriction is small and negative capacity temperature coefficient (- 2500ppm/ DEG C), but exists Breakdown strength is not high, the not high feature of voltage endurance；SrZrO3With stable system, the spies such as breakdown strength is high, electric leakage density is small Point；SrZrO3It can be with SrTiO3The advantages of formation solid solution, comprehensive the two, can be used as negative temperature coefficient adding ingredient, and keep good Good microwave property.
Summary of the invention
At least one of regarding to the issue above, the present invention provides a kind of low-temperature sintering microwave medium materials, with CaO- MgO-SiO2Based on microwave dielectric ceramic, Sr (Zr is expected by pairxTi1-x)O3Temperature coefficient is adjusted to OK range and to use Sintering aid reduces sintering temperature most down to 830 DEG C, and reselection adds modified additive fine tuning temperature coefficient of capacity and dielectricity Energy.
To achieve the above object, the present invention provides a kind of low-temperature sintering microwave medium materials, comprising: major ingredient, changes secondary material Property additive and sintering aid, the major ingredient is CaO-MgO-SiO2, the secondary material is Sr (ZrxTi1-x)O3, wherein 0.05≤x ≤ 0.4, the modified additive is MnO, CoO, CeO2、Nb2O5At least one of, the sintering aid include LMZBS and/ Or LBSCA, the sintering aid LMZBS is by Li2O、MgO、ZnO、B2O3And SiO2Composition, the sintering aid LBSCA is by Li2O、 B2O3、SiO2, CaO and Al2O3Composition；Wherein, major ingredient described in each component is 68.35~84.84wt%, the secondary material is 7.5 ~15.71wt%, the modified additive are 0.2~9.25wt%, the total amount of the sintering aid is 2~15wt%, wherein LMZBS is 0~15wt%, LBSCA is 0~8wt%, and the major ingredient, the secondary material, the modified additive and the sintering help Agent mixing obtains microwave dielectric material after ball milling, drying, sieving.
In the above-mentioned technical solutions, it is preferable that the major ingredient CaO-MgO-SiO2By CaO, MgO, SiO2Presoma ball milling After mixing, it is made after being calcined 2~5 hours after being dried, being sieved at 1070~1170 DEG C, with CaO, MgO, SiO2It is total Amount is that 100mol% is counted, and CaO is 25~31mol%, MgO is 23~25mol%, SiO2For 46~50mol%.
In the above-mentioned technical solutions, it is preferable that the presoma of the CaO is CaO, Ca (OH)2、CaCO3One of or it is more Kind；The presoma of the MgO is MgO, Mg (OH)2、MgCO3And one of basic magnesium carbonate or a variety of；The SiO2Forerunner Body is SiO2、H2SiO3One or both of.
In the above-mentioned technical solutions, it is preferable that the secondary material Sr (ZrxTi1-x)O3By SrO, ZrO2And TiO2Ball milling mixing After uniformly, it is made after being calcined 3~5 hours after being dried, being sieved at 1050~1170 DEG C.
In the above-mentioned technical solutions, it is preferable that the presoma of the SrO is SrO, Sr (OH)2、SrCO3One of or it is more Kind；The ZrO2Presoma be ZrO2、Zr(OH)4、Zr3CO8And one of zirconium oxycarbonate or a variety of.
In the above-mentioned technical solutions, it is preferable that the composition in the modified additive relative to entire microwave dielectric material Be MnO be 0~1wt%, CoO is 0~1.5wt%, CeO2For 0~2wt% and Nb2O5For 0~8wt%.
In the above-mentioned technical solutions, it is preferable that the composition material form of the modified additive and the sintering aid is Or mixtures thereof oxide, hydroxide, carbonate.
Compared with prior art, the invention has the benefit that the microwave dielectric material that the present invention obtains is realized in temperature It is sintered down to 830 DEG C, it is good to meet C0G characteristic, microwave property；Gained dielectric ceramic preparation process of the invention is simple, raw material It is at low cost and environmentally protective, it can be used for the manufacture of the microwave devices such as MLCC, microwave antenna.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention Technical solution be clearly and completely described, it is clear that described embodiment is a part of the embodiments of the present invention, without It is whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention is described in further detail below:
A kind of low-temperature sintering microwave medium material provided according to the present invention, comprising: major ingredient, secondary material, modified additive and Sintering aid, major ingredient CaO-MgO-SiO2, pair material is Sr (ZrxTi1-x)O3, wherein 0.05≤x≤0.4, modified additive are MnO、CoO、CeO2、Nb2O5At least one of, sintering aid includes LMZBS and/or LBSCA, sintering aid LMZBS by Li2O、MgO、ZnO、B2O3And SiO2Composition, sintering aid LBSCA is by Li2O、B2O3、SiO2, CaO and Al2O3Composition；Wherein, respectively Major ingredient is 68.35~84.84wt% in component, secondary material is 7.5~15.71wt%, modified additive be 0.2~9.25wt%, The total amount of sintering aid is 2~15wt%, and wherein LMZBS is 0~15wt%, LBSCA is 0~8wt%, and major ingredient, is modified secondary material Additive and sintering aid mixing obtain microwave dielectric material after ball milling, drying, sieving.
In the above embodiment, it is preferable that major ingredient CaO-MgO-SiO2By CaO, MgO, SiO2Presoma ball milling mixing it is equal It is made after being calcined 2~5 hours after after even, being dried, being sieved at 1070~1170 DEG C, with CaO, MgO, SiO2Total amount be 100mol% meter, CaO is 25~31mol%, MgO is 23~25mol%, SiO2For 46~50mol%.
In the above embodiment, it is preferable that the presoma of CaO is CaO, Ca (OH)2、CaCO3One of or it is a variety of；MgO Presoma be MgO, Mg (OH)2、MgCO3And one of basic magnesium carbonate or a variety of；SiO2Presoma be SiO2、H2SiO3 One or both of.
In the above embodiment, it is preferable that secondary material Sr (ZrxTi1-x)O3By SrO, ZrO2And TiO2After ball milling mixing is uniform, It is made after being calcined 3~5 hours after being dried, being sieved at 1050~1170 DEG C.
In the above embodiment, it is preferable that the presoma of SrO is SrO, Sr (OH)2、SrCO3One of or it is a variety of； ZrO2Presoma be ZrO2、Zr(OH)4、Zr3CO8And one of zirconium oxycarbonate or a variety of.
In the above embodiment, it is preferable that the composition in modified additive relative to entire microwave dielectric material is that MnO is 0~1wt%, CoO are 0~1.5wt%, CeO2For 0~2wt% and Nb2O5For 0~8wt%.
In the above embodiment, it is preferable that the composition material form of modified additive and sintering aid is oxide, hydrogen-oxygen Or mixtures thereof compound, carbonate.
Specifically, in above-described embodiment the preparation of each component and microwave dielectric material prepare it is as follows:
(1) major ingredient CaO-MgO-SiO2Preparation
The CaCO for being 99% or more by purity3、Mg(OH)2、SiO2Raw material by CaO be 25~31mol%, MgO 23 ~25mol%, SiO2After 46~50mol% ingredient, after deionized water and abrasive media is added, ball milling, drying, sieving are carried out Afterwards, it is obtained after being calcined 2~5 hours at 1070~1170 DEG C.
(2) secondary material Sr (ZrxTi1-x)O3Preparation
The SrCO for being 99% or more by purity3、ZrO2And TiO2After 1 ingredient of according to the form below, deionized water and abrasive media is added Afterwards, ball milling, drying are carried out, after sieving, 1050~1170 DEG C obtain after calcining 3~5 hours.
The secondary material Sr (Zr of table 1xTi1-x)O3Formula design
(3) preparation of sintering aid
The preparation of LMZBS frit: Li is pressed2CO330mol%, Mg (OH)220mol%, ZnO 10mol%, H3BO3 25mol% and SiO215mol% weighs raw material, is added zirconia ball and suitable deionized water, after ball milling 6h, dries at 80 DEG C After dry, sieve with 100 mesh sieve, obtained after 550~690 DEG C of calcining 3h.
The preparation of LBSCA frit: Li is pressed2CO350mol%, H3BO330mol%, SiO210mol%, CaCO3 5mol% and Al2O35mol% weighs raw material, is added zirconia ball and suitable deionized water, after ball milling 6h, dries at 80 DEG C Afterwards, it sieves with 100 mesh sieve, is obtained after 550~650 DEG C of calcining 3h.
(4) preparation and dielectric properties of microwave dielectric material
The preparation of microwave dielectric ceramic materials: this low-temperature sintering C0G characteristic microwave dielectric material formula as shown in table 2, is pressed Design proportion adds sintering aid and modified additive in master/slave material, and zirconia ball is added and carries out ball milling, Ball-milling Time 5 Hour, 6 hours are dried at 120 DEG C to drying, are obtained after sieving with 100 mesh sieve.
The test of dielectric properties: PVA (polyvinyl alcohol) the aqueous solution bonding that 6.5wt% is added in microwave dielectric material is made Grain；Rounding piece and cylinder green body are pushed in 4Mpa and 6MPa pressure respectively, by green body dumping, dump temperature is 540 DEG C, heating is fast Rate is 3 DEG C/min, keeps the temperature 2 hours, removes adhesive；Green body after dumping is sintered at 830~970 DEG C, heat preservation 2~5 is small When, with furnace natually cooled to room temperature, microwave dielectric ceramic materials are made.
Two surface of disk fired is coated into silver paste, fires silver electrode, tests its room temperature electrical property after capacitor is made Can, it the results are shown in Table 3: relative dielectric constant 8.30~11.30, the equal < 3 × 10 of loss angle tangent-4, insulation resistivity > 1 × 1012 Ω cm meets C0G capacitance temperature factor within the scope of -55~125 DEG C.
The diameter of cylindrical sample is 8.4 ± 0.5mm, with a thickness of 5.0 ± 1.0mm, the Qf value of cylindrical sample is 19100~ 49300GHz。
2 formula components of table and content composition (wt%)
The performance parameter of product obtained by the above-mentioned formula of table 3
These are only the preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification, Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (7)

1. a kind of low-temperature sintering microwave medium material, comprising: major ingredient, secondary material, modified additive and sintering aid, feature exist In:
The major ingredient is CaO-MgO-SiO2, the secondary material is Sr (ZrxTi1-x)O3, wherein 0.05≤x≤0.4, the modification adds Adding agent is MnO, CoO, CeO2、Nb2O5At least one of, the sintering aid includes LMZBS and/or LBSCA, the sintering Auxiliary agent LMZBS is by Li2O、MgO、ZnO、B2O3And SiO2Composition, the sintering aid LBSCA is by Li2O、B2O3、SiO2, CaO and Al2O3Composition；
Wherein, major ingredient described in each component is 68.35~84.84wt%, the secondary material is 7.5~15.71wt%, the modification Additive is 0.2~9.25wt%, the total amount of the sintering aid is 2~15wt%, wherein LMZBS be 0~15wt%, LBSCA is 0~8wt%；
The major ingredient, the secondary material, the modified additive and sintering aid mixing obtain after ball milling, drying, sieving Obtain microwave dielectric material.
2. low-temperature sintering microwave medium material according to claim 1, which is characterized in that the major ingredient CaO-MgO-SiO2 By CaO, MgO, SiO2Presoma ball milling mixing it is uniform after, it is 2~5 small in 1070~1170 DEG C of calcinings after being dried, being sieved When after be made, with CaO, MgO, SiO2Total amount be 100mol% meter, CaO is 25~31mol%, MgO be 23~25mol%, SiO2For 46~50mol%.
3. low-temperature sintering microwave medium material according to claim 2, it is characterised in that:
The presoma of the CaO is CaO, Ca (OH)2、CaCO3One of or it is a variety of；
The presoma of the MgO is MgO, Mg (OH)2、MgCO3And one of basic magnesium carbonate or a variety of；
The SiO2Presoma be SiO2、H2SiO3One or both of.
4. low-temperature sintering microwave medium material according to claim 1, which is characterized in that the secondary material Sr (ZrxTi1-x)O3 By SrO, ZrO2And TiO2It is made after being calcined 3~5 hours after after ball milling mixing is uniform, being dried, being sieved at 1050~1170 DEG C ?.
5. low-temperature sintering microwave medium material according to claim 4, it is characterised in that:
The presoma of the SrO is SrO, Sr (OH)2、SrCO3One of or it is a variety of；
The ZrO2Presoma be ZrO2、Zr(OH)4、Zr3CO8And one of zirconium oxycarbonate or a variety of.
6. low-temperature sintering microwave medium material according to claim 1, which is characterized in that opposite in the modified additive In the composition of entire microwave dielectric material be MnO be 0~1wt%, CoO is 0~1.5wt%, CeO2For 0~2wt% and Nb2O5 For 0~8wt%.
7. low-temperature sintering microwave medium material according to claim 1, which is characterized in that the modified additive and described The composition material form of sintering aid is or mixtures thereof oxide, hydroxide, carbonate.
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 true CN109987930A (en) 2019-07-09
CN109987930B 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)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111908494A (en) * 2020-08-17 2020-11-10 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 (4)

* 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
US20170334785A1 (en) * 2016-05-17 2017-11-23 Walsin Technology Corporation Low-temperature co-fired microwave dielectric ceramic material and preparation 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

Patent Citations (4)

* 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
US20170334785A1 (en) * 2016-05-17 2017-11-23 Walsin Technology Corporation Low-temperature co-fired microwave dielectric ceramic material and preparation 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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111908494A (en) * 2020-08-17 2020-11-10 浙江钙科机械设备有限公司 Low-energy-consumption calcium carbonate suspension calcination process
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

Also Published As

Publication number Publication date
CN109987930B (en) 2021-12-24

Similar Documents

Publication Publication Date Title
US11292747B2 (en) Barium strontium titanate-based dielectric ceramic materials, preparation method and application thereof
CN101006027B (en) Dielectric ceramic and monolithic ceramic capacitor
JP5332807B2 (en) Dielectric porcelain composition
CN104177083B (en) X8R type MLCC medium material with bias voltage characteristic and stable temperature for medium temperature sintering
CN106699150B (en) Low Jie C0G microwave dielectric material of a kind of low-temperature sintering and preparation method thereof
CN103508730B (en) A kind of low sintering huge Jie&#39;s ceramic capacitor dielectric and preparation method thereof
CN106587987A (en) C0G microwave dielectric material, preparation method thereof, and preparation method of ceramic material
CN103408301B (en) Ultrahigh voltage ceramic capacitor medium and preparation method thereof
KR20120075347A (en) Dielectric ceramic composition and electronic component
CN113582683B (en) BaTiO for X8R MLCC 3 Preparation method of base ceramic material
CN101386534A (en) High performance middle and low temperature sintered high-voltage ceramic capacitor medium
CN103351161B (en) Low temperature sintering high voltage ceramic capacitor dielectric
CN109987930A (en) Low-temperature sintering microwave medium material
CN113880569A (en) Dielectric material of multilayer chip ceramic capacitor and preparation method thereof
CN103408302A (en) High permittivity and high temperature stability ceramic capacitor medium and its preparation method
CN108147809A (en) Low temperature sintering barium-titanium series microwave dielectric material and preparation method
CN108585834A (en) High-dielectric-constant ceramics powder and obtained ceramic capacitor and manufacturing method
CN103113100A (en) High-temperature stabilization ceramic capacitor dielectric
KR102106974B1 (en) Method for manufacturing dielectirc ceramic composition using rare earth glass frit
CN102627456B (en) Low-loss high-voltage ceramic capacitor dielectric
CN109437896A (en) A kind of positive temperature coefficient X7R ceramic medium material and preparation method thereof
CN114823137A (en) Co-doped barium titanate ceramic dielectric material, preparation method and application thereof
JP4837204B2 (en) Dielectric porcelain composition, porcelain capacitor using the same, and manufacturing method thereof
KR100444221B1 (en) Dielectric ceramic composition, ceramic capacitor using the same and process of producing thereof
JPS6120084B2 (en)

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