CN106699164B - Microwave ceramics SrO-ZnO (MgO)-TiO2And preparation method - Google Patents

Microwave ceramics SrO-ZnO (MgO)-TiO2And preparation method Download PDF

Info

Publication number
CN106699164B
CN106699164B CN201710050198.8A CN201710050198A CN106699164B CN 106699164 B CN106699164 B CN 106699164B CN 201710050198 A CN201710050198 A CN 201710050198A CN 106699164 B CN106699164 B CN 106699164B
Authority
CN
China
Prior art keywords
sro
zno
mgo
tio
raw 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
CN201710050198.8A
Other languages
Chinese (zh)
Other versions
CN106699164A (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 CN201710050198.8A priority Critical patent/CN106699164B/en
Publication of CN106699164A publication Critical patent/CN106699164A/en
Application granted granted Critical
Publication of CN106699164B publication Critical patent/CN106699164B/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
    • C04B35/453—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 zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
    • 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
    • C04B2235/3205—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
    • C04B2235/3231—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
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C04B2235/3267—MnO2
    • 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
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
    • 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
    • C04B2235/02—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
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint

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)

Abstract

The present invention provides a kind of microwave ceramics SrO-ZnO (MgO)-TiO2And preparation method, the microwave ceramics SrO-ZnO (MgO)-TiO2Chemical expression be (1-z) [SrO-xZnO-yMgO]-zTiO2, wherein 0 < x < 1, x+y=1.0, the molar ratio content of z=0.1~0.2；With SrO, ZnO, MgO and TiO2For raw material, according to SrO:ZnO:MgO:TiO2=(1-z): x (1-z): y (1-z): z molar ratio, the auxiliary agent that addition accounts for 2.5%~5% mass ratio of raw material are made.Ceramics of the invention have lower sintering temperature, and dielectric constant is moderate, and quality factor are higher, and temperature coefficient of resonance frequency is small and continuously adjustable, can be used for microwave dielectric resonator, filter.

Description

Microwave ceramics SrO-ZnO (MgO)-TiO2And preparation method
Technical field
The present invention relates to field of electronic materials, especially relate to a kind of microwave ceramics SrO-ZnO (MgO)-TiO2And system Method.
Background technique
Microwave-medium ceramics refer to the stable information of the low-loss suitable for microwave frequency band (300MHz~3000GHz), temperature Ceramic material is widely used in resonator, filter, capacitor, oscillator, duplexer, Medium Wave Guide, substrate and antenna Deng being mobile communication, satellite communication, GPS (GPS), military radar, WLAN (WLAN) and object The critical material for modern microwave communications technologies such as (IOT) of networking, the selectivity of miniaturization and raising device to microwave device Have great importance.Recently as the fast development of short-wave communication tedhnology, microwave-medium ceramics become to be studied both at home and abroad Hot spot is increasingly subject to the great attention of various countries.The dielectric properties of microwave-medium ceramics mainly include three parameters: dielectric constant εr, dielectric loss tan δ (quality factor q=1/tan δ) and temperature coefficient of resonance frequency τf.High performance microwave-medium ceramics Different from general function ceramics, it needs to meet, and relative dielectric constant is big, quality factor are high, temperature coefficient of resonance frequency nearly 0 And the requirement such as adjustable.
In order to reduce cost, it is necessary to prepare the ceramics with lower sintering temperature.LTCC material is as entire low temperature co-fired The basis of ceramic technology, wherein the chemical compatibility problems of electrode material and baseplate material are one of the main contents of research.Choosing It uses Ag metal as electrode material, is primarily due to that its conductivity is high, irons in a little relatively low (961 DEG C) and sintering process and is not easy The advantages of being oxidized.In order to carry out cofiring with Ag electrode, the optimal sintering temperature of LTCC material must not be higher than 950 DEG C, and Any chemical reaction does not occur with Ag electrode.However, the sintering temperature of most of ceramic medium materials haveing excellent performance is all opposite It is higher, it needs to research and develop low sintering microwave ceramics energetically.We have invented a kind of new low-temperature sintered microwave composite ceramics thus Porcelain SrO-ZnO (MgO)-TiO2And preparation method, the needs of LTCC technique are met, are a kind of promising microwave materials.
Summary of the invention
An object of the present invention is to provide a kind of microwave composite ceramic with moderate dielectric constant, dielectric properties are excellent Porcelain can be used as microwave ceramics SrO-ZnO (MgO)-TiO of microwave dielectric resonator, filter2；The second purpose is to provide micro- Wave ceramics SrO-ZnO (MgO)-TiO2Preparation method.
An object of the present invention can be achieved by the following technical measures:
The microwave ceramics SrO-ZnO (MgO)-TiO2Chemical expression be (1-z) [SrO-xZnO-yMgO]-zTiO2, Wherein 0 < x < 1, x+y=1.0, z=0.1~0.2 molar ratio content；With SrO, ZnO, MgO and TiO2For raw material, according to SrO: ZnO:MgO:TiO2=(1-z): x (1-z): y (1-z): z molar ratio, the sintering that addition accounts for 2.5%~5% mass ratio of raw material help Agent is made.
An object of the present invention can be also achieved by the following technical measures:
Further, the raw material is SrO, ZnO, MgO and TiO2According to SrO:ZnO:MgO:TiO2=(1- (0.14~ 0.18)): x (1- (0.14~0.18)): y (1- (0.14~0.18)): 0.14~0.18 molar ratio proportion mixes.
Further, the raw material is SrO, ZnO, MgO and TiO2According to SrO:ZnO:MgO:TiO2=0.84: 0.84x:0.84y:0.16 molar ratio proportion mixes.
Further, the raw material is SrO, ZnO, MgO and TiO2According to SrO:ZnO:MgO:TiO2=(1-z): (1-z) (0.1~0.9): (1-z) (1- (0.1~0.9)): z molar ratio proportion mixes.
Further, the raw material is SrO, ZnO, MgO and TiO2According to SrO:ZnO:MgO:TiO2=(1-z): 0.8 (1-z): 0.2 (1-z): z molar ratio proportion mixes.
Further, the raw material is SrO, ZnO, MgO and TiO2According to SrO:ZnO:MgO:TiO2=0.84:0.672: 0.168:0.16 molar ratio proportion mixes.
Further, the sintering aid is SrCu (B2O5), composite oxides, MnO2One or more arbitrarily match The mixing of ratio.
Further, the sintering aid accounts for 3%~4.5% mass parts of raw material.
Further, the sintering aid accounts for 4% mass parts of raw material.
The second object of the present invention can be achieved by the following technical measures:
Microwave ceramics SrO-ZnO (MgO)-TiO is prepared with above-mentioned raw material and sintering aid2Preparation method, it is described Preparation method carries out as follows:
Step 1, raw material is weighed according to raw material proportioning；
Step 2, the raw material of step 1 is put into ball mill, addition deionized water and zirconia ball, ball milling 2~8 hours, Again by the raw material stoving after ball milling, sieving obtains evengranular powder；
Step 3, the powder handled by step 2 is warming up to 1000 DEG C -1100 DEG C, keeps the temperature 2~8 hours, obtains Preburning material；
Step 4, the Preburning material handled by step 3 is put into ball mill, adds sintering aid, then adds Ionized water and zirconia ball, ball milling 2~12 hours, finally by the raw material stoving after ball milling；
Step 5, it takes step 4 Preburning material after drying that POLYPROPYLENE GLYCOL PVA solution is added, is granulated, then use powder compressing machine It is pressed into green body；
Step 6, green body was fired at 850~950 DEG C by 2~12 hours in air, obtains product.
The second object of the present invention can be also achieved by the following technical measures:
Further, Ball-milling Time described in step 2 is 5 hours；Heating described in step 3 is 1080 DEG C, and heat preservation 5 is small When；Ball-milling Time described in step 4 is 6 hours；Green body described in step 6 is fired 8 hours at 910 DEG C.
Further, microwave ceramics SrO-ZnO (MgO)-TiO2Preparation method further include after step 6, passing through The microwave dielectric property of Network Analyzer test article, the microwave dielectric property of test include permittivity εr, quality factor q f And temperature coefficient of resonance frequency τf。
Microwave ceramics SrO-ZnO (MgO)-TiO in the present invention2And preparation method, belong to technical field of electronic materials, the ceramics With SrO-ZnO (MgO)-TiO2It is SrCu (B for main material, additive 12O5), additive 2 be composite oxides, additive 3 is MnO2.With the SrCO of high-purity3, ZnO, basic magnesium carbonate and TiO2For Material synthesis SrO-ZnO (MgO)-TiO2Main material；With B2O3, CuO and SrCO3For Material synthesis additive 1；With SrCO3、TiO2、ZnO、B2O3And SiO2For Material synthesis additive 2；It will This 3 kinds of additives of additive 1~3 are added to SrO-ZnO (MgO)-TiO2In main material (additive level between 2.5wt%~ 5wt%), in air in 850~950 DEG C after ball milling, drying, sieving, PVAC polyvinylalcohol granulation, molding and dumping processing It is lower to be burnt by 2~12 hours.Low temperature sintering microwave ceramic material prepared by the present invention has moderate permittivity εr(30 ~40) and high Q value (Qf is between 23000~40000), frequency-temperature coefficient nearly zero and (- 20ppm/ DEG C≤τ adjustablef≤+ 15ppm/ DEG C), good technology stability.
Detailed description of the invention
Fig. 1 is microwave ceramics SrO-ZnO (MgO)-TiO of the invention2The flow chart of one specific embodiment of preparation method.
Specific embodiment
To enable above and other objects, features and advantages of the invention to be clearer and more comprehensible, combined with specific embodiments below Invention is further described in detail.Formula is non-limiting implementation involved in following embodiment, is only intended to have Body illustrates the present invention, and the formula that those skilled in the art can be filtered out completely with thinking according to the present invention and sorting proportion is equal For protection scope of the present invention.
Referring to Fig.1:
In step 101, SrO, ZnO, MgO and TiO2According to SrO:ZnO:MgO:TiO2=(1-z): x (1-z): y (1-z): z Molar ratio proportion weighs raw material；
In step 102, the raw material of step 101 is put into ball mill, deionized water and zirconia ball, ball milling 2~8 is added Hour；The raw material after ball milling is dried in 110 DEG C again, 40 meshes is crossed, obtains evengranular powder；
In step 103, by the powder after the sieving of step 102 in 1000 DEG C of -1100 DEG C of pre-burnings, and keep the temperature at this temperature 2~8 hours；
In step 104, the Preburning material of step 103 is added with a small amount of SrCu (B2O5), composite oxides, MnO2For sintering Auxiliary agent (content is between 2.5wt%~5wt%) is put into ball mill, and deionized water is added and zirconia ball, ball milling 2~12 are small When；The raw material after ball milling is dried in 110 DEG C again；
Additional POLYPROPYLENE GLYCOL PVA solution is granulated as adhesive after step 105, drying, and 80 meshes are crossed after drying, is obtained Evengranular powder is pressed into green body with powder compressing machine；
In step 106, above-mentioned green body was burnt at 850~950 DEG C by 2~12 hours in air, microwave is made Ceramics；
In step 107, pass through the microwave dielectric property of Network Analyzer test article.The microwave dielectric property of test includes Permittivity εr, dielectric loss tan δ (quality factor q=1/tan δ) and temperature coefficient of resonance frequency τf。
Ceramics of the invention have lower sintering temperature, and dielectric constant is moderate, and quality factor are higher, resonance frequency temperature Coefficient is small and continuously adjustable, can be used for microwave dielectric resonator, filter.Present invention process is simple, and process is pollution-free, is one The rising medium dielectric constant microwave medium microwave dielectric material of kind.
The following are several concrete application embodiments of the invention.
Embodiment 1:
The microwave ceramics SrO-ZnO (MgO)-TiO2Chemical expression be 0.9 [SrO- (Zn0.1Mg0.9)O]- 0.1TiO2, preparation method are as follows:
Microwave ceramics SrO-ZnO (MgO)-TiO is prepared with above-mentioned raw material and sintering aid2Method, this method is by such as Lower step carries out:
Step 1, by SrO, ZnO, MgO and TiO of high-purity2According to SrO:ZnO:MgO:TiO2=0.9:0.09:0.81: 0.1 molar ratio proportion weighs raw material；
Step 2, the raw material of step 1 is put into planetary ball mill, deionized water is added and zirconia ball, ball milling 8 are small When, then the raw material after ball milling is dried in 110 DEG C under the conditions of in electric heating blowing-type drying box, the powder after drying crosses 50 mesh Sieve, obtains evengranular powder；
Step 3, the powder handled by step 2 is warming up to 1000 DEG C, keeps the temperature 2 hours, obtains Preburning material；
Step 4, the Preburning material handled by step 3 is put into ball mill, adds SrCu (B2O5), composite oxides, MnO2One or more sintering aids arbitrarily matched, the additional amount of sintering aid accounts for 5% mass parts of raw material, then in poly- ammonia Deionized water and zirconia ball are added in ester ball mill, ball milling 12 hours, finally dries the raw material after ball milling at 110 DEG C；
Step 5, it takes step 4 Preburning material after drying that POLYPROPYLENE GLYCOL PVA solution is added, is granulated, then use powder compressing machine It is pressed into green body, is pressed into the green body cylinders of certain size；
Step 6, green body was fired at 950 DEG C by 12 hours in air, obtains product.Through surveying after furnace cooling Examination, dielectric properties εr=30；Qf=40000, τf=-20ppm/ DEG C.
Embodiment 2:
The microwave ceramics SrO-ZnO (MgO)-TiO2Chemical expression be 0.8 [SrO- (Zn0.9Mg0.1)O]- 0.2TiO2, preparation method are as follows:
Microwave ceramics SrO-ZnO (MgO)-TiO is prepared with above-mentioned raw material and sintering aid2Method, this method is by such as Lower step carries out:
Step 1, by SrO, ZnO, MgO and TiO of high-purity2According to SrO:ZnO:MgO:TiO2=0.8:0.72:0.08: 0.2 molar ratio proportion weighs raw material；
Step 2, the raw material of step 1 is put into planetary ball mill, deionized water is added and zirconia ball, ball milling 2 are small When, then the raw material after ball milling is dried in 110 DEG C under the conditions of in electric heating blowing-type drying box, the powder after drying crosses 50 mesh Sieve, obtains evengranular powder；
Step 3, the powder handled by step 2 is warming up to 1100 DEG C, keeps the temperature 8 hours, obtains Preburning material；
Step 4, the Preburning material handled by step 3 is put into ball mill, adds SrCu (B2O5), composite oxides, MnO2One or more sintering aids arbitrarily matched, the additional amount of sintering aid accounts for 2.5% mass parts of raw material, then poly- Deionized water and zirconia ball are added in urethane ball mill, ball milling 2 hours, finally dries the raw material after ball milling at 110 DEG C；
Step 5, it takes step 4 Preburning material after drying that POLYPROPYLENE GLYCOL PVA solution is added, is granulated, then use powder compressing machine It is pressed into green body, is pressed into the green body cylinders of certain size；
Step 6, green body was fired at 850 DEG C by 2 hours in air, obtains product.After furnace cooling after tested, Dielectric properties are εr=40；Qf=23000, τf=15ppm/ DEG C.
Embodiment 3:
The microwave ceramics SrO-ZnO (MgO)-TiO2Chemical expression be 0.86 [SrO- (Zn0.5Mg0.5)O]- 0.14TiO2, preparation method are as follows:
Microwave ceramics SrO-ZnO (MgO)-TiO is prepared with above-mentioned raw material and sintering aid2Method, this method is by such as Lower step carries out:
Step 1, by SrO, ZnO, MgO and TiO of high-purity2According to SrO:ZnO:MgO:TiO2=0.86:0.43: The molar ratio proportion of 0.43:0.14 weighs raw material；
Step 2, the raw material of step 1 is put into planetary ball mill, deionized water is added and zirconia ball, ball milling 4 are small When, then the raw material after ball milling is dried in 110 DEG C under the conditions of in electric heating blowing-type drying box, the powder after drying crosses 50 mesh Sieve, obtains evengranular powder；
Step 3, the powder handled by step 2 is warming up to 1050 DEG C, keeps the temperature 4 hours, obtains Preburning material；
Step 4, the Preburning material handled by step 3 is put into ball mill, adds SrCu (B2O5), composite oxides, MnO2One or more sintering aids arbitrarily matched, the additional amount of sintering aid accounts for 3% mass parts of raw material, then in poly- ammonia Deionized water and zirconia ball are added in ester ball mill, ball milling 6 hours, finally dries the raw material after ball milling at 110 DEG C；
Step 5, it takes step 4 Preburning material after drying that POLYPROPYLENE GLYCOL PVA solution is added, is granulated, then use powder compressing machine It is pressed into green body, is pressed into the green body cylinders of certain size；
Step 6, green body was fired at 900 DEG C by 6 hours in air, obtains product.After furnace cooling after tested, Dielectric properties are εr=35.4；Qf=32789, τf=-8.5ppm/ DEG C.
Embodiment 4:
The microwave ceramics SrO-ZnO (MgO)-TiO2Chemical expression be 0.82 [SrO- (Zn0.6Mg0.4)O]- 0.18TiO2, preparation method are as follows:
Microwave ceramics SrO-ZnO (MgO)-TiO is prepared with above-mentioned raw material and sintering aid2Method, this method is by such as Lower step carries out:
Step 1, by SrO, ZnO, MgO and TiO of high-purity2According to SrO:ZnO:MgO:TiO2=0.82:0.492: The molar ratio proportion of 0.328:0.18 weighs raw material；
Step 2, the raw material of step 1 is put into planetary ball mill, deionized water is added and zirconia ball, ball milling 4 are small When, then the raw material after ball milling is dried in 110 DEG C under the conditions of in electric heating blowing-type drying box, the powder after drying crosses 50 mesh Sieve, obtains evengranular powder；
Step 3, the powder handled by step 2 is warming up to 1060 DEG C, keeps the temperature 4 hours, obtains Preburning material；
Step 4, the Preburning material handled by step 3 is put into ball mill, adds SrCu (B2O5), composite oxides, MnO2One or more sintering aids arbitrarily matched, the additional amount of sintering aid accounts for 4.5% mass parts of raw material, then poly- Deionized water and zirconia ball are added in urethane ball mill, ball milling 6 hours, finally dries the raw material after ball milling at 110 DEG C；
Step 5, it takes step 4 Preburning material after drying that POLYPROPYLENE GLYCOL PVA solution is added, is granulated, then use powder compressing machine It is pressed into green body, is pressed into the green body cylinders of certain size；
Step 6, green body was fired at 930 DEG C by 6 hours in air, obtains product.After furnace cooling after tested, Dielectric properties are εr=35.8；Qf=23200, τf=-19.7ppm/ DEG C.
Embodiment 5:
The microwave ceramics SrO-ZnO (MgO)-TiO2Chemical expression be 0.84 [SrO- (Zn0.8Mg0.2)O]- 0.16TiO2, preparation method are as follows:
Microwave ceramics SrO-ZnO (MgO)-TiO is prepared with above-mentioned raw material and sintering aid2Method, this method is by such as Lower step carries out:
Step 1, by SrO, ZnO, MgO and TiO of high-purity2According to SrO:ZnO:MgO:TiO2=0.84:0.672: The molar ratio proportion of 0.168:0.16 weighs raw material；
Step 2, the raw material of step 1 is put into planetary ball mill, deionized water is added and zirconia ball, ball milling 5 are small When, then the raw material after ball milling is dried in 110 DEG C under the conditions of in electric heating blowing-type drying box, the powder after drying crosses 50 mesh Sieve, obtains evengranular powder；
Step 3, the powder handled by step 2 is warming up to 1080 DEG C, keeps the temperature 5 hours, obtains Preburning material；
Step 4, the Preburning material handled by step 3 is put into ball mill, adds SrCu (B2O5), composite oxides, MnO2One or more sintering aids arbitrarily matched, the additional amount of sintering aid accounts for 4% mass parts of raw material, then in poly- ammonia Deionized water and zirconia ball are added in ester ball mill, ball milling 6 hours, finally dries the raw material after ball milling at 110 DEG C；
Step 5, it takes step 4 Preburning material after drying that POLYPROPYLENE GLYCOL PVA solution is added, is granulated, then use powder compressing machine It is pressed into green body, is pressed into the green body cylinders of certain size；
Step 6, green body was fired at 910 DEG C by 8 hours in air, obtains product.After furnace cooling after tested, Dielectric properties are εr=32.1；Qf=36884, τf=-12.8ppm/ DEG C.
The above, specific embodiment therein only of the invention, but the scope of protection of the patent of the present invention is not limited to In this, anyone skilled in the art is in the technical scope that the invention patent discloses, the change that can readily occur in Change or replace, should all cover within the scope of protection of the patent of the invention.

Claims (11)

1. microwave ceramics SrO-ZnO-MgO-TiO2, which is characterized in that microwave ceramics SrO-ZnO-MgO-TiO2Chemistry expression Formula is (1-z) [SrO-xZnO-yMgO]-zTiO2, wherein 0 < x < 1, x+y=1.0, the molar ratio content of z=0.1~0.2；With SrO, ZnO, MgO and TiO2For raw material, according to SrO:ZnO:MgO:TiO2=(1-z): x (1-z): y (1-z): z molar ratio is added The sintering aid for accounting for 2.5%~5% mass ratio of raw material is made.
2. microwave ceramics SrO-ZnO-MgO-TiO according to claim 12, which is characterized in that the raw material be SrO, ZnO, MgO and TiO2According to SrO:ZnO:MgO:TiO2=(1- (0.14~0.18)): x (1- (0.14~0.18)): y (1- (0.14~0.18)): 0.14~0.18 molar ratio proportion mixes.
3. microwave ceramics SrO-ZnO-MgO-TiO according to claim 12, which is characterized in that the raw material be SrO, ZnO, MgO and TiO2According to SrO:ZnO:MgO:TiO2=0.84:0.84x:0.84y:0.16 molar ratio proportion mixes.
4. microwave ceramics SrO-ZnO-MgO-TiO according to claim 12, which is characterized in that the raw material be SrO, ZnO, MgO and TiO2According to SrO:ZnO:MgO:TiO2=(1-z): (1-z) (0.1~0.9): (1-z) (1- (0.1~0.9)): z Molar ratio proportion mixes.
5. microwave ceramics SrO-ZnO-MgO-TiO according to claim 12, which is characterized in that the raw material be SrO, ZnO, MgO and TiO2According to SrO:ZnO:MgO:TiO2=(1-z): 0.8 (1-z): 0.2 (1-z): z molar ratio proportion mixing and At.
6. microwave ceramics SrO-ZnO-MgO-TiO according to claim 12, which is characterized in that the raw material be SrO, ZnO, MgO and TiO2According to SrO:ZnO:MgO:TiO2=0.84:0.672:0.168:0.16 molar ratio proportion mixes.
7. microwave ceramics SrO-ZnO-MgO-TiO according to claim 12, which is characterized in that the sintering aid accounts for 3%~4.5% mass parts of raw material.
8. microwave ceramics SrO-ZnO-MgO-TiO according to claim 12, which is characterized in that the sintering aid accounts for 4% mass parts of raw material.
9. microwave ceramics SrO-ZnO-MgO-TiO according to any one of claims 1 to 82Preparation method, which is characterized in that institute The preparation method stated carries out as follows:
Step 1, raw material is weighed according to raw material proportioning；
Step 2, the raw material of step 1 is put into ball mill, addition deionized water and zirconia ball, ball milling 2~8 hours, then will Raw material stoving after ball milling, sieving, obtains evengranular powder；
Step 3, the powder handled by step 2 is warming up to 1000 DEG C -1100 DEG C, keeps the temperature 2~8 hours, obtains Preburning material；
Step 4, the Preburning material handled by step 3 is put into ball mill, adds sintering aid, then adds deionization Water and zirconia ball, ball milling 2~12 hours, finally by the raw material stoving after ball milling；
Step 5, it takes step 4 Preburning material after drying that POLYPROPYLENE GLYCOL PVA solution is added, is granulated, then suppressed with powder compressing machine At green body；
Step 6, green body was fired at 850~950 DEG C by 2~12 hours in air, obtains product.
10. microwave ceramics SrO-ZnO-MgO-TiO according to claim 92Preparation method, which is characterized in that step 2 Described in Ball-milling Time be 5 hours；Heating described in step 3 is 1080 DEG C, keeps the temperature 5 hours；Ball milling described in step 4 Time is 6 hours；Green body described in step 6 is fired 8 hours at 910 DEG C.
11. microwave ceramics SrO-ZnO-MgO-TiO according to claim 92Preparation method, which is characterized in that the microwave Ceramic SrO-ZnO-MgO-TiO2Preparation method further include after step 6, passing through the microwave of Network Analyzer test article Dielectric properties, the microwave dielectric property of test include permittivity εr, quality factor q f and temperature coefficient of resonance frequency τf。
CN201710050198.8A 2017-01-23 2017-01-23 Microwave ceramics SrO-ZnO (MgO)-TiO2And preparation method Active CN106699164B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710050198.8A CN106699164B (en) 2017-01-23 2017-01-23 Microwave ceramics SrO-ZnO (MgO)-TiO2And preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710050198.8A CN106699164B (en) 2017-01-23 2017-01-23 Microwave ceramics SrO-ZnO (MgO)-TiO2And preparation method

Publications (2)

Publication Number Publication Date
CN106699164A CN106699164A (en) 2017-05-24
CN106699164B true CN106699164B (en) 2019-10-15

Family

ID=58909486

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710050198.8A Active CN106699164B (en) 2017-01-23 2017-01-23 Microwave ceramics SrO-ZnO (MgO)-TiO2And preparation method

Country Status (1)

Country Link
CN (1) CN106699164B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110540420B (en) * 2019-10-12 2021-09-03 无锡鑫圣慧龙纳米陶瓷技术有限公司 Low sintering temperature and low dielectric microwave dielectric ceramic and preparation method thereof
CN112341189B (en) * 2020-11-25 2022-08-02 无锡鑫圣慧龙纳米陶瓷技术有限公司 Temperature-stable low-dielectric-constant microwave dielectric ceramic and preparation method thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1307122C (en) * 2003-01-24 2007-03-28 宇部兴产株式会社 Dielectric ceramic composition, dielectric ceramic and laminated ceramic part including the same
US20050121833A1 (en) * 2003-12-09 2005-06-09 Jenn-Shing Wang Processing method for ceramic
CN101343178A (en) * 2008-08-14 2009-01-14 广东风华高新科技股份有限公司 (ZrSnZnNb)TiO4 microwave ceramic dielectric material and preparation thereof
CN102838347B (en) * 2012-09-06 2014-01-01 北京元六鸿远电子技术有限公司 Microwave dielectric ceramic powder and preparation method thereof
CN102863221B (en) * 2012-09-20 2014-04-16 广东风华高新科技股份有限公司 Method, sintering aid and materials for preparation of low-temperature cofired medium ceramic and application

Also Published As

Publication number Publication date
CN106699164A (en) 2017-05-24

Similar Documents

Publication Publication Date Title
CN101318815B (en) Bismuth-based molybdenum-based microwave dielectric ceramic material sintered at ultra low temperature and manufacture of the same
CN101362647A (en) Low temperature sintering lithium-base microwave dielectric ceramic material and preparation thereof
CN108249902A (en) Low dielectric microwave media ceramic of a kind of silicate-base and preparation method thereof
CN103232243A (en) Vanadate microwave dielectric ceramic Ca1. 5M3V3O12 and preparation method thereof
CN104003722A (en) Ultralow-dielectric constant microwave dielectric ceramic Li3AlV2O8 capable of being sintered at low temperature and preparation method thereof
CN104261825A (en) Ultralow dielectric constant microwave dielectric ceramic Li3BiW8O27 capable of performing low-temperature sintering
WO2023159896A1 (en) Silicate-based low-temperature sintered microwave dielectric ceramic material and preparation method therefor
CN103113103B (en) Low temperature sintered microwave dielectric ceramic BiZn2VO6 and preparation method thereof
CN109231967A (en) Bi2O3-B2O3Binary system microwave dielectric ceramic materials and preparation method thereof
CN104311031A (en) Low-temperature sinterable microwave dielectric ceramic Ca3Y4V2O14 having low dielectric constant
CN106699164B (en) Microwave ceramics SrO-ZnO (MgO)-TiO2And preparation method
CN106187107A (en) A kind of highly reliable A G characteristic microwave dielectric material and preparation method thereof
CN103496981A (en) Low-temperature sintering temperature-stable microwave dielectric ceramic Bi14W2O27 and preparation method thereof
CN104045344A (en) Low temperature sinterable microwave dielectric ceramic Li2Zn3WO7 and preparation method thereof
CN104193336A (en) Low-sintering-temperature microwave dielectric ceramic material and preparation method thereof
CN103319177A (en) Microwave dielectric ceramic Ba3WTiO8 with low-temperature sintering characteristic and preparation method thereof
CN106938924A (en) Microwave composite ceramics of small dielectric constant and high Q value and preparation method thereof
CN106866143A (en) Microwave complex phase ceramic AWO4 TiO2 and preparation method thereof
CN105503202A (en) Novel low-loss Li2MgZrO4 microwave dielectric ceramic material and preparing method
CN101265097B (en) Low-temperature sintering composite microwave medium ceramic and preparation method thereof
CN104003721A (en) Microwave dielectric ceramic Li2W2Zn3O10 capable of being sintered at low temperature and preparation method thereof
CN103922719A (en) Low-temperature sintering available microwave dielectric ceramic TiP2O7 with ultralow dielectric constant and preparation method thereof
CN102531568A (en) Low-temperature sinterable microwave dielectric ceramic LiBa4Bi3O11 and preparation method thereof
CN101805170B (en) Low temperature sintering lithium-based microwave dielectric ceramics and preparation method thereof
CN104876576A (en) Temperature-stable and ultra-low dielectric constant microwave dielectric ceramic SrLiEu3Mo5O21

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant