CN116283282A - Vanadium-based low-dielectric-constant microwave dielectric ceramic material and preparation method thereof - Google Patents
Vanadium-based low-dielectric-constant microwave dielectric ceramic material and preparation method thereof Download PDFInfo
- Publication number
- CN116283282A CN116283282A CN202211586763.XA CN202211586763A CN116283282A CN 116283282 A CN116283282 A CN 116283282A CN 202211586763 A CN202211586763 A CN 202211586763A CN 116283282 A CN116283282 A CN 116283282A
- Authority
- CN
- China
- Prior art keywords
- powder
- vanadium
- ball milling
- ceramic material
- based low
- 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
Links
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 62
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 54
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 35
- 229910005793 GeO 2 Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 195
- 238000000498 ball milling Methods 0.000 claims description 133
- 239000002994 raw material Substances 0.000 claims description 93
- 238000001035 drying Methods 0.000 claims description 74
- 239000000463 material Substances 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 46
- 238000003825 pressing Methods 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 45
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 45
- -1 polytetrafluoroethylene Polymers 0.000 claims description 44
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 44
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 44
- 239000002245 particle Substances 0.000 claims description 30
- 239000002223 garnet Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000007873 sieving Methods 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 15
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 15
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 15
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000005642 Oleic acid Substances 0.000 claims description 15
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 15
- 238000011068 loading method Methods 0.000 claims description 15
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 15
- 235000011837 pasties Nutrition 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 229910052732 germanium Inorganic materials 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 30
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000003746 solid phase reaction Methods 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical group 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241001591005 Siga Species 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3287—Germanium oxides, germanates or oxide forming salts thereof, e.g. copper germanate
-
- 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
-
- 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
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/442—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
The invention discloses a vanadium-based low-dielectric-constant microwave dielectric ceramic material and a preparation method thereof. The chemical formula of the microwave dielectric ceramic is Ca 3 Mg 2 Ti 1‑x M x V 2 O 12 (0.ltoreq.x.ltoreq.0.5; M=Si, ge). The invention adopts a solid phase reaction sintering method, the preparation method is simple, and the prepared vanadium-based low-dielectric-constant microwave dielectric ceramic material does not need to be additionally added with CaTiO 3 In the case of (2) can be obtained by CaTiO formed during sintering 3 To optimize the temperature coefficient of the resonant frequency of the ceramic. The vanadium-based low-dielectric-constant microwave dielectric ceramic material does not contain or contains little expensive GeO 2 The process is simple and is beneficial to industrial mass production. 1230 ℃ sintered Ca 3 Mg 2 TiV 2 O 12 The ceramic has excellent propertiesThe microwave dielectric properties of (2) are: epsilon r ＝12.22，Q×f＝36347GHz，τ f ＝‑4.8ppm/℃。
Description
Technical Field
The invention belongs to the technical field of electronic ceramics and preparation thereof, and particularly relates to a vanadium-based low-dielectric-constant microwave dielectric ceramic material and a preparation method thereof.
Background
With the popularization of the 5G technology and the layout of the 6G technology, the microwave communication technology extends to millimeter wave bands, and the microwave dielectric ceramic material needs to meet the following requirements under the millimeter wave bands with extremely high frequency: 1. has a low dielectric constant (. Epsilon.) r 15) to reduce the delay time of signal transmission between chips; 2. high quality factor Q x f
(low dielectric loss) to help improve device signal strength and resonant frequency resolution; 3. near zero resonant frequency temperature coefficient (|τ) f And the temperature stability of the microwave device is ensured by the temperature of the microwave device is less than or equal to 10 ppm/DEG C).
Three parameters of microwave dielectric Properties (. Epsilon.) r Q×f and τ f ) There is a relationship of mutual restriction. Generally τ f Low epsilon with small absolute value r Microwave dielectric ceramics generally have high dielectric losses, while low epsilon with Q x f values greater than 35000GHz r Microwave dielectric ceramics typically have a large negative τ f Values. For example, low epsilon has received much attention in recent years r Garnet-type microwave dielectric ceramics generally have τ with a large negative direction f Value: vanadium-based garnet LiCa 3 MV 3 O 12 τ of (m=mg, zn) f The value is-72 ppm/DEG C to-61 ppm/DEG C, and the aluminum-based garnet Y 3 MAl 3 SiO 12 τ of (m=mg, zn) f The value is-32 ppm/. Degree.C to-31.7 ppm/. Degree.C, and the lithium-based garnet Nd 3 W 2 Li 3 O 12 And zinc-based garnet Ca 3 Te 2 Zn 3 O 12 τ of (V) f The values are-30 ppm/DEG C and-31 ppm/DEG C, respectively, of gallium-based garnet Ca 3 B 2 SiGa 2 O 12 τ of (b=sn, zr) f The value is-45.8 ppm/DEG C to-32.8 ppm/DEG C.
Recently, germanium-based garnet microwave dielectric ceramics have received high attention from researchers due to their generally high Q.times.f. values, such as Ca 3 B 2 Ge 3 O 12 (A＝Ga,Al)(Ceramics International,2020,46:28710～28715)、Ca 3 Y 2 Ge 3 O 12 (Journal ofthe European Ceramic Society,2020,40:3989～3995)、Ca 4 ZrGe 3 O 12 (Materials Letters,2020,275:128149)、Ca 3 MgBGe 3 O 12 (B＝Zr,Sn)(Ceramics International 48(2022)4658–4664)、Ca 2 AMg 2 Ge 2 VO 12 Germanium-based garnet such as (a=y, eu) (Materials Today Communications 33 (2022) 104706), but τ thereof f The values are between-70 ppm/DEG C and-40 ppm/DEG C, and the temperature coefficient (|tau) of the near zero resonance frequency is still difficult to meet f I.ltoreq.10 ppm/. Degree.C.). τ for optimizing germanium-based garnet microwave dielectric ceramics f Values, tang Ying et al (Journal of the European Ceramic Society,2020, 40:3989-3995, CN202010358668.9) by the method described in Ca 3 Ln 2 Ge 3 O 12 Substitution of Mg for Ca at a position (ln=y and Yb) to obtain a solid solution ceramic with adjustable temperature coefficient of resonance frequency, and substitution of Mg at Ca 0.5 Mg 2.5 Ln 2 Ge 3 O 12 Obtaining near zero tau on component ceramics f However, the Q.times.f. value at this time suddenly drops to less than 25000GHz, and the dielectric properties are seriously deteriorated. In addition, the subject group is also Ca 4 ZrGe 3-x Ti x O 12 Discovery of Ca in series microwave dielectric ceramics 4 ZrGe 2.5 Ti 0.5 O 12 Has excellent temperature stability, tau f =0.4 ppm/°c, but its sintering temperature is as high as 1370 ℃ (CN 202011197879.5), which is very energy-intensive to produce.
V. Mill et al found a series of Ge-free or Ge-depleted vanadium-based garnet including Ca 3 Mg 2 GeV 2 O 12 And Ca 3 Mg 2 SiV 2 O 12 Etc. (Russian Journal ofInorganic Chemistry,2014, vol.59, no.11, pp.1208-1213), which states that elements with larger ionic radii will cause the appearance of hetero-phases and even no garnet ceramic is obtained, from which it is possible to obtain a technical suggestion that tetrahedral sites of the series of compounds should be placed with elements with smaller ionic radii, i.e. cations in the tetrahedral sites, whose ionic radii should be smaller than or equal to Si 4+ 
Ge 4+ />
And V 5+ 
Is a metal ion radius. Tang Ying (garnet type low dielectric constant microwave dielectric ceramic preparation and performance [ D)]Beijing, university of Beijing technology and technology 2020) to prepare low dielectric constant microwave dielectric ceramic Ca with less Ge-containing raw material and sintering temperature lower than 1300 DEG C 3 Mg 2 GeV 2 O 12 The ceramic has a quality factor higher than 35000GHz, however τ f The value was still very large in the negative direction, reaching-61.2 ppm/. Degree.C.
It should be further noted that these germanium-based microwave dielectric ceramics are produced by GeO as a raw material 2 Expensive and sintering temperatures above substantially 1300 c make practical production costs prohibitive. How to keep sintering temperature low<1300 ℃, the cost of the obtained raw materials is relatively low, and the material can have near zero tau without adding composite modified materials f The value of the ceramic material and the higher Q multiplied by f value (more than or equal to 35000 GHz) are difficult problems to solve, and the problem is also a common problem of most of low-dielectric-constant microwave dielectric ceramics.
In general, solving for a material of greater negative τ f The main method of the value is to add a positive tau with a larger value f Value-modifying materials (e.g. CaTiO 3 Or TiO 2 Etc.) to perform a two-phase compounding of the materials, thereby adjusting tau of the material system f The value is near zero. But this method requires a tedious process: to be pure phaseHost material and modified material CaTiO 3 Weighing, ball milling, presintering, secondary ball milling, granulating, sieving and column pressing sintering according to a certain proportion. Before this, the host material and CaTiO 3 It is also necessary to carry out the steps of weighing, ball milling, presintering, secondary ball milling, granulating, sieving and column sintering in proportion. Tau finally obtained by this method f Composite ceramics with near zero values require significant process time and production energy consumption.
In summary, the preparation process is simple, the sintering temperature is lower than 1300 ℃, the material components do not contain or contain little Ge raw materials, and tau is not added additionally f In the case of value-modified materials, τ can be obtained f The low-dielectric-constant microwave dielectric ceramic material with the value close to zero and the Q multiplied by f value more than or equal to 35000GHz has obvious progress compared with most of the existing low-dielectric-constant microwave dielectric ceramic materials, and tau is not required to be additionally added f Value-modifying material obtainable τ f The preparation method of the low-dielectric-constant microwave dielectric ceramic material with the value of near zero and the Q multiplied by f value of more than or equal to 35000GHz can be an important answer for solving the common problem of the low-dielectric-constant microwave dielectric ceramic due to the outstanding substantial characteristics.
Disclosure of Invention
To solve the problems, the invention aims to provide a T f A vanadium-based low-dielectric constant microwave dielectric ceramic material with adjustable value and a preparation method thereof. The vanadium-based low-dielectric-constant microwave dielectric ceramic material is designed by taking the concept that the initial composition of the material does not contain Ge at the beginning of preparation, then carrying out ion substitution by taking the concept of not containing or containing little Ge, and finally obtaining the vanadium-based low-dielectric-constant microwave dielectric ceramic material with high quality factor (35093 GHz-52871 GHz) and adjustable resonant frequency temperature coefficient within the interval of-44.3 ppm/DEGC to-4.8 ppm/DEGC. In addition, the method for preparing the ceramic is simple and low in cost, and the ceramic is prepared by CaTiO formed in the sintering process 3 Ceramic τ f The value is adjusted to around zero and still maintain a high figure of merit.
In order to overcome the defects in the prior art, the technical scheme of the invention is as follows:
sintering temperature is 1200-1250 ℃, and resonant frequency temperatureCoefficient τ f The vanadium-based low-dielectric-constant microwave dielectric ceramic material with adjustable temperature between-44.3 ppm/DEG C and-4.8 ppm/DEG C is characterized in that: the chemical formula of the vanadium-based low-dielectric-constant microwave dielectric ceramic material is Ca 3 Mg 2 Ti 1-x M x V 2 O 12 (0.ltoreq.x.ltoreq.0.5; m=si, ge); the relative dielectric constant epsilon of the vanadium-based low-dielectric-constant microwave dielectric ceramic material r 11.13-12.22, and the quality factor Q multiplied by f is 35093-52871 GHz; when the value of x is 0, the phase structure of the vanadium-based low-dielectric-constant microwave dielectric ceramic material is garnet phase and CaTiO 3 And (3) phase (C). When M is Si,0<When x is less than or equal to 0.25, the phase structure of the vanadium-based low-dielectric-constant microwave dielectric ceramic material is garnet phase and CaTiO 3 A phase; when 0.25<And when x is less than or equal to 0.5, the phase structure of the vanadium-based low-dielectric-constant microwave dielectric ceramic material is garnet phase. When M is Ge,0<When x is less than or equal to 0.5, the phase structure of the vanadium-based low-dielectric-constant microwave dielectric ceramic material is garnet phase and CaTiO 3 And (3) phase (C). In the technical proposal, when the design material is initially composed, the ion radius in the four coordination environment is selected as
Ti of (2) 4+ And->
V of (2) 5+ Occupying tetrahedral positions, designing Ca 3 Mg 2 TiV 2 O 12 Then ion substitution is performed in the idea of not containing or containing little Ge.
The preparation method of the vanadium-based low-dielectric-constant microwave dielectric ceramic material comprises the following steps:
(1) CaCO as raw material 3 、MgO、TiO 2 、SiO 2 、GeO 2 NH (NH) 4 VO 3 Separately loading into polytetrafluoroethylene ball milling tanks, ball milling for 1 hour by taking zirconium dioxide balls and absolute ethyl alcohol as ball milling media, then placing the raw materials into a drying oven for drying at 120 ℃, and preserving heat at the temperature for later use;
(2) Drying the step (1) to obtain the standby raw materialThe materials are taken out according to Ca 3 Mg 2 Ti 1-x M x V 2 O 12 Weighing and proportioning the stoichiometric ratio of x is more than or equal to 0 and less than or equal to 0.5, M=Si and Ge, putting the prepared powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank, and then ball milling for 4 hours; drying the pasty raw materials after ball milling to obtain mixture powder;
(3) Pressing the mixture powder dried in the step (2) into a cylinder, placing the cylinder in a high-temperature furnace and presintering for 4 hours at 1000 ℃ to enable the raw material mixture to initially react to obtain a presintering material;
(4) Grinding the presintered material obtained by the preliminary reaction in the step (3) into powder, putting the powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank together, ball milling for 4 hours, and drying to obtain dry powder;
(5) Adding adhesive and oleic acid into the powder obtained after the step (4) is dried, granulating and sieving to obtain powder with uniformly dispersed particles and refined particle size, wherein the powder is divided into two parts for standby;
(6) Placing a part of the powder in the step (5) into a mould, and pressing into a cylinder under 150 MPa;
(7) Placing the cylinder formed by pressing in the step (6) into a crucible, pouring the powder serving as the buried powder in the other part of the step (5) into the crucible, enabling the powder to wrap and cover the cylinder, placing the crucible into a high-temperature furnace for sintering, keeping the sintering target temperature at 1200-1250 ℃ for 4 hours, and cooling along with the furnace to obtain the vanadium-based low-dielectric-constant microwave dielectric ceramic material.
Preferably, the purity of the raw material in the step (1) is more than or equal to 99%.
Preferably, the ball mill is operated at a rotational speed of 300 rpm.
Preferably, the polyvinyl alcohol solution has a mass concentration of 5%.
Preferably, the sintering process of the step (7) is divided into two different heating rates, wherein the heating rate before 500 ℃ is 2 ℃/min; the temperature rise rate from 500 ℃ to the target temperature was 5 ℃/min.
Advantages of the invention compared with the prior artThe method comprises the following steps: the material provided by the invention has low dielectric constant (11.13-12.22) and high quality factor (35093-52871 GHz), can improve the transmission rate of electric signals, can improve the selectivity of the working frequency of devices, and can adjust tau to be near zero f And the thermal stability of the device can be ensured. The ceramic preparation process of the invention can adjust the proportion of raw materials to form a second phase CaTiO in the material sintering process 3 Thereby significantly optimizing tau f A value; and the whole optimization process is carried out in one ceramic preparation process, and simultaneously, the use of expensive raw material GeO is avoided or reduced 2 The sintering temperature is lower than 1300 ℃, the process is simple, the energy consumption is lower, and the method is beneficial to industrial scale production.
Drawings
FIG. 1 is Ca 3 Mg 2 Ti 1-x M x V 2 O 12 (0.ltoreq.x.ltoreq.0.5; M=Si, ge) XRD pattern of the ceramic at optimum sintering temperature.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Ca according to the present invention 3 Mg 2 Ti 1-x M x V 2 O 12 (x is more than or equal to 0 and less than or equal to 0.5; M=Si, ge) the preparation method of the microwave dielectric ceramic material comprises the following steps:
(1) CaCO as raw material 3 、MgO、TiO 2 、SiO 2 、GeO 2 NH (NH) 4 VO 3 Separately loading into polytetrafluoroethylene ball milling tanks, ball milling for 1 hour by taking zirconium dioxide balls and absolute ethyl alcohol as ball milling media, then placing the raw materials into a drying oven for drying at 120 ℃, and preserving heat at the temperature for later use;
(2) Taking out the raw materials for standby after drying in the step (1) according to Ca 3 Mg 2 Ti 1-x M x V 2 O 12 Weighing and proportioning the stoichiometric ratio of x is more than or equal to 0 and less than or equal to 0.5, M=Si and Ge, putting the prepared powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank, and then ball milling for 4 hours; drying the pasty raw materials after ball milling to obtain mixture powder;
(3) Pressing the mixture powder dried in the step (2) into a cylinder, placing the cylinder in a high-temperature furnace and presintering for 4 hours at 1000 ℃ to enable the raw material mixture to initially react to obtain a presintering material;
(4) Grinding the presintered material obtained by the preliminary reaction in the step (3) into powder, putting the powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank together, ball milling for 4 hours, and drying to obtain dry powder;
(5) Adding adhesive and oleic acid into the powder obtained after the step (4) is dried, granulating and sieving to obtain powder with uniformly dispersed particles and refined particle size, wherein the powder is divided into two parts for standby;
(6) Placing a part of the powder in the step (5) into a mould, and pressing into a cylinder under 150 MPa;
(7) Placing the cylinder formed by pressing in the step (6) into a crucible, pouring the powder serving as the buried powder in the other part of the step (5) into the crucible, enabling the powder to wrap and cover the cylinder, placing the crucible into a high-temperature furnace for sintering, keeping the sintering target temperature at 1200-1250 ℃ for 4 hours, and cooling along with the furnace to obtain the vanadium-based low-dielectric-constant microwave dielectric ceramic material.
Example 1:
(1) CaCO as raw material 3 、MgO、TiO 2 NH (NH) 4 VO 3 Separately loading into polytetrafluoroethylene ball milling tanks, ball milling for 1 hour by taking zirconium dioxide balls and absolute ethyl alcohol as ball milling media, then placing the raw materials into a drying oven for drying at 120 ℃, and preserving heat at the temperature for later use;
(2) Taking out the raw materials for standby after drying in the step (1) according to Ca 3 Mg 2 TiV 2 O 12 Weighing the ingredients according to the stoichiometric ratio of the powder, zirconium dioxide balls and absolute ethyl alcohol, placing the ingredients in a polytetrafluoroethylene ball milling tank, and then ball milling for 4 hours; drying the pasty raw materials after ball milling to obtain mixture powder;
(3) Pressing the mixture powder dried in the step (2) into a cylinder, placing the cylinder in a high-temperature furnace and presintering for 4 hours at 1000 ℃ to enable the raw material mixture to initially react to obtain a presintering material;
(4) Grinding the presintered material obtained by the preliminary reaction in the step (3) into powder, putting the powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank together, ball milling for 4 hours, and drying to obtain dry powder;
(5) Adding adhesive and oleic acid into the powder obtained after the step (4) is dried, granulating and sieving to obtain powder with uniformly dispersed particles and refined particle size, wherein the powder is divided into two parts for standby;
(6) Placing a part of the powder in the step (5) into a mould, and pressing into a cylinder under 150 MPa;
(7) Placing the cylinder formed by pressing in the step (6) into a crucible, pouring the powder serving as the buried powder in the other part of the step (5) into the crucible, enabling the powder to wrap and cover the cylinder, placing the crucible into a high-temperature furnace for sintering, keeping the sintering target temperature at 1220 ℃, keeping the temperature at the target temperature for 4 hours, and cooling along with the furnace to obtain the vanadium-based low-dielectric-constant microwave dielectric ceramic material.
In a specific embodiment, the purity of the raw materials is more than or equal to 99%, the rotation speed of ball milling is 300 rpm, the mass concentration of the polyvinyl alcohol solution is 5%, the sintering process in the step (7) is divided into two different heating rates, and the heating rate before 500 ℃ is 2 ℃/min; the temperature rise rate from 500 ℃ to the target temperature was 5 ℃/min.
Example 2:
(1) CaCO as raw material 3 、MgO、TiO 2 NH (NH) 4 VO 3 Separately loading into polytetrafluoroethylene ball milling tanks, ball milling for 1 hour by taking zirconium dioxide balls and absolute ethyl alcohol as ball milling media, then placing the raw materials into a drying oven for drying at 120 ℃, and preserving heat at the temperature for later use;
(2) Taking out the raw materials for standby after drying in the step (1) according to Ca 3 Mg 2 TiV 2 O 12 Weighing the ingredients according to the stoichiometric ratio of the powder, zirconium dioxide balls and absolute ethyl alcohol, placing the ingredients in a polytetrafluoroethylene ball milling tank, and then ball milling for 4 hours; drying the pasty raw materials after ball milling to obtain mixture powder;
(3) Pressing the mixture powder dried in the step (2) into a cylinder, placing the cylinder in a high-temperature furnace and presintering for 4 hours at 1000 ℃ to enable the raw material mixture to initially react to obtain a presintering material;
(4) Grinding the presintered material obtained by the preliminary reaction in the step (3) into powder, putting the powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank together, ball milling for 4 hours, and drying to obtain dry powder;
(5) Adding adhesive and oleic acid into the powder obtained after the step (4) is dried, granulating and sieving to obtain powder with uniformly dispersed particles and refined particle size, wherein the powder is divided into two parts for standby;
(6) Placing a part of the powder in the step (5) into a mould, and pressing into a cylinder under 150 MPa;
(7) Placing the cylinder formed by pressing in the step (6) into a crucible, pouring the powder serving as the buried powder in the other part of the step (5) into the crucible, enabling the powder to wrap and cover the cylinder, placing the crucible into a high-temperature furnace for sintering, keeping the sintering target temperature at 1230 ℃ for 4 hours, and cooling along with the furnace to obtain the vanadium-based low-dielectric-constant microwave dielectric ceramic material.
In a specific embodiment, the purity of the raw materials is more than or equal to 99%, the rotation speed of ball milling is 300 rpm, the mass concentration of the polyvinyl alcohol solution is 5%, the sintering process in the step (7) is divided into two different heating rates, and the heating rate before 500 ℃ is 2 ℃/min; the temperature rise rate from 500 ℃ to the target temperature was 5 ℃/min.
Example 3
(1) CaCO as raw material 3 、MgO、TiO 2 NH (NH) 4 VO 3 Separately loading into polytetrafluoroethylene ball milling tanks, ball milling for 1 hour by taking zirconium dioxide balls and absolute ethyl alcohol as ball milling media, then placing the raw materials into a drying oven for drying at 120 ℃, and preserving heat at the temperature for later use;
(2) Taking out the raw materials for standby after drying in the step (1) according to Ca 3 Mg 2 TiV 2 O 12 Weighing the ingredients according to the stoichiometric ratio, and then placing the prepared powder, zirconium dioxide balls and absolute ethyl alcohol into polytetrafluoroethylene ball millBall milling for 4 hours in a tank; drying the pasty raw materials after ball milling to obtain mixture powder;
(3) Pressing the mixture powder dried in the step (2) into a cylinder, placing the cylinder in a high-temperature furnace and presintering for 4 hours at 1000 ℃ to enable the raw material mixture to initially react to obtain a presintering material;
(4) Grinding the presintered material obtained by the preliminary reaction in the step (3) into powder, putting the powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank together, ball milling for 4 hours, and drying to obtain dry powder;
(5) Adding adhesive and oleic acid into the powder obtained after the step (4) is dried, granulating and sieving to obtain powder with uniformly dispersed particles and refined particle size, wherein the powder is divided into two parts for standby;
(6) Placing a part of the powder in the step (5) into a mould, and pressing into a cylinder under 150 MPa;
(7) Placing the cylinder formed by pressing in the step (6) into a crucible, pouring the powder serving as the buried sintered powder in the other part of the step (5) into the crucible, enabling the powder to wrap and cover the cylinder, placing the crucible into a high-temperature furnace for sintering, keeping the sintering target temperature at 1240 ℃ for 4 hours, and cooling along with the furnace to obtain the vanadium-based low-dielectric-constant microwave dielectric ceramic material.
In a specific embodiment, the purity of the raw materials is more than or equal to 99%, the rotation speed of ball milling is 300 rpm, the mass concentration of the polyvinyl alcohol solution is 5%, the sintering process in the step (7) is divided into two different heating rates, and the heating rate before 500 ℃ is 2 ℃/min; the temperature rise rate from 500 ℃ to the target temperature was 5 ℃/min.
The ceramic materials obtained by sintering in examples 1 to 3 showed phase structures of garnet phase and CaTiO by XRD test 3 And (3) phase (C).
Example 4
(1) CaCO as raw material 3 、MgO、TiO 2 、SiO 2 NH (NH) 4 VO 3 Separately loading into polytetrafluoroethylene ball milling tank, ball milling with zirconium dioxide ball and absolute ethyl alcohol as ball milling medium for 1 hr, and dryingOven drying at 120deg.C, and keeping the temperature;
(2) Taking out the raw materials for standby after drying in the step (1) according to Ca 3 Mg 2 Ti 0.75 Si 0.25 V 2 O 12 Weighing the ingredients according to the stoichiometric ratio of the powder, zirconium dioxide balls and absolute ethyl alcohol, placing the ingredients in a polytetrafluoroethylene ball milling tank, and then ball milling for 4 hours; drying the pasty raw materials after ball milling to obtain mixture powder;
(3) Pressing the mixture powder dried in the step (2) into a cylinder, placing the cylinder in a high-temperature furnace and presintering for 4 hours at 1000 ℃ to enable the raw material mixture to initially react to obtain a presintering material;
(4) Grinding the presintered material obtained by the preliminary reaction in the step (3) into powder, putting the powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank together, ball milling for 4 hours, and drying to obtain dry powder;
(5) Adding adhesive and oleic acid into the powder obtained after the step (4) is dried, granulating and sieving to obtain powder with uniformly dispersed particles and refined particle size, wherein the powder is divided into two parts for standby;
(6) Placing a part of the powder in the step (5) into a mould, and pressing into a cylinder under 150 MPa;
(7) Placing the cylinder formed by pressing in the step (6) into a crucible, pouring the powder serving as the buried powder in the other part of the step (5) into the crucible, enabling the powder to wrap and cover the cylinder, placing the crucible into a high-temperature furnace for sintering, keeping the sintering target temperature at 1230 ℃ for 4 hours, and cooling along with the furnace to obtain the vanadium-based low-dielectric-constant microwave dielectric ceramic material.
In a specific embodiment, the purity of the raw materials is more than or equal to 99%, the rotation speed of ball milling is 300 rpm, the mass concentration of the polyvinyl alcohol solution is 5%, the sintering process in the step (7) is divided into two different heating rates, and the heating rate before 500 ℃ is 2 ℃/min; the temperature rise rate from 500 ℃ to the target temperature was 5 ℃/min.
Example 5
(1) CaCO as raw material 3 、MgO、TiO 2 、SiO 2 NH (NH) 4 VO 3 Separately loading into polytetrafluoroethylene ball milling tanks, ball milling for 1 hour by taking zirconium dioxide balls and absolute ethyl alcohol as ball milling media, then placing the raw materials into a drying oven for drying at 120 ℃, and preserving heat at the temperature for later use;
(2) Taking out the raw materials for standby after drying in the step (1) according to Ca 3 Mg 2 Ti 0.75 Si 0.25 V 2 O 12 Weighing the ingredients according to the stoichiometric ratio of the powder, zirconium dioxide balls and absolute ethyl alcohol, placing the ingredients in a polytetrafluoroethylene ball milling tank, and then ball milling for 4 hours; drying the pasty raw materials after ball milling to obtain mixture powder;
(3) Pressing the mixture powder dried in the step (2) into a cylinder, placing the cylinder in a high-temperature furnace and presintering for 4 hours at 1000 ℃ to enable the raw material mixture to initially react to obtain a presintering material;
(4) Grinding the presintered material obtained by the preliminary reaction in the step (3) into powder, putting the powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank together, ball milling for 4 hours, and drying to obtain dry powder;
(5) Adding adhesive and oleic acid into the powder obtained after the step (4) is dried, granulating and sieving to obtain powder with uniformly dispersed particles and refined particle size, wherein the powder is divided into two parts for standby;
(6) Placing a part of the powder in the step (5) into a mould, and pressing into a cylinder under 150 MPa;
(7) Placing the cylinder formed by pressing in the step (6) into a crucible, pouring the powder serving as the buried sintered powder in the other part of the step (5) into the crucible, enabling the powder to wrap and cover the cylinder, placing the crucible into a high-temperature furnace for sintering, keeping the sintering target temperature at 1240 ℃ for 4 hours, and cooling along with the furnace to obtain the vanadium-based low-dielectric-constant microwave dielectric ceramic material.
In a specific embodiment, the purity of the raw materials is more than or equal to 99%, the rotation speed of ball milling is 300 rpm, the mass concentration of the polyvinyl alcohol solution is 5%, the sintering process in the step (7) is divided into two different heating rates, and the heating rate before 500 ℃ is 2 ℃/min; the temperature rise rate from 500 ℃ to the target temperature was 5 ℃/min.
The ceramic materials obtained by sintering in example 4 and example 5 showed phase structures of garnet phase and CaTiO by XRD test 3 And (3) phase (C).
Example 6
(1) CaCO as raw material 3 、MgO、TiO 2 、SiO 2 NH (NH) 4 VO 3 Separately loading into polytetrafluoroethylene ball milling tanks, ball milling for 1 hour by taking zirconium dioxide balls and absolute ethyl alcohol as ball milling media, then placing the raw materials into a drying oven for drying at 120 ℃, and preserving heat at the temperature for later use;
(2) Taking out the raw materials for standby after drying in the step (1) according to Ca 3 Mg 2 Ti 0.625 Si 0.375 V 2 O 12 Weighing the ingredients according to the stoichiometric ratio of the powder, zirconium dioxide balls and absolute ethyl alcohol, placing the ingredients in a polytetrafluoroethylene ball milling tank, and then ball milling for 4 hours; drying the pasty raw materials after ball milling to obtain mixture powder;
(3) Pressing the mixture powder dried in the step (2) into a cylinder, placing the cylinder in a high-temperature furnace and presintering for 4 hours at 1000 ℃ to enable the raw material mixture to initially react to obtain a presintering material;
(4) Grinding the presintered material obtained by the preliminary reaction in the step (3) into powder, putting the powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank together, ball milling for 4 hours, and drying to obtain dry powder;
(5) Adding adhesive and oleic acid into the powder obtained after the step (4) is dried, granulating and sieving to obtain powder with uniformly dispersed particles and refined particle size, wherein the powder is divided into two parts for standby;
(6) Placing a part of the powder in the step (5) into a mould, and pressing into a cylinder under 150 MPa;
(7) Placing the cylinder formed by pressing in the step (6) into a crucible, pouring the powder serving as the buried powder in the other part of the step (5) into the crucible, enabling the powder to wrap and cover the cylinder, placing the crucible into a high-temperature furnace for sintering, keeping the sintering target temperature at 1250 ℃, preserving the temperature for 4 hours at the target temperature, and cooling along with the furnace to obtain the vanadium-based low-dielectric-constant microwave dielectric ceramic material.
In a specific embodiment, the purity of the raw materials is more than or equal to 99%, the rotation speed of ball milling is 300 rpm, the mass concentration of the polyvinyl alcohol solution is 5%, the sintering process in the step (7) is divided into two different heating rates, and the heating rate before 500 ℃ is 2 ℃/min; the temperature rise rate from 500 ℃ to the target temperature was 5 ℃/min.
The ceramic material obtained by sintering in example 6 shows that the phase structure is garnet phase through XRD test.
Example 7
(1) CaCO as raw material 3 、MgO、TiO 2 、SiO 2 NH (NH) 4 VO 3 Separately loading into polytetrafluoroethylene ball milling tanks, ball milling for 1 hour by taking zirconium dioxide balls and absolute ethyl alcohol as ball milling media, then placing the raw materials into a drying oven for drying at 120 ℃, and preserving heat at the temperature for later use;
(2) Taking out the raw materials for standby after drying in the step (1) according to Ca 3 Mg 2 Ti 0.5 Si 0.5 V 2 O 12 Weighing the ingredients according to the stoichiometric ratio of the powder, zirconium dioxide balls and absolute ethyl alcohol, placing the ingredients in a polytetrafluoroethylene ball milling tank, and then ball milling for 4 hours; drying the pasty raw materials after ball milling to obtain mixture powder;
(3) Pressing the mixture powder dried in the step (2) into a cylinder, placing the cylinder in a high-temperature furnace and presintering for 4 hours at 1000 ℃ to enable the raw material mixture to initially react to obtain a presintering material;
(4) Grinding the presintered material obtained by the preliminary reaction in the step (3) into powder, putting the powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank together, ball milling for 4 hours, and drying to obtain dry powder;
(5) Adding adhesive and oleic acid into the powder obtained after the step (4) is dried, granulating and sieving to obtain powder with uniformly dispersed particles and refined particle size, wherein the powder is divided into two parts for standby;
(6) Placing a part of the powder in the step (5) into a mould, and pressing into a cylinder under 150 MPa;
(7) Placing the cylinder formed by pressing in the step (6) into a crucible, pouring the powder serving as the buried sintered powder in the other part of the step (5) into the crucible, enabling the powder to wrap and cover the cylinder, placing the crucible into a high-temperature furnace for sintering, keeping the sintering target temperature at 1240 ℃ for 4 hours, and cooling along with the furnace to obtain the vanadium-based low-dielectric-constant microwave dielectric ceramic material.
In a specific embodiment, the purity of the raw materials is more than or equal to 99%, the rotation speed of ball milling is 300 rpm, the mass concentration of the polyvinyl alcohol solution is 5%, the sintering process in the step (7) is divided into two different heating rates, and the heating rate before 500 ℃ is 2 ℃/min; the temperature rise rate from 500 ℃ to the target temperature was 5 ℃/min.
Example 8
(1) CaCO as raw material 3 、MgO、TiO 2 、SiO 2 NH (NH) 4 VO 3 Separately loading into polytetrafluoroethylene ball milling tanks, ball milling for 1 hour by taking zirconium dioxide balls and absolute ethyl alcohol as ball milling media, then placing the raw materials into a drying oven for drying at 120 ℃, and preserving heat at the temperature for later use;
(2) Taking out the raw materials for standby after drying in the step (1) according to Ca 3 Mg 2 Ti 0.5 Si 0.5 V 2 O 12 Weighing the ingredients according to the stoichiometric ratio of the powder, zirconium dioxide balls and absolute ethyl alcohol, placing the ingredients in a polytetrafluoroethylene ball milling tank, and then ball milling for 4 hours; drying the pasty raw materials after ball milling to obtain mixture powder;
(3) Pressing the mixture powder dried in the step (2) into a cylinder, placing the cylinder in a high-temperature furnace and presintering for 4 hours at 1000 ℃ to enable the raw material mixture to initially react to obtain a presintering material;
(4) Grinding the presintered material obtained by the preliminary reaction in the step (3) into powder, putting the powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank together, ball milling for 4 hours, and drying to obtain dry powder;
(5) Adding adhesive and oleic acid into the powder obtained after the step (4) is dried, granulating and sieving to obtain powder with uniformly dispersed particles and refined particle size, wherein the powder is divided into two parts for standby;
(6) Placing a part of the powder in the step (5) into a mould, and pressing into a cylinder under 150 MPa;
(7) Placing the cylinder formed by pressing in the step (6) into a crucible, pouring the powder serving as the buried powder in the other part of the step (5) into the crucible, enabling the powder to wrap and cover the cylinder, placing the crucible into a high-temperature furnace for sintering, keeping the sintering target temperature at 1250 ℃, preserving the temperature for 4 hours at the target temperature, and cooling along with the furnace to obtain the vanadium-based low-dielectric-constant microwave dielectric ceramic material.
In a specific embodiment, the purity of the raw materials is more than or equal to 99%, the rotation speed of ball milling is 300 rpm, the mass concentration of the polyvinyl alcohol solution is 5%, the sintering process in the step (7) is divided into two different heating rates, and the heating rate before 500 ℃ is 2 ℃/min; the temperature rise rate from 500 ℃ to the target temperature was 5 ℃/min.
XRD testing of examples 7 and 8 showed that the phase structure was garnet phase.
Example 9
(1) CaCO as raw material 3 、MgO、TiO 2 、GeO 2 NH (NH) 4 VO 3 Separately loading into polytetrafluoroethylene ball milling tanks, ball milling for 1 hour by taking zirconium dioxide balls and absolute ethyl alcohol as ball milling media, then placing the raw materials into a drying oven for drying at 120 ℃, and preserving heat at the temperature for later use;
(2) Taking out the raw materials for standby after drying in the step (1) according to Ca 3 Mg 2 Ti 0.75 Ge 0.25 V 2 O 12 Weighing the ingredients according to the stoichiometric ratio of the powder, zirconium dioxide balls and absolute ethyl alcohol, placing the ingredients in a polytetrafluoroethylene ball milling tank, and then ball milling for 4 hours; drying the pasty raw materials after ball milling to obtain mixture powder;
(3) Pressing the mixture powder dried in the step (2) into a cylinder, placing the cylinder in a high-temperature furnace and presintering for 4 hours at 1000 ℃ to enable the raw material mixture to initially react to obtain a presintering material;
(4) Grinding the presintered material obtained by the preliminary reaction in the step (3) into powder, putting the powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank together, ball milling for 4 hours, and drying to obtain dry powder;
(5) Adding adhesive and oleic acid into the powder obtained after the step (4) is dried, granulating and sieving to obtain powder with uniformly dispersed particles and refined particle size, wherein the powder is divided into two parts for standby;
(6) Placing a part of the powder in the step (5) into a mould, and pressing into a cylinder under 150 MPa;
(7) Placing the cylinder formed by pressing in the step (6) into a crucible, pouring the powder serving as the buried sintered powder in the other part of the step (5) into the crucible, enabling the powder to wrap and cover the cylinder, placing the crucible into a high-temperature furnace for sintering, keeping the sintering target temperature at 1210 ℃, preserving the temperature for 4 hours at the target temperature, and cooling along with the furnace to obtain the vanadium-based low-dielectric-constant microwave dielectric ceramic material.
In a specific embodiment, the purity of the raw materials is more than or equal to 99%, the rotation speed of ball milling is 300 rpm, the mass concentration of the polyvinyl alcohol solution is 5%, the sintering process in the step (7) is divided into two different heating rates, and the heating rate before 500 ℃ is 2 ℃/min; the temperature rise rate from 500 ℃ to the target temperature was 5 ℃/min.
Example 10
(1) CaCO as raw material 3 、MgO、TiO 2 、GeO 2 NH (NH) 4 VO 3 Separately loading into polytetrafluoroethylene ball milling tanks, ball milling for 1 hour by taking zirconium dioxide balls and absolute ethyl alcohol as ball milling media, then placing the raw materials into a drying oven for drying at 120 ℃, and preserving heat at the temperature for later use;
(2) Taking out the raw materials for standby after drying in the step (1) according to Ca 3 Mg 2 Ti 0.75 Ge 0.25 V 2 O 12 Weighing the ingredients according to the stoichiometric ratio of the powder, zirconium dioxide balls and absolute ethyl alcohol, placing the ingredients in a polytetrafluoroethylene ball milling tank, and then ball milling for 4 hours; drying the pasty raw materials after ball milling to obtain mixture powder;
(3) Pressing the mixture powder dried in the step (2) into a cylinder, placing the cylinder in a high-temperature furnace and presintering for 4 hours at 1000 ℃ to enable the raw material mixture to initially react to obtain a presintering material;
(4) Grinding the presintered material obtained by the preliminary reaction in the step (3) into powder, putting the powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank together, ball milling for 4 hours, and drying to obtain dry powder;
(5) Adding adhesive and oleic acid into the powder obtained after the step (4) is dried, granulating and sieving to obtain powder with uniformly dispersed particles and refined particle size, wherein the powder is divided into two parts for standby;
(6) Placing a part of the powder in the step (5) into a mould, and pressing into a cylinder under 150 MPa;
(7) Placing the cylinder formed by pressing in the step (6) into a crucible, pouring the powder serving as the buried powder in the other part of the step (5) into the crucible, enabling the powder to wrap and cover the cylinder, placing the crucible into a high-temperature furnace for sintering, keeping the sintering target temperature at 1220 ℃, keeping the temperature at the target temperature for 4 hours, and cooling along with the furnace to obtain the vanadium-based low-dielectric-constant microwave dielectric ceramic material.
In a specific embodiment, the purity of the raw materials is more than or equal to 99%, the rotation speed of ball milling is 300 rpm, the mass concentration of the polyvinyl alcohol solution is 5%, the sintering process in the step (7) is divided into two different heating rates, and the heating rate before 500 ℃ is 2 ℃/min; the temperature rise rate from 500 ℃ to the target temperature was 5 ℃/min.
Example 11
(1) CaCO as raw material 3 、MgO、TiO 2 、GeO 2 NH (NH) 4 VO 3 Separately loading into polytetrafluoroethylene ball milling tanks, ball milling for 1 hour by taking zirconium dioxide balls and absolute ethyl alcohol as ball milling media, then placing the raw materials into a drying oven for drying at 120 ℃, and preserving heat at the temperature for later use;
(2) Taking out the raw materials for standby after drying in the step (1) according to Ca 3 Mg 2 Ti 0.5 Ge 0.5 V 2 O 12 Weighing the ingredients according to the stoichiometric ratio, and placing the prepared powder, zirconium dioxide balls and absolute ethyl alcohol into a poly-reactorBall milling for 4 hours in a tetrafluoroethylene ball milling tank; drying the pasty raw materials after ball milling to obtain mixture powder;
(3) Pressing the mixture powder dried in the step (2) into a cylinder, placing the cylinder in a high-temperature furnace and presintering for 4 hours at 1000 ℃ to enable the raw material mixture to initially react to obtain a presintering material;
(4) Grinding the presintered material obtained by the preliminary reaction in the step (3) into powder, putting the powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank together, ball milling for 4 hours, and drying to obtain dry powder;
(5) Adding adhesive and oleic acid into the powder obtained after the step (4) is dried, granulating and sieving to obtain powder with uniformly dispersed particles and refined particle size, wherein the powder is divided into two parts for standby;
(6) Placing a part of the powder in the step (5) into a mould, and pressing into a cylinder under 150 MPa;
(7) Placing the cylinder formed by pressing in the step (6) into a crucible, pouring the powder serving as the buried sintered powder in the other part of the step (5) into the crucible, enabling the powder to wrap and cover the cylinder, placing the crucible into a high-temperature furnace for sintering, keeping the sintering target temperature at 1200 ℃, preserving the temperature for 4 hours at the target temperature, and cooling along with the furnace to obtain the vanadium-based low-dielectric-constant microwave dielectric ceramic material.
In a specific embodiment, the purity of the raw materials is more than or equal to 99%, the rotation speed of ball milling is 300 rpm, the mass concentration of the polyvinyl alcohol solution is 5%, the sintering process in the step (7) is divided into two different heating rates, and the heating rate before 500 ℃ is 2 ℃/min; the temperature rise rate from 500 ℃ to the target temperature was 5 ℃/min.
Example 12
(1) CaCO as raw material 3 、MgO、TiO 2 、GeO 2 NH (NH) 4 VO 3 Separately loading into polytetrafluoroethylene ball milling tanks, ball milling for 1 hour by taking zirconium dioxide balls and absolute ethyl alcohol as ball milling media, then placing the raw materials into a drying oven for drying at 120 ℃, and preserving heat at the temperature for later use;
(2) Taking out the spare raw materials after drying in the step (1), and pressingAccording to Ca 3 Mg 2 Ti 0.5 Ge 0.5 V 2 O 12 Weighing the ingredients according to the stoichiometric ratio of the powder, zirconium dioxide balls and absolute ethyl alcohol, placing the ingredients in a polytetrafluoroethylene ball milling tank, and then ball milling for 4 hours; drying the pasty raw materials after ball milling to obtain mixture powder;
(3) Pressing the mixture powder dried in the step (2) into a cylinder, placing the cylinder in a high-temperature furnace and presintering for 4 hours at 1000 ℃ to enable the raw material mixture to initially react to obtain a presintering material;
(4) Grinding the presintered material obtained by the preliminary reaction in the step (3) into powder, putting the powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank together, ball milling for 4 hours, and drying to obtain dry powder;
(5) Adding adhesive and oleic acid into the powder obtained after the step (4) is dried, granulating and sieving to obtain powder with uniformly dispersed particles and refined particle size, wherein the powder is divided into two parts for standby;
(6) Placing a part of the powder in the step (5) into a mould, and pressing into a cylinder under 150 MPa;
(7) Placing the cylinder formed by pressing in the step (6) into a crucible, pouring the powder serving as the buried sintered powder in the other part of the step (5) into the crucible, enabling the powder to wrap and cover the cylinder, placing the crucible into a high-temperature furnace for sintering, keeping the sintering target temperature at 1210 ℃, preserving the temperature for 4 hours at the target temperature, and cooling along with the furnace to obtain the vanadium-based low-dielectric-constant microwave dielectric ceramic material.
In a specific embodiment, the purity of the raw materials is more than or equal to 99%, the rotation speed of ball milling is 300 rpm, the mass concentration of the polyvinyl alcohol solution is 5%, the sintering process in the step (7) is divided into two different heating rates, and the heating rate before 500 ℃ is 2 ℃/min; the temperature rise rate from 500 ℃ to the target temperature was 5 ℃/min.
The ceramic materials obtained by sintering in examples 9 to 12 showed phase structures of garnet phase and CaTiO by XRD test 3 And (3) phase (C).
Table 1 shows the microwave dielectric properties of the various embodiments.
TABLE 1
FIG. 1 is Ca 3 Mg 2 Ti 1-x M x V 2 O 12 (0.ltoreq.x.ltoreq.0.5; M=Si, ge). As can be seen from the graph, when the value of x is 0, the phase structure of the vanadium-based low-dielectric-constant microwave dielectric ceramic material is garnet phase and CaTiO 3 And (3) phase (C). When M is Si,0<When x is less than or equal to 0.25, the phase structure of the vanadium-based low-dielectric-constant microwave dielectric ceramic material is garnet phase and CaTiO 3 A phase; when 0.25<And when x is less than or equal to 0.5, the phase structure of the vanadium-based low-dielectric-constant microwave dielectric ceramic material is garnet phase. When M is Ge,0<When x is less than or equal to 0.5, the phase structure of the vanadium-based low-dielectric-constant microwave dielectric ceramic material is garnet phase and CaTiO 3 And (3) phase (C). In the presence of CaTiO 3 In the XRD pattern of the material, caTiO is formed during sintering 3 Is gradually evident on the diffraction peak as the x value increases.
While the invention has been described in detail in connection with specific preferred embodiments thereof, it is to be understood that the specific embodiments of the invention are not limited thereto, and that several simple deductions or substitutions may be made by those skilled in the art without departing from the spirit of the invention, and it is intended that the claims appended hereto define the scope of the invention.
Claims (10)
1. Sintering temperature is 1200-1250 ℃, and resonant frequency temperature coefficient tau f The vanadium-based low-dielectric-constant microwave dielectric ceramic material with adjustable temperature between-44.3 ppm/DEG C and-4.8 ppm/DEG C is characterized in that: the chemical formula of the vanadium-based low-dielectric-constant microwave dielectric ceramic material is Ca 3 Mg 2 Ti 1-x M x V 2 O 12 (0≤x≤0.5；M＝Si、Ge)。
2. Vanadium according to claim 1The microwave dielectric ceramic material with low dielectric constant is characterized in that: the relative dielectric constant epsilon of the vanadium-based low-dielectric-constant microwave dielectric ceramic material r The quality factor Q multiplied by f is 35093-52871 GHz, and is 11.13-12.22.
3. The vanadium-based low dielectric constant microwave dielectric ceramic material according to claim 1, wherein: when the value of x is 0, the phase structure of the vanadium-based low-dielectric-constant microwave dielectric ceramic material is garnet phase and CaTiO 3 And (3) phase (C).
4. The vanadium-based low dielectric constant microwave dielectric ceramic material according to claim 1, wherein: when M is Si,0<When x is less than or equal to 0.25, the phase structure of the vanadium-based low-dielectric-constant microwave dielectric ceramic material is garnet phase and CaTiO 3 A phase; when 0.25<And when x is less than or equal to 0.5, the phase structure of the vanadium-based low-dielectric-constant microwave dielectric ceramic material is garnet phase.
5. The vanadium-based low dielectric constant microwave dielectric ceramic material according to claim 1, wherein: when M is Ge,0<When x is less than or equal to 0.5, the phase structure of the vanadium-based low-dielectric-constant microwave dielectric ceramic material is garnet phase and CaTiO 3 And (3) phase (C).
6. A method for preparing a vanadium-based low-dielectric-constant microwave dielectric ceramic material according to any one of claims 1 to 5, wherein: the method comprises the following steps:
(1) CaCO as raw material 3 、MgO、TiO 2 、SiO 2 、GeO 2 NH (NH) 4 VO 3 Separately loading into polytetrafluoroethylene ball milling tanks, ball milling for 1 hour by taking zirconium dioxide balls and absolute ethyl alcohol as ball milling media, then placing the raw materials into a drying oven for drying at 120 ℃, and preserving heat at the temperature for later use;
(2) Taking out the raw materials for standby after drying in the step (1) according to Ca 3 Mg 2 Ti 1-x M x V 2 O 12 Stoichiometric ratio weighing of (0.ltoreq.x.ltoreq.0.5; m=si, ge)Proportioning, namely placing the prepared powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank, and then ball milling for 4 hours; drying the pasty raw materials after ball milling to obtain mixture powder;
(3) Pressing the mixture powder dried in the step (2) into a cylinder, placing the cylinder in a high-temperature furnace and presintering for 4 hours at 1000 ℃ to enable the raw material mixture to initially react to obtain a presintering material;
(4) Grinding the presintered material obtained by the preliminary reaction in the step (3) into powder, putting the powder, zirconium dioxide balls and absolute ethyl alcohol into a polytetrafluoroethylene ball milling tank together, ball milling for 4 hours, and drying to obtain dry powder;
(5) Adding adhesive and oleic acid into the powder obtained after the step (4) is dried, granulating and sieving to obtain powder with uniformly dispersed particles and refined particle size, wherein the powder is divided into two parts for standby;
(6) Placing a part of the powder in the step (5) into a mould, and pressing into a cylinder under 150 MPa;
(7) Placing the cylinder formed by pressing in the step (6) into a crucible, pouring the powder serving as the buried powder in the other part of the step (5) into the crucible, enabling the powder to wrap and cover the cylinder, placing the crucible into a high-temperature furnace for sintering, keeping the sintering target temperature at 1200-1250 ℃ for 4 hours, and cooling along with the furnace to obtain the vanadium-based low-dielectric-constant microwave dielectric ceramic material.
7. The method for preparing a vanadium-based low dielectric constant microwave dielectric ceramic material according to claim 6, wherein the purity of the raw material in the step (1) is not less than 99%.
8. The method for preparing a vanadium-based low dielectric constant microwave dielectric ceramic material according to claim 6, wherein the rotation speed of the ball mill is 300 rpm.
9. The method for preparing a vanadium-based low dielectric constant microwave dielectric ceramic material according to claim 6, wherein the binder is a polyvinyl alcohol solution with a mass concentration of 5%.
10. The method of preparing a vanadium-based low dielectric constant microwave dielectric ceramic material according to claim 6, wherein the sintering process of step (7) is divided into two different heating rates, and the heating rate before 500 ℃ is 2 ℃/min; the temperature rise rate from 500 ℃ to the target temperature was 5 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211586763.XA CN116283282B (en) | 2022-12-09 | 2022-12-09 | Vanadium-based low-dielectric-constant microwave dielectric ceramic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211586763.XA CN116283282B (en) | 2022-12-09 | 2022-12-09 | Vanadium-based low-dielectric-constant microwave dielectric ceramic material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116283282A true CN116283282A (en) | 2023-06-23 |
| CN116283282B CN116283282B (en) | 2024-03-08 |
Family
ID=86802047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211586763.XA Active CN116283282B (en) | 2022-12-09 | 2022-12-09 | Vanadium-based low-dielectric-constant microwave dielectric ceramic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116283282B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002362974A (en) * | 2002-06-07 | 2002-12-18 | Kyocera Corp | Sintered compact sintered at low temperature |
| US20030158031A1 (en) * | 2001-03-30 | 2003-08-21 | Isuhak Naseemabeevi Jawahar | Microwave dielectric ceramic composition and a process for the preparation thereof |
| US20100105538A1 (en) * | 2008-10-29 | 2010-04-29 | Walsin Technology Corporation | Microwave Dielectric Ceramics And Method For Manufacturing The Same |
| CN108358633A (en) * | 2018-05-24 | 2018-08-03 | 电子科技大学 | A kind of low-temperature sintering Ca5Mn4-xMgxV6O24Microwave dielectric material and preparation method thereof |
| CN111517789A (en) * | 2020-04-29 | 2020-08-11 | 桂林理工大学 | Low-dielectric microwave dielectric ceramic material and preparation method thereof |
| CN112408980A (en) * | 2020-10-31 | 2021-02-26 | 桂林理工大学 | Low-dielectric-constant microwave dielectric ceramic with adjustable resonant frequency temperature coefficient and preparation method thereof |
| CN112479704A (en) * | 2020-12-09 | 2021-03-12 | 江苏科技大学 | Low-temperature sintered high-permittivity microwave dielectric ceramic material and preparation method thereof |
| US20210355035A1 (en) * | 2020-03-17 | 2021-11-18 | Guangdong Fenghua Advanced Technology Holding Co., Ltd. | Ltcc microwave dielectric material and preparation method thereof |
-
2022
- 2022-12-09 CN CN202211586763.XA patent/CN116283282B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030158031A1 (en) * | 2001-03-30 | 2003-08-21 | Isuhak Naseemabeevi Jawahar | Microwave dielectric ceramic composition and a process for the preparation thereof |
| JP2002362974A (en) * | 2002-06-07 | 2002-12-18 | Kyocera Corp | Sintered compact sintered at low temperature |
| US20100105538A1 (en) * | 2008-10-29 | 2010-04-29 | Walsin Technology Corporation | Microwave Dielectric Ceramics And Method For Manufacturing The Same |
| CN108358633A (en) * | 2018-05-24 | 2018-08-03 | 电子科技大学 | A kind of low-temperature sintering Ca5Mn4-xMgxV6O24Microwave dielectric material and preparation method thereof |
| US20210355035A1 (en) * | 2020-03-17 | 2021-11-18 | Guangdong Fenghua Advanced Technology Holding Co., Ltd. | Ltcc microwave dielectric material and preparation method thereof |
| CN111517789A (en) * | 2020-04-29 | 2020-08-11 | 桂林理工大学 | Low-dielectric microwave dielectric ceramic material and preparation method thereof |
| CN112408980A (en) * | 2020-10-31 | 2021-02-26 | 桂林理工大学 | Low-dielectric-constant microwave dielectric ceramic with adjustable resonant frequency temperature coefficient and preparation method thereof |
| CN112479704A (en) * | 2020-12-09 | 2021-03-12 | 江苏科技大学 | Low-temperature sintered high-permittivity microwave dielectric ceramic material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| HUIZI QIU等人: "Tuning of microwave dielectric properties of garnets Ca3Mg2CV2O12 (C =Si, Ti) through compression and expansion effects", 《CERAMICS INTERNATIONAL》, vol. 49, pages 565 - 570 * |
| WEISAN FANG等人: "Relationship between the structure and microwave dielectric properties of garnet ceramics Ca3B2GeV2O12 (B =Mg, Mn)", 《CERAMICS INTERNATIONAL》, vol. 48, pages 4318 - 4323 * |
| 王焕平;张启龙;杨辉;: "纳米(Ca_(0.7)Mg_(0.3))SiO_3粉体的低温合成与微波介电性能研究", 浙江大学学报(工学版), no. 08, pages 140 - 143 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116283282B (en) | 2024-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ren et al. | Novel Al 2 Mo 3 O 12-based temperature-stable microwave dielectric ceramics for LTCC applications | |
| CN107010942B (en) | Ceramic dielectric resonator for high-Q-value communication | |
| CN108358632B (en) | Ultralow-temperature sintered high-Q x f-value microwave dielectric material and preparation method thereof | |
| CN110282968A (en) | A kind of microwave dielectric ceramic materials and preparation method thereof | |
| CN111517789B (en) | Low-dielectric microwave dielectric ceramic material and preparation method thereof | |
| CN107117967B (en) | Low-temperature sintered composite microwave dielectric ceramic material and preparation method thereof | |
| CN114394827B (en) | Low-dielectric-constant silicate microwave dielectric ceramic and preparation method thereof | |
| CN113105231B (en) | Microwave dielectric ceramic material and preparation method thereof | |
| CN112408980A (en) | Low-dielectric-constant microwave dielectric ceramic with adjustable resonant frequency temperature coefficient and preparation method thereof | |
| CN111470864B (en) | Silicon-based temperature-stable microwave dielectric ceramic material and preparation method thereof | |
| CN105254293A (en) | Microwave dielectric ceramic material and preparation method thereof | |
| CN115010489B (en) | Mineral-based microwave dielectric ceramic material and preparation method and application thereof | |
| CN107244916B (en) | Niobate-series low-temperature sintered microwave dielectric ceramic material and preparation method thereof | |
| CN114634352A (en) | Silicon-germanium-based low-dielectric microwave dielectric ceramic and preparation method thereof | |
| CN116283282B (en) | Vanadium-based low-dielectric-constant microwave dielectric ceramic material and preparation method thereof | |
| CN112299837A (en) | Low-dielectric microwave dielectric ceramic material and temperature-frequency characteristic regulation and control method thereof | |
| CN112960971A (en) | Microwave dielectric ceramic material and preparation method thereof | |
| CN111848151A (en) | Titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material and preparation method and application thereof | |
| CN110903078A (en) | Ultralow dielectric constant LTCC microwave ceramic material and preparation method thereof | |
| CN114736012B (en) | Low dielectric microwave dielectric ceramic with ultrahigh Q value and LTCC material thereof | |
| CN111943670B (en) | LiWVO 6 -K 2 MoO 4 Base composite ceramic microwave material and preparation method thereof | |
| CN112830780B (en) | Regulating agent, LTCC microwave dielectric material and preparation method thereof | |
| CN112079631B (en) | Low-dielectric LTCC material with near-zero temperature coefficient and preparation method thereof | |
| CN114835480A (en) | Cordierite microwave dielectric material with ultralow dielectric constant and near-zero resonant frequency temperature coefficient and preparation method thereof | |
| CN111960821B (en) | Microwave dielectric ceramic material and preparation method and application thereof |
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 |