CN116924782A - Microwave dielectric material with bionic structure and preparation method thereof - Google Patents
Microwave dielectric material with bionic structure and preparation method thereof Download PDFInfo
- Publication number
- CN116924782A CN116924782A CN202210341679.5A CN202210341679A CN116924782A CN 116924782 A CN116924782 A CN 116924782A CN 202210341679 A CN202210341679 A CN 202210341679A CN 116924782 A CN116924782 A CN 116924782A
- Authority
- CN
- China
- Prior art keywords
- glass
- microwave dielectric
- dielectric material
- lrabs
- source
- 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.)
- Pending
Links
- 239000003989 dielectric material Substances 0.000 title claims abstract description 42
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 144
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 24
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 9
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 9
- 238000013329 compounding Methods 0.000 claims abstract description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 3
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 126
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 91
- 238000001035 drying Methods 0.000 claims description 57
- 239000000919 ceramic Substances 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 41
- 238000007873 sieving Methods 0.000 claims description 41
- 239000002270 dispersing agent Substances 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- 239000003292 glue Substances 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 17
- 238000007599 discharging Methods 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 16
- 229910001597 celsian Inorganic materials 0.000 claims description 11
- 238000010791 quenching Methods 0.000 claims description 11
- 230000000171 quenching effect Effects 0.000 claims description 11
- 238000009736 wetting Methods 0.000 claims description 10
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052863 mullite Inorganic materials 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 229910052661 anorthite Inorganic materials 0.000 claims description 7
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 239000010433 feldspar Substances 0.000 claims description 6
- 239000012634 fragment Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000391 magnesium silicate Substances 0.000 claims description 5
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 5
- 235000019792 magnesium silicate Nutrition 0.000 claims description 5
- 229910052916 barium silicate Inorganic materials 0.000 claims description 4
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000378 calcium silicate Substances 0.000 claims description 4
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 4
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 4
- 229910001648 diaspore Inorganic materials 0.000 claims description 4
- 238000005189 flocculation Methods 0.000 claims description 4
- 230000016615 flocculation Effects 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000010345 tape casting Methods 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002667 nucleating agent Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 238000010344 co-firing Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 230000003592 biomimetic effect Effects 0.000 claims 5
- 230000003311 flocculating effect Effects 0.000 claims 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 62
- 239000000463 material Substances 0.000 description 49
- 238000000498 ball milling Methods 0.000 description 41
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 28
- 239000008367 deionised water Substances 0.000 description 25
- 229910021641 deionized water Inorganic materials 0.000 description 25
- 239000002002 slurry Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000004698 Polyethylene Substances 0.000 description 24
- -1 polyethylene Polymers 0.000 description 24
- 229920000573 polyethylene Polymers 0.000 description 24
- 238000012360 testing method Methods 0.000 description 21
- 238000005266 casting Methods 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 239000004615 ingredient Substances 0.000 description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 14
- 239000004014 plasticizer Substances 0.000 description 14
- 239000008096 xylene Substances 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000010030 laminating Methods 0.000 description 11
- 239000011812 mixed powder Substances 0.000 description 11
- 238000009740 moulding (composite fabrication) Methods 0.000 description 11
- 239000004576 sand Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 8
- 239000000156 glass melt Substances 0.000 description 8
- 238000007731 hot pressing Methods 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 229910015999 BaAl Inorganic materials 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000008429 bread Nutrition 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000007499 fusion processing Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000648001 Anolis alumina Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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
- C04B35/10—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 aluminium oxide
- C04B35/111—Fine ceramics
- C04B35/117—Composites
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
- C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
-
- 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
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/20—Glass-ceramics matrix
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/30—Methods of making the composites
-
- 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
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3218—Aluminium (oxy)hydroxides, e.g. boehmite, gibbsite, alumina sol
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
- C04B2235/365—Borosilicate glass
-
- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5292—Flakes, platelets or plates
-
- 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
-
- 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
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to a microwave dielectric material with a bionic structure and a preparation method thereof. The microwave dielectric material of the bionic structure is formed by directionally arranging flaky Al 2 O 3 The ceramic material with the simulated pearl layer structure is formed by compounding a phase and an LRABS microcrystalline glass phase; the LRABS glass ceramic is Ln 2 O 3 ‑RO‑Al 2 O 3 ‑B 2 O 3 ‑SiO 2 The microcrystalline glass comprises the following raw materials in parts by weight: 0 to 30mol% Ln 2 O 3 0 to 60mol% of RO, 0 to 10mol% of B 2 O 3 0 to 30mol% of Al 2 O 3 30 to 80mol percent of SiO 2 The sum of the mole percentages of the components is 100 mole percent; wherein ln=at least one of the lanthanides and r= Mg, ca, sr, ba.
Description
Technical Field
The invention relates to a high-strength, high-toughness, high-frequency and low-dielectric-constant bionic structure microcrystalline glass/ceramic composite microwave dielectric material and a preparation method thereof, belonging to the field of electronic information functional materials.
Background
In recent years, microwave technology has been developed toward higher frequencies, and mobile communication and portable terminals have been developed toward miniaturization, integration, weight saving, high reliability, and low cost while expanding the frequency bandwidth and fully utilizing the frequency bandwidth resources. With the rapid development of millimeter wave communication and radar technology, research on low dielectric constant materials at home and abroad is increasingly strengthened, and the researched materials are also various, wherein the important class is the low dielectric microwave dielectric ceramic material. However, these materials are used at a slow rate in millimeter wave communication and integrated circuit production processes, and many low dielectric constant materials do not meet the application requirements of electronic device and integrated circuit processes in millimeter wave communication. The main reason is that there are now much attention paid to the following two problems: (1) the sintering temperature is too high, so that low-temperature sintering is difficult to realize; (2) The requirements of microwave electronic components cannot be met by regulating dielectric properties, such as a larger frequency temperature coefficient or a lower quality factor. A more important problem is often ignored, and in a high-frequency working environment, the device can instantaneously generate relatively large heat, so that new requirements on the temperature impact resistance and mechanical properties of the material are put forward. In the future, how to optimize the dielectric property and mechanical property of the low-dielectric-constant microwave dielectric ceramic material at the same time and accelerate the industrialization process is an important point of research by people.
Therefore, the exploration of a new preparation method ensures that the dielectric loss value does not rise or does not rise much while improving the dielectric property and optimizing the mechanical property of the microwave dielectric ceramic, and is still a main problem facing the research of low-dielectric microwave dielectric ceramic at present.
Disclosure of Invention
In order to solve the problems, the invention designs a bionic structure and combines low dielectric and low-loss microcrystalline glass with low dielectric and high-strength microwave dielectric ceramics, so that the obtained composite material has excellent performances of low dielectric, low loss, high strength, high toughness and the like.
Specifically, the invention provides a microwave dielectric material with a bionic structure, wherein the microwave dielectric material with the bionic structure is formed by directionally arranging flaky Al 2 O 3 The ceramic material with the simulated pearl layer structure is formed by compounding a phase and an LRABS microcrystalline glass phase; the LRABS glass ceramic is Ln 2 O 3 -RO-Al 2 O 3 -B 2 O 3 -SiO 2 The microcrystalline glass comprises the following raw materials in parts by weight: 0 to 30mol% Ln 2 O 3 0 to 60mol% of RO, 0 to 10mol% of B 2 O 3 0 to 30mol% of Al 2 O 3 30 to 80mol percent of SiO 2 The sum of the mole percentages of the components is 100 mole percent; wherein ln=at least one of the lanthanides and r= Mg, ca, sr, ba.
Preferably, the flaky Al 2 O 3 The mass ratio of the phase to the LRABS microcrystalline glass phase is (9.5-0.1): 1.
Preferably, the microwave dielectric material of the bionic structure further comprises non-flaky alumina; the mass ratio of the non-flaky alumina to the flaky alumina phase is not more than 2:1.
preferably, the LRABS microcrystalline glass is also doped with a nucleating agent or a colorant which is not more than 5 weight percent of the total mass of the raw materials; the glass transition temperature of the LRABS microcrystalline glass is 600-900 ℃, and the crystallization temperature is 700-1200 ℃; preferably, the devitrified phase of the LRABS microcrystalline glass comprises at least one of mullite, magnesium silicate, calcium silicate, barium silicate, celsian, anorthite, and diaspore.
Preferably, when the sintering temperature is 1200-1650 ℃, the microwave dielectric material of the bionic structure is a microcrystalline glass and alumina phase composite material containing one or more crystalline phases of mullite, celsian, anorthite and strontium feldspar; when the sintering temperature is 800-1200 ℃, the microwave dielectric material of the bionic structure is an LRABS microcrystalline glass and alumina phase composite material containing one or more crystal phases of mullite, magnesium silicate, calcium silicate, barium silicate, celsian, anorthite, strontium feldspar and diasporite.
According to the invention, the microwave dielectric material with comprehensive excellent performance can be obtained by adjusting the percentage mass ratio of microcrystalline glass to ceramic phase in the composite material and the directional arrangement of the sheet-shaped materials. The ceramic material can be matched with silver, silver palladium, copper, gold and tungsten electrodes for co-firing.
Preferably, the bending strength of the glass ceramic/ceramic composite microwave dielectric material is 200-500 MPa (preferably 300-500 MPa), the dielectric constant is 4-10, and the dielectric loss is 2 multiplied by 10 -4 ～2×10 -3 The thermal expansion coefficient is 7-11 ppm/DEG C, and the thermal conductivity coefficient is more than or equal to 5W/(m.K).
On the other hand, the invention also provides a preparation method of the microcrystalline glass/ceramic composite microwave dielectric material, which comprises the following steps:
preparing LRABS glass powder;
LRABS glass powder and flaky Al 2 O 3 Mixing powder, a non-flaky alumina source, an organic solvent, a binder and a dispersing agent, carrying out tape casting and forming, and carrying out hot press forming to obtain a blank;
and discharging the glue from the obtained blank, and sintering at 800-1600 ℃ for 0.1-6 hours to obtain the microcrystalline glass/ceramic composite microwave dielectric material.
In the invention, the following components are added: firstly, the melting point and crystallization behavior of microcrystalline glass are compounded with microwave dielectric ceramics with good microwave dielectric property and mechanical propertyMixing the prepared glass powder and ceramic powder according to the mass ratio, drying, casting, laminating, pressing and forming, and firing at 800-1650 ℃ to prepare the ceramic/glass ceramic composite microwave dielectric ceramic material. The LRABS glass powder required for the present invention can be obtained by a conventional glass fusion process. The glass transformation temperature Tg (600-800 ℃) is regulated by the glass component, so that the adjustment of the sintering temperature is realized, and the type and the content of low-medium crystallization phases (shown in table 1) are regulated and controlled, and then Al is used 2 O 3 Ceramic composite (epsilon) r 10), the dielectric constant of the obtained composite material can be adjusted by 5-10 according to the microwave dielectric property mixing rule of the composite material. Secondly, the oriented arrangement of the flaky structure is realized by regulating and controlling the proportion of the irregular phase and the flaky phase in the alumina ceramic and the tape casting process, so that the high-strength and high-toughness bionic structure with the pearl layer structure is formed. In the invention, the microwave dielectric property and the mechanical property of the low-temperature ceramic material can be adjusted by adjusting the microcrystalline glass and the ceramic phase: bending strength of 200-500 MPa, dielectric constant of 4-10, dielectric loss of 2X 10 -4 ～2×10 -3 The preparation process is simple, pollution-free and low in cost, can be used for manufacturing microwave devices such as low-temperature co-fired ceramic, medium-temperature co-fired ceramic, high-temperature co-fired ceramic, multilayer dielectric resonator, microwave antenna sheet, filter and the like, and is a ceramic material with potential application value.
Preferably, the non-platelet alumina source comprises at least one of non-platelet alumina powder and aluminum hydroxide; preferably, the particle size D of the non-platelet alumina source 50 =0.5 to 5 μm; the size of the flaky alumina is 1-30 mu m in diameter and 100-3000 nm in thickness; preferably, the mass ratio of the flaky alumina to the non-flaky alumina source is 1: (0-2).
Preferably, the particle diameter D of the LRABS glass powder 90 ＝2～5μm。
Preferably, the preparation of the LRABS glass powder comprises the following steps: (1) according to (0-30): (0-60): (0-10): (0-10): (30-80 mol percent) mixing Ln source, R source, al source, B source and Si source to obtain a raw material mixture A; (2) Melting and quenching the raw material mixture A to obtain glass fragments; (3) And (3) carrying out dry grinding-sanding, drying and sieving on the glass fragments to obtain the LRABS glass powder.
Preferably, the Ln source is Ln with the purity more than or equal to 99 percent 2 O 3 The Mg source is one or more of magnesium oxide, magnesium hydroxide and basic magnesium carbonate with the purity of more than or equal to 99 percent; the R source includes: at least one of oxides, carbonates and nitrates of Ca, sr and Ba with purity more than or equal to 99 percent; the B source is H with the purity more than or equal to 99 percent 3 BO 3 The method comprises the steps of carrying out a first treatment on the surface of the The Si source is SiO with the purity more than or equal to 99 percent 2 。
Preferably, the melting temperature is 1500-1650 ℃ and the melting time is 1-4 hours.
Preferably, when the non-platelet alumina source contains aluminum hydroxide, the non-platelet alumina source is heat treated at 800 to 1200 ℃ for 2 to 6 hours.
Preferably, the dispersing agent is at least one of a low molecular weight polymer type wetting dispersing agent (DISPERBYK-107 and-108) and a controllable flocculation type wetting dispersing agent (BYK-P104, 255); the low molecular weight polymer type wetting dispersant is at least one of DISPERBYK-107 and DISPERBYK-108; the controllable flocculation type wetting dispersant is at least one of BYK-P104 and BYK-255;
The addition amount of the dispersing agent is LRABS glass powder and flaky Al 2 O 3 0.5 to 2wt% of a powder and a non-platelet alumina source.
Preferably, the temperature of the adhesive discharge is 450-550 ℃ and the time is 2-4 hours; preferably, the system for removing the glue comprises: firstly, raising the temperature to 250-350 ℃ at the heating rate of 0.5-2 ℃/min for 2-4 hours, and then raising the temperature to 450-550 ℃ at the heating rate of 0.5-2 ℃/min for 2-4 hours.
Drawings
FIG. 1 is 70SiO employed in examples 1 to 4 2 -20BaO-10Y 2 O 3 XRD patterns of the original glass and the microcrystalline glass show that the original glass has typical steamed bread peaks, and Ba appears after microcrystallization 2 SiO 5 Diffraction peaks of the phases;
FIG. 2 is an XRD pattern of the sample obtained in example 2, from which it is seen that the composite material is composed of an alumina phase (Al 2 O 3 ) And celsian phase (BaAl) 2 Si 2 O 8 ) Composition of alumina powder and 70SiO during high temperature sintering 2 -20BaO-10Y 2 O 3 The glass chemically reacts to form celsian phase, and Ba cannot be obtained 2 SiO 5 A phase;
FIG. 3 is an XRD pattern of the sample obtained in example 5, from which it is seen that the composite material is composed of an alumina phase (Al 2 O 3 ) And celsian phase (BaAl) 2 Si 2 O 8 ) Composition of alumina powder during high temperature sintering process and 34.23BaO-40SiO 2 -1.61Al 2 O 3 -14.2B 2 O 3 Chemical reaction of 9.96MgO glass to produce celsian phase and no microcrystalline glass BaSiO 3 A phase;
FIG. 4 is a surface and cross-section microtopography of the sample obtained in example 2, from which it is known that the composite material can obtain a nacreous layer-like composite microcrystalline dielectric material having a "brick-mud" structure by a tape casting-laminating method: the flaky alumina has a 'brick' structure, while the residual glass phase is in a BaAl phase 2 SiO 8 The phase is a mud structure;
FIG. 5 is an XRD pattern of the sample obtained in example 7, from which it is seen that the composite material is composed of an alumina phase (Al 2 O 3 ) And magnesium silicate phase (Mg 2 SiO 4 ) Composition of alumina powder and 21.86BaO-21.86SiO during low temperature sintering 2 -3.15Al 2 O 3 -6.23B 2 O 3 -46.9 co-existence of a crystal phase of MgO glass precipitation;
FIG. 6 shows 82.86SiO employed in examples 9 to 14 2 -11.16Al 2 O 3 -5.11B 2 O 3 -0.87La 2 O 3 XRD patterns of the original glass and the microcrystalline glass show that the original glass has typical steamed bread peaks, and Al appears after microcrystallization 6 Si 2 O 13 Diffraction peaks of the phases;
FIG. 7 is an XRD pattern of the samples obtained in examples 9-14, from which it is seen that the composite material is composed of an alumina phase (Al 2 O 3 ) And mullite phase (Al) 6 Si 2 O 13 ) Is composed of and is along with glassThe content of the glass is increased, and the content of the mullite phase in the composite material is gradually increased;
FIG. 8 is an SEM image of the sample obtained in example 11 and a co-fired with tungsten paste, from which it is known that a composite material can be obtained by a casting-laminating method to obtain a pseudo-nacreous layer composite microcrystalline dielectric material having a "brick-mud" structure: the flaky alumina has a 'brick' structure, and the residual glass phase is in phase with Al 6 Si 2 O 13 The phase is a mud structure; in graph b, the composite material and the tungsten paste are excellent in cofiring matching.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
In the invention, the low-temperature co-fired ceramic material LRABS microcrystalline glass-flaky Al is obtained by compounding low-melting-point microcrystalline glass with microwave dielectric ceramic with good microwave dielectric property 2 O 3 . The low-temperature co-fired ceramic material LRABS microcrystalline glass-flaky Al prepared by the method is specifically described below 2 O 3 Is a method of (2).
In the present invention, the composition is used in an amount of 0 to 30mol% Ln 2 O 3 -0～60mol％RO-0～10mol％B 2 O 3 -0～10mol％Al 2 O 3 -30～80mol％SiO 2 As glass-ceramic, LRABS glass with 0 to 5mol% of nucleating agent or colorant, which has a low glass transition temperature (600 to 850 ℃).
In the present invention, LRABS glass powder may be prepared by a conventional glass fusion process. Specifically, the process of preparing LRABS glass frit may include: the weight (wt%) of various raw materials required by the LRABS glass proportioning (mol%) is calculated to be proportioned, namely, the raw materials are proportioned according to (0-30): (0-60): (0-10): (0-10): (30-80) molar ratio of Ln source (e.g. La 2 O 3 ) R sources (e.g. MgO or BaCO 3 ) Al source (e.g. Al 2 O 3 ) B sources (e.g. H 3 BO 3 ) Si source (e.g. SiO 2 ) Mixing to obtain a raw material mixture; melting and quenching the raw material mixture to obtain glass fragments; and grinding, drying and sieving the glass fragmentsObtaining the LRABS glass powder. The purity of the used raw materials is more than 99%, and the LRABS glass powder is prepared by adopting the raw materials with the purity of more than 99%, so that the stability of a glass crystallization phase can be ensured, and the influence of impurities on dielectric properties can be reduced. The melting system can be as follows: 1500-1650 ℃, preferably 1520-1620 ℃; and 1-6 hours.
The glass cullet grinding can be performed by dry grinding and sand grinding. In one example, the obtained glass fragments are put into a ball milling tank with an alumina or zirconia lining according to a certain proportion (for example, the materials are ball-milled for 1-2 hours (experimental type) or a roller ball-milled for 12-36 hours (batch type), and are uniformly mixed into a sand mill according to a certain proportion (for example, the materials are solvent is ball-milled for 1:2) after passing through a 200-mesh sieve, so that the average particle size D is obtained 90 Glass powder with the thickness of less than or equal to 2-5 mu m. The ground glass powder slurry can be placed in a constant temperature drying oven (for example, 110 ℃) to be dried for 6 to 12 hours, and the glass powder is obtained for standby after the drying is finished and is sieved (for example, 120-mesh sieve). The particle size of the glass powder is D 90 ≤2～5μm。
In the invention, flaky Al is adopted 2 O 3 The ceramic powder is used as microwave dielectric ceramic, and has good microwave dielectric property, mechanical property and heat conductivity coefficient (epsilon) r ＝10，tan＜10 -5 (10 GHz), bending strength is more than or equal to 400MPa, and heat conductivity coefficient is 30.
In the present invention, the non-flaky alumina source and the flaky alumina are premixed in advance and heat-treated as necessary. Specifically, L is prepared 2 ZT 3 The premixing and heat treatment process of the ceramic powder can comprise: mixing a non-flaky alumina source (alumina powder, aluminum hydroxide) with flaky alumina according to a mass ratio to obtain a raw material mixture B; drying and sieving the raw material mixture B to obtain precursor powder; and pre-firing the precursor powder at 850-950 ℃ (e.g., 900 ℃) for 2-8 hours (e.g., 4 hours) to obtain the mixed ceramic powder for later use. Wherein the purity of the raw materials used is more than 99.5%. The raw materials can be mixed by ball milling. In one example, the raw material mixture is added to a polyethylene tetrachlorotank in a ratio (e.g., in the ratio of material: ball: deionized water=1:3:2) and ball milled in a planetary ball mill for 1-2 hours.During drying, the ball-milled raw powder slurry can be placed into a constant-temperature drying oven, dried for 6-12 h at 130-180 ℃, and then screened (for example, 20-mesh screen) after drying, so as to obtain uniformly mixed powder.
Then, the prepared LRABS glass powder and Al 2 O 3 Ceramic powder (flake Al) 2 O 3 Powder and non-platelet alumina powder) are mixed in mass proportions. The mixing mode can adopt ball milling mixing. In one example, LRABS glass frit and Al 2 O 3 Ceramic powder is added into a polyethylene tetrachloro tank according to a certain proportion (for example, according to the proportion of material: ball: absolute ethyl alcohol=1:3:2), and ball-milled for 1-2 h in a planetary ball mill.
And then, drying the mixture after ball milling and mixing, uniformly mixing the mixture with a solvent, a binder and a dispersing agent, carrying out tape casting molding, and carrying out hot press molding to obtain a blank body. In the invention, the dispersing agent in the casting process is one or more of a low molecular weight polymer type wetting dispersing agent (DISPERBYK-107 and-108) and a controllable flocculation type wetting dispersing agent (BYK-P104, 255), and the adding amount is 0.5-2 wt%.
And then, sintering the blank at a certain temperature after the gel is discharged, so as to obtain the microwave dielectric material. The adhesive discharging process is divided into two sections: the temperature is kept for 2 to 4 hours at 250 to 350 ℃ and 2 to 4 hours at 450 to 550 ℃, and the temperature rising rate is within the range of 0.5 to 2 ℃/min. The sintering process may be performed, for example, by sintering under an air atmosphere, a protective gas (nitrogen, argon) or a mixed gas of nitrogen and hydrogen at 800 to 1650 ℃ (preferably 800 to 1600 ℃) for 0.5 to 6 hours at a temperature rising rate of 3 to 10 ℃/min. The surface of the prepared composite ceramic material can be processed, and the dielectric property and mechanical property of the microwave dielectric ceramic material can be tested. When the sintering temperature of the microwave dielectric material is 1200-1650 ℃ and the sintering temperature is 800-1200 ℃, the microwave dielectric material is prepared from one or more of mullite, celsian, anorthite, strontium feldspar and alumina phase composite material, and the sintering temperature is prepared from one or more of mullite, magnesium silicate, calcium silicate, barium silicate, celsian, anorthite, strontium feldspar and diaspore phase composite material, see the following table 1:
The testing method comprises the following steps:
(1) Microcosmic morphology testing: characterizing the surface and section properties of the obtained sample by adopting a field emission scanning electron microscope;
(2) Phase analysis (XRD): the composite sample was ground in an agate mortar to a finer particle powder and then tested on a D8 ADVANCE high resolution powder X-ray diffractometer manufactured by Bruce, germany, to give an XRD diffraction pattern. Adopting copper target K alpha rays, testing voltage 40Kv, current 40mA, scanning range of 10-80 degrees and scanning speed of 10 degrees/min;
(3) Microwave dielectric properties: the measurement adopts a Hakki-Coleman open cylinder network medium resonance method, and uses TE 011 Mode determination of the relative permittivity epsilon of a sample at microwave frequencies r And the quality factor Q multiplied by f, the instrument used is an Agilent E8362B vector network analyzer, and the test sample is a cylinder with phi 12 multiplied by 6 mm;
(4) Mechanical property test: flexural strength was measured using a 5566 universal tester, with sample sizes of 3X 4X 36mm.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1:
(1) According to 70SiO 2 -20BaO-10Y 2 O 3 (SBY) glass proportion (mol%) 807.99gH was weighed 3 BO 3 、433.8gLa 2 O 3 And 758.2g BaCO 3 Adding proper deionized water, stirring uniformly, placing into a 1600 ℃ platinum crucible, preserving heat for 2 hours, then directly pouring the melted glass melt into the deionized water for quenching to obtain glassA sample;
(2) 1000g of glass scraps plus 4000g of zirconia balls (with the diameter of 5 mu m) obtained in the step (1) are put into an alumina ceramic pot, and ball-milled for 2 hours in a planetary ball mill with the rotating speed of 450 r/min;
(3) Sieving the glass powder ball-milled in the step (2) by a 120-mesh sieve, putting 500g of glass powder plus 1000mL of absolute ethyl alcohol into a sand mill, and ball-milling for 2 hours at the rotating speed of 2000 r/min;
(4) Placing the glass powder slurry ball-milled in the step (3) in a constant-temperature drying oven at 100 ℃, drying for 6 hours, and sieving with a 120-mesh sieve after the drying is finished to obtain glass powder for later use;
(5) Alumina premix ingredients, 100g of non-flaky alumina powder (1 μm) and 100g of flaky alumina powder ingredients, which are 200g in total; 200g of material plus 300g of zirconia balls (with the diameter of 5 mu m) +100mL of deionized water are added into a polyethylene tetrachlorotank, ball milling is carried out for 1 hour in a planetary ball mill with the rotating speed of 300r/min, and the mixture is sieved by a 20-mesh sieve;
(6) Placing the original powder slurry ball-milled in the step (5) into a constant-temperature drying oven, drying at 150 ℃ for 12 hours, and sieving with a 20-mesh sieve after drying to obtain uniformly mixed powder;
(7) Mixing 20g of SBY glass powder obtained in the step (4) and the step (6) with 180g of premixed uniform ceramic powder to obtain 200g in total; 200g of material plus 300g of zirconia balls (the mass ratio of 1 μm to 5 μm is 1:1) +80mL of xylene and acetone mixed organic solvent and 2g of BYK dispersing agent are added into a polyethylene tetrachloro tank, ball milling is carried out for 1h in a planetary ball mill with the rotating speed of 450 r/min; then adding 14g of PVB binder and 9g of plasticizer, and ball milling for 1h by using 450r/min planet; sieving with 60 mesh sieve to separate ball material, vacuum defoaming;
(8) Placing the slurry obtained in the step (7) into a casting machine for forming, wherein the casting thickness is 150 mu m; cutting, laminating and hot-pressing the raw material tape according to the test requirement;
(9) Placing the sample obtained in the step (8) in a muffle furnace, respectively preserving heat at 300 ℃ and 450 ℃ for 2 hours to finish glue discharging, and preserving heat at 1500 ℃ in an air atmosphere to sinter for 4 hours to prepare the bionic structural ceramic;
(10) The microwave dielectric properties of the samples obtained in this example were tested by a network analyzer and associated test fixtures, the mechanical properties of the samples obtained in this example were performed using a 5566 universal tester, and the phase analysis of the samples obtained in this example was performed using X-rays.
Example 2:
the seal preparation process in this example 2 is described with reference to example 1, with the difference that:
a. Mixing 40g of SBY glass powder obtained in the step (4) and the step (6) with 160g of premixed uniform ceramic powder, and adding 200g of mixed material; 200g of material plus 300g of zirconia balls (the mass ratio of 1 μm to 5 μm is 1:1) +77.5mL of xylene and acetone mixed organic solvent and 2g of BYK dispersing agent are added into a polyethylene tetrachloro tank, ball milling is carried out for 1h in a planetary ball mill with the rotating speed of 450 r/min; 13.5g PVB binder and 9g plasticizer are added, and the mixture is ball-milled for 1h by a planetary ball mill with the speed of 450 r/min; sieving with 60 mesh sieve to separate ball material, vacuum defoaming;
b. and (3) placing the sample obtained in the step (8) in a muffle furnace, respectively preserving heat at 300 ℃ and 450 ℃ for 2 hours to finish glue discharging, and preserving heat at 1450 ℃ in an air atmosphere to sinter for 4 hours to prepare the bionic structural ceramic.
Example 3:
(1) According to 70SiO 2 -20BaO-10Y 2 O 3 Glass proportion (mol%) 807.99g SiO 2 、433.8g Y 2 O 3 And 758.2g BaCO 3 Adding a proper amount of deionized water, uniformly stirring, placing the mixture in a platinum crucible at 1600 ℃ for heat preservation for 2 hours, and then directly pouring the melted glass melt into the deionized water for quenching to obtain a glass sample;
(2) 1000g of glass scraps plus 4000g of zirconia balls (with the diameter of 5 mu m) obtained in the step (1) are put into an alumina ceramic pot, and ball-milled for 2 hours in a planetary ball mill with the rotating speed of 450 r/min;
(3) Sieving the glass powder ball-milled in the step (2) by a 120-mesh sieve, putting 500g of glass powder plus 1000mL of absolute ethyl alcohol into a sand mill, and ball-milling for 2 hours at the rotating speed of 2000 r/min;
(4) Placing the glass powder slurry ball-milled in the step (3) in a constant-temperature drying oven at 100 ℃, drying for 6 hours, and sieving with a 120-mesh sieve after the drying is finished to obtain glass powder for later use;
(5) An alumina premix, namely 153g of irregular aluminum hydroxide powder and 100g of flaky alumina powder, wherein the total amount of the ingredients is 200g; 200g of material plus 300g of zirconia balls (with the diameter of 5 mu m) +100mL of deionized water are added into a polyethylene tetrachlorotank, ball milling is carried out for 1 hour in a planetary ball mill with the rotating speed of 300r/min, and the mixture is sieved by a 20-mesh sieve;
(6) Placing the original powder slurry ball-milled in the step (5) into a constant-temperature drying oven, drying at 150 ℃ for 12 hours, and sieving with a 20-mesh sieve after drying to obtain uniformly mixed powder;
(7) Placing the aluminum hydroxide and the flaky alumina powder which are uniformly mixed in the step (6) into a muffle furnace, and drying for 4 hours at 1150 ℃ with a heating rate of 5 ℃/min;
(8) Mixing 40g of SBY glass powder obtained in the step (4) and the step (7) with 160g of premixed uniform ceramic powder, and adding 200g of mixed material; 200g of material plus 300g of zirconia balls (the mass ratio of 1 mu m to 5 mu m is 1:1) +75mL of xylene and acetone mixed organic solvent and 2g of BYK dispersing agent are added into a polyethylene tetrachloro tank, ball milling is carried out for 1h in a planetary ball mill with the rotating speed of 450 r/min; 13g PVB binder and 9g plasticizer are added, and the mixture is ball milled for 1h by a planetary ball mill with the speed of 450 r/min; sieving with 60 mesh sieve to separate ball material, vacuum defoaming;
(9) Placing the slurry obtained in the step (8) into a casting machine for forming, wherein the casting thickness is 150 mu m; cutting, laminating and hot-pressing the raw material tape according to the test requirement;
(10) Placing the sample obtained in the step (9) in a muffle furnace, respectively preserving heat at 300 ℃ and 450 ℃ for 2 hours to complete glue discharging, and preserving heat at 1475 ℃ in air atmosphere for 4 hours to prepare the bionic structural ceramic;
(11) The microwave dielectric properties of the samples obtained in this example were tested by a network analyzer and associated test fixtures, the mechanical properties of the samples obtained in this example were performed using a 5566 universal tester, and the phase analysis of the samples obtained in this example was performed using X-rays.
Example 4:
the seal preparation process in this example 4 is described with reference to example 1, with the difference that:
a. alumina premix ingredients, 100g of non-flaky alumina powder (1 μm) and 100g of flaky alumina powder ingredients, which are 200g in total; 200g of material plus 300g of zirconia balls (with the diameter of 5 mu m) +100mL of deionized water are added into a polyethylene tetrachlorotank, ball milling is carried out for 1 hour in a planetary ball mill with the rotating speed of 300r/min, and the mixture is sieved by a 20-mesh sieve;
b. mixing 40g of SBY glass powder obtained in the step (4) and the step (6) with 160g of premixed uniform ceramic powder, and adding 200g of mixed material; 200g of material plus 300g of zirconia balls (the mass ratio of 1 μm to 5 μm is 1:1) +70mL of xylene and acetone mixed organic solvent and 2g of BYK dispersing agent are added into a polyethylene tetrachloro tank, ball milling is carried out for 1h in a planetary ball mill with the rotating speed of 450 r/min; 13.5g PVB binder and 9g plasticizer are added, and the mixture is ball-milled for 1h by a planetary ball mill with the speed of 450 r/min; sieving with 60 mesh sieve to separate ball material, vacuum defoaming;
c. And (3) placing the sample obtained in the step (8) in a muffle furnace, respectively preserving heat at 300 ℃ and 450 ℃ for 2 hours to finish glue discharging, and preserving heat at 1450 ℃ in an air atmosphere to sinter for 4 hours to prepare the bionic structural ceramic.
Example 5:
(1) According to 34.23BaO-40SiO 2 -1.61Al 2 O 3 -14.2B 2 O 3 -9.96MgO (BSABM) glass formulation (mol%) 1176.81g BaCO 3 、418.71SiO 2 、305.94g H 3 BO 3 、28.6gAl 2 O 3 And 69.94MgO, adding a proper amount of deionized water, uniformly stirring, placing in a platinum crucible at 1520 ℃ for heat preservation for 2 hours, and then directly pouring the melted glass melt into the deionized water for quenching to obtain a glass sample;
(2) 1000g of glass scraps plus 4000g of zirconia balls (with the diameter of 5 mu m) obtained in the step (1) are put into an alumina ceramic pot, and ball-milled for 2 hours in a planetary ball mill with the rotating speed of 450 r/min;
(3) Sieving the glass powder ball-milled in the step (2) by a 120-mesh sieve, putting 500g of glass powder plus 1000mL of absolute ethyl alcohol into a sand mill, and ball-milling for 2 hours at the rotating speed of 2000 r/min;
(4) Placing the glass powder slurry ball-milled in the step (3) in a constant-temperature drying oven at 100 ℃, drying for 6 hours, and sieving with a 120-mesh sieve after the drying is finished to obtain glass powder for later use;
(5) Alumina premix ingredients, 100g of non-flaky alumina powder (1 μm) and 100g of flaky alumina powder ingredients, which are 200g in total; 200g of material plus 300g of zirconia balls (with the diameter of 5 mu m) +100mL of deionized water are added into a polyethylene tetrachlorotank, ball milling is carried out for 1 hour in a planetary ball mill with the rotating speed of 300r/min, and the mixture is sieved by a 20-mesh sieve;
(6) Placing the original powder slurry ball-milled in the step (5) into a constant-temperature drying oven, drying at 150 ℃ for 12 hours, and sieving with a 20-mesh sieve after drying to obtain uniformly mixed powder;
(7) Mixing 40g of BSABM glass powder obtained in the step (4) and the step (6) with 160g of premixed uniform ceramic powder, and adding 200g of the mixed powder; 200g of material plus 300g of zirconia balls (the mass ratio of 1 μm to 5 μm is 1:1) +80mL of xylene and acetone mixed organic solvent and 2g of BYK dispersing agent are added into a polyethylene tetrachloro tank, ball milling is carried out for 1h in a planetary ball mill with the rotating speed of 450 r/min; then adding 14g of PVB binder and 9g of plasticizer, and ball milling for 1h by using 450r/min planet; sieving with 60 mesh sieve to separate ball material, vacuum defoaming;
(8) Placing the slurry obtained in the step (7) into a casting machine for forming, wherein the casting thickness is 150 mu m; cutting, laminating and hot-pressing the raw material tape according to the test requirement;
(9) Placing the sample obtained in the step (8) in a muffle furnace, respectively preserving heat at 300 ℃ and 450 ℃ for 2 hours to finish glue discharging, and preserving heat at 1200 ℃ in an air atmosphere to sinter for 2 hours to prepare the bionic structural ceramic;
(10) The microwave dielectric properties of the samples obtained in this example were tested by a network analyzer and associated test fixtures, the mechanical properties of the samples obtained in this example were performed using a 5566 universal tester, and the phase analysis of the samples obtained in this example was performed using X-rays.
Example 6:
the seal preparation process in this example 2 is described with reference to example 1, with the difference that:
a. mixing 120g of BSABM glass powder obtained in the step (4) and the step (6) with 80g of premixed uniform ceramic powder, and adding 200g of the mixed powder; 200g of material plus 300g of zirconia balls (the mass ratio of 1 mu m to 5 mu m is 1:1) +75mL of xylene and acetone mixed organic solvent and 2g of BYK dispersing agent are added into a polyethylene tetrachloro tank, ball milling is carried out for 1h in a planetary ball mill with the rotating speed of 450 r/min; 13.5g PVB binder and 9g plasticizer are added, and the mixture is ball-milled for 1h by a planetary ball mill with the speed of 450 r/min; sieving with 60 mesh sieve to separate ball material, vacuum defoaming;
b. and (3) placing the sample obtained in the step (8) in a muffle furnace, respectively preserving heat at 300 ℃ and 450 ℃ for 2 hours to finish glue discharging, and preserving heat at 850 ℃ in an air atmosphere to sinter for 2 hours to prepare the bionic structural ceramic.
Table 2 shows the microwave dielectric material composition tables and the performance data tables prepared in examples 1 to 6
Example 7:
(1) According to 21.86BaO-21.86SiO 2 -3.15Al 2 O 3 -6.23B 2 O 3 -46.9MgO (BSABM-2) glass formulation (mol%) 1002.14g BaCO 3 、305.13SiO 2 、178.98g H 3 BO 3 、74.61g Al 2 O 3 And 439.13MgO, adding a proper amount of deionized water, uniformly stirring, placing in a 1550 ℃ platinum crucible, preserving heat for 2 hours, and then directly pouring the melted glass melt into the deionized water for quenching to obtain a glass sample;
(2) 1000g of glass scraps plus 4000g of zirconia balls (with the diameter of 5 mu m) obtained in the step (1) are put into an alumina ceramic pot, and ball-milled for 2 hours in a planetary ball mill with the rotating speed of 450 r/min;
(3) Sieving the glass powder ball-milled in the step (2) by a 120-mesh sieve, putting 500g of glass powder plus 1000mL of absolute ethyl alcohol into a sand mill, and ball-milling for 2 hours at the rotating speed of 2000 r/min;
(4) Placing the glass powder slurry ball-milled in the step (3) in a constant-temperature drying oven at 100 ℃, drying for 6 hours, and sieving with a 120-mesh sieve after the drying is finished to obtain glass powder for later use;
(5) Alumina premix ingredients, 100g of non-flaky alumina powder (1 μm) and 100g of flaky alumina powder ingredients, which are 200g in total; 200g of material plus 300g of zirconia balls (with the diameter of 5 mu m) +100mL of deionized water are added into a polyethylene tetrachlorotank, ball milling is carried out for 1 hour in a planetary ball mill with the rotating speed of 300r/min, and the mixture is sieved by a 20-mesh sieve;
(6) Placing the original powder slurry ball-milled in the step (5) into a constant-temperature drying oven, drying at 150 ℃ for 12 hours, and sieving with a 20-mesh sieve after drying to obtain uniformly mixed powder;
(7) Mixing 120g of BSABM-2 glass powder obtained in the step (4) and the step (6) with 80g of premixed uniform ceramic powder, and 200g in total; 200g of material plus 300g of zirconia balls (the mass ratio of 1 mu m to 5 mu m is 1:1) +75mL of xylene and acetone mixed organic solvent and 2g of BYK dispersing agent are added into a polyethylene tetrachloro tank, ball milling is carried out for 1h in a planetary ball mill with the rotating speed of 450 r/min; then adding 14g of PVB binder and 9g of plasticizer, and ball milling for 1h by using 450r/min planet; sieving with 60 mesh sieve to separate ball material, vacuum defoaming;
(8) Placing the slurry obtained in the step (7) into a casting machine for forming, wherein the casting thickness is 150 mu m; cutting, laminating and hot-pressing the raw material tape according to the test requirement;
(9) Placing the sample obtained in the step (8) in a muffle furnace, respectively preserving heat at 300 ℃ and 450 ℃ for 2 hours to finish glue discharging, and preserving heat at 950 ℃ in air atmosphere to sinter for 2 hours to prepare the bionic structural ceramic;
(10) The microwave dielectric properties of the samples obtained in this example were tested by a network analyzer and associated test fixtures, the mechanical properties of the samples obtained in this example were performed using a 5566 universal tester, and the phase analysis of the samples obtained in this example was performed using X-rays.
Example 8:
(1) According to 21.86BaO-21.86SiO 2 -3.15Al 2 O 3 -6.23B 2 O 3 -46.9MgO glass blend (mol%), 1002.14g BaCO 3 、305.13SiO 2 、178.98g H 3 BO 3 、74.61gAl 2 O 3 And 439.13MgO, adding a proper amount of deionized water, uniformly stirring, placing in a 1550 ℃ platinum crucible, preserving heat for 2 hours, and then directly pouring the melted glass melt into the deionized water for quenching to obtain a glass sample;
(2) 1000g of glass scraps plus 4000g of zirconia balls (with the diameter of 5 mu m) obtained in the step (1) are put into an alumina ceramic pot, and ball-milled for 2 hours in a planetary ball mill with the rotating speed of 450 r/min;
(3) Sieving the glass powder ball-milled in the step (2) by a 120-mesh sieve, putting 500g of glass powder plus 1000mL of absolute ethyl alcohol into a sand mill, and ball-milling for 2 hours at the rotating speed of 2000 r/min;
(4) Placing the glass powder slurry ball-milled in the step (3) in a constant-temperature drying oven at 100 ℃, drying for 6 hours, and sieving with a 120-mesh sieve after the drying is finished to obtain glass powder for later use;
(5) Mixing 140g of BLMT glass powder obtained in the step (4) with 60g of flaky alumina powder, and adding 200g of the mixture; 200g of material plus 300g of zirconia balls (the mass ratio of 1 μm to 5 μm is 1:1) +70mL of xylene and acetone mixed organic solvent and 2g of BYK dispersing agent are added into a polyethylene tetrachloro tank, ball milling is carried out for 1h in a planetary ball mill with the rotating speed of 450 r/min; then adding 14g of PVB binder and 9g of plasticizer, and ball milling for 1h by using 450r/min planet; sieving with 60 mesh sieve to separate ball material, vacuum defoaming;
(6) Placing the slurry obtained in the step (5) into a casting machine for forming, wherein the casting thickness is 150 mu m; cutting, laminating and hot-pressing the raw material tape according to the test requirement;
(7) Placing the sample obtained in the step (6) in a muffle furnace, respectively preserving heat at 300 ℃ and 450 ℃ for 2 hours to finish glue discharging, and preserving heat at 950 ℃ in air atmosphere to sinter for 2 hours to prepare the bionic structural ceramic;
(8) The microwave dielectric properties of the samples obtained in this example were tested by a network analyzer and associated test fixtures, the mechanical properties of the samples obtained in this example were performed using a 5566 universal tester, and the phase analysis of the samples obtained in this example was performed using X-rays.
Table 3 shows the microwave dielectric material composition and performance data tables prepared in examples 7-8
Example 9:
(1) According to 82.86SiO 2 -11.16Al 2 O 3 -5.11B 2 O 3 -0.87La 2 O 3 (SABL for short) glass proportion (mol%) and weighing 1416SiO 2 、323.64gAl 2 O 3 、179.73g H 3 BO 3 And 80.62g La 2 O 3 Adding a proper amount of deionized water, uniformly stirring, placing the mixture in a 1620 ℃ platinum crucible, preserving heat for 2 hours, and then directly pouring the melted glass melt into the deionized water for quenching to obtain a glass sample;
(2) 1000g of glass scraps plus 4000g of zirconia balls (with the diameter of 5 mu m) obtained in the step (1) are put into an alumina ceramic pot, and ball-milled for 2 hours in a planetary ball mill with the rotating speed of 450 r/min;
(3) Sieving the glass powder ball-milled in the step (2) by a 120-mesh sieve, putting 500g of glass powder plus 1000mL of absolute ethyl alcohol into a sand mill, and ball-milling for 2 hours at the rotating speed of 2000 r/min;
(4) Placing the glass powder slurry ball-milled in the step (3) in a constant-temperature drying oven at 100 ℃, drying for 6 hours, and sieving with a 120-mesh sieve after the drying is finished to obtain glass powder for later use;
(5) Alumina premix ingredients, 100g of non-flaky alumina powder (1 μm) and 100g of flaky alumina powder ingredients, which are 200g in total; 200g of material plus 300g of zirconia balls (with the diameter of 5 mu m) +100mL of deionized water are added into a polyethylene tetrachlorotank, ball milling is carried out for 1 hour in a planetary ball mill with the rotating speed of 300r/min, and the mixture is sieved by a 20-mesh sieve;
(6) Placing the original powder slurry ball-milled in the step (5) into a constant-temperature drying oven, drying at 150 ℃ for 12 hours, and sieving with a 20-mesh sieve after drying to obtain uniformly mixed powder;
(7) Mixing 20g of SABL glass powder obtained in the step (4) and the step (6) with 180g of premixed uniform ceramic powder to obtain 200g in total; 200g of material plus 300g of zirconia balls (the mass ratio of 1 mu m to 5 mu m is 1:1) +85mL of xylene and acetone mixed organic solvent and 2g of BYK dispersing agent are added into a polyethylene tetrachloro tank, ball milling is carried out for 1h in a planetary ball mill with the rotating speed of 450 r/min; then adding 14g of PVB binder and 9g of plasticizer, and ball milling for 1h by using 450r/min planet; sieving with 60 mesh sieve to separate ball material, vacuum defoaming;
(8) Placing the slurry obtained in the step (7) into a casting machine for forming, wherein the casting thickness is 150 mu m; cutting, laminating and hot-pressing the raw material tape according to the test requirement;
(9) Placing the sample obtained in the step (8) in a muffle furnace, respectively preserving heat at 300 ℃ and 450 ℃ for 2 hours to finish glue discharging, and preserving heat at 1500 ℃ in an air atmosphere to sinter for 2 hours to prepare the bionic structural ceramic;
(10) The microwave dielectric properties of the samples obtained in this example were tested by a network analyzer and associated test fixtures, the mechanical properties of the samples obtained in this example were performed using a 5566 universal tester, and the phase analysis of the samples obtained in this example was performed using X-rays.
Example 10:
a. mixing 60g of SABL glass powder obtained in the step (4) and the step (6) with 140g of premixed uniform ceramic powder, and adding 200g of the mixed powder; 200g of material plus 300g of zirconia balls (the mass ratio of 1 μm to 5 μm is 1:1) +82.5mL of xylene and acetone mixed organic solvent and 2g of BYK dispersing agent are added into a polyethylene tetrachloro tank, ball milling is carried out for 1h in a planetary ball mill with the rotating speed of 450 r/min; 13.5g PVB binder and 9g plasticizer are added, and the mixture is ball-milled for 1h by a planetary ball mill with the speed of 450 r/min; sieving with 60 mesh sieve to separate ball material, vacuum defoaming;
b. and (3) placing the sample obtained in the step (8) in a muffle furnace, respectively preserving heat at 300 ℃ and 450 ℃ for 2 hours to finish glue discharging, and preserving heat at 1400 ℃ in an air atmosphere to sinter for 2 hours to prepare the bionic structural ceramic.
Example 11:
a. mixing 100g of SABL glass powder obtained in the step (4) and the step (6) with 100g of premixed uniform ceramic powder to obtain 200g in total; 200g of material plus 300g of zirconia balls (the mass ratio of 1 μm to 5 μm is 1:1) +82.5mL of xylene and acetone mixed organic solvent and 2g of BYK dispersing agent are added into a polyethylene tetrachloro tank, ball milling is carried out for 1h in a planetary ball mill with the rotating speed of 450 r/min; 13.5g PVB binder and 9g plasticizer are added, and the mixture is ball-milled for 1h by a planetary ball mill with the speed of 450 r/min; sieving with 60 mesh sieve to separate ball material, vacuum defoaming;
b. And (3) placing the sample obtained in the step (8) in a muffle furnace, respectively preserving heat at 300 ℃ and 450 ℃ for 2 hours to finish glue discharging, and preserving heat at 1400 ℃ in an air atmosphere to sinter for 2 hours to prepare the bionic structural ceramic.
Example 12:
a. mixing 140g of SABL glass powder and 60g of premixed uniform ceramic powder obtained in the step (4) and the step (6), and 200g in total; 200g of material plus 300g of zirconia balls (the mass ratio of 1 μm to 5 μm is 1:1) +82.5mL of xylene and acetone mixed organic solvent and 2g of BYK dispersing agent are added into a polyethylene tetrachloro tank, ball milling is carried out for 1h in a planetary ball mill with the rotating speed of 450 r/min; 13.5g PVB binder and 9g plasticizer are added, and the mixture is ball-milled for 1h by a planetary ball mill with the speed of 450 r/min; sieving with 60 mesh sieve to separate ball material, vacuum defoaming;
b. and (3) placing the sample obtained in the step (8) in a muffle furnace, respectively preserving heat at 300 ℃ and 450 ℃ for 2 hours to finish glue discharging, and preserving heat at 1400 ℃ in an air atmosphere to sinter for 2 hours to prepare the bionic structural ceramic.
Example 13:
(1) According to (82.86 SiO) 2 -11.16Al 2 O 3 -5.11B 2 O 3 -0.87La 2 O 3 )+1wt％Co 2 O 3 (SABL-C for short) glass proportion (mol%) and weighing 1416SiO 2 、323.64gAl 2 O 3 、179.73g H 3 BO 3 、80.62g La 2 O 3 And 20g Co 2 O 3 Adding a proper amount of deionized water, uniformly stirring, placing the mixture in a 1620 ℃ platinum crucible, preserving heat for 2 hours, and then directly pouring the melted glass melt into the deionized water for quenching to obtain a glass sample;
(2) 1000g of glass scraps plus 4000g of zirconia balls (with the diameter of 5 mu m) obtained in the step (1) are put into an alumina ceramic pot, and ball-milled for 2 hours in a planetary ball mill with the rotating speed of 450 r/min;
(3) Sieving the glass powder ball-milled in the step (2) by a 120-mesh sieve, putting 500g of glass powder plus 1000mL of absolute ethyl alcohol into a sand mill, and ball-milling for 2 hours at the rotating speed of 2000 r/min;
(4) Placing the glass powder slurry ball-milled in the step (3) in a constant-temperature drying oven at 100 ℃, drying for 6 hours, and sieving with a 120-mesh sieve after the drying is finished to obtain glass powder for later use;
(5) Alumina premix ingredients, 100g of non-flaky alumina powder (1 μm) and 100g of flaky alumina powder ingredients, which are 200g in total; 200g of material plus 300g of zirconia balls (with the diameter of 5 mu m) +100mL of deionized water are added into a polyethylene tetrachlorotank, ball milling is carried out for 1 hour in a planetary ball mill with the rotating speed of 300r/min, and the mixture is sieved by a 20-mesh sieve;
(6) Placing the original powder slurry ball-milled in the step (5) into a constant-temperature drying oven, drying at 150 ℃ for 12 hours, and sieving with a 20-mesh sieve after drying to obtain uniformly mixed powder;
(7) Mixing 20g of SABL glass powder obtained in the step (4) and the step (6) with 180g of premixed uniform ceramic powder to obtain 200g in total; 200g of material plus 300g of zirconia balls (the mass ratio of 1 mu m to 5 mu m is 1:1) +85mL of xylene and acetone mixed organic solvent and 2g of BYK dispersing agent are added into a polyethylene tetrachloro tank, ball milling is carried out for 1h in a planetary ball mill with the rotating speed of 450 r/min; then adding 14g of PVB binder and 9g of plasticizer, and ball milling for 1h by using 450r/min planet; sieving with 60 mesh sieve to separate ball material, vacuum defoaming;
(8) Placing the slurry obtained in the step (7) into a casting machine for forming, wherein the casting thickness is 150 mu m; cutting, laminating and hot-pressing the raw material tape according to the test requirement;
(9) Placing the sample obtained in the step (8) in a muffle furnace, respectively maintaining the temperature at 300 ℃ and 450 ℃ for 2 hours to complete the glue discharging (95% humidity nitrogen-hydrogen mixed gas), and placing the sample in a muffle furnace in the nitrogen-hydrogen mixed gas (N) 2 :H 2 Heat-preserving sintering 2 at 1500 ℃ in =1:3)h, preparing the ceramic with the bionic structure;
(10) The microwave dielectric properties of the samples obtained in this example were tested by a network analyzer and associated test fixtures, the mechanical properties of the samples obtained in this example were performed using a 5566 universal tester, and the phase analysis of the samples obtained in this example was performed using X-rays.
Example 14:
(1) According to (82.86 SiO) 2 -11.16Al 2 O 3 -5.11B 2 O 3 -0.87La 2 O 3 )+1wt％Co 2 O 3 +1wt％TiO 2 (SABL-C for short) glass proportion (mol%) and weighing 1416SiO 2 、323.64gAl 2 O 3 、179.73g H 3 BO 3 、80.62g La 2 O 3 And 20g Co 2 O 3 、20g TiO 2 Adding a proper amount of deionized water, uniformly stirring, placing the mixture in a 1620 ℃ platinum crucible, preserving heat for 2 hours, and then directly pouring the melted glass melt into the deionized water for quenching to obtain a glass sample;
(2) 1000g of glass scraps plus 4000g of zirconia balls (with the diameter of 5 mu m) obtained in the step (1) are put into an alumina ceramic pot, and ball-milled for 2 hours in a planetary ball mill with the rotating speed of 450 r/min;
(3) Sieving the glass powder ball-milled in the step (2) by a 120-mesh sieve, putting 500g of glass powder plus 1000mL of absolute ethyl alcohol into a sand mill, and ball-milling for 2 hours at the rotating speed of 2000 r/min;
(4) Placing the glass powder slurry ball-milled in the step (3) in a constant-temperature drying oven at 100 ℃, drying for 6 hours, and sieving with a 120-mesh sieve after the drying is finished to obtain glass powder for later use;
(5) Alumina premix ingredients, 100g of non-flaky alumina powder (1 μm) and 100g of flaky alumina powder ingredients, which are 200g in total; 200g of material plus 300g of zirconia balls (with the diameter of 5 mu m) +100mL of deionized water are added into a polyethylene tetrachlorotank, ball milling is carried out for 1 hour in a planetary ball mill with the rotating speed of 300r/min, and the mixture is sieved by a 20-mesh sieve;
(6) Placing the original powder slurry ball-milled in the step (5) into a constant-temperature drying oven, drying at 150 ℃ for 12 hours, and sieving with a 20-mesh sieve after drying to obtain uniformly mixed powder;
(7) Mixing 20g of SABL glass powder obtained in the step (4) and the step (6) with 180g of premixed uniform ceramic powder to obtain 200g in total; 200g of material plus 300g of zirconia balls (the mass ratio of 1 mu m to 5 mu m is 1:1) +85mL of xylene and acetone mixed organic solvent and 2g of BYK dispersing agent are added into a polyethylene tetrachloro tank, ball milling is carried out for 1h in a planetary ball mill with the rotating speed of 450 r/min; then adding 14g of PVB binder and 9g of plasticizer, and ball milling for 1h by using 450r/min planet; sieving with 60 mesh sieve to separate ball material, vacuum defoaming;
(8) Placing the slurry obtained in the step (7) into a casting machine for forming, wherein the casting thickness is 150 mu m; cutting, laminating and hot-pressing the raw material tape according to the test requirement;
(9) Placing the sample obtained in the step (8) in a muffle furnace, respectively maintaining the temperature at 300 ℃ and 450 ℃ for 2 hours to complete the glue discharging (95% humidity nitrogen-hydrogen mixed gas), and mixing the glue with the nitrogen-hydrogen mixed gas (volume ratio N 2 :H 2 Heat preservation and sintering for 2h at 1500 ℃ in the ratio of 1:3) to prepare the bionic structural ceramic;
(10) The microwave dielectric properties of the samples obtained in this example were tested by a network analyzer and associated test fixtures, the mechanical properties of the samples obtained in this example were performed using a 5566 universal tester, and the phase analysis of the samples obtained in this example was performed using X-rays.
Table 4 shows the microwave dielectric material composition and performance data tables prepared in examples 9-14
Example 15:
the preparation process of the microwave dielectric material with the bionic structure in this embodiment 15 is different from that in embodiment 6 only in that: non-platelet alumina was not added.
Example 16:
the preparation process of the microwave dielectric material with the bionic structure in this embodiment 16 is different from that in embodiment 6 only in that: the mass ratio of the non-flaky alumina to the flaky alumina phase is 0.1:1.
example 17:
the preparation process of the microwave dielectric material with the bionic structure in this embodiment 17 is different from that in embodiment 6 only in that: the mass ratio of the non-flaky alumina to the flaky alumina phase is 0.5:1.
Example 18:
the preparation process of the microwave dielectric material with the bionic structure in this embodiment 18 is different from that in embodiment 6 only in that: the mass ratio of the non-flaky alumina to the flaky alumina phase is 1.5:1.
example 19:
the preparation process of the microwave dielectric material with the bionic structure in this embodiment 19 is different from that in embodiment 6 only in that: the mass ratio of the non-flaky alumina to the flaky alumina phase is 2:1.
comparative example 1
The preparation process of the microwave dielectric material with the bionic structure in this comparative example 1 is different from that of example 6 only in that: the mass ratio of the non-flaky alumina to the flaky alumina phase is 2.5:1.
Claims (14)
1. a microwave dielectric material with a bionic structure is characterized in that the microwave dielectric material with the bionic structure is formed by directionally arranging flaky Al 2 O 3 The ceramic material with the simulated pearl layer structure is formed by compounding a phase and an LRABS microcrystalline glass phase;
the LRABS glass ceramic is Ln 2 O 3 -RO-Al 2 O 3 -B 2 O 3 -SiO 2 The microcrystalline glass comprises the following raw materials in parts by weight: 0 to 30mol% Ln 2 O 3 0 to 60mol% of RO, 0 to 10mol% of B 2 O 3 0 to 30mol% of Al 2 O 3 30 to 80mol percent of SiO 2 The sum of the mole percentages of the components is 100 mole percent; wherein ln=at least one of the lanthanides and r= Mg, ca, sr, ba.
2. The biomimetic structured microwave dielectric material according to claim 1, wherein the sheet-like Al 2 O 3 The mass ratio of the phase to the LRABS microcrystalline glass phase is (9.5-0.1): 1.
3. the biomimetic structured microwave dielectric material according to claim 1 or 2, wherein the biomimetic structured microwave dielectric material further comprises non-platelet alumina; the mass ratio of the non-flaky alumina to the flaky alumina phase is not more than 2:1.
4. a biomimetic structured microwave dielectric material according to any one of claims 1-3, wherein the LRABS glass ceramic is further doped with no more than 5wt% nucleating agent or colorant based on the total mass of the raw materials; the glass transition temperature of the LRABS microcrystalline glass is 600-900 ℃, and the crystallization temperature is 700-1200 ℃.
5. The microwave dielectric material of a bionic structure according to any one of claims 1 to 4, wherein the microwave dielectric material of the bionic structure is a composite material of glass ceramics and alumina phase containing one or more crystalline phases of mullite, celsian, anorthite, strontium feldspar when the sintering temperature is 1200 to 1650 ℃;
when the sintering temperature is 800-1200 ℃, the microwave dielectric material of the bionic structure is an LRABS microcrystalline glass and alumina phase composite material containing one or more crystal phases of mullite, magnesium silicate, calcium silicate, barium silicate, celsian, anorthite, strontium feldspar and diasporite.
6. The biomimetic structured microwave dielectric material according to any one of claims 1-5, wherein the microwave dielectric material has a flexural strength of 200-500 MPa, a dielectric constant of 4-10, and a dielectric loss of 2 x 10 -4 ～2×10 -3 The thermal expansion coefficient is 7-11 ppm/DEG C, and the thermal conductivity coefficient is more than or equal to 5W/(m.K); the microwave dielectric material with the bionic structure is matched with silver, silver palladium, copper, gold and tungsten electrodes for co-firing.
7. A method for preparing the glass ceramic/ceramic composite microwave dielectric material with the bionic structure according to any one of claims 1 to 6, which is characterized by comprising the following steps:
preparing LRABS glass powder;
LRABS glass powder and flaky Al 2 O 3 Mixing powder, a non-flaky alumina source, an organic solvent, a binder and a dispersing agent, carrying out tape casting and forming, and carrying out hot press forming to obtain a blank;
and discharging the glue from the obtained blank, and sintering at 800-1600 ℃ for 0.1-6 hours to obtain the microcrystalline glass/ceramic composite microwave dielectric material.
8. The method of producing according to claim 7, wherein the non-flaky alumina source comprises at least one of non-flaky alumina powder and aluminum hydroxide;
preferably, the particle size D of the non-platelet alumina source 50 =0.5 to 5 μm; the size of the flaky alumina is 1-30 mu m in diameter and 100-3000 nm in thickness;
Preferably, the mass ratio of the flaky alumina to the non-flaky alumina source is 1: (0-2).
9. The method according to claim 7 or 8, wherein the LRABS glass frit has a particle size D 90 =2～5μm；
Preparing LRABS glass frit comprising: (1) according to (0-30): (0-60): (0-10): (0-10): (30-80 mol% of Ln source, R source, al source, B source and Si source are mixed to obtain a raw material mixture A; (2) Melting and quenching the raw material mixture A to obtain glass fragments; (3) And (3) carrying out dry grinding-sanding, drying and sieving on the glass fragments to obtain the LRABS glass powder.
10. The method of claim 9, wherein the Ln source is Ln with purity greater than or equal to 99% 2 O 3 The purity of the Mg source is more than or equal to 99 percentOne or more of magnesium oxide, magnesium hydroxide, basic magnesium carbonate; the R source includes: at least one of oxides, carbonates and nitrates of Ca, sr and Ba with purity more than or equal to 99 percent; the B source is H with the purity more than or equal to 99 percent 3 BO 3 The method comprises the steps of carrying out a first treatment on the surface of the The Si source is SiO with the purity more than or equal to 99 percent 2 。
11. The method according to claim 9, wherein the melting temperature is 1500 to 1650 ℃ and the time is 1 to 4 hours.
12. The production method according to any one of claims 7 to 11, wherein when the non-flaky alumina source contains aluminum hydroxide, the non-flaky alumina source is first heat-treated at 800 to 1200 ℃ for 2 to 6 hours.
13. The method of any one of claims 7-12, wherein the dispersant is at least one of a low molecular weight polymeric wetting dispersant (DISPERBYK-107 and-108) and a controllable flocculating wetting dispersant (BYK-P104, 255); the low molecular weight polymer type wetting dispersant is at least one of DISPERBYK-107 and DISPERBYK-108; the controllable flocculation type wetting dispersant is at least one of BYK-P104 and BYK-255;
the addition amount of the dispersing agent is LRABS glass powder and flaky Al 2 O 3 0.5 to 2wt% of the total mass of the powder and the non-flaky alumina source.
14. The method according to any one of claims 7 to 13, wherein the temperature of the paste ejection is 450 to 550 ℃ for 2 to 4 hours; preferably, the system for removing the glue comprises: firstly, raising the temperature to 250-350 ℃ at the heating rate of 0.5-2 ℃/min for 2-4 hours, and then raising the temperature to 450-550 ℃ at the heating rate of 0.5-2 ℃/min for 2-4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210341679.5A CN116924782A (en) | 2022-04-02 | 2022-04-02 | Microwave dielectric material with bionic structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210341679.5A CN116924782A (en) | 2022-04-02 | 2022-04-02 | Microwave dielectric material with bionic structure and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116924782A true CN116924782A (en) | 2023-10-24 |
Family
ID=88376048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210341679.5A Pending CN116924782A (en) | 2022-04-02 | 2022-04-02 | Microwave dielectric material with bionic structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116924782A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107326432A (en) * | 2017-06-30 | 2017-11-07 | 哈尔滨工业大学 | A kind of preparation method and application of the template seed crystal of texture aluminium oxide ceramics |
| CN109608050A (en) * | 2018-12-25 | 2019-04-12 | 中国人民解放军国防科技大学 | High-frequency low-dielectric low-loss microcrystalline glass/ceramic LTCC substrate material and preparation method thereof |
| CN110372347A (en) * | 2018-04-12 | 2019-10-25 | 中国科学院上海硅酸盐研究所 | A kind of low-loss dielectric constant microwave ceramic material and preparation method thereof |
| US20200308054A1 (en) * | 2019-03-26 | 2020-10-01 | Shanghai Institute Of Ceramics, Chinese Academy Of Sciences | Magnesium oxide based dielectric ceramics with ultrahigh dielectric breakdown strength and its preparation method |
| CN112299825A (en) * | 2020-10-09 | 2021-02-02 | 华中科技大学 | Preparation method of low dielectric low temperature co-fired ceramic material |
-
2022
- 2022-04-02 CN CN202210341679.5A patent/CN116924782A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107326432A (en) * | 2017-06-30 | 2017-11-07 | 哈尔滨工业大学 | A kind of preparation method and application of the template seed crystal of texture aluminium oxide ceramics |
| CN110372347A (en) * | 2018-04-12 | 2019-10-25 | 中国科学院上海硅酸盐研究所 | A kind of low-loss dielectric constant microwave ceramic material and preparation method thereof |
| CN109608050A (en) * | 2018-12-25 | 2019-04-12 | 中国人民解放军国防科技大学 | High-frequency low-dielectric low-loss microcrystalline glass/ceramic LTCC substrate material and preparation method thereof |
| US20200308054A1 (en) * | 2019-03-26 | 2020-10-01 | Shanghai Institute Of Ceramics, Chinese Academy Of Sciences | Magnesium oxide based dielectric ceramics with ultrahigh dielectric breakdown strength and its preparation method |
| CN112299825A (en) * | 2020-10-09 | 2021-02-02 | 华中科技大学 | Preparation method of low dielectric low temperature co-fired ceramic material |
Non-Patent Citations (1)
| Title |
|---|
| 陈涛: "层状结构氧化铝复相陶瓷的制备研究", 《万方学位论文》, 31 December 2012 (2012-12-31), pages 2 - 16 * |
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 | |
| WO2001083395A1 (en) | Low temperature sinterable and low loss dielectric ceramic compositions and method thereof | |
| CN114573333B (en) | Low-temperature co-fired ceramic material of low-dielectric wollastonite and preparation method thereof | |
| JP2011509232A (en) | Low temperature co-fired ceramic powder and special raw materials and their use | |
| JP4632534B2 (en) | Dielectric porcelain and manufacturing method thereof | |
| CN111848145B (en) | Inorganic ceramic powder, preparation method thereof and LTCC (Low temperature Co-fired ceramic) green ceramic tape | |
| WO2023159896A1 (en) | Silicate-based low-temperature sintered microwave dielectric ceramic material and preparation method therefor | |
| CN110229004B (en) | Low-temperature sintered microwave dielectric ceramic material and preparation method thereof | |
| Ebrahimi et al. | Fabrication and microwave dielectric characterization of cordierite/BZBS (Bi2O3-ZnO-B2O3-SiO2) glass composites for LTCC applications | |
| Chen et al. | Fabrication, characterization and sintering of glass-ceramics for low-temperature co-fired ceramic substrates | |
| CN116924782A (en) | Microwave dielectric material with bionic structure and preparation method thereof | |
| CN114656155B (en) | Low-dielectric low-loss low-expansion glass material and preparation method and application thereof | |
| CN112830780B (en) | Regulating agent, LTCC microwave dielectric material and preparation method thereof | |
| CN111574213B (en) | Low-dielectric-constant LTCC material and preparation method thereof | |
| CN113354412A (en) | Temperature-stable low-temperature sintered microwave dielectric ceramic material and preparation method thereof | |
| CN116041062B (en) | Low-temperature co-fired ceramic material and preparation method thereof | |
| CN116813341B (en) | Medium-dielectric low-loss low-temperature co-fired ceramic material and preparation method thereof | |
| CN114315334B (en) | LTCC material and preparation method thereof | |
| CN116924774A (en) | High-strength low-dielectric composite microwave dielectric ceramic material and preparation method thereof | |
| CN114573235B (en) | High-strength low-loss temperature-stable LTCC dielectric material and preparation method thereof | |
| CN115466109B (en) | Calcium-boron-silicon LTCC ceramic material and preparation method thereof | |
| CN114634353B (en) | Low-dielectric low-loss near-zero temperature drift low-temperature co-fired ceramic material and preparation method thereof | |
| WO2023040035A1 (en) | Low-temperature co-fired ceramic powder, preparation method therefor and application thereof | |
| CN116924784A (en) | High-strength low-dielectric microwave dielectric ceramic material and preparation method thereof | |
| JP5037898B2 (en) | Low temperature sintered porcelain and multilayer circuit board using the same |
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 |