CN113149628B - 一种可提高抗还原能力的微波陶瓷介质材料及其制备方法 - Google Patents
一种可提高抗还原能力的微波陶瓷介质材料及其制备方法 Download PDFInfo
- Publication number
- CN113149628B CN113149628B CN202110433664.7A CN202110433664A CN113149628B CN 113149628 B CN113149628 B CN 113149628B CN 202110433664 A CN202110433664 A CN 202110433664A CN 113149628 B CN113149628 B CN 113149628B
- Authority
- CN
- China
- Prior art keywords
- percent
- ball milling
- sio
- dielectric material
- ceramic dielectric
- 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.)
- Expired - Fee Related
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 59
- 239000003989 dielectric material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229910004283 SiO 4 Inorganic materials 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000013078 crystal Substances 0.000 claims abstract description 33
- 238000000498 ball milling Methods 0.000 claims description 68
- 239000011777 magnesium Substances 0.000 claims description 60
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 23
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000011787 zinc oxide Substances 0.000 claims description 21
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 19
- 239000011575 calcium Substances 0.000 claims description 17
- 239000000395 magnesium oxide Substances 0.000 claims description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 14
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims 1
- 229910017625 MgSiO Inorganic materials 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 238000004891 communication Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- -1 titanium ions Chemical class 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/20—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in magnesium oxide, e.g. forsterite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3213—Strontium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
- C04B2235/3267—MnO2
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Insulating Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
本发明公开一种可提高抗还原能力的微波陶瓷介质材料及其制备方法,所述微波陶瓷介质材料的主晶相结构为(1‑x)Mg2SiO4‑x(Ca0.55Sr0.45)ZrO3,其中0.4≤x≤0.7;其Qf值为66000~88000GHz,相对介电常数εr为8.6~13.6,谐振频率温度系数在±9ppm/℃以内。本发明不仅有效地降低了Mg2SiO4晶相合成温度,还抑制了MgSiO3第二相的形成,同时制得的材料性能优良、制备工艺易控、成本低廉等优点,因此具有广阔的市场前景。
Description
技术领域
本发明属于无机非金属材料领域,具体是一种可提高抗还原能力的微波陶瓷介质材料及其制备方法。
背景技术
微波介质陶瓷是指应用于微波频段(300MHz-300GHz频段)电路中作为介质材料并完成一种或多种功能的陶瓷,在现代通信中被广泛用作谐振器、滤波器、介质基片、介质天线、介质导波回路等。微波介质谐振器与金属空腔谐振器相比,具有体积小、质量轻、温度稳定性好、价格便宜等优点。
随着微波通信的快速发展,微波通信系统迫切需要高性能的微波介质器件。目前移动通信的频率范围在800~5500MHz,相应的微波介质器件趋于成熟,但当频率向高端发展时,如华为在2021年4月提出的5-5.5G无线通信,面向2025共同启动5.5G创新和标准化;又如卫星通信的频率位于K波段(12~40GHz),已开发的微波介质材料的εr较大(εr≥20)、Q·f值较小,无法制造出低损耗、合适尺寸的微波介质器件,因此有必要开发低介电常数、低频率温度系数、高Q·f值的微波介质材料。
镁橄榄石(Mg2SiO4)具有低的介电常数、较高的Q·f值,比A12O3陶瓷烧结温度低,适合作为低介电常数介质谐振器或基板的一种微波介质材料。Mg2SiO4陶瓷作为介质谐振器材料存在着以下缺陷。其一,Mg2SiO4陶瓷具有较大的负谐振频率温度系数(-67ppm/℃);其二,Mg2SiO4晶相合成温度高(1260℃),Mg2SiO4陶瓷在合成和烧结过程中容易出现MgSiO3第二相,这个第二相有较高的介电损耗,它的出现降低了Mg2SiO4陶瓷的微波介电性能。在对Mg2SiO4陶瓷研究工作中人们发现,SiO2过量10%至20%的情况下,在1160~1240℃烧结均获得较纯的Mg2SiO4相,但过量SiO2同样增大了材料的微波损耗。0vchar在2007年报道了MgO和SiO2按摩尔比为2:1合成Mg2SiO4过程中,1200℃以下会产生MgSiO3和MgO,在1300℃以上烧结可以获得纯的Mg2SiO4相。国内专利CN102659396A采用Mg2SiO4-BaTiO3添加烧结助剂和掺杂剂,在1320~1380℃氧化气氛下烧结,制备了εr从3~8之间可调、Q·f值大于60000、温度系数控制在±20ppm/℃的微波介质材料。国内专利CN103319166A采用MgTiO3-Mg2SiO4-CaTiO3添加掺杂剂,制备了εr从10~22之间,温度系数控制在±10ppm/℃,在1320~1350℃氧化气氛下烧结的微波介质材料,都不能满足在还原气氛下烧结。主要是组成中含钛,含有钛离子的陶瓷在还原气氛烧结、或烧结温度过高都极易引起钛离子获得电子,这是些是弱束缚电子,在电场作用下导致电性能下降。
目前,报道能够做到介电常数εr从8~14之间可调,温度系数控制在±9ppm/℃内,在还原气氛下烧结,同时Q·f在66000~88000GHz之间的材料体系非常少,当前迫切需要开发一种工艺简单、原材料成本低同时满足低损耗特征、介电常数系列可调的微波介质陶瓷,以满足微波通信行业的应用需求。
发明内容
本发明的目的在于克服现有技术的不足,提供一种性能优良、工艺易控、成本低廉的可提高抗还原能力的微波陶瓷介质材料及其制备方法。
本发明通过以下技术方案予以实现:一种可提高抗还原能力的微波陶瓷介质材料,其特征在于:所述微波陶瓷介质材料的主晶相结构为(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3,其中0.4≤ x≤ 0.7;其Qf值为66000~88000GHz,相对介电常数εr为8.6~13.6,谐振频率温度系数在±9ppm/℃以内。
上述微波陶瓷介质材料的制备方法,其特征在于包括以下步骤:
步骤1:Mg2SiO4主晶相粉料合成:
以粒径D50和纯度分别为2um、99%的氧化镁,1.5um、99.5%的二氧化硅,1.8um、99.5%的氧化锌为起始原料,按摩尔比Mg:Si=2:l进行氧化镁和二氧化硅的配料,按微波陶瓷介质材料总质量的1%添加ZnO;原料经球磨混合均匀后在1120~1200℃下保温3~4小时,随炉冷却得到含有ZnO的Mg2SiO4 主晶相粉料;
步骤 2:(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3预烧料混合:
将步骤1所得的Mg2SiO4主晶相粉料,与粒径D50和纯度分别为1.5um、99.9%的氧化锆,1.5um、99.5%的碳酸钙,1.5um、99.5%碳酸锶混合,混合时控制配比:(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3,其中0.4≤ x≤ 0.7;按微波陶瓷介质材料总质量比的0.2%掺入MnO2、0.2~1.0%掺入La2O3、0.2~1.0%掺入SnO2为添加剂,然后将混合粉料进行第二次球磨,球磨浆料在100℃下烘干并过40目筛,最后混合粉料在1050~1180℃温度下保温2~4小时,得到预烧料,并进行第三次球磨,球磨浆料在100℃下烘干并过40目筛;
步骤3:造粒、成型:
按微波陶瓷介质材料总质量的15~18%向步骤2所得预烧料中添加质量浓度为8%的聚乙烯醇水溶液造粒,造粒尺寸控制在60~250目,并在10~15MPa下压制成生坯;
步骤4 :烧结:
将步骤3所得生坯,在1280~1350℃温度和还原气氛下保温3~4小时,得到最终的微波陶瓷介质材料。
所述步骤1和步骤2中球磨工序的工艺为:以二氧化锆球为球磨介质、蒸馏水/去离子水作为溶剂,按照料:球:水=1:4:2~5重量比,球磨4~6小时。
所述步骤2中添加剂MnO2的粒径D50为0.8um、La2O3的粒径D50为0.9um、SnO2的粒径D50为0.88um。
本发明制备的是可提高抗还原能力的微波陶瓷介质材料,其主晶相结构为(1-x)Mg2SiO4-x(Ca0.55Sr0.45)ZrO3,其中0.4≤ x≤ 0.7;其Qf值为66000~88000GHz,相对介电常数εr为8.6~13.6,谐振频率温度系数在±9ppm/℃以内。本发明不仅有效地降低了Mg2SiO4晶相合成温度,还抑制了MgSiO3第二相的形成,同时制得的材料性能优良、制备工艺易控、成本低廉等优点,因此具有广阔的市场前景。
附图说明
图1 为实施例1中合成Mg2SiO4的XRD检测图。
具体实施方式
实施例1
一种可提高抗还原能力的微波陶瓷介质材料的制备方法,包括以下步骤:
步骤1:Mg2SiO4主晶相粉料合成:
以粒径D50和纯度分别为2um、99%的氧化镁,1.5um、99.5%的二氧化硅,1.8um、99.5%的氧化锌为起始原料,按摩尔比Mg:Si=2:l进行氧化镁和二氧化硅的配料,按微波陶瓷介质材料总质量的1%添加ZnO;原料经球磨混合均匀后在1160℃下保温3小时,随炉冷却得到含有ZnO的Mg2SiO4 主晶相粉料;
步骤2:(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3预烧料混合:
将步骤1所得的Mg2SiO4主晶相粉料,与粒径D50和纯度分别为1.5um、99.9%的氧化锆,1.5um、99.5%的碳酸钙,1.5um、99.5%碳酸锶混合,混合时控制配比:(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3,其中x=0.45;按微波陶瓷介质材料总质量的0.2%掺入MnO2、0.2%掺入La2O3、1.0%掺入SnO2为添加剂,然后将混合粉料进行第二次球磨,球磨浆料在100℃下烘干并过40目筛,最后混合粉料在1060℃温度下保温3小时,得到预烧料,并进行第三次球磨,球磨浆料在100℃下烘干并过40目筛;
步骤3:造粒、成型:
按微波陶瓷介质材料总质量的15%向步骤2所得预烧料中添加质量浓度为8%的聚乙烯醇水溶液造粒,造粒尺寸控制在60~250目,并在15MPa下压制成生坯;
步骤4 :烧结:
将步骤3所得生坯,在1280℃温度和还原气氛下保温4小时,得到最终的微波陶瓷介质材料。
所述步骤1和步骤2中球磨工序的工艺为:以二氧化锆球为球磨介质、蒸馏水/去离子水作为溶剂,按照料:球:水=1:4:2重量比,球磨4小时。
所述步骤2中添加剂MnO2的粒径D50为0.8um、La2O3的粒径D50为0.9um、SnO2的粒径D50为0.88um。
材料的Qf值为84000GHz,相对介电常数εr为8.9,-40~25℃范围内谐振频率温度系数为+1.2ppm/℃,25~85℃范围内谐振频率温度系数为-1.8ppm/℃。
实施例2
一种可提高抗还原能力的微波陶瓷介质材料的制备方法,包括以下步骤:
步骤1:Mg2SiO4主晶相粉料合成:
以粒径D50和纯度分别为2um、99%的氧化镁,1.5um、99.5%的二氧化硅,1.8um、99.5%的氧化锌为起始原料,按摩尔比Mg:Si=2:l进行氧化镁和二氧化硅的配料,按微波陶瓷介质材料总质量的1%添加ZnO;原料经球磨混合均匀后在1120℃下保温4小时,随炉冷却得到含有ZnO的Mg2SiO4 主晶相粉料;
步骤 2:(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3预烧料混合:
将步骤1所得的Mg2SiO4主晶相粉料,与粒径D50和纯度分别为1.5um、99.9%的氧化锆,1.5um、99.5%的碳酸钙,1.5um、99.5%碳酸锶混合,混合时控制配比:(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3,其中x=0.6;按微波陶瓷介质材料总质量的0.2%掺入MnO2、0.6%掺入La2O3、0.6%掺入SnO2为添加剂,然后将混合粉料进行第二次球磨,球磨浆料在100℃下烘干并过40目筛,最后混合粉料在1080℃温度下保温2小时,得到预烧料,并进行第三次球磨,球磨浆料在100℃下烘干并过40目筛;
步骤3:造粒、成型:
按微波陶瓷介质材料总质量的16%向步骤2所得预烧料中添加质量浓度为8%的聚乙烯醇水溶液造粒,造粒尺寸控制在60~250目,并在14MPa下压制成生坯;
步骤4 :烧结:
将步骤3所得生坯,在1290℃温度和还原气氛下保温3小时,得到最终的微波陶瓷介质材料。
所述步骤1和步骤2中球磨工序的工艺为:以二氧化锆球为球磨介质、蒸馏水/去离子水作为溶剂,按照料:球:水=1:4:3重量比,球磨4小时。
所述步骤2中添加剂MnO2的粒径D50为0.8um、La2O3的粒径D50为0.9um、SnO2的粒径D50为0.88um。
材料的Qf值为88000GHz,相对介电常数εr为10.2,-40~25℃范围内谐振频率温度系数为+3.6ppm/℃,25~85℃范围内谐振频率温度系数为-3.6ppm/℃。
实施例3
一种可提高抗还原能力的微波陶瓷介质材料的制备方法,包括以下步骤:
步骤1:Mg2SiO4主晶相粉料合成:
以粒径D50和纯度分别为2um、99%的氧化镁,1.5um、99.5%的二氧化硅,1.8um、99.5%的氧化锌为起始原料,按摩尔比Mg:Si=2:l进行氧化镁和二氧化硅的配料,按微波陶瓷介质材料总质量的1%添加ZnO;原料经球磨混合均匀后在1190℃下保温4小时,随炉冷却得到含有ZnO的Mg2SiO4 主晶相粉料;
步骤 2:(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3预烧料混合:
将步骤1所得的Mg2SiO4主晶相粉料,与粒径D50和纯度分别为1.5um、99.9%的氧化锆,1.5um、99.5%的碳酸钙,1.5um、99.5%碳酸锶混合,混合时控制配比:(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3,其中x=0.5;按微波陶瓷介质材料总质量的0.2%掺入MnO2、1.0%掺入La2O3、0.2%掺入SnO2为添加剂,然后将混合粉料进行第二次球磨,球磨浆料在100℃下烘干并过40目筛,最后混合粉料在1120℃温度下保温4小时,得到预烧料,并进行第三次球磨,球磨浆料在100℃下烘干并过40目筛;
步骤3:造粒、成型:
按微波陶瓷介质材料总质量的17%向步骤2所得预烧料中添加质量浓度为8%的聚乙烯醇水溶液造粒,造粒尺寸控制在60~250目,并在13MPa下压制成生坯;
步骤4 :烧结:
将步骤3所得生坯,在1300℃温度和还原气氛下保温4小时,得到最终的微波陶瓷介质材料。
所述步骤1和步骤2中球磨工序的工艺为:以二氧化锆球为球磨介质、蒸馏水/去离子水作为溶剂,按照料:球:水=1:4:4重量比,球磨5小时。
所述步骤2中添加剂MnO2的粒径D50为0.8um、La2O3的粒径D50为0.9um、SnO2的粒径D50为0.88um。
材料的Qf值为86000GHz,相对介电常数εr为12.4,-40~25℃范围内谐振频率温度系数为+5.4ppm/℃,25~85℃范围内谐振频率温度系数为-6.4ppm/℃。
实施例4
一种可提高抗还原能力的微波陶瓷介质材料的制备方法,包括以下步骤:
步骤1:Mg2SiO4主晶相粉料合成:
以粒径D50和纯度分别为2um、99%的氧化镁,1.5um、99.5%的二氧化硅,1.8um、99.5%的氧化锌为起始原料,按摩尔比Mg:Si=2:l进行氧化镁和二氧化硅的配料,按微波陶瓷介质材料总质量的1%添加ZnO;原料经球磨混合均匀后在1140℃下保温4小时,随炉冷却得到含有ZnO的Mg2SiO4 主晶相粉料;
步骤 2:(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3预烧料混合:
将步骤1所得的Mg2SiO4主晶相粉料,与粒径D50和纯度分别为1.5um、99.9%的氧化锆,1.5um、99.5%的碳酸钙,1.5um、99.5%碳酸锶混合,混合时控制配比:(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3,其中x=0.65;按微波陶瓷介质材料总质量的0.2%掺入MnO2、1.0%掺入La2O3、0.9%掺入SnO2为添加剂,然后将混合粉料进行第二次球磨,球磨浆料在100℃下烘干并过40目筛,最后混合粉料在1150℃温度下保温4小时,得到预烧料,并进行第三次球磨,球磨浆料在100℃下烘干并过40目筛;
步骤3:造粒、成型:
按微波陶瓷介质材料总质量的17%向步骤2所得预烧料中添加质量浓度为8%的聚乙烯醇水溶液造粒,造粒尺寸控制在60~250目,并在12MPa下压制成生坯;
步骤4 :烧结:
将步骤3所得生坯,在1310℃温度和还原气氛下保温4小时,得到最终的微波陶瓷介质材料。
所述步骤1和步骤2中球磨工序的工艺为:以二氧化锆球为球磨介质、蒸馏水/去离子水作为溶剂,按照料:球:水=1:4:5重量比,球磨5小时。
所述步骤2中添加剂MnO2的粒径D50为0.8um、La2O3的粒径D50为0.9um、SnO2的粒径D50为0.88um。
材料的Qf值为76000GHz,相对介电常数εr为11.5,-40℃~25℃范围内谐振频率温度系数为+6.4ppm/℃,25~85℃范围内谐振频率温度系数为-7.6ppm/℃。
实施例5
一种可提高抗还原能力的微波陶瓷介质材料的制备方法,包括以下步骤:
步骤1:Mg2SiO4主晶相粉料合成:
以粒径D50和纯度分别为2um、99%的氧化镁,1.5um、99.5%的二氧化硅,1.8um、99.5%的氧化锌为起始原料,按摩尔比Mg:Si=2:l进行氧化镁和二氧化硅的配料,按微波陶瓷介质材料总质量的1%添加ZnO;原料经球磨混合均匀后在1180℃下保温4小时,随炉冷却得到含有ZnO的Mg2SiO4 主晶相粉料;
步骤 2:(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3预烧料混合:
将步骤1所得的Mg2SiO4主晶相粉料,与粒径D50和纯度分别为1.5um、99.9%的氧化锆,1.5um、99.5%的碳酸钙,1.5um、99.5%碳酸锶混合,混合时控制配比:(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3,其中x=0.65;按微波陶瓷介质材料总质量的0.2%掺入MnO2、0.3%掺入La2O3、0.3%掺入SnO2为添加剂,然后将混合粉料进行第二次球磨,球磨浆料在100℃下烘干并过40目筛,最后混合粉料在1180°C温度下保温4小时,得到预烧料,并进行第三次球磨,球磨浆料在100℃下烘干并过40目筛;
步骤3:造粒、成型:
按微波陶瓷介质材料总质量的18%向步骤2所得预烧料中添加质量浓度为8%的聚乙烯醇水溶液造粒,造粒尺寸控制在60~250目,并在11MPa下压制成生坯;
步骤4 :烧结:
将步骤3所得生坯,在1340℃温度和还原气氛下保温4小时,得到最终的微波陶瓷介质材料。
所述步骤1和步骤2中球磨工序的工艺为:以二氧化锆球为球磨介质、蒸馏水/去离子水作为溶剂,按照料:球:水=1:4:4重量比,球磨6小时。
所述步骤2中添加剂MnO2的粒径D50为0.8um、La2O3的粒径D50为0.9um、SnO2的粒径D50为0.88um。
材料的Qf值为67500GHz,相对介电常数εr为13.5,-40~25℃范围内谐振频率温度系数为+8.0ppm/℃,25~85℃范围内谐振频率温度系数为-8.8ppm/℃。
上述谐振频率温度系数τƒ是根据Hakki-Coleman介质谐振法, 用网络分析仪(Aglient technologies E5071C)由(ft1-f0)/f0(t1-t0)计算所得,其中(25-85℃)t0=25℃、t1=85℃;(-40-25℃)t0=25℃、t1=-40℃覆盖全温度范围。
Claims (4)
1.一种可提高抗还原能力的微波陶瓷介质材料,其特征在于:所述微波陶瓷介质材料的主晶相结构为(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3,其中0.4≤ x≤ 0.7;其Qf值为66000~88000GHz,相对介电常数εr为8.6~13.6,谐振频率温度系数在±9ppm/℃以内。
2.根据权利要求1所述微波陶瓷介质材料的制备方法,其特征在于包括以下步骤:
步骤1:Mg2SiO4主晶相粉料合成:
以粒径D50和纯度分别为2μm 、99%的氧化镁,1.5μm 、99.5%的二氧化硅,1.8μm 、99.5%的氧化锌为起始原料,按摩尔比Mg:Si=2:l进行氧化镁和二氧化硅的配料,按微波陶瓷介质材料总质量的1%添加ZnO;原料经球磨混合均匀后在1120~1200℃下保温3~4小时,随炉冷却得到含有ZnO的Mg2SiO4 主晶相粉料;
步骤 2:(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3预烧料混合:
将步骤1所得的Mg2SiO4主晶相粉料,与粒径D50和纯度分别为1.5μm 、99.9%的氧化锆,1.5μm 、99.5%的碳酸钙,1.5μm 、99.5%碳酸锶混合,混合时控制配比:(1-x) Mg2SiO4-x(Ca0.55Sr0.45)ZrO3,其中0.4≤ x≤ 0.7;按微波陶瓷介质材料总质量比的0.2%掺入MnO2、0.2~1.0%掺入La2O3、0.2~1.0%掺入SnO2为添加剂,然后将混合粉料进行第二次球磨,球磨浆料在100℃下烘干并过40目筛,最后混合粉料在1050~1180℃温度下保温2~4小时,得到预烧料,并进行第三次球磨,球磨浆料在100℃下烘干并过40目筛;
步骤3:造粒、成型:
按微波陶瓷介质材料总质量的15~18%向步骤2所得预烧料中添加质量浓度为8%的聚乙烯醇水溶液造粒,造粒尺寸控制在60~250目,并在10~15MPa下压制成生坯;
步骤4 :烧结:
将步骤3所得生坯,在1280~1350℃温度和还原气氛下保温3~4小时,得到最终的微波陶瓷介质材料。
3.根据权利要求2所述的制备方法,其特征在于:所述步骤1和步骤2中球磨工序的工艺为:以二氧化锆球为球磨介质、蒸馏水/去离子水作为溶剂,按照料:球:水=1:4:2~5重量比,球磨4~6小时。
4.根据权利要求2所述的制备方法,其特征在于:所述步骤2中添加剂MnO2的粒径D50为0.8μm 、La2O3的粒径D50为0.9μm 、SnO2的粒径D50为0.88μm 。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110433664.7A CN113149628B (zh) | 2021-04-22 | 2021-04-22 | 一种可提高抗还原能力的微波陶瓷介质材料及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110433664.7A CN113149628B (zh) | 2021-04-22 | 2021-04-22 | 一种可提高抗还原能力的微波陶瓷介质材料及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113149628A CN113149628A (zh) | 2021-07-23 |
CN113149628B true CN113149628B (zh) | 2022-09-13 |
Family
ID=76869269
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110433664.7A Expired - Fee Related CN113149628B (zh) | 2021-04-22 | 2021-04-22 | 一种可提高抗还原能力的微波陶瓷介质材料及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113149628B (zh) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107522481A (zh) * | 2016-06-22 | 2017-12-29 | 华新科技股份有限公司 | 低温共烧微波介电陶瓷材料及其制法 |
CN108249917A (zh) * | 2018-01-05 | 2018-07-06 | 杭州电子科技大学 | 具有中介电常数和超低介电损耗的微波介质陶瓷、制备方法及其应用 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI592384B (zh) * | 2016-05-17 | 2017-07-21 | Low temperature co-fired microwave dielectric ceramic material and its preparation method |
-
2021
- 2021-04-22 CN CN202110433664.7A patent/CN113149628B/zh not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107522481A (zh) * | 2016-06-22 | 2017-12-29 | 华新科技股份有限公司 | 低温共烧微波介电陶瓷材料及其制法 |
CN108249917A (zh) * | 2018-01-05 | 2018-07-06 | 杭州电子科技大学 | 具有中介电常数和超低介电损耗的微波介质陶瓷、制备方法及其应用 |
Non-Patent Citations (2)
Title |
---|
Effect of Zr substitution on the microwave dielectric properties of (Ca0.8Sr0.2)TiO3 ceramics;Cheng-Hsing Hsu et al;《Materials Research Bulletin》;20131026;第103-107页 * |
Li2CO3掺杂对0.94Mg2SiO4-0.06Ca0.9Sr0.1TiO3陶瓷微波介电性能的影响;刘玲等;《人工晶体学报》;20150228;第44卷(第2期);第430-434页 * |
Also Published As
Publication number | Publication date |
---|---|
CN113149628A (zh) | 2021-07-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103232235B (zh) | 一种低温烧结复合微波介质陶瓷材料及其制备方法 | |
CN108358632B (zh) | 一种超低温烧结高Q×f值微波介质材料及其制备方法 | |
CN111995383B (zh) | Mg2-xMxSiO4-CaTiO3复合微波介质陶瓷及其制备方法 | |
CN107117967B (zh) | 一种低温烧结复合微波介质陶瓷材料及其制备方法 | |
CN114394827B (zh) | 一种低介电常数硅酸盐微波介质陶瓷及其制备方法 | |
CN111302788B (zh) | 一种具有高Qf值低介电常数的陶瓷材料及其制备方法 | |
CN112194483B (zh) | 一种高强度钙镁钛系微波介质陶瓷材料及其制备方法 | |
CN113105226B (zh) | 一种微波陶瓷介质材料及其制备方法 | |
CN105254293A (zh) | 一种微波介质陶瓷材料及其制备方法 | |
CN111470864B (zh) | 一种硅基温度稳定型微波介质陶瓷材料及其制备方法 | |
CN111302775B (zh) | 一种具有高品质因数低介电常数的陶瓷材料及其制备方法 | |
KR101732422B1 (ko) | 유전체 제조용 소결 전구체 분말 및 이의 제조 방법 | |
CN105669195B (zh) | 低介电常数高q值微波介质陶瓷材料及其制备方法 | |
CN105198423A (zh) | Sr-La-Al基微波介质陶瓷材料及其制备方法 | |
CN107188557A (zh) | 一种微波介质陶瓷材料及其制备方法 | |
CN111499375B (zh) | 一种高品质因数微波介质陶瓷材料及其制备方法 | |
CN113149628B (zh) | 一种可提高抗还原能力的微波陶瓷介质材料及其制备方法 | |
CN106587991B (zh) | 一种低温烧结复合微波介质陶瓷材料及其制备方法 | |
CN112266238B (zh) | 一种微波器件用的低介电常数陶瓷材料及其制备方法 | |
JP2004018365A (ja) | マイクロ波誘電体磁器組成物およびその磁器の製造方法 | |
CN109650886B (zh) | 一种Ba-Mg-Ta系LTCC材料及其制备方法 | |
CN102030527B (zh) | 一种BaO-TiO 2系微波电容器介质材料及其制备方法 | |
CN104402430A (zh) | 一种温度稳定型中k值微波介质陶瓷及其制备方法 | |
CN113292338B (zh) | 一种Ba-Co-V基低介低烧微波陶瓷材料及其制备方法 | |
JP3330024B2 (ja) | 高周波用誘電体磁器組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220913 |
|
CF01 | Termination of patent right due to non-payment of annual fee |