CN108821764A - 一种谐振器用微波介质陶瓷及其制备方法 - Google Patents

一种谐振器用微波介质陶瓷及其制备方法 Download PDF

Info

Publication number
CN108821764A
CN108821764A CN201810965324.7A CN201810965324A CN108821764A CN 108821764 A CN108821764 A CN 108821764A CN 201810965324 A CN201810965324 A CN 201810965324A CN 108821764 A CN108821764 A CN 108821764A
Authority
CN
China
Prior art keywords
microwave
medium ceramics
tio
resonator
hours
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
Application number
CN201810965324.7A
Other languages
English (en)
Inventor
李玲霞
罗伟嘉
孙正
张博文
杜明昆
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University
Original Assignee
Tianjin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin University filed Critical Tianjin University
Priority to CN201810965324.7A priority Critical patent/CN108821764A/zh
Publication of CN108821764A publication Critical patent/CN108821764A/zh
Pending legal-status Critical Current

Links

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
    • C04B35/46—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 titanium oxides or titanates
    • C04B35/462—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 titanium oxides or titanates based on titanates
    • 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
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6565—Cooling 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
    • C04B2235/65—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
    • C04B2235/6567—Treatment time
    • 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

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 Insulating Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

本发明公开了一种谐振器用微波介质陶瓷，合成物表达式为：Ba4Sm9.33Ti18O54‑xwt％TiO2，其中x＝0.5～1。先将BaCO3、TiO2于80～120℃烘干，并将Sm2O3于950℃煅烧，按化学计量式配料；再经球磨、烘干、过筛后于1200℃煅烧，经过造粒后压制成坯体，坯体于1250℃～1350℃烧结，再以0.5～2℃/min速率降温至1100℃进行降温退火处理，制成复合微波介质陶瓷。本发明介电常数εr为79.7～83.5，品质因数Qf值为6000GHz～9500GHz，谐振频率温度系数τf为‑18～+12ppm/℃，制备工艺简单，应用前景广泛。

Description

一种谐振器用微波介质陶瓷及其制备方法
技术领域
本发明属于一种以成分为特征的陶瓷组合物，尤其涉及一种以Ba4Sm9.33Ti18O54-xwt％TiO2(x＝0.5,0.75,1)为化学式，可用于微波介质谐振器的介质陶瓷及其制备方法。
背景技术
在微波频段的无线通信中，介质谐振器以其优异的性能、较低的成本而得到广泛应用。随着信息时代无线移动通信向更高频率发展，对这类无源器件提出了高性能化、小型化的要求。以此作为支撑，研发谐振器用高性能微波介质陶瓷成为了一个重要课题。
为满足谐振器小型化、优异的频率选择特性、良好的温度稳定性要求，谐振器用高性能微波介质陶瓷需要具备高介电常数、高Q值、近零的频率温度系数。基于诸多微波介质陶瓷体系的研究，晶体结构被认为是影响其微波介电性能的最主要因素。对微波介质陶瓷相组成及微观结构进行调控，有望实现微波介电性能的综合提升。高介电常数谐振器用微波介质陶瓷(εr＞70，Q＞5000at 1GHz，|τf|≤10ppm/℃)通常具有类钙钛矿钨青铜结构，以氧八面体按复杂的共顶点方式连接形成，具有较低的晶体对称性，其结构调控成为一个难题，因而对其微波介电性能进行优化难以得到预期的结果。本发明对钨青铜结构Ba4Sm9.33Ti18O54进行相组成和结构调控，采用具有高介电常数、正谐振频率温度系数的TiO2，结合改良的固相法工艺，制备出了均匀致密、高性能的Ba4Sm9.33Ti18O54-xwt％TiO2(x＝0.5～1)复合微波介质陶瓷。
发明内容
本发明的目的，为满足微波介质谐振器小型化、优异性能的需要，以BaCO3、Sm2O3、TiO2为原料，采用改良的固相制备工艺，提供一种具有良好微波介电性能的Ba4Sm9.33Ti18O54-xwt％TiO2(x＝0.5～1)微波介质陶瓷，以满足微波介质谐振器的性能要求。
本发明通过如下技术方案予以实现。
一种谐振器用微波介质陶瓷，合成物表达式为：Ba4Sm9.33Ti18O54-xwt％TiO2，其中x＝0.5～1；
上述谐振器用微波介质陶瓷的制备方法，具体实施步骤如下：
(1)将BaCO3、TiO2放入干燥箱中，于80～120℃烘干24h；将Sm2O3放于中温炉中，于950℃煅烧5～8小时；
(2)将步骤(1)预处理后的原料按化学计量式Ba4Sm9.33Ti18O54，其中x＝0.5～1进行配料；将粉料放入聚酯罐中，加入无水乙醇和氧化锆球，球磨4～8小时；
(3)将步骤(2)球磨后的原料放入干燥箱中，于80～120℃烘干，然后过40目筛，再过80目筛；
(4)将烘干、过筛后的粉料放入中温炉中，于1200℃煅烧5～8小时；
(5)在步骤(4)煅烧后的粉料中外加质量百分比含量为0.5wt％～1wt％的TiO2，再外加0.9wt％～1.1wt％的聚乙烯醇作为粘合剂进行造粒，将混合后的粉料放入球磨罐中，加入氧化锆球和无水乙醇，球磨9～12小时后烘干过80目筛，再用粉末压片机压制成坯体；
(6)将步骤(5)的坯体于1250℃～1350℃烧结，保温2～8小时，再降温至1100℃进行降温退火处理，降温速率为0.5～2℃/min，制成Ba4Sm9.33Ti18O54-xwt％TiO2，其中x＝0.5～1的谐振器用复合微波介质陶瓷；
所述步骤(1)采用原料BaCO3、TiO2和Sm2O3的质量纯度均大于99.9％。
所述步骤(2)采用行星式球磨机进行球磨，球磨机转速为400转/分。
所述步骤(2)的粉料与去离子水和氧化锆球的质量比为1︰10︰6。
所述步骤(2)的氧化锆球的直径为2mm。
所述步骤(4)的生坯直径为10mm，厚度为5mm。
所述步骤(5)的烧结温度为1300℃。
所述步骤(6)的降温速率为1℃/min。
本发明通过改良的固相合成法制备了一种谐振器用复合高介电常数微波介质陶瓷Ba4Sm9.33Ti18O54-xwt％TiO2(x＝0.5～1)。其介电常数εr为78.9～83.5，品质因数Qf值为6000GHz～9500GHz，谐振频率温度系数τf为-18～+12ppm/℃。该制备工艺简单，应用前景广泛。
具体实施方式
本发明以BaCO3(＞99％)、Sm2O3(＞99.9％)、TiO2(＞99％)为初始原料，通过简单固相合成法制备微波介质陶瓷。具体实施方案如下：
1.将BaCO3(＞99％)、TiO2(＞99％)放入干燥箱中，于80℃烘干24h；将Sm2O3(＞99.9％)放于中温炉中，于950℃煅烧6小时；
2.将步骤(1)预处理后的原料按化学计量式Ba4Sm9.33Ti18O54进行配料粉料配比为：5.2026g BaCO3、10.6253g Sm2O3、9.4752gTiO2。将25g粉料放入聚酯罐中，加入250ml无水乙醇、60g氧化锆球后，在行星式球磨机上球磨6小时，转速为400转/分；
3.将步骤(2)球磨后的原料放入干燥箱中，于80℃烘干，然后过40目筛，再过80目筛；
4.将烘干、过筛后的粉料放入中温炉中，于1200℃煅烧8小时；
5.在步骤(4)煅烧后的粉料中加入0.5～1wt％的TiO2，再加入1wt％的聚乙烯醇作为粘合剂进行造粒，将混合后的粉料放入球磨罐中，加入氧化锆球和无水乙醇，球磨12小时后烘干过80目筛，再用粉末压片机以2MPa的压力压制成坯体；
6.将步骤(5)的生坯于1300℃烧结，保温6小时，再降温至1100℃进行降温退火处理，降温速率0.5～2℃/min，制成Ba4Sm9.33Ti18O54-xwt％TiO2(x＝0.5～1)复合微波介质陶瓷；
本发明具体实施例的相关工艺参数及其微波介电性能详见表1。
表1
本发明并不局限于上述实施例，很多细节的变化是可能的，但这并不因此违背本发明的范围和精神。

Claims (8)

1.一种谐振器用微波介质陶瓷，合成物表达式为：Ba4Sm9.33Ti18O54-xwt％TiO2，其中x＝0.5～1。
上述谐振器用微波介质陶瓷的制备方法，具体实施步骤如下：
(1)将BaCO3、TiO2放入干燥箱中，于80～120℃烘干24h；将Sm2O3放于中温炉中，于950℃煅烧5～8小时；
(2)将步骤(1)预处理后的原料按化学计量式Ba4Sm9.33Ti18O54，其中x＝0.5～1进行配料；将粉料放入聚酯罐中，加入无水乙醇和氧化锆球，球磨4～8小时；
(3)将步骤(2)球磨后的原料放入干燥箱中，于80～120℃烘干，然后过40目筛，再过80目筛；
(4)将烘干、过筛后的粉料放入中温炉中，于1200℃煅烧5～8小时；
(5)在步骤(4)煅烧后的粉料中外加质量百分比含量为0.5wt％～1wt％的TiO2，再外加0.9wt％～1.1wt％的聚乙烯醇作为粘合剂进行造粒，将混合后的粉料放入球磨罐中，加入氧化锆球和无水乙醇，球磨9～12小时后烘干过80目筛，再用粉末压片机压制成坯体；
(6)将步骤(5)的坯体于1250℃～1350℃烧结，保温2～8小时，再降温至1100℃进行降温退火处理，降温速率为0.5～2℃/min，制成Ba4Sm9.33Ti18O54-xwt％TiO2，其中x＝0.5～1的谐振器用复合微波介质陶瓷。
2.根据权利要求1所述的一种谐振器用微波介质陶瓷，其特征在于，所述步骤(1)采用原料BaCO3、TiO2和Sm2O3的质量纯度均大于99.9％。
3.据权利要求1所述的一种谐振器用微波介质陶瓷，其特征在于，所述步骤(2)采用行星式球磨机进行球磨，球磨机转速为400转/分。
4.据权利要求1所述的一种谐振器用微波介质陶瓷，其特征在于，所述步骤(2)的粉料与去离子水和氧化锆球的质量比为1︰10︰6。
5.据权利要求1所述的一种谐振器用微波介质陶瓷，其特征在于，所述步骤(2)的氧化锆球的直径为2mm。
6.据权利要求1所述的一种谐振器用微波介质陶瓷，其特征在于，所述步骤(4)的生坯直径为10mm，厚度为5mm。
7.据权利要求1所述的一种谐振器用微波介质陶瓷，其特征在于，所述步骤(5)的烧结温度为1300℃。
8.权利要求1所述的一种谐振器用微波介质陶瓷，其特征在于，所述步骤(6)的降温速率为1℃/min。
CN201810965324.7A 2018-08-22 2018-08-22 一种谐振器用微波介质陶瓷及其制备方法 Pending CN108821764A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810965324.7A CN108821764A (zh) 2018-08-22 2018-08-22 一种谐振器用微波介质陶瓷及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810965324.7A CN108821764A (zh) 2018-08-22 2018-08-22 一种谐振器用微波介质陶瓷及其制备方法

Publications (1)

Publication Number Publication Date
CN108821764A true CN108821764A (zh) 2018-11-16

Family

ID=64150509

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810965324.7A Pending CN108821764A (zh) 2018-08-22 2018-08-22 一种谐振器用微波介质陶瓷及其制备方法

Country Status (1)

Country Link
CN (1) CN108821764A (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110092655A (zh) * 2019-06-06 2019-08-06 无锡鑫圣慧龙纳米陶瓷技术有限公司 一种钡钐钛系低损耗微波介质陶瓷及其制备方法
CN111943664A (zh) * 2020-07-29 2020-11-17 无锡鑫圣慧龙纳米陶瓷技术有限公司 一种低烧结温度钡钐钛系微波介质陶瓷及其制备方法
CN113087518A (zh) * 2021-03-03 2021-07-09 华中科技大学 一种负热膨胀系数微波陶瓷及其3d打印介质谐振器天线
CN113666737A (zh) * 2021-07-23 2021-11-19 清华大学 高介电常数低损耗微波介质陶瓷及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107573056A (zh) * 2017-09-24 2018-01-12 天津大学 谐振频率温度系数近零的微波介质材料及其制备方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107573056A (zh) * 2017-09-24 2018-01-12 天津大学 谐振频率温度系数近零的微波介质材料及其制备方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
HITOSHI OHSATO ET AL.: "Microwave Dielectric Properties and Sintering of Ba6-3xR8+2xTi18O54 (R = Sm, x=2/3) Solid Solution with Added Rutile", 《JPN. J. APPL. PHYS.》 *
N. QIN ET AL.: "Microstructure dependence of microwave dielectric characteristics in Ba6-3xSm8+2xTi18O54 (x=2/3) ceramics", 《J ELECTROCERAM》 *
周张健: "《无机非金属材料工艺学》", 31 January 2010, 中国轻工业出版社 *
姚晓刚等: "Al2O3掺杂对Ba4Sm9.33Ti18O54陶瓷显微结构和介电性能的影响", 《无机材料学报》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110092655A (zh) * 2019-06-06 2019-08-06 无锡鑫圣慧龙纳米陶瓷技术有限公司 一种钡钐钛系低损耗微波介质陶瓷及其制备方法
CN110092655B (zh) * 2019-06-06 2022-01-25 无锡鑫圣慧龙纳米陶瓷技术有限公司 一种钡钐钛系低损耗微波介质陶瓷及其制备方法
CN111943664A (zh) * 2020-07-29 2020-11-17 无锡鑫圣慧龙纳米陶瓷技术有限公司 一种低烧结温度钡钐钛系微波介质陶瓷及其制备方法
CN113087518A (zh) * 2021-03-03 2021-07-09 华中科技大学 一种负热膨胀系数微波陶瓷及其3d打印介质谐振器天线
CN113666737A (zh) * 2021-07-23 2021-11-19 清华大学 高介电常数低损耗微波介质陶瓷及其制备方法

Similar Documents

Publication Publication Date Title
CN108821764A (zh) 一种谐振器用微波介质陶瓷及其制备方法
JP2003531808A (ja) 低温焼結低損失高周波用誘電体セラミックス組成物およびその製造方法
JP2003531097A (ja) 低温焼結低損失高周波用誘電体セラミックス組成物およびその製造方法
CN107188557B (zh) 一种微波介质陶瓷材料及其制备方法
CN110282968A (zh) 一种微波介质陶瓷材料及其制备方法
Tang et al. Low-temperature sintering and microwave dielectric properties of ZnZrNb2O8 ceramics with BaCu (B2O5) addition
CN108439973A (zh) 一种高q值高介电常数微波介质陶瓷材料及其制备方法
CN107311646A (zh) 一种提高钛酸锶陶瓷材料介电性能的制备方法
CN109111229A (zh) 一种高温烧结微波介质陶瓷材料及其制备方法
CN108147809B (zh) 中低温烧结钡-钛系微波介质材料及制备方法
CN108975905A (zh) 一种异种氧化物共掺钛酸锂基微波介质材料的制备方法
CN105198423A (zh) Sr-La-Al基微波介质陶瓷材料及其制备方法
CN106904969A (zh) 一种谐振频率温度系数可调的中介电常数微波介质陶瓷
Ma et al. Low-fired Mg2SiO4-based dielectric ceramics with temperature stable for LTCC applications
CN110229004A (zh) 一种低温烧结微波介质陶瓷材料及其制备方法
Peng et al. Crystal structure, sintering behavior and microwave dielectric properties of Ca x Y 3− x Al 5− x Ti x O 12 (0≤ x≤ 2.0) solid solution ceramics
Qi et al. Effects of Bi2O3–ZnO–B2O3–SiO2 glass addition on the sintering and microwave dielectric properties of ZnZrNb2O8 ceramics for LTCC applications
CN108285344A (zh) 一种低损耗锰钽矿结构微波介质陶瓷材料
CN109111225A (zh) 通过镁铌组分调控微波介电性能的钛酸锂基微波介质材料
CN108793994A (zh) 一种施主掺杂中介电常数微波介质陶瓷及其制备方法
CN107162592A (zh) 一种铌酸盐微波介质陶瓷材料及其制备方法
CN106866143A (zh) 微波复相陶瓷AWO4‑TiO2及其制备方法
CN112939599A (zh) 铌钽锆镁微波介质陶瓷材料及其制备方法
CN108455986A (zh) 一种复合微波介质陶瓷材料及其制备方法
Ma et al. Studies of phase transitions, Raman spectra and microwave dielectric properties of perovskite-structured (Na1− x Li x) 0.5 Nd0. 5TiO3 ceramics

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
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20181116

WD01 Invention patent application deemed withdrawn after publication