CN113548888B - 一种频率温度系数改善的微波介质材料及其制备方法 - Google Patents

一种频率温度系数改善的微波介质材料及其制备方法 Download PDF

Info

Publication number
CN113548888B
CN113548888B CN202110910902.9A CN202110910902A CN113548888B CN 113548888 B CN113548888 B CN 113548888B CN 202110910902 A CN202110910902 A CN 202110910902A CN 113548888 B CN113548888 B CN 113548888B
Authority
CN
China
Prior art keywords
microwave dielectric
temperature coefficient
dielectric ceramic
catio
ceramic material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110910902.9A
Other languages
English (en)
Other versions
CN113548888A (zh
Inventor
吴伟杰
陶锋烨
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.)
Zhejiang Jiakang Electronics Co ltd
Original Assignee
Zhejiang Jiakang Electronics Co ltd
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 Zhejiang Jiakang Electronics Co ltd filed Critical Zhejiang Jiakang Electronics Co ltd
Priority to CN202110910902.9A priority Critical patent/CN113548888B/zh
Publication of CN113548888A publication Critical patent/CN113548888A/zh
Application granted granted Critical
Publication of CN113548888B publication Critical patent/CN113548888B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C04B35/465—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 based on alkaline earth metal 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—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
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium 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
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C04B2235/3234—Titanates, not containing zirconia
    • C04B2235/3236—Alkaline earth 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
    • 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
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, 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
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • 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
    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Insulating Materials (AREA)

Abstract

本发明公开了一种频率温度系数改善的微波介质陶瓷材料及其制备方法，属于微波介质材料技术领域。该微波介质陶瓷材料的组成表达式为：(1‑x)Mg2TiO4‑x[CaTiO3‑yMO]，其中：0≤x≤0.3，0.1≤y≤0.2，MO为助剂。该材料制备时，首先合成CaTiO3‑yMO，使其频率温度系数相比于单相CaTiO3得到改善；然后再与Mg2TiO4进行两相复合。本发明微波介质陶瓷材料的介电常数为18.5～24，Q×f值为40000～70000GHz，频率温度系数|τf(‑40℃→20℃)|+|τf(20℃→135℃)|≤10ppm/℃。

Description

一种频率温度系数改善的微波介质材料及其制备方法
技术领域
本发明涉及微波介质材料技术领域，具体涉及一种频率温度系数改善的微波介质材料及其制备方法。
背景技术
谐振频率温度系数τf是用来衡量材料元件谐振频率随温度漂移程度的参数，单位ppm/℃。谐振频率温度系数的正负值并不代表元件性能好坏，但是谐振频率温度系数接近零才是元件的稳定关键。τf＝[f(T2)-f(T1)]/f(T0)/(T2-T1)，其中，f(T2)为T2温度点的谐振峰频率，f(T1)为T1温度点的谐振峰频率，f(T0)为室温时的谐振峰频率。大多数情况下，大部分微波介质材料的谐振频率随温度呈线性变化，研究人员一般选取T1＝-40℃、T2＝80℃、T0＝20℃作为测试温度点，即用τf(-40℃→80℃)来评价微波介质材料的谐振频率随温度的变化。
(1-x)Mg2TiO4-xCaTiO3系微波介质材料是应用最广的微波介质材料之一，但其谐振频率随温度变化却是呈抛物线状(非线性)，τf(-40℃→80℃)并不能代表其真正的温漂特性，需要引入更多温度点变化下的频率温度系数τf来进行更全面的评价。对于谐振频率随温度呈抛物线变化的材料来说，|τf(T1℃→20℃)|+|τf(20℃→T2℃)|来评价其温漂特性更为合适。随着5G通讯技术的发展，特别是微波介质陶瓷在介质波导滤波器领域内的应用，高功率带来的放热问题，也使得元件需要适应更高使用环境温度的变化。传统的(1-x)Mg2TiO4-xCaTiO3系微波介质材料的频率温度系数(τf(-40℃→80℃)≤±10ppm/℃，|τf(-40℃→20℃)|+|τf(20℃→80℃)|≥15ppm/℃)已不能满足介质波导滤波器等新型射频元器件在-40℃～135℃温度区间内正负两端同时近零的设计要求。
发明内容
针对现有(1-x)Mg2TiO4-xCaTiO3系微波介质材料的频率温度系数|τf(T1℃→20℃)|+|τf(20℃→T2℃)|值过大的缺点，本发明提供一种频率温度系数改善的微波介质陶瓷材料，该材料频率温度系数|τf(-40℃→20℃)|+|τf(20℃→135℃)|≤10ppm/℃。
为实现上述目的，本发明所采用的技术方案如下：
一种频率温度系数改善的微波介质陶瓷材料，其特征在于：该微波介质陶瓷材料的组成表达式为：(1-x)Mg2TiO4-x[CaTiO3-yMO]，其中：0≤x≤0.3，0.1≤y≤0.2，MO为助剂。
所述助剂MO为Yb2BaZnO5、Mg3CoNb2O9、Nd3Ga5O12和SrAlLnO4中的一种或几种。
该微波介质陶瓷材料的介电常数为18.5～24，Q×f值为40000～70000GHz，Q×f用于衡量微波介质陶瓷损耗的大小，其中Q＝1/tanδ表示材料的品质因数，f代表谐振频率；频率温度系数|τf(-40℃→20℃)|+|τf(20℃→135℃)|≤10ppm/℃。
所述频率温度系数改善的微波介质陶瓷材料的制备方法为：首先合成CaTiO3-yMO，使其频率温度系数相比于单相CaTiO3的得到改善；然后再与Mg2TiO4进行两相复合。该方法具体包括如下步骤：
(1)配料：以氧化镁、二氧化钛、碳酸钙和MO助剂为原料，首先按照Mg2TiO4中Mg和Ti的摩尔比称取氧化镁和二氧化钛并混合均匀后得到混合料Ⅰ，再根据CaTiO3-yMO中Ca、Ti和MO的摩尔比称取二氧化钛、碳酸钙和MO助剂并混合均匀后得到混合料Ⅱ；
(2)混合：将配料后的混合料Ⅰ和混合料Ⅱ分别进行球磨处理并干燥后，得到Mg2TiO4干燥粉料和CaTiO3-yMO干燥粉料；
(3)预烧：将得到的Mg2TiO4干燥粉料和CaTiO3-yMO干燥粉料分别置于不同的氧化铝坩埚中，在碳棒炉中预烧后得到Mg2TiO4预合成粉和CaTiO3-yMO预合成粉；
(4)二次配料：将Mg2TiO4预合成粉和CaTiO3-yMO预合成粉按所述微波介质陶瓷材料的组成称量配料并混合，得到二次原料粉；
(5)造浆：将二次原料粉球磨粉碎20～26小时，球磨介质为锆球与去离子水，得到粘稠状的浆料；
(6)成型：在步骤(5)所得浆料中添加占浆料5～20wt％的粘结剂，然后依次进行喷雾造粒和压制成型，最后在碳棒炉中烧结成型，即得到所述频率温度系数改善的微波介质陶瓷材料。
上述步骤(2)中，所述球磨过程中，球磨介质为锆球与去离子水；球磨后置于150℃烘箱中经12小时干燥处理。
上述步骤(3)中，在碳棒炉中预烧温度1000℃～1150℃，预烧时间2～4小时。
上述步骤(6)中，在碳棒炉中烧结温度1250℃～1350℃烧结时间3小时。
本发明的优点和有益效果如下：
1、本发明配方设计中CaTiO3-yMO进行了单独预合成，使得单相CaTiO3的频率温度系数得到改善后，再与Mg2TiO4进行两相复合。
2、本发明的频率温度系数改善的微波介质材料，其介电常数为18.5～24，品质因数Q×f值为40000～70000GHz，频率温度系数|τf(-40℃→20℃)|+|τf(20℃→135℃)|≤10ppm/℃，可广泛应用在基带天线、导航天线、介质波导滤波器等领域。
具体实施方式
为了使本发明的目的及优点更加清楚明白，以下结合实施例对本发明进行进一步详细说明。
实施例1-4和对比例1：
本发明中微波介质陶瓷材料组成表达式为：(1-x)Mg2TiO4-x[CaTiO3-yMO]，其中：0≤x≤0.3，0.1≤y≤0.2，MO为助剂。所述助剂MO为Yb2BaZnO5、Mg3CoNb2O9、Nd3Ga5O12和SrAlLnO4中的一种或几种。
实施例1-4及对比例1的具体组成见表1。对比例1中未加入助剂MO。
所述微波介质陶瓷材料的制备方法具体如下：
(1)配料：以氧化镁、二氧化钛、碳酸钙和MO助剂为原料，首先按照Mg2TiO4中Mg和Ti的摩尔比称取氧化镁和二氧化钛并混合均匀后得到混合料Ⅰ，再根据CaTiO3-yMO中Ca、Ti和MO的摩尔比称取二氧化钛、碳酸钙和MO助剂并混合均匀后得到混合料Ⅱ；
(2)混合：将配料后的混合料Ⅰ和混合料Ⅱ分别进行球磨处理，球磨介质为锆球与去离子水；球磨后置于150℃烘箱中经12小时干燥处理，得到Mg2TiO4干燥粉料和CaTiO3-yMO干燥粉料；
(3)预烧：将得到的Mg2TiO4干燥粉料和CaTiO3-yMO干燥粉料分别置于不同的氧化铝坩埚中，在碳棒炉中进行1100℃、3小时的预烧后得到Mg2TiO4预合成粉和CaTiO3-yMO预合成粉；
(4)二次配料：将Mg2TiO4预合成粉和CaTiO3-yMO预合成粉按所述微波介质陶瓷材料的组成称量配料并混合，得到二次原料粉；
(5)造浆：将二次原料粉球磨粉碎20～26小时，球磨介质为锆球与去离子水，得到粘稠状的浆料；
(6)成型：在步骤(5)所得浆料中添加占浆料10wt％的聚乙烯醇粘结剂，然后依次进行喷雾造粒和压制成型，最后在碳棒炉中进行1300℃、3小时的烧结成型，即得到微波介质陶瓷材料。
表1～2示出了实施例1-4及对比例1各组成材料的微波介电性能。
表1(1-x)Mg2TiO4-x[CaTiO3-yMO]的微波介电性能
编号 x y ε<sub>r</sub> Q×f |τ<sub>f(-40℃→20℃)</sub>|+|τ<sub>f(20℃→135℃)</sub>|
对比例1 0.07 0 19.5 65000 16.7
实施例1 0.135 0.1 18.6 64129 9.7
实施例2 0.205 0.15 20.9 62005 9.9
实施例3 0.13 0.05 22.8 57473 9.8
实施例4 0.135 0.1 23.2 56540 9.9
表2(1-x)Mg2TiO4-x[CaTiO3-yMO]的各温度区间段的频率温度系数
编号 τ<sub>f(-40℃→20℃)</sub> τ<sub>f(-10℃→20℃)</sub> τ<sub>f(20℃→80℃)</sub> τ<sub>f(20℃→110℃)</sub> τ<sub>f(20℃→135℃)</sub>
对比例1 12.9 8.5 0.8 -1.5 -3.8
实施例1 4.8 1.9 -3.3 -4.1 -4.9
实施例2 8.5 5.6 1.5 0.1 -1.4
实施例3 3.1 0.0 -3.7 -5.5 -6.7
实施例4 7.5 7.4 0.8 -1.1 -2.4
由表1～2可知，未经本发明改善的对比例1的|τf(-40℃→20℃)|+|τf(20℃→135℃)|值高达16.7，而引入适量MO后的实施例1-4的|τf(-40℃→20℃)|+|τf(20℃→135℃)|值都小于10。其中，频率温度系数最为优异的是实施例3，其介电常数为22.8，Q×f值为57473GHz，τf(-40℃→20℃)为3.1ppm/℃，τf(20℃→80℃)为-3.7ppm/℃，|τf(-40℃→20℃)|+|τf(20℃→135℃)|为9.8ppm/℃。为使本发明的(1-x)Mg2TiO4-x[CaTiO3-yMO]微波介质材料的各温度区间段的频率温度系数都尽可能的近零，达到|τf(-40℃→20℃)|+|τf(20℃→135℃)|值减小的目的，配方设计中的x值应随y值的变化而进行微调。因此，本发明设计的组分比例为0≤x≤0.3，0.1≤y≤0.2。

Claims (6)

1.一种频率温度系数改善的微波介质陶瓷材料，其特征在于：该微波介质陶瓷材料的组成表达式为：(1-x)Mg2TiO4-x[CaTiO3-yMO]，其中：0.13≤x≤0.3，0.1≤y≤0.2，MO为助剂；所述助剂MO为Yb2BaZnO5、Mg3CoNb2O9、Nd3Ga5O12和SrAlLnO4中的一种或几种；
所述频率温度系数改善的微波介质陶瓷材料在制备时，首先合成CaTiO3-yMO，使其频率温度系数相比于单相CaTiO3的得到改善；然后再与Mg2TiO4进行两相复合。
2.根据权利要求1所述的频率温度系数改善的微波介质陶瓷材料，其特征在于：该微波介质陶瓷材料的介电常数为18.5～24，Q×f值为40000～70000GHz，Q×f用于衡量微波介质陶瓷损耗的大小，其中Q＝1/tanδ表示材料的品质因数，f代表谐振频率；频率温度系数|τf(-40℃→20℃)|+|τf(20℃→135℃)|≤10ppm/℃。
3.根据权利要求1所述的频率温度系数改善的微波介质陶瓷材料的制备方法，其特征在于：该方法包括如下步骤：
(1)配料：以氧化镁、二氧化钛、碳酸钙和MO助剂为原料，首先按照Mg2TiO4中Mg和Ti的摩尔比称取氧化镁和二氧化钛并混合均匀后得到混合料Ⅰ，再根据CaTiO3-yMO中Ca、Ti和MO的摩尔比称取二氧化钛、碳酸钙和MO助剂并混合均匀后得到混合料Ⅱ；
(2)混合：将配料后的混合料Ⅰ和混合料Ⅱ分别进行球磨处理并干燥后，得到Mg2TiO4干燥粉料和CaTiO3-yMO干燥粉料；
(3)预烧：将得到的Mg2TiO4干燥粉料和CaTiO3-yMO干燥粉料分别置于不同的氧化铝坩埚中，在碳棒炉中预烧后得到Mg2TiO4预合成粉和CaTiO3-yMO预合成粉；
(4)二次配料：将Mg2TiO4预合成粉和CaTiO3-yMO预合成粉按所述微波介质陶瓷材料的组成称量配料并混合，得到二次原料粉；
(5)造浆：将二次原料粉球磨粉碎20～26小时，球磨介质为锆球与去离子水，得到粘稠状的浆料；
(6)成型：在步骤(5)所得浆料中添加占浆料5～20wt％的粘结剂，然后依次进行喷雾造粒和压制成型，最后在碳棒炉中烧结成型，即得到所述频率温度系数改善的微波介质陶瓷材料。
4.根据权利要求3所述的频率温度系数改善的微波介质陶瓷材料的制备方法，其特征在于：步骤(2)中，所述球磨过程中，球磨介质为锆球与去离子水；球磨后置于150℃烘箱中经12小时干燥处理。
5.根据权利要求3所述的频率温度系数改善的微波介质陶瓷材料的制备方法，其特征在于：步骤(3)中，在碳棒炉中预烧温度1000℃～1150℃，预烧时间2～4小时。
6.根据权利要求3所述的频率温度系数改善的微波介质陶瓷材料的制备方法，其特征在于：步骤(6)中，在碳棒炉中烧结温度1250℃～1350℃烧结时间3小时。
CN202110910902.9A 2021-08-10 2021-08-10 一种频率温度系数改善的微波介质材料及其制备方法 Active CN113548888B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110910902.9A CN113548888B (zh) 2021-08-10 2021-08-10 一种频率温度系数改善的微波介质材料及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110910902.9A CN113548888B (zh) 2021-08-10 2021-08-10 一种频率温度系数改善的微波介质材料及其制备方法

Publications (2)

Publication Number Publication Date
CN113548888A CN113548888A (zh) 2021-10-26
CN113548888B true CN113548888B (zh) 2022-07-08

Family

ID=78133757

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110910902.9A Active CN113548888B (zh) 2021-08-10 2021-08-10 一种频率温度系数改善的微波介质材料及其制备方法

Country Status (1)

Country Link
CN (1) CN113548888B (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114031393A (zh) * 2021-11-29 2022-02-11 成都理工大学 一种谐振频率温度系数近零的微波介电材料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0867556A (ja) * 1994-08-26 1996-03-12 Matsushita Electric Ind Co Ltd 平面アンテナ用誘電体セラミックス及びそれを用いた平面アンテナ
CN1557770A (zh) * 2004-01-14 2004-12-29 浙江大学 一种低损耗微波介质陶瓷
CN106587987A (zh) * 2016-12-26 2017-04-26 北京元六鸿远电子科技股份有限公司 C0g微波介质材料及制备方法及陶瓷材料的制备方法
CN111732429A (zh) * 2020-05-31 2020-10-02 深圳陶陶科技有限公司 一种微波介质陶瓷材料及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0867556A (ja) * 1994-08-26 1996-03-12 Matsushita Electric Ind Co Ltd 平面アンテナ用誘電体セラミックス及びそれを用いた平面アンテナ
CN1557770A (zh) * 2004-01-14 2004-12-29 浙江大学 一种低损耗微波介质陶瓷
CN106587987A (zh) * 2016-12-26 2017-04-26 北京元六鸿远电子科技股份有限公司 C0g微波介质材料及制备方法及陶瓷材料的制备方法
CN111732429A (zh) * 2020-05-31 2020-10-02 深圳陶陶科技有限公司 一种微波介质陶瓷材料及其制备方法

Also Published As

Publication number Publication date
CN113548888A (zh) 2021-10-26

Similar Documents

Publication Publication Date Title
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
CN113087507A (zh) 低介硅酸镁微波介质陶瓷材料及其制备方法
CN111635223B (zh) 一种复合微波介质陶瓷及其制备方法
CN111302787A (zh) 一种具有高Qf高强度的微波介质陶瓷材料及其制备方法
CN111153694B (zh) 一种微波介质陶瓷材料及制备方法
CN113548888B (zh) 一种频率温度系数改善的微波介质材料及其制备方法
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
CN113735580B (zh) 一种复相微波介质陶瓷及其冷烧结制备方法
CN110372369B (zh) 一种具有高介、低损耗的ptfe/clst复合介质材料及其制备方法
JP2000007429A (ja) 誘電体材料及びその製造方法
CN108503353B (zh) 一种复合磷酸盐系微波介质陶瓷及其制备方法
CN112759383B (zh) 一种中介电常数微波介质陶瓷及其制备方法
CN111925210B (zh) 一种金属化合物和微波介质陶瓷及其制备方法
CN111825445B (zh) 一种高介电常数微波介质陶瓷材料、制备及其应用
CN111960821B (zh) 一种微波介质陶瓷材料及其制备方法和应用
CN110357628B (zh) 一种Ca5Mg4-xCox(VO4)6低温烧结微波陶瓷材料及其制备方法
CN114804867B (zh) 适合热压烧结的陶瓷介质材料、陶瓷器件及其制备方法
CN113277848A (zh) 一种中介复合钒酸盐系微波介质陶瓷的制备方法
CN112939595A (zh) 高温下近零温度系数的微波介质陶瓷材料及其制备方法
CN102030527B (zh) 一种BaO-TiO 2系微波电容器介质材料及其制备方法
CN111302795A (zh) 一种锂镁铌铝钨系微波介质陶瓷及其制备方法
CN115925401B (zh) 一种低介硅酸盐微波介质陶瓷材料及其制备方法
CN115259849B (zh) 旋磁铁氧体材料及制备方法和应用
CN112898021B (zh) 一种低温烧结微波介质材料Mg2-xCoxV2O7及其制备方法
JPH01140505A (ja) 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