CN111302775B - 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 - Google Patents
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 Download PDFInfo
- Publication number
- CN111302775B CN111302775B CN202010242917.8A CN202010242917A CN111302775B CN 111302775 B CN111302775 B CN 111302775B CN 202010242917 A CN202010242917 A CN 202010242917A CN 111302775 B CN111302775 B CN 111302775B
- Authority
- CN
- China
- Prior art keywords
- powder
- ceramic material
- casio
- mixing
- mgal
- 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
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
- C04B35/10—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
-
- 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
- C04B35/63—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 using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/638—Removal 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
- C04B2235/3206—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
- C04B2235/3215—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
- C04B2235/3224—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
- C04B2235/3232—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
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
-
- 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
- C04B2235/3294—Antimony oxides, antimonates, antimonites or oxide forming salts thereof, indium antimonate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
- C04B2235/3454—Calcium silicates, e.g. wollastonite
-
- 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
- C04B2235/65—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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
- C04B2235/662—Annealing after sintering
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
本发明提供一种具有高品质因数低介电常数的陶瓷材料,涉及信息功能材料领域。该陶瓷材料包括主材及改性添加物。其中,主材包括MgAl2O4、CaSiO3和CaTiO3。按质量计算,MgAl2O4:CaSiO3:CaTiO3=(55~75):(20~40):(1~30)。改性添加物选自BaCO3、MnCO3、MnO2、La2O3、ZnO、Sb2O3中的一种或几种。本发明的陶瓷介质材料是一种无铅环保型材料,采用固相合成方法分别合成MgAl2O4、CaSiO3和CaTiO3,并将这三种化合物混合作为主材,结合了它们的微波介电性质,并掺杂改性添加物,经过合理设计配方,优化合成工艺,利用该材料制成的电子陶瓷器件可在1500~1540℃的温度范围内烧结成瓷,其介电常数ε介于5~8之间,品质因数Qf值≥70000GHz,温度系数τf(‑40~85℃):±10ppm/℃。本发明制备的陶瓷材料均匀性好,满足微波器件的高性能要求。
Description
技术领域
本发明属于信息功能材料领域,具体涉及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。
背景技术
微波介质陶瓷材料是近年来迅速发展起来的一类新型功能陶瓷材料。它具有低介电损耗、高介电常数ε及介电常数温度系数τf稳定等特点。它是介质谐振器、滤波器、振荡器、双工器、天线、介质基板等在内的新型微波电路和器件的核心基础材料,在现代微波通信和卫星导航系统和设备中有广泛的应用。近年来,由于微波技术设备向小型化、集成化、低功耗,尤其是向民用的大批量、低价格化方向迅速发展,目前已经开发出一大批适用于各个微波频段的微波介质陶瓷材料。为克服不同微波频段应用带来的众多问题,亟需开发具备高品质因数Qf、低介电常数(ε<10)和介电常数温度系数τf近零可调的微波介质材料体系。低介电损耗即高的品质因数Qf有利于降低器件的功耗和提高器件工作频率的可选择性,较低的介电常数ε能减小介质陶瓷与金属电极之间的交互耦合损耗,而近零的介电常数温度系数τf有助于提高器件工作的稳定性。
发明内容
本发明的目的是提供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,其应用于制作微波器件时,具有高品质因数Qf、中低介电常数(ε<10)、介电常数温度系数τf近零可调以及高强度的特点。
为实现本发明目的,本发明采用如下技术方案。
本发明提供一种具有高品质因数低介电常数的陶瓷材料,包括主材及改性添加物;所述主材包括MgAl2O4、CaSiO3和CaTiO3;MgAl2O4、CaSiO3和CaTiO3的质量比为(55~75):(20~40):(1~30);所述改性添加物选自BaCO3、MnCO3、MnO2、La2O3、ZnO和Sb2O3中的一种或几种。
优选地,所述主材在所述陶瓷材料的中所占的质量分数为99~99.5%;所述改性添加物在所述陶瓷材料中所占的质量分数为0.5~1%。
优选地,所述的陶瓷材料烧结后,介电常数ε介于5~8,介电常数温度系数τf(-40~85℃):±10ppm/℃,品质因数Qf值≥70000GHz。
本发明还提供一种上述陶瓷材料的制备方法,包括以下步骤:
S1,按照固相合成法制得MgAl2O4粉末;
S2,按照固相合成法制得CaTiO3粉末;
S3,按照固相合成法制得CaSiO3粉末;
S4,制备成品粉末:将所述MgAl2O4粉末、所述CaTiO3粉末和所述CaSiO3粉末按陶瓷材料组成比例混合,得到所述主材,然后加入所述改性添加物以及水进行砂磨,再干燥,得到粉末态的陶瓷材料。
优选地:
步骤S1中,所述MgAl2O4的制得,是通过将MgO和Al2O3按1:(0.9~1.1)的摩尔比混合,加入水进行球磨,再干燥,在空气气氛炉中1200℃~1250℃的温度范围煅烧2~4小时,得到MgAl2O4粉末;
步骤S2中,所述CaTiO3的制得,是通过将CaCO3及TiO2按1:(0.9~1.1)的摩尔比混合,加入水进行球磨,再干燥,在空气气氛炉中1250℃~1300℃的温度范围煅烧1~2小时,得到CaTiO3粉末;
步骤S3中,所述CaSiO3的制得,是通过将CaCO3及SiO2按1:(0.9~1.1)的摩尔比混合,加入水进行球磨,再干燥,在空气气氛炉中1050℃~1100℃的温度范围煅烧1~2小时,得到CaSiO3粉末。
优选地:
步骤S1中,按MgO和Al2O3混合后得到的固体混合物与水的质量比为1:(1~2)的比例加入水;
步骤S2中,按CaCO3及TiO2混合后得到的固体混合物与水的质量比为1:(1~2)的比例加入水;
步骤S3中,按CaCO3及SiO2混合后得到的固体混合物与水的质量比为1:(1~2)的比例加入水;
步骤S4中,按所述MgAl2O4粉末、所述CaTiO3粉末和所述CaSiO3粉末混合后的物料与水的质量比为1:(0.6~1)的比例加入水。
优选地,上述的制备方法还包括以下步骤:
S5,将步骤S4得到粉末态的陶瓷材料加入粘合剂、增塑剂和分散剂,球磨,获得浆料,再干燥,获得流动性良好的粉料;
S6,将所述粉料压制成型,制成生坯器件;
S7,将所述生坯器件置于500℃~650℃的条件下,保温20~28小时进行排胶;
S8,烧结:将排胶好的坯体,在空气气氛中升温到1500~1540℃,保温时间3~5小时;
S9,退火:烧结后的坯体在950℃~1050℃条件下,保温2~3小时,得到成型后的陶瓷材料。
优选地,所述粘合剂为聚乙烯醇,所述增塑剂为聚乙二醇,所述分散剂为羧酸铵盐类。
本发明的陶瓷材料,适用于制作微波器件。
本发明的有益效果是:MgAl2O4陶瓷在微波频段内具有优异的介电性能,其介电常数约为8.5,Qf值约70000GHz,但其介电常数温度系数为-75ppm/℃,影响了它的实际应用。CaTiO3是扭曲的正交钙钛矿结构,室温下,其介电常数为170,有着很高的正的温度系数为800ppm/℃。CaSiO3是一种具有良好性能的低介电常数陶瓷材料,其介电常数为5,并且拥有正的介电常数温度系数约为45ppm/℃。发明人付出创造性的劳动后发现,通过将MgAl2O4、CaSiO3和CaSiO3进行复合,可获取介电常数在5~8,Qf值≥70000GHz,介电常数温度系数在±10ppm/℃以内的微波材料。
本发明的陶瓷介质材料是一种无铅环保型材料,采用固相合成方法分别合成MgAl2O4、CaSiO3和CaTiO3,并将这三种化合物混合作为主材,结合了它们的微波介电性质,并掺杂改性添加物,经过合理设计配方,优化合成工艺,利用该材料制成的电子陶瓷器件可在1500~1540℃的温度范围内烧结成瓷,其介电常数ε介于5~8之间,品质因数Qf值≥70000GHz,温度系数τf(-40~85℃):±10ppm/℃。本发明制备的陶瓷材料均匀性好,满足微波器件的高性能要求。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
本发明提供一种具有高品质因数低介电常数的陶瓷材料,包括主材及改性添加物;主材包括MgAl2O4、CaSiO3和CaTiO3;按质量计算,MgAl2O4:CaSiO3:CaTiO3=(55~75):(20~40):(1~30);改性添加物选自BaCO3、MnCO3、MnO2、La2O3、ZnO和Sb2O3中的一种或几种。主材在陶瓷材料的中所占的质量分数为99~99.5%;改性添加物在陶瓷材料中所占的质量分数为0.5~1%。
改性添加物在满足上述质量分数的基础上,改性添加物中每个组分占陶瓷材料的优选添加质量比为:BaCO3为0~0.5%,La2O3为0~0.5%,ZnO为0~0.2%,MnCO3为0~0.6%,Sb2O3为0~0.5%,MnO2为0~0.3%。
通过各个改性添加物的选用,材料的配比,本发明的陶瓷材料烧结后,介电常数ε介于5~8,介电常数温度系数τf(-40~85℃):±10ppm/℃,品质因数Qf值≥70000GHz,适用于制作微波器件。
本发明还提供一种上述陶瓷材料的制备方法,包括以下步骤:
S1,制备MgAl2O4粉末:将MgO和Al2O3按1:(0.9~1.1)的摩尔比混合;按(MgO+Al2O3):去离子水=1:(1~2)的优选质量比例加入去离子水;将混合物置入球磨机中进行球磨,再用喷雾干燥塔或其他方法进行干燥;然后在空气气氛炉中1200℃~1250℃的温度范围煅烧2~4小时,得到MgAl2O4粉末。MgAl2O4陶瓷在微波频段内具有优异的介电性能,其介电常数约为8.5,Qf值约70000,其介电常数温度系数为-75ppm/℃。
S2,制备CaTiO3粉末:将CaCO3及TiO2按1:(0.9~1.1)的摩尔比混合;按(CaCO3+TiO2):去离子水=1:(1~2)的优选质量比例加入去离子水;将混合物置入球磨机中进行球磨,再用喷雾干燥塔或其他方法进行干燥;然后在空气气氛炉中1250℃~1300℃的温度范围煅烧1~2小时,得到CaTiO3粉末。CaTiO3是扭曲的正交钙钛矿结构,室温下,其介电常数为170,有着很高的正的温度系数为800ppm/℃。
S3,制备CaSiO3粉末:将CaCO3及SiO2按1:(0.9~1.1)的摩尔比混合;按(CaCO3+SiO2):去离子水=1:(1~2)的优选质量比例加入去离子水;将混合物置入球磨机中进行球磨,再用喷雾干燥塔或其他方法进行干燥;然后在空气气氛炉中1050℃~1100℃的温度范围煅烧1~2小时,得到CaSiO3粉末。CaSiO3是一种具有良好性能的低介电常数陶瓷材料,其介电常数为5,并且拥有正的介电常数温度系数约为45ppm/℃。
S4,制备成品粉末:将MgAl2O4粉末、CaTiO3粉末和CaSiO3粉末按陶瓷材料组成比例混合,得到主材,加入改性添加物以及去离子水进行砂磨,要求物料混合均匀,使砂磨后的粉体平均颗粒尺寸达0.90~1.2um。再用喷雾干燥塔或其他方法进行干燥,得到本发明粉末态的陶瓷材料。其中,按质量计,主材各组分的添加比例为,MgAl2O4:CaSiO3:CaTiO3=(55~75):(20~40):(1~30);按质量计,主材和改性添加物的添加比例为(99~99.5):(0.5~1);按质量计,以(主材+改性添加物):去离子水=1:(0.6~1)的比例加入去离子水。
将MgAl2O4、CaSiO3和CaSiO3进行复合,结合它们的微波介电性质,可获取介电常数在5~8,Qf值≥70000GHz,介电常数温度系数在±10ppm/℃以内的微波材料,在温度变化时,仍有较高的电性能稳定性。
上述步骤S4获得的粉末态的陶瓷材料通过以下步骤制作成型。
S5,将步骤S4得到粉末态的陶瓷材料加入粘合剂、增塑剂、分散剂,用氧化锆球为磨介在球磨罐中球磨1~2小时,获得浆料,再进行离心喷雾干燥,获得流动性良好的粉料。其中,粘合剂可选用聚乙烯醇,增塑剂可选用聚乙二醇,分散剂可选用羧酸铵盐类。
S6,将粉料压制成型,制成生坯器件。
S7,将生坯器件置于500℃~650℃的温度范围内,保温20~28小时进行排胶,以排除生坯片中的有机物,整个排胶过程的升温速度小于10℃/小时。
S8,烧结:将排胶好的坯体,在空气气氛中,以150℃~200℃/h的升温速度升温到1500~1540℃,保温时间为3~5小时。烧结能使陶瓷坯体中的粉粒晶界移动,气孔逐步排除,坯体收缩成为具有一定强度的致密陶瓷体。
S9,退火:高温烧结后,坯体在950℃~1050℃条件下,保温2~3小时。退火可以减小坯体内部应力,细化晶粒,弥合微裂纹,改善材料的组织结构,提高陶瓷的力学性能。
实施例
本实施例提供一种具有高品质因数低介电常数的陶瓷材料,通过以下步骤制备,并进行微波性能测试。
S1,制备MgAl2O4粉末:将MgO和Al2O3按1:1的摩尔比混合;按(MgO+Al2O3):去离子水=1:1.5的质量比例加入去离子水;将混合物置入球磨机中进行球磨,再用喷雾干燥塔或其他方法进行干燥;然后在空气气氛炉中1200℃的温度中煅烧3小时,得到MgAl2O4粉末。
S2,制备CaTiO3粉末:将CaCO3及TiO2按1:1的摩尔比混合;按(CaCO3+TiO2):去离子水=1:1.5的质量比例加入去离子水;将混合物置入球磨机中进行球磨,再用喷雾干燥塔或其他方法进行干燥;然后在空气气氛炉中1250℃的温度中煅烧1.5小时,得到CaTiO3粉末。
S3,制备CaSiO3粉末:将CaCO3及SiO2按1:1的摩尔比混合;按(CaCO3+SiO2):去离子水=1:1.5的质量比例加入去离子水;将混合物置入球磨机中进行球磨,再用喷雾干燥塔或其他方法进行干燥;然后在空气气氛炉中1050℃的温度中煅烧1.5小时,得到CaSiO3粉末。
S4,制备成品粉末:将MgAl2O4粉末、CaTiO3粉末和CaSiO3粉末按陶瓷材料组成比例混合,得到主材,加入改性添加物,再以(主材+改性添加物):去离子水=1:0.8的质量比例加入去离子水进行砂磨。要求物料混合均匀,使砂磨后的粉体平均颗粒尺寸达0.90~1.2um。再用喷雾干燥塔或其他方法进行干燥,得到本发明粉末态的陶瓷材料。其中,按质量计,主材各组分MgAl2O4、CaSiO3和CaTiO3的添加比例如表1所示。按质量计,主材和改性添加物的添加比例如表2所示。
表1主材配方
表2陶瓷材料粉末配比
上述粉末态的陶瓷材料通过以下步骤制作成型。
S5,将步骤S4得到粉末态的陶瓷材料加入粘合剂、增塑剂、分散剂,用氧化锆球为磨介在球磨罐中球磨1.5小时,获得浆料,再进行离心喷雾干燥,获得流动性良好的粉料。其中,粘合剂可选用聚乙烯醇,增塑剂可选用聚乙二醇,分散剂可选用羧酸铵盐类。
S6,将粉料压制成型,制成生坯器件。
S7,将生坯器件置于600℃的温度中保温24小时进行排胶,以排除生坯片中的有机物,整个排胶过程的升温速度为8℃/小时。
S8,烧结:将排胶好的坯体,在空气气氛中,以160℃/h的升温速度升温到1500~1540℃,保温时间为3小时。烧结能使陶瓷坯体中的粉粒晶界移动,气孔逐步排除,坯体收缩成为具有一定强度的致密陶瓷体。
S9,退火:高温烧结后,坯体在1000℃条件下,保温2.5小时。退火可以减小坯体内部应力,细化晶粒,弥合微裂纹,改善材料的组织结构,提高陶瓷的力学性能。
将制作好的坯体采用安捷伦网分仪,在频率10~11GHz下进行微波性能测试。测试结果如表3。
表3陶瓷坯体微波性能测试
经过上述过程制成的陶瓷材料,可以在1500℃~1540℃的温度范围内,通过调整材料合成的配比可形成介电常数介于5~8,温度系数τf(-40~85℃):±10ppm/℃,Qf值≥70000GHz,连续可调系列陶瓷材料,可满足微波的应用要求。
以上所描述的实施例仅是本发明的部分实施例,而不是全部的实施例,本发明的实施例的详细描述并非旨在限制本发明要求保护的范围,而仅仅表示本发明的选定实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
Claims (8)
1.一种具有高品质因数低介电常数的陶瓷材料,包括主材及改性添加物;其特征在于:所述主材包括MgAl2O4、CaSiO3和CaTiO3;MgAl2O4、CaSiO3和CaTiO3的质量比为(55~75):(20~40):(1~30);所述改性添加物选自BaCO3、MnCO3、MnO2、La2O3、ZnO和Sb2O3中的一种或几种;
其中,所述的陶瓷材料烧结后,介电常数ε介于5~8,介电常数温度系数τf在-40~85℃时为±10ppm/℃,品质因数Qf值≥70000GHz。
2.根据权利要求1所述的陶瓷材料,其特征在于:所述主材在所述陶瓷材料中所占的质量分数为99~99.5%;所述改性添加物在所述陶瓷材料中所占的质量分数为0.5~1%。
3.一种如权利要求1~2任意一项所述的陶瓷材料的制备方法,其特征在于,包括以下步骤:
S1,按照固相合成法制得MgAl2O4粉末;
S2,按照固相合成法制得CaTiO3粉末;
S3,按照固相合成法制得CaSiO3粉末;
S4,制备成品粉末:将所述MgAl2O4粉末、所述CaTiO3粉末和所述CaSiO3粉末按陶瓷材料组成比例混合,得到所述主材,然后加入所述改性添加物以及水进行砂磨,再干燥,得到粉末态的陶瓷材料。
4.根据权利要求3所述的陶瓷材料的制备方法,其特征在于:
步骤S1中,所述MgAl2O4的制得,是通过将MgO和Al2O3按1:(0.9~1.1)的摩尔比混合,加入水进行球磨,再干燥,在空气气氛炉中1200℃~1250℃的温度范围煅烧2~4小时,得到MgAl2O4粉末;
步骤S2中,所述CaTiO3的制得,是通过将CaCO3及TiO2按1:(0.9~1.1)的摩尔比混合,加入水进行球磨,再干燥,在空气气氛炉中1250℃~1300℃的温度范围煅烧1~2小时,得到CaTiO3粉末;
步骤S3中,所述CaSiO3的制得,是通过将CaCO3及SiO2按1:(0.9~1.1)的摩尔比混合,加入水进行球磨,再干燥,在空气气氛炉中1050℃~1100℃的温度范围煅烧1~2小时,得到CaSiO3粉末。
5.根据权利要求4所述的陶瓷材料的制备方法,其特征在于:
步骤S1中,按MgO和Al2O3混合后得到的固体混合物与水的质量比为1:(1~2)的比例加入水;
步骤S2中,按CaCO3及TiO2混合后得到的固体混合物与水的质量比为1:(1~2)的比例加入水;
步骤S3中,按CaCO3及SiO2混合后得到的固体混合物与水的质量比为1:(1~2)的比例加入水;
步骤S4中,按所述MgAl2O4粉末、所述CaTiO3粉末和所述CaSiO3粉末混合后的物料与水的质量比为1:(0.6~1)的比例加入水。
6.根据权利要求3所述的陶瓷材料的制备方法,其特征在于,还包括以下步骤:
S5,将步骤S4得到粉末态的陶瓷材料加入粘合剂、增塑剂和分散剂,球磨,获得浆料,再干燥,获得流动性良好的粉料;
S6,将所述粉料压制成型,制成生坯器件;
S7,将所述生坯器件置于500℃~650℃的条件下,保温20~28小时进行排胶;
S8,烧结:将排胶好的坯体,在空气气氛中升温到1500~1540℃,保温时间3~5小时;
S9,退火:烧结后的坯体在950℃~1050℃条件下,保温2~3小时,得到成型后的陶瓷材料。
7.根据权利要求6所述的陶瓷材料的制备方法,其特征在于:所述粘合剂为聚乙烯醇,所述增塑剂为聚乙二醇,所述分散剂为羧酸铵盐类。
8.一种如权利要求1~2任意一项所述的陶瓷材料,用于制作微波器件。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010242917.8A CN111302775B (zh) | 2020-03-31 | 2020-03-31 | 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 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010242917.8A CN111302775B (zh) | 2020-03-31 | 2020-03-31 | 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 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111302775A CN111302775A (zh) | 2020-06-19 |
CN111302775B true CN111302775B (zh) | 2022-03-11 |
Family
ID=71159046
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010242917.8A Active CN111302775B (zh) | 2020-03-31 | 2020-03-31 | 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 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111302775B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111689771B (zh) * | 2020-06-28 | 2022-05-03 | 厦门松元电子股份有限公司 | 一种微波介质陶瓷材料及其制备方法 |
CN112174653B (zh) * | 2020-10-23 | 2022-09-16 | 厦门松元电子股份有限公司 | 一种高Qf低介电常数的微波介质陶瓷材料及其制备方法 |
CN113105231B (zh) * | 2021-04-12 | 2023-01-13 | 无锡市高宇晟新材料科技有限公司 | 一种微波介质陶瓷材料及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000344571A (ja) * | 1999-06-03 | 2000-12-12 | Japan Fine Ceramics Center | 磁器組成物 |
TW201439020A (zh) * | 2013-04-03 | 2014-10-16 | Walsin Technology Corp | 微波介電玻璃陶瓷組成物及其材料 |
CN104829239A (zh) * | 2015-03-27 | 2015-08-12 | 电子科技大学 | Ltcc功率电感器件基体与陶瓷介质材料匹配共烧方法 |
CN105272192A (zh) * | 2015-06-29 | 2016-01-27 | 福建火炬电子科技股份有限公司 | 一种低介电常数ag特性多层瓷介电容器瓷料及其制备方法 |
-
2020
- 2020-03-31 CN CN202010242917.8A patent/CN111302775B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000344571A (ja) * | 1999-06-03 | 2000-12-12 | Japan Fine Ceramics Center | 磁器組成物 |
TW201439020A (zh) * | 2013-04-03 | 2014-10-16 | Walsin Technology Corp | 微波介電玻璃陶瓷組成物及其材料 |
CN104829239A (zh) * | 2015-03-27 | 2015-08-12 | 电子科技大学 | Ltcc功率电感器件基体与陶瓷介质材料匹配共烧方法 |
CN105272192A (zh) * | 2015-06-29 | 2016-01-27 | 福建火炬电子科技股份有限公司 | 一种低介电常数ag特性多层瓷介电容器瓷料及其制备方法 |
Non-Patent Citations (1)
Title |
---|
CaSiO3基微波介质陶瓷的组成设计与介电性能;胡伟;《中国优秀博硕士学位论文全文数据库(博士)•工程科技Ⅰ辑》;20180115(第1期);第B015-73页 * |
Also Published As
Publication number | Publication date |
---|---|
CN111302775A (zh) | 2020-06-19 |
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 | |
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 | |
CN111689771B (zh) | 一种微波介质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 | |
CN112919894B (zh) | 一种频率稳定型低介微波介质陶瓷材料及其制备方法 | |
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 | |
CN110981439A (zh) | 一种微波陶瓷粉料及其制备方法和其在介质滤波器中的应用 | |
CN113087507A (zh) | 低介硅酸镁微波介质陶瓷材料及其制备方法 | |
CN105254293A (zh) | 一种微波介质陶瓷材料及其制备方法 | |
WO2023159896A1 (zh) | 一种硅酸盐系低温烧结微波介质陶瓷材料及其制备方法 | |
CN111925187A (zh) | 一种无铅高压中温烧结的锶铋钛基介质材料及制备方法 | |
CN114804897A (zh) | 一种陶瓷用烧结助剂及制法、锆酸锌微波介质陶瓷及制法 | |
CN112174653B (zh) | 一种高Qf低介电常数的微波介质陶瓷材料及其制备方法 | |
CN113105226A (zh) | 一种微波陶瓷介质材料及其制备方法 | |
CN111320473B (zh) | 一种低烧微波介质陶瓷材料及其制备方法 | |
CN112939595B (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 | |
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 | |
CN111635226B (zh) | 一种低介电常数陶瓷材料及其制备方法 | |
CN113754425B (zh) | 5g通信基站用陶瓷滤波器材料及其制备方法 | |
CN112759383B (zh) | 一种中介电常数微波介质陶瓷及其制备方法 | |
CN102030527B (zh) | 一种BaO-TiO 2系微波电容器介质材料及其制备方法 | |
CN112266245B (zh) | 一种高介电常数高Qf值的陶瓷材料及其制备方法与应用 | |
CN112250434B (zh) | 一种zmat系微波陶瓷材料及其制备方法与应用 | |
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 | |
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 | ||
CB02 | Change of applicant information | ||
CB02 | Change of applicant information |
Address after: 361022 No. 1203, Jinting Road, Jimei District, Xiamen City, Fujian Province (Zone A and B of plant 2) Applicant after: Xiamen Songyuan Electronics Co.,Ltd. Address before: No. 1203, Jinting Road, Jimei District, Xiamen City, Fujian Province 361022 Applicant before: Xiamen Sunyear Electronics Co.,Ltd. |
|
GR01 | Patent grant | ||
GR01 | Patent grant |