CN110357624A - 高介电常数玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料及其制备方法 - Google Patents

高介电常数玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料及其制备方法 Download PDF

Info

Publication number
CN110357624A
CN110357624A CN201910616131.5A CN201910616131A CN110357624A CN 110357624 A CN110357624 A CN 110357624A CN 201910616131 A CN201910616131 A CN 201910616131A CN 110357624 A CN110357624 A CN 110357624A
Authority
CN
China
Prior art keywords
ball
dielectric constant
ceramic material
sio
frit
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.)
Granted
Application number
CN201910616131.5A
Other languages
English (en)
Other versions
CN110357624B (zh
Inventor
晁小练
任晓丹
杨祖培
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.)
Shaanxi Normal University
Original Assignee
Shaanxi Normal 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 Shaanxi Normal University filed Critical Shaanxi Normal University
Priority to CN201910616131.5A priority Critical patent/CN110357624B/zh
Publication of CN110357624A publication Critical patent/CN110357624A/zh
Application granted granted Critical
Publication of CN110357624B publication Critical patent/CN110357624B/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
    • C04B35/495—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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • 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
    • C04B35/64—Burning or sintering processes
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5116—Ag or Au
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • 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
    • C04B2235/3201—Alkali metal 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
    • C04B2235/3213—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
    • C04B2235/3248—Zirconates or hafnates, e.g. zircon
    • 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
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • 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
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646—Optical properties
    • C04B2235/9653—Translucent or transparent ceramics other than alumina

Abstract

本发明公开了一种高介电常数玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料及其制备方法，该陶瓷材料的通式为0.93K0.5Na0.5NbO3‑0.07SrZrO3‑x％(La2O3‑B2O3‑SiO2)，式中x代表La2O3‑B2O3‑SiO2占0.93K0.5Na0.5NbO3‑0.07SrZrO3的质量百分比，x的取值为0.05～0.3。该陶瓷材料通过配料、预烧、球磨、压片、无压密闭烧结、抛光及烧银等工艺步骤制备而成。本发明制备方法简单、重复性好、成品率高，所得陶瓷材料具有高的介电常数、高居里温度、低介电损耗，介电常数为11200～13600，居里温度为229～253℃、透过率为49％～72％(近红外区)，介电损耗在30～350℃范围内均小于0.05。

Description

高介电常数玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材 料及其制备方法
技术领域
本发明属于陶瓷材料技术领域，具体涉及一种高介电常数玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料及其制备方法。
背景技术
透明陶瓷作为一种先进功能材料，由于其具有优异的力学、热学、光学和电学等性能，应用十分广泛。自1962年美国首次制备氧化铝透明陶瓷以来，世界各国对透明陶瓷进行了大量研究，开发了氧化物和非氧化物透明陶瓷、掺镧的锆钛酸铅(PLZT)电光透明陶瓷、钇铝石榴石激光透明陶瓷、钆镓石榴石(GGG)透明闪烁陶瓷等。
由于铅基透明陶瓷含有约70％PbO或Pb3O4，在生产、使用以及废弃后的处理过程中都会给人类和生态环境造成严重损害，因此开发和研究新型无铅透明铁电陶瓷对于国家安全和电子信息领域的发展具有重大战略意义。2004年Kosec教授成功制备了钛酸锶(SrTiO3)掺杂铌酸钾钠(KNN)的透明陶瓷，其介电常数在3000左右，同时具有较高的居里温度，达到了230℃，成为最有希望替代锆钛酸铅(PZT)和铌镁酸铅-钛酸铅(PMN-PT)等的无铅陶瓷材料。2013年，空军工程大学的杜红亮等通过引入ABO3钙钛矿结构的Ba(Sc0.5Nb0.5)O3获得了具有优良光学性能铌酸钾钠基透明陶瓷。2015年，西北工业大学樊慧庆等人研究了Bi2O3掺杂的(K0.5Na0.5)0.9Sr0.1Nb0.9Ti0.1O3透明陶瓷并对其光学和电学性能进行了研究。
近年来，越来越多的具有优异光学性能的铌酸盐系的铌酸钾钠(KNN)陶瓷被报道。遗憾的是，对于无铅透明陶瓷材料而言，其优异的光学与电学性能的兼顾始终未能实现。
发明内容
本发明的目的是提供一种高介电常数且具有较好光学性能的玻璃料改性锆酸锶掺杂铌酸钾钠基无铅透明陶瓷材料铌酸钾钠陶瓷材料，以及该陶瓷材料的制备方法。
针对上述目的，本发明陶瓷材料的通式是：0.93K0.5Na0.5NbO3-0.07SrZrO3-x％(La2O3-B2O3-SiO2)，式中x代表La2O3-B2O3-SiO2占0.93K0.5Na0.5NbO3-0.07SrZrO3的质量百分比，x的取值为0.05～0.3，La2O3-B2O3-SiO2中La2O3、B2O3、SiO2的物质的量之比为1:1:1；该陶瓷材料介电常数为11200～13600、居里温度为229～253℃、介电损耗在30～350℃范围内均小于0.05，在近红外区的透明度为49％～72％。
上述高介电常数玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料的制备方法如下：
1、配料
按照0.93K0.5Na0.5NbO3-0.07SrZrO3-x％(La2O3-B2O3-SiO2)的化学计量，分别称取纯度均为99.99％的Na2CO3、K2CO3、Nb2O5、La2O3、B2O3、SiO2，纯度99.00％的ZrO2，纯度99.95％的SrCO3，将称取的所有原料混合均匀后装入尼龙罐中，以锆球为磨球、无水乙醇为球磨介质，充分混合球磨18～24小时，分离锆球，将原料混合物在80～100℃下干燥12～24小时，用研钵研磨，过80目筛。
2、预烧
将步骤1过80目筛后的原料混合物置于氧化铝坩埚内，用玛瑙棒压实，使其压实密度为1.5g/cm3，加盖，800～900℃预烧4～6小时，自然冷却至室温，用研钵研磨，得到预烧粉。
3、二次球磨
将预烧粉装入尼龙罐中，以锆球为磨球、无水乙醇为球磨介质，充分混合球磨12～24小时，分离锆球，将预烧粉在80～100℃下干燥12～24小时，用研钵研磨，过180目筛。
4、压片
将过180目筛后的预烧粉用粉末压片机压制成圆柱状坯件，然后在200～300MPa的压力下进行冷等静压15～20分钟。
5、无压密闭烧结
将圆柱状坯件放在氧化锆平板上，将氧化锆平板置于氧化铝密闭匣钵中，先用118分钟升温至500℃，保温2小时，再以2～5℃/分钟的升温速率升温至1200～1260℃，烧结5～8小时，随炉自然冷却至室温。
6、抛光
将步骤5烧结后的陶瓷选取其中一个样品表面用320目的砂纸打磨，然后用800目的砂纸打磨，最后用1500目的砂纸和金刚砂抛光至0.5～0.6mm厚，用酒精搽拭干净。
7、烧银
在步骤6抛光后的陶瓷上下表面涂覆厚度为0.01～0.03mm的银浆，置于电阻炉中840℃保温30分钟，自然冷却至室温，制备成玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料。
上述步骤5中，优选以3℃/分钟的升温速率升温至1240℃，烧结6小时。
本发明制备方法简单、重复性好、成品率高，所得陶瓷材料的介电常数高、居里温度高、介电损耗低、具有较好的光学性能，实用性强、易于生产，能兼顾电学性能和光学性能，是一种性能优良的无铅透明陶瓷。
附图说明
图1是实施例1～3制备的玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料的XRD图。
图2是实施例1～3制备的玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料的透过率图。
图3是实施例1～3制备的玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料在10KHz下的介电常数随温度的变化关系图。
图4是实施例1～3制备的玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料在10KHz下的介电损耗随温度的变化关系图。
图5是实施例1～3制备的玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料在10KHz下的介电常数随温度的变化关系图。
具体实施方式
下面结合附图和实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。
实施例1
1、配料
按照0.93K0.5Na0.5NbO3-0.07SrZrO3-0.05％(La2O3-B2O3-SiO2)的化学计量，分别称取纯度为99.99％的Na2CO3 2.4685g、纯度为99.99％的K2CO3 3.2189g、纯度为99.99％的Nb2O5 12.3815g、纯度为99.95％的SrCO3 1.0356g、纯度为99.00％的ZrO2 0.8727g、纯度为99.99％的La2O3 0.0163g、纯度为99.99％的B2O3 0.0035g、纯度为99.99％的SiO2 0.0030g混合均匀，将原料混合物装入尼龙罐中，以锆球为磨球、无水乙醇为球磨介质，无水乙醇与原料混合物的质量比为1:1.2，用球磨机401转/分钟球磨24小时，分离锆球，将原料混合物置于干燥箱内在80℃下干燥14小时，用研钵研磨30分钟，过80目筛。
2、预烧
将步骤1过80目筛后的原料混合物置于氧化铝坩埚内，用玛瑙棒压实，使其压实密度为1.5g/cm3，加盖，置于电阻炉内，以3℃/分钟的升温速率升温至850℃预烧5小时，自然冷却至室温，出炉，用研钵研磨10分钟，得到预烧粉。
3、二次球磨
将预烧粉装入尼龙罐中，以锆球为磨球、无水乙醇为球磨介质，无水乙醇与预烧粉的质量比为1:1.2，用球磨机401转/分钟球磨24小时，分离锆球，将预烧粉置于干燥箱内在80℃下干燥15小时，用研钵研磨10分钟，过180目筛。
4、压片
将过180目筛后的预烧粉用粉末压片机压制成直径为11.5mm、厚度为0.8mm的圆柱状坯件；然后将成型试样在250MPa的压力下进行冷等静压15分钟。
5、无压密闭烧结
将圆柱状坯件放在氧化锆平板上，将氧化锆平板置于氧化铝密闭匣钵中，先用118分钟升温至500℃，保温2小时，再以3℃/分钟的升温速率升温至1240℃，烧结6小时，随炉自然冷却至室温。
6、抛光
将步骤5烧结后的陶瓷选取其中一个表面用320目的砂纸打磨，然后用800目的砂纸打磨，最后用1500目的砂纸和金刚砂抛光至0.5mm厚，用酒精搽拭干净。采用日本理学MiniFlex600型衍射仪进行XRD测试，采用UV-3600型紫外可见近红外光分光光度计进行光学透过率测试，结果见图1和2。
7、烧银
在步骤6抛光后的陶瓷上下表面涂覆厚度为0.02mm的银浆，置于电阻炉中840℃保温30分钟，自然冷却至室温，制备成分子式为0.93K0.5Na0.5NbO3-0.07SrZrO3-0.05％(La2O3-B2O3-SiO2)的玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料。
实施例2
本实施例的步骤1中，按照0.93K0.5Na0.5NbO3-0.07SrZrO3-0.1％(La2O3-B2O3-SiO2)的化学计量分别称取纯度为99.99％的Na2CO3 2.4657g、纯度为99.99％的K2CO33.2153g、纯度为99.99％的Nb2O5 12.3674g、纯度为99.95％的SrCO3 1.0344g、纯度为99.00％的ZrO20.8717g、纯度为99.99％的La2O3 0.0326g、纯度为99.99％的B2O30.0070g、纯度为99.99％的SiO2 0.0060g，其他步骤与实施例1相同，制备成分子式为0.93K0.5Na0.5NbO3-0.07SrZrO3-0.1％(La2O3-B2O3-SiO2)的锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料。
实施例3
本实施例的步骤1中，按照0.93K0.5Na0.5NbO3-0.07SrZrO3-0.3％(La2O3-B2O3-SiO2)的化学计量分别称取纯度为99.99％的Na2CO3 2.4545g、纯度为99.99％的K2CO33.2007g、纯度为99.99％的Nb2O5 12.3113g、纯度为99.95％的SrCO3 1.0297g、纯度为99.00％的ZrO20.8677g、纯度为99.99％的La2O3 0.0974g、纯度为99.99％的B2O30.0208g、纯度为99.99％的SiO2 0.0180g，其他步骤与实施例1相同，制备成分子式为0.93K0.5Na0.5NbO3-0.07SrZrO3-0.3％(La2O3-B2O3-SiO2)的玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料。
采用日本理学MiniFlex600型衍射仪对实施例1～3步骤6抛光后的陶瓷材料进行XRD测试，结果见图1；采用UV-3600型紫外可见近红外光分光光度计对实施例1～3步骤6抛光后的陶瓷材料进行光学透过率测试，结果见图2；采用Agilient4980A型精密阻抗分析仪对实施例1～3得到的玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料的介电性能进行测试，结果见图3～5。
由图1可见，实施例1～3制备的陶瓷材料均为纯的钙钛矿结构。由图2可见，实施例1～3制备的陶瓷材料在近红外区(790～1600nm)的透过率可达49％～72％，其中实施例1制备的陶瓷材料在近红外区的透过率可达62％～72％。由3～5可见，实施例1～3制备的陶瓷材料均呈现高介电常数，高居里温度以及较低的介电损耗，其中x＝0.05时，陶瓷材料的介电常数为12845、居里温度为250℃、介电损耗在30～350℃范围内均小于0.05；x＝0.1时，陶瓷材料的介电常数高达13551、居里温度为253℃、介电损耗在30～350℃范围内均小于0.05；x＝0.3时，陶瓷材料的介电常数为11257、居里温度为229℃、介电损耗在30～350℃范围内均小于0.05。由此可见，本发明陶瓷材料在具有优异的电学性能的同时也具有较好的光学透明性。

Claims (3)

1.一种高介电常数玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料，其特征在于：该陶瓷材料的通式为0.93K0.5Na0.5NbO3-0.07SrZrO3-x％(La2O3-B2O3-SiO2)，式中x代表La2O3-B2O3-SiO2占0.93K0.5Na0.5NbO3-0.07SrZrO3的质量百分比，x的取值为0.05～0.3，La2O3-B2O3-SiO2中La2O3、B2O3、SiO2的物质的量之比为1:1:1；该陶瓷材料介电常数为11200～13600、居里温度为229～253℃、介电损耗在30～350℃范围内均小于0.05，在近红外区的透明度为49％～72％。
2.一种权利要求1所述的高介电常数玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料的制备方法，其特征在于它由下述步骤组成：
(1)配料
按照0.93K0.5Na0.5NbO3-0.07SrZrO3-x％(La2O3-B2O3-SiO2)的化学计量，分别称取纯度均为99.99％的Na2CO3、K2CO3、Nb2O5、La2O3、B2O3、SiO2，纯度99.00％的ZrO2，纯度99.95％的SrCO3，将称取的所有原料混合均匀后装入尼龙罐中，以锆球为磨球、无水乙醇为球磨介质，充分混合球磨18～24小时，分离锆球，将原料混合物在80～100℃下干燥12～24小时，用研钵研磨，过80目筛；
(2)预烧
将步骤(1)过80目筛后的原料混合物置于氧化铝坩埚内，用玛瑙棒压实，使其压实密度为1.5g/cm3，加盖，800～900℃预烧4～6小时，自然冷却至室温，用研钵研磨，得到预烧粉；
(3)二次球磨
将预烧粉装入尼龙罐中，以锆球为磨球、无水乙醇为球磨介质，充分混合球磨12～24小时，分离锆球，将预烧粉在80～100℃下干燥12～24小时，用研钵研磨，过180目筛；
(4)压片
将过180目筛后的预烧粉用粉末压片机压制成圆柱状坯件，然后在200～300MPa的压力下进行冷等静压15～20分钟；
(5)无压密闭烧结
将圆柱状坯件放在氧化锆平板上，将氧化锆平板置于氧化铝密闭匣钵中，先用118分钟升温至500℃，保温2小时，再以2～5℃/分钟的升温速率升温至1200～1260℃，烧结5～8小时，随炉自然冷却至室温；
(6)抛光
将步骤(5)烧结后的陶瓷选取其中一个样品表面用320目的砂纸打磨，然后用800目的砂纸打磨，最后用1500目的砂纸和金刚砂抛光至0.5～0.6mm厚，用酒精搽拭干净；
(7)烧银
在步骤(6)抛光后的陶瓷上下表面涂覆厚度为0.01～0.03mm的银浆，置于电阻炉中840℃保温30分钟，自然冷却至室温，制备成玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料。
3.根据权利要求2所述的高介电常数玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料的制备方法，其特征在于：在步骤(5)中，将圆柱状坯件放在氧化锆平板上，将氧化锆平板置于氧化铝密闭匣钵中，先用118分钟升温至500℃，保温2小时，再以3℃/分钟的升温速率升温至1240℃，烧结6小时，随炉自然冷却至室温。
CN201910616131.5A 2019-07-09 2019-07-09 高介电常数玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料及其制备方法 Active CN110357624B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910616131.5A CN110357624B (zh) 2019-07-09 2019-07-09 高介电常数玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910616131.5A CN110357624B (zh) 2019-07-09 2019-07-09 高介电常数玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料及其制备方法

Publications (2)

Publication Number Publication Date
CN110357624A true CN110357624A (zh) 2019-10-22
CN110357624B CN110357624B (zh) 2021-12-21

Family

ID=68218761

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910616131.5A Active CN110357624B (zh) 2019-07-09 2019-07-09 高介电常数玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料及其制备方法

Country Status (1)

Country Link
CN (1) CN110357624B (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113024250A (zh) * 2021-03-30 2021-06-25 陕西师范大学 高储能密度和储能效率的Sb5+掺杂铌酸锶钠银钨青铜铁电陶瓷材料及制备方法
CN113233771A (zh) * 2021-04-20 2021-08-10 陕西科技大学 一种调控析晶动力协调高透光率和高介电常数的玻璃陶瓷及其制备方法
CN113233772A (zh) * 2021-04-20 2021-08-10 陕西科技大学 一种调控玻璃网络结构实现高介电常数及高击穿性能的玻璃陶瓷及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102584233A (zh) * 2012-01-11 2012-07-18 深圳顺络电子股份有限公司 一种中高介电常数低温共烧陶瓷材料及其制备方法
WO2014123488A1 (en) * 2013-02-06 2014-08-14 Agency For Science, Technology And Research Electro-optic ceramic materials
CN104446447A (zh) * 2014-11-09 2015-03-25 桂林理工大学 一种大应变无铅压电陶瓷复合物及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102584233A (zh) * 2012-01-11 2012-07-18 深圳顺络电子股份有限公司 一种中高介电常数低温共烧陶瓷材料及其制备方法
WO2014123488A1 (en) * 2013-02-06 2014-08-14 Agency For Science, Technology And Research Electro-optic ceramic materials
CN104446447A (zh) * 2014-11-09 2015-03-25 桂林理工大学 一种大应变无铅压电陶瓷复合物及其制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DONG YANG等: "High transmittance in lead-free lanthanum modified potassium-sodium niobate ceramics", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *
WANG, RUIPING等: "Effects of A-Site Ions on the Phase Transition Temperatures and Dielectric Properties of (1-x)(Na0.5K0.5)NbO3-xAZrO(3) Solid Solutions", 《JAPANESE JOURNAL OF APPLIED PHYSICS》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113024250A (zh) * 2021-03-30 2021-06-25 陕西师范大学 高储能密度和储能效率的Sb5+掺杂铌酸锶钠银钨青铜铁电陶瓷材料及制备方法
CN113233771A (zh) * 2021-04-20 2021-08-10 陕西科技大学 一种调控析晶动力协调高透光率和高介电常数的玻璃陶瓷及其制备方法
CN113233772A (zh) * 2021-04-20 2021-08-10 陕西科技大学 一种调控玻璃网络结构实现高介电常数及高击穿性能的玻璃陶瓷及其制备方法

Also Published As

Publication number Publication date
CN110357624B (zh) 2021-12-21

Similar Documents

Publication Publication Date Title
CN105819856B (zh) 铌酸钾钠基无铅透明铁电陶瓷材料及其制备方法
CN110357624A (zh) 高介电常数玻璃料改性锆酸锶掺杂铌酸钾钠无铅透明陶瓷材料及其制备方法
CN101486570B (zh) 一种无铅压电织构厚膜及其制备方法
CN102924078A (zh) 一种bctz基钙钛矿体系多元无铅压电陶瓷及其制备方法
CN102815939B (zh) 一种无铅压电织构陶瓷材料及其制备方法
CN106588011B (zh) 高剩余极化强度和居里温度的铌酸钾钠基无铅透明铁电陶瓷及其制备方法
CN102167585B (zh) 一种多元素掺杂钛酸铋基无铅压电陶瓷材料及其制备方法
CN105948736A (zh) 一种氧化锂-三价氧化物共掺杂abo3结构高温度稳定性压电陶瓷材料及其制备方法
CN106747669B (zh) 一种高居里温度和温度稳定性好的铌酸钾钠基透明铁电陶瓷材料及其制备方法
CN109384465A (zh) 一种钐掺杂铌酸钾钠透明陶瓷的制备方法
CN101429027A (zh) 一种铌酸钾钠基无铅压电陶瓷及其低温烧结制备方法
CN106673650B (zh) 一种高透明铌酸钾钠基压电陶瓷材料及其制备方法
CN108863360A (zh) 一种铒掺杂铌酸钾钠-钛酸锶透明陶瓷的制备方法
CN105819855B (zh) 铌镁酸铋改性的铌酸钾钠透明铁电陶瓷材料及其采用低纯度原料制备的方法
CN106064942A (zh) 高居里温度无铅snkbt压电陶瓷及其制备方法
CN113979748B (zh) 一种铌酸钠钾基无铅压电陶瓷及其制备方法
CN101337815A (zh) 无铅压电陶瓷及其制备方法
CN102180670A (zh) 铌酸钾钠锂-钛酸铋钠钾无铅压电陶瓷及其制备方法
CN107216149A (zh) 一种透明无铅压电陶瓷材料及其制备方法
CN109251030A (zh) 一种高光学温度传感特性的钬掺杂铌酸钾钠-钛酸锶透明陶瓷的制备方法
CN109320243A (zh) 一种高透明度的铌酸钾钠-钛酸钡锶透明陶瓷的制备方法
CN113582692A (zh) 低温烧结的铌酸钾钠基无铅压电陶瓷材料及其制备方法
CN102718482B (zh) 压电陶瓷材料及其制备方法、压电发电振子
CN107253859B (zh) 高发光热稳定性的Eu-Bi共掺杂钨青铜结构发光铁电陶瓷材料及其制备方法
CN103172377B (zh) 反应固相生长制备高性能压电陶瓷的方法

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