CN107032785A - 一种窄带隙高极性的无铅铁电陶瓷及其制备方法 - Google Patents
一种窄带隙高极性的无铅铁电陶瓷及其制备方法 Download PDFInfo
- Publication number
- CN107032785A CN107032785A CN201710330701.5A CN201710330701A CN107032785A CN 107032785 A CN107032785 A CN 107032785A CN 201710330701 A CN201710330701 A CN 201710330701A CN 107032785 A CN107032785 A CN 107032785A
- Authority
- CN
- China
- Prior art keywords
- hours
- babio
- ball milling
- insulations
- dispensing
- 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
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 32
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 238000009768 microwave sintering Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 230000015572 biosynthetic process Effects 0.000 claims description 30
- 238000003786 synthesis reaction Methods 0.000 claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 24
- 238000009413 insulation Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 239000006104 solid solution Substances 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 238000000462 isostatic pressing Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910010293 ceramic material Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000005621 ferroelectricity Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
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
- C04B35/468—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 based on barium 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
- C04B35/64—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
- C04B41/45—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
- C04B2235/3205—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
- C04B2235/3215—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
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3258—Tungsten oxides, tungstates, 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
- C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
-
- 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
- C04B2235/667—Sintering using wave energy, e.g. microwave sintering
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
本发明公开了一种可调窄带隙高极性无铅铁电陶瓷，组成通式为：(1‑x)Ba0.9Ca0.1TO3‑xBaBiO3+0.06Bi2WO6；其中x表示摩尔分数，0.01≤x≤0.3。这种陶瓷用多步合成方法，结合球磨混合添加分散剂以及等静压与微波烧结制备方法制备而成，该系列产品具有可调窄带隙Eg=1.2‑2.2eV，高的稳定性，优良的铁电性能P max=21‑35μC/cm2，绿色环保。
Description
技术领域
本发明涉及光电应用的无铅铁电陶瓷材料，具体是一种ABO3型钙钛矿结构的具有窄带隙高极性的无铅铁电陶瓷及其制备方法。
背景技术
光伏发电技术可以将能量来源巨大的太阳辐射光能直接转换为清洁的电能，是新能源中最具开发规模和商业化发展前景的发电方式。光伏发电是利用半导体界面p-n结的光生伏特效应，将光能直接转变为电能的一种技术。光伏效应依赖于两个基本过程来实现：光生载流子的产生与内建电场的作用下光生电子和空穴分离和收集，形成向特定方向流动的净电流。其中最核心的问题之一是通过光伏材料吸收太阳光子分离电子-空穴产生光伏效应，但是传统p-n 结分离电子-空穴的光伏器件的能量转换效率受到限制。为了避免上述缺陷、获得更高的能量转换效率，需要开发无结场结构光伏器件。
铁电材料是指在居里温度以下具有铁电自发极化的功能材料，铁电极化所形成的极化电场可有效地分离光激发下产生的电子—空穴对，可产生明显的光伏效应。然而铁电材料是宽带隙的绝缘体，无法有效地吸收太阳光中的可见光，光电转换效率低。为了提高铁电材料的光电转换效率，必须同时具有窄带隙、高极性。但是，传统的钙钛矿结构氧化物铁电材料很难同时具有铁电性与半导特性。因此开发高极性铁电半导体材料是目前的研究热点。
发明内容
本发明的目的是正对现有技术的不足，而提供一种窄带隙高极性的无铅铁电陶瓷及其制备方法。这种陶瓷材料可有效吸收太阳光能量，同时保持合理内建电场，获得光生电子和空穴分离、收集，具有高的稳定性、优良的铁电性能P max=21-35μC/cm2，绿色环保,内建电场可有效分离电子与空穴，具有优良的光电转换效率。
实现本发明目的的技术方案是：
一种窄带隙高极性的无铅铁电陶瓷，组成通式为：
(1-x)Ba0.9Ca0.1TO3-xBaBiO3+0.06Bi2WO6；其中x表示摩尔分数，0.01≤x≤0.3。
上述窄带隙高极性的无铅铁电陶瓷的制备方法，该方法为多步合成，球磨混合添加分散剂以及等静压与微波烧结结合，具体包括如下步骤：
(1) 第一步以分析纯BaCO3、CaCO3、TiO2为原料按照化学计量式Ba0.9Ca0.1TO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于1200℃保温6小时预合成主晶相Ba0.9Ca0.1TO3；
(2) 第二步以分析纯BaCO3、Bi2O3为原料按照化学计量式BaBiO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于760℃保温3小时预合成主晶相BaBiO3；
(3) 第三步以分析纯WO3、Bi2O3为原料按照化学计量式Bi2WO6配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于600℃保温2小时预合成主晶相Bi2WO6；
(4) 第四步以合成好的Ba0.9Ca0.1TO3、BaBiO3、Bi2WO6为原料按照化学计量式(1-x)Ba0.9Ca0.1TO3-xBaBiO3+0.06Bi2WO6，其中x表示摩尔分数(0.01≤x≤0.3)配料；以无水乙醇为介质，加入甲基戊醇分散剂球磨，干燥，再在高铝坩埚中于980℃保温3小时预合成固溶体；
(5) 预合成的固溶体以无水乙醇为介质，加入甲基戊醇分散剂球磨12小时，干燥，加入5%的PVA造粒，150Mpa等静压成型；
(6) 在950-1000℃微波烧结0.3小时，粉碎，粉碎后的粉末测量吸收光谱；
(7) 烧结的样品加工成两面光滑，直径12.0mm，厚度0.5mm的薄片，两面镀银电极即成，测量铁电性能。
这种方法通过Bi2WO6的辅助烧结与提供A位Bi离子协同作用，结合BaBiO3组成中B位Bi的变价，在B位出现相同元素的不同价态Bi3+/ Bi5+，诱导出现特殊的同素异价B位离子有序态，产生电子跳跃导电机制，由于这种电子跳跃是局域束缚状态，产生类似极化子的导电与极化双重作用，结合多步合成主晶相，微波短时烧结，形成多层次成分/结构梯度层结构，一方面降低带隙，同时保持铁电高极性。
这种方法所得陶瓷材料可有效吸收太阳光能量，同时保持合理内建电场，获得光生电子和空穴分离、收集，具有高的稳定性、优良的铁电性能P max=21-35μC/cm2，绿色环保。
具体实施方式：
下面结合具体实施例对本发明内容作进一步的阐述，但不是对本发明的限定。
实施例1：
制备成分为：(1-x)Ba0.9Ca0.1TO3-xBaBiO3+0.06Bi2WO6 的陶瓷材料，其中x=0.015。
制备方法包括如下步骤：
(1)第一步以分析纯BaCO3、CaCO3、TiO2为原料，按照化学计量式Ba0.9Ca0.1TO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于1200℃保温6小时预合成主晶相Ba0.9Ca0.1TO3；
(2)第二步以分析纯BaCO3、Bi2O3为原料按照化学计量式BaBiO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于760℃保温3小时预合成主晶相BaBiO3；
(3)第三步以分析纯WO3、Bi2O3为原料按照化学计量式Bi2WO6配料；以无水乙醇为介质球磨12h，干燥，再在高铝坩埚中于600℃保温2小时预合成主晶相Bi2WO6；
(4)第四步以合成好的Ba0.9Ca0.1TO3、BaBiO3、Bi2WO6为原料，按照化学计量式(1-x)Ba0.9Ca0.1TO3-xBaBiO3+0.06Bi2WO6；其中x表示摩尔分数(x=0.015)配料；以无水乙醇为介质，加入甲基戊醇分散剂球磨，干燥，再在高铝坩埚中于980℃保温3小时预合成固溶体；
(5)预合成的固溶体以无水乙醇为介质，加入甲基戊醇分散剂球磨12h，干燥，加入5%的PVA造粒，150Mpa等静压成型；
(6)在990℃微波烧结0.3小时，粉碎，粉碎后的粉末测量吸收光谱；
（7）烧结的样品加工成两面光滑，直径12.0mm，厚度0.5mm的薄片，两面镀银电极即成，镀银电极可测量铁电性能。
性能测量结果如表1所示。
实施例2：
制备成分为：(1-x)Ba0.9Ca0.1TO3-xBaBiO3+0.06Bi2WO6的陶瓷材料，其中x=0.025。
制备方法包括如下步骤：
（1）第一步以分析纯BaCO3、CaCO3、TiO2为原料按照化学计量式Ba0.9Ca0.1TO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于1200℃保温6小时预合成主晶相Ba0.9Ca0.1TO3；
（2）第二步以分析纯BaCO3、Bi2O3为原料按照化学计量式BaBiO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于760℃保温3小时预合成主晶相BaBiO3；
（3）第三步以分析纯WO3、Bi2O3为原料按照化学计量式Bi2WO6配料；以无水乙醇为介质球磨12h，干燥，再在高铝坩埚中于600℃保温2小时预合成主晶相Bi2WO6；
（4）第四步以合成好的Ba0.9Ca0.1TO3、BaBiO3、Bi2WO6为原料按照化学计量式(1-x)Ba0.9Ca0.1TO3-xBaBiO3+0.06Bi2WO6；其中x表示摩尔分数(x=0.25)配料；以无水乙醇为介质，加入甲基戊醇分散剂球磨，干燥，再在高铝坩埚中于980℃保温3小时预合成固溶体；
（5）预合成的固溶体以无水乙醇为介质，加入甲基戊醇分散剂球磨12h，干燥，加入5%的PVA造粒，150Mpa等静压成型；
（6）在950℃微波烧结0.3小时，粉碎，粉碎后的粉末可测量吸收光谱；
（7）烧结的样品加工成两面光滑，直径12.0mm，厚度0.5mm的薄片，两面镀银电极即成，镀银电极可测量铁电性能。
性能测量结果如表1所示。
实施例3：
制备成分为：(1-x)Ba0.9Ca0.1TO3-xBaBiO3+0.06Bi2WO6的陶瓷材料，其中x=0.15。
制备方法包括如下步骤：
（1）第一步以分析纯BaCO3、CaCO3、TiO2为原料按照化学计量式Ba0.9Ca0.1TO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于1200℃保温6小时预合成主晶相Ba0.9Ca0.1TO3；
（2）第二步以分析纯BaCO3、Bi2O3为原料按照化学计量式BaBiO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于760℃保温3小时预合成主晶相BaBiO3；
（3）第三步以分析纯WO3、Bi2O3为原料按照化学计量式Bi2WO6配料；以无水乙醇为介质球磨12h，干燥，再在高铝坩埚中于600℃保温2小时预合成主晶相Bi2WO6；
（4）第四步以合成好的Ba0.9Ca0.1TO3、BaBiO3、Bi2WO6为原料按照化学计量式(1-x)Ba0.9Ca0.1TO3-xBaBiO3+0.06Bi2WO6；其中x表示摩尔分数(x=0.15)配料；以无水乙醇为介质，加入甲基戊醇分散剂球磨，干燥，再在高铝坩埚中于980℃保温3小时预合成固溶体；
（5）预合成的固溶体以无水乙醇为介质，加入甲基戊醇分散剂球磨12h，干燥，加入5%的PVA造粒，150Mpa等静压成型；
（6）在970℃微波烧结0.3小时，粉碎，粉碎后的粉末可测量吸收光谱；
（7）烧结的样品加工成两面光滑，直径12.0mm，厚度0.5mm的薄片，两面镀银电极即成，镀银电极可测量铁电性能。
性能测量结果如表1所示。
实施例4：
制备成分为：(1-x)Ba0.9Ca0.1TO3-xBaBiO3+0.06Bi2WO6的陶瓷材料，其中x=0.2。
制备方法包括如下步骤：
（1）第一步以分析纯BaCO3、CaCO3、TiO2为原料按照化学计量式Ba0.9Ca0.1TO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于1200℃保温6小时预合成主晶相Ba0.9Ca0.1TO3；
（2）第二步以分析纯BaCO3、Bi2O3为原料按照化学计量式BaBiO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于760℃保温3小时预合成主晶相BaBiO3；
（3）第三步以分析纯WO3、Bi2O3为原料按照化学计量式Bi2WO6配料；以无水乙醇为介质球磨12h，干燥，再在高铝坩埚中于600℃保温2小时预合成主晶相Bi2WO6；
（4）第四步以合成好的Ba0.9Ca0.1TO3、BaBiO3、Bi2WO6为原料按照化学计量式(1-x)Ba0.9Ca0.1TO3-xBaBiO3+0.06Bi2WO6；其中x表示摩尔分数(x=0.015)配料；以无水乙醇为介质，加入甲基戊醇分散剂球磨，干燥，再在高铝坩埚中于980℃保温3小时预合成固溶体；
（5）预合成的固溶体以无水乙醇为介质，加入甲基戊醇分散剂球磨12h，干燥，加入5%的PVA造粒，150Mpa等静压成型；
（6）在990℃微波烧结0.3小时，粉碎，粉碎后的粉末可测量吸收光谱；
（7）烧结的样品加工成两面光滑，直径12.0mm，厚度0.5mm的薄片，两面镀银电极即成，镀银电极可测量铁电性能。
性能测量结果如表1所示。
表1 ：(1-x)Ba0.9Ca0.1TO3-xBaBiO3+0.06Bi2WO6陶瓷的带隙Eg与铁电最大极性P max(为了对比，表中列出了Ba0.9Ca0.1TO3陶瓷的带隙Eg与铁电最大极性P max)
| 成分x | 带 隙Eg(eV) | 最大极性P max(μC/cm2) | 最大极性电场E(kV/cm) | 实施例 |
| Ba0.9Ca0.1TO3 | 3.1 | 28 | 25 | 对比 |
| 0.015 | 2.1 | 35 | 20 | 1 |
| 0.25 | 1.2 | 23 | 18 | 2 |
| 0.15 | 1.5 | 26 | 21 | 3 |
| 0.2 | 1.8 | 29 | 23 | 4 |
通过以上给出的实施例，可以进一步的清楚的了解本发明的内容，但他们不是对本发明的限定。
Claims (2)
1.一种窄带隙高极性的无铅铁电陶瓷，其特征在于，组成通式为：
(1-x)Ba0.9Ca0.1TO3-xBaBiO3+0.06Bi2WO6；其中x表示摩尔分数，0.01≤x≤0.3。
2.如权利要求1所述的窄带隙高极性的无铅铁电陶瓷的制备方法，其特征是多步合成，球磨混合添加分散剂以及等静压与微波烧结结合，具体包括如下步骤：
（1）第一步以分析纯BaCO3、CaCO3、TiO2为原料按照化学计量式Ba0.9Ca0.1TO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于1200℃保温6小时预合成主晶相Ba0.9Ca0.1TO3；
（2）第二步以分析纯BaCO3、Bi2O3为原料按照化学计量式BaBiO3配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于760℃保温3小时预合成主晶相BaBiO3；
（3）第三步以分析纯WO3、Bi2O3为原料按照化学计量式Bi2WO6配料；以无水乙醇为介质球磨12小时，干燥，再在高铝坩埚中于600℃保温2小时预合成主晶相Bi2WO6；
（4）第四步以合成好的Ba0.9Ca0.1TO3、BaBiO3、Bi2WO6为原料按照化学计量式(1-x)Ba0.9Ca0.1TO3-xBaBiO3+0.06Bi2WO6，其中x表示摩尔分数(0.01≤x≤0.3)配料；以无水乙醇为介质，加入甲基戊醇分散剂球磨，干燥，再在高铝坩埚中于980℃保温3小时预合成固溶体；
（5）预合成的固溶体以无水乙醇为介质，加入甲基戊醇分散剂球磨12小时，干燥，加入5%的PVA造粒，150Mpa等静压成型；
（6）在950-1000℃微波烧结0.3小时，粉碎；
（7）烧结的样品加工成两面光滑，直径12.0mm，厚度0.5mm的薄片，两面镀银电极即成。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710330701.5A CN107032785B (zh) | 2017-05-11 | 2017-05-11 | 一种窄带隙高极性的无铅铁电陶瓷及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710330701.5A CN107032785B (zh) | 2017-05-11 | 2017-05-11 | 一种窄带隙高极性的无铅铁电陶瓷及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107032785A true CN107032785A (zh) | 2017-08-11 |
| CN107032785B CN107032785B (zh) | 2020-04-17 |
Family
ID=59538080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710330701.5A Expired - Fee Related CN107032785B (zh) | 2017-05-11 | 2017-05-11 | 一种窄带隙高极性的无铅铁电陶瓷及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107032785B (zh) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100563364B1 (ko) * | 2002-12-20 | 2006-03-22 | 요업기술원 | 무연(無鉛)계 압전 세라믹스 및 그 제조방법 |
| CN103086712A (zh) * | 2012-12-14 | 2013-05-08 | 广西新未来信息产业股份有限公司 | 一种Bi2WO6改性的钛酸钡基无铅正温度系数电阻材料及其制备方法 |
| CN103787652A (zh) * | 2013-12-17 | 2014-05-14 | 江苏省陶瓷研究所有限公司 | 一种新型复相的ntc热敏电阻材料及其制备方法 |
| CN104557024A (zh) * | 2014-12-18 | 2015-04-29 | 天津大学 | 高居里温度无铅钛酸钡基ptcr陶瓷材料及制备和应用 |
| CN105884350A (zh) * | 2016-04-08 | 2016-08-24 | 江苏大学 | 一种锆钛酸钡钙无铅压电陶瓷材料及其制备方法 |
-
2017
- 2017-05-11 CN CN201710330701.5A patent/CN107032785B/zh not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100563364B1 (ko) * | 2002-12-20 | 2006-03-22 | 요업기술원 | 무연(無鉛)계 압전 세라믹스 및 그 제조방법 |
| CN103086712A (zh) * | 2012-12-14 | 2013-05-08 | 广西新未来信息产业股份有限公司 | 一种Bi2WO6改性的钛酸钡基无铅正温度系数电阻材料及其制备方法 |
| CN103787652A (zh) * | 2013-12-17 | 2014-05-14 | 江苏省陶瓷研究所有限公司 | 一种新型复相的ntc热敏电阻材料及其制备方法 |
| CN104557024A (zh) * | 2014-12-18 | 2015-04-29 | 天津大学 | 高居里温度无铅钛酸钡基ptcr陶瓷材料及制备和应用 |
| CN105884350A (zh) * | 2016-04-08 | 2016-08-24 | 江苏大学 | 一种锆钛酸钡钙无铅压电陶瓷材料及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107032785B (zh) | 2020-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lin et al. | Effects of annealing temperature on the microstructure, optical, ferroelectric and photovoltaic properties of BiFeO3 thin films prepared by sol–gel method | |
| Feizpour et al. | Microwave-assisted synthesis and sintering of potassium sodium niobate lead-free piezoelectric ceramics | |
| Cao et al. | Novel perovskite/TiO 2/Si trilayer heterojunctions for high-performance self-powered ultraviolet-visible-near infrared (UV-Vis-NIR) photodetectors | |
| Pascual-Gonzalez et al. | Band gap narrowing in ferroelectric KNbO3-Bi (Yb, Me) O3 (Me= Fe or Mn) ceramics | |
| Liu et al. | Thermoelectric properties of Gd, Y co-doped Ca3Co4O9+ δ | |
| Yan et al. | Surface dipole affords high-performance carbon-based CsPbI2Br perovskite solar cells | |
| Zhao et al. | First-principles study on the doping effects of nitrogen on the electronic structure and optical properties of Cu 2 O | |
| Nie et al. | The ferroelectric photovoltaic effect of BiCrO3/BiFeO3 bilayer composite films | |
| CN104725042B (zh) | 一种多元复合热释电陶瓷材料及其制备方法 | |
| Pang et al. | Anomalous photovoltaic effect in Bi (Ni2/3Ta1/3) O3‐PbTiO3 ferroelectric solid solutions | |
| CN104477991A (zh) | 一种低热导CuSbS2+X热电材料的制备方法 | |
| CN102403376A (zh) | 含有硅量子点的n-i-p异质结太阳能电池及其制备方法 | |
| CN102976748B (zh) | 高致密钛酸锶钡陶瓷及其制备方法 | |
| Zhong et al. | High photocurrent densities in Bi0. 5Na0. 5TiO3 ferroelectric semiconductors | |
| Ma et al. | Boosting the photoresponse speed of visible-light-active bismuth ferrite thin films based on Fe-site substitution strategy and favorable heterostructure design | |
| Miranda et al. | Role of Ga presence into the heterojunction of metal oxide semiconductor on the stability and tunability ZnO ceramics | |
| CN107331774A (zh) | 双钝化层结构的钙钛矿太阳能电池 | |
| Lan et al. | Semiconducting tailoring and electrical properties of A-site Co substituted Bi0· 5Na0· 5TiO3-δ ferroelectric ceramics | |
| CN107032785A (zh) | 一种窄带隙高极性的无铅铁电陶瓷及其制备方法 | |
| CN104966784A (zh) | BiFeO3/CH3NH3PbI3异质结构铁电光伏薄膜及其制备方法 | |
| Fu et al. | Synthesis, crystal structure and optical properties of Ce doped CuInSe2 powders prepared by mechanically alloying | |
| Zhuang et al. | Synthesis, structure and dielectric properties of (1− x)[0.9 BiFeO3–0.1 DyFeO3]–xPbTiO3 pseudo-binary ceramics | |
| CN113004038B (zh) | 一种高击穿场强、高光电流密度的铌酸钠基无铅铁电陶瓷材料及其制备方法 | |
| CN105702762A (zh) | 一种制备t相铁酸铋薄膜的方法 | |
| Zhao et al. | Analysis of the electronic structures of 3d transition metals doped CuGaS2 based on DFT calculations |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200417 |