CN117881642A - 钙钛矿型陶瓷成型体和其制造方法 - Google Patents
钙钛矿型陶瓷成型体和其制造方法 Download PDFInfo
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- CN117881642A CN117881642A CN202280058264.5A CN202280058264A CN117881642A CN 117881642 A CN117881642 A CN 117881642A CN 202280058264 A CN202280058264 A CN 202280058264A CN 117881642 A CN117881642 A CN 117881642A
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- molded body
- perovskite
- precursor
- gel
- perovskite ceramic
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- 239000000919 ceramic Substances 0.000 title claims abstract description 92
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 84
- 239000013078 crystal Substances 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 17
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 17
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 60
- 239000002994 raw material Substances 0.000 claims description 41
- 239000007863 gel particle Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000499 gel Substances 0.000 description 29
- 229910021523 barium zirconate Inorganic materials 0.000 description 20
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 14
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 10
- 229910001863 barium hydroxide Inorganic materials 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 229920006395 saturated elastomer Polymers 0.000 description 9
- 239000000017 hydrogel Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000011246 composite particle Substances 0.000 description 4
- 238000001887 electron backscatter diffraction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FFQALBCXGPYQGT-UHFFFAOYSA-N 2,4-difluoro-5-(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=C(F)C=C1F FFQALBCXGPYQGT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- JXDXDSKXFRTAPA-UHFFFAOYSA-N calcium;barium(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[Ca+2].[Ti+4].[Ba+2] JXDXDSKXFRTAPA-UHFFFAOYSA-N 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000009694 cold isostatic pressing Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000011802 pulverized particle Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- -1 that is Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- WDPNDYZXVYLCAB-UHFFFAOYSA-N [Sr].[Hf] Chemical compound [Sr].[Hf] WDPNDYZXVYLCAB-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- YUFHQHKPBOHTRC-UHFFFAOYSA-N barium(2+);hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ba+2].[Hf+4] YUFHQHKPBOHTRC-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- JPVPMCFJLLNEDN-UHFFFAOYSA-N strontium;hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sr+2].[Hf+4] JPVPMCFJLLNEDN-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000003826 uniaxial pressing Methods 0.000 description 1
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Abstract
本发明为一种包含碱土金属元素、选自Ti、Zr和Hf中的至少1种元素以及氧、且具有60％以上的相对密度的致密质的钙钛矿型陶瓷成型体的制造方法，所述制造方法具备如下的接触反应工序：使单独包含含有选自Ti、Zr和Hf中的至少1种的氧化物以及水的凝胶的前体成型体、和包含碱土金属元素的氢氧化物的液体接触。得到的成型体是钙钛矿型陶瓷晶体(1)的集合体形成晶畴(2)、该晶畴(2)多个连接而成的。
Description
技术领域
本发明涉及：致密质的钙钛矿型陶瓷成型体和其制造方法以及其制造中使用的钙钛矿型陶瓷成型体制造用前体原料。
背景技术
已知钛酸钡、锆酸钡、锆酸锶、钛酸锆酸钡钙等钙钛矿型复合氧化物作为适合于电气设备、电子制品等的压电材料、介电材料等。据说配置于这些制品的构件优选由高密度的烧结体形成以充分发挥其性能。而且，这种烧结体(烧结成型体)以往可以如下制造：将复合氧化物的粉末或颗粒与根据需要的粘结剂混合，接着，形成规定形状的成型体，之后，例如在1700℃(锆酸钡的情况下)这样的高的温度下进行热处理，从而制造。
形成上述那样的高的温度的制造条件时，需要大量的热能，因此，经济上并不优选，因此，例如寻求能在200℃以下制造由钙钛矿型复合氧化物形成的烧结成型体的方法。
例如，非专利文献1中公开了一种锆酸钡烧结成型体的制造方法，所述制造方法如下：用氧化锆凝胶涂布锆酸钡的颗粒表面，接着，对得到的复合体颗粒进行压制成型，形成规定形状的成型体，之后，使该成型体浸渍于75℃的氢氧化钡的饱和水溶液。
现有技术文献
非专利文献
非专利文献1：Yuki Yamaguchi,J.Ceram.Soc.Jpn.,128[10](2020)747-755
发明内容
发明要解决的问题
本发明的目的在于，提供：制造具有60％以上的相对密度的致密质的钙钛矿型陶瓷成型体的方法。另外，本发明的另一目的在于，提供：适合于这种成型体的制造的钙钛矿型陶瓷成型体制造用前体成型体的原料。进而，本发明的另一目的在于，提供：通过为致密质从而适合于固体氧化物形燃料电池的电解质等的钙钛矿型陶瓷成型体。
需要说明的是，本发明中，钙钛矿型陶瓷的相对密度是实测密度相对于根据X射线衍射测定和Rietveld解析得到的理论密度(锆酸钡的情况下，为6.117g/cm3)的比例。氧化物水凝胶的相对密度是实测密度相对于以阿基米德法测得的氧化物水凝胶颗粒的表观密度(氧化锆凝胶的情况下，为3.869g/cm3)的比例。另外，实测密度(以下，也简称为“密度”)是根据尺寸法而测得的体积密度。
用于解决问题的方案
本发明人等发现：与使用非专利文献1中记载的复合体颗粒(用氧化锆凝胶涂布锆酸钡的颗粒表面而成者)相比，如果仅使用氧化锆凝胶，即，使用由含有选自Ti、Zr和Hf中的至少1种的氧化物的凝胶形成的颗粒，则得到具有高的相对密度的致密质的钙钛矿型陶瓷成型体。
本发明如以下所示。
(1)一种钙钛矿型陶瓷成型体的制造方法，其特征在于，其为由包含碱土金属元素、选自Ti、Zr和Hf中的至少1种元素以及氧的钙钛矿型陶瓷形成的成型体的制造方法，所述制造方法具备如下的接触反应工序：
使单独包含含有选自Ti、Zr和Hf中的至少1种的氧化物的凝胶的前体成型体、和包含上述碱土金属元素的氢氧化物的液体接触。
(2)根据上述(1)所述的钙钛矿型陶瓷成型体的制造方法，其中，上述凝胶为非晶态。
(3)根据上述(1)或(2)所述的钙钛矿型陶瓷成型体的制造方法，其中，上述前体成型体为由上述凝胶形成的颗粒的压粉成型体。
(4)根据上述(1)～(3)中任一项所述的钙钛矿型陶瓷成型体的制造方法，其中，上述前体成型体为由上述凝胶形成的颗粒、和由上述钙钛矿陶瓷形成的颗粒的混合物的压粉成型体。
(5)一种钙钛矿型陶瓷成型体，其特征在于，钙钛矿型陶瓷晶体的集合体形成晶畴且该晶畴多个连接而成，所述钙钛矿型陶瓷晶体包含碱土金属元素、选自Ti、Zr和Hf中的至少1种元素以及氧，所述钙钛矿型陶瓷成型体的相对密度为60％以上。
(6)根据上述(5)所述的钙钛矿型陶瓷成型体，其中，上述晶畴中，包含沿相同的朝向取向的多个上述钙钛矿型陶瓷晶体。
(7)一种钙钛矿型陶瓷成型体制造用前体成型体的原料，其特征在于，其为在上述(1)～(4)中任一项所述的钙钛矿型陶瓷成型体的制造方法中使用的前体成型体的原料，
其包含：由含有选自Ti、Zr和Hf中的至少1种的氧化物的凝胶形成的颗粒。
(8)根据上述(7)所述的钙钛矿型陶瓷成型体制造用前体成型体的原料，其中，上述凝胶为非晶态。
(9)根据上述(7)或(8)所述的钙钛矿型陶瓷成型体制造用前体成型体的原料，其中，上述凝胶颗粒的体积平均粒径为0.05～10μm。
发明的效果
根据本发明，可以效率良好地且经济地制造以高的密度(相对密度60％以上)包含由期望的钙钛矿型氧化物形成的晶体(钙钛矿型陶瓷晶体)的致密质的钙钛矿型陶瓷成型体而使接触反应工序例如不形成1000℃以上的高温条件下、即、无需大量的热能。优选的方式中，可以使相对密度为80％以上。
根据本发明，可以将上述致密质的钙钛矿型陶瓷成型体适合用于陶瓷电容器用电介质、固体氧化物形燃料电池用电解质、气体传感器用电解质、全固体电池用的电极或电解质、光催化电极等。
附图说明
图1为示出本发明的钙钛矿型陶瓷成型体的晶体组织的1例的概要图。
图2为示出本发明的钙钛矿型陶瓷成型体的晶体组织的另一例的概要图。
图3为示出〔实施例〕中使用的原料颗粒X1的粒径分布的图。
图4为示出〔实施例〕中使用的原料颗粒X2的粒径分布的图。
图5为实验例1中使用的前体成型体P1的SEM图像。
图6为实验例1中得到的钙钛矿型陶瓷成型体Q1的SEM图像。
图7为图6的放大图像。
图8为实验例1中得到的钙钛矿型陶瓷成型体Q1的高倍率FE-SEM图像。
图9为图8的放大图像。
图10为实验例1中得到的钙钛矿型陶瓷成型体Q1的晶体取向映射的图。
图11为示出实验例1～8中得到的钙钛矿型陶瓷成型体Q1～Q8的相对密度的图。
图12为实验例8中得到的钙钛矿型陶瓷成型体Q8的SEM图像。
图13为实验例9中使用的前体成型体P2的SEM图像。
图14为实验例9中得到的钙钛矿型陶瓷成型体R1的SEM图像。
图15为实验例12中使用的前体成型体P10的SEM图像。
图16为实验例12中得到的钙钛矿型陶瓷成型体S1的SEM图像。
图17为图16的放大图像。
图18为实验例13中得到的钙钛矿型陶瓷的X射线衍射图形。
具体实施方式
本发明中，钙钛矿型陶瓷为包含碱土金属元素、选自Ti、Zr和Hf中的至少1种元素以及氧的通式M1M2O3(式中，M1为碱土金属元素，M2为选自Ti、Zr和Hf中的至少1种元素)所示的氧化物。碱土金属元素M1优选Ca、Sr和Ba。
本发明的钙钛矿型陶瓷成型体的制造方法具备如下的接触反应工序：使单独包含含有选自Ti、Zr和Hf中的至少1种的氧化物的凝胶的前体成型体、和包含上述碱土金属元素的氢氧化物的液体接触，根据需要可以具备后处理工序(后述)。
上述接触反应工序中使用的前体成型体是单独包含上述凝胶的物品。“单独包含凝胶”不是指不含其他成分的“仅由凝胶构成”，而是在包含其他成分的情况下，例如使用以凝胶为基质、使其他成分分散于其中而成的复合物，结果有时变得不具有“单独包含凝胶”的构成，因此，排除这种复合体。因此，本发明的前体成型体是以上述凝胶为必须、且任选包含其他成分的物品。本发明中，优选的方式的前体成型体是包含经颗粒化的凝胶(以下，称为“由凝胶形成的颗粒”或“凝胶颗粒”)的原料(是指另一本发明的“钙钛矿型陶瓷成型体制造用前体原料”，以下，称为“前体原料”)经压制成型而成的压粉成型体。需要说明的是，从由钙钛矿型陶瓷的晶体经高密度化的成型体的形成性的观点出发，上述凝胶优选为非晶态。另外，通常用通式M2O2·nH2O(n为正的数)表示。
上述凝胶颗粒的形状没有特别限定，例如可以形成球状(包含大致球状)、椭圆球状、线状、板状等。前体原料和前体成型体中所含的凝胶颗粒的形状无需在全部颗粒中一样，前述形状中、可以仅为1种，也可以为2种以上。
另外，上述凝胶颗粒的尺寸也没有特别限定，从得到高的密度的前体成型体的方面出发，最大长度优选100μm、更优选1μm。其中，最小长度优选1nm、更优选30nm。球状的凝胶颗粒的情况下，基于激光衍射法的体积平均粒径优选0.01～10μm、更优选0.05～1μm。
上述前体原料可以由凝胶颗粒形成，或者也可以由凝胶颗粒和其他成分形成。后者的情况下，其他成分优选为不经包含碱土金属元素的氢氧化物的液体而改性的无机化合物。例如可以形成氧化物、硫化物、碳化物、氮化物、耐碱性金属等，优选为氧化物，更优选为钙钛矿型陶瓷，特别优选为想要制造的钙钛矿型陶瓷。其他成分可以为晶态和非晶态，均可。另外，其他成分的形状和尺寸优选为凝胶颗粒中的上述形状和尺寸。
上述前体原料由凝胶颗粒和其他成分形成的情况下，将前体原料的总质量设为100质量％，凝胶颗粒的含有比例的下限优选30质量％、更优选50质量％。
通过压制成型制作压粉成型体(前体成型体)的情况下，为了抑制凝胶的改性，优选在10℃以上且低于150℃下进行。压制成型可以根据前体成型体的形状适宜选择带来高密度化的方法来进行。本发明中，例如可以应用依次进行单轴成型和冷等静压成型(CIP)的方法。通过使用了凝胶颗粒的压制成型，凝胶颗粒发生塑性变形，可以使前体成型体高密度化。
上述压粉成型体(前体成型体)的相对密度优选45～75％、更优选60～75％。
本发明的接触反应工序中，使用包含碱土金属元素的氢氧化物的液体。作为该氢氧化物，可以举出氢氧化钙、氢氧化锶、氢氧化钡等。上述液体中所含的氢氧化物可以仅为1种，也可以为2种以上。
作为上述液体中所含的介质，可以举出水、包含水的醇等。另外，上述液体在不妨碍构成前体成型体的凝胶与上述氢氧化物的反应的范围内，可以含有有机化合物等其他成分。
上述液体优选为碱土金属元素的氢氧化物的饱和水溶液。
上述接触反应工序中的接触方法根据前体成型体的形状和尺寸而适宜选择，没有特别限定。作为接触方法，可以举出如下方法：使前体成型体浸渍于上述液体的方法；对前体成型体喷雾上述液体的方法；将上述液体涂布于前体成型体的方法；等。这些之中，从效率良好地得到以高密度包含钙钛矿型陶瓷晶体的成型体的方面出发，优选使前体成型体浸渍于上述液体的方法。
使上述液体与前体成型体接触的情况下，为了使上述液体中所含的氢氧化物与凝胶的反应顺利进行而不使前体成型体溶解、即、不使前体成型体中所含的凝胶溶解，接触温度的上限优选200℃、更优选180℃、进一步优选160℃，下限优选20℃、更优选50℃、进一步优选75℃。
另外，上述液体与前体成型体的接触时间根据前体成型体的形状和尺寸而适宜选择，通常为12小时以上、优选50小时以上。
本发明的钙钛矿型陶瓷成型体的制造方法如上述在接触反应工序后根据需要可以具备后处理工序。作为后处理工序，可以举出如下工序：用于去除接触反应工序时附着于钙钛矿型陶瓷成型体的剩余的上述液体的清洗工序；用于调整为规定形状和尺寸的制品形态的修整工序；热处理工序等。
清洗工序中，例如可以应用如下方法：对带有液体的钙钛矿型陶瓷成型体喷雾水、乙酸水溶液等、或使钙钛矿型陶瓷成型体浸渍于水、乙酸水溶液等等后，进行干燥。使钙钛矿型陶瓷成型体干燥的情况下，可以在常压条件或减压条件下，优选在20～200℃、更优选在70℃～150℃下进行干燥。
修整工序中，为了调整为规定形状和尺寸的制品形态，可以进行磨削加工、开孔加工、表面研磨加工等。
热处理工序中，为了构成钙钛矿型陶瓷成型体的内部的颗粒的生长，例如可以形成在大气气氛中、在500℃～1500℃下进行加热的工序。
通过本发明的钙钛矿型陶瓷成型体的制造方法而得到的钙钛矿型陶瓷成型体是以高的密度包含由钛酸钡、锆酸钡、锆酸锶、钛酸锆酸钡钙、钛酸锶、铪酸锶等钙钛矿型氧化物形成的晶体、副产而不含有碱土金属的碳酸盐的致密质的成型体。如上述，可以使用由凝胶颗粒形成的前体原料、或由凝胶颗粒和其他成分形成的前体原料，但任意情况下，得到的成型体均是致密质。另外，通过本发明的钙钛矿型陶瓷成型体的制造方法而得到的成型体的、实测密度相对于理论密度的比例即相对密度优选可以设为60％以上，更优选可以设为70％以上，特别优选可以设为80％以上。
本发明的钙钛矿型陶瓷成型体如图1和图2所示包括：钙钛矿型陶瓷晶体1的集合体(图中，仅对一部分的六边形部分进行斜线表示)形成晶畴2且该晶畴2多个连接而成的部分。图1为示出用由凝胶颗粒形成的前体原料的前体成型体得到的钙钛矿型陶瓷成型体的晶体组织的概要图，图2为示出用由凝胶颗粒和其他成分形成的前体原料的前体成型体得到的钙钛矿型陶瓷成型体的晶体组织的概要图。另外，1个晶畴中所含的多个晶体在图1和图2中如示意性地用箭头表示，可以形成沿相同的朝向取向。晶体的尺寸优选1～200nm、更优选10～100nm。
本发明的钙钛矿型陶瓷成型体具有图1和图2那样的、包含晶畴2多个连接而成的部分的晶体组织可以根据利用了电子背散射衍射法的EBSD解析而确认。对成型体照射电子束而产生的电子发生非弹性散射，在晶格面被衍射，作为具有所谓EBSD图的衍射图形的反射电子被释放，因此，将其投影进行取向的指数的赋予，从而可以得到晶体取向。扫描电子束，映射EBSD图，例如得到逆极点图晶体取向映射，从而可以确认晶体1的取向和由它们的集合体形成的晶畴2。本发明的钙钛矿型陶瓷成型体通过具有这种组织，从而认为，减少离子传导、极化方向的波动，后面所示的各种功能改善。
本发明的钙钛矿型陶瓷成型体根据无需在基于一般的烧结的制造时形成1500℃以上的温度的工序、即、无需大量的热能的上述本发明的制造方法而得到，且可以形成高的相对密度的成型体，因此，适合作为电介质元件、离子传导元件、电气传导元件、压电元件、强介电元件、强磁性元件、光催化剂的构成材料。
实施例
以下，对钙钛矿型陶瓷成型体的制造例进行说明。
1.钙钛矿型陶瓷成型体的制造原料
以下示出成型体的制造中使用的碱土金属的氢氧化物和作为前体成型体的制造原料的原料颗粒。
(1)碱土金属的氢氧化物
使用FUJIFILM Wako Pure Chemical Corporation制氢氧化钡8水合物。
(2)原料颗粒X1和X2
在离子交换水中，放入FUJIFILM Wako Pure Chemical Corporation制氯氧化锆并搅拌，得到水溶液。接着，在该水溶液中添加氨水，在室温下进行反应，得到包含由ZrO2·nH2O形成的氧化物水凝胶的反应产物。之后，为了去除副产物，进行过滤和水洗，将氧化物水凝胶回收。然后，在150℃下干燥12小时，得到固体化凝胶。根据X射线衍射测定评价固体化凝胶，结果观察不到源自晶体的衍射峰，因此，可知为非晶态。
接着，使用研杵和乳钵将固体化凝胶进行预粉碎。然后，将预粉碎物和乙醇以质量比10：90进行混合，将与该混合液等体积的氧化锆球(直径5mm)和混合液封入至聚乙烯容器。之后，使该容器以150rpm自转10小时，将固体化凝胶粉碎，将包含粉碎物(前体原料、以下，称为“原料颗粒X1”)的混合液回收。接着，将与该混合液等体积的氧化锆球(直径0.5mm)和混合液封入至氧化锆制罐。然后，用行星式球磨机，以450rpm粉碎3小时，将包含粉碎颗粒的混合液回收。之后，将与该混合液等体积的氧化锆球(直径0.1mm)和混合液封入至氧化锆制罐。然后，用行星式球磨机，以450rpm粉碎3小时，得到包含粉碎颗粒(前体原料、以下，称为“原料颗粒X2”)的混合液。
从包含原料颗粒X1和X2的各混合液中去除乙醇，将这些颗粒清洗、回收后，在150℃下干燥，用堀场制作所制激光衍射/散射式粒径分布测定装置“LA-960V2”(型号名称)测定粒径分布(参照图3和图4)。平均粒径d50如下：原料颗粒X1为2.182μm、原料颗粒X2为0.083μm。
(3)原料颗粒Y1
依据Yuki Yamaguchi,J.Ceram.Soc.Jpn.,128[10](2020)747-755，将以溶液法合成的锆酸钡在大气气氛中、在1300℃下进行10小时烧成，之后，将经粉碎而得到的粉末和FUJIFILM Wako Pure Chemical Corporation制氯氧化锆放入至离子交换水并搅拌，制备含锆酸钡颗粒的水溶液，接着，在该水溶液中滴加氨水，在室温下进行反应，从而得到ZrO2·nH2O，将由得到的ZrO2·nH2O形成的氧化物水凝胶覆盖型复合颗粒作为原料颗粒Y1使用。测定该原料颗粒Y1的粒径分布，结果平均粒径d50为6.921μm。
2.成型体的制造和评价
将上述各原料颗粒等供于单轴加压成型和冷等静压压制成型，得到圆板型的前体成型体(直径20mm、厚度0.5～1.0mm)后，浸渍于氢氧化钡8水合物的饱和水溶液，从而得到由作为钙钛矿型陶瓷的锆酸钡的晶体形成的成型体。之后，测定得到的成型体的密度，由其实测密度相对于氧化物水凝胶的表观密度(3.869g/cm3)和锆酸钡的理论密度(6.117g/cm3)的比例算出相对密度。
实验例1
将0.5g的原料颗粒X2(氧化物水凝胶颗粒)供于单轴加压成型(20kN)和冷等静压压制成型(300MPa)，得到前体成型体(以下，称为“前体成型体P1”)。该前体成型体P1的密度为2.717g/cm3、相对密度为71.38％。
接着，以使前体成型体P1浸渍于20g的氢氧化钡8水合物的饱和水溶液中的方式在容器中放入两者，在密封条件下、在100℃下静置100小时，之后，进行基于水和乙酸水溶液的清洗以及在大气气氛中、150℃下的干燥，得到由致密质的锆酸钡晶体形成的钙钛矿型陶瓷成型体(以下，称为“成型体Q1”)。该成型体Q1的密度为5.138g/cm3、相对密度为84.00％(参照表1)。
根据扫描型电子显微镜观察前体成型体P1的断裂面，结果得到图5的图像。根据图5，可知，前体成型体P1的内部致密地集合为细的颗粒，具有光滑的组织。另外，根据扫描型电子显微镜观察得到的成型体Q1的断裂面，结果得到图6和图7的图像。根据图6，可知，粗大颗粒、孔隙等不存在。图7为图6的放大图像，根据该图7，可知，得到了由微细的晶体形成的致密的成型体。
接着，用日本电子株式会社制场发射型扫描电子显微镜“JSM-6330F”(型号名称)观察成型体Q1的断裂面，结果得到图8和图9。根据作为图8的放大图的图9，可知，尺寸10～100nm的晶体颗粒聚集，形成尺寸0.5～10μm的晶畴。另外可知，相邻的晶畴彼此连接，具有三级的分层结构。另一方面，对成型体Q1的断裂面进行研磨制作EBSD测定用的样品，用日本电子株式会社制热场发射型扫描电子显微镜“JSM-6500F”(型号名称)，进行组织观察，进行锆酸钡的晶体取向映射测定，结果得到图10。根据图10，可知，图8和图9中观察到的尺寸10～100nm的晶体颗粒聚集，形成的尺寸0.5～10μm的晶畴内的晶体包围全部示出相同的方向，因此，晶畴内的尺寸10～100nm的晶体颗粒发生取向而聚集。
实验例2～4
使反应时间(氢氧化钡8水合物的饱和水溶液中的前体成型体P1的浸渍时间)分别为12小时、50小时和200小时来代替100小时，除此之外，进行与实验例1同样的操作，得到钙钛矿型陶瓷成型体(以下，称为“成型体Q2～Q4”)。然后，算出这些成型体Q2～Q4中的相对密度(参照表1)。
实验例5～8
使反应温度为150℃来代替100℃，使反应时间分别为12小时、70小时、100小时和200小时，除此之外，进行与实验例1同样的操作，得到钙钛矿型陶瓷成型体(以下，称为“成型体Q5～Q8”)。然后，算出这些成型体Q5～Q8中的相对密度(参照表1和图11)。根据电子显微镜观察得到的成型体Q8的表面，结果得到图12的图像。根据该图12，可知，为由微细的晶体形成的致密的成型体。
[表1]
表1
实验例9
使用原料颗粒X1(氧化物水凝胶颗粒)代替原料颗粒X2，除此之外，进行与实验例1同样的操作，制作前体成型体(以下，称为“前体成型体P2”)，接着，与实验例1同样地浸渍于氢氧化钡8水合物的饱和水溶液中，之后，进行清洗和干燥，从而得到由致密质的锆酸钡晶体形成的钙钛矿型陶瓷成型体(以下，称为“成型体R1”)。
前体成型体P2的密度为2.646g/cm3、相对密度为69.50％。另外，得到的成型体R1的密度为4.285g/cm3、相对密度为70.05％。
根据电子显微镜观察前体成型体P2的断裂面，结果得到图13的图像。根据图13，可知，大的颗粒与细的颗粒混合存在于前体成型体P2的内部，这些颗粒致密地集合，具有光滑的组织。另外，根据电子显微镜观察得到的成型体R1的断裂面，结果得到图14的图像。根据该图14，可知，为由微细的晶体形成的致密的成型体。
实验例10
使用52.6质量％的原料颗粒X1和47.4质量％的锆酸钡颗粒(将成型体R1进行粉碎、在大气气氛中、在1300℃下进行10小时的热处理而得到的粉末颗粒、平均粒径d50：0.969μm)的混合物，除此之外，进行与实验例1同样的操作，制作前体成型体(以下，称为“前体成型体P3”)，接着，同样地浸渍于氢氧化钡8水合物的饱和水溶液中，之后，进行清洗和干燥，从而得到由致密质的锆酸钡晶体形成的钙钛矿型陶瓷成型体(以下，“称为成型体R2”)。
前体成型体P3的相对密度为61.25％。另外，得到的成型体R2的相对密度为73.80％。
实验例11
使用82.0质量％的原料颗粒X1和18.0质量％的锆酸钡颗粒(将成型体R1进行粉碎、在大气气氛中、在1300℃下进行10小时的热处理而得到的粉末颗粒、平均粒径d50：0.969μm)的混合物，除此之外，进行与实验例1同样的操作，制作前体成型体(以下，称为“前体成型体P4”)，接着，同样地浸渍于氢氧化钡8水合物的饱和水溶液中，之后，进行清洗和干燥，从而得到由致密质的锆酸钡晶体形成的钙钛矿型陶瓷成型体(以下，称为“成型体R3”)。
前体成型体P4的相对密度为61.39％。另外，得到的成型体R3的密度为4.569g/cm3、相对密度为74.69％。
实验例12(比較例)
使用原料颗粒Y1(复合颗粒)代替原料颗粒X2，除此之外，进行与实验例1同样的操作，制作前体成型体(以下，称为“前体成型体P10”)，接着，与实验例1同样地浸渍于氢氧化钡8水合物的饱和水溶液中，之后，进行清洗和干燥，从而得到由致密质的锆酸钡晶体形成的钙钛矿型陶瓷成型体(以下，称为“成型体S1”)。
前体成型体P10的密度为2.579g/cm3、相对密度为53.26％。另外，得到的成型体S1的密度为3.291g/cm3、相对密度为53.80％。
根据电子显微镜观察前体成型体P10的断裂面，结果得到图15的图像。根据图15，可知，由粗糙的组织构成。另外，根据电子显微镜观察得到的成型体S1的表面，结果得到图16和图17的图像。根据图16，可知，无法作为致密质得到，形成脆的结构。图17为图16的放大图像，根据该图17，可知，得到了有大量孔隙的成型体。
实验例13
利用使用用通式M2O2·nH2O(式中，M2为选自Ti和Hf中的至少1种元素，n为正的数)表示、具体而言、由TiO2·nH2O或HfO2·nH2O形成的凝胶的颗粒得到的各前体成型体、以及锶或钡的氢氧化物，在反应温度100℃、反应时间12小时下，进行与实验例1同样的步骤的操作。图18为得到的各种钙钛矿型陶瓷成型体的X射线衍射图形。根据图18，可知，与锆酸钡同样地得到了钛酸锶、钛酸钡、铪酸锶、铪酸钡。
产业上的可利用性
本发明的钙钛矿型陶瓷成型体为致密质，因此，可以作为陶瓷电容器用电介质、固体氧化物形燃料电池用电解质、气体传感器用电解质、全固体电池用的电极或电解质、光催化电极等利用。
附图标记说明
1：晶体
2：晶畴
3：其他成分
Claims (9)
1.一种钙钛矿型陶瓷成型体的制造方法，其特征在于，其为由包含碱土金属元素、选自Ti、Zr和Hf中的至少1种元素以及氧的钙钛矿型陶瓷形成的成型体的制造方法，所述制造方法具备如下的接触反应工序：
使单独包含含有选自Ti、Zr和Hf中的至少1种的氧化物以及水的凝胶的前体成型体、和包含所述碱土金属元素的氢氧化物的液体接触。
2.根据权利要求1所述的钙钛矿型陶瓷成型体的制造方法，其中，所述凝胶为非晶态。
3.根据权利要求1或2所述的钙钛矿型陶瓷成型体的制造方法，其中，所述前体成型体为由所述凝胶形成的颗粒的压粉成型体。
4.根据权利要求1～3中任一项所述的钙钛矿型陶瓷成型体的制造方法，其中，所述前体成型体为由所述凝胶形成的颗粒、和由所述钙钛矿陶瓷形成的颗粒的混合物的压粉成型体。
5.一种钙钛矿型陶瓷成型体，其特征在于，其包括钙钛矿型陶瓷晶体的集合体形成晶畴且该晶畴多个连接而成的部分，所述钙钛矿型陶瓷晶体包含碱土金属元素、选自Ti、Zr和Hf中的至少1种元素以及氧，
所述钙钛矿型陶瓷成型体的相对密度为60％以上。
6.根据权利要求5所述的钙钛矿型陶瓷成型体，其中，所述晶畴中包含沿相同的朝向取向的多个所述钙钛矿型陶瓷晶体。
7.一种钙钛矿型陶瓷成型体制造用前体成型体的原料，其特征在于，其为在权利要求1～4中任一项所述的钙钛矿型陶瓷成型体的制造方法中使用的前体成型体的原料，
其包含：由含有选自Ti、Zr和Hf中的至少1种的氧化物以及水的凝胶形成的颗粒。
8.根据权利要求7所述的钙钛矿型陶瓷成型体制造用前体成型体的原料，其中，所述凝胶为非晶态。
9.根据权利要求7或8所述的钙钛矿型陶瓷成型体制造用前体成型体的原料，其中，所述凝胶颗粒的体积平均粒径为0.05～10μm。
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