CN106478086A - 陶瓷 - Google Patents
陶瓷 Download PDFInfo
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- CN106478086A CN106478086A CN201610918029.7A CN201610918029A CN106478086A CN 106478086 A CN106478086 A CN 106478086A CN 201610918029 A CN201610918029 A CN 201610918029A CN 106478086 A CN106478086 A CN 106478086A
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- pottery
- solid solution
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- ceramic
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- 239000006104 solid solution Substances 0.000 claims abstract description 45
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- 239000002019 doping agent Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 16
- 229910010252 TiO3 Inorganic materials 0.000 claims description 15
- 229910002902 BiFeO3 Inorganic materials 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 13
- 229910003781 PbTiO3 Inorganic materials 0.000 claims description 10
- 239000008240 homogeneous mixture Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 230000018199 S phase Effects 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- -1 BiTiO3 Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910021165 KTiO3 Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims 2
- 239000010936 titanium Substances 0.000 description 23
- 238000005245 sintering Methods 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000005684 electric field Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- 229910002113 barium titanate Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910002897 Bi2Fe4O9 Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229960004592 isopropanol Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910003334 KNbO3 Inorganic materials 0.000 description 1
- 229910003378 NaNbO3 Inorganic materials 0.000 description 1
- 229910020698 PbZrO3 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- MUPJWXCPTRQOKY-UHFFFAOYSA-N sodium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Na+].[Nb+5] MUPJWXCPTRQOKY-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- 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
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Abstract
本发明涉及一种包含固溶体(或基本上由其组成)的陶瓷，所述固溶体含有Bi、K、Ti和Fe(以及可选地Pb)，所述陶瓷表现出压电行为。
Description
本申请是以下申请的分案申请：申请日：2011年7月19日；申请号：201180036636.6；发明名称“陶瓷”。
技术领域
本发明涉及一种包含固溶体(或基本上由其组成)的陶瓷，所述固溶体含有Bi、K、Ti和Fe(以及可选地Pb)，所述陶瓷表现出压电行为。
背景技术
基于对被施加的机械应变的响应，压电材料产生电场。该效应归因于材料内极化密度的改变。在压电效应是可逆的情况下，当电场被施加于材料时可以诱导出应力或应变。这些性质被用于压电传感器和驱动器，它们被广泛使用于一些具体的应用程序和仪器中。使用压电材料的例子包括医疗超声和声纳、声学、振动控制、火花点火器和(最近的)柴油燃油喷射。
具有钙钛矿或者钨青铜结构的一类陶瓷表现出压电行为。已有许多含铅的钙钛矿结构陶瓷的例子。例如，锆钛酸铅(Pb[ZrxTi1-x]O3 0<x<1)，即众所周知的PZT，它表现出显著的压电效应，且是目前使用中最普通的压电陶瓷。然而它具有仅约200℃的最高工作温度。WO-A-2006/032872公开了含铅的钙钛矿化合物(BiFeO3)x–(PbTiO3)1-x，它表现出压电行为。
含铅装置的毒性正日益受到关注，这种关注也体现在环保法规和政策上。结果表明对无铅压电材料是越来越大的兴趣。已知的无铅压电材料有NaNbO3、BiFeO3、(Bi1/2Na1/2)TiO3、(Bi1/2K1/2)TiO3、BaTiO3、KNbO3和固溶体如(Bi1/2Na1/2)TiO3–(Bi1/2K1/2)TiO3–BaTiO3、(Bi1/2Na1/2)TiO3–(Bi1/2K1/2)TiO3–BiFeO3(见Zhou et al,Mat.Chem.&Phys.,114,2009,832-836)、(Bi1/2Na1/2)TiO3–(Bi1/2K1/2)TiO3、(Bi1/2K1/2)TiO3–BaTiO3、(Bi1/2Na1/2)TiO3–BaTiO3、(Bi1/2Na1/2)TiO3–BaTiO3–BiFeO3(见Nagata et al,Ferroelectrics,229,Issue 1May1999,273-278)以及(K,Na)NbO3。
JP-2008-069051公开了一种含有x(BiaK1-a)TiO3–(l-x)BiFeO3和相当比例的非钙钛矿三元氧化物如Bi2Fe4O9和Bi3Ti4O12的压电陶瓷。当x是0.3时该陶瓷报道的最高居里点为480℃。
发明内容
本发明是基于这样的认识：通式为x(BiaK1-a)TiO3–y BiFeO3–z PbTiO3(如x(BiaK1-a)TiO3–(l-x)BiFeO3(下文为xKBT-l-xBF))的固溶体基本上不含非钙钛矿相，通常表现出高的居里点(Curie point)和/或优异的压电活性。
因此，从第一个方面看，本发明提供了一种陶瓷，其包含如下通式的固溶体(例如，基本上由其组成或由其组成)：
x(BiaK1-a)TiO3–y BiFeO3–z PbTiO3
其中，0.4≤a≤0.6；
0<x<1；
0<y<1；
0≤z≤0.5；且
x+y+z＝1，
其中，所述陶瓷基本上不含非钙钛矿相。
通常情况下，本发明的陶瓷有利地表现出超过350℃的居里点，但一般为700℃或更多。
优选地，所述陶瓷基本上由固溶体组成。例如，该固溶体在陶瓷中的含量可以为50wt％或更多(例如在50-99wt％的范围内)，优选地为75wt％或更多，特别优选地为90wt％或更多，更优选地为95wt％或更多。
优选地，所述陶瓷还包含一种或多种钙钛矿相。特别优选地，所述(或每个)钙钛矿相选自由(BiaK1-a)TiO3、BiTiO3、KTiO3、BiFeO3和PbTiO3组成的组中。所述(或每个)钙钛矿相存在的量可以为75wt％或更少，优选地为50wt％或更少，特别优选地为25wt％或更少，更优选地为5wt％或更少。所述(或每个)钙钛矿相可以痕量地存在。
非钙钛矿相可以是混合Bi、K、Ti、Fe或Pb中的两种或多种(例如三种)的金属相。例子包括Bi2O3、K2O、Bi2Fe4O9和Bi3Ti4O12。
所述陶瓷中存在的非钙钛矿相的量可以是其相位在X-射线衍射图案中是无法识别的。所述陶瓷中存在的非钙钛矿相的量可以是痕量。
优选地，所述陶瓷中存在的非钙钛矿相的总量是小于10wt％，特别优选地是小于8wt％，更优选地是小于5wt％，再更优选地是小于2wt％，仍再更优选地是小于1wt％，最优选地是小于0.1wt％。
所述固溶体可以是部分的固溶体。优选地，所述固溶体是完全的固溶体。
所述固溶体可以基本上是单相的。
所述固溶体可以是双相的。优选地，所述固溶体具有由三方相、单斜相、正交相以及四方相组成的组中的两个。所述固溶体可以具有三方相和单斜相。所述固溶体可以具有三方相和正交相。优选地，所述固溶体具有四方相和三方相。
优选地，0≤z≤0.3。
在优选的具体实施方式中，z为0。优选地，该具体实施方式中所述的陶瓷包含如下通式的固溶体(例如，基本上由其组成或由其组成)：
x(BiaK1-a)TiO3–(1-x)BiFeO3
其中，a是在0.4-0.6的范围内，x是0.01-0.99的范围内；其中，所述陶瓷是基本上不含非钙钛矿相。
所述固溶体可以是(BiaK1-a)TiO3固溶在BiFeO3中。所述固溶体可以是BiFeO3固溶在(BiaK1-a)TiO3中。
优选地，x在0.1到0.9的范围内。
特别优选地，x在0.7到0.9的范围内。在这个范围内特别优选地是四方相和三方相的双相固溶体。
特别优选地，x是在0.1到0.4的范围内。在此范围内的所述陶瓷表现出令人惊奇的高居里点，并且在高温环境下是潜在有用的。
特别优选地，x是在0.5到0.6的范围内。
优选地，a是在0.45到0.55的范围内。特别优选地，a是在0.48至0.52的范围内。更优选地，a为0.50。
在所述固溶体中，一个或多个Bi、K、Fe和Ti中的可以被金属掺杂剂替代。每种替代的金属掺杂剂可以是相同的或不同的。金属掺杂剂的存在可以显著地和不可预知地影响所述固溶体的性能。例如，可以是提高居里点和/或压电活性。
所述(或每个)金属掺杂剂存在的量可以高达50at％，优选地高达20at％，特别优选地多达10at％，更特别优选地高达5at％，仍更优选地高达3at％，最优选地高达1at％。
所述金属掺杂剂可以是A位金属掺杂剂。例如，所述A位金属掺杂剂可以替代Bi和/或K。优选地，所述A位金属掺杂剂是选自由Li、Na、Ca、Sr、Ba及稀土金属组成的组。
所述金属掺杂剂可以是B位金属掺杂剂。例如，所述B位金属掺杂剂可替代Fe和/或Ti。
优选的A位金属掺杂剂是Li或Na。Li或Na在A位上的替代可以改变(例如增加)居里点和/或有利地移动任何双相固溶体的相组分(例如三方相-四方相固溶体)。
优选的A位金属掺杂剂是Ca、Sr或Ba。Ca、Sr或Ba在A位上的替代可以降低介电损耗，改变(例如增加)居里点和/或有利地移动任何双相固溶体的相组分(例如三方相-四方相固溶体)。
优选的A位金属掺杂剂是稀土金属。特别优选的A位金属掺杂剂是La或Nd。通常情况下，La或Nd替代K。La或Nd的替代以牺牲居里点的情况下可以增加压电活性。通过实施例的方法(对于给定的BiFeO3浓度)，La和Nd的替代通常会降低约100-200℃的居里点，并且增加50％的压电活性。
在特别优选的具体实施方式中，A位金属掺杂剂是替代K(即K+)的La(例如La3+)。该替代可以显著地提高电阻率。
优选的B位金属掺杂剂具有比被替代金属更高的化合价。钙钛矿的导电性通常归因于电子空穴或氧空位。B位上较高价态的金属掺杂剂可以明显地提高电阻率(即抑制导电性)。
在特别优选的具体实施方式中，B位金属掺杂剂具有从四价至七价范围的化合价。更特别优选的是，B位金属掺杂剂选自由Ti、Zr、W、Nb、V、Ta、Mo和Mn组成的组。再更特别优选的是，B位金属掺杂剂选自由Nb、Ta、Mo、W、Zr和V组成的组。
优选的B位金属掺杂剂选自由Ti、Fe、Co和Ni组成的组。特别优选的是替代Fe(即Fe3+)的Ti(例如Ti4+)。
在优选的具体实施方式中，所述B位金属掺杂剂具有混合化合价。B位上混合价态的金属掺杂剂可以显著地提高电阻率。
在特别优选的具体实施方式中，所述B位金属掺杂剂是Mn。Mn的优点是，在某种意义上它作为缓冲，可以采用一定范围的氧化态，从而可以提高陶瓷的电阻率范围。
在特别优选的具体实施方式中，所述B位金属掺杂剂是Co。通常地，Co替代Fe(即Fe3+)。
所述陶瓷可以采用织构化陶瓷、单晶、薄膜、或复合材料(例如，陶瓷/玻璃或陶瓷/聚合物的复合材料)的形式。
优选地，所述陶瓷的居里点为350℃或更高，特别优选地为400℃或更高，更优选地为700℃或更高。
优选地，所述陶瓷具有基本上如图2或图7所示的X-射线衍射图案。
所述陶瓷可以是通过烧结含有Bi、K、Fe和Ti(及可选地Pb)的易烧结形式的混合金属氧化物制成陶瓷获得的。
优选地，所述陶瓷还包含预烧结添加剂。
所述预烧结添加剂存在的量可以为75wt％或更少，优选地为50wt％或更少，特别优选地为25wt％或更少，更优选地为5wt％或更少。所述预烧结的添加剂可以痕量地存在。
所述预烧结添加剂可以是钙钛矿。所述预烧结添加剂可以是层状钙钛矿，如Bi4Ti3O12。所述预烧结添加剂可以是含铅的钙钛矿。含铅的钙钛矿可以是PbTiO3或PbZrO3。
可以在后续反应(例如，后煅烧)中加入所述预烧结添加剂以形成含有Bi、K、Fe和Ti(及可选地Pb)的混合金属氧化物。所述预烧结添加剂可用作烧结助剂。
在优选的具体实施方式中，所述陶瓷是通过以下方法获得的，该方法包括：
(A)制备基本上按化学计量配比各个Bi、K、Ti和Fe(及可选地Pb)化合物的均一混合物；
(B)将该均一混合物转化成均一粉体；
(C)诱导该均一粉体中的反应以产生混合金属氧化物；
(D)处理混合金属氧化物成为可烧结的形式；以及
(E)烧结可烧结形式的混合金属氧化物以产生陶瓷。
从进一步的一个方面来看，本发明提供了一种用于制备如上文所定义的陶瓷的方法，包括：
(A)制备基本上按化学计量配比各个Bi、K、Ti和Fe(及可选地Pb)化合物的均一混合物；
(B)将该均一混合物转化成均一粉体；
(C)诱导均一粉体中的反应以产生混合金属氧化物；
(D)处理混合金属氧化物成为可烧结的形式；以及
(E)烧结可烧结形式的混合金属氧化物以产生陶瓷。
在步骤(A)中，一个或多个Fe、Ti、K和Bi(及可选地Pb)化合物偏离化学计量配比量可能是有利的。例如，存在多于化学计量配比量的一个或多个Fe、Ti、K和Bi(及可选地Pb)。例如，原子百分比可以偏离化学计量比±20％或更小，优选地为±10％或更少，特别优选地为±5％或更少。通过偏离化学计量比，陶瓷可有利地配备有用的氧化物相(例如钙钛矿相)。
优选地，在步骤(A)中，各个基本上按化学计量配比的Bi、K、Ti和Fe(及可选地Pb)化合物由下面组成式表示：
x(BibKc)TiO3–y(BiFe1-dBdO3)–z PbTiO3
其中：
B是如上所定义的B位金属掺杂剂；
b是在0.4到0.6的范围；
c是在0.4到0.6的范围；
d是在0到0.5的范围；且
x，y和z的定义同上。
在特别优选的具体实施方式中，B为Ti。
在特别优选的具体实施方式中，B是Co。
在特别优选的具体实施方式中，d是在0到0.2的范围。更优选地，d为零。
在特别优选的具体实施方式中，z为零。
在特别优选的具体实施方式中，b是如上文所定义的a，c是(1-a)。
步骤(A)可以包含金属掺杂氧化物，该金属掺杂氧化物提供了如上文所定义的金属掺杂剂。
各个Bi、K、Ti和Fe(及任可选地Pb)化合物可以独立地选自由氧化物、硝酸盐、氢氧化物、碳酸氢盐、异丙醇盐、聚合物和碳酸盐组成的组，优选为氧化物和碳酸盐。例如为Bi2O3和K2CO3。
所述均一混合物可以是浆料(例如研磨的浆料)、溶液(例如水溶液)、悬浮液、分散液、溶胶-凝胶或熔融体。
步骤(C)可以包含加热(例如煅烧)。优选地，步骤(C)包含阶段性的或者间隔的加热。步骤(C)可以包含阶段性的或者间隔的冷却。
当所述均一混合物是溶液时，所述化合物可以是盐(例如硝酸盐)。
当所述均一混合物是溶胶-凝胶时，所述化合物可以是异丙醇盐。
当所述均一混合物是熔融体时，所述化合物可以是溶解在熔盐中的氧化物。由步骤(C)得到的所述混合金属氧化物可以在冷却时析出。
优选地，所述均一粉体是研磨粉体。步骤(A)可以是：
(A1)制备基本上按化学计量配比各个Bi、K、Ti和Fe(及可选Pb)化合物的浆料；
(A2)研磨该浆料；
并且步骤(B)可以是
(B1)干燥该浆料以产生研磨的粉体。
步骤(E)可以是阶段性的或间隔的烧结。优选地，步骤(E)包括阶段性的或间隔的加热和阶段性的或间隔的冷却。
可以在有烧结助剂存在的情况下实施步骤(E)。烧结助剂的存在促进致密化。所述烧结助剂可以是CuO2。
步骤(D)可包括研磨所述混合金属氧化物。步骤(D)可包括所述混合金属氧化物的造粒。
仍然从进一步的一个方面看，本发明提供了如上文定义的陶瓷在压电器件中的用途。
优选地，在根据本发明所述的用途中，所述压电器件在温度超过400℃是可操作的。
所述的压电器件可以是压电驱动器、传感器或变压器。例如所述压电器件可以是工业蒸汽传感器。
优选地，在根据本发明所述的用途中，所述压电器件可装备在航空发动机中。
将参照非限制性的实施例和附图描述本发明。
附图说明
图1：固溶体xKBT-1-xBF的理论密度对测量密度的曲线图，其中x＝0.1-0.9；
图2：固溶体xKBT-1-xBF的X-射线衍射图案，其中x＝0.1-0.6；
图3：固溶体xKBT-1-xBF的介电常数对温度的曲线图，其中x＝0.4，0.5和0.6；
图4：作为组份函数的固溶体xKBT-1-xBF的居里点；
图5：各个固溶体xKBT-1-xBF的应变场响应；
图6：作为组份函数的固溶体xKBT-1-xBF的室温介电常数；
图7：0.6BiFe0.9Co0.1O3–0.4Bi1/2K1/2TiO3和0.6BiFe0.8Co0.2O3–0.4Bi1/2K1/2TiO3的X-射线衍射图案；
图8：0.6BiFe0.8Co0.2O3–0.4Bi1/2K1/2TiO3的应变场曲线；
图9：(a)0.475BF-0.45KBT-0.075PT，(b)0.55BF-0.3KBT-0.15PT，和(c)0.625BF-0.15KBT-0.225PT的X-射线衍射图案；
图10：室温下0.55BF-0.3KBT-0.15PT在0.1Hz下收集的极化场回线；
图11：室温下0.55BF-0.3KBT-0.15PT在0.1Hz下收集的双极应变场回线；
图12：室温下0.55BF-0.3KBT-0.15PT在0.1Hz下收集的单极应变场回线；
图13：0.55BF-0.3KBT-0.15PT(标记为0.15PT)和0.625BF-0.15KBT-0.225PT(标记为0.225PT)的介电常数对温度的曲线图。
具体实施方式
实施例1
实验步骤
通过混合氧化的方法分别制备固溶体x(BiaK1-a)TiO3–(1-x)BiFeO3的九个组份样品，其中x＝0.1，0.2，0.3，0.4，0.5，0.6，0.7，0.8和0.9。制备x＝0和x＝1的端点组份以用于比较。正式的组份是：
前驱体粉末(Bi2O3、Fe2O3、TiO2及K2CO3，99.9％纯度，Sigma-Aldrich)在130℃干燥24小时以去除任何水分，然后允许准确的称量。以正确的比例称重该粉末以制造下面列出的目标氧化物(见表1)，并且在2-丙醇中采用钇稳定的氧化锆珠球磨17小时。在加热灯下干燥所得的浆料并同时搅拌，通过300微米目的尼龙纱布筛分。
表1
干燥、研磨过的粉末的混合物在带盖的氧化铝坩埚中煅烧，以诱导化学反应产生所需的钙钛矿相。此步骤的温度程序是：以150℃/小时加热至800℃，在800℃停留4小时，然后以300℃/小时冷却至室温。
所述粉末是通过300μm目筛分，并如上所述研磨。然后将0.6g该粉末加到直径10mm的模具中加压50MPa造粒。
尝试850℃，950℃，975℃，1000℃，1040℃和1050℃的烧结温度以获得高密度陶瓷。以50℃/小时进行加热至600℃，然后以300℃/小时至所需的烧结温度。将烧结温度以150℃/小时冷却至600℃，然后以300℃/小时冷却至室温。使用较低的冷却速度以最小化热冲击。
在密度分析、X-射线衍射分析、电气和机电分析之前，磨平烧结过的颗粒，且平行厚度分别为1mm。
结果
最佳烧结温度和所得密度如表2所示。
表2
密度对通过X-射线衍射分析计算的理论密度的曲线也在图1中示出。
对烧结过的颗粒进行X-射线衍射分析以便确认晶体结构。这一分析的结果如图2所示。图2的解读显示所有这些组份都是菱面体对称的单一相。没有有害的非钙钛矿第二相。
居里点是铁电材料转变为顺电的温度。在本发明的xKBT-1-xBF体系中，这种情况发生在极性的菱面体结构到非极性的立方结构的转变，并通过相对介电常数对温度的图(见图3)测量。相对介电常数对温度曲线的最大值表示居里点。对于x＝0.1-0.4的组份的居里点，使用这种技术(即居里点是>约600℃)是无峰的。
为了确定x＝0.3和0.4的组份的居里点，对晶体结构随温度的函数进行了研究。其表明所述x＝0.3的组份的居里点为720℃，x＝0.4的组份的居里点为700℃。
根据已知的BiFeO3的居里点，假定x＝0.1和0.2的组份的居里点在720和820℃之间。然而，在这些温度下，K2O和Bi2O3挥发且组成改变。该数据示于图4。
各个组合物的压电活性如图5中所示。x＝0.6的组份表现出最佳的压电活性。
当在相同的驱动场(7.5kVmm-1)驱动时，各个组份的压电活性(定义为最大应变/最大电场)如表3所示。x＝0.1的组份在该电场下没有应变产生。
表3
图6显示了作为组份函数的室温介电常数。
实施例2
x＝0.6 y＝0.05 (1-x)Bi(Fe(1-y)Coy)O3–x(Bi0.5K0.5)TiO3
x＝0.6 y＝0.1 (1-x)Bi(Fe(1-y)Coy)O3–x(Bi0.5K0.5)TiO3
x＝0.6 y＝0.2 (1-x)Bi(Fe(1-y)Coy)O3–x(Bi0.5K0.5)TiO3
前驱体粉末(Bi2O3、Fe2O3、TiO2、K2CO3和CoO，99.9％纯度，Sigma-Aldrich)在130℃干燥24小时以去除任何水分，然后允许准确的称量。以正确的比例称重该粉末以制造下面列出的目标氧化物(见表4)，并且在2-丙醇中采用钇稳定的氧化锆珠球磨17小时。在加热灯下干燥所得的浆料并同时搅拌，通过300微米目的尼龙纱布筛分。
表4
干燥、研磨过的粉末的混合物在带盖的氧化铝坩埚中煅烧，以诱导化学反应产生所需的钙钛矿相。此步骤的温度程序是：以150℃/小时加热至800℃，在800℃停留4小时，然后以300℃/小时冷却至室温。
该粉末再次通过300μm目筛分，与1wt％的Glascol HA40粘合剂进行如上所述的研磨，并再筛分最后一次。然后将0.6g该粉末加到直径10毫米的模具中，并加压30MPa 5分钟以造粒。然后颗粒在350MPa下冷静压5分钟。
尝试1000℃和1025℃的烧结温度以获得高密度的陶瓷。烧结制度如下：以50℃/小时加热至600℃，然后以300℃/小时至上述的烧结温度。以150℃/小时从烧结温度冷却至600℃，然后以300℃/小时至室温。使用较低的冷却速度以最小化热冲击。
在密度分析和X-射线衍射分析之前，将颗粒磨平，且平行厚度为1mm。
在电气测试如应变场回线和介电常数对温度分析之前，将颗粒磨平，且平行厚度为0.3mm。
结果
图7显示了0.6BiFe0.9Co0.1O3–0.4(Bi1/2K1/2)TiO3和0.6BiFe0.8Co0.2O3–0.4(Bi1/ 2K1/2)TiO3的X-射线衍射图案。该图案是单相的钙钛矿，且显示无非钙钛矿第二相。
x＝0.6，y＝0.2的组份的应变/电场响应如图8中所示。使用的外加电场为4kVmm-1，产生具有d33 1100pm V-1高场的0.44％应变，其远高于PZT中所观察的。
实施例3
通过前面实施例中所述的混合氧化方法合成以下各个组分的固溶体x(BiaK1-a)TiO3–y BiFe1-dBdO3–(1-x-y)PbTiO3样品，
0.475BF-0.45KBT-0.075PT
0.55BF-0.3KBT-0.15PT
0.625BF-0.15KBT-0.225PT
以正确的比例称量该粉末以制造这些目标氧化物(见表5)。
表5
X-射线衍射数据如图9所示。
结果
表6示出了三种组份的密度和烧结温度。
表6
图10是室温下0.55BF-0.3KBT-0.15PT在0.1Hz下收集的极化场回线。剩余极化强度和矫顽场与在PZT中观察的相似。
图11是室温下0.55BF-0.3KBT-0.15PT在0.1Hz下收集的双极应变场回线。总峰/应变峰为大于0.7％。
图12是室温下0.55BF-0.3KBT-0.15PT在0.1Hz下收集的单极应变场回线。在7.5kV/mm下的总应变超过0.43％，高场d33(最大应变/最大场)为575pm V-1。
图13示出了0.55BF-0.3KBT-0.15PT(标记为0.15PT)和0.625BF-0.15KBT-0.225PT(标记为0.225PT)的介电常数对温度的曲线图。通过最大电介质常数推断的铁电-顺电化转变温度是520℃和590℃。该数据是在频率为100kHz下从高温冷却过程中收集的。
总结
组份0.55BF-0.3KBT-0.15PT表现出高场d33为575pm V-1，其高于最硬的商业PZT材料，且Tc为525(PZT最大为350)。此外，其低于PZT(通常为7700至7900)的密度对于某些应用可能是有用的。总应变(单极性和双极性)超过传统的PZT基材料。
Claims (13)
1.一种包含固溶体的陶瓷，所述固溶体的通式为：
x(BiaK1-a)TiO3–y BiFeO3–z PbTiO3
其中，0.48≤a≤0.52；
x在0.1-0.4的范围；
0<y<1；
0＜z≤0.3；且
x+y+z＝1，
其中，所述陶瓷基本上不含非钙钛矿相。
2.如权利要求1所述的陶瓷，其中0＜z≤0.3。
3.一种如前述任一权利要求中所述的陶瓷，还包含一个或多个选自由(BiaK1-a)TiO3、BiTiO3、KTiO3、BiFeO3和PbTiO3组成的组中的钙钛矿相。
4.一种如权利要求1所述的陶瓷，其中所述固溶体具有由三方相、单斜相、正交相和四方相组成的组中的两个。
5.一种如权利要求1所述的陶瓷，其中，x在0.1-0.4的范围。
6.一种如权利要求1所述的陶瓷，其中，a为0.50。
7.一种如权利要求1所述的陶瓷，其中所述固溶体中，Bi和/或K被选自由Li、Na、Ca、Sr、Ba和稀土金属组成的组中的A位金属掺杂剂替代。
8.一种如权利要求1所述的陶瓷，其中所述固溶体中，Fe和/或Ti被具有比被替代金属更高价态或者具有混合价态的B位金属掺杂剂替代。
9.一种如权利要求1所述的陶瓷，其中所述固溶体中，Fe和/或Ti被选自由Ti、Zr、W、Nb、V、Ta、Mo和Mn组成的组中的B位金属掺杂剂替代。
10.一种如权利要求1所述的陶瓷，其中所述固溶体中，Fe和/或Ti被选自由Ti、Fe、Co和Ni组成的组中的B位金属掺杂剂替代。
11.一种如权利要求1所述的陶瓷，通过下述方法获得：
(A)制备基本上按化学计量配比各个Bi、K、Ti、Fe和Pb化合物的均一混合物；
(B)将所述均一混合物转化成均一粉体；
(C)诱导所述均一粉体中的反应以产生混合金属氧化物；
(D)处理所述混合金属氧化物成可烧结的形式；以及
(E)烧结所述可烧结形式的混合金属氧化物以产生所述陶瓷。
12.一种制备如权利要求1-11中任一权利要求所述的陶瓷的方法，包含：
(A)制备基本上按化学计量配比各个Bi、K、Ti、Fe和Pb化合物的均一混合物；
(B)将所述均一混合物转化成均一粉体；
(C)诱导所述均一粉体中的反应以产生混合金属氧化物；
(D)处理所述混合金属氧化物成可烧结的形式；以及
(E)烧结所述可烧结形式的混合金属氧化物以产生所述陶瓷。
13.如权利要求12所述的方法，其中步骤(A)中所述基本上按化学计量配比各个Bi、K、Ti、Fe和Pb化合物由如下组成通式表示：
x(BibKc)TiO3–y(BiFe1-dBdO3)–z PbTiO3
其中：
B是B位金属掺杂剂；
b是在0.4-0.6的范围；
c是在0.4-0.6的范围；
d是在0-0.5的范围；并且
x，y和z的定义如前述任一权利要求中所述。
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- 2011-07-19 US US13/812,039 patent/US9312469B2/en active Active
- 2011-07-19 ES ES11738788.6T patent/ES2637287T3/es active Active
- 2011-07-19 SG SG2013005509A patent/SG187182A1/en unknown
- 2011-07-19 JP JP2013521215A patent/JP5845540B2/ja active Active
- 2011-07-19 CN CN2011800366366A patent/CN103080043A/zh active Pending
- 2011-07-19 KR KR1020137004892A patent/KR101812507B1/ko active IP Right Grant
- 2011-07-19 CN CN201610918029.7A patent/CN106478086A/zh active Pending
- 2011-07-19 DK DK11738788.6T patent/DK2598462T3/en active
- 2011-07-19 EP EP11738788.6A patent/EP2598462B1/en active Active
- 2011-07-19 AU AU2011284482A patent/AU2011284482B2/en active Active
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| IL224426A (en) | 2017-03-30 |
| US20130207020A1 (en) | 2013-08-15 |
| CA2806756C (en) | 2017-08-01 |
| US20160225977A1 (en) | 2016-08-04 |
| GB201012637D0 (en) | 2010-09-15 |
| KR20130093104A (ko) | 2013-08-21 |
| SG187182A1 (en) | 2013-02-28 |
| EP2598462A1 (en) | 2013-06-05 |
| CA2806756A1 (en) | 2012-02-02 |
| KR101812507B1 (ko) | 2017-12-27 |
| JP2013537513A (ja) | 2013-10-03 |
| GB201100696D0 (en) | 2011-03-02 |
| AU2011284482A1 (en) | 2013-03-14 |
| EP2598462B1 (en) | 2017-07-05 |
| CN103080043A (zh) | 2013-05-01 |
| JP5845540B2 (ja) | 2016-01-20 |
| US10020442B2 (en) | 2018-07-10 |
| WO2012013956A1 (en) | 2012-02-02 |
| US20180315916A1 (en) | 2018-11-01 |
| ES2637287T3 (es) | 2017-10-11 |
| AU2011284482B2 (en) | 2014-09-18 |
| DK2598462T3 (en) | 2017-10-09 |
| US9312469B2 (en) | 2016-04-12 |
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