CN114956175B - 一种片状的掺杂铌酸铋钙及其制备方法和应用 - Google Patents
一种片状的掺杂铌酸铋钙及其制备方法和应用 Download PDFInfo
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- PMVFCJGPQOWMTE-UHFFFAOYSA-N bismuth calcium Chemical compound [Ca].[Bi] PMVFCJGPQOWMTE-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 75
- 150000003839 salts Chemical class 0.000 claims abstract description 45
- 230000007935 neutral effect Effects 0.000 claims abstract description 34
- 238000000498 ball milling Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 239000011575 calcium Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 abstract description 15
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 24
- 239000013078 crystal Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000005621 ferroelectricity Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
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Abstract
本发明公开了一种片状的掺杂铌酸铋钙及其制备方法和应用，将CaCO3粉体、Bi2O3粉体、Nb2O5粉体、Sm2O3粉体和NaCO3粉体，混合获得混合料，将混合料与中性盐球磨获得球磨粉，将球磨粉烧结即得片状的掺杂铌酸铋钙，所述中性盐由NaCl和KCl组成；本发明所制备的Na，Sm共掺杂的铌酸铋钙，其微观形貌为片状，最大尺寸接近45μm，且尺寸均匀，这种大尺寸片状粉体适合用于作为模板晶粒生长法的模板晶粒，尤其适合用于制备同质的铌酸铋钙基织构陶瓷，有利于提高其织构度。另外，这种大尺寸片状粉体也适合用于压电‑光催化降解，大的形变有利于产生压电势，提到其压电催化活性。
Description
技术领域
本发明属于陶瓷粉末制备技术领域，具体涉及一种片状的掺杂铌酸铋钙及其制备方法和应用。
背景技术
铌酸铋钙(CaBi2Nb2O9，简称CBN)是一种典型的铋层状结构压电陶瓷，由萤石结构的铋氧层((Bi2O2)2+)和类钙钛矿结构的((CaNb2O7)2-)层沿c轴交替堆叠而成。铌酸铋钙具有居里温度高(Tc～940℃)、介电常数低、老化率低以及电阻率高等特点，非常适合用于制造在高温环境下服役的电子元器件，如监测航空和航天发动机运行状态的加速度传感器、高级轿车上的压电喷油嘴等。然而，由于具有特殊的二维结构，自发极化被限制a-b平面内，使其具有高的矫顽场、极低的压电系数(5～7pC/N)，很难通过人工极化获得压电性能优异的陶瓷体。
为了获得高压电系数的铌酸铋钙陶瓷，模板晶粒生长法(TGG)被用来制备织构化的铌酸铋钙陶瓷。通过使陶瓷的晶粒定向生长，获得一定的织构度，陶瓷的压电性能将获得较大的提升。籽晶作为TGG法的关键原料，严重影响织构陶瓷的织构度。通常，为了获得更高的取向度，具有较大尺寸的片状籽晶更加容易被选择。
目前制备铁电片状籽晶的方法主要有溶胶-凝胶法、水热法、熔盐法等方法。但是溶胶-凝胶法原料成本高、反应时间长且容易残留碳杂质和有机溶剂；而水热法需要施加高温高压、反应时间长且尺寸不均匀。熔盐法通过加入低熔点的中性盐，在加热时中性盐融化形成液相，加快了物质传输，可以降低物质合成温度，有望制备大尺寸的片状晶体。
目前制备铁电片状铌酸铋钙的方法主要采用熔盐法和拓扑微晶转化法结合的拓扑化学熔盐合成法。这种方法首先利用熔盐法合成一种与目标产物晶体结构相似的前驱体，随后通过离子交换和置换等过程获得与前驱体成分不同的最终产物。这种方法可以有效地合成片状的铌酸铋钙，但是其工艺复杂、操作较为困难。
发明内容
针对现有技术的不足，本发明的目的在于提供一种粒度分布集中、大尺寸的具有优异铁电性能的片状的掺杂铌酸铋钙及其一步法制备方法和应用。
为了实现上述目的，本发明采用如下技术方案：
本发明一种片状的掺杂铌酸铋钙的制备方法，将CaCO3粉体、Bi2O3粉体、Nb2O5粉体、Sm2O3粉体和NaCO3粉体，混合获得混合料，将混合料与中性盐球磨获得球磨粉，将球磨粉烧结即得片状的掺杂铌酸铋钙，
所述中性盐由NaCl和KCl组成；
所述片状的掺杂铌酸铋钙，其化学通式为：Ca1-2xSmxNaxBi2Nb2O9，其中，0.005≤x＜0.05；
在上述通式中，x表示Sm、Na两种元素的摩尔分数。
本发明所提供的是，Na，Sm共掺杂的铌酸铋钙，由于Na+和Sm3+离子分别为+1价和+3价，两者等摩尔的平均价态与Ca2+价态相同，从而可以构成等价掺杂，由于掺杂前后的价态相同，陶瓷不需产生A位空位或氧空位平衡电荷，空位的减少使得陶瓷保持较高的居里温度；另外由于Na+和Sm3+的离子半径与Ca2+的离子半径存在差异，造成晶格畸变，使得正负电荷中心进一步分离，从而增强压电性能。
另外本发明采用一步熔盐法制备出了大尺寸的Na，Sm共掺杂的铌酸铋钙，本发明中选用中性盐作为熔盐，熔点低，在较低温度就可以形成液相，可以极大的提高物质传输速率，产物物质分布更加均匀。由于在铋层状结构铁电体中，(001)晶面的表面能较低，导致在烧结过程中晶体沿a-b面的生长速率远大于沿c轴的生长速率，使得其晶体形貌呈片状。获得大尺寸且具有优异的铁电性的片状掺杂的铌酸铋钙。
而发明人意外的发现，即使在相同的条件下，采用Na，Sm共掺杂的铌酸铋钙，最终所得的尺寸要大于未经掺杂的铌酸铋钙，因此，在尺寸与掺杂的协同作用下使得大尺寸的片状的掺杂铌酸铋钙大幅优于未掺杂的铌酸铋钙。
而这种高铁电性以及大尺寸的形貌，作为铋层状结构铁电体织构的模板，从而得到取向度较高的陶瓷，使所得陶瓷的压电性能将获得较大的提升
另外，在催化降解方面，大尺寸的片状铌酸铋钙更容易产生形变，从而进一步产生压电势，进一步的提高催化降解的效率。
优选的方案，所述混合料与中性盐的质量比为0.5～2：1，优选为0.8～1.2：1。
将中性盐的范围控制在上述范围内，最终所得片状掺杂铌酸铋钙的尺寸最大。
优选的方案，所述中性盐中，按摩尔比计，NaCl：KCl＝0.8：1.2～1。优选为1：1。
优选的方案，所述球磨为湿法球磨，球磨介质为无水乙醇，磨球的材料为氧化锆，其中，球磨介质与磨球的质量比为0.65：1～2，球料比为1～2：1。
优选的方案，所述球磨的转速为300～400r/min，所述球磨的时间为12～24h。
发明人发现，球磨对于形貌具有一定的影响，在上述条件下的湿法球磨，可以使原料与中性盐混合最为均匀，原料粉末更细小，活性更高，从而更有利于热过程中物质的扩散速率，最终得到的材料尺寸越大。
优选的方案，所述烧结的温度为950℃～1100℃，烧结的时间为6～9h。
进一步的优选，所述烧结的温度为1050℃～1100℃，烧结的时间为6～7h。
进一步的优选，所述烧结时的升温速率为3～5℃/min。
在实际操作过程中，将烧结所得的样品用去离子水清洗，直到清洗的水的电导率降至3μS/cm，得到所需粉体。
优选的方案，所述掺杂铌酸铋钙，其化学通式为：Ca1-2xSmxNaxBi2Nb2O9，其中，0.02≤x＜0.03。
在上述范围的掺杂，最终所得掺杂铌酸铋钙的尺寸最大，最终性能最优。
本发明还提供上述制备方法所制备的片状的掺杂铌酸铋钙。
本发明还提供上述制备方法所制备的片状的掺杂铌酸铋钙的应用，将片状的掺杂铌酸铋钙作为铋层状结构铁电体织构的模板。
有益效果
本发明采用熔盐法制备Na，Sm共掺杂的铌酸铋钙，本发明中选用中性盐作为熔盐，熔点低，在较低温度就可以形成液相，可以极大的提高物质传输速率，产物物质分布更加均匀。由于在铋层状结构铁电体中，(001)晶面的表面能较低，导致在烧结过程中晶体沿a-b面的生长速率远大于沿c轴的生长速率，使得其晶体形貌呈片状。获得大尺寸且具有优异铁电性的片状掺杂的铌酸铋钙。
本发明所制备的Na，Sm共掺杂的铌酸铋钙，其微观形貌为片状，片尺寸普遍超过10μm，最大尺寸接近45μm，且尺寸均匀、具有铁电性，这种尺寸均匀的大尺寸片状晶体适合用于作为模板晶粒生长法的模板晶粒，尤其适合用于制备同质的铌酸铋钙基织构陶瓷，有利于提高其织构度。另外，这种大尺寸的片状粉体也适合用于压电-光催化降解，大的形变有利于产生压电势，进一步的提高其压电催化活性。
附图说明
图1实施例1所制备的Ca0.95Na0.025Sm0.025Bi2Nb2O9粉体的XRD图。
图2实施例1所制备的Ca0.95Na0.025Sm0.025Bi2Nb2O9粉体的SEM图。
图3实施例2所制备的Ca0.95Na0.025Sm0.025Bi2Nb2O9粉体的XRD图。
图4实施例2所制备的Ca0.95Na0.025Sm0.025Bi2Nb2O9粉体的SEM图。
图5实施例3所制备的Ca0.95Na0.025Sm0.025Bi2Nb2O9粉体的XRD图。
图6实施例3所制备的Ca0.95Na0.025Sm0.025Bi2Nb2O9粉体的SEM图。
图7实施例4所制备的Ca0.95Na0.025Sm0.025Bi2Nb2O9粉体的XRD图。
图8实施例4所制备的Ca0.95Na0.025Sm0.025Bi2Nb2O9粉体的SEM图。
图9实施例4所制备的Ca0.95Na0.025Sm0.025Bi2Nb2O9粉体的晶粒尺寸分布图。
图10实施例5所制备的Ca0.95Na0.025Sm0.025Bi2Nb2O9粉体的XRD图。
图11实施例5所制备的Ca0.95Na0.025Sm0.025Bi2Nb2O9粉体的SEM图。
图12对比例1所制备的CaBi2Nb2O9粉体的XRD图。
图13对比例1所制备的CaBi2Nb2O9粉体的SEM图。
图14对比例2所制备的CaBi2Nb2O9粉体的XRD图。
图15对比例2所制备的CaBi2Nb2O9粉体的SEM图。
从上述图中可以看到，本发明所提供的所有XRD图像均与标准PDF卡片(PDF#49-0608)吻合，没有杂质出现。所有实施例的XRD图与固相法的粉体的XRD图像比，(00l)晶面，如(002)、(004、(006)(008)、(0010)、(0014)晶面，所对应的衍射峰强度都有明显提升，这是因为铋层状结构铁电体的a-b面的生长速率远大于沿c轴方向的生长速率，且液态的熔盐为物质传输提供了良好的条件，使得CaBi2Nb2O9能够生长成片状的形貌，而(00l)晶面都是平行于a-b面的晶面，因此这些晶面的强度都得到了不同程度的增强。
SEM图像和粒径分布图：
对比例1中的粉体形貌呈不规则的颗粒状，尺寸为纳米级，且尺寸分布范围较大(400～1200nm)。而对比例2虽然也为熔盐法，但是由于未进行掺杂，虽所得也为片状粉体，但是片状尺寸相对于实施例来说小。
从实施例1-4可以看到，所制得的均为片状，片状尺寸分布较为集中，且随着加热温度升高或保温时间增加，片的尺寸逐渐增大，最大的片尺寸可达45μm。
具体实施方式
实施例1
Ca0.95Na0.025Sm0.025Bi2Nb2O9，烧结条件：950℃、6h
1.按照化学计量比称取掺杂铌酸铋钙的原料，选择中性盐NaCl-KCl(NaCl和KCl的摩尔比为1：1)，原料与中性盐的质量比为1：1；
2.将原料和中性盐、锆球、无水乙醇以1：1.5：0.65的质量比置于球磨罐以300r/min的转速球磨24h，然后干燥、筛粉；
3.将干燥后的粉末倒入坩埚以950℃的温度保温6h，升温速率为5℃/min；
4.将合成的样品用去离子水清洗，直到清洗的水的电导率降至3μS/cm，得到所需粉体。
由图2可以看到所制得的均为片状，片状尺寸分布较为集中，平均尺寸3～6μm，最大约15μm，厚度为300-400nm。
使用全弧光的氙灯作为光源和超声机作为振动源，将50mg的该粉末用于降解200mL的10mg/L罗丹明B水溶液，在30min内可以将溶液变澄清。
实施例2
Ca0.95Na0.025Sm0.025Bi2Nb2O9，烧结条件：1000℃、6h
1.按照化学计量比称取掺杂铌酸铋钙的原料，选择中性盐NaCl-KCl(NaCl和KCl的摩尔比为1：1)，原料与中性盐的质量比为1：1；
2.将原料和中性盐、锆球、无水乙醇以1：1.5：0.65的质量比置于球磨罐以300r/min的转速球磨24h，然后干燥、筛粉；
3.将干燥后的粉末倒入坩埚以1000℃的温度保温6h，升温速率为5℃/min；
4.将合成的样品用去离子水清洗，直到清洗的水的电导率降至3μS/cm，得到所需粉体。
实施例3
Ca0.95Na0.025Sm0.025Bi2Nb2O9，烧结条件：1000℃、9h
1.按照化学计量比称取掺杂铌酸铋钙的原料，选择中性盐NaCl-KCl(NaCl和KCl的摩尔比为1：1)，原料与中性盐的质量比为1：1；
2.将原料和中性盐、锆球、无水乙醇以1：1.5：0.65的质量比置于球磨罐以300r/min的转速球磨24h，然后干燥、筛粉；
3.将干燥后的粉末倒入坩埚以1000℃的温度保温9h，升温速率为5℃/min；
4.将合成的样品用去离子水清洗，直到清洗的水的电导率降至3μS/cm，得到所需粉体。
实施例4
Ca0.95Na0.025Sm0.025Bi2Nb2O9，烧结条件：1050℃、6h
1.按照化学计量比称取掺杂铌酸铋钙的原料，选择中性盐NaCl-KCl(NaCl和KCl的摩尔比为1：1)，原料与中性盐的质量比为1：1；
2.将原料和中性盐、锆球、无水乙醇以1：1.5：0.65的质量比置于球磨罐以300r/min的转速球磨24h，然后干燥、筛粉；
3.将干燥后的粉末倒入坩埚以1050℃的温度保温6h，升温速率为5℃/min；
4.将合成的样品用去离子水清洗，直到清洗的水的电导率降至3μS/cm，得到所需粉体。
使用全弧光的氙灯作为光源和超声机作为振动源，将50mg的该粉末用于降解200mL的10mg/L罗丹明B水溶液，在20min内可以将溶液变澄清。
实施例5
Ca0.95Na0.025Sm0.025Bi2Nb2O9，烧结条件：1100℃、6h
1.按照化学计量比称取掺杂铌酸铋钙的原料，选择中性盐NaCl-KCl(NaCl和KCl的摩尔比为1：1)，原料与中性盐的质量比为1：1；
2.将原料和中性盐、锆球、无水乙醇以1：1.5：0.65的质量比置于球磨罐以300r/min的转速球磨24h，然后干燥、筛粉；
3.将干燥后的粉末倒入坩埚以1100℃的温度保温6h，升温速率为5℃/min；
4.将合成的样品用去离子水清洗，直到清洗的水的电导率降至3μS/cm，得到所需粉体。
图11可以看到所制得的均为片状，片状尺寸分布较为集中，平均尺寸最大约45μm，其降解罗丹明B所需的时间只需15min。
对比例1
固相法制备CaBi2Nb2O9粉体
(1)按照化学计量比称取原料；
(2)将原料、锆球以1：3的质量比置于球磨罐内，加入无水乙醇末过锆球，以300r/min的转速球磨24h，干燥、筛粉；
(3)将干燥后的粉末以5℃/min中的升温速率至925℃保温2h；
(4)将烧结后的粉末倒入球磨罐内球磨，方法与步骤(2)相同，干燥、筛粉，得到CaBi2Nb2O9粉体。
由图13可以看到，对比例1中的粉体形貌呈不规则的颗粒状，尺寸为纳米级，范围较宽。
使用全弧光的氙灯作为光源和超声机作为振动源，将50mg的该粉末用于降解200mL的10mg/L罗丹明B水溶液，在90min才可以将溶液变澄清。
对比例2
(1)CaBi2Nb2O9，烧结条件：950℃、6h
1.按照化学计量比称取掺杂铌酸铋钙的原料，选择中性盐NaCl-KCl(NaCl和KCl的摩尔比为1：1)，原料与中性盐的质量比为1：1；
2.将原料和中性盐、锆球、无水乙醇以1：1.5：0.65的质量比置于球磨罐以300r/min的转速球磨24h，然后干燥、筛粉；
3.将干燥后的粉末倒入坩埚以950℃的温度保温6h，升温速率为5℃/min；
4.将合成的样品用去离子水清洗，直到清洗的水的电导率降至3μS/cm，得到所需粉体。
由图15可以看到所制得的均为片状，片状尺寸分布较为集中，平均尺寸最大仅约1-2μm，厚度为300-400nm。
使用全弧光的氙灯作为光源和超声机作为振动源，将50mg的该粉末用于降解200mL的10mg/L罗丹明B水溶液，在60min才可以将溶液变澄清。
Claims (6)
1.一种片状的掺杂铌酸铋钙的制备方法，其特征在于：将CaCO3粉体、Bi2O3粉体、Nb2O5粉体、Sm2O3粉体和NaCO3粉体，混合获得混合料，将混合料与中性盐球磨获得球磨粉，将球磨粉烧结即得片状的掺杂铌酸铋钙，
所述中性盐由NaCl和KCl组成；
所述混合料与中性盐的质量比为0.5~2：1；
所述球磨为湿法球磨，球磨介质为无水乙醇，磨球的材料为氧化锆，其中，球磨介质与磨球的质量比为0.65：1~2；
所述球磨的转速为300~400r/min，所述球磨的时间为12~24h；
所述烧结的温度为1050℃~1100℃，烧结的时间为6~7h；
所述片状的掺杂铌酸铋钙，其化学通式为：Ca1-2xSmxNaxBi2Nb2O9，其中，0.005≤ x＜0.05；
在上述通式中，x表示Sm、Na两种元素的摩尔分数；
所述片状的掺杂铌酸铋钙平均片尺寸≥10µm。
2.根据权利要求1所述的一种片状的掺杂铌酸铋钙的制备方法，其特征在于：所述中性盐中，按摩尔比计，NaCl：KCl=0.8：1.2~1。
3.根据权利要求1所述的一种片状的掺杂铌酸铋钙的制备方法，其特征在于：所述烧结时的升温速率为3~5℃/min。
4.根据权利要求1所述的一种片状的掺杂铌酸铋钙的制备方法，其特征在于：所述片状的掺杂铌酸铋钙，其化学通式为：Ca1-2xSmxNaxBi2Nb2O9，其中，0.02≤ x＜0.03。
5.根据权利要求1-4任意一项所述的制备方法所制备的片状的掺杂铌酸铋钙。
6.根据权利要求1-4任意一项所述的制备方法所制备的片状的掺杂铌酸铋钙的应用，其特征在于，将片状的掺杂铌酸铋钙作为铋层状结构铁电体织构的模板或用于催化降解。
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