CN111018517A - 一种多功能铁电陶瓷材料及其制备方法 - Google Patents

一种多功能铁电陶瓷材料及其制备方法 Download PDF

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CN111018517A
CN111018517A CN201911233145.5A CN201911233145A CN111018517A CN 111018517 A CN111018517 A CN 111018517A CN 201911233145 A CN201911233145 A CN 201911233145A CN 111018517 A CN111018517 A CN 111018517A
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马春林
谭伟石
陈贵宾
周卫平
翟章印
程菊
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Huaiyin Normal University
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Abstract

本发明公开了一种多功能铁电陶瓷材料及其制备方法，该材料属于ABO3钙钛矿结构的无铅铁电陶瓷材料，其化学式为(1‑x)Na0.5Bi0.497Sm0.003TiO3‑xCaTiO3，其中0≤x≤0.08，该材料在蓝光480 nm波长激发下，能产生肉眼可见的橙红光，具有光致发光性能。本发明在20‑200 oC的温度范围内，光致发光的热稳定性优异，且在室温下具有良好的防水性，工艺简单、生产成本低、绿色环保，所得材料铁电/压电性能良好，可以取代对生态环境有危害且市面上广泛应用的铅基陶瓷，在光电多功能材料和器件领域具有广泛的应用前景。

Description

一种多功能铁电陶瓷材料及其制备方法
技术领域
本发明属于铁电材料制备技术领域，具体涉及一种多功能铁电陶瓷材料及其制备方法。
背景技术
近年来，随着人们对全球环境保护意识的提高和可持续发展的战略的提出，无铅压电陶瓷因对环境友好，热稳定性和化学稳定性良好，机械性能出色和多功能的独特特性而成为人们关注的焦点。因此，寻找新型无铅铁电材料取代对人类健康和生态环境有危害的铅基陶瓷材料迫在眉睫。
属于ABO3钙钛矿家族材料之一的Na0.5Bi0.5TiO3(NBT) 在室温下具有较大的剩余极化强度(P r~38 μC/cm2)、较高的居里温度(T c~320ºC)，较低的烧结温度和良好的声学性能等优点，因此，激发了国内外学者广泛的研究兴趣，被认为是一种很有潜力的无铅压电候选材料。然而，纯NBT陶瓷具有矫顽场高，且在铁电相区电导率高而难以极化，压电性能偏低(d 33=58 pC/N)，高温下Na+和Bi3+易挥发，难以形成致密样品等缺点，因而限制了其实际应用。
稀土(RE)离子由于其独特的电子结构以及4f壳层衍生的光学，电学和磁学特性而受到新材料开发人员的极大关注。通常，这些RE离子不仅用作激活剂离子来合成高效发光材料，而且还用作铁电/压电材料的结构改性剂，以提高机械和电性能，从而开发新的多功能材料。RE掺杂铁电/压电材料激发了研究人员越来越多的兴趣，通过将发光特性与其固有的铁电/压电性能相结合，将铁电/压电材料的应用范围扩展为一类新型多功能材料，即“荧光-铁电/压电”材料。目前，具有高荧光热稳定性的荧光-铁电种类非常少，这在很大程度上限制了铁电材料的实际应用。另外，先前研究报道的一些发光材料因水解反应，其发光强度随着浸没水中时间的延长而显著衰减，严重限制了其在水环境中的应用。
发明内容
本发明的首要目的是提供一种热稳定性高、防水性能优异的的荧光无铅铁电陶瓷材料，其同时具备光致发光、铁电/压电特性。
本发明的另一个目的是提供一种生产工艺简单，成本低廉，过程绿色环保的致密多功能铁电陶瓷材料的制备方法。
为实现本发明的第一个目的，本发明采用的技术方案是：一种绿色环保多功能铁电陶瓷材料，该材料属于ABO3钙钛矿结构的无铅铁电陶瓷材料，其化学式为(1-x)Na0.5Bi0.497Sm0.003TiO3-xCaTiO3，其中0≤x≤0.08。
较佳的，该陶瓷材料通过在A位添加0.003含量的稀土元素Sm3+取代Bi3+，实现光致发光性能。
较佳的，该陶瓷材料在蓝光480 nm波长激发下，能产生很强的肉眼可见的橙红光，从而实现光致发光性能。
较佳的，该陶瓷材料通过调控基质组分中CaTiO3的摩尔分数x，x优选取值为0.04，此时，所测得的光致发光性能最强。
为实现本发明的第二个目的，本发明采用的技术方案是：一种绿色环保多功能铁电陶瓷材料制备方法，包括如下步骤：
(1)按照所述材料的化学通式(1-x)Na0.5Bi0.497Sm0.003TiO3-xCaTiO3中的Na、Bi、Sm、Ca、Ti的化学计量比，计算并称量如下原料Na2CO3、Bi2O3、Sm2O3、CaCO3和TiO2，其中x的取值范围为0~0.08；
(2)将原料放入球磨罐中球磨混合，球磨后的原料烘干，烘干后的原料放入坩埚中，置于马弗炉中以800 ºC保温2 小时预烧；
(3)将上述预烧产物碾碎研磨并进行二次球磨并烘干，利用压片机将烘干后的粉末在750 psi压力下压片，得到生胚；
(4)使用埋烧法，将所述生胚置于马弗炉中1150 ºC保温3 小时，即可得到(1-x)Na0.5Bi0.497Sm0.003TiO3-xCaTiO3铁电陶瓷。
较佳的，步骤(2)中，将原料放入球磨罐中球磨混合12 小时，球磨后的原料在60 ºC温度下烘干12小时。
较佳的，步骤(2)中，球磨混合中，玛瑙球：原料：无水乙醇的质量比为2:1:0.8~1。
较佳的，步骤(3)中，将预烧产物碾碎研磨并进行二次球磨并烘干，其中，球磨时间12小时，烘干温度是60 ºC，烘干时间为12小时。
与现有技术相比，本发明有如下优点：(1)本发明制备材料的原料所需成本较低，产品的物理化学稳定性好；当陶瓷材料480 nm辐照后，能够实现可见橙红光发射，并且调整基体材料中CaTiO3的组分，可实现光致发光性能的调控，当x=0.04时，发光性能最佳；(2)当在20~260 ºC范围内对0.96Na0.5Bi0.497Sm0.003TiO3-0.04CaTiO3陶瓷样品加热时，发射峰的峰形和峰位几乎不变，发光强度也变化很小，说明该发光材料的热稳定性良好；(3)将陶瓷材料子在去离子水中浸泡不同的时间(12、24、36、48、60和72 小时)后，再次测量发射光谱，发射谱峰的位置和形状没有明显变化，且浸没时间对发射强度影响非常小，因此该荧光铁电体的耐水性能高；(4)另外，三价的Sm3+离子取代陶瓷材料中的Bi3+离子，不会产生额外的缺陷，不需要电荷补偿；(5)本发明所述材料采用固相烧结法合成，在空气中烧结而成，无需提供还原性气体，操作流程简单，且合成的陶瓷材料物理化学稳定。与氧气接触时，无变质，对后续的光致发光性能无影响。
附图说明
图1 是本发明实施例中(1-x)Na0.5Bi0.497Sm0.003TiO3-xCaTiO3陶瓷材料XRD图谱。
图2 是本发明实施例中(1-x)Na0.5Bi0.497Sm0.003TiO3-xCaTiO3陶瓷材料的扫描电镜照片。
图3 是本发明实施例中(1-x)Na0.5Bi0.497Sm0.003TiO3-xCaTiO3陶瓷材料的发射光谱。
图4是本发明实施例中主发射光谱强度(4G5/2→6H7/2)与CaTiO3掺杂含量之间的关系图。
图5是本发明实施例中0.96Na0.5Bi0.497Sm0.003TiO3-0.04CaTiO3样品的PL光谱对不同温度测试下的发射光谱。
图6是本发明实施例位于597 nm处归一化发射强度随着温度的变化关系。
图7是本发明实施例在480 nm激发下，不同温度0.96Na0.5Bi497Sm0.003TiO3-0.04CaTiO3陶瓷材料的CIE色度坐标。
图8是本发明实施例中0.96Na0.5Bi497Sm0.003TiO3-0.04CaTiO3陶瓷水中浸泡不同时间的发射光谱，右上插图为相对发射强度(4G5/2→6H7/2)对水中浸泡时间的依赖关系。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
实施例
采用纯度为的99.99%的Na2CO3、99.90%的Bi2O3、99.00%的Sm2O3、99.99%的CaCO3和99.99%的TiO2为原料，制备五组不同组分的无铅荧光铁电陶瓷材料。通常，少量稀土掺杂(<0.5 mol%)铁电材料不会明显改变晶体结构，还有助于增强压电性能。因此，在本发明中，Sm3+的摩尔分数为0.003。首先按照化学式(1-x)Na0.5Bi0.497Sm0.003TiO3-xCaTiO3(x=0、0.02、0.04、0.06、0.08)中的Na、Bi、Sm、Ca、Ti化学计量比进行计算并称量，放入玛瑙球磨罐中进行球磨使其混合均匀，球磨条件为：玛瑙球中大粒和小粒的质量比约为1:1，且玛瑙球质量：原料的质量：球磨介质无水乙醇的质量比为2:1:0.8~1，球磨12小时后，将料浆放入烘箱在60 ºC烘12小时。将烘干后的粉末放入刚玉坩埚中，置入箱式马弗炉中800 ºC保温2 小时，预烧合成具有钙钛矿结构的(1-x)Na0.5Bi0.497Sm0.003TiO3-xCaTiO3陶瓷材料的前驱体；将预烧得到的前驱体碾碎并进行二次球磨12小时并烘干；烘干后的粉末通过压片机在750 psi压力作用下，形成厚度为1~2 mm，直径为10 mm圆片；将所述圆片生胚通过埋烧法，置于箱式马弗炉中以1150 ºC烧结3 小时，获得最终陶瓷材料(1-x)Na0.5Bi0.497Sm0.003TiO3-xCaTiO3(x=0、0.02、0.04、0.06、0.08)。
所述的样品物相采用德国布鲁克公司D8 Advanced型X射线粉末衍射仪进行检测；陶瓷圆片的形貌采用美国FEI公司生产的Quanta FEG450型场发射扫描电镜观察；发射光谱由英国爱丁堡公司分光荧光计系统(EI-FS5)测得。
该陶瓷圆片在蓝光480 nm波长的激发下，看见很强的橙红可见光。
对该陶瓷片进行相关测试，测试结果请参见图1~8。
从图1中可以看出Ca2+、Sm3+完全融入到Na0.5Bi0.5TiO3中，所得到的样品为纯的钙钛矿结构，无不纯的第二相存在，所有的衍射峰均和Na0.5Bi0.5TiO3基的标准卡片(PDF#36-0340)一致，说明制备的样品属于三方晶系，且无杂相产生。
图2(a)-(d)为(1-x)Na0.5Bi0.497Sm0.003TiO3-xCaTiO3陶瓷样品的扫描电子显微镜照片，表明所有陶瓷样品的晶粒尺寸不均匀，但晶粒生长良好，晶粒边界的气孔很少，均具有较高的烧结致密度。
图3、4显示了不同CaTiO3含量所得到的发光强度，其中当CaTiO3含量x=0.04 时荧光发光强度最强，也即0.94Na0.5Bi0.497Sm0.003TiO3-0.06CaTiO3陶瓷组分具有最大的发光强度。
图3中发光峰为所对应于Sm3+稀土离子的4f-4f组态内能级跃迁，即位于563 nm、597 nm、644 nm和709 nm处的四个峰分别归因于Sm3+稀土离子的4G5/2→6H5/2、4G5/2→6H7/2、4G5/2→6H9/2和4G5/2→6H11/2跃迁。
本发明中0.96Na0.5Bi0.497Sm0.003TiO3-0.04CaTiO3发光铁电陶瓷材料具有良好的温度稳定性，具体请参见图5、6、7。
图5是0.96Na0.5Bi0.497Sm0.003TiO3-0.04CaTiO3陶瓷材料在20~260 ºC的温度下，随着温度的升高，在480 nm波长激发下得到的发射光谱。
将与温度相关Sm3+的597 nm发射峰处发射强度(4G5/2→6H J=5/2，7/2，9/2，11/2跃迁)对室温T=20 ºC的强度做归一化处理，如图6所示。根据位于597 nm (4G5/2→6H7/2)处的主发射谱带，随着环境温度从室温增加到140 ºC，发射强度逐渐增加到室温的10％以上，这归因于热释光效应。当温度进一步增加到200 ºC时，发射强度逐渐降低至其室温时的80％左右，然后继续增加测量温度归一化强度开始快速下降，出现热猝灭效应。表明，0.96Na0.5Bi0.497Sm0.003TiO3-0.04CaTiO3陶瓷材料在20~200 ºC温度范围内具有良好的荧光热稳定性，有望在近紫外到蓝光的白光LED领域得到应用。为了精确确定0.96Na0.5Bi0.497Sm0.003TiO3-0.04CaTiO3陶瓷的发光颜色，相应的国际照明委员会(CIE)1931色度坐标如图7所示。通过图5测得的不同温度下的发射光谱，计算了激发波长为480 nm的0.96Na0.5Bi0.497Sm0.003TiO3-0.04CaTiO3陶瓷的相应色度坐标，如图7所示。该样品的色度坐标(x，y)在室温T=20 ºC时为(0.5922，0.4069)，位于橙红色区域。随着温度的升高，0.96Na0.5Bi0.497Sm0.003TiO3-0.04CaTiO3陶瓷的CIE(x，y)色度坐标从室温时的橙红色区域偏移到260 ºC处的浅橙色(0.5558，0.4422)区域。最初，当温度低于200 ºC时，色坐标变化不大，即发光的颜色几乎不变，进一步说明该样品在20~200 ºC温度范围内具有良好的热稳定性。
图8为制备好的0.96Na0.5Bi0.497Sm0.003TiO3-0.04CaTiO3陶瓷浸入去离子水中，浸泡不同的时间(12、24、36、48、60和72 h)后，再次测量发射光谱如图8所示。图8的右上插图为4G5/2→6H7/2跃迁产生的发光强度随浸入水中的时间的变化关系。由图8和其右上插图可以看出，在水浸泡前后，0.96Na0.5Bi0.497Sm0.003TiO3-0.04CaTiO3陶瓷的发射谱峰的位置和形状没有明显变化。浸没时间对发射强度影响非常小。表明该陶瓷荧光材料具有优异的耐水性能。
本发明采用固相烧结方法获得一种具有热稳定性、耐水性性高的绿色环保多功能荧光铁电陶瓷材料，有望在荧光热稳定性要求较高的固态照明或水环境中得到应用。

Claims (7)

1.一种多功能铁电陶瓷材料，其特征在于，该材料属于ABO3钙钛矿结构的无铅铁电陶瓷材料，其化学式为(1-x)Na0.5Bi0.497Sm0.003TiO3-xCaTiO3，其中0≤x≤0.08。
2.如权利要求1所述的陶瓷材料，其特征在于，该陶瓷材料在蓝光480 nm波长激发下，能产生肉眼可见的橙红光，具有光致发光性能。
3.如权利要求1所述的陶瓷材料，其特征在于，x取值为0.04。
4.一种多功能铁电陶瓷材料的制备方法，其特征在于，包括如下步骤：
(1)按照所述陶瓷材料的化学通式(1-x)Na0.5Bi0.497Sm0.003TiO3-xCaTiO3中的Na、Bi、Sm、Ca、Ti的化学计量比，计算并称量如下原料Na2CO3、Bi2O3、Sm2O3、CaCO3和TiO2，其中x的取值范围为0~0.08；
(2)将上述原料球磨混合、干燥，置于800 ±20ºC下保温2 小时预烧；
(3)将上述预烧产物研磨、球磨、干燥，在750 psi压力下压片，得到生胚；
(4)使用埋烧法，将上述生胚置于1150±20 ºC下保温3 小时，即可得到所述陶瓷材料。
5.如权利要求4所述的方法，其特征在于，步骤(2)中，将原料放入球磨罐中球磨混合12小时，在60 ºC下干燥12小时。
6.如权利要求4所述的方法，其特征在于，步骤(2)中，球磨混合中，玛瑙球：原料：无水乙醇的质量比为2:1:0.8~1。
7. 如权利要求4所述的方法，其特征在于，步骤(3)中，将预烧产物研磨、球磨、干燥，其中，球磨时间为12小时，干燥温度为60 ºC，干燥时间为12小时。
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