CN108569902B - 一种蓝绿色蓄能型发光石及其制备方法 - Google Patents

一种蓝绿色蓄能型发光石及其制备方法 Download PDF

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CN108569902B
CN108569902B CN201810602820.6A CN201810602820A CN108569902B CN 108569902 B CN108569902 B CN 108569902B CN 201810602820 A CN201810602820 A CN 201810602820A CN 108569902 B CN108569902 B CN 108569902B
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吴梅华
郑子山
陈雯
陈国良
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Minnan Normal University
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Abstract

本发明公开了一种新型蓝绿色蓄能型发光石及其制备方法。该蓝绿色蓄能型发光石是以蓝绿色长余辉发光粉xMnO·(1‑0.5x)ZrO2·SiO2（x=0.003~0.15）、硼酸以及磷酸氢锆为原料，将其混合后压制成型，再通过高温煅烧制得。本发明发光石制备方法简单、成本低，所得蓝绿色发光石经灯光照射15分钟后，可在黑暗中观察到蓝绿色的光，发光时间长达10‑13小时；且其硬度高，经玉石硬度测试仪测试，发光石的莫氏硬度为6.2‑7.0Mohs，经抛光打磨后表面晶莹剔透，具有很好的观赏价值。

Description

一种蓝绿色蓄能型发光石及其制备方法
技术领域
本发明属于无机材料制备技术领域，具体涉及一种新型蓝绿色蓄能型发光石及其制备方法。
背景技术
发光石又称为夜明珠，其经光激发后能在黑暗中持续发光。由于天然夜明珠非常稀有，其价格十分昂贵，普通人很难拥有。此外，天然夜明珠中一般含有放射性元素，影响人体健康。因此，人工合成无毒、无害、发光时间长、具有观赏及收藏价值的夜明珠具有良好的商业应用前景。
长余辉发光材料是一种具有“夜明珠”现象的发光粉末。通过加工将长余辉粉末制成硬度很大的块状石头，再经过切割、打磨、抛光，就可以获得形状不一的人造夜明珠（发光石）。中国发明专利CN 101403475A公开了以长余辉发光粉和二氧化硅为原料，制备出蓝绿色、黄绿色、紫色和天蓝色的发光石；中国发明专利CN 106010533A公开了一种蓄能型红色发光石的制备方法，它是将红色长余辉材料与氧化铝、氧化锆混合均匀后压制成型，再经高温煅烧制成的；中国发明专利CN 106010531A公开了将一种蓝色长余辉发光粉与磷酸锆粉末高温煅烧制成蓝色发光石的制备方法。本发明以蓝绿色长余辉发光粉xMnO·(1-0.5x)ZrO2·SiO2为主体材料，硼酸及磷酸氢锆作为辅助材料，制成硬度大、发光性能良好、无毒无害且成本低的发光石。
发明内容
本发明的目的在于提供一种新型蓝绿色蓄能型发光石及其制备方法，其原料价廉易得、配比合理，制作工艺简单，所得产品无毒无害、发光性能良好。
为实现上述目的，本发明采用如下技术方案：
一种蓝绿色蓄能型发光石的制备方法包括以下步骤：
（1）将蓝绿色长余辉发光粉与硼酸、磷酸氢锆及水混合均匀，置于密闭容器中熟化1h，再在0.2-2.0 MPa下用压片机压制成型或通过等静压成型；其中，所述蓝绿色长余辉发光粉为xMnO·(1-0.5x)ZrO2·SiO2（x=0.003~0.15）；硼酸的用量为蓝绿色长余辉发光粉的50-200 wt%，磷酸氢锆的用量为蓝绿色长余辉发光粉的3-15 mol%，水的用量为蓝绿色长余辉发光粉的0.1-5 wt%；
（2）将压制成型的坯体置于坩埚中，在H2与N2按体积比V(H2):V(N2)=2~5:98~95组成的混合气体或CO气体等弱的还原性气氛中，于1000-1150℃下煅烧2-4h，制得所述蓝绿色蓄能型发光石。
所述蓝绿色长余辉发光粉的制备方法包括以下步骤：
（1）按xMnO·(1-0.5x)ZrO2·SiO2（x=0.003~0.15）的化学计量比分别称取ZrOCl2·8H2O、SiO2、MnCO3，并称取其30-70 mol%的矿化剂NaF；
（2）将称取好的ZrOCl2·8H2O、SiO2、MnCO3、NaF混合后置于球磨罐中，并加入无水乙醇至罐高的一半，然后以600~1000 r/min的转速研磨2~4h后，取出，风干后转移至坩埚中；
（3）将坩埚置于箱式炉中，在H2与N2按体积比V(H2):V(N2)=2~5:98~95组成的混合气体或CO气体等弱的还原性气氛中，于1100-1300℃下煅烧3-4h，制得所述蓝绿色长余辉发光粉。
本发明的显著优点在于：
（1）本发明原料价廉易得，其中硼酸的加入可以降低发光石的煅烧温度、改善其结晶性能及发光性能；磷酸氢锆的加入不仅可以有效改善发光石的发光性能同时可以显著提高发光石的硬度。
（2）本发明所得蓝绿色蓄能型发光石无毒无害、发光性能良好，经抛光打磨后，外观晶莹。所得蓝绿色蓄能型发光石经灯光照射15分钟后，可在黑暗中观察到蓝绿色的光，发光时间长达10-13小时。经玉石硬度测试仪测试，发光石的莫氏硬度为6.2-7.0Mohs，经抛光打磨后表面晶莹剔透，具有很好的观赏价值。
附图说明
图1为实施例3所得蓝绿色长余辉发光石的X-射线衍射谱图；
图2为实施例3所得蓝绿色长余辉发光石的激发和发射光谱图。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
所用到的药品均为分析纯。
实施例1
（1）按0.003MnO·0.9985ZrO2·SiO2的化学计量比分别称取ZrOCl2·8H2O、SiO2、MnCO3，并称取其30 mol%的矿化剂NaF；
（2）将称取好的ZrOCl2·8H2O、SiO2、MnCO3、NaF混合后置于球磨罐中，并加入无水乙醇至罐高的一半，然后以600 r/min的转速研磨4h后，取出，风干后转移至坩埚中；
（3）将坩埚置于箱式炉中，在H2与N2按体积比V(H2):V(N2)=2:98组成的弱还原性气氛中，于1100℃下煅烧4h，制得蓝绿色长余辉发光粉；
（4）将蓝绿色长余辉发光粉与其用量50 wt%的硼酸、3 mol%的磷酸氢锆及0.1 wt%的水混合均匀，置于密闭容器中熟化1h，再在0.2 MPa下用压片机压制成型；
（5）将压制成型的坯体置于坩埚中，在H2与N2按体积比V(H2):V(N2)=5:95组成的弱还原性气氛中，于1000℃下煅烧4h，制得所述蓝绿色蓄能型发光石。
经灯光照射15分钟后，可在黑暗中观察到蓝绿色的光，发光时间达10小时。经玉石硬度测试仪测试，发光石的莫氏硬度为6.2Mohs。
实施例2
（1）按0.15MnO·0.925ZrO2·SiO2的化学计量比分别称取ZrOCl2·8H2O、SiO2、MnCO3，并称取其70 mol%的矿化剂NaF；
（2）将称取好的ZrOCl2·8H2O、SiO2、MnCO3、NaF混合后置于球磨罐中，并加入无水乙醇至罐高的一半，然后以1000 r/min的转速研磨3h后，取出，风干后转移至坩埚中；
（3）将坩埚置于箱式炉中，在H2与N2按体积比V(H2):V(N2)=3:97组成的弱还原性气氛中，于1300℃下煅烧3h，制得蓝绿色长余辉发光粉；
（4）将蓝绿色长余辉发光粉与其用量200 wt%的硼酸、15 mol%的磷酸氢锆及5 wt%的水混合均匀，置于密闭容器中熟化1h，再在2.0 MPa下通过等静压成型；
（5）将压制成型的坯体置于坩埚中，在CO气体构成的弱还原性气氛中，于1150℃下煅烧3h，制得所述蓝绿色蓄能型发光石。
经灯光照射15分钟后，可在黑暗中观察到蓝绿色的光，发光时间达11小时。经玉石硬度测试仪测试，发光石的莫氏硬度为6.8Mohs。
实施例3
（1）按0.05MnO·0.975ZrO2·SiO2的化学计量比分别称取ZrOCl2·8H2O、SiO2、MnCO3，并称取其50 mol%的矿化剂NaF；
（2）将称取好的ZrOCl2·8H2O、SiO2、MnCO3、NaF混合后置于球磨罐中，并加入无水乙醇至罐高的一半，然后以800 r/min的转速研磨2h后，取出，风干后转移至坩埚中；
（3）将坩埚置于箱式炉中，在H2与N2按体积比V(H2):V(N2)=4:96组成的弱还原性气氛中，于1200℃下煅烧3h，制得蓝绿色长余辉发光粉；
（4）将蓝绿色长余辉发光粉与其用量100 wt%的硼酸、10 mol%的磷酸氢锆及1 wt%的水混合均匀，置于密闭容器中熟化1h，再在1.0 MPa下通过等静压成型；
（5）将压制成型的坯体置于坩埚中，在H2与N2按体积比V(H2):V(N2)=2:98组成的弱还原性气氛中，于1100℃下煅烧2h，制得所述蓝绿色蓄能型发光石。
经灯光照射15分钟后，可在黑暗中观察到蓝绿色的光，发光时间达13小时。经玉石硬度测试仪测试，发光石的莫氏硬度为7.0Mohs。
图1为实施例3所得蓝绿色长余辉发光石的X-射线衍射图。由图中可见，所得蓝绿色长余辉发光石XRD图谱的主强峰与标准图谱PDF#06-0266相吻合并归属于主材料蓝绿色长余辉发光材料xMnO·(1-0.5x)ZrO2·SiO2，同时一些比较弱的杂质峰与标准谱图的PDF#49-1079相吻合归属于辅助增强材料磷酸锆。
图2为实施例3所得蓝绿色长余辉发光石的激发和发射光谱图。由图中可以看出，发光石在450~550 nm之间具有比较宽的发射光谱，在460、486、529、542 nm附近有发射峰，与所观察的蓝绿色光一致。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (4)

1.一种蓝绿色蓄能型发光石的制备方法，其特征在于：包括以下步骤：
（1）将蓝绿色长余辉发光粉与硼酸、磷酸氢锆及水混合均匀，置于密闭容器中熟化1h，再在0.2-2.0 MPa下用压片机压制成型或通过等静压成型；
（2）将压制成型的坯体置于坩埚中，在还原性气氛中，于1000-1150℃下煅烧2-4h，制得所述蓝绿色蓄能型发光石；
其中，所述蓝绿色长余辉发光粉为xMnO·(1-0.5x)ZrO2·SiO2，x=0.003~0.15；其制备方法包括以下步骤：
（1）按xMnO·(1-0.5x)ZrO2·SiO2的化学计量比分别称取ZrOCl2·8H2O、SiO2、MnCO3，并称取其30-70 mol%的矿化剂NaF；
（2）将称取好的ZrOCl2·8H2O、SiO2、MnCO3、NaF混合后置于球磨罐中，并加入无水乙醇至罐高的一半，然后以600~1000 r/min的转速研磨2~4h后，取出，风干后转移至坩埚中；
（3）将坩埚置于箱式炉中，在还原性气氛中，于1100-1300℃下煅烧3-4h，制得所述蓝绿色长余辉发光粉。
2. 根据权利要求1所述蓝绿色蓄能型发光石的制备方法，其特征在于：步骤（1）中硼酸的用量为蓝绿色长余辉发光粉的50-200 wt%，磷酸氢锆的用量为蓝绿色长余辉发光粉的3-15 mol%，水的用量为蓝绿色长余辉发光粉的0.1-5 wt%。
3.根据权利要求1所述蓝绿色蓄能型发光石的制备方法，其特征在于：所述还原性气氛为H2与N2按体积比2~5:98~95组成的混合气体或CO气体。
4.一种如权利要求1所述方法制得的蓝绿色蓄能型发光石。
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