CN110204321B - 一种具有超高亮度的蓄光型复相陶瓷材料及其制备方法 - Google Patents

一种具有超高亮度的蓄光型复相陶瓷材料及其制备方法 Download PDF

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CN110204321B
CN110204321B CN201910587392.9A CN201910587392A CN110204321B CN 110204321 B CN110204321 B CN 110204321B CN 201910587392 A CN201910587392 A CN 201910587392A CN 110204321 B CN110204321 B CN 110204321B
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张乐
孙炳恒
王蕊
李亮亮
杨顺顺
黄国灿
康健
邵岑
周天元
陈浩
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Jiangsu Normal University
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Abstract

本发明公开了一种具有超高亮度的蓄光型复相陶瓷材料及其制备方法，将长余辉荧光粉、石英陶瓷粉体与造孔剂均化配置成浆料，经浇注成型和干燥、烧结后制成具有“气孔+蓄光陶瓷”复相结构，该陶瓷材料内部具有微气孔，气孔球型度高，直径尺寸在100‑1000nm范围内，满足陶瓷内部荧光发生米氏散射的条件，使荧光的改变传播路径，弱化全反射效应。本发明提供的具有超高亮度的蓄光型复相陶瓷材料，相较于现有的复相蓄光陶瓷材料，前置光提取效率明显提高提升10‑30％，制备工艺简单、快速，烧结温度低，易于批量化生产。

Description

一种具有超高亮度的蓄光型复相陶瓷材料及其制备方法
技术领域
本发明属于无机非金属材料制备领域，涉及一种蓄光陶瓷材料，具体涉及一种具有超高亮度的蓄光型复相陶瓷材料及其制备方法。
背景技术
铕、镝共掺的铝酸锶长余辉荧光粉是一种化学性质稳定的黄绿色长余辉发光材料，可广泛应用于建筑指示与应急照明、救灾与消防逃生、园艺与景观艺术设计等领域。
目前，实际应用中的长余辉发光指示产品是将烧结好的长余辉荧光粉通过二次旋涂的方法涂敷在黏土或者聚氯乙烯塑料(PVC)基底上。这种制备方法过程繁琐，须经过两步烧结(荧光粉烧结+基底烧结)以及后期旋涂，在实际生产中效率低，能耗高。此外长余辉粉体只是涂敷在基底的表层，最外部只靠一层釉料进行保护，在特殊条件下应用时(如火场，水下)，长余辉粉体以及基底材料本身均极易分解，大大缩短了其使用寿命，最终限制了长余辉发光材料的消防逃生，水下景观等应用范围。因此，研究人员开发出一种“一体式”蓄光型复相陶瓷。其中，石英陶瓷由于具有较高的耐酸碱侵蚀性能和抗热震性，此外热膨胀系数低，体积稳定性好等优势，被选作基质相。将长余辉蓄光粉与石英陶瓷原料粉经过称量、混合、成型、干燥以及烧结等步骤制备得到“一体式”蓄光型复相陶瓷。
然而，由于蓄光陶瓷(折射率为1.45-1.56)与空气(折射率为1.0)间的较大的折射率差，受到外界能量的激发后产生荧光从陶瓷上表面出射时会产生全发射效应，经计算全反射临界角为44°，即只有24.4％的荧光能够从陶瓷上表面出射，实现前置光的提取，其余荧光受限于全反射效应，将在陶瓷内部以波导效应形式传输，直至完全损耗。因此，为实现“一体化”蓄光型陶瓷在消防指示、园艺景观等领域更为广泛的应用，迫切需要一种简便、有效的方法来提高复相蓄光陶瓷的前置光提取率。
中国专利申请CN109467453A公开了一种具有特征微观结构的荧光陶瓷，在固态照明用荧光陶瓷内部引入弥散分布的气孔作为第二相，有效改变了陶瓷的微观结构，增加入射光的利用率，提高出射亮度。该专利申请采用Y3-x-y-zCexLuyGdzAl5-aGaaO12荧光粉作为荧光结晶颗粒，通过加入造孔剂(如淀粉、聚乙烯醇、糊精等)在陶瓷内部引入气孔，提高出射亮度。这类造孔剂的分解温度与陶瓷烧制温度差距大，不利于形成圆润的气孔，荧光入射到气孔后易产生折射，使荧光以散射或者反射的形式在陶瓷内部传播。
发明内容
本发明的目的之一是提供一种具有超高亮度的蓄光型复相陶瓷材料的制备方法。
本发明的目的之二是提供由上述制备方法制得的具有超高亮度的蓄光型复相陶瓷材料。
为实现上述目的，本发明采用的技术方案如下：一种具有超高亮度的蓄光型复相陶瓷材料的制备方法，具体步骤如下：
(1)称量：以原料粉体总质量为100％计，分别称取质量百分比为50％～55％的10～30目的石英原料、25％～29％的50～100目的石英原料、6％～15％的150～250目的石英原料，其余为制备铕、镝共掺的铝酸锶长余辉荧光粉的原料粉体；再称取占原料粉体总质量0.5％～1.5％的造孔剂，所述造孔剂为碳酸氢铵与淀粉按质量比1：3～6组成的混合物；
(2)混料：将步骤(1)称量的粉体原料置于球磨罐内，同时加入磨球和去离子水进行球磨混合；
(3)成型：将步骤(2)球磨后的浆料进行真空除泡处理，然后将除泡后的浆料注入模具中成型，得到素坯；
(4)干燥：将步骤(3)得到的素坯静置7～12小时后进行脱模，然后置于干燥箱内干燥；
(5)烧结：将步骤(4)干燥后的素坯在还原气氛下进行高温煅烧，煅烧温度为800～1200℃，保温时间为3～6h，随后随炉冷却至室温，即得到具有超高亮的蓄光型复相陶瓷材料。
步骤(1)中，所述制备铕、镝共掺的铝酸锶长余辉荧光粉的原料粉体为SrCO3、Al2O3、Eu2O3和Dy2O3，根据化学式SrAl2O4:Eu2+,Dy3+中各元素的化学计量比称量得到。
步骤(2)中，所述磨球与原料粉体总质量的质量比为1.5～3：1，所述去离子水的添加量为原料粉体总质量的12％～17％。
步骤(2)中，所述球磨的转速为160～300r/min，球磨时间为20～25h。
步骤(3)中，所述真空除泡的真空度为-10～-30kpa，除泡时间为30～50min。
步骤(4)中，所述干燥温度为60～100℃，干燥时间为15～24h。
本发明还提供由上述制备方法制得的具有超高亮度的蓄光型复相陶瓷材料，所述陶瓷材料中富含微气孔，气孔球型度高，尺寸在100-1000nm范围内，具有“气孔+蓄光陶瓷”复相结构。
本发明采用碳酸氢铵与淀粉的混合物为造孔剂，并将二者的比例合理控制，可使该造孔剂在蓄光陶瓷熔制温度范围内分解，降低成球时陶瓷内部的表面张力，使气孔保持较好的球型度。
与现有技术相比，本发明具有如下有益效果：
1.本发明提供的具有超高亮度可自发光的石英陶瓷材料，经过20min蓄光，可实现720min的持续发光，初始1min强度，>4000mcd/m2；60min，>30mcd/m2。(室外阳光直射20min，日光灯30min，紫外线5min，室温25℃测试)。
2.本发明提供的具有超高亮度的可自发光的石英陶瓷材料，相较于现有的复相蓄光陶瓷材料，前置光提取效率明显提高提升10-30％。
3.本发明提供的提高蓄光陶瓷材料效率的方法，简便有效、过程可控、实验周期短、产品稳定性好。
附图说明
图1为实施例1制备的具有超高亮度的蓄光型复相陶瓷材料的X射线粉末衍射图谱，横坐标为x射线的入射角，纵坐标为衍射强度；
图2为实施例1制备得到的具有超高亮度的蓄光型复相陶瓷材料的扫面电子显微镜图像(SEM)；
图3为实施例1制备得到的具有超高亮度的蓄光型复相陶瓷材料的微区EDS元素含量分布图；
图4为实施例1制备得到了具有超高亮度的蓄光型复相材料与未添加造孔剂的样品发光强度衰减变化图；
图5为具有超高亮度的蓄光型复相陶瓷材料从石英陶瓷材料内部由于散射导致的前置光提取率的光路模型图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明。
以制备100g目标产物，分别称量原料粉体，各原料粉体的纯度均为分析纯及以上，配料表见表1。
表1实施例配料表
编号 1<sup>#</sup> 2<sup>#</sup> 3<sup>#</sup>
石英(10～30目) 55g 53g 50g
石英(50～100目) 25g 27g 29g
石英(150～250目) 15g 10g 6g
造孔剂 0.5g 1g 1.5g
荧光粉添加量 5wt.％ 10wt.％ 15wt.％
SrCO<sub>3</sub> 2.756g 5.512g 8.268g
Al<sub>2</sub>O<sub>3</sub> 2.025g 4.050g 6.075g
Eu<sub>2</sub>O<sub>3</sub> 0.070g 0.140g 0.210g
Dy<sub>2</sub>O<sub>3</sub> 0.148g 0.296g 0.345g
去离子水 12g 15g 17g
实施例1
(1)称量：按照表1中1#所示，分别称量不同粒径的石英、SrCO3、Al2O3、Eu2O3、Dy2O3的原料粉体以及造孔剂；
(2)混料：将步骤(1)所称得的粉体置于装有150g高纯氧化铝球的球磨罐内，同时加入12g去离子水进行球磨混合，球磨转速为160r/min，球磨时间为20h；
(3)成型：将步骤(2)得到的浆料进行真空除泡处理，真空环境-15kpa下除泡30min；然后将除泡后的浆料注入石膏模具，成型得到素坯；
(4)干燥：将步骤(3)得到的素坯静置7h后进行脱模，脱模后将其放置于干燥箱内干燥20h，干燥温度为60℃；
(5)烧结：将步骤(4)干燥后的素坯在还原气氛下进行高温煅烧，煅烧温度为800℃，升温速率为3℃/min，保温时间为3h，随后随炉冷却至室温，即得到所述具有超高亮的蓄光型复相陶瓷材料。
见附图1，本实施例制备的样品的X射线衍射图谱，XRD的测试结果显示，所制备的样品的X射线衍射峰与铝酸锶(JCPDS(#34-0379))的标准卡片相吻合。此外，XRD图谱在20～40的衍射角范围内，呈现非常明显的馒头峰，证明了非晶态二氧化硅的存在。
见附图2，本实施例制备的样品断面的扫面电子显微镜图像，SEM的测试结果显示，所制备的样品内部有气孔的存在，同时也发现长余辉荧光粉的存在。
见附图3，本实施例制备的样品的不同微区的元素种类与含量分析，EDS的测试结果显示，石英玻璃与铝酸锶长余辉荧光粉二者同时存在于所制备的样品中。
见附图4，本实施例制备的样品与未加造孔剂的样品陶瓷发光及余晖时间对比，测试结果显示，添加造孔剂的样品的发光初始强度提高了26.3％。
见附图5，本实施例制备的样品的内部荧光传播的光路示意图，从图中可以看出，气孔散射点的引入可有效改变荧光的传播路径，提高激发光利用率并弱化全反射效应。
实施例2
(1)称量：按照表1中2#所示，分别称量不同粒径的石英、SrCO3、Al2O3、Eu2O3、Dy2O3的原料粉体以及造孔剂；
(2)混料：将步骤(1)所称得的粉体置于装有200g高纯氧化铝球的球磨罐内，同时加入15g去离子水进行球磨混合，球磨转速为180r/min，球磨时间为22h；
(3)成型：将步骤(2)得到的浆料进行真空除泡处理，真空环境-10kpa下除泡40min；然后将除泡后的浆料注入石膏模具，成型得到素坯；
(4)干燥：将步骤(3)得到的素坯静置9h后进行脱模，脱模后将其放置于干燥箱内干燥22h，干燥温度为70℃；
(5)烧结：将步骤(4)的素坯在还原气氛下进行高温煅烧，煅烧温度为1000℃，升温速率为4℃/min，保温时间为4.5h，随后随炉冷却至室温，即得到所述可自发光的石英陶瓷。
经过观测，本实施例2中所制备得到可自发光的石英陶瓷材料的主要结构性能，机械发光光谱与实施例1相似。
实施例3
(1)称量：按照表1中3#所示，分别称量不同粒径的石英、SrCO3、Al2O3、Eu2O3、Dy2O3的原料粉体以及造孔剂；
(2)混料：将步骤(2)所称得的粉体置于装有300g高纯氧化铝球的球磨罐内，同时加入17g去离子水进行球磨混合，球磨转速为300r/min，球磨时间为25h；
(3)成型：将步骤(2)得到的浆料进行真空除泡处理，真空环境-30kpa下除泡50min；然后将除泡后的浆料注入石膏模具，成型得到素坯；
(4)干燥：将步骤(3)得到的素坯静置12h后进行脱模，脱模后将其放置于干燥箱内干燥24h，干燥温度为100℃；
(5)烧结：将步骤(4)的素坯在还原气氛下进行高温煅烧，煅烧温度为1200℃，升温速率为4℃/min，保温时间为6h，随后随炉冷却至室温，即得到所述可自发光的石英陶瓷。
经过观测，本实施例3中所制备得到的可自发光的石英陶瓷材料的主要结构性能，机械发光光谱与实施例1相似。

Claims (7)

1.一种具有超高亮度的蓄光型复相陶瓷材料的制备方法，其特征在于，具体步骤如下：
(1)称量：以原料粉体总质量为100％计，分别称取质量百分比为50％～55％的10～30目的石英原料、25％～29％的50～100目的石英原料、6％～15％的150～250目的石英原料，其余为制备铕、镝共掺的铝酸锶长余辉荧光粉的原料粉体；再称取占原料粉体总质量0.5％～1.5％的造孔剂，所述造孔剂为碳酸氢铵与淀粉按质量比1：3～6组成的混合物；
(2)混料：将步骤(1)称量的粉体原料置于球磨罐内，同时加入磨球和去离子水进行球磨混合；
(3)成型：将步骤(2)球磨后的浆料进行真空除泡处理，然后将除泡后的浆料注入模具中成型，得到素坯；
(4)干燥：将步骤(3)得到的素坯静置7～12小时后进行脱模，然后置于干燥箱内干燥；
(5)烧结：将步骤(4)干燥后的素坯在还原气氛下进行高温煅烧，煅烧温度为800～1200℃，保温时间为3～6h，随后随炉冷却至室温，即得到具有超高亮的蓄光型复相陶瓷材料。
2.根据权利要求1所述的具有超高亮度的蓄光型复相陶瓷材料的制备方法，其特征在于，步骤(1)中，所述制备铕、镝共掺的铝酸锶长余辉荧光粉的原料粉体为SrCO3、Al2O3、Eu2O3和Dy2O3，根据化学式SrAl2O4:Eu2+,Dy3+中各元素的化学计量比称量得到。
3.根据权利要求1所述的具有超高亮度的蓄光型复相陶瓷材料的制备方法，其特征在于，步骤(2)中，所述磨球与原料粉体总质量的质量比为1.5～3：1，所述去离子水的添加量为原料粉体总质量的12％～17％。
4.根据权利要求1所述的具有超高亮度的蓄光型复相陶瓷材料的制备方法，其特征在于，步骤(2)中，所述球磨的转速为160～300r/min，球磨时间为20～25h。
5.根据权利要求1所述的具有超高亮度的蓄光型复相陶瓷材料的制备方法，其特征在于，步骤(3)中，所述真空除泡的真空度为-10～-30kP a，除泡时间为30～50min。
6.根据权利要求1所述的具有超高亮度的蓄光型复相陶瓷材料的制备方法，其特征在于，步骤(4)中，所述干燥温度为60～100℃，干燥时间为15～24h。
7.权利要求1至6任一项所述的制备方法制得的具有超高亮度的蓄光型复相陶瓷材料，其特征在于，所述陶瓷材料中富含微气孔，气孔球型度高，尺寸在100-1000nm范围内。
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