CN110294628A - 发光陶瓷及其制备方法 - Google Patents

发光陶瓷及其制备方法 Download PDF

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CN110294628A
CN110294628A CN201810235810.3A CN201810235810A CN110294628A CN 110294628 A CN110294628 A CN 110294628A CN 201810235810 A CN201810235810 A CN 201810235810A CN 110294628 A CN110294628 A CN 110294628A
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yag
luminescent ceramic
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李乾
胡飞
许颜正
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Shenzhen Appotronics Corp Ltd
Shenzhen Appotronics Technology Co Ltd
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Abstract

一种发光陶瓷及其制备方法，所述发光陶瓷包括Al2O3基质(210)以及均匀分布在Al2O3基质中的Nd:YAG发光中心(220)。本发明通过预先制备Nd:YAG前驱粉体，之后采用真空烧结法、热压/SPS烧结法等工艺将加有助熔剂的Nd:YAG前驱粉体、Al2O3粉末烧结成发光陶瓷，这种发光陶瓷可以与808nm的红色激光半导体搭配，制备出体积小巧、光通量高的红外光源，用于安全监控、军事探测等红外成像领域。

Description

发光陶瓷及其制备方法
技术领域
本发明涉及一种发光陶瓷及其制备方法，属于固体发光材料制造技术领域。
背景技术
为了满足全天候监控的需要，主动红外摄像技术获得了极大关注，经过20多年的发展，产品种类层出不穷，应用领域横跨军民两用，已经形成了一个巨大的市场。红外摄像技术的核心是红外光源，最早的红外光源使用卤素灯+滤光片的技术，卤素灯的最大缺点是体积大、散热不充分且寿命极短，红暴现象严重，因此这种技术已经被淘汰。取代卤素灯的是LED，如同照明市场LED的发展，红外用LED也经历了单颗LED、LED阵列、LED点阵(类似COB)三个阶段。单颗LED的缺点是功率太小且光照不均匀；LED阵列易产生偏心现象，且照不远；LED点阵改善了前述两种方式的缺点，但是在远距离、高功率的要求下表现还是不足。除LED外还有激光红外光源，但当前的激光红外光源还有能量太集中、散斑现象、角度太小、成本高、近距离时的安全性等问题没有得到很好解决。
使用激光激发红外光的光致发光技术，可以使高能量密度的激光集中照射于发光体之上，激发出单点发光的朗伯红外光，这种光的光学扩展量小，易调制，无散斑，强度可远大于LED红外光，安全性高，是未来大功率红外光源的最理想解决方案技术。因此，亟需一种高亮度、高均匀性、长寿命、弱光衰的红外光源。
发明内容
本发明所要解决的技术问题在于针对现有技术的不足，提供一种发光陶瓷及其制备方法，通过预先制备Nd:YAG前驱粉体，之后采用真空烧结法、热压/SPS烧结法等工艺将加有助熔剂的Nd:YAG前驱粉体、Al2O3粉末烧结成发光陶瓷，这种发光陶瓷可以与808nm的红色激光半导体搭配，制备出体积小巧、光通量高的红外光源，用于安全监控、军事探测等红外成像领域。
本发明所要解决的技术问题是通过如下技术方案实现的：
本发明提供一种发光陶瓷，所述发光陶瓷包括Al2O3基质以及均匀分布在Al2O3基质中的Nd:YAG发光中心。
优选地，所述Al2O3的晶粒粒径为0.5μm-20μm，Nd:YAG的晶粒粒径为1μm-30μm。
优选地，所述Al2O3的晶粒粒径为1μm-5μm，所述Nd:YAG的晶粒粒径为5μm-17μm。
优选地，所述Nd:YAG发光中心的组分为Y3Al5O12:Nd。
优选地，所述Nd:YAG发光中心(220)占发光陶瓷总质量的15％-90％。
优选地，所述发光陶瓷还包括BaF2和/或MgO，所述BaF2、MgO的质量分别占所述Al2O3基质的0.01％～3.5％、0.01％～3.0％。
本发明还提供一种发光陶瓷的制备方法，所述制备方法包括：
S1：制备Nd:YAG前驱粉体；
S2：制备含Al2O3粉末的水溶液；
S3：将Nd:YAG前驱粉体与含Al2O3粉末的水溶液混合后干燥造粒获得干粉，所述干粉煅烧后造粒，然后烧结得到发光陶瓷。
优选地，在S1中，按Y3Al5O12:Nd的化学计量比称量Y2O3、Al(OH)3、Nd2O3粉末，并加入BaF2粉末作为助熔剂，以水或乙醇作为载体进行球磨，球磨后的粉料进行煅烧，煅烧产物粉碎后在还原气氛下烧结，烧结产物粉碎后得到Nd：YAG前驱粉体。
优选地，在S2中，配置1wt％-3wt％的聚乙二醇水溶液，将Al2O3粉末与聚乙二醇水溶液混合，并在制得的含Al2O3粉末的聚乙二醇水溶液中加入MgO粉末和BaF2粉末后球磨，其中，MgO粉末、BaF2粉末分别占Al2O3粉末的0.01wt％-3wt％。
优选地，在S2中，按照MgO与Al2O3的质量比为(0.01-3):100的比例，称取Mg(NO3)2·6H2O，配置成浓度为0.01(mol/L)-1(mol/L)的硝酸盐乙醇溶液，加入Al2O3粉末后球磨。
优选地，在S3中，Nd：YAG前驱粉体占总粉体质量的15wt％-90wt％。
综上所述，本发明通过预先制备Nd:YAG前驱粉体，之后采用真空烧结法、热压/SPS烧结法等工艺将Nd:YAG前驱粉体、Al2O3粉末烧结成发光陶瓷，这种发光陶瓷可以与808nm的红色激光半导体搭配，制备出体积小巧、光通量高的红外光源，用于安全监控、军事探测等红外成像领域。
下面结合附图和具体实施例，对本发明的技术方案进行详细地说明。
附图说明
图1为本发明发光陶瓷的SEM图一；
图2为本发明发光陶瓷的SEM图二；
图3为本发明发光陶瓷的结构示意图；
图4为本发明发光陶瓷在激光激发下的发射光谱图。
具体实施方式
图1为本发明发光陶瓷的SEM图一；图2为本发明发光陶瓷的SEM图二；图3为本发明发光陶瓷的结构示意图。如图1至图3所示，本发明提供一种发光陶瓷，所述发光陶瓷包括Al2O3基质210以及均匀分布在Al2O3基质210中的Nd:YAG(Neodymium-doped YttriumAluminium Garnet)发光中心220。图1和图2中的黑色连续相为Al2O3基质210，灰白色的颗粒为Nd:YAG发光中心220。
其中，Al2O3的晶粒粒径为0.5μm-20μm，Nd:YAG的晶粒粒径为1μm-30μm，优选地，所述Al2O3的晶粒粒径为1μm-5μm，所述Nd:YAG的晶粒粒径为5μm-17μm。
所述发光陶瓷可以被500nm-820nm波长的红光激发，特别的，适用于808nm波长的红激光激发，可以发出860-1100nm波长的红外光，特别地，被激发光中1064nm波长的光强度最为显著。图4为本发明发光陶瓷在激光激发下的发射光谱图。如图4所示，得益于4F3/2→4I9/2的能级跃迁，Nd:YAG晶体在808nm时有最大吸收峰，可发出最大发射峰为1064nm波长的红外光，同时散发热量。
目前现有的Nd:YAG陶瓷无论是单晶陶瓷还是多晶陶瓷，其在808nm波长的光激发时，仅陶瓷表面部分晶粒进行了激发，因为其材料和晶体结构属性等多个因素的影响，使得对于纯相陶瓷的Nd：YAG，激发光经过晶界会直接透过而较少发生反射，使得激发光在陶瓷中被反射的机会较少从而光程短，进而激发Nd:YAG的光量少，激发光的光效不高，同时产生的受激光也少。同时，Nd:YAG的热导率不高，纯相的Nd:YAG陶瓷被激发而发光所产生的大量热量，若热量未及时传导散发出去，会导致陶瓷温度上升，容易引起Nd:YAG陶瓷的热衰而降低光转换效率。
而本发明中，作为基质的Al2O3透明陶瓷在800nm-1600nm的近红外区都有非常良好的透光性能，在不会影响光传播的情况下，可将激发光传导至发光陶瓷内部以激发更多的作为发光中心的Nd:YAG陶瓷颗粒，且其热导率可以达到20W/(k·m)-30W/(k·m)，能有效将波长转换过程中产生的热量传导出去，是理想的基质材料。本发明中由Al2O3基质210以及均匀分布在Al2O3基质210中的Nd:YAG发光中心220组成的发光陶瓷，Nd:YAG均匀分散在Al2O3中，增加了相界面，激发光可以在向界面之间发生反射和/或折射；同时，Al2O3的晶格结构及其材料特性也使得在Al2O3的晶界上也会发生较多的反射和/或折射，从而使得入射光被多次导向不同的Nd:YAG进行激发。因此相比纯相陶瓷，入射光在这种发光陶瓷中的光程更长，对入射激发光的吸收也更充分。
其中，所有Nd:YAG发光中心220的质量和占发光陶瓷总质量的15％-90％。当Nd:YAG发光中心含量过低时，发光中心太少，效率不高；当Nd:YAG发光中心含量过高时，基质粘接相氧化铝含量太少，烧结困难，难以形成致密的陶瓷。优选地，在本发明中，Nd:YAG发光中心220的质量占比为40％～60％，此时发光中心数量适中，基质相也易于烧结，发光陶瓷的相对密度易于达到最高，因此发光效率、导热性能、力学性能均达到最优。
优选地，发光陶瓷还包括BaF2和/或MgO，所述BaF2、MgO的质量分别占所述Al2O3基质的0.01％～3.5％、0.01％～3.0％。例如BaF2占Al2O3基质的0.5％，MgO占Al2O3基质的0.4％。
BaF2作为助熔剂，能有效降低发光陶瓷在烧结成型工艺中的温度，从而使Nd:YAG不易进入烧结，避免Nd:YAG颗粒的形貌受到破坏，影响发光效果；MgO的加入，则是为了净化基质氧化铝的晶界，并抑制氧化铝晶粒的异常长大，能使基质相的烧结性能更好，透光性能更强。
本发明还提供一种上述发光陶瓷的制备方法，所述制备方法包括：
S1：制备Nd:YAG前驱粉体；
S2：制备含Al2O3粉末的水溶液；
S3：将Nd:YAG前驱粉体与含Al2O3粉末的水溶液混合后干燥造粒获得干粉，所述干粉煅烧后造粒，然后烧结得到发光陶瓷。
下面结合具体实施例对制备方法进行详细说明。
实施例一
在S1中，按Y3Al5O12:Nd的化学计量比准确称量Y2O3、Al(OH)3、Nd2O3粉末，之后加入粉末总质量0.5wt％的BaF2粉末作为助熔剂，以水或乙醇作为载体，用氧化铝球进行球磨混合24h。
将球磨好的粉料干燥后在研钵上进行研磨细化，在1400℃下煅烧2h，煅烧产物使用研钵粉碎。
将研钵粉碎的粉体放入气氛炉中，在还原气氛(如氮氢气气氛)下，1500℃烧结2h-12h，产物经粉碎、洗涤、烘干、筛分后获得组分为Y3Al5O12:Nd的Nd:YAG前驱粉体，Nd:YAG前驱粉体的颗粒D50(50％通过粒径)的范围为1μm-30μm，优选为5μm-17μm。
需要说明的是，制备Nd:YAG前驱粉体除了可以采用上述固相法外还可以采用共沉淀法。
在S2中，称取一定数量的高纯Al2O3粉末，粉末粒径为0.05μm-1μm，优选为0.06μm-0.2μm，配置1wt％-3wt％的PEG(聚乙二醇)水溶液，将Al2O3纳米粉末与PEG水溶液混合。优选地，为了破坏Al2O3粉末颗粒之间的二次团聚，让Al2O3粉末在溶液中尽可能地分散，将Al2O3溶液超声1h-3h后备用。
称取适量的高纯MgO、BaF2粉末作为助熔剂，将这两种粉末添加入含Al2O3粉末的PEG水溶液中。所述MgO、BaF2粉末分别占Al2O3粉末质量的0.01wt％-3wt％，优选地，MgO、BaF2粉末的质量一样，均占Al2O3粉末质量的0.05wt％-0.4wt％。之后将上述加入MgO、BaF2粉末的Al2O3溶液装入聚四氟乙烯球磨罐中，用超低磨失率的氧化锆球进行球磨，球磨时间为1h-72h，优选为24h-36h。
在S3中，将S1中制备的Nd：YAG前驱粉体，装入上述聚四氟乙烯球磨罐，与球磨后的含有MgO、BaF2的Al2O3溶液混合后，低速进行再次球磨，球磨时间为10min-120min，优选为40min。其中，Nd：YAG前驱粉体占总粉体质量的15wt％-90wt％。
球磨结束后，所得浆料使用喷雾干燥设备干燥造粒，获得干粉。
所述干粉在马弗炉中进行500℃-650℃的煅烧，除去粉末中的有机成分，时间为1h-10h。煅烧后的粉末过80目、150目、200目筛造粒，得到高流动性的原料粉。
称取适量原料粉末装入石墨模具中，在5MPa-15MPa压强下进行预压制，然后将石墨模具放入SPS放电等离子烧结炉内，在真空或氩气保护气氛下烧结，烧结温度1250℃-1650℃，保温0.5h-6h，烧结压力为30MPa-200MPa，优选为40MPa-100MPa。烧结完成后，卸除压力并随炉冷却。最后获得发光陶瓷。
需要补充的是，本发明并不限制上述工艺参数(温度、压力、时间等)，本领域技术人员可以根据实际需要对上述工艺参数进行调整，另外，除SPS和热压烧结外，还可以使用真空烧结炉进行烧结。
对本实施例中所制备的发光陶瓷进行光效测试，本发明中的光效特指每瓦808nm激光所激发的1000nm-1100nm红外光，其光效达62lm/W。
实施例二
本实施例与实施例一相比，其S1和S2工序相同，不同处在于，在S2中，在称取一定数量的粉末粒径为0.05μm-1μm(优选为0.06μm-0.2μm)的高纯Al2O3粉末后，按照MgO与Al2O3的质量比为(0.01-3):100的比例，称取一定数量的Mg(NO3)2·6H2O，配置成浓度为0.01(mol/L)-1(mol/L)的硝酸盐乙醇溶液，加入Al2O3粉末后搅拌。
之后将上述加入Al2O3粉末的硝酸盐乙醇溶液装入聚四氟乙烯球磨罐中，用超低磨失率的氧化锆球进行球磨，球磨时间为1h-72h，优选为24h-36h。
本实施例与实施例一相比，用Mg(NO3)2·6H2O制备的硝酸盐乙醇溶液来代替PEG(聚乙二醇)水溶液以及MgO、BaF2粉末，制备方法较为简单，且在S3中干粉在煅烧时，Mg(NO3)2·6H2O能够分解为MgO，其同样具有助熔剂的作用。
对本实施例中所制备的发光陶瓷进行光效测试，其光效达66lm/W。
综上所述，本发明预先制备Nd:YAG前驱粉体，之后采用真空烧结法、热压/SPS烧结法等工艺将加有助熔剂的Nd:YAG前驱粉体、Al2O3粉末烧结成发光陶瓷，这种发光陶瓷可以与808nm的红色激光半导体搭配，制备出体积小巧、光通量高的红外光源，用于安全监控、军事探测等红外成像领域。

Claims (10)

1.一种发光陶瓷，其特征在于，所述发光陶瓷包括Al2O3基质(210)以及均匀分布在Al2O3基质中的Nd:YAG发光中心(220)。
2.如权利要求1所述的发光陶瓷，其特征在于，所述Al2O3的晶粒粒径为0.5μm-20μm，Nd:YAG的晶粒粒径为1μm-30μm；优选地，所述Al2O3的晶粒粒径为1μm-5μm，所述Nd:YAG的晶粒粒径为5μm-17μm。
3.如权利要求1所述的发光陶瓷，其特征在于，所述Nd:YAG发光中心(220)的组分为Y3Al5O12:Nd。
4.如权利要求1所述的发光陶瓷，其特征在于，所述Nd:YAG发光中心(220)占发光陶瓷总质量的15％-90％。
5.如权利要求1所述的发光陶瓷，其特征在于，所述发光陶瓷还包括BaF2和/或MgO，所述BaF2、MgO的质量分别占所述Al2O3基质的0.01％～3.5％、0.01％～3.0％。
6.一种发光陶瓷的制备方法，其特征在于，所述制备方法包括：
S1：制备Nd:YAG前驱粉体；
S2：制备含Al2O3粉末的水溶液；
S3：将Nd:YAG前驱粉体与含Al2O3粉末的水溶液混合后干燥造粒获得干粉，所述干粉煅烧后造粒，然后烧结得到发光陶瓷。
7.如权利要求6所述的制备方法，其特征在于，在S1中，按Y3Al5O12:Nd的化学计量比称量Y2O3、Al(OH)3、Nd2O3粉末，并加入BaF2粉末作为助熔剂，以水或乙醇作为载体进行球磨，球磨后的粉料进行煅烧，煅烧产物粉碎后在还原气氛下烧结，烧结产物粉碎后得到Nd：YAG前驱粉体。
8.如权利要求6所述的制备方法，其特征在于，在S2中，配置1wt％-3wt％的聚乙二醇水溶液，将Al2O3粉末与聚乙二醇水溶液混合，并在制得的含Al2O3粉末的聚乙二醇水溶液中加入MgO粉末和BaF2粉末后球磨，其中，MgO粉末、BaF2粉末分别占Al2O3粉末的0.01wt％-3wt％。
9.如权利要求6所述的制备方法，其特征在于，在S2中，按照MgO与Al2O3的质量比为(0.01-3):100的比例，称取Mg(NO3)2·6H2O，配置成浓度为0.01(mol/L)-1(mol/L)的硝酸盐乙醇溶液，加入Al2O3粉末后球磨。
10.如权利要求6至9任一项所述的制备方法，其特征在于，在S3中，Nd：YAG前驱粉体占总粉体质量的15wt％-90wt％。
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