CN115215651A - 一种稀土掺杂氧化镥基复合发光陶瓷的制备方法 - Google Patents
一种稀土掺杂氧化镥基复合发光陶瓷的制备方法 Download PDFInfo
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- 229910003443 lutetium oxide Inorganic materials 0.000 title claims abstract description 27
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 24
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
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Abstract
本发明提供了一种稀土掺杂氧化镥基复合发光陶瓷的制备方法;包括:步骤1,原料中加入烧结助剂混合;步骤2,研磨均匀,使混合后的材料充分分散;步骤3,放入真空热压烧结炉内,调整位置;步骤4,热压烧结,保温;步骤5,随炉降温,脱模,即可。本发明方法对原料的粒径没有要求;本发明采用真空热压烧结技术,获得了发光性能优异、透过率可调的稀土掺杂GLO复合发光陶瓷。本发明方法无需合成前驱粉体,无需成型等工艺步骤;而是直接将原料按照产物的化学计量比均匀混合,放置在热压炉中直接烧结,即可;本发明方法速度快、成本低。本发明方法合成过程中的高压和真空作用,陶瓷可以实现多相复合,且在较低的温度下、较短的时间内就可以获得。
Description
技术领域
本发明属于光电功能材料技术领域;尤其涉及一种稀土掺杂氧化镥基复合发光陶瓷的制备方法。
背景技术
随着人类科技的进步,人类对于新型光学功能材料的需求也越来越大。稀土激活氧化镥基发光材料具有发光效率高、物理化学性能优异的特点,在照明、场发射显示、等离子显示、白光LED、高能粒子探测等领域具有广阔的前景和重要的应用价值。
氧化镥基陶瓷材料具有极高的密度(9.42g/cm3左右),对各类射线(x射线、γ射线)的阻止本领异乎寻常的高,即光吸收系数高。在导热性能方面,Lu2O3基体材料的热导率(12.5w/mk)比当前广泛使用的YAG基激光材料(11W/mk)略高,具有很强的抗热震性能。Lu2O3具有立方晶系结构,便于制备多晶透明材料,是一种极具应用前景的发光基质材料。
然而,光学陶瓷制备工艺一般都较为复杂,首先需要制备超细前驱粉体,然后成型、预烧、再在高温真空条件下长时间烧结,最后还需要退火,工艺极其复杂,过程非常耗时、耗能。针对制备工艺的研究如下,波兰科学家Zych等人采用燃烧法制备出Eu3+:Lu2O3纳米粉体和微米级的烧结体,研究了前驱体对烧结性能的影响。2006年,陈等采用湿化学法合成前驱体,然后采用气氛烧结法(H2)成功制备出高光学质量的Eu3+:Lu2O3透明陶瓷,经其研究发现陶瓷在600-800nm可以达到80.3%的透过率。2010年,Trojan-Piegza等人分别在空气中、真空及N2-H2气氛中制备了Eu3+:Lu2O3闪烁陶瓷,研究了不同的陶瓷的余辉性能,研究表明,当Eu离子浓度较小时,陶瓷有着较强的且时间较长的余辉。2013年,Dulina等研究了前驱体的化学组成对Eu3+:Lu2O3陶瓷粉体的影响,通过调节沉淀剂/Lu3+的比值,采用的共沉淀法控合成了平均晶粒尺寸为40nm的前驱体,利用真空烧结技术制备了在611nm波长处41%透过率的5at%Eu3+:Lu2O3透明陶瓷。2015年,Ma等采用尿素为沉淀剂、均相沉淀法合成单分散球形颗粒的陶瓷粉体,采用1700℃、5h真空烧结制备Eu3+:Lu2O3(5mol%)透明陶瓷,在800nm处可以达到61%的透过率。可见制备氧化镥陶瓷的工艺复杂。基于此,本发明提出了一种稀土掺杂氧化镥基复合发光陶瓷的制备技术,该技术无需合成前驱粉体,无需成型,而是直接将原料按照产物的化学计量比均匀混合,放置在热压炉中利用石墨模具直接烧结。由于合成过程中的高压和真空作用,陶瓷可以实现多相复合,且在较低的温度下、较短的时间内就可以获得。
发明内容
本发明的目的是提供了一种稀土掺杂氧化镥基复合发光陶瓷的制备方法。
本发明是通过以下技术方案实现的:
本发明涉及一种稀土掺杂氧化镥基复合发光陶瓷的制备方法,包括以下步骤:
步骤1,选用Lu2O3(99.99%),Gd2O3(99.99%),Eu2O3(99.99%)为原料、烧结助剂MgO(99.99%),按照(Lu1-xGdx)2O3:yEu3+的化学计量比分别计算各原料的量,其中x可以从0到1连续可调,y为稀土发光离子的掺杂量,y的取值为0.01-5at%,其烧结助剂的含量为0.1-5wt%。
所述原料中Lu2O3,Gd2O3,Eu2O3三者的用量比为:51-70:48-25:0.001-5。
优选地,所述原料中Lu2O3,Gd2O3,Eu2O3三者的用量比为:51-60:48-35:0.001-5。
优选地,所述原料中Lu2O3,Gd2O3,Eu2O3三者的用量比为:55-60:48-40:0.001-3。
步骤2,采用精密电子天平称取相应量的Lu2O312.377g(99.99%),Gd2O37.591g(99.99%),Eu2O3(99.99%)0.021g、MgO(99.99%)0.003g原料,将称取的原料放入玛瑙研钵内;用玛瑙棒仔细研磨均匀,使混合后的材料充分分散;
步骤3,将混合均匀的原料放入预处理后的石墨模具中,然后放入真空热压烧结炉内,合理调整位置;
步骤4,开始烧结,设置烧结温度为1400~1700℃,保温时间为2~10h,压力为0~200Mpa;
步骤5,烧结完成后,随炉降温,将取出模具,脱模,即可获得发光陶瓷样品。
本发明具有以下优点:
(1)本发明选用Lu2O3(99.99%),Gd2O3(99.99%),Eu2O3(99.99%)等为原料,合成方法对原料的粒径没有要求(微纳米尺寸均可),选取烧结助剂MgO、SiO2、CaO、正硅酸乙酯等;本发明通过在热压炉中利用石墨模具成型和烧结,在高温过程中边烧结边热压,减少了前期粉体制备的复杂工艺。,本发明工艺参数如下:控制升温速率≤10℃/min,1400~1700℃下保温2~10h,压力为0-100MPa,真空度为1×10-1~1×10-3Pa,最终获得了发光性能优异、透过率可调的稀土掺杂GLO复合发光陶瓷,本发明方法速度快、成本低。
(2)本发明提出了一种稀土掺杂氧化镥基复合发光陶瓷的制备方法,无需合成前驱粉体,无需成型等工艺步骤;而是直接将原料按照产物的化学计量比均匀混合,放置在热压炉中直接烧结,即可制备得到最终的复合发光陶瓷;本发明方法合成过程中的高压和真空作用,陶瓷可以实现多相复合,且在较低的温度下、较短的时间内就可以获得。
附图说明
图1是制备稀土掺杂GLO发光陶瓷的工艺流程图;
图2是不同Gd3+含量GLO样品的XRD图;
图3是不同Eu3+含量GLO样品的XRD图;
图4是不同Gd3+含量GLO样品的发射光谱图(5at%Eu3+);
图5是不同Gd3+含量GLO样品的发射光谱图(7at%Eu3+)。
图6是本发明方法制备得到的稀土掺杂氧化镥基复合发光陶瓷的样品图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。应当指出的是,以下的实施实例只是对本发明的进一步说明,但本发明的保护范围并不限于以下实施例。
实施例1
本实施例涉及一种稀土掺杂氧化镥基复合发光陶瓷的制备方法,见图1所示,步骤如下:
(1)以Lu2O3,Gd2O3,Eu2O3、MgO和正硅酸乙酯原料,其中,固定Eu3+离子含量为5at%和7at%,制备不同Gd3+离子的含量的(Lu1-xGdx)2O3:Eu3+(x=0、0.1、0.3、0.5、0.7、0.9)陶瓷,其中,烧结助剂MgO为产物质量的0.1wt%,正硅酸乙酯为0.4wt%。
(2)按照制备5g产物,采用精密电子天平称取相应量的Lu2O3,Gd2O3,Eu2O3、MgO和正硅酸乙酯,将称取的原料放入玛瑙研钵内。
(3)将称取的原料倒入玛瑙研钵内,用玛瑙棒仔细研磨30min,是粉体原料混合均匀。
(4)研磨后,将混合粉末放入预先涂覆Si3N4涂层的石墨模具内,保证粉体均匀分布,准备烧结。
(5)将处理好的模具放入真空热压烧结炉内,以5℃/min的升温速率从室温加热到1350℃,烧结2h;最后,然后在升温到1600℃,保温6h,在第二段升温时,开始加压,压力为20MP,在保温结束前1h停止加压,在此过程中,真空系统一直工作,升温结束后的真空度为102Pa,最后,随炉降温至室温,获得样品。
图2为5at%Eu3+离子掺杂不同Gd3+离子浓度GLO的样品XRD图,表明合成GLO陶瓷,当Gd3+离子浓度小时(0.5以下)为Lu2O3相,当Gd3+离子浓度大时为Gd2O3相为主,两者相非常相似,且衍射峰尖锐,强度高,结晶度好。
图3和图4分别为5at%和7at%Eu3+离子掺杂不同Gd3+离子浓度GLO的样品发光光谱图,可以看出不同Eu3+离子掺杂浓度,在不同基质中样品的发射峰位基本一致,均为Eu3+离子的典型特征发射,Eu3+离子掺杂浓度大时,发光强度高,Gd3+离子为0.5时,发光强度最强。
实施例2
本实施例涉及一种稀土掺杂氧化镥基复合发光陶瓷的制备方法,见图1所示,步骤如下:
(1)选用Lu2O3(99.99%),Gd2O3(99.99%),Eu2O3(99.99%)、MgO(99.99%)等为原料,按照(Lu0.5Gd0.5)2O3:yEu3+的化学计量比分别计算各原料的量,其中,y为稀土发光离子的掺杂量,y的取值为1-9at%,MgO为烧结助剂,其含量为0.3wt%。
(2)按照制备5g产物,采用精密电子天平称取相应量的Lu2O3,Gd2O3,Eu2O3、MgO,将称取的原料放入玛瑙研钵内。
(3)将称取的原料倒入球磨罐内,加入适量的玛瑙球,在100转/min的转速下,球磨300min,将原料混合均匀。
(4)研磨后,将混合粉末放入预先涂覆SiC涂层的石墨模具内,保证粉体均匀分布,准备烧结。
(5)将处理好的模具放入真空热压烧结炉内,以5℃/min的升温速率从室温加热到1350℃,烧结2h;最后,然后在升温到1650℃,保温8h,在第二段升温时,开始加压,压力为10MP,在保温结束前1h停止加压,在此过程中,真空系统一直工作,升温结束后的真空度为102Pa,最后,随炉降温至室温,获得样品。
图5为合成不同Eu3+离子掺杂浓度(Lu0.5Gd0.5)2O3:yEu3+陶瓷样品的XRD图。Eu3+离子的掺杂并不会改变产物晶体结构。
图6为本发明方法制备得到的稀土掺杂氧化镥基复合发光陶瓷的样品图。
实施例3
本实施例涉及一种稀土掺杂氧化镥基复合发光陶瓷的制备方法,包括以下步骤:
步骤1,选用Lu2O3(99.99%),Gd2O3(99.99%),Eu2O3(99.99%)为原料、烧结助剂MgO(99.99%),按照(Lu1-xGdx)2O3:yEu3+的化学计量比分别计算各原料的量,其中x可以从0到1连续可调,y为稀土发光离子的掺杂量,y的取值为0.01-5at%,其烧结助剂的含量为3wt%。
所述原料中Lu2O3,Gd2O3,Eu2O3三者的用量比为:55:45:0.001。
步骤2,采用精密电子天平按比例称取:Lu2O3(99.99%),Gd2O3(99.99%),Eu2O3(99.99%)、MgO(99.99%)原料,将称取的原料放入玛瑙研钵内;用玛瑙棒仔细研磨均匀,使混合后的材料充分分散;
步骤3,将混合均匀的原料放入预处理后的石墨模具中,然后放入真空热压烧结炉内,合理调整位置;
步骤4,开始烧结,设置烧结温度为1400~1700℃,保温时间为2~10h,压力为0~200Mpa;
步骤5,烧结完成后,随炉降温,将取出模具,脱模,即可获得发光陶瓷样品。
实施例4
本实施例涉及一种稀土掺杂氧化镥基复合发光陶瓷的制备方法,包括以下步骤:
步骤1,选用Lu2O3(99.99%),Gd2O3(99.99%),Eu2O3(99.99%)为原料、烧结助剂MgO(99.99%),按照(Lu1-xGdx)2O3:yEu3+的化学计量比分别计算各原料的量,其中x可以从0到1连续可调,y为稀土发光离子的掺杂量,y的取值为0.01-5at%,其烧结助剂的含量为5wt%。
所述原料中Lu2O3,Gd2O3,Eu2O3三者的用量比为:60:35:5。
步骤2,采用精密电子天平按比例称取:Lu2O3(99.99%),Gd2O3(99.99%),Eu2O3(99.99%)、MgO(99.99%)原料,将称取的原料放入玛瑙研钵内;用玛瑙棒仔细研磨均匀,使混合后的材料充分分散;
步骤3,将混合均匀的原料放入预处理后的石墨模具中,然后放入真空热压烧结炉内,合理调整位置;
步骤4,开始烧结,设置烧结温度为1400~1700℃,保温时间为2~10h,压力为0-200Mpa;
步骤5,烧结完成后,随炉降温,将取出模具,脱模,即可获得发光陶瓷样品。
实施例5
本实施例涉及一种稀土掺杂氧化镥基复合发光陶瓷的制备方法,包括以下步骤:
步骤1,选用Lu2O3(99.99%),Gd2O3(99.99%),Eu2O3(99.99%)为原料、烧结助剂MgO(99.99%),按照(Lu1-xGdx)2O3:yEu3+的化学计量比分别计算各原料的量,其中x可以从0到1连续可调,y为稀土发光离子的掺杂量,y的取值为0.01-5at%,其烧结助剂的含量为0.5%。
所述原料中Lu2O3,Gd2O3,Eu2O3三者的用量比为:51:25:0.001。
步骤2,采用精密电子天平按比例称取:Lu2O3(99.99%),Gd2O3(99.99%),Eu2O3(99.99%)、MgO(99.99%)原料,将称取的原料放入玛瑙研钵内;用玛瑙棒仔细研磨均匀,使混合后的材料充分分散;
步骤3,将混合均匀的原料放入预处理后的石墨模具中,然后放入真空热压烧结炉内,合理调整位置;
步骤4,开始烧结,设置烧结温度为1400~1700℃,保温时间为2~10h,压力为0~200Mpa;
步骤5,烧结完成后,随炉降温,将取出模具,脱模,即可获得发光陶瓷样品。
本发明选用Lu2O3(99.99%),Gd2O3(99.99%),Eu2O3(99.99%)为原料,选MgO、SiO2、CaO、正硅酸乙酯为烧结助剂,经过合成方法处理;该方法对原料的粒径没有要求(微纳米尺寸均可);本发明采用真空热压烧结技术,控制升温速率≤10℃/min,在以下条件:1400~1700℃下保温2~10h,压力为0-100MPa,真空度为1×10-1~1×10-3Pa,获得了发光性能优异、透过率可调的稀土掺杂GLO复合发光陶瓷,本发明方法速度快、成本低。本发明方法无需合成前驱粉体,无需成型等工艺步骤;而是直接将原料按照产物的化学计量比均匀混合,放置在热压炉中直接烧结,即可制备得到最终的复合发光陶瓷;本发明方法合成过程中的高压和真空作用,陶瓷可以实现多相复合,且在较低的温度下、较短的时间内就可以获得。
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变形或修改,这并不影响本发明的实质。
Claims (10)
1.一种稀土掺杂氧化镥基复合发光陶瓷的制备方法,其特征在于,包括以下步骤:
步骤1,选Lu2O3,Gd2O3,Eu2O3为原料,加入烧结助剂混合;
步骤2,研磨均匀,使混合后的材料充分分散;
步骤3,放入预处理后的石墨模具中,然后放入真空热压烧结炉内,调整位置;
步骤4,热压烧结,保温;
步骤5,待烧结完成后,随炉降温,将取出模具,脱模,即可获得发光陶瓷样品。
2.如权利要求1所述的稀土掺杂氧化镥基复合发光陶瓷的制备方法,其特征在于,所述原料中Lu2O3,Gd2O3,Eu2O3三者的用量比为:51-70:48-25:0.001-5。
3.如权利要求1所述的稀土掺杂氧化镥基复合发光陶瓷的制备方法,其特征在于,步骤1中,所述烧结助剂为MgO、SiO2、CaO、正硅酸乙酯中的一种或多种混合。
4.如权利要求1所述的稀土掺杂氧化镥基复合发光陶瓷的制备方法,其特征在于,步骤1中,所述烧结助剂的用量占产物质量的0.01~5wt%。
5.如权利要求1所述的稀土掺杂氧化镥基复合发光陶瓷的制备方法,其特征在于,步骤2中,所述研磨为玛瑙研钵研磨或球磨。
6.如权利要求1所述的稀土掺杂氧化镥基复合发光陶瓷的制备方法,其特征在于,步骤2中,所述研磨的时间为10~60min。
7.如权利要求1所述的稀土掺杂氧化镥基复合发光陶瓷的制备方法,其特征在于,步骤3中,所述预处理后的石墨模具为涂覆Si3N4涂层的石墨模具。
8.如权利要求1所述的稀土掺杂氧化镥基复合发光陶瓷的制备方法,其特征在于,步骤4中,所述烧结的温度为1400~1700℃。
9.如权利要求1所述的稀土掺杂氧化镥基复合发光陶瓷的制备方法,其特征在于,步骤4中,所述保温时间为2~10h。
10.如权利要求1所述的稀土掺杂氧化镥基复合发光陶瓷的制备方法,其特征在于,步骤4中,所述热压烧结的压力为0-200Mpa,真空度为1×10-1~1×10-3Pa。
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