CN107338053B - 有余辉的磷光复合材料 - Google Patents

有余辉的磷光复合材料 Download PDF

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CN107338053B
CN107338053B CN201710591320.2A CN201710591320A CN107338053B CN 107338053 B CN107338053 B CN 107338053B CN 201710591320 A CN201710591320 A CN 201710591320A CN 107338053 B CN107338053 B CN 107338053B
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phase
ceramic composite
metal oxide
afterglow
content
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CN107338053A (zh
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D·伯纳
R·吉罗德
O·普杰尔
I·里戈蒂
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Rolex SA
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Rolex SA
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Abstract

本发明涉及一种有余辉的磷光陶瓷复合材料，其是包含如下两个以上的相的烧结致密体：由至少一种金属氧化物组成的第一相以及由含至少一种经还原的氧化态的活化元素的金属氧化物组成的第二相。本发明还涉及一种用于制备前述权利要求中任一项所限定的磷光陶瓷复合材料的方法，所述方法包括以下步骤：制备金属氧化物和磷光体的混合物；由所述混合物制造生坯；以及将所述生坯在还原性气氛中热处理。

Description

有余辉的磷光复合材料
本申请是2013年11月7日提交的发明名称为“有余辉的磷光复合材料”的第201310548190.6号发明专利申请的分案申请。
技术领域
本发明涉及一种陶瓷复合材料，其呈现高的机械强度并能够呈现有余辉的磷光(persistent phosphorescence)，以及涉及一种制备所述陶瓷复合材料的方法。
背景技术
二氧化锆(或氧化锆，ZrO2)是研究最多的陶瓷材料之一。ZrO2在室温下具有单斜晶结构并在高温下转变为四方结构和立方结构。由立方至四方至单斜变换所产生的体积膨胀引起较大的应力，且这些应力导致ZrO2在从高温冷却时破裂。当氧化锆与其他氧化物掺混时，所述四方相和/或立方相是稳定的。有效的掺杂物包括氧化镁(MgO)、氧化钇(Y2O3，三氧化二钇)、氧化钙(CaO)以及氧化铈(Ce2O3)。
氧化锆的相“稳定”状态通常更有用。在加热时，氧化锆会经历破坏性相变。通过加入例如少量三氧化二钇，所述相变会最小化，且得到的材料具有优异的热性能、机械性能和电性能。在某些情况下，所述四方相可为亚稳态的。如果存在足量的亚稳态的四方相，则由裂纹尖端的应力集中所放大的外加应力可导致所述四方相转变为单斜相，伴随着相应的体积膨胀。然后，该相转变可将裂纹压缩，延迟其生长，并增强机械性能。该机制已知为相变增韧(transformation toughening)，其显著地增加了由稳定化的氧化锆制成的产品的可靠性和使用寿命。
Drennan和Hanninck(J.A.Ceram.Soc.1986；69(7):541-546)已描述了加入SrO可有效地抵消SiO2污染物在用氧化镁部分稳定的氧化锆中的不利作用。似乎所述效果通过形成包含Si和Sr的玻璃相而获得，所述玻璃相在烧结期间从大部分陶瓷中产生。
Cutler和Virkar(J.A.Ceram.Soc.1991；74(1):179-186)已示出了将SrO和Al2O3加入到掺杂Ce的氧化锆中通过形成铝酸锶片晶(SrAl12O19)而引起氧化锆的机械增强。这使得可制备具有良好硬度和强度的坚韧Ce-氧化锆。还已知当将适合的稀土掺杂物纳入该材料中时，SrAl12O19表现出有余辉的磷光特性。但是，由Cutler和Virkar描述的铝酸锶相无磷光性，这大概是因为Ce没有掺入铝酸锶相中且氧化态不是非活性Ce4+态。
一种用于光转换应用的复合陶瓷材料记载于EP 1 588 991 A1中，其中一个相为荧光相。该文献中的实例集中于Al2O3和掺杂Ce的Y3Al5O12的复合物。该材料通过将基础材料混合，然后在1900-2000℃下于真空中融合而得到，不进行任何其他热处理。已记载该材料可将430至480nm的蓝光(例如由蓝色LED发射的光)转换为“白”光。为此，该材料传输一部分所述发射的蓝光，而另一部分发射的蓝光通过Y3Al5O12:Ce相转换为黄光(围绕530nm的宽的发射光谱)。所得到的呈现白光的颜色可通过改变材料的厚度来调整。
文献WO 2006/097876 A1记载了一种多晶陶瓷材料，其包含一种荧光材料。理想地，所述陶瓷为氧化铝且所述磷光体(phosphor)为掺杂Ce的YAG(例如Y3Al5O12:Ce3+)。所述陶瓷材料旨在将由LED发射的一部分蓝光转换为黄光，从而获得白光。该材料通过将氧化铝和磷光体粉末在浆液中混合，然后进行冲压和HIP烧结而获得。该材料通常包含80至99.99体积％的氧化铝和0.01至20体积％的磷光体。
用于光转换的其他陶瓷复合物记载于WO 2008/096301 A1，其中发光相和非发光相均包含Si和N。该申请具体公开了BaSi7N和(Ba,Sr)2Si5-xAlxN8-xOx:Eu(通过在还原性气氛中烧结，随后在酸性溶液中洗涤获得)的实现，将两种组分混合并在1550℃和80MPa下进行HIP热处理，任选随后在N2下于1300℃下进行热处理。
WO 2011/094404 A1中记载了一种用于光转换的陶瓷，其具有含控制良好的尺寸和形状的孔的YAG:Ce的荧光相。所述孔的形成通过热处理进行，由此成孔添加剂被除去或烧尽。该方法包括：第一步通过在空气中在通常1150℃下加热来脱脂(debinding)，随后的第二步在湿氢气气氛中在1700-1825℃下烧结。通过该方法得到了一种具有高度透明性或半透明性的材料。
发明内容
没有公开一种陶瓷材料，特别是基于氧化锆的材料，其包含有余辉的磷光相，具体而言包含在被激发后数小时仍发射显著光强度的有余辉的磷光相。在不同的技术领域中，对得到呈现高机械稳定性且同时呈现余辉发光性的材料存在兴趣。例如，在用于手表或指示器、或用于例如安全应用的发光涂料或颜料的应用中需要有余辉的磷光效应。
本发明的一个目的是避免现有技术的缺点。具体而言，本发明的一个目的是提供一种陶瓷复合材料，其呈现机械强度且能够呈现有余辉的磷光。
本发明的另一个目的是提供一种获得呈现机械强度且能够呈现有余辉的磷光的陶瓷复合材料的方法。
附图说明
图1.包含不同铝酸锶相以及稀土活化元素的本发明磷光材料的发光强度Lv随时间t的变化。
图2.分别用标准和超细粒度测定的磷光材料实现的本发明陶瓷复合材料的两个样品的微结构。
图3.初始磷光体的颗粒尺寸对本发明的磷光材料的发光性能的影响。
图4.不进行洗涤步骤和进行洗涤步骤的磷光材料实现的本发明的磷光复合材料的两个样品的微结构。
图5.洗涤步骤以及处理温度对本发明的磷光材料的发光性能的影响。
图6.磷光体浓度对本发明的磷光材料的发光性能的影响。
图7.磷光体浓度对本发明的磷光材料的发光性能的影响。
图8.本发明的磷光材料与纯磷光体样品的发光性能的比较。
具体实施方式
首先，描述有余辉的磷光陶瓷复合材料。
在本发明的上下文中，“有余辉的磷光材料”意指一种固体发光材料，其在激发辐射停止后表现出光发射，余辉大约为几分钟至几小时。所述材料包括——但不一定限于——表现出相当于超过500分钟的余辉持续时间的长磷光或长余辉的固体发光材料。所述持续时间指的是余辉降至0.3mCd/m2亮度——其为人眼的感光下限——所花费的时间(参见，例如“Phosphor Handbook”,S.Shionoya and W.M.Yen,编,CRC Press 1999,第12章)。
所述有余辉的磷光陶瓷复合材料为致密体。所述有余辉的磷光陶瓷复合材料的致密特性提供想要的增强的磷光性能以及有利的机械特性。关于“致密”体的理解将在下文中描述。为获得所述有余辉的磷光陶瓷复合材料的致密特征，所述制备包括产生致密体的致密化步骤。所述致密化步骤的方式将在下文中于本发明方法的上下文中描述。
重要的是致密体在其制备过程中已被烧结，这是因为不进行合适方式的烧结，则本发明想要的效果——特别是有余辉的磷光效果——无法实现。烧结或热处理的合适方式将在下文中于本发明方法的上下文中描述。
所述烧结的固化体包括两个以上的相，特别是两个以上的结晶相。第一相——通常是以最高重量含量存在的相——是机械特性的基础，而第二相负责所述陶瓷复合材料的磷光性且显示出通常称作磷光体的组成类别。所述有余辉的磷光陶瓷复合材料是一种复合材料。在本发明的上下文中，“复合材料”是整体复合物，这意指所述两个以上的相在致密体的不同部分中不分离。例如，第二相不在第一相上形成薄层或涂层。
所述第一相由至少一种金属氧化物组成。可选择任意呈现高度机械稳定性的金属氧化物。因此，所述金属氧化物可选自氧化铝、氧化锆、氧化镁、二氧化硅、二氧化钛、氧化钡、氧化铍、氧化钙和三氧化二铬。
在用于第一相的可能有用的材料中，优选氧化锆。氧化锆高度稳定且呈现优异的机械特性。所述材料本身是可靠的，但是根据一个优选的实施方案，其以稳定形式使用。该稳定化作用可通过存在特定量的其他材料来实现。所述其他存在的稳定材料可选自源于铈、镁和钇的材料。
可使用掺杂Ce的氧化锆，但在还原性气氛中处理后会得到橙色的氧化锆。
也可使用掺杂Mg的氧化锆，但是必须在所述复合物的日间颜色、发光性能和机械特性之间进行折衷。
在本发明的上下文中，已证明三氧化二钇在氧化锆中作为掺杂物存在导致高度的机械稳性且所述掺杂三氧化二钇的氧化锆是第一相的优选材料。用三氧化二钇稳定的氧化锆由例如公司Tosoh Corporation制得且特别适用于制备本发明的陶瓷复合材料的常见产品为3mol％三氧化二钇稳定的四方氧化锆。从发明人的角度来看，掺杂三氧化二钇的氧化锆提供在以下方面的最佳潜能：日间颜色、磷光体相的优异余辉以及非常好的机械特性。
还可使用氧化铝作为另一个优选种类代替氧化锆或代替优选实施方案的三氧化二钇化的氧化锆，但是这可能不太成功，因为在烧结过程中可形成非发光相。此外，在制备本发明的磷光陶瓷复合材料中必须进行的热处理必须在比用于氧化锆的更高温度下进行。
氧化锆还可以掺杂的形式使用和/或加入颜料来改变其日间颜色，条件是氧化锆已被稳定。
所述陶瓷复合材料的第二相由金属氧化物组成，所述金属氧化物包含至少一种被还原的氧化态的活化元素。
作为所述金属氧化物材料，可使用Ca、Ba、Sr和/或Mg-铝酸盐、或Ca、Ba、Sr和/或Mg硅酸盐、或Ca和/或Sr硅铝酸盐。在本发明的上下文中，优选的金属氧化物材料为铝酸锶。作为这类铝酸锶，可使用例如SrAl2O4、SrAl4O7、SrAl12O19或Sr4Al14O25，其中最优选的种类为Sr4Al14O25。Sr4Al14O25的优势之一是其在水中不溶的情况，这在制备陶瓷复合材料的方法中可以是一个优势，这是因为其容许在水中将粉末磨细以及将得到的浆液雾化。另一个优势是其在作为第一相的金属氧化物的优选实施方案的三氧化二钇化的氧化锆的常用烧结温度下是稳定的。
所述陶瓷复合材料的第二相的金属氧化物掺有至少一种活化元素。作为这类活化元素，可选择任意稀土元素La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu。将任意这些元素加入到所述陶瓷复合材料的第二相的金属氧化物中——特别是加入到作为所述陶瓷复合材料的第二相的金属氧化物的优选实施方案的铝酸锶中——可产生想要的陶瓷复合材料的磷光效果。所述活化元素的优选类型为Eu和Dy，且已发现第二相的最优选的实施方案为掺有Eu和Dy的Sr4Al14O25(掺杂Eu2+/Dy3+的Sr4Al14O25)。
可选择其他类型的第二相材料。但是，使用这类其他材料可导致陶瓷复合材料的性能下降，这是因为在烧结过程中可形成非发光相。
在第二相的金属氧化物中所述至少一种活化元素的含量可基于应当实现的效果来选择。在作为第二相的金属氧化物的铝酸锶中Eu的通常含量为0.05至4重量％，优选为0.15至1重量％(相对于第二相材料的总重量计)。该低浓度的Eu得到白色的磷光体粉末，其不呈现在市售可得的磷光体中通常得到的常见的淡黄色，而是保持高的发光强度以及磷光强度，如专利申请EP 2 626 401 A1中所示例的。对于本发明的最终磷光陶瓷复合材料而言，该低浓度的Eu还有益于在最终磷光陶瓷复合材料中的强度。
所述第一相的至少一种金属氧化物的含量应当为5至95％，相对于第一相和第二相的材料的总重量计。在这种情况下，所述含有至少一种第二相的活化元素的金属氧化物的含量应当为5至95％，也相对于第一相和第二相的材料的总重量计。所述第一相的至少一种金属氧化物的优选含量应当为40至95重量％，进一步优选的含量应当为50至95重量％且最优选的含量应当为50至80重量％，所有的情况均相对于第一相和第二相的材料的总重量计，且含有至少一种第二相的活化元素的金属氧化物的对应含量应当分别为5至60重量％、5至50重量％以及20至50重量％，相对于第一相和第二相的材料的总重量计。
最终得到的陶瓷复合材料为致密材料。如下文将描述的，所述陶瓷复合材料以如下方式制备：例如通过加热步骤将粘合剂材料(其通常作为陶瓷复合材料的前体存在于制备生坯的第一步中)移除，且在该移除粘合剂材料的步骤中产生孔。这些生成的孔随后在后续加热步骤中消除，如将在制备本发明的有余辉的磷光陶瓷复合材料的方法中描述。
在本发明的上下文中，“致密体”意指基本上不具有剩余孔的坯体，换句话说，为其中多孔特征被最小化的坯体。所述致密体呈现的密度为至少90％的理论最大密度。所述理论最大密度为一种不具有任何剩余孔的密度。其可通过考虑每个存在的相和每个相的相对浓度和密度来估量。
所述理论最大密度可基于复合材料中不同组分的密度值的常识来计算。例如，对于包含80重量％的含3％mol三氧化二钇的氧化锆作为烧结固化体的第一相的优选材料类型且包含20重量％的Sr4Al14O25作为烧结固化体的第二相的优选实施方案的复合材料而言，理论最大密度可计算如下。基于三氧化二钇化的氧化锆的密度为6.1g/cm3且Sr4Al14O25的密度为3.65g/cm3，计算出该组合物的理论密度为5.38g/cm3。在30重量％的Sr4Al14O25和70重量的％的三氧化二钇化的氧化锆的情况下，计算的密度值为5.08g/cm3；在50重量％的Sr4Al14O25和50重量％的三氧化二钇化的氧化锆的情况下，计算的密度值为4.57g/cm3。所述计算值是计算密度的合适基础，但必须承认，由于相浓度的测量不精确且不同的相不一定是纯相的情形，因此存在不确定性的方面。
致密体的一个优选实施方案是，其密度为至少97％的理论最大密度且在一个更优选的实施方案中，密度为至少98％的理论最大密度。
如上所述，因为将存在一个通过例如加热除去粘合剂材料的步骤，因此在最终烧结的陶瓷复合材料中不会识别出所述粘合剂材料本身。
接下来，描述制备本发明的有余辉的磷光陶瓷复合材料的方法。
在第一步中，将用于陶瓷复合材料的材料以粉末混合。
用于混合所述材料的方式无特别限制且可使用任意常规的混合步骤。
本发明的方法包括将金属氧化物和磷光体粉末——任选与稳定剂和粘合剂——混合，随后塑形为粉末压块(powder compact)(下文中称作生坯)。
本发明方法所用的金属氧化物为上述陶瓷复合材料的第一相的金属氧化物。本发明方法所用的磷光体为含有至少一种上述陶瓷复合材料的第二相的活化元素的金属氧化物。
任选在制备生坯中所用的粘合剂无特别限制且可使用适于帮助形成生坯的任意材料。所述粘合剂材料通常为有机材料且作为这类有机材料，可选择聚合材料，例如聚乙二醇(PEG)、聚乙酸乙烯酯(PVA)、聚四氟乙烯、乙烯-乙酸乙烯酯、聚乙基丙烯酸乙酯(polyethylethacrylate)或聚(甲基丙烯酸酯)-共聚-二甲基丙烯酸乙二醇酯(PMMA)。
这类有机粘合剂的存在可使生坯的形成更容易。制备生坯的方法包括注塑成型、流延成型(tape casting)、干压、滑移浇铸、凝胶灌制、直接凝固铸造和挤出。
此后，将生坯在多个不同步骤中加热处理。第一任选的步骤是加热处理生坯，从而除去在制备生坯的过程中存在的粘合剂材料。这被称作脱脂步骤。在该脱脂步骤中，通过移除经热处理的生坯中的粘合剂材料而产生孔。
当所述脱脂步骤通过加热进行时，其通常在至少450℃的温度下进行，优选在氧化性气氛中进行，所选的温度以及所选的气氛取决于粘合剂材料的特征。
或者，根据粘合剂材料的性质，该脱脂步骤可通过其他方式进行，例如通过催化脱脂或基于溶剂脱脂进行。
该脱脂步骤后进行第一烧结步骤。所述第一烧结步骤在通常800至1600℃范围内的温度下进行。第一烧结步骤的目的是使材料致密化。这通过对存在的孔加热，由此开始消除孔的效应来实现。第一烧结步骤的优选温度范围可为850至1200℃的范围，且第一烧结的常用温度选择为900℃。已观察到，在高温——例如在1450至1500℃范围内的温度下——预烧结可导致磷光复合材料的性能略微下降。
所述第一烧结优选在氧化性气氛中进行。所述氧化性气氛通常为环境气氛，意指存在正常大气压力下的空气。还可使用富含氧的气氛代替空气，但这不具有技术优势。所述脱脂和第一烧结还可在中性或还原性条件下进行，但测试已显示该方法是不太有利的。
可将脱脂和第一烧结的两个步骤合并成一个单独步骤。该单独处理步骤的条件必须符合脱脂以及第一步骤的烧结的需要。这意指处理温度必须在如下范围内选择：所述范围允许在形成具有适合尺寸的孔的情况下除去有机粘合剂材料，或选择用于脱脂步骤和第一烧结步骤的两个温度，在这两个步骤中间不将材料冷却至室温。
如果所想要的效果没有在一个单独步骤中实现，则将在氧化性条件下的脱脂和烧结在两个独立的步骤中进行，但是在一个单独步骤中处理通常更有利。
所述第一烧结步骤后进行第二烧结步骤，第二烧结步骤在还原性条件下进行。对本发明而言，还原性条件为如下的条件：其中实现了作为所述陶瓷复合材料的第二相的磷光体中的一种或多种活化元素的还原，但同时避免了所述陶瓷复合材料的第一相中的金属氧化物的还原。
用于实施第二烧结步骤的常用温度条件为选择在800至1600℃范围内的温度，优选的温度为1350至1550℃且更优选的温度为1450至1500℃。在该温度下的处理持续时间取决于所述复合物的组成以及所选取的温度。常规处理条件为在1450℃温度下处理的持续时间为3小时。这意指在该3小时持续时间内，恒定地保持1450℃的有效温度。总的热处理包括涉及例如150℃/小时的加热的直线上升期以及例如4小时的冷却期。
用于第二烧结步骤的气氛为还原性气氛。可选择成功地还原经活化的金属氧化物相中的活化元素的任意类型的气氛。常用的还原性气氛为含氢气的氩气气氛(Ar/H2)或含氢气的氮气气氛(N2/H2)。
作为在还原性条件下在第二烧结步骤中处理的替代方法，在中性条件下烧结是可行的。在该情况下可实现在中性气氛中的高等静压法(High Isostatic Pressing(HIP))处理(在已烧结材料且封闭孔隙后)，或可在中性气氛中使用火花等离子体烧结(SPS)。在这两种情况中，总的效果是使材料还原，因为这类处理通常在石墨模具中进行。在这些热处理下，氧化锆的颜色可受到影响，这是因为氧化锆在该处理过程中也可被还原，至少薄表面层被还原。但是应当可通过机械抛光或通过在氧化性气氛中在T<900℃下的热处理来除去这些灰色或黑色。
已证实在制备具有所想要程度的磷光性外还具有呈现有利的机械特性的所想要的效应的复合材料中，在还原性条件下的烧结步骤是关键步骤。在还原性条件下的第二烧结步骤前，所述材料没有呈现磷光体的特性且未观察到发光。需要至少一个在还原性或中性气氛中、在至少800℃温度下的热处理，以得到功能性材料。
在还原性条件下的烧结步骤引起磷光体中活化元素的还原。本发明的一个关键特征正是制备中的该步骤仅还原所述陶瓷复合材料的第二磷光相中的活化元素。如果例如第一相中的金属氧化物是氧化锆，则氧化锆的还原将导致该组分的变色。氧化锆具有白色，但是其还原形式为灰黑色，这通常会是非常不想要的颜色变化。本发明方法的出人意料的效果是，在还原性条件下的烧结步骤优先还原磷光相中的活化元素而不还原存在的其他组分，特别是不还原第一相的材料。
氧化锆未被还原是非常出人意料的，这是因为文献表明了对氧化锆在还原性气氛下在高温下的热处理导致陶瓷黑化。一种可能性可能是陶瓷中存在的比ZrO2更易被还原的活化元素阻止了氧化锆的变色，所述活化元素例如第二相所含的稀土元素(例如Eu3+)。
在还原性条件下的烧结步骤优选优化了所述复合材料的密度，由此所述密度达到最大值且在脱脂步骤中已产生的孔基本上被消除且在最终产物中未检测到剩余孔。在完全消除孔的情况下，最大密度水平明显得以实现。
根据本发明特别优选的实施方案，还可能的是在一个单独的加热步骤中进行不同的热处理，即脱脂步骤、在氧化性条件下的烧结以及在还原性条件下的烧结。上文已经描述了在还原性条件下的烧结步骤是制备本发明的复合陶瓷中的关键步骤。在一个合并的单独加热步骤中，该单独加热步骤将首先提供在还原性条件下的烧结。尽管在一个单独步骤中进行热处理的可能性在技术上和经济上是有吸引力的可能性，但是该可能性应当仅在不同功能的加热步骤可在所述单独加热步骤中实现时才成立。在某些情况下，脱脂步骤的功能不能在还原性条件下实现，特别是对于某些粘合剂材料。
在最后步骤中，可将所述材料进一步处理以得到所需美学效果或功能性效果，例如通过PVD和/或电镀法将各层沉积在部分表面和/或外观上，如例如记载于EP 1 548 524A1和EP 1 548 525 A1，或通过将生坯用金属盐溶液浸渍。
通过本发明的方法，得到具有优异机械特性以及优异余辉发光性的陶瓷-陶瓷复合物。所获得的材料开启了在性能和设计方面的许多可能性，这是因为所述材料是坚韧的、硬的，且是机械上耐受性的。其可用来实现例如手表的外部部件(表壳、表框)以及内部元件(刻度盘、发光指针)。
实施例
接下来，通过参照以下实施例来更详细地描述本发明。
同时，所述陶瓷复合材料的特性通过以下方法测定。
密度按照阿基米德法用无水乙醇进行测量。每个样品测量三次，然后计算平均值。
L*a*b*比色法测量在将样品机械加工和抛光后、在自由侧(即在热处理过程中不与样品架接触的一侧)进行，在三个不同的位置有7mm的孔。该仪器为Minolta CM3610d。
韧性的测量用KB250Prüftechnik GmbH仪器通过压痕进行。在15秒内施加5kg负荷来实现HV5压痕。韧性通过压痕测量且通过由K.Niihara(参见Niihara K.,A fracturemechanics analysis of indentation induced Palmqvist crack in ceramics,J.Mater.Sci.Lett.,1983,2,221-223)提出的公式来评估：
KIc＝0.018Hv a0.5(E/Hv)0.4·(a/c-1)-0.5
其中E为弹性(或杨氏)模量(测量值：220GPa)，Hv是以GPa计的维克斯硬度，c为压痕后形成的从压痕的中心测量的裂纹的长度，a为压痕的对角线长度的一半。
HV1显微硬度用LEICA VMHT MOT仪器、在15秒内载荷1Kg来测量。每个样品进行10次测量。
杨氏模量和泊松比通过声学显微术(通过超声波的非破坏性控制)测量。对于这两个参数的相对测量不确定度为2％。
发射的光的强度和衰变在黑室中用Pritchard PR-880光度计对至多六个样品进行测量。在测量前的磷光体的激发在配有标准荧光管的室中完成。该测量分三步进行：(a)将样品在荷载前保持在黑室中8小时；(b)在D65氟灯(fluorocompact lamp)下于400lux的激发强度下20分钟内实现激发；(c)在至少900分钟内用3°的物镜孔径测量发射的光，其中一个样品为参照样品。与0.3mCd/m2——人眼的感光下限——相比，光度计的灵敏度为0.9mCd/m2，。
X射线衍射测量以Bragg-Brentano几何结构采用经45kV电子激发的Cu阳极进行。不同的相是基于来自文献的参照图案来识别，且相浓度(下表以重量％给出)以1重量％的常用精确度估算。
实施例1.
含20重量％磷光体的样品1制备如下：
-将以下成分混合：80.0g含3mol％三氧化二钇(购自TOSOH公司的TZ-3YS)的氧化锆粉末和20.0g Sr4Al14O25:Eu,Dy粉末与3.0g由1.2g(40％)PVA和1.8g(60％)PEG 20 000组成的有机粘合剂的50％的水溶液，以及200ml蒸馏水和1kg氧化锆球；
-在氧化锆辊筒中以400U/min进行研磨/磨碎30分钟；
-将悬浮液过滤、用450ml IPA冲洗所述球和辊筒，将过滤的悬浮液和冲洗液体喷雾干燥。
然后将7g粉末压入
Figure BDA0001354815170000121
模具中。在第一热处理期间，在大气气氛下、在1475℃下在炉中以一步进行脱脂和烧结，其中有2小时的浸透时间、21小时的直线上升时间和11小时的冷却时间(总处理时间为34小时)。
将得到的小球进行机械加工和抛光。通过阿基米德法测量的常规密度为5.371g.cm-3。常规的比色分析为L*(D65)＝97.01、a*(D65)＝-1.81；b*(D65)＝2.21。通过X射线衍射进行的相分析表明氧化锆的相比例(四方比立方)相对于不含磷光体的样品而言未发生改变，且磷光体保留在Sr4Al14O25相中。在此阶段，磷光体没有发挥作用且未检测到有余辉的发光。
第二热处理在还原性气氛中、在1450℃下在4小时期间在Ar/H2气氛下以150℃.h-1直线上升速率进行。在该处理后，样品表现出有余辉的发光。处理后的密度为5.37g.cm-3且小球的硬度为约1250Hv、韧度为约5.1MPa.m-0.5，比色分析为L*(D65)＝92.86、a*(D65)＝-1.31、b*(D65)＝2.53，非常接近于烧结前的颜色。
实施例2–铝酸锶相的影响
研究了两种不同的含稀土(RE)掺杂物的铝酸锶得到适用于例如手表应用的有余辉的磷光陶瓷复合材料的潜力。
如下的两个相均表现出适用于所述应用的性能：在约520nm(绿色)发射的掺杂Eu2 +/Dy3+的SrAl2O4相以及在约495nm(蓝色)发射的较少使用的掺杂Eu2+/Dy3+的Sr4Al14O25相。尽管发射绿光的相非常广泛地使用，但是发射蓝光的材料表现出在余辉和感知强度方面极有益的特性。
含20重量％的活性SrAlO材料的两个样品如实施例1中所述的方式制备，并且在900℃下在空气中进行预烧结以及在还原性气氛中在1450℃下烧结3小时(样品2.1掺入发射绿光的SrAl2O4材料且样品2.2掺入发射蓝光的Sr4Al14O25材料)。结果在下表1和图1中给出。
表1
Figure BDA0001354815170000131
该数据证明含Sr4Al14O25的样品表现出比发射绿光的材料高10倍的发射强度。尽管SrAl2O4可功能性地掺入氧化锆基质中，但是明显优选使用Sr4Al14O25。
但是，含SrAl2O4的样品的较低性能可归因于某些方法步骤。例如，因为SrAl2O4是水溶性的，可优选不使用水基方法来进行雾化。
实施例3-Sr4Al14O25颗粒尺寸和烧结条件的影响
在两个不同的烧结条件下研究初始磷光体的颗粒尺寸对所得的性能的影响。
图2中的图像示出用标准粒度测定的样品(DV10＝1.2μm；DV50＝2.5μm；DV90＝6.4μm，如左侧的样品3.1和3.2)和所称的“超细”粒度测定的样品(DV10＝0.1μm；DV50＝1.4μm,DV90＝4.7μm，如右侧的样品3.3和3.4)的微结构。
四个样品的性能在表2和图3中呈现。
表2
Figure BDA0001354815170000132
Figure BDA0001354815170000141
尽管所有四个样品均显示出有余辉的发光，但是在该情况下优选使用具有标准颗粒尺寸的铝酸锶粉末，因为具有小的粉末颗粒尺寸的样品系统地表现出较低的发光强度。此外，对于余辉而言，在900℃下预烧结比在1475℃下预烧结表现得更有利。在1500℃下预烧结的样品与在1475℃下预烧结的样品相当，在还原性气氛中在1500℃下烧结的样品与在1450℃下烧结的样品(本文未示出)相当。
实施例4-Sr4Al14O25预处理的影响
在不同烧结条件下研究在掺入氧化锆浆液前对磷光体粉末进行预处理的影响。该预处理包括将粉末在酸性水溶液(例如稀乙酸溶液(浓度为例如10质量％))中在70℃温度下洗涤数小时。已知洗涤步骤导致无定型相从粉末制备中移除。
图4中的图像示出未经洗涤的样品(左侧的实施例3的样品3.1和3.2)和经额外的洗涤步骤的样品(右侧的样品4.1和4.2)的微结构。
图5的显示概括了两类样品的性能，所述样品各自在两种不同条件下得到。在该图中，未经洗涤的两个样品为实施例3中描述的样品3.1和3.2。
两个经洗涤的样品4.1和4.2的特性在下表3中提供。
表3
Figure BDA0001354815170000142
Figure BDA0001354815170000151
再次，所有样品均表现出有余辉的发光，但磷光体的预处理导致更低的发光强度。该影响不能被完全理解且可能具有多种起因(例如，颗粒尺寸差异)。
该结果还确证了，对于余辉而言，在900℃下的预烧结比在1475℃下的初始处理更有利。经1500℃下烧结的初始处理的样品与在1475℃下加热的样品相当，在还原性气氛下于1500℃下烧结的样品与在1450℃下烧结的样品相当。
实施例5-Sr4Al14O25浓度的影响
研究了复合材料中Sr4Al14O25浓度的影响，样品含有20重量％、30重量％和50重量％的磷光体。
这些实验的结果在图6和7中呈现。在图6中，含20重量％的磷光体的样品的数据对应于实施例3中的样品3.1的数据。在图7中，含20％的磷光体的样品的数据对应于实施例3中的样品3.2的数据。
含30重量％的磷光体的样品5.1和5.2的特性以及含50重量％的磷光体的样品5.3和5.4的特性在下表4中提供。
表4
Figure BDA0001354815170000152
Figure BDA0001354815170000161
所有样品均表现出有余辉的发光。较高的磷光体浓度导致显著增加的发光强度。再次，对于余辉而言，在900℃下的预烧结比在1475℃下的初始处理更有利。经1500℃下烧结的初始处理的样品与在1475℃下加热的样品相当，在还原性气氛下于1500℃下烧结的样品与在1450℃下烧结的样品相当。在发射光方面，烧结时间为3小时、6小时和9小时也产生相当的结果。
弹性(杨氏)模量随着磷光体含量的增加而降低，从纯的氧化锆的216GPa降至含50重量％磷光体的样品的182GPa。泊松比也趋于随着磷光体含量的增加而降低。对于20重量％和50重量％的Sr4Al14O25，测量的韧度分别为5.9MPa.m-0.5和3.9MPa.m-0.5。
最后，图8表现出在900℃下于空气中处理，然后在1450℃下于还原性气氛中处理的20％和50％磷光体-氧化锆复合物的发射光，与如实施例1中所用的相同类型的纯磷光体样品以及本申请的其他样品(160μm厚的Sr4Al14O25膜)的发射光进行比较。显然，所述强度在开始时是相当的，但是在200分钟以上时间后，氧化锆-磷光体样品的强度甚至比纯磷光体更高。这是出人意料的结果且显示出本发明人方法的巨大潜力：得到坚韧的技术陶瓷，其具有高韧性和高弹性模量，以及与纯磷光体粉末相当的发光性能。
还可注意到，对0.6mm和2mm厚的样品来说，测量的发光度是相当的。

Claims (9)

1.一种有余辉的磷光陶瓷复合材料，其是包含如下两相或更多相的烧结致密体：
由至少一种金属氧化物组成的第一相，
所述第一相中的金属氧化物为用选自Ce、Mg和Y的掺杂物稳定的氧化锆；以及
由含至少一种经还原的氧化态的活化元素的金属氧化物组成的第二相，
所述第二相为掺杂Eu2+/Dy3+的Sr4Al14O25相；
所述致密体是指密度为至少97％的理论最大密度的坯体，其中理论最大密度为不具有任何剩余孔的密度；并且
所述有余辉的磷光陶瓷复合材料通过包括以下步骤的方法制备：
制备金属氧化物和磷光体的混合物；
由所述混合物制造生坯；
在850至1200℃的温度下用氧化性气氛下的第一烧结步骤处理所述生坯；以及
在还原性气氛中对烧结的生坯进行热处理作为第二烧结步骤。
2.权利要求1的有余辉的磷光陶瓷复合材料，其中在所述方法中，将粘合剂材料加入到所述金属氧化物和磷光体的混合物中并将所制成的生坯在第一烧结步骤之前通过热处理来进行处理以除去所述粘合剂材料。
3.权利要求1的有余辉的磷光陶瓷复合材料，其中在所述方法中，在还原性气氛中的热处理在800至1600℃的温度范围内进行。
4.权利要求1的有余辉的磷光陶瓷复合材料，其中在所述方法中，在还原性气氛中的热处理在Ar/H2或N2/H2的气氛中进行。
5.权利要求1的有余辉的磷光陶瓷复合材料，其中第一相中的金属氧化物为用三氧化二钇稳定的氧化锆。
6.前述权利要求中任一项的有余辉的磷光陶瓷复合材料，其中第一相的含量为5至95重量％且第二相的含量为5至95重量％，相对于两个相的总重量计。
7.权利要求6的有余辉的磷光陶瓷复合材料，其中第一相的含量为40至95重量％且第二相的含量为5至60重量％，相对于两个相的总重量计。
8.权利要求6的有余辉的磷光陶瓷复合材料，其中第一相的含量为50至95重量％且第二相的含量为5至50重量％，相对于两个相的总重量计。
9.权利要求6的有余辉的磷光陶瓷复合材料，其中第一相的含量为50至80重量％且第二相的含量为20至50重量％，相对于两个相的总重量计。
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