CN116462510A - 一种氟化钙基荧光陶瓷材料及其制备方法 - Google Patents
一种氟化钙基荧光陶瓷材料及其制备方法 Download PDFInfo
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- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 title claims abstract description 52
- 229910001634 calcium fluoride Inorganic materials 0.000 title claims abstract description 52
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 50
- 239000000919 ceramic Substances 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 11
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011698 potassium fluoride Substances 0.000 claims description 8
- 235000003270 potassium fluoride Nutrition 0.000 claims description 7
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical group [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000009877 rendering Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 9
- 239000011575 calcium Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000009766 low-temperature sintering Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001748 luminescence spectrum Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
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- 239000004593 Epoxy Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
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- 239000006060 molten glass Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
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- 235000013619 trace mineral Nutrition 0.000 description 1
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Abstract
本发明涉及一种氟化钙基荧光陶瓷材料及其制备方法，按照重量百分比，由94～99％氟化钙基体和1～6％的荧光粉组成。本发明采用的超低温烧结技术极大地降低了氟化钙基荧光陶瓷的烧结温度，可以有效的保留商用荧光粉的发光特性，大幅度的提高了陶瓷基LED器件的光效和显色指数，并且有效提升了荧光陶瓷的耐热性和稳定性。
Description
技术领域
本发明属于荧光粉封装材料领域，特别涉及一种氟化钙基荧光陶瓷材料及其制备方法。
背景技术
固态照明作为***照明光源，因其高效、环保的优势在近30年来得到了飞速的发展，广泛应用于各种场景，例如汽车大灯、投影显示、工业生产和远距离照明。而大功率、高亮度的白色发光二极管(WLED)及激光照明技术对颜色转换材料的服役稳定性提出了新的要求。因此，开发和研究高性能的荧光粉封装材料是目前固态照明的重中之重。
目前市面上常见的荧光粉封装材料为硅胶或者环氧树脂，导热性差(0.1-0.4W·m-1·K-1),耐热性差(低于150℃)。为了解决这一问题，人们研究了许多新型荧光转换材料，如玻璃，玻璃陶瓷，玻璃荧光体(PiG)，单晶等。其中PiG由于制备工艺简单，荧光粉含量易于调节，被认为是一种很有前途的替代材料，但是相对对于传统玻璃复合荧光粉的制备方法，熔融玻璃的高温会使嵌入的荧光粉变质，在熔体淬火的过程中遭受热损伤，从而导致转换效率的损失。相对来说荧光陶瓷具有较高的吸收系数和折射率，且透明性好，硬度高，耐腐蚀和耐高温，因此具有高导热系数和良好的热猝灭性能使得荧光陶瓷成为目前最有前景的大功率照明/显示用荧光转换材料。目前，荧光陶瓷主要以YAG:Ce黄色荧光陶瓷为主，极高的制备温度限制了其荧光粉的掺杂种类和带来高的能耗，很难实现在高温的条件下通过掺杂氮化物红色荧光粉的方式增加荧光陶瓷的红光成分，进而实现高的显色效率。
发明内容
本发明所要解决的技术问题是提供一种氟化钙基荧光陶瓷材料及其制备方法，该荧光陶瓷材料极大的降低了荧光陶瓷的烧结温度，可以最大程度的保留荧光粉本身的发光特性。
本发明提供了一种氟化钙基荧光陶瓷材料，按照重量百分比，由94～99％氟化钙基体和1～6％的荧光粉组成；其中，所述氟化钙基体掺杂镱。
所述氟化钙基体为立方状粉体，粒径为20-50mm；所述镱的摩尔分数为2-3％。
所述氟化钙基体的制备方法包括如下步骤：
在室温的条件下先将硝酸钙和硝酸镱溶液混合，然后将氟化钾溶液滴入到混合溶液中，反应得到悬浊液，悬浊液中镱的摩尔分数为2-3％；将悬浊液静置，水洗、醇洗后干燥，得到氟化钙基体。
所述硝酸钙溶液的浓度为0.5-1mol/L，硝酸镱溶液的浓度为0.01-0.05mol/L，氟化钾溶液的浓度为0.5-1mol/L。
所述氟化钾溶液的滴入速度为1-5ml/min。
所述反应的时间控制在2～5h，反应过程中用氨水调节pH值维持在10。
所述离心的转速为10000～12000rpm。
本发明还提供了一种氟化钙基荧光陶瓷材料的制备方法，包括如下步骤：
按照重量百分比，将94～99％的氟化钙基体和1～6％的荧光粉混合均匀，将混合好的粉末与盐酸溶液均匀研磨得到润湿的烧结粉体，然后在放置入模具中加上单轴压力并且进行升温控制，在空气气氛、200～350℃下进行烧结得到致密化的荧光陶瓷块体，最后进行打磨抛光，即得到氟化钙基荧光陶瓷材料。
所述盐酸溶液的浓度为0.5-2M，加入粉体中盐酸的质量分数为1％-20％。
所述研磨时间为1-10min。
所述单轴压力的大小为300-500MPa，模具温度的保温时间控制在0.5h-4h，升温速率保持在5～10℃/min。
本发明表面富氧的高活性掺镱氟化钙粉末具有极高的烧结活性，使得氟化钙陶瓷在350℃现完全的透明化，在800nm左右的透过率达到接近80％。与传统的玻璃或者环氧树脂比，氟化钙陶瓷本身具有较高的热导率。氟化钙本身的立方相晶体结构，极大的减少光在晶体内部的传输散射和损失，可以使得外界入射光更好的激发荧光粉，带来较高的发光效率。更为重要的一点是，极低的烧结温度，使得氟化钙陶瓷不光可以和YAG:Ce荧光粉进行复合，也可以很好的与红色CASN:Eu荧光粉进行复合，并且不会带来荧光粉量子效率的下降，使得荧光陶瓷能够同时实现高光效和高显色指数的可调性，具有极大的商业运用价值。
有益效果
本发明采用的氟化钙基体极大的降低了荧光陶瓷的烧结温度，使得氟化钙荧光陶瓷可以在350℃实现完全的致密化，对制备的设备要求更加简单，烧结温度低时间短，能耗极低；可以有效的保留商用荧光粉的发光特性，大幅度的提高了陶瓷基LED器件的光效和显色指数，并且有效提升了荧光陶瓷的耐热性及稳定性。制备工艺简单，可直接用来替代传统的高分子基LED封装器件。
附图说明
图1a为实施例1制备的氟化钙基体的TEM形貌图；
图1b为实施例1制备的氟化钙基体的微观元素分布图；
图2a为实施例1-3制备的氟化钙基荧光陶瓷材料的XRD图；
图2b为实施例1-3制备的氟化钙基荧光陶瓷材料的数码照片；
图2c为实施例1-3制备的氟化钙基荧光陶瓷材料和原始荧光粉的内量子效率；
图3a为实施例1、3制备的氟化钙基荧光陶瓷材料的色坐标图；
图3b为实施例1、3制备的氟化钙基荧光陶瓷材料的发光性能。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
称取14.84g的氟化钾粉末溶解于250ml的烧杯中，在500rpm的转速下进行搅拌，完全溶解后得到澄清的溶液，并且持续搅拌15min，得到溶液A；称取30.22g的Ca(NO3)2·5H2O和1.45g的Yb(NO3)3·8H2O粉末溶解于125ml的烧杯中，并且在500rpm的转速下进行搅拌，得到完全澄清的溶液后，持续搅拌15min，得到溶液B，保证溶液B中离子摩尔比Yb:Ca＝0.025:1；将A溶液以5ml/min的滴加速度滴加入B溶液，滴定完成后得到乳浊的溶液后持续搅拌1h，然后静置24h，通过水洗、醇洗后，以10000rpm的转速离心并且在烘箱中70℃进行干燥12小时后得到氟化钙基体，所得的氟化钙基体的形貌图如图1所示。
将商用的YAG:Ce黄色荧光粉按照质量百分比4％与96％的氟化钙基体研磨混合，混合后的粉体粉末与盐酸溶液均匀研磨得到润湿的烧结粉体，然后在放置入特定的钢制模具中加上单轴压力并且进行升温控制，在低温烧结过程中盐酸溶液的浓度为1mol/L，加入粉体中盐酸的质量分数为10％。研磨的时间保持在10min。单轴压力的大小为500MPa，控温模具的温度保持在350℃，保温时间控制在1h，升温速率保持在5～10℃/min；磨平抛光后获得厚度为1mm的荧光透明陶瓷，采用量子效率测试设备测试其量子效率的具体数值如图2所示，测试荧光粉高温烧结后的物相变化如图2所示，该荧光陶瓷与蓝光LED芯片封装后进行电致发光光谱测试，发光照片和发光光谱如图3所示，相关色温：4385K，光效:176.4lm/W,显色指数：63.2，色坐标：(0.3760，0.4220)，实验结果证明通过本实施例的制备方法，成功制备得到了可用于白光LED的氟化钙基荧光陶瓷。
实施例2
将商用的CASN:Eu红色荧光粉按照质量百分比2％与98％的实施例1制备的氟化钙基体研磨混合，混合后的粉体与一定浓度的盐酸溶液均匀研磨得到润湿的烧结粉体，然后在放置入特定的钢制模具中加上单轴压力并且进行升温控制，在低温烧结过程中盐酸溶液的浓度为2mol/L，加入粉体中盐酸的质量分数为15％。研磨的时间保持在10min。单轴压力的大小为500MPa，控温模具的温度保持在350℃，保温时间控制在1h，升温速率保持在5～10℃/min；磨平抛光后获得厚度为1mm的荧光透明陶瓷，采用量子效率测试设备测试其量子效率的具体数值如图2所示，测试荧光粉高温烧结后的物相变化如图2所示。
实施例3
称取14.84g的KF粉末溶解于250ml的烧杯中，在500rpm的转速下进行搅拌，完全溶解后得到澄清的溶液，并且持续搅拌15min，得到溶液A；称取30.22g的Ca(NO3)2·5H2O和2.7g的Yb(NO3)3·8H2O粉末溶解于125ml的烧杯中，并且在700rpm的转速下进行搅拌，得到完全澄清的溶液后，持续搅拌15min，得到溶液B，保证溶液B中离子摩尔比Yb:Ca＝0.05:1；将A溶液以10ml/min的滴加速度地加入B溶液，滴定完成后得到乳浊的溶液后持续搅拌0.5h,然后静置24h，离心并且在烘箱中充分干燥后得到氟化钙的烧结粉体。
将商用的红色荧光粉，商用黄色荧光粉按照质量百分比2％，4％和94％的氟化钙基体研磨混合，混合后的粉体与一定浓度的盐酸溶液均匀研磨得到润湿的烧结粉体，然后在放置入特定的钢制模具中加上单轴压力并且进行升温控制，在低温烧结过程中盐酸溶液的浓度为1mol/L，加入粉体中盐酸的质量分数为20％。研磨的时间保持在20min。单轴压力的大小为550MPa，控温模具的温度保持在350℃，保温时间控制在2h，升温速率保持在5～10℃/min；磨平抛光后获得厚度为1mm的荧光透明陶瓷，采用量子效率测试设备测试其量子效率的具体数值如图2所示，测试荧光粉高温烧结后的物相变化如图2所示。发光照片和发光光谱如图3所示，相关色温：1497K，显色指数：92，色坐标：(0.5600，0.3669)，实验结果证明通过本实施例的制备方法，成功制备得到了可用于暖光照明的，且具有高显色指数的白光LED的氟化钙基荧光陶瓷。
Claims (10)
1.一种氟化钙基荧光陶瓷材料，其特征在于：按照重量百分比，由94～99％氟化钙基体和1～6％的荧光粉组成；其中，所述氟化钙基体掺杂镱。
2.根据权利要求1所述的一种氟化钙基荧光陶瓷材料，其特征在于：所述氟化钙基体为立方状粉体，粒径为20-50mm；所述镱的摩尔分数为2-3％。
3.根据权利要求1所述的一种氟化钙基荧光陶瓷材料，其特征在于：所述氟化钙基体的制备方法包括如下步骤：
在室温的条件下先将硝酸钙和硝酸镱溶液混合，然后将氟化钾溶液滴入到混合溶液中，反应得到悬浊液，悬浊液中镱的摩尔分数为2-3％；将悬浊液静置，水洗、醇洗后干燥，得到氟化钙基体。
4.根据权利要求3所述的一种氟化钙基荧光陶瓷材料，其特征在于：所述硝酸钙溶液的浓度为0.5-1mol/L，硝酸镱溶液的浓度为0.01-0.05mol/L，氟化钾溶液的浓度为0.5-1mol/L。
5.根据权利要求3所述的一种氟化钙基荧光陶瓷材料，其特征在于：所述氟化钾溶液的滴入速度为1-5ml/min。
6.根据权利要求3所述的一种氟化钙基荧光陶瓷材料，其特征在于：所述反应的时间控制在2～5h，反应过程中用氨水调节pH值维持在10。
7.一种氟化钙基荧光陶瓷材料的制备方法，包括如下步骤：
按照重量百分比，将94～99％的氟化钙基体和1～6％的荧光粉混合均匀，将混合好的粉末与盐酸溶液均匀研磨得到润湿的烧结粉体，然后在放置入模具中加上单轴压力并且进行升温控制，在空气气氛、200～350℃下进行烧结得到致密化的荧光陶瓷块体，最后进行打磨抛光，即得到氟化钙基荧光陶瓷材料。
8.根据权利要求7所述的制备方法，其特征在于：所述盐酸溶液的浓度为0.5-2M，加入粉体中盐酸的质量分数为1％-20％。
9.根据权利要求7所述的制备方法，其特征在于：所述研磨时间为1-10min。
10.根据权利要求7所述的制备方法，其特征在于：所述单轴压力的大小为300-500MPa，模具温度的保温时间控制在0.5h-4h，升温速率保持在5～10℃/min。
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