CN106947472B - 一种氟硅酸盐基红色荧光陶瓷材料、制备方法和应用 - Google Patents
一种氟硅酸盐基红色荧光陶瓷材料、制备方法和应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 21
- 239000002253 acid Substances 0.000 title claims abstract description 17
- 239000003513 alkali Substances 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000003836 solid-state method Methods 0.000 claims abstract 2
- 239000011575 calcium Substances 0.000 claims description 41
- 238000001354 calcination Methods 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- -1 silicon ion Chemical class 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 13
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910001424 calcium ion Inorganic materials 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052693 Europium Inorganic materials 0.000 claims description 9
- 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
- 239000002994 raw material Substances 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- SULCVUWEGVSCPF-UHFFFAOYSA-L europium(2+);carbonate Chemical compound [Eu+2].[O-]C([O-])=O SULCVUWEGVSCPF-UHFFFAOYSA-L 0.000 claims description 3
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 3
- WLYAEQLCCOGBPV-UHFFFAOYSA-N europium;sulfuric acid Chemical compound [Eu].OS(O)(=O)=O WLYAEQLCCOGBPV-UHFFFAOYSA-N 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 12
- 230000005284 excitation Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 238000005286 illumination Methods 0.000 abstract description 9
- 238000000695 excitation spectrum Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000001228 spectrum Methods 0.000 abstract description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002341 toxic gas Substances 0.000 abstract description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 abstract description 2
- 239000012620 biological material Substances 0.000 abstract 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 238000004020 luminiscence type Methods 0.000 description 9
- 238000012544 monitoring process Methods 0.000 description 8
- 229910001634 calcium fluoride Inorganic materials 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000002284 excitation--emission spectrum Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 229910001940 europium oxide Inorganic materials 0.000 description 3
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 229910016644 EuCl3 Inorganic materials 0.000 description 2
- 229910003641 H2SiO3 Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 229910014813 CaC2 Inorganic materials 0.000 description 1
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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Abstract
本发明公开了一种氟硅酸盐基红色荧光陶瓷材料、制备方法和应用,化学式为Ca10‑ 10xEu10xSi3O15F2,其中x为Eu3+掺杂的化学计量分数,0.001≤x≤0.20,属于无机发光材料的技术领域。本发明制备得到的荧光陶瓷材料可以被200‑500纳米附近的近紫外光和蓝光有效激发,与近紫外LED芯片的发射波长非常吻合,在近紫外光激发下,该荧光陶瓷能够发射出明亮的红色荧光,发射波长以617nm为主,具有很宽的激发光谱和发光光谱;得到的荧光陶瓷材料其发光效率高,化学稳定性好,在紫外线辐射下不会产生硫化物等有毒气体,对环境友好,可应用于白光LED和其它发光领域;将含有合成生物材料所需元素的化合物按比例混合,采用高温固相法制备,制备该材料的工艺简单、无任何污染,对环境友好,适合工业化生产。
Description
技术领域
本发明涉及一种发光材料,特别涉及一种氟硅酸盐基红色荧光陶瓷材料、制备方法及应用,属于发光材料技术领域。
背景技术
在全球节能减排、能源紧张和强化环保的需求下,LED照明作为继白炽灯、荧光灯和高压气体放电灯之后的***照明光源正在逐步替换传统照明器件。近年来,用白光LED替代传统的白炽灯和荧光灯已逐渐成为一种趋势。白光LED照明已经显示出巨大的市场潜力,其在室内、室外、汽车照明和显示等领域的应用将极大的改变人类的生活方式,按照Philips公司的预测,LED照明占通用照明领域的比例在2015年将达到50%,到2020年将达到80%,并成为全球主要的照明方式。据预测,整个白光LED市场在2012年将达到204亿美金的市场规模,市场机遇极大。功率型白光LED器件由于具有附加值高、用途广等优点,是市场的焦点,也代表着该行业的发展趋势。飞利浦、日亚、欧司朗等行业巨头均对此市场尤为重视。我国尽管近年来投资了大量LED照明的相关项目,但是功率型LED方面我国占全世界的市场份额在2011年仅占2%!通过稀土离子掺杂,陶瓷荧光体可以实现在蓝光或者紫外光激发下的高效率发光,作为白光LED用荧光材料,最近在功率型白光LED和远程荧光体方面的应用引起了市场关注,比如Philips公司最近已经成功制备出120lm/W的高功率白光LED产品,并成功应用于奥迪A8汽车的前大灯。由于功率型LED在将来照明市场巨大的应用规模,陶瓷荧光体产品具有极大的市场需求。
目前,使用最广泛且技术很成熟的白光LED主要是以发蓝光的GaN基芯片搭配YAG:Ce的荧光粉,通过激发YAG:Ce来发射黄光与蓝光混合来实现的,其效率高、制造成本低,但由于其发射光谱中缺少绿色和红色成分,尤其在红色区域发光效率不高,导致它的显色指数比较低,色彩还原性差,色调偏冷色调,从而使得其应用受到一定的限制,另外其制取过程花费的成本也较高。因此研究性能好的红色荧光粉不仅具有一定的理论意义,更具有重要的实际应用意义。
发明内容
本发明的目的在于提供一种稳定性高、发光效率高,制备工艺简单易行、成本低廉,且对环境无污染的氟硅酸盐基红色荧光陶瓷材料,本发明的另一目的在于提供一种上述氟硅酸盐基红色荧光陶瓷材料的制备方法及氟硅酸盐基红色荧光陶瓷材料的应用。
为实现上述目的,本发明采用的技术方案是:一种氟硅酸盐基红色荧光陶瓷材料,化学式为Ca10-10xEu10xSi3O15F2,其中x为Eu3+掺杂的化学计量分数,0.001≤x≤0.20。
本发明还提供了一种氟硅酸盐基红色荧光陶瓷材料的制备方法,包括以下步骤:
(1)按照Ca10-10xEu10xSi3O15F2中各元素的化学计量比,其中0.001≤x≤0.20,分别称取含有钙离子Ca2+的化合物、含有硅离子Si4+的化合物、含有铕离子Eu3+的化合物、含有氟离子F-的化合物作为原料,并将含有钙离子Ca2+的化合物、含有硅离子Si4+的化合物、含有铕离子Eu3+的化合物混合并研磨均匀,得到混合物;
(2)将步骤(1)得到的混合物在空气气氛下进行煅烧,煅烧温度750~950℃,煅烧时间为3~10小时,煅烧完成后自然冷却,研磨混合均匀;
(3)将步骤(2)得到的粉体混合物与含有氟离子F-的化合物研磨均匀,压制成陶瓷片,压制压力为10MPa~15MPa,在空气气氛中再次煅烧,煅烧温度为900~1200℃,煅烧时间为3~15小时;自然冷却后研磨混合均匀,得到红色荧光陶瓷材料。
作为上述制备方法的一个优选方案:步骤(2)的煅烧温度为800~950℃,煅烧时间为4~10小时。
作为上述制备方法的一个优选方案:步骤(3)的煅烧温度为950~1200℃,烧结时间为5~10小时。
本发明制备方法中,所述的含有钙离子Ca2+的化合物为碳酸钙、硝酸钙、氢氧化钙、草酸钙、氧化钙的一种;所述含有硅离子Si4+的化合物为二氧化硅或硅酸中的一种;所述的含有铕离子Eu3+的化合物为氧化铕、硝酸铕、碳酸铕、硫酸铕、氯化铕中的一种,所述含有氟离子F-的化合物为氟化钙。
作为制备方法的优选方案,所述含有钙离子Ca2+的化合物有两种,其中一种是氟化钙,氟化钙提供的钙占总钙量的10vol%~40vol%,另一种来源于碳酸钙、硝酸钙、氢氧化钙、草酸钙、氧化钙中的一种。
最后,本发明公开了氟硅酸盐基红色荧光陶瓷材料的应用,将本文所述红色荧光陶瓷材料在250-500nm波长激发下,可以发射出红色荧光,可应用在被紫外光激发的各种照明设备及白光LED的色度调节中。
与现有技术相比,本发明具有如下有益效果:
1、本发明提供的氟硅酸酸盐基红色荧光陶瓷材料,有良好的物理和化学性能,颗粒度均匀、结晶度好,发光效率高,可以广泛应用于制备功率型LED;同时在紫外线辐射下不会产生硫化物等有毒气体,对环境友好,在光致发光方面有很大的应用价值。
2、所制备出的新型红色荧光陶瓷可以有效地吸收近紫外到蓝光区域(200~500纳米)的光,并将能量传递给掺杂在基质材料中的三价铕离子Eu3+,发射出617纳米附近的红光,色度纯正、亮度高,且激发光范围宽;将其配合适量的绿色、蓝色荧光粉,涂敷和封装于InGaN二极管外,可制备高效率的白光LED照明器件,还可以用于被紫外光激发的其他各种照明设备中,在照明、显示和检测等方面具有广泛的应用前景。
3、本发明提供的氟硅酸酸盐基红色荧光陶瓷,制备工艺简单、易于操作,方法安全可控、对生产条件和设备要求不高,无任何污染,适于工业化生产。
附图说明
图1是本发明实施例1制备样品Ca9.9Eu0.1Si3O15F2的X射线粉末衍射图谱;
图2是本发明实施例1制备样品Ca9.9Eu0.1Si3O15F2的扫描电子显微镜图;
图3是本发明实施例1制备样品Ca9.9Eu0.1Si3O15F2在617纳米波长监测下的激发光谱图;
图4是本发明实施例1制备样品Ca9.9Eu0.1Si3O15F2在392.5纳米波长激发下的发射光谱图;
图5是本发明实施例1制备样品Ca9.9Eu0.1Si3O15F2在313纳米波长激发、617纳米波长监测下的发光衰减曲线;
图6是本发明实施例4制备样品Ca8.5Eu1.5Si3O15F2在617纳米波长监测下的激发光谱图;
图7是本发明实施例4制备样品Ca8.5Eu1.5Si3O15F2在392.5纳米波长激发下的发射光谱图;
图8是本发明实施例4制备样品Ca8.5Eu1.5Si3O15F2在313纳米波长激发、617纳米波长监测下的发光衰减曲线;
图9是本发明实施例4制备样品Ca8.5Eu1.5Si3O15F2的扫描电子显微镜图。
具体实施方式
下面结合附图和实施例对本发明作进一步描述。
实施例1:
制备Ca9.9Eu0.1Si3O15F2,根据化学式Ca9.9Eu0.1Si3O15F2中各元素的化学计量比,称取碳酸钙CaCO3:8.908克,氧化硅SiO2:1.8024克,氧化铕Eu2O3:0.0018克,在玛瑙研钵中研磨并混合均匀后,选择空气气氛烧结,煅烧温度是800℃,煅烧时间10小时,然后冷却至室温,取出样品并研磨均匀;将煅烧过的原料再次与0.7808克氟化钙CaF2充分混合研磨均匀,将混合粉体进行压制成型,压力为10MPa,在空气气氛中再次煅烧,煅烧温度1200℃,煅烧时间5小时,自然冷却研磨混合均匀即得到氟硅酸钙荧光陶瓷。
参见附图1,它是本实施例技术方案制备样品的X射线粉末衍射图谱,XRD测试结果显示,所制备的Ca9.9Eu0.1Si3O15F2为单相材料,没有其它杂相存在,而且结晶度较好,表明三价铕离子Eu3+的掺杂对基质的结构无影响。
参见附图2,它是本实施例技术方案制备样品的扫描电子显微镜图谱,从图中可以看出,所得样品颗粒分散较为均匀。
参见附图3,它是按本实施例技术方案制备的样品在617纳米波长监测下的激发光谱图,在200~500纳米范围内有宽峰出现,在270纳米、392.5纳米和462纳米有强峰出现,表明该材料可有效地被近紫外到蓝光区域的光激发,适用于白光LED。
参见附图4,它是按本实施例技术方案制备的样品在392.5纳米波长激发下的发射光谱图,从图中可以看出,该材料的发射波长为617纳米波段范围的红光。
参见附图5,它是按本实施例技术方案制备的样品在313纳米波长激发、617纳米波长监测下的发光衰减曲线,计算可得衰减时间为1.99毫秒。
实施例2:
制备Ca9.99Eu0.01Si3O15F2,根据化学式Ca9.9Eu0.1Si3O15F2中各元素的化学计量比,分别称取氢氧化钙Ca(OH)2:5.1793克,硅酸H2SiO3:2.34克,氧化铕Eu2O3:0.0002克在玛瑙研钵中研磨并混合均匀后,选择空气气氛烧结,煅烧温度是950℃,煅烧时间3小时,然后冷却至室温,取出样品研磨混合均匀;将煅烧过的原料再次与2.3424克氟化钙CaF2充分混合研磨均匀,将混合粉体进行压制成型,压力为15MPa,在空气气氛中再次煅烧,煅烧温度900℃,煅烧时间15小时,自然冷却研磨均匀即得到氟硅酸钙荧光陶瓷。
本实施例制备的样品,其主要结构形貌、激发光谱、发射光谱以及发光衰减曲线与实施例1相似。
实施例3:
制备Ca9.5Eu0.5Si3O15F2,根据化学式Ca9.5Eu0.5Si3O15F2中各元素的化学计量比,分别称取草酸钙CaC2O4:9.608克,硅酸H2SiO3:2.34克,硝酸铕Eu(NO3)3·6H2O:0.0169克,在玛瑙研钵中研磨并混合均匀后,选择空气气氛烧结,煅烧温度是900℃,煅烧时间6小时,然后冷却至室温,取出样品;将煅烧过的原料再次与1.5616克氟化钙CaF2充分混合研磨均匀,将混合粉体进行压制成型,压力为12MPa,在空气气氛中再次煅烧,煅烧温度1000℃,煅烧时间9小时,自然冷却即得到氟硅酸钙荧光陶瓷。
本实施例制备的样品,其主要结构形貌、激发光谱、发射光谱以及发光衰减曲线与实施例1相似。
实施例4:
制备Ca8.5Eu1.5Si3O15F2,根据化学式Ca8.5Eu1.5Si3O15F2中各元素的化学计量比,分别称取氧化钙CaO:3.3646克,二氧化硅SiO2:1.8027克,碳酸铕Eu2(CO3)3·H2O:0.038克,在玛瑙研钵中研磨并混合均匀后,选择空气气氛烧结,煅烧温度是750℃,煅烧时间10小时,然后冷却至室温,取出样品研磨混合均匀;将预煅烧的原料再次与1.952克氟化钙CaF2充分混合研磨均匀,将混合粉体进行压制成型,压力为13MPa,在空气气氛中再次煅烧,煅烧温度1200℃,煅烧时间3小时,自然冷却后研磨混合均匀即得到氟硅酸钙荧光陶瓷。
参见附图6,是按本实施例技术方案制备的样品在617纳米波长监测下的激发光谱图,从图中可以看出,在200~500纳米范围内有宽峰出现,在270纳米、392.5纳米和462纳米有强峰出现,表明该材料可有效地被近紫外到蓝光区域的光激发,适用于白光LED。
参见附图7,它是按本实施例技术方案制备的样品在392.5纳米波长激发下的发射光谱图,从图中可以看出,该材料的发射波长为617纳米波段范围的红光。
参见附图8,它是按本实施例技术方案制备的样品在313纳米波长激发、617纳米波长监测下的发光衰减曲线,计算可得衰减时间为1.92毫秒。
参见附图9,它是本实施例技术方案制备样品的扫描电子显微镜图谱,从图中可以看出,所得样品颗粒分散较为均匀。
实施例5:
制备Ca9EuSi3O15F2,根据化学式Ca9EuSi3O15F2中各元素的化学计量比,分别称取称取硝酸钙Ca(NO3)2·4H2O:17.711克,氧化硅SiO2:1.8027克,氯化铕EuCl3:0.026克,在玛瑙研钵中研磨并混合均匀后,选择空气气氛烧结,煅烧温度是870℃,煅烧时间5小时,然后冷却至室温,取出样品研磨混合均匀;将预煅烧的原料再次与1.1712克氟化钙CaF2充分混合研磨均匀,将混合粉体进行压制成型,压力为14MPa,在空气气氛中再次煅烧,煅烧温度980℃,煅烧时间7小时,自然冷却即得到氟硅酸钙荧光陶瓷。
本实施例制备的样品,其主要结构形貌、激发光谱、发射光谱以及发光衰减曲线与实施例4相似。
实施例6:
制备Ca8Eu2Si3O15F2,根据化学式Ca8Eu2Si3O15F2中各元素的化学计量比,分别称取氧化钙CaO:3.365克,氧化硅SiO2:1.8027克,氯化铕EuCl3:0.052克,在玛瑙研钵中研磨并混合均匀后,选择空气气氛烧结,煅烧温度是920℃,煅烧时间7小时,然后冷却至室温,取出样品研磨混合均匀;将煅烧过的原料再次与3.1232克氟化钙CaF2充分混合研磨均匀,将混合粉体进行压制成型,压力为14MPa,在空气气氛中再次煅烧,煅烧温度1050℃,煅烧时间6小时,自然冷却即得到氟硅酸钙荧光陶瓷。
本实施例制备的样品,其主要结构形貌、激发光谱、发射光谱以及发光衰减曲线与实施例4相似。
Claims (5)
1.一种氟硅酸盐基红色荧光陶瓷材料,其特征在于:化学式为Ca10-10xEu10xSi3O15F2,其中x为Eu3+掺杂的化学计量分数,0.001≤x≤0.20。
2.一种如权利要求1所述的氟硅酸盐基红色荧光陶瓷材料的制备方法,其特征在于,采用高温固相法,包括以下步骤:
(1)按照Ca10-10xEu10xSi3O15F2中各元素的化学计量比,其中0.001≤x≤0.20,分别称取含有钙离子Ca2+的化合物、含有硅离子Si4+的化合物、含有铕离子Eu3+的化合物、含有氟离子F-的化合物作为原料,并将含有钙离子Ca2+的化合物、含有硅离子Si4+的化合物、含有铕离子Eu3+的化合物混合并研磨均匀,得到混合物;
(2)将步骤(1)得到的混合物在空气气氛下进行煅烧,煅烧温度750~950℃,煅烧时间为3~10小时,煅烧完成后自然冷却,研磨混合均匀;
(3)将步骤(2)得到的粉体混合物与含有氟离子F-的化合物研磨均匀,压制成陶瓷片,压制压力为10 MPa~15MPa,在空气气氛中再次煅烧,煅烧温度为900~1200℃,煅烧时间为3~15小时;自然冷却后研磨混合均匀,得到红色荧光陶瓷材料。
3.根据权利要求2所述的氟硅酸盐基红色荧光陶瓷材料的制备方法,其特征在于:步骤(2)的煅烧温度为800~950℃,煅烧时间为4~10小时。
4.根据权利要求2所述的氟硅酸盐基红色荧光陶瓷材料的制备方法,其特征在于:步骤(3)的煅烧温度为950~1200℃,烧结时间为5~10小时。
5.根据权利要求2所述的氟硅酸盐基红色荧光陶瓷材料的制备方法,其特征在于:所述的含有钙离子Ca2+的化合物为碳酸钙、硝酸钙、氢氧化钙、草酸钙、氧化钙的一种;所述含有硅离子Si4+的化合物为二氧化硅或硅酸中的一种;所述的含有铕离子Eu3+的化合物为氧化铕、硝酸铕、碳酸铕、硫酸铕、氯化铕中的一种,所述含有氟离子F-的化合物为氟化钙。
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