WO2018170975A1 - 一种高功率照明与显示用荧光玻璃陶瓷及其制备方法和应用 - Google Patents

一种高功率照明与显示用荧光玻璃陶瓷及其制备方法和应用 Download PDF

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WO2018170975A1
WO2018170975A1 PCT/CN2017/080642 CN2017080642W WO2018170975A1 WO 2018170975 A1 WO2018170975 A1 WO 2018170975A1 CN 2017080642 W CN2017080642 W CN 2017080642W WO 2018170975 A1 WO2018170975 A1 WO 2018170975A1
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glass ceramic
fluorescent glass
yag
display
illumination
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王静
张学杰
余金波
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Sun Yat Sen University
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Sun Yat Sen University
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass

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  • the invention belongs to the field of high-power illumination and display technology, and more particularly to a high-power illumination and display fluorescent glass ceramic and a preparation method and application thereof.
  • high-power illumination and display have important application prospects in indoor and outdoor lighting, theater and home projectors, and automotive headlights.
  • the packaging material used in conventional high-power illumination and display is silica gel. Due to its low thermal conductivity and aging characteristics, the long-term use reduces the light efficiency of the illumination and display devices, and the light color drifts. In order to solve this technical problem, it is necessary to develop a novel all-inorganic light conversion material having high thermal conductivity. There are three main types that can meet this requirement at present: single crystal, transparent ceramic and fluorescent glass ceramic.
  • Fluorescent glass ceramic is a kind of all-inorganic light-converting material which is prepared by mixing phosphor and mother glass powder. It has excellent luminescent properties of phosphor and high thermal conductivity and heat aging resistance of glass. Compared with the conventional fluorescent paste, the thermal conductivity of the all-inorganic fluorescent conversion material is greatly improved and the luminescent property is well maintained. In addition, the fluorescent glass ceramics have a simple synthesis process and strong plasticity, and are expected to replace the traditional "silica gel + phosphor" mode. The fluorescent glass ceramic has both the function of a conventional phosphor and the function of a packaging material, and can be applied to a modular high-power white light illumination and display device.
  • the object of the present invention is to provide a high-power illumination and display fluorescent glass ceramic according to the deficiencies in the prior art.
  • the invention also provides a method for preparing the above-mentioned high-power illumination and display fluorescent glass ceramic.
  • the invention also provides the use of the above fluorescent glass ceramic in preparing a modular high power white light illumination and display device.
  • the invention provides a high-power illumination and display fluorescent glass ceramic
  • the composition of the fluorescent glass ceramic is: (1-x) A: xB, wherein x is the weight percentage of B, and the value of x ranges from 1 ⁇ 40%;
  • a 2 O in A Representing an alkali metal A 2 O is an oxide or carbonate of an alkali metal
  • M in the MO represents an alkaline earth metal
  • MO is an oxide or carbonate of an alkaline earth metal
  • B is a YAG:Ce 3+ phosphor.
  • a:b:c:d (40-60):(5-15):(10-30):(5-25).
  • a: b: c: d (52-55): (7-10): (18-23): (10-22).
  • A is Li, Na or K; M is Ca, Ba or Sr.
  • the invention simultaneously provides the preparation method of the high-power illumination and display fluorescent glass ceramic, comprising the following steps:
  • the pulverized glass precursor in S1 is mixed with YAG:Ce 3+ phosphor according to the weight percentage, and pressed;
  • the high temperature melting temperature in the step S1 is 1300 ° C to 1500 ° C, and the high temperature melting time is 0.5 to 2 h.
  • the pressing time in step S2 is 10 to 30 minutes, and the pressing pressure is 10 to 30 MPa.
  • the temperature of sintering in step S3 is 600 to 750 °C.
  • the invention simultaneously protects the use of the high-power illumination and display fluorescent glass ceramics in the preparation of high-power white light illumination and display materials.
  • the high power illumination and display fluorescent glass ceramic of the present invention is excited under a high power semiconductor light source to produce high brightness white light.
  • the fluorescent glass ceramic provided by the invention is prepared into a high-power white light device, and the luminous efficacy thereof can reach 100 lm/W or more.
  • the present invention has the following advantages and benefits:
  • the glass mother of the present invention has a lower body temperature melting temperature, and better maintains the YAG:Ce 3+ luminescence when mixed with YAG:Ce 3+ remelting sintering.
  • Efficiency and the glass matrix has almost no absorption of blue light; in addition, the glass matrix itself has a high thermal conductivity, which can effectively dissipate the heat generated by the semiconductor excitation source (blue LED and blue LD);
  • Fluorescent glass ceramics excel in heat resistance, and there is substantially no transmission loss for long-term aging.
  • the fluorescent glass ceramic is simple in preparation process, low in cost, non-toxic and non-polluting, and mechanically and physically and chemically stable.
  • Figure 1 is a photograph of a glass substrate (left) and a YAG:Ce 3+ -PiG sample (right) in Example 1;
  • Example 2 is an SEM spectrum of the matrix glass and YAG:Ce 3+ -PiG in Example 1;
  • Figure 3 is an XRD pattern of the glass precursor powder, YAG:Ce 3+ -PiG powder, YAG:Ce 3+ powder of Example 2;
  • Example 4 is an application of YAG:Ce 3+ -PiG fluorescent glass ceramic in Example 3 in a high power white LED;
  • Example 5 is an application of YAG:Ce 3+ -PiG fluorescent glass ceramics in Example 5 in a high power white light LD;
  • Example 6 is a graph showing the lumen change with the driving current of the laser illumination device based on YAG:Ce 3+ -PiG in Example 6;
  • Example 7 is an emission spectrum and an excitation spectrum of YAG:Ce 3+ -PiG fluorescent glass ceramics and YAG:Ce 3+ phosphors in Example 7;
  • the rubber molds of different sizes are selected, and the mixed powder is pressed by a cold isostatic pressing tableting machine (with a pressing condition of 20 MPa for 30 minutes), and then held in a 700 ° C box furnace for 0.5 h to obtain YAG:Ce. 3+ -PiG fluorescent glass ceramic.
  • the YAG:Ce 3+ -PiG fluorescent glass ceramic sheets of different thicknesses can be obtained by cutting and polishing the synthesized YAG:Ce 3+ -PiG ceramics.
  • the glass substrate obtained by this method and a 5% YAG:Ce 3+ -PiG physical photograph are shown in Fig. 1. Its distribution in the glass matrix is shown in Figure 2.
  • a, c, e, g are SEM photographs of the glass matrix at different magnifications
  • b, d, f, h are YAG: Ce 3+ - PiG are different
  • the SEM photograph at magnification shows that the phosphor is uniformly dispersed in the glass matrix.
  • Example 2 Synthesis of Glass Matrix 55SiO 2 -8A 2 O-20ZnO-22MO and Preparation of YAG:Ce 3+ -PiG Fluorescent Glass Ceramics
  • the phosphor and glass powder mass fraction of 7:93 after accurate weighing, grind in an agate mortar for 0.5h, select different size rubber molds, and press the mixed powder through cold isostatic pressing tablet press (The pressing condition was 30 minutes at 10 MPa), and the YAG:Ce 3+ -PiG fluorescent glass ceramic was obtained by holding in a box furnace at 720 ° C for 0.5 h.
  • the synthesized YAG:Ce 3+ -PiG ceramics are cut and polished to obtain PiG fluorescent glass ceramic sheets of different thicknesses.
  • the 7wt% YAG:Ce 3+ -PiG was ground into a powder, and the XRD was tested as shown in Fig. 3.
  • Example 3 Synthesis of glass matrix 55SiO 2 -10A 2 O-23ZnO-12MO and preparation of YAG:Ce 3+ -PiG fluorescent glass ceramic
  • the phosphor and glass powder mass fraction of 6:94 after accurate weighing, grind in an agate mortar for 0.5h, select different size rubber molds, and press the mixed powder through cold isostatic pressing tablet press (The pressing condition was 10 minutes at 30 MPa), and the YAG:Ce 3+ -PiG fluorescent glass ceramic was obtained by holding in a box furnace at 680 ° C for 0.5 h.
  • the YAG:Ce 3+ -PiG fluorescent glass ceramic sheets of different thicknesses can be obtained by cutting and polishing the synthesized YAG:Ce 3+ -PiG ceramics.
  • a white LED device is prepared by combining YAG:Ce 3+ -PiG fluorescent glass ceramic piece and blue light COB chip (12W), and the illuminating photograph, electroluminescence spectrum and color coordinate are shown in Fig. 4, wherein Fig. 4a is the original part of the device. 4b is a illuminating photograph, 4c is an electro-spectral spectrum, 4d is a color coordinate, and the high-power white light device has a luminous efficacy of up to 100 lm/W.
  • Example 4 Synthesis of Glass Matrix 52SiO 2 -10A 2 O-22ZnO-16MO and Preparation of YAG:Ce 3+ -PiG Fluorescent Glass Ceramics
  • the phosphor and glass powder mass fraction of 6:94 after accurate weighing, grind in an agate mortar for 0.5h, select different size rubber molds, and press the mixed powder through cold isostatic pressing tablet press (The pressing condition was 20 minutes at 25 MPa), and the YAG:Ce 3+ -PiG fluorescent glass ceramic was obtained by holding in a box furnace at 680 ° C for 0.5 h.
  • the YAG:Ce 3+ -PiG fluorescent glass ceramic sheets of different thicknesses can be obtained by cutting and polishing the synthesized YAG:Ce 3+ -PiG ceramics.
  • Example 5 2 O-20ZnO-10MO glass matrix synthesis and YAG 53SiO 2 -7A: Preparation of Ce 3+ -PiG fluorescent glass ceramic
  • the phosphor and glass powder mass fraction of 15:85 After accurate weighing, grind in an agate mortar for 0.5h, select different sizes of rubber molds, and press the mixed powder through cold isostatic pressing tablet press (The pressing condition was 30 minutes at 30 MPa), and the YAG:Ce 3+ -PiG fluorescent glass ceramic was obtained by holding in a box furnace at 750 ° C for 1 h.
  • the YAG:Ce 3+ -PiG fluorescent glass ceramic sheets of different thicknesses can be obtained by cutting and polishing the synthesized YAG:Ce 3+ -PiG ceramics.
  • the fluorescent glass ceramic sheet is combined with the laser LD to prepare white light LD devices of different light colors, and one of the white light LD devices has an electroluminescence spectrum as shown in FIG. 5.
  • Example 6 Synthesis of glass precursor 54SiO 2 -8A 2 O-18ZnO-20MO and preparation of YAG:Ce 3+ --PiG fluorescent glass ceramic
  • the phosphor and glass powder mass fraction of 20:80 after accurate weighing, grind in an agate mortar for 0.5h, select different sizes of rubber molds, and then mix the mixed powder by cold isostatic pressing tablet press (The pressing condition was 30 minutes at 25 MPa), and the YAG:Ce 3+ -PiG fluorescent glass ceramic was obtained by keeping it in a box furnace at 600 ° C for 0.5 h.
  • the YAG:Ce 3+ -PiG fluorescent glass ceramic sheets of different thicknesses can be obtained by cutting and polishing the synthesized YAG:Ce 3+ -PiG ceramics.
  • the obtained YAG:Ce 3+ -PiG fluorescent glass ceramic sheet performs well under different currents (alternating current) driven by the blue laser. As shown in Fig. 6, as the driving current of the laser increases, the lumen of the device gradually increases, and at 1.4A. When the time is optimal.
  • Example 7 Synthesis of glass precursor 54SiO 2 -8A 2 O-18ZnO-20MO and preparation of YAG:Ce 3+ -PiG fluorescent glass ceramic
  • the phosphor and glass powder mass fraction of 40:60 after accurate weighing, grind in an agate mortar for 0.5h, select different sizes of rubber molds, and press the mixed powder through cold isostatic pressing tablet press (The pressing condition was 20 minutes at 20 MPa), and the YAG:Ce 3+ -PiG fluorescent glass ceramic was obtained by holding in a box furnace at 710 ° C for 1 h.
  • the YAG:Ce 3+ -PiG fluorescent glass ceramic sheets of different thicknesses can be obtained by cutting and polishing the synthesized YAG:Ce 3+ -PiG ceramics.
  • the excitation and emission spectra of the prepared YAG:Ce 3+ -PiG fluorescent glass ceramic sheets are shown in Fig. 7.

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Abstract

一种高功率照明与显示用荧光玻璃陶瓷，该荧光玻璃陶瓷的组成为：(1-x)A:xB，其中，x为B的重量百分比，x的取值范围为1～40％；A为玻璃母体，组成为：aSiO 2-bA 2O-cZnO-dMO，a、b、c、d均为摩尔百分比，a+b+c+d＝100，A 2O中A代表碱金属，MO中M代表碱土金属；B为YAG:Ce 3+荧光粉。该荧光玻璃陶瓷中，玻璃母体具有较低的重熔温度、原料简单易得且成本低、绿色无污染。结合YAG:Ce 3+荧光粉后，具有光转换效率高、耐热老化性能优异等特性。

Description

一种高功率照明与显示用荧光玻璃陶瓷及其制备方法和应用 技术领域
本发明属于高功率照明与显示技术领域，更具体地，涉及一种高功率照明与显示用荧光玻璃陶瓷及其制备方法和应用。
背景技术
伴随蓝光LED光效的提升及蓝光LD成为新的激发光源，高功率照明与显示在室内外照明，影院及家庭投影仪，汽车前灯等领域具有重要的应用前景。然而，传统高功率照明与显示所用的封装材料为硅胶，由于其较低的热导率及易老化特性，长时间使用使得照明与显示器件的光效降低，光色漂移。为解决这一技术难题，需要开发新型的具有高热导率的全无机光转换材料。目前能够满足此要求的主要有三类：单晶，透明陶瓷及荧光玻璃陶瓷。单晶及透明陶瓷虽具有高热导率及优异的耐热老化性能，但是其制备过程复杂，造价昂贵，重复性差，不适宜大规模生产。这些因素限制了全无机光转换材料在高功率照明与显示中的应用。
荧光玻璃陶瓷是将荧光粉与母体玻璃粉末混合烧制的一种全无机光转换材料，既具有荧光粉优异的发光性能，同时也具备玻璃高热导率及耐热老化的性能。此全无机荧光转换材料与传统荧光浆料相比，热导率得到了较大的提升且发光性能也得到了较好的保持。此外，荧光玻璃陶瓷合成过程简单、可塑性强，有望替代传统“硅胶+荧光粉”的模式。此种荧光玻璃陶瓷既具有传统荧光粉的功能同时也具备封装材料的功能，可应用于模块化高功率白光照明与显示设备中。
发明内容
本发明的目的在于根据现有技术中的不足，提供了一种高功率照明与显示用荧光玻璃陶瓷。
本发明同时提供上述高功率照明与显示用荧光玻璃陶瓷的制备方法。
本发明还提供上述荧光玻璃陶瓷在制备模块化高功率白光照明与显示设备中的应用。
本发明的目的通过以下技术方案实现：
本发明提供了一种高功率照明与显示用荧光玻璃陶瓷，所述荧光玻璃陶瓷的 组成为：(1-x)A:xB，其中，x为B的重量百分比，x的取值范围为1～40％；A为玻璃母体，组成为：aSiO2-bA2O-cZnO-dMO，a、b、c、d均为摩尔百分比，a+b+c+d＝100，A2O中A代表碱金属，A2O为碱金属的氧化物或碳酸盐，MO中M代表碱土金属，MO为碱土金属的氧化物或碳酸盐；B为YAG:Ce3+荧光粉。
优选地，a:b:c:d＝(40-60):(5-15):(10-30):(5-25)。
优选地，a:b:c:d＝(52-55):(7-10):(18-23):(10-22)。
优选地，A为Li、Na或K；M为Ca、Ba或Sr。
本发明同时提供所述的高功率照明与显示用荧光玻璃陶瓷的制备方法，包括如下步骤：
S1.按照摩尔百分比将玻璃母体A的各组成原料混合，高温熔融后，冷却得到玻璃母体，粉碎；
S2.将S1中经过粉碎的玻璃母体与YAG:Ce3+荧光粉按照重量百分比混合，压制；
S3.将S2中经过压制的混合物烧结，抛光后得到所述高功率照明与显示用荧光玻璃陶瓷。
优选地，步骤S1中所述的高温熔融的温度为1300℃～1500℃，高温熔融的时间为0.5～2h。
优选地，步骤S2中压制的时间为10～30min，压制的压力为10～30MPa。
优选地，步骤S3中烧结的温度为600～750℃。
本发明同时保护所述的高功率照明与显示用荧光玻璃陶瓷在制备高功率白光照明与显示材料中的应用。
进一步地，本发明所述高功率照明与显示用荧光玻璃陶瓷在高功率半导体光源下被激发产生高亮度白光。
将本发明提供的荧光玻璃陶瓷制备成高功率白光器件，其光效可达100lm/W以上。
与现有技术相比，本发明具有如下优点和有益效果：
与传统封装的白光LED及白光LD相比，本发明荧光玻璃陶瓷中玻璃母体重熔温度较低，在与YAG:Ce3+混合重熔烧结时较好的保持了YAG:Ce3+的发光效率，且此玻璃母体对蓝光几乎没有吸收；此外，玻璃母体本身的热导率较高，可 有效散失半导体激发源(蓝光LED及蓝光LD)所产生的热；相比于传统硅胶材料，该荧光玻璃陶瓷在耐热性能上表现优异，长时间老化基本无透过损失。同时，该荧光玻璃陶瓷的制备工艺简单、成本低廉、无毒无污染、机械及物理化学性质稳定。
附图说明
图1为实例1中玻璃基质(左)及YAG:Ce3+-PiG样品(右)照片图；
图2为实例1中基质玻璃及YAG:Ce3+-PiG的SEM图谱；
图3为实例2中玻璃母体粉末、YAG:Ce3+-PiG粉末、YAG:Ce3+粉末的XRD图谱；
图4为实例3中YAG:Ce3+-PiG荧光玻璃陶瓷在高功率白光LED中的应用；
图5为实例5中YAG:Ce3+-PiG荧光玻璃陶瓷在高功率白光LD中的应用；
图6为实例6中基于YAG:Ce3+-PiG制备激光照明设备流明随驱动电流变化；
图7为实例7中YAG:Ce3+-PiG荧光玻璃陶瓷与YAG:Ce3+荧光粉的发射光谱和激发光谱图；
具体实施方式
以下结合具体实施例和附图来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明，本发明所用试剂和材料均为市购。
实施例1：
玻璃母体55SiO2-10A2O-20ZnO-15MO合成工艺及YAG:Ce3+-PiG荧光玻璃陶瓷的制备
表1：实施例1玻璃母体的原料组成
原料 SiO2 Na2CO3 ZnO CaCO3
质量(g) 33.046 15.898 16.282 10.009
按照表1精确称量分析纯的二氧化硅(SiO2)、碳酸钠(Na2CO3)、氧化锌(ZnO)、碳酸钙(CaCO3)。将精确称量的原料采用球磨机研磨6～8h后，倒入氧化铝坩埚中，然后，在1350℃箱式炉中熔融1h，将熔融玻璃液倒入蒸馏水中冷却，烘干后磨成粉。按照荧光粉YAG:Ce3+(市售，其组成为Y3Al5O12:Ce3+) 和玻璃粉质量分数为5:95，精确称量后，在玛瑙研钵中研磨0.5h，选择不同尺寸的橡胶模具，将混合好的粉经冷等静压压片机压片后(压制条件为20MPa下30分钟)，在700℃箱式炉中保温0.5h，即可得到YAG:Ce3+-PiG荧光玻璃陶瓷。将合成的YAG:Ce3+-PiG陶瓷经切割、抛光处理后即可得到不同厚度的YAG:Ce3+-PiG荧光玻璃陶瓷片。采用此方法获得的玻璃基质及5％YAG:Ce3+-PiG实物照片如图1所示。其在玻璃基质中的分布情况如图2所示，a,c,e,g为玻璃基质在不同放大倍数下的SEM照片，b,d,f,h为YAG:Ce3+-PiG在不同放大倍数下的SEM照片，可见，荧光粉均匀分散在玻璃基质中。
实施例2：玻璃母体55SiO2-8A2O-20ZnO-22MO合成工艺及YAG:Ce3+-PiG荧光玻璃陶瓷的制备
表2实施例2玻璃母体的原料组成
原料 SiO2 Na2CO3 ZnO CaO
质量(g) 33.046 8.479 16.282 12.34
按照表2精确称量分析纯的二氧化硅(SiO2)、碳酸钠(Na2CO3)、氧化锌(ZnO)、氧化钙(CaO)。将精确称量的原料采用球磨机研磨10～12h后，倒入氧化铝坩埚中，然后，在1400℃箱式炉中熔融1.5h，将熔融玻璃液倒入蒸馏水中冷却，烘干后磨成粉。按照荧光粉和玻璃粉质量分数为7:93，精确称量后，在玛瑙研钵中研磨0.5h，选择不同尺寸的橡胶模具，将混合好的粉经冷等静压压片机压片后(压制条件为10MPa下30分钟)，在720℃箱式炉中保温0.5h，即可得到YAG:Ce3+-PiG荧光玻璃陶瓷。将合成的YAG:Ce3+-PiG陶瓷经切割、抛光处理后即可得到不同厚度的PiG荧光玻璃陶瓷片。把7wt％YAG:Ce3+-PiG磨成粉末，测试XRD如图3所示，对比基质玻璃及YAG:Ce3+荧光粉的XRD图谱可知，在制备YAG:Ce3+-PiG的过程中，并未发生玻璃的析晶，且荧光玻璃陶瓷中的晶体为YAG:Ce3+荧光粉。
实施例3：玻璃母体55SiO2-10A2O-23ZnO-12MO合成工艺及YAG:Ce3+-PiG荧光玻璃陶瓷的制备
表3实施例3玻璃母体的原料组成
原料 SiO2 Li2CO3 ZnO CaCO3
质量(g) 33.046 7.389 18.724 10.009
按照表3精确称量分析纯的二氧化硅(SiO2)、碳酸锂(Li2CO3)、氧化锌(ZnO)、碳酸钙(CaCO3)。将精确称量的原料采用球磨机研磨6～8h后，倒入氧化铝坩埚中，然后，在1350℃箱式炉中熔融1.5h，将熔融玻璃液倒入蒸馏水中冷却，烘干后磨成粉。按照荧光粉和玻璃粉质量分数为6:94，精确称量后，在玛瑙研钵中研磨0.5h，选择不同尺寸的橡胶模具，将混合好的粉经冷等静压压片机压片后(压制条件为30MPa下10分钟)，在680℃箱式炉中保温0.5h，即可得到YAG:Ce3+-PiG荧光玻璃陶瓷。将合成的YAG:Ce3+-PiG陶瓷经切割、抛光处理后即可得到不同厚度的YAG:Ce3+-PiG荧光玻璃陶瓷片。结合YAG:Ce3+-PiG荧光玻璃陶瓷片及蓝光COB芯片(12W)制备白光LED器件，其发光照片，电致光谱图及色坐标如图4所示，其中,图4a为器件原件图，4b为发光照片图，4c为电致光谱，4d为色坐标，该高功率白光器件光效可达100lm/W。
实施例4：玻璃母体52SiO2-10A2O-22ZnO-16MO合成工艺及YAG:Ce3+-PiG荧光玻璃陶瓷的制备
表4实施例4玻璃母体的原料组成
原料 SiO2 K2O ZnO CaO
质量(g) 31.244 11.30 17.910 8.97
按照表4精确称量分析纯的二氧化硅(SiO2)、氧化钾(K2O)、氧化锌(ZnO)、氧化钙(CaO)。将精确称量的原料采用球磨机研磨16～48h后，倒入氧化铝坩埚中，然后，在1450℃箱式炉中熔融0.5h，将熔融玻璃液倒入蒸馏水中冷却，烘干后磨成粉。按照荧光粉和玻璃粉质量分数为6:94，精确称量后，在玛瑙研钵中研磨0.5h，选择不同尺寸的橡胶模具，将混合好的粉经冷等静压压片机压片后(压制条件为25MPa下20分钟)，在680℃箱式炉中保温0.5h，即可得到YAG:Ce3+-PiG荧光玻璃陶瓷。将合成的YAG:Ce3+-PiG陶瓷经切割、抛光处理后即可得到不同厚度的YAG:Ce3+-PiG荧光玻璃陶瓷片。
实施例5：玻璃母体53SiO2-7A2O-20ZnO-10MO合成工艺及YAG:Ce3+-PiG 荧光玻璃陶瓷的制备
表5实施例5玻璃母体的原料组成
原料 SiO2 Na2CO3 ZnO BaCO3
质量(g) 31.845 7.419 16.282 19.734
按照表5精确称量分析纯的二氧化硅(SiO2)、碳酸钠(Na2CO3)、氧化锌(ZnO)、碳酸钡(BaCO3)。将精确称量的原料采用球磨机研磨24～48h后，倒入氧化铝坩埚中，然后，在1500℃箱式炉中熔融1h，将熔融玻璃液倒入蒸馏水中冷却，烘干后磨成粉。按照荧光粉和玻璃粉质量分数为15:85，精确称量后，在玛瑙研钵中研磨0.5h，选择不同尺寸的橡胶模具，将混合好的粉经冷等静压压片机压片后(压制条件为30MPa下30分钟)，在750℃箱式炉中保温1h，即可得到YAG:Ce3+-PiG荧光玻璃陶瓷。将合成的YAG:Ce3+-PiG陶瓷经切割、抛光处理后即可得到不同厚度的YAG:Ce3+-PiG荧光玻璃陶瓷片。将此荧光玻璃陶瓷片与激光LD结合可制备出不同光色的白光LD器件，其中之一白光LD器件电致光谱图如图5所示。
实施例6：玻璃母体54SiO2-8A2O-18ZnO-20MO合成工艺及YAG:Ce3+--PiG荧光玻璃陶瓷的制备
表6实施例6玻璃母体的原料组成
原料 SiO2 Na2O ZnO CaCO3
质量(g) 32.446 16.585 14.654 20.017
按照表6精确称量分析纯的二氧化硅(SiO2)、碳酸钠(Na2CO3)、氧化锌(ZnO)、碳酸钙(CaCO3)。将精确称量的原料采用球磨机研磨6～18h后，倒入氧化铝坩埚中，然后，在1450℃箱式炉中熔融0.5h，将熔融玻璃液倒入蒸馏水中冷却，烘干后磨成粉。按照荧光粉和玻璃粉质量分数为20:80，精确称量后，在玛瑙研钵中研磨0.5h，选择不同尺寸的橡胶模具，将混合好的粉经冷等静压压片机压片后(压制条件为25MPa下30分钟)，在600℃箱式炉中保温0.5h，即可得到YAG:Ce3+-PiG荧光玻璃陶瓷。将合成的YAG:Ce3+-PiG陶瓷经切割、抛光处理后即可得到不同厚度的YAG:Ce3+-PiG荧光玻璃陶瓷片。获得的YAG:Ce3+-PiG荧光玻璃陶瓷片在蓝色激光器不同电流(交流电)驱动下表现优 异，如图6所示，随着激光器驱动电流的增加，器件流明逐渐增加，且在1.4A时达到最优。
实施例7：玻璃母体54SiO2-8A2O-18ZnO-20MO合成工艺及YAG:Ce3+-PiG荧光玻璃陶瓷的制备
表7实施例7玻璃母体的原料组成
原料 SiO2 Na2CO3 ZnO SrO
质量(g) 3.2446 1.6585 1.4654 20.72
按照表7精确称量分析纯的二氧化硅(SiO2)、碳酸钠(Na2CO3)、氧化锌(ZnO)、氧化锶(SrO)。将精确称量的原料采用球磨机研磨12～36h后，倒入氧化铝坩埚中，然后，在1300℃箱式炉中熔融2h，将熔融玻璃液倒入蒸馏水中冷却，烘干后磨成粉。按照荧光粉和玻璃粉质量分数为40:60，精确称量后，在玛瑙研钵中研磨0.5h，选择不同尺寸的橡胶模具，将混合好的粉经冷等静压压片机压片后(压制条件为20MPa下20分钟)，在710℃箱式炉中保温1h，即可得到YAG:Ce3+-PiG荧光玻璃陶瓷。将合成的YAG:Ce3+-PiG陶瓷经切割、抛光处理后即可得到不同厚度的YAG:Ce3+-PiG荧光玻璃陶瓷片。制备的YAG:Ce3+-PiG荧光玻璃陶瓷片激发与发射光谱如图7所示。

Claims (10)

  1. 一种高功率照明与显示用荧光玻璃陶瓷，其特征在于，所述荧光玻璃陶瓷的组成为：(1-x)A:xB，其中，x为B的重量百分比，x的取值范围为1～40％；A为玻璃母体，组成为：aSiO2-bA2O-cZnO-dMO，a、b、c、d均为摩尔百分比，a+b+c+d＝100，A2O中A代表碱金属，A2O为碱金属的氧化物或碳酸盐，MO中M代表碱土金属，MO为碱土金属的氧化物或碳酸盐；B为YAG:Ce3+荧光粉。
  2. 根据权利要求1所述的高功率照明与显示用荧光玻璃陶瓷，其特征在于，a:b:c:d＝(40-60):(5-15):(10-30):(5-25)。
  3. 根据权利要求2所述的高功率照明与显示用荧光玻璃陶瓷，其特征在于，a:b:c:d＝(52-55):(7-10):(18-23):(10-22)。
  4. 根据权利要求1所述的高功率照明与显示用荧光玻璃陶瓷，其特征在于，A为Li、Na或K；M为Ca、Ba或Sr。
  5. 一种权利要求1所述的高功率照明与显示用荧光玻璃陶瓷的制备方法，其特征在于，包括如下步骤：
    S1.按照摩尔百分比将玻璃母体A的各组成原料混合，高温熔融后，冷却得到玻璃母体，粉碎；
    S2.将S1中经过粉碎的玻璃母体与YAG:Ce3+荧光粉按照重量百分比混合，压制；
    S3.将S2中经过压制的混合物烧结，抛光后得到所述高功率照明与显示用荧光玻璃陶瓷。
  6. 根据权利要求5所述的制备方法，其特征在于，步骤S1中所述的高温熔融的温度为1300℃～1500℃，高温熔融的时间为0.5～2h。
  7. 根据权利要求5所述的制备方法，其特征在于，步骤S2中压制的时间为10～30min，压制的压力为10～30MPa。
  8. 根据权利要求5所述的制备方法，其特征在于，步骤S3中烧结的温度为600～750℃。
  9. 权利要求1至5任一所述的高功率照明与显示用荧光玻璃陶瓷在制备高功率白光照明与显示材料中的应用。
  10. 根据权利要求9所述的应用，其特征在于，所述高功率照明与显示用荧光玻璃陶瓷在高功率半导体光源下被激发产生高亮度白光。
PCT/CN2017/080642 2017-03-20 2017-04-14 一种高功率照明与显示用荧光玻璃陶瓷及其制备方法和应用 Ceased WO2018170975A1 (zh)

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