WO2017177923A1 - 一种氧化铝基质的荧光陶瓷的制备方法及相关荧光陶瓷 - Google Patents

一种氧化铝基质的荧光陶瓷的制备方法及相关荧光陶瓷 Download PDF

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WO2017177923A1
WO2017177923A1 PCT/CN2017/080279 CN2017080279W WO2017177923A1 WO 2017177923 A1 WO2017177923 A1 WO 2017177923A1 CN 2017080279 W CN2017080279 W CN 2017080279W WO 2017177923 A1 WO2017177923 A1 WO 2017177923A1
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sintering
fluorescent ceramic
phosphor
ceramic precursor
powder
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李乾
王艳刚
陈雨叁
许颜正
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Shenzhen Appotronics Corp Ltd
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Definitions

  • the invention relates to the field of fluorescent ceramics, in particular to a method for preparing a fluorescent ceramic of an alumina matrix and related fluorescent ceramics.
  • the technology of blue laser excitation of fluorescent materials to obtain visible light has been paid more and more attention with the development of laser display technology.
  • the current research direction is mainly to develop new fluorescent materials (wavelength conversion materials) for the characteristics of laser-excited phosphors.
  • the requirements are high luminous brightness, high-power laser irradiation, high optical conversion efficiency, and high thermal conductivity.
  • a common YAG fluorescent ceramic is mainly calcined by raw material powders Al 2 O 3 , Y 2 O 3 , and CeO 2 , pressed into a sheet by a press, and then sintered to obtain a fluorescent ceramic. Since the fluorescent ceramic generally covers the surface of the LED, it is required to pursue a certain light transmittance. Therefore, the YAG fluorescent ceramic is more biased toward the transmittance, and the degree of grain growth is lower, resulting in a lower luminance of the light.
  • the thermal conductivity of conventional YAG ceramics is relatively low, generally 10 ⁇ 14W/(m ⁇ K).
  • the power of the light source is getting larger and larger, and the light conversion material is required to have higher
  • the thermal conductivity can quickly transfer a large amount of heat generated during the light conversion process.
  • the prepared fluorescent ceramic has low thermal conductivity and low luminous efficiency.
  • the invention provides a method for preparing a fluorescent ceramic with high thermal conductivity and high luminous efficiency, which comprises the following steps:
  • the photoceramic precursor slurry has an alumina particle size of 0.05 to 1 ⁇ m, and the phosphor is a YAG-doped lanthanide phosphor or a LuAG-doped lanthanide phosphor, and the phosphor has a particle diameter of 10 to 30 ⁇ m.
  • the sintering aid is a magnesium oxide-yttria mixed sintering aid, and the sintering aid has a particle diameter of 0.05-0.1 ⁇ m; calcination: drying the fluorescent ceramic precursor slurry, and then calcining it in an aerobic atmosphere to remove the same Water and organic matter, obtaining a fluorescent ceramic precursor powder; sintering: sintering the fluorescent ceramic precursor powder to obtain a fluorescent ceramic, the sintering temperature is 1250-1550 ° C, the sintering pressure is 30-200 MPa, and the sintering is performed under an oxygen-free atmosphere, wherein The fluorescent ceramic precursor powder is pretreated by a high pressure of 5 MPa or more before sintering to keep the powder dense.
  • the phosphor comprises YAG:Ce 3+ or LuAG:Ce 3+ .
  • the phosphor accounts for 30% to 80% by mass of the total amount of the fluorescent ceramic precursor powder
  • the sintering aid accounts for 0.01% to 1% by mass of the total amount of the fluorescent ceramic precursor powder.
  • the mixing step comprises first loading alumina and a sintering aid into a ball mill tank, adding a grinding solvent, a thickener and a dispersing agent for the first ball milling; then adding the phosphor to the ball mill tank for a second time Ball milling, wherein the first ball milling time is greater than the second ball milling time.
  • the calcination temperature is from 500 to 650 °C.
  • the oxygen-free atmosphere is a nitrogen gas, a hydrogen gas, a nitrogen gas mixture gas, an inert gas or a vacuum atmosphere.
  • the sintering step comprises pre-forming the fluorescent ceramic precursor powder in a mold at a high pressure of 5 to 15 MPa, and then placing the fluorescent ceramic precursor powder together with the mold in a hot press sintering furnace to make the fluorescent ceramic precursor powder in 30 ⁇ . Sintered at 200 MPa.
  • the sintering step comprises pre-forming the fluorescent ceramic precursor powder in a mold at a high pressure of 5-15 MPa, and then placing the fluorescent ceramic precursor powder together with the mold into a spark plasma sintering furnace to make the fluorescent ceramic precursor powder 30- Sintering was carried out at 200 MPa, and sintering was carried out under a vacuum atmosphere.
  • a reduction treatment step of the fluorescent ceramic is further included, the reduction treatment step is performed under a reducing atmosphere, and the temperature environment of the reduction treatment step is 1100 to 1700 °C.
  • the present invention also provides a fluorescent ceramic prepared by the above preparation method.
  • the present invention includes the following beneficial effects:
  • the present invention comprises a magnesia-yttria mixed sintering aid and an alumina having a particle diameter of 0.05 to 1 ⁇ m, a YAG doped lanthanide phosphor having a particle diameter of 10 to 30 ⁇ m, or a LuAG-doped lanthanide phosphor.
  • the powder is subjected to high-pressure sintering at 3050 to 150 ° C at 3050 to 1550 ° C to obtain a fluorescent ceramic.
  • the selection of the alumina particle size and the high pressure treatment process enable the alumina to enter the liquid phase at a lower temperature, and the presence of the magnesium oxide-yttria mixed sintering aid further lowers the temperature of the alumina into the liquid phase.
  • the sintering aid does not have a destructive effect on the phosphor of the selected particle size, so that the surface morphology can be kept substantially unchanged, so that the formed fluorescent ceramic can retain the luminescent property of the original phosphor;
  • the fluorescent ceramic precursor powder can maintain a dense and low porosity state before and after sintering, greatly improving the thermal conductivity of the fluorescent ceramic, thereby preparing Fluorescent ceramics with high thermal conductivity and high luminous efficiency.
  • FIG. 1 is a flow chart showing a method of preparing a fluorescent ceramic according to an embodiment of the present invention
  • the preparation of the fluorescent ceramics in the prior art is obtained by sintering the phosphor raw materials (ie, various types of oxides), and the light transmittance thereof is required.
  • the fluorescent ceramic thus obtained has a significantly low luminous efficiency.
  • the phosphor powder prepared in the same raw material, and the thermal conductivity of the YAG ceramic is low, which is very disadvantageous for heat dissipation during use.
  • the fluorescent ceramic prepared by the invention adopts the existing commercial phosphor as the raw material, and does not undergo the step of preparing the phosphor during the preparation process, thereby avoiding various kinds of phosphor powder growth processes in the preparation of the fluorescent ceramics.
  • the problem is that, by selecting a small-diameter alumina and a high-pressure treatment process, the alumina matrix of the obtained fluorescent ceramic is dense and high in thermal conductivity, and the finished product has good heat dissipation performance.
  • the melting point of the phosphor is close to that of alumina and slightly lower than the melting point of alumina (for example, the melting point of YAG is 1950 ° C, the melting point of alumina is 2050 ° C), during the preparation, when the alumina enters the liquid phase, the fluorescence The original structure of the powder is easily destroyed, and the obtained fluorescent ceramic of the alumina matrix has low luminous efficiency.
  • the phosphor makes the particle size of the alumina powder much smaller than the phosphor, which reduces the temperature required for the alumina to enter the liquid phase without lowering the temperature at which the phosphor enters the liquid phase, ensuring that the phosphor maintains the physical structure at the sintering temperature.
  • the phosphor has a high luminous efficiency of a large particle size phosphor.
  • the small particle size of the alumina enables the high pressure treatment in the preparation process to sufficiently fill the pores in the fluorescent ceramic, thereby increasing the density (and thus the thermal conductivity and light transmission) of the produced fluorescent ceramic.
  • the present invention introduces a magnesium oxide-yttria mixed sintering aid in the preparation process, and the sintering aid first enters the liquid phase during the sintering process, and promotes the alumina to enter the liquid phase at a lower temperature, thereby promoting sintering.
  • the function not only improves the heat conduction and light transmission properties of the sintered body, but also ensures that as many phosphors as possible are not affected by excessive temperature during the sintering process, and the physical structure and surface morphology are maintained, thereby making the system
  • the obtained fluorescent ceramic has good luminous efficiency.
  • the refractive index of the magnesia-yttria mixed sintering aid is close to that of the alumina, which can reduce the light scattering loss of the light in the fluorescent ceramic and contribute to the improvement of the light transmittance of the ceramic. Moreover, the sintering aid does not cause damage to the surface topography of the phosphor.
  • the particle size referred to in the present invention means a median diameter D50.
  • the nanometer-sized alumina powder can be used to greatly reduce the temperature of entering the liquid phase, so that the alumina can enter the liquid phase before the phosphor, thereby avoiding the destruction of the physical structure of the phosphor.
  • the phosphor is YAG:Ce 3+ , and a LuAG:Ce 3+ , YAG-doped lanthanide phosphor or a LuAG-doped lanthanide-based phosphor may be selected.
  • the sintering aid is a magnesia-yttria mixed sintering aid. It has been proved that the sintering aid has an effect on the surface of the alumina without affecting the surface morphology of the phosphor.
  • the phosphor is subjected to a second ball milling to finally obtain a fluorescent ceramic precursor slurry.
  • the method of two-step ball milling is adopted, the first ball milling time is greater than the second ball milling time, so that the alumina powder with smaller particle size and less uniform dispersion can be fully dispersed first, and then the phosphor ball milling is added to avoid fluorescence.
  • the ball milled for a long time reduces the damage to the phosphor during the ball milling process.
  • the purpose of this step is to remove impurities such as a grinding solvent, a thickener, a dispersant, and the like in the slurry obtained in the mixing step to obtain a high-purity fluorescent ceramic precursor powder.
  • the sintering aid At the sintering temperature, the sintering aid first enters the liquid phase and promotes the entry of the alumina into the liquid phase, thereby causing phase migration; while the phosphor does not enter or enter the liquid phase in a small amount, only a very small amount of phase migration occurs, so that The phosphor can maintain the original crystal morphology, and its luminous intensity is not easily affected.
  • sintering is performed under a vacuum atmosphere, which is more advantageous for gas exclusion inside the raw material, reducing the number of closed-cell pores and open-cell pores, and is advantageous for obtaining a high-density sintered body.
  • the light transmission performance of the sintered body is also improved due to a large reduction in the refractive and scattering effects of the micropores.
  • the sintering process can also be carried out in other inert gases or a mixture of nitrogen, hydrogen, nitrogen and hydrogen to avoid the reaction of the alumina or phosphor with the atmosphere.
  • the obtained high-purity fluorescent ceramic precursor powder is weighed in an appropriate amount, placed in a graphite mold, pre-formed at 5 to 15 MPa, and then the powder is together with the mold. It is placed in a spark plasma sintering furnace, and the fluorescent ceramic precursor powder is sintered at 30 to 200 MPa (pressure is applied to the fluorescent ceramic precursor powder through a mold), and sintering is performed under vacuum at a sintering temperature of 1,250 to 1,550 °C.
  • the raw material is high-purity ultrafine alumina nano powder, the particle size of the powder is 0.08-0.2 ⁇ m, and the high-purity ultra-fine nano-cerium oxide powder is selected, the particle size is 0.05-0.1 ⁇ m, and the high-purity ultrafine nanometer magnesium oxide powder is selected.
  • the particle size is 15-20 ⁇ m.

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  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

一种氧化铝基质的荧光陶瓷的制备方法，依序包括以下步骤：将氧化铝、荧光粉与烧结助剂混合并煅烧，得到荧光陶瓷前驱体粉末，然后将粉末烧结，得到荧光陶瓷。各组分的粒径选择为预设大小，荧光陶瓷前驱体粉末在烧结前经过5MPa以上高压处理，在烧结中承受30-200MPa的高压，烧结温度为1250-1550℃，在无氧气氛下进行。

Description

一种氧化铝基质的荧光陶瓷的制备方法及相关荧光陶瓷 技术领域
本发明涉及荧光陶瓷领域，特别是涉及一种氧化铝基质的荧光陶瓷的制备方法及相关荧光陶瓷。
背景技术
蓝色激光激发荧光材料获得可见光的技术，随着激光显示技术的发展不断获得重视，当前的研究大方向主要是针对激光激发荧光粉的特性来开发新型的荧光材料(波长转换材料)，主要的要求是发光亮度高、能够承受大功率激光照射、光学转换效率高、导热性能高等特点。
传统的荧光陶瓷主要针对LED的发光特性开发，由于LED芯片的功率较小，发出的蓝光功率密度较低，因此针对LED开发的发光陶瓷的发光效率并没有得到足够的重视。比如常见的YAG荧光陶瓷主要由原料粉末Al2O3、Y2O3、CeO2煅烧后，压力机下压制成片，然后烧结得到荧光陶瓷。由于荧光陶瓷一般覆盖LED表面，需追求一定的透光性能，因此YAG荧光陶瓷比较偏向透光度性能，其中的晶粒成长程度较低，导致其发光亮度偏低。此外，传统的YAG陶瓷的热导率也相对较低，一般为10～14W/(m·K)，随着激光光源技术的发展，光源功率越来越大，要求光转换材料具有更高的热导性能，能够将光转化过程中产生的大量热量迅速的传递出去。
因此，一种获得高热导率、高发光效率的荧光陶瓷的制备方法亟待开发。
发明内容
针对上述现有技术中，制备得到的荧光陶瓷热导率低、发光效率低的缺陷，本发明提供一种获得高热导率、高发光效率的荧光陶瓷的制备方法，依序包括以下步骤：
混料：将氧化铝、荧光粉、烧结助剂与研磨溶剂均匀混合，得到荧 光陶瓷前驱体浆料，氧化铝的粒径为0.05～1μm，荧光粉为YAG掺杂镧系元素的荧光粉或LuAG掺杂镧系元素的荧光粉，荧光粉的粒径为10～30μm，烧结助剂为氧化镁-氧化钇混合烧结助剂，烧结助剂的粒径为0.05～0.1μm；煅烧：将荧光陶瓷前驱体浆料干燥，然后将其在有氧气氛下煅烧，除去其中的水和有机物，获得荧光陶瓷前驱体粉末；烧结：将荧光陶瓷前驱体粉末烧结，得到荧光陶瓷，烧结温度为1250～1550℃，烧结压力为30～200MPa，烧结在无氧气氛下进行，其中，该荧光陶瓷前驱体粉末在烧结前经过5MPa以上高压预处理，使粉末保持致密。
优选地，荧光粉包括YAG:Ce3+或LuAG:Ce3+。
优选地，荧光粉占荧光陶瓷前驱体粉末总量的质量百分比为30～80％，烧结助剂占荧光陶瓷前驱体粉末总量的质量百分比为0.01～1％。
优选地，混料步骤包括，首先将氧化铝和烧结助剂装入球磨罐，加入研磨溶剂、增稠剂和分散剂，进行第一次球磨；然后将荧光粉加入球磨罐，进行第二次球磨，其中，第一次球磨时间大于第二次球磨时间。
优选地，煅烧步骤中，煅烧温度为500～650℃。
优选地，烧结步骤中，无氧气氛为氮气、氢气、氮气氢气混合气、惰性气体或真空气氛。
优选地，烧结步骤包括，将荧光陶瓷前驱体粉末在模具中5～15MPa高压预成型，然后将荧光陶瓷前驱体粉末连同模具一同放入热压烧结炉中，使荧光陶瓷前驱体粉末在30～200MPa下烧结。
优选地，烧结步骤包括，将荧光陶瓷前驱体粉末在模具中5～15MPa高压预成型，然后将荧光陶瓷前驱体粉末连同模具一同放入放电等离子烧结炉中，使荧光陶瓷前驱体粉末在30～200MPa下烧结，烧结在真空气氛下进行。
优选地，在烧结步骤后，还包括对荧光陶瓷的还原处理步骤，该还原处理步骤在还原气氛下进行，且还原处理步骤的温度环境为1100～1700℃。
本发明还提供了一种荧光陶瓷，该荧光陶瓷由上述的制备方法制备。
与现有技术相比，本发明包括如下有益效果：
本发明通过将氧化镁-氧化钇混合烧结助剂与粒径为0.05～1μm的氧化铝、粒径为10～30μm的YAG掺杂镧系元素的荧光粉或LuAG掺杂镧系元素的荧光粉混合，将粉末在1250～1550℃下进行30～200MPa高压烧结，从而得到荧光陶瓷。本发明技术方案中，氧化铝粒径的选择及高压处理过程使得氧化铝得以在较低温度下进入液相，氧化镁-氧化钇混合烧结助剂的存在使得氧化铝进入液相的温度进一步降低，而且该温度下，该烧结助剂不会对所选粒径的荧光粉产生破坏影响，使其能够保持表面形貌基本不变，使得成型后的荧光陶瓷能够保留原荧光粉的发光性能；同时，由于选择了小粒径，并在高压处理的协同作用下，荧光陶瓷前驱体粉末能够在烧结前后保持致密、低孔隙率的状态，极大的提高了荧光陶瓷的导热性能，从而制备出高热导率、高发光效率的荧光陶瓷。
附图说明
图1为本发明实施例的荧光陶瓷的制备方法的流程图；
具体实施方式
正如背景技术所述，现有技术中的荧光陶瓷的制备通过将荧光粉原料(即各类氧化物)烧结制得，对其透光性有一定要求，这样得到的荧光陶瓷，发光效率明显低于同样原料制备得到的荧光粉粉末，而且YAG陶瓷的热导率低，对于使用过程中的散热非常不利。本发明制备氧化铝基质的荧光陶瓷，直接采用已有的商用荧光粉作为原料，在制备过程中不经历荧光粉制备的步骤，避免了荧光陶瓷制备中荧光粉晶粒生长过程带来的各种问题，同时以通过选用小粒径的氧化铝并配合高压处理过程，使得制得的荧光陶瓷的氧化铝基质致密、高导热，成品具有良好的散热性能。
由于荧光粉与氧化铝的熔点接近，且略低于氧化铝的熔点(如YAG的熔点为1950℃，氧化铝的熔点为2050℃)，在制备过程中，当氧化铝进入液相时，荧光粉的原有结构容易遭到破坏，这样得到的氧化铝基质的荧光陶瓷发光效率低。本发明中，通过选择合适粒径的氧化铝粉末和 荧光粉，使得氧化铝粉末的粒径远小于荧光粉，降低了氧化铝进入液相所需的温度，而不降低荧光粉进入液相的温度，确保了荧光粉在烧结温度下能够保持物理结构稳定，使荧光粉具备大粒径荧光粉的高发光效率。此外，氧化铝粒径小，使得制备过程中的高压处理能够充分填充荧光陶瓷内的孔隙，提高了制得的荧光陶瓷的致密度(进而提高导热性能和透光性能)。此外，本发明在制备过程中引入了氧化镁-氧化钇混合烧结助剂，该烧结助剂在烧结过程中率先进入液相，并促使氧化铝在更低温度下进入液相，起到了促进烧结的作用，不但提高了烧结体的导热和透光性能，同时还确保了尽可能多的荧光粉在烧结过程中没有受到过高温度的影响，得以保持物理结构、表面形貌稳定，从而使得制得的荧光陶瓷具备良好的发光效率。氧化镁-氧化钇混合烧结助剂的折射率与氧化铝接近，能够减少光在荧光陶瓷中的光散射损失，有助于提高陶瓷的透光性能。而且该烧结助剂不会对荧光粉的表面形貌造成破坏。
本发明区别于制备单独的氧化铝陶瓷的技术方案的特点在于，烧结助剂、各组分的粒径的选择必须考虑到对荧光粉的影响，同时考虑荧光粉对氧化铝、烧结助剂的反作用，使得在烧结过程中，尽可能不影响荧光粉的情况下，使得氧化铝进入液相，形成对大粒径荧光粉的包裹。
下面结合附图和实施方式对本发明实施例进行详细说明。
本发明所述的粒径，指中位粒径D50。
如图1为本发明实施例的荧光陶瓷的制备方法的流程图。如图所示，该制备方法依序包括以下步骤：
①混料：将氧化铝、荧光粉、烧结助剂与研磨溶剂均匀混合，得到荧光陶瓷前驱体浆料，烧结助剂为氧化镁-氧化钇混合烧结助剂，烧结助剂的粒径为0.05～0.1μm；
②煅烧：将荧光陶瓷前驱体浆料干燥，然后将其在有氧气氛下煅烧，除去其中的水和有机物，获得荧光陶瓷前驱体粉末；
③烧结：将荧光陶瓷前驱体粉末烧结，得到荧光陶瓷，烧结温度为1250～1550℃，烧结压力为30～200MPa，烧结在无氧气氛下进行，其中，该荧光陶瓷前驱体粉末在烧结前经过5MPa以上高压预处理。
在混料步骤中，首先是原料的选择，本实施例选用小粒径的超细氧 化铝粉，粒径为0.05～1μm，更优选的，选择0.06～0.2μm的氧化铝粉；荧光粉的粒径则远大于氧化铝，为10～30μm。一般而言，荧光粉YAG:Ce3+的熔点为1970℃左右，而氧化铝的熔点为2050℃，在氧化铝进入液相之前，荧光粉的物理结构已经被破坏，这样的荧光粉即使再成型，其发光效率也将明显下降。本实施例采用纳米级的氧化铝粉，可以大幅降低其进入液相的温度，使得氧化铝能够先于荧光粉进入液相，避免了荧光粉物理结构的破坏。本实施例中，荧光粉为YAG:Ce3+，也可以选择LuAG:Ce3+、YAG掺杂镧系元素的荧光粉或LuAG掺杂其他镧系元素的荧光粉。烧结助剂选用氧化镁-氧化钇混合烧结助剂，实验证明，这种烧结助剂对氧化铝的表面产生作用，而不影响荧光粉的表面形貌。
本实施例中，荧光粉占荧光陶瓷前驱体粉末总量的质量百分比为30～80％。荧光粉作为发光中心，必须要有足够的量，才能保证荧光陶瓷发光强度，而且荧光粉的比重越高，越有利于荧光陶瓷最大发光强度的提高；但是，氧化铝作为基质，须达到足够的量才能保证连续分布，因此荧光粉不能过多。烧结助剂占粉末总量的质量百分比为0.01～1％，烧结助剂的量太少时作用不明显；但当烧结助剂的量过多，超过1wt％时，会限制氧化铝的生长，并产生杂相，降低荧光陶瓷的热导率和透光性。
本实施例中，采用球磨的方式混合。首先称取一定量的氧化铝粉末，装入球磨罐，添加适量的研磨溶剂(如乙醇)、增稠剂和分散剂，然后进行第一次球磨，得到粘稠悬浮状的浆料，再加入荧光粉，进行第二次球磨，最终得到荧光陶瓷前驱体浆料。本实施例采用二步球磨的方法，第一次球磨时间大于第二次球磨时间，使得粒径较小、不易分散均匀的氧化铝粉能够先充分分散，然后再加入荧光粉球磨，避免了荧光粉过长时间的球磨，减少了该球磨过程对荧光粉的损害。
在煅烧步骤中，该步骤的目的为将混料步骤中得到的浆料中的研磨溶剂、增稠剂、分散剂等杂质除去，得到高纯度荧光陶瓷前驱体粉末。
本实施例中，首先对荧光陶瓷前驱体浆料进行干燥，得到干粉，然后将干粉进行煅烧，使干粉中的有机成分分解、挥发。由于氧化铝和荧光粉的熔点高、热稳定性好，除去有机物的温度(一般在1000℃以下)不会对氧化铝和荧光粉的结构造成影响；本实施例中，煅烧温度为 500～650℃，在该温度下，氧化铝和荧光粉也不会氧化，因此可以在有氧气氛(如空气)下进行煅烧。
本实施例中，在烧结步骤之前，先对荧光陶瓷前驱体粉末进行造粒，将其转为颗粒大小为50～200μm的粉末。该造粒结果可以增加烧结过程中粉末的流动性，有利于烧结前后的高压成型，促使制备得到的荧光陶瓷致密而均匀。
在烧结步骤中，将得到的高纯度荧光陶瓷前驱体粉末称取适量，装入石墨模具中，在5～15MPa下预压成型，然后将荧光陶瓷前驱体粉末连同模具一同放入热压烧结炉中，使荧光陶瓷前驱体粉末在30～200MPa下烧结(压力的施加通过模具传递给荧光陶瓷前驱体粉末)，烧结在氩气气氛下，烧结温度为1250～1550℃。该烧结温度下，烧结助剂率先进入液相，并促使氧化铝进入液相，产生物相迁移；而荧光粉不进入或很少量进入液相，只产生极小量的物相迁移，使得荧光粉能够保持原有的晶体形貌，其发光强度不易受到影响。
在本发明的另一个实施例中，烧结在真空气氛下进行，该气氛下，更有利于原料内部的气体排除，减少闭孔气孔和开孔气孔的数量，有利于获得高致密度的烧结体，由于大量减少的了微型气孔的折射与散射效应，烧结体的透光性能也获得提高。
此外，烧结过程也可以在其他惰性气体或氮气、氢气、氮氢混合气中进行，避免氧化铝或荧光粉与气氛反应。
在本发明的另一个实施例中，在烧结步骤中，将得到的高纯度荧光陶瓷前驱体粉末称取适量，装入石墨模具中，在5～15MPa下预压成型，然后将粉末连同模具一同放入放电等离子烧结炉中，使荧光陶瓷前驱体粉末在30～200MPa下烧结(压力的施加通过模具传递给荧光陶瓷前驱体粉末)，烧结在真空下进行，烧结温度为1250～1550℃。该烧结过程中，晶粒间的放电及电离化产生局部高温，在粉末颗粒表面引起蒸发和融化，促进了荧光陶瓷致密化的过程，有效的降低了烧结温度。
在本实施例中，热处理烧结过程的优选升温速率为30～200℃/min(根据各烧结设备的升温能力)，由于烧结之前的煅烧步骤及高压处理，使得荧光陶瓷前驱体粉末在升温过程中保持内部致密无孔隙，不会因为 升温速率快而体积明显膨胀以致产物荧光陶瓷开裂。同时，快速的升温速率使得荧光陶瓷前驱体避免了长时间升温带来的副反应(例如与周围环境的反应、及荧光粉内部的反应)，确保了荧光陶瓷具有良好的透光性、导热性和发光性能。本发明中，由于烧结过程主要涉及物理变化，快速的升温速率对其的影响不如其他化学物反应中的大。
在本发明的实施例中，经过烧结后得到的荧光陶瓷，还进一步包括对荧光陶瓷的还原处理步骤，该步骤在还原气氛下进行(如氮气/氢气混合气体)，该还原处理在略低于热处理烧结温度下进行，还原温度为1100～1700℃。该还原处理过程可以将烧结步骤中附着在荧光陶瓷上的杂质去除，避免杂质成为荧光陶瓷在工作环境下的产热中心而影响荧光陶瓷的使用。
以下为不同条件下制备荧光陶瓷的各实施例对比。
实施例一
原料选用高纯度超细氧化铝纳米粉末，粉末粒径为0.08-0.2μm，选用高纯度超细纳米氧化钇粉末，粒径为0.05-0.1μm，选用高纯度超细纳米氧化镁粉末，粒径为0.05-0.1μm，选用YAG:Ce3+荧光粉，粒径为15-20μm。
称取一定数量的氧化铝粉末(39.9wt％)、氧化钇粉末(0.05wt％)、氧化镁粉末(0.05wt％)和YAG:Ce3+荧光粉粉末(60wt％)。将氧化铝粉末、氧化钇粉末和氧化镁粉末装入聚四氟乙烯球磨罐中，添加适量的乙醇作为研磨溶剂，添加适量的陶瓷分散剂作为分散剂，用超低磨失率的氧化锆球进行第一次球磨，球磨时间为5h。
第一次球磨结束后，添加YAG:Ce3+荧光粉到球磨罐中，进行第二次球磨，球磨时间为20min。
两次球磨结束后，采用真空恒温干燥获得干粉。
干粉在马弗炉中进行500℃的煅烧，除去粉末中的有机成分，时间为2小时。煅烧后的粉末过筛造粒，得到高流动性的荧光陶瓷前驱体粉末。
称取适量荧光陶瓷前驱体粉末装入石墨模具中，在5MPa压强下进行预压制，然后将石墨模具放入热压烧结炉内，在氩气气氛下烧结，烧 结温度1250℃，保温8h，烧结压力为200MPa。烧结完成后，卸除压力并随炉冷却，获得氧化铝基质的荧光陶瓷复合材料。
实施例二
原料选用高纯度超细氧化铝纳米粉末，粉末粒径为0.08-0.2μm，选用高纯度超细纳米氧化钇粉末，粒径为0.05-0.1μm，选用高纯度超细纳米氧化镁粉末，粒径为0.05-0.1μm，选用YAG:Ce3+荧光粉，粒径为15-20μm。
称取一定数量的氧化铝粉末(30wt％)、氧化钇粉末(0.5wt％)、氧化镁粉末(0.5wt％)和YAG:Ce3+荧光粉粉末(69wt％)。将氧化铝粉末、氧化钇粉末和氧化镁粉末装入聚四氟乙烯球磨罐中，添加适量的乙醇作为研磨溶剂，添加适量的陶瓷分散剂作为分散剂，用超低磨失率的氧化锆球进行第一次球磨，球磨时间为24h。
第一次球磨结束后，添加YAG:Ce3+荧光粉到球磨罐中，进行第二次球磨，球磨时间为40min。
两次球磨结束后，采用真空恒温干燥获得干粉。
干粉在马弗炉中进行600℃的煅烧，除去粉末中的有机成分，时间为2小时。煅烧后的粉末过筛造粒，得到高流动性的荧光陶瓷前驱体粉末。
称取适量荧光陶瓷前驱体粉末装入石墨模具中，在15MPa压强下进行预压制，然后将石墨模具放入放电等离子烧结炉内，在真空下烧结，烧结温度1450℃，保温2h，烧结压力为40MPa。烧结完成后，卸除压力并随炉冷却，获得氧化铝基质的荧光陶瓷复合材料。
实施例三
原料选用高纯度超细氧化铝纳米粉末，粉末粒径为0.08-0.2μm，选用高纯度超细纳米氧化钇粉末，粒径为0.05-0.1μm，选用高纯度超细纳米氧化镁粉末，粒径为0.05-0.1μm，选用LuAG:Ce3+荧光粉，粒径为15-20μm。
称取一定数量的氧化铝粉末(30wt％)、氧化钇粉末(0.5wt％)、氧化镁粉末(0.5wt％)和YAG:Ce3+荧光粉粉末(69wt％)。将氧化铝粉末、氧化钇粉末和氧化镁粉末装入聚四氟乙烯球磨罐中，添加适量的乙醇作 为研磨溶剂，添加适量的陶瓷分散剂作为分散剂，用超低磨失率的氧化锆球进行第一次球磨，球磨时间为24h。
第一次球磨结束后，添加YAG:Ce3+荧光粉到球磨罐中，进行第二次球磨，球磨时间为50min。
两次球磨结束后，采用真空恒温干燥获得干粉。
干粉在马弗炉中进行650℃的煅烧，除去粉末中的有机成分，时间为3小时。煅烧后的粉末过筛造粒，得到高流动性的荧光陶瓷前驱体粉末。
称取适量荧光陶瓷前驱体粉末装入石墨模具中，在10MPa压强下进行预压制，然后将石墨模具放入放电等离子烧结炉内，在真空下烧结，烧结温度1450℃，保温3h，烧结压力为50MPa。烧结完成后，卸除压力并随炉冷却，获得氧化铝基质的荧光陶瓷复合材料。
本发明还涉及用上述制备方法制备的氧化铝基质的荧光陶瓷，该荧光陶瓷包括基质氧化铝和被基质包裹的荧光粉，以及微量的烧结助剂，其中基质氧化铝呈连续分布状态，致密无气孔、热导率高，使得荧光粉发出的热量能够被迅速导出。而且氧化铝透明度高，烧结助剂与氧化铝的折射率接近，氧化铝表面的光散射少，不会对荧光粉发出的光形成阻挡。
本说明书中各个实施例之间相同相似部分互相参见即可。
以上所述仅为本发明的实施方式，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (10)

  1. 一种氧化铝基质的荧光陶瓷的制备方法，其特征在于，依序包括以下步骤：
    混料：将氧化铝、荧光粉、烧结助剂与研磨溶剂均匀混合，得到荧光陶瓷前驱体浆料，所述氧化铝的粒径为0.05～1μm，所述荧光粉为YAG掺杂镧系元素的荧光粉或LuAG掺杂镧系元素的荧光粉，荧光粉的粒径为10～30μm，所述烧结助剂为氧化镁-氧化钇混合烧结助剂，烧结助剂的粒径为0.05～0.1μm；
    煅烧：将所述荧光陶瓷前驱体浆料干燥，然后将其在有氧气氛下煅烧，除去其中的水和有机物，获得荧光陶瓷前驱体粉末；
    烧结：将所述荧光陶瓷前驱体粉末烧结，得到荧光陶瓷，烧结温度为1250～1550℃，烧结压力为30～200MPa，烧结在无氧气氛下进行，其中，该荧光陶瓷前驱体粉末在烧结前经过5MPa以上高压预处理，使粉末保持致密。
  2. 根据权利要求1所述的制备方法，其特征在于，所述荧光粉包括YAG:Ce3+或LuAG:Ce3+。
  3. 根据权利要求1所述的制备方法，其特征在于，所述荧光粉占所述荧光陶瓷前驱体粉末总量的质量百分比为30～80％，所述烧结助剂占所述荧光陶瓷前驱体粉末总量的质量百分比为0.01～1％。
  4. 根据权利要求1所述的制备方法，其特征在于，所述混料步骤包括，首先将所述氧化铝和烧结助剂装入球磨罐，加入研磨溶剂、增稠剂和分散剂，进行第一次球磨；然后将所述荧光粉加入球磨罐，进行第二次球磨，其中，第一次球磨时间大于第二次球磨时间。
  5. 根据权利要求1所述的制备方法，其特征在于，所述煅烧步骤中，煅烧温度为500～650℃。
  6. 根据权利要求1所述的制备方法，其特征在于，所述烧结步骤中，所述无氧气氛为氮气、氢气、氮气氢气混合气、惰性气体或真空气氛。
  7. 根据权利要求1所述的制备方法，其特征在于，所述烧结步骤 包括，将所述荧光陶瓷前驱体粉末在模具中5～15MPa高压预成型，然后将所述荧光陶瓷前驱体粉末连同模具一同放入热压烧结炉中，使所述荧光陶瓷前驱体粉末在30～200MPa下烧结。
  8. 根据权利要求1所述的制备方法，其特征在于，所述烧结步骤包括，将所述荧光陶瓷前驱体粉末在模具中5～15MPa高压预成型，然后将所述荧光陶瓷前驱体粉末连同模具一同放入放电等离子烧结炉中，使所述荧光陶瓷前驱体粉末在30～200MPa下烧结，烧结在真空气氛下进行。
  9. 根据权利要求7或8所述的制备方法，其特征在于，在烧结步骤后，还包括对荧光陶瓷的还原处理步骤，该还原处理步骤在还原气氛下进行，且还原处理步骤的温度环境为1100～1700℃。
  10. 一种荧光陶瓷，其特征在于，该荧光陶瓷由权利要求1～9中任一项所述的制备方法制备。
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