WO2018233114A1 - 一种发光陶瓷复合材料的制备方法以及发光陶瓷复合材料 - Google Patents

一种发光陶瓷复合材料的制备方法以及发光陶瓷复合材料 Download PDF

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WO2018233114A1
WO2018233114A1 PCT/CN2017/103432 CN2017103432W WO2018233114A1 WO 2018233114 A1 WO2018233114 A1 WO 2018233114A1 CN 2017103432 W CN2017103432 W CN 2017103432W WO 2018233114 A1 WO2018233114 A1 WO 2018233114A1
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sintering aid
ceramic composite
sintering
luminescent ceramic
phosphor
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李乾
陈雨叁
许颜正
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Shenzhen Appotronics Corp Ltd
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Appotronics Corp Ltd
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Definitions

  • the invention relates to a method for preparing a luminescent ceramic composite material, and a luminescent ceramic composite material prepared by the method.
  • Blue laser-excited fluorescent material to obtain visible light laser fluorescence technology as a new light source technology, rapid development in the field of laser display, various companies have rushed to launch laser light sources that meet various powers in different markets, and achieved great Success.
  • the hotspots and difficulties in current research are mainly to develop new fluorescent materials (wavelength conversion materials, luminescent materials) for the characteristics of laser-excited phosphors, among which these materials must have excellent performance, such as high optical conversion efficiency, high brightness, and unit luminescence.
  • the area can withstand higher power laser irradiation, high thermal conductivity and long life.
  • garnet is the most commonly used laser matrix material, including yttrium aluminum garnet (Y 3 Al 5 O 12 , YAG), yttrium aluminum pomegranate. Stone (Lu 3 Al 5 O 12 , LuAG), yttrium gallium garnet (Y 3 Ga 5 O 12 , YGG), yttrium gallium garnet (Gd 3 Ga 5 O 12 , GGG), yttrium gallium garnet (Lu 3 Ga 5 O 12 , LuGG), etc.
  • Luminescent ceramics are one of the ideal luminescent materials due to their good heat resistance and excellent thermal conductivity.
  • the traditional YAG pure phase luminescent ceramics are still weaker in luminescent properties than the composite illuminating devices of silica gel and glass package; especially in ultra-thin packaging, the light effect caused by total reflection of the interface is greatly lost. Therefore, the use of ceramic materials to encapsulate phosphors is worthy of further research.
  • Preparation of YAG-YAG:Ce phosphor or Ce:YAG-YAG:Ce phosphor ceramic material, such as undoped YAG pure phase material or different Ce doping YAG material encapsulated YAG phosphor can obtain specific phase YAG luminescence Ceramics have better optical properties.
  • Patent Document 1 discloses a method for preparing a yttrium aluminum garnet-based transparent ceramic by using L ⁇ 2 O 3 , RE 2 O 3 , Al 2 O 3 , etc. as raw materials.
  • the oxide powder or L ⁇ 3-x RE x Al 5 O 12 as a raw material is mixed with SiO 2 or tetraethyl orthosilicate (TEOS) as a sintering aid, and then formed by dry pressing, cold isostatic pressing or the like. Any one of the processes is molded, and then subjected to pressureless sintering, hot press sintering, annealing, or the like.
  • TEOS tetraethyl orthosilicate
  • Patent Document 2 discloses a method of preparing a transparent luminescent ceramic using a compound having a structural formula of RX (wherein R represents a luminescent ion and X represents a volatile anion) as a sintering aid and The constituent material of the luminescent activated ion is mixed with the raw material, and then subjected to grinding, pressing, sintering (sintering may be vacuum sintering, atmosphere sintering, hot press sintering), annealing, or the like.
  • sintering may be vacuum sintering, atmosphere sintering, hot press sintering
  • annealing or the like.
  • voids are formed between the particles due to problems of powder fluidity and filling property. The presence of voids can affect the properties of the material.
  • the sintering densification process of ceramics is mainly driven by the formation of a liquid phase inside the ceramic body during sintering.
  • the raw material powder is pre-mixed, and then pre-pressed into a green body using a mold, and then placed in a furnace for sintering.
  • the sintering aid as described above, the usual method is to mix the ceramic powder and the sintering aid as uniformly as possible. Put it together and fill it into the mold for pre-pressing.
  • the powder is mixed in the process of filling the mold and being pressed into the mold.
  • the ideal green body, the shape of each part should be Relatively uniform.
  • MgO is used as a sintering aid when preparing a YAG-YAG:Ce phosphor or a Ce:YAG-YAG:Ce phosphor is described as an example.
  • YAG or YAG: Ce phase particles are distributed around the YAG:Ce phosphor particles, and MgO is evenly distributed between them.
  • the internal structure will have more structure as shown in Fig. 2; this is because the powder is subjected to pressure in the mold and is subjected to pressure inconsistency, uneven friction between particles and inconsistent particle flow.
  • the present invention provides a method for preparing a luminescent ceramic composite material, characterized in that the method comprises the following steps:
  • a green body comprising a phosphor and an encapsulating material for encapsulating the phosphor and optionally a sintering aid a is impregnated into the precursor solution of the sintering aid b, and the infiltrated green body is calcined to make the sintering aid b
  • the precursor is converted into an infiltration-calcination step of the sintering aid b;
  • the green body after calcination is subjected to normal pressure sintering or vacuum sintering to obtain a sintering step of the luminescent ceramic composite material.
  • the method for preparing a luminescent ceramic composite according to the present invention wherein the total amount of the sintering aid is 0.1 to 5%, preferably 0.5% to 1.5%, based on the total mass of the phosphor and the encapsulating material.
  • the method for producing a luminescent ceramic composite according to the present invention wherein the concentration of the precursor solution of the sintering aid b is from 0.01 to 10 M, preferably from 0.1 M to 10 M, more preferably from 0.1 to 1 M.
  • the method for preparing a luminescent ceramic composite according to the present invention wherein the immersion time of the green immersion sintering aid is from 10 min to 120 min, preferably from 30 min to 90 min, more preferably from 40 min to 60 min. And/or, the calcination temperature is 200 to 500 ° C, preferably 300 to 500 ° C, more preferably 350 to 450 ° C.
  • the method for producing a luminescent ceramic composite according to the present invention wherein the above wetting-calcining step can be repeated 1 to 5 times, preferably 1 to 3 times.
  • a method of producing a luminescent ceramic composite according to the present invention further comprising a step of preparing a green body, the step comprising mixing a powder comprising a phosphor and an encapsulating material for encapsulating the phosphor and optionally a sintering aid a Ball milling, drying, sieving, and pressing are performed to obtain a green body.
  • the sintering aids a and b are independently one or more of MgO, SiO 2 , CaF 2 and BaF 2 .
  • the method for producing a luminescent ceramic composite according to the present invention wherein the precursor of the sintering aid b is an inorganic salt or an alkoxide of a sintering aid.
  • the present invention also provides a luminescent ceramic composite material comprising a phosphor, an encapsulating material for encapsulating the phosphor, and a sintering aid.
  • the relative density of the luminescent ceramic composite material is 94% or more.
  • the particles of the encapsulating material are uniformly distributed around the particles of the phosphor, and the sintering aid is distributed at the grain boundary of the encapsulating material.
  • the total amount of the sintering aid in the luminescent ceramic composite material is 0.1 to 5%, preferably 0.5% to 1.5%, of the total mass of the phosphor and the encapsulating material.
  • the total amount of the sintering aid is the sum of the masses of the sintering aids a and b.
  • the sintering aids a and b are independently one or more of MgO, SiO 2 , CaF 2 , and BaF 2 .
  • the encapsulating material is one or more of YAG, YAG: Ce or Al 2 O 3 .
  • the void inside the green body is filled with the precursor solution of the sintering aid by immersing the pre-compressed green body in the precursor solution of the sintering aid, and then infiltrating After the green body is taken out, dried and calcined, the content of the sintering aid in the inner void of the green body is improved. According to actual requirements, the green body can be infiltrated multiple times to obtain the auxiliary content in accordance with the demand. After the infiltration-calcining aid process, the internal structure of FIG. 2 will become the structure of FIG. 3; It can be seen from Fig. 2 and Fig.
  • the present invention does not require a hot press sintering method in which the equipment is complicated, the production environment is strict, the mold material requirements are high, the energy consumption is high, the production efficiency is low, and the production cost is high, and the sintering is improved by using the liquid phase infiltration method.
  • the auxiliaries are added under the conditions of normal pressure sintering or vacuum sintering to obtain luminescent ceramic composite materials with less voids, higher relative density and more excellent optical properties.
  • Figure 1 is a schematic view of powder particles of each phase having a uniform distribution inside the green body.
  • Fig. 2 is a schematic view showing powder particles of respective phases in which the internal distribution of the green body is uneven.
  • Fig. 3 is a schematic view showing the distribution of powder particles in each phase of the green body after infiltration-calcination.
  • Figure 5 is a preparation step of one embodiment of a luminescent ceramic composite.
  • Figure 6 is a preparation step of another embodiment of a luminescent ceramic composite.
  • the method for preparing the luminescent ceramic composite material of the present invention comprises the following steps:
  • step S: 4 further includes the steps:
  • the green body is ball-milled, dried, sieved, and pressed by mixing powder containing a phosphor, an encapsulating material for encapsulating the phosphor, and optionally a sintering aid a. The steps are made.
  • a mixed powder containing a phosphor, an encapsulating material for encapsulating the phosphor, and an optional sintering aid a is charged into a polytetrafluoroethylene ball mill tank, and an appropriate amount of ethanol is added as a grinding solvent, and no dispersion is used.
  • Agent ball milling with ultra-low wear rate zirconia balls.
  • the ball milling time can be selected as needed, and therefore is not particularly limited, but is usually from 1 to 120 min, preferably from 30 to 50 min. If the ball milling time is too long, it is easy to damage the grain surface morphology of the phosphor and affect the luminescence properties.
  • the ball milling After the ball milling is completed, it is then dried to obtain a dry powder.
  • it is dried by vacuum constant temperature, and the drying temperature may be 40 to 120 ° C, preferably 50 to 100 ° C, and the drying time may be 1 h to 12 h, preferably 4 to 8 h.
  • the mesh was passed through a mesh of 80 mesh, 150 mesh, and 200 mesh to obtain a raw material powder having high fluidity.
  • the method of pressing is not particularly limited and can be carried out by a conventional pressing method such as cold isostatic pressing or the like.
  • the pressing pressure is usually from 5 to 200 MPa, preferably from 15 to 100 MPa. If the pressure is too small, it will lead to more pores, which will affect the density of the final sintered product.
  • the two powders may be mixed. Further, the weight ratio of the phosphor to the encapsulating material is from 1:0.1 to 0.1:1, preferably 1:1.
  • the mixed powder of the previously prepared encapsulating material and the sintering aid a is usually mixed with the fluorescent powder. Further, the total mass ratio of the sintering aid a to the phosphor and the encapsulating material is (0.01 to 5): 100, preferably (0.05 to 1): 100.
  • the phosphor is not particularly limited, and may be any commercially available phosphor that is resistant to temperatures of 1,300 or more.
  • Examples of commonly used phosphors include YAG:RE, LuAG:RE, YGG:RE, GGG:RE, and LuGG:RE, wherein RE is selected from the group consisting of Ce, Pr, Eu, Nd, Sm, Gd, Yb, Ho, Elements in Tm, Dy, and Er.
  • the mixed powder of the encapsulating material and the sintering aid a passes through a suspension of the encapsulating material
  • a solution of a precursor of the sintering aid a (hereinafter referred to as "solution a") is mixed, and then a precipitant is added to coprecipitate them, followed by centrifugation, washing, drying, calcination, and cooling.
  • solution a a solution of a precursor of the sintering aid a
  • it can also be obtained by directly mixing the encapsulating material with the sintering aid a by ball milling.
  • the method for preparing the suspension of the encapsulating material is not particularly limited as long as it can be dispersed.
  • the following method may be employed: 1-3% by mass of PEG aqueous solution is prepared; 50 g of encapsulating material is mixed with 500 ml of PEG aqueous solution; and then ultrasonicated for 1 to 3 hours and then used. Ultrasound is to destroy the secondary agglomeration between the particles and to disperse the powder as much as possible in the solution.
  • the method for preparing the solution of the precursor of the sintering aid a will be further described below.
  • the precursor of the sintering aid a may be a water-soluble inorganic salt or alkoxide of the sintering aid.
  • the precursor of the appropriate amount of the sintering aid a is weighed and prepared by making the weight ratio of the precursor of the sintering aid a to the packaging material a desired ratio.
  • the aqueous solution of the metal inorganic salt may be used in a concentration.
  • the two are preferably mixed in a volume ratio of 5:1 to obtain a mixed suspension, which is placed on a magnetic stirrer and continuously stirred, and the temperature is set to 20 to 80 ° C. It is preferably 40 to 60 ° C and has a rotation speed of 100 to 300 r/m, preferably 170 to 250 r/m.
  • Ammonium bicarbonate is used as a precipitant to prepare an aqueous solution of about 0.01 to 0.1 mol/L, and the mixed suspension which is continuously stirred is slowly dropped until the pH of the mixed suspension is controlled to about 8 to 10, preferably 9 to 9.5.
  • the pH is maintained and stirring is continued for 1 to 5 hours, preferably 2 to 3 hours, to obtain a coprecipitated composite powder suspension.
  • a suitable pH value is important for the dispersion and deflocculation of the ultrafine powder particles of the encapsulating material.
  • at least one of YAG, YAG:Ce or Al 2 O 3 in the present invention may be used as an encapsulating material according to actual needs.
  • the suspension is centrifuged, and the obtained powder is washed with water for 2 to 8 times, preferably 3 to 5 times, and then dried under vacuum at 50 to 150 ° C, preferably 50 to 100 ° C for 1 to 10 hours, preferably 1 to 5 hours.
  • the obtained dry powder is calcined at 200 to 500 ° C, preferably 300 to 400 ° C to remove impurities, and kept for 1 to 5 hours, preferably 2 to 3 hours, and then air-cooled with the furnace to obtain a mixed powder of the encapsulating material and the sintering aid a.
  • the precursor of the sintering aid a is an alkoxide
  • a method capable of making the alkoxide a sol is employed.
  • the following preparation method may be employed: the precursor of the appropriate amount of the sintering aid a is weighed so that the mass ratio of the precursor of the sintering aid a to the encapsulating material is a desired ratio, and the sintering aid a of the desired concentration is prepared.
  • TEOS ethyl orthosilicate
  • n water / n alkoxide 4 / 1
  • the molar ratio of n water / n alkoxide should be equal to less than 4 / 1.
  • the two are preferably mixed in a volume ratio of 5:1 to obtain a mixed suspension, which is placed on a magnetic stirrer and continuously stirred, and the temperature is set to 20 ⁇ . 80 ° C, preferably 40 to 60 ° C, the number of revolutions is 100 to 300 r / m, preferably 170 to 250 r / m. Then, drying is carried out at 120 ° C for 1 to 10 hours, preferably 1 to 5 hours.
  • the obtained dry powder is calcined at 200 to 500 ° C, preferably 300 to 400 ° C to remove impurities, and is kept for 1 to 5 hours, preferably 2 to 3 hours, and then air-cooled with the furnace to obtain a mixed powder of the encapsulating material and the alkoxide sintering aid a. .
  • the solution a When the solution a is prepared, it is prepared in a ratio of (0.01 to 2):100, preferably (0.05 to 1):100, based on the mass ratio of the sintering aid a to the encapsulating material.
  • the concentration of the solution a may be from 0.01 to 1 M, preferably from 0.01 M to 0.1 M, more preferably from 0.01 M to 0.05 M.
  • examples of the encapsulating material include garnet and rare earth doped garnet, specifically, YAG, LuAG, YGG, GGG, LuGG, YAG: RE, LuAG: RE, YGG: RE, GGG: RE And LuGG:RE, wherein RE is an element selected from the group consisting of Ce, Pr, Eu, Nd, Sm, Gd, Yb, Ho, Tm, Dy, and Er.
  • the sintering aid a is not particularly limited, and a sintering aid commonly used in the art may be employed.
  • the sintering aid a may be one or more of MgO, SiO 2 , CaF 2 , and BaF 2 .
  • the magnesium inorganic salt used as the MgO precursor include water-soluble magnesium salts such as Mg(NO 3 ) 2 ⁇ 6H 2 O, MgCl 2 ⁇ 6H 2 O, and MgSO 4 ⁇ 7H 2 O.
  • the magnesium alkoxide used as the MgO precursor include magnesium ethoxide, magnesium isopropoxide, magnesium t-butoxide, and the like.
  • alkoxide used as the SiO 2 precursor examples include methyl orthosilicate, tetraethyl orthosilicate, propyl orthosilicate, butyl orthosilicate, and the like. Among them, tetraethyl orthosilicate is preferred.
  • the wetting-calcining step of the present invention is a method of impregnating a precursor solution of a sintering aid b with a green body comprising a phosphor and an encapsulating material for encapsulating the phosphor and optionally a sintering aid a (hereinafter referred to as "solution b" And the step of calcining the infiltrated green body to convert the precursor of the sintering aid b into the sintering aid b.
  • the wetting time is not particularly limited and is usually from 10 min to 120 min, preferably from 30 min to 90 min, more preferably from 40 min to 60 min.
  • the green body After the completion of the wetting, the green body is taken out, dried, and then calcined to convert the precursor of the sintering aid b mainly attached to the inner void of the green body into particles of the sintering aid b.
  • the drying temperature is not particularly limited and may be usually from 50 to 80 °C.
  • the calcination temperature and calcination time vary depending on the sintering aid, but usually the calcination temperature may be 200 to 500 ° C, preferably 300 to 500 ° C, more preferably 350 to 450 ° C, and the calcination time may be 1 to 5 h, preferably 2 to 3 h. . It should be noted that the drying can also be carried out together with the calcination, that is, the appropriate heating curve is selected to directly calcine.
  • the wetting-calcining process may be repeated as many times as necessary, preferably 1 to 5 times, more preferably 1 to 3 times. It should be noted that each time it is necessary to calcine to convert the sintering aid precursor into sintering aid particles.
  • the preparation of the infiltration solution was identical to the preparation of the above solution a.
  • the concentration of the solution b may be from 0.01 to 10 M, preferably from 0.1 to 10 M, more preferably from 0.1 to 1 M.
  • the content of the sintering aid precursors in the solution a and the solution b may be equal or unequal, and the concentrations of the two solutions may be the same or different.
  • the concentration of the solution b is 5 to 20 times, preferably 5 to 10 times the solution a. Because solution a is used for coprecipitation to uniformly add auxiliary agents, the concentration is relatively low to facilitate uniform precipitation; solution b is used for infiltration, and the concentration can be high.
  • the sintering aid precursor in solution a will all enter the green body, and the sintering aid precursor in solution b will only enter a small portion into the green body.
  • the total sintering aid content in the green sample can be calculated by this principle.
  • the mass of the dry billet before the infiltration of the sintering aid b solution is m; after the infiltration of the sintering aid b solution, and then The mass of the green sheet after calcination is M; then the final addition amount of the sintering aid b is (Mm); and the addition amount of the sintering aid a is determined before the pressing of the dry billet, and the total sintering aid is sintered.
  • the content of the sintering aid b is related to the 1 infiltration time, the concentration of the 2 auxiliary solution b, the volume and surface area of the 3 green sheets, and the degree of looseness inside the 4 sheets; wherein the first three factors can be precisely controlled; the fourth The factor is determined by factors such as the pressure applied to the powder and the shape of the powder particles themselves, and can be controlled within a certain range. Therefore, the content of the total sintering aid in the luminescent ceramic composite can be controlled to a certain extent more accurately.
  • the sintering aid b is not particularly limited, and a sintering aid commonly used in the art may be used.
  • a sintering aid commonly used in the art may be used.
  • one or more of MgO, SiO 2 , CaF 2 and BaF 2 may be used.
  • the sintering aid b may be the same as the sintering aid a.
  • the green body subjected to the wetting-calcining step is tableted under a large pressure.
  • the tableting method is preferably isostatic pressing; the pressure ranges from 100 to 300 MPa, preferably from 180 to 220 MPa. It can be understood that the green sheet subjected to the wetting-calcining step can further reduce the porosity of the green body and increase the density of the finished luminescent ceramic composite material by further pressing under a large pressure.
  • the tableting method can also be a compression molding method such as dry pressing, and the pressure ranges from 100 to 300 MPa. It will be understood that this step is only a preferred implementation step, which may not be included in some specific embodiments.
  • the green sample subjected to the infiltration-calcination process or the tableting step is placed in a sintering furnace and sintered under a vacuum or a nitrogen/nitrogen hydrogen atmosphere to obtain a luminescent ceramic composite material, that is, a phosphor-encapsulating material-sintering auxiliaries composite material. .
  • the sintering temperature and the sintering time vary depending on the packaging material, the sintering aid, and the phosphor, but usually the sintering temperature is 1450 to 1700 ° C, preferably 1500 to 1600 ° C, and the sintering time is 1 to 10 h, preferably 2 to 4 h.
  • the method for preparing a luminescent ceramic composite material of the present invention is added by a liquid phase infiltration method.
  • the auxiliaries improve the fluidity of the raw materials during normal pressure sintering or vacuum sintering, and the liquid phase in the voids is more remarkable, which can promote the transfer of particles around the voids, which is beneficial to eliminate pores, thereby reducing the final
  • the void ratio of the product increases the relative density of the green body after sintering and improves the optical properties of the luminescent ceramic composite.
  • the present invention also provides a luminescent ceramic composite material which is produced by the above-described method of the present invention.
  • the luminescent ceramic composite of the present invention is characterized in that it comprises a phosphor, an encapsulating material for encapsulating the phosphor, and a sintering aid.
  • the relative density of the luminescent ceramic composite material is 94% or more.
  • the particles of the encapsulating material are uniformly distributed around the particles of the phosphor, and the sintering aid is distributed at the grain boundary of the encapsulating material.
  • the total amount of the sintering aid in the luminescent ceramic composite material is 0.1 to 5%, preferably 0.5% to 1.5%, of the total mass of the phosphor and the encapsulating material.
  • the total amount of the sintering aid is the sum of the masses of the sintering aids a and b.
  • the sintering aids a and b are independently one or more of MgO, SiO 2 , CaF 2 , and BaF 2 .
  • the encapsulating material is one or more of YAG, YAG: Ce or Al 2 O 3 .
  • the content of the auxiliary agent in the void increases, and the liquid phase in the void is more remarkable during the normal pressure sintering or the vacuum sintering process, and the particles around the void can be promoted to transfer the substance, which is advantageous for eliminating the pores and improving the growth.
  • the relative density of the billet after sintering Thereby, the luminescent ceramic composite material of the present invention has a small void and a relatively high density, and thus has more excellent luminescent properties.
  • the role of the sintering aid is to produce a liquid phase at a lower temperature, reduce the surface energy of the grain and increase the migration rate of the grain boundary, provide more grain boundary channels for the discharge of the pores, and inhibit the grain.
  • the abnormal growth slows down the continuous growth of the grains and provides ample time for the discharge of the pores.
  • the amount of the sintering aid to be added must be strictly controlled. When the amount is too large, a second phase is formed in the ceramic, which affects the transmittance and luminous efficiency of the ceramic.
  • a 1% by mass aqueous solution of PEG was prepared, and 50 g of YAG nanopowder prepared by a coprecipitation method as a packaging material was mixed with 500 ml of an aqueous PEG solution.
  • the YAG powder suspension was sonicated for 3 hours and then used.
  • Ammonium bicarbonate was used as a precipitant to prepare an aqueous solution of about 0.1 mol/L, and the mixed suspension which was continuously stirred was slowly dropped until the pH of the mixed suspension was controlled to about 9. The pH was maintained and stirring was continued for 2 h to obtain a coprecipitated composite powder suspension.
  • the suspension was centrifuged, and the obtained powder was washed with water three times, and then vacuum dried at 100 ° C for 5 hours.
  • the obtained dry powder was calcined at 300 ° C to remove impurities, kept for 2 h, and then air-cooled with a furnace to obtain a YAG-MgO mixed powder.
  • the ball mill After the ball mill was finished, it was dried under vacuum at a temperature of 120 ° C for 1 hour to obtain a dry powder, and then passed through a mesh of 80 mesh, 150 mesh, and 200 mesh to obtain a raw material powder having high fluidity. 0.5 g of the raw material powder was weighed into a steel mold, pre-compressed under a pressure of 100 MPa, and a green body was obtained after demolding.
  • the wetting process can be repeated as many times as needed, but each time must be calcined to convert the magnesium nitrate.
  • the infiltration-calcination process was repeated twice in this example.
  • the green sample subjected to the wetting process was placed in a sintering furnace and sintered under a vacuum or a nitrogen/nitrogen hydrogen atmosphere at a sintering temperature of 1600 ° C and a holding time of 4 h. After the sintering is completed, a luminescent ceramic composite YAG:Ce phosphor-YAG-MgO is obtained.
  • Example 1 Except that the YAG powder raw material in Example 1 was replaced with the YAG:Ce powder material, other process parameters and schemes were the same as in Example 1, thereby obtaining a luminescent ceramic composite material YAG:Ce phosphor-YAG:Ce- MgO.
  • the dry powder is obtained by vacuum constant temperature drying, and then passed through a mesh of 80 mesh, 150 mesh, and 200 mesh to obtain a raw material powder having high fluidity.
  • 0.5 g of the raw material powder was weighed into a steel mold, pre-compressed under a pressure of 100 MPa, and a green body was obtained after demolding.
  • the green sample subjected to the wetting process was placed in a sintering furnace and sintered under vacuum or a nitrogen/nitrogen hydrogen atmosphere at a sintering temperature of 1500 ° C and a holding time of 6 h. After the sintering was completed, a luminescent ceramic composite material YAG:Ce phosphor-YAG-SiO 2 was obtained .
  • Example 3 The process parameters and schemes were the same as those in Example 3 except that the YAG powder raw material in Example 3 was replaced with the powder material of YAG:Ce, thereby obtaining a luminescent ceramic composite material YAG:Ce phosphor-YAG: Ce-SiO 2 .
  • Example 5 The process parameters and schemes were the same as in Example 5 except that the YAG powder raw material in Example 5 was replaced with the powder material of YAG:Ce, thereby obtaining a luminescent ceramic composite material YAG:Ce phosphor-YAG: C-MgO-SiO 2 .
  • Example 1 Other process parameters and schemes were the same as in Example 1 except that the concentration of the solution b in Example 1 was changed to 1 M, thereby obtaining a luminescent ceramic composite material YAG:Ce phosphor-YAG-MgO.
  • Example 1 Other process parameters and schemes were the same as in Example 1 except that the concentration of the solution b in Example 1 was changed to 10 M, thereby obtaining a luminescent ceramic composite material YAG:Ce phosphor-YAG-MgO.
  • a luminescent ceramic composite material of Comparative Example 1 as a general sample was prepared in the same manner as in Example 1 except that both the solution a and the solution b were mixed with the YAG powder suspension and the wetting process was not performed.
  • the density of the sample is tested by using the Archimedes drainage method.
  • the details are as follows.
  • In-light efficiency IE excitation light power / (total blue light power - residual blue light power);
  • EFF luminous flux (lm) / excitation light power (w) participating in excitation
  • Blue light absorption rate (total blue light power - residual blue light power) / total blue light power.
  • the density and relative density of the infiltrated sample obtained by the method of the present invention are higher than those of the ordinary sample, thereby demonstrating an increase in the content of the sintering aid by the method of the present invention, and thus an increase in the yield. Density of luminescent ceramic composites.
  • the in-luminescence efficiency, EFF, blue light absorption rate, and the like of the infiltrated sample obtained by the method of the present invention were higher than those of the ordinary sample.
  • the sample prepared by the green body infiltration method was compared with the sample prepared in Comparative Example 1, and the emission spectrum of the former was stronger and the peak value was better, under the same test system. , showing higher luminous efficiency. It is thus illustrated that the optical properties of the luminescent ceramic composite prepared by the method of the present invention are improved compared to conventional samples.

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Abstract

一种发光陶瓷复合材料的制备方法以及发光陶瓷复合材料。该方法包括以下步骤：将包含荧光粉和用于封装荧光粉的封装材料以及任选的烧结助剂a的生坯浸润于烧结助剂b的前体溶液中，并将经过浸润的生坯煅烧以使烧结助剂b的前体转变为烧结助剂b的浸润-煅烧步骤；煅烧之后的生坯进行烧结，获得发光陶瓷复合材料的烧结步骤。

Description

一种发光陶瓷复合材料的制备方法以及发光陶瓷复合材料 技术领域
本发明涉及一种发光陶瓷复合材料的制备方法，以及通过所述方法制备的发光陶瓷复合材料。
背景技术
蓝色激光激发荧光材料获得可见光的激光荧光技术，作为一种全新的光源技术，在激光显示领域中飞速发展，各个企业已争相推出满足不同市场的各种功率的激光光源，并取得了巨大的成功。当前研究的热点和难点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、发光材料)，其中这些材料须拥有优秀的性能，比如光学转换效率高，亮度高，单位发光面积能够承受更大功率激光照射，具有高导热性能，寿命长等。石榴石因其具有较高的热导率、高机械强度以及良好的化学稳定性，是目前最常用的激光基质材料，包括钇铝石榴石(Y3Al5O12，YAG)、镥铝石榴石(Lu3Al5O12，LuAG)、钇镓石榴石(Y3Ga5O12，YGG)、钆镓石榴石(Gd3Ga5O12，GGG)、镥镓石榴石(Lu3Ga5O12，LuGG)等。
发光陶瓷由于其具有较好的耐热性和优异的热导率，是目前理想的发光材料之一。但是，传统的YAG纯相发光陶瓷在发光性能上还弱于硅胶和玻璃封装复合发光装置；特别是超薄封装时，界面全反射造成的光效损失很大。因此，使用陶瓷材料对荧光粉进行封装是值得深入研究的方向。如无掺杂的YAG纯相材料或者不同Ce掺杂量的YAG材料封装YAG荧光粉制备YAG-YAG:Ce荧光粉或者Ce:YAG-YAG:Ce荧光粉陶瓷材料，能够获得比纯相YAG发光陶瓷更优秀的光学性能。
目前的荧光粉陶瓷材料，一般需要采用热压烧结的方式或其他高压烧结 方式，才能获得高性能的陶瓷体。但是热压烧结的设备复杂、生产环境要求严格、模具材料要求高、能源消耗大、生产效率较低，成本较高。
另外，在发光陶瓷复合材料的制备中，关于烧结助剂的添加，通常的办法都是将陶瓷粉末和烧结助剂尽可能均匀地混合起来，再填入模具中进行预压制。专利文献1(CN1837142A)公开了一种镥铝石榴石基透明陶瓷的制备方法，所述镥铝石榴石基透明陶瓷通过将作为原料的Lμ2O3、RE2O3、Al2O3等氧化物粉体或作为原料的Lμ3-xRExAl5O12与作为烧结助剂的SiO2或正硅酸乙酯(TEOS)混合，然后采用干压成型、冷等静压成型等成型工艺中的任意一种进行成型，之后进行无压烧结或热压烧结、退火等处理而得到。
另外，专利文献2(CN104177092A)公开了一种制备透明发光陶瓷的方法，所述方法使用结构通式为RX(其中R表示发光离子，X表示易挥发的阴离子)的化合物同时作为烧结助剂和发光激活离子的组成原料，并将该RX化合物与原料混合，然后进行研磨、压制、烧结(烧结可采用真空烧结、气氛烧结、热压烧结)、退火等处理。上述专利文献1和2中将原料粉末与烧结助剂直接混合的情况下，由于粉末流动性和填充性的问题，会导致在颗粒之间会形成空隙。空隙的存在，会影响材料的性能。
因此，需要一种空隙较少、相对密度较高且性能更加优异的发光陶瓷复合材料以及这种材料的制备方法。
发明内容
发明要解决的问题
在目前发光陶瓷的制备中，陶瓷的烧结致密化过程，主要是由烧结过程中陶瓷体内部形成液相来推动。在常压或者真空烧结中，原料粉体会被预先混制好，再使用模具预先压制成生坯，然后放入炉内烧结。关于烧结助剂的添加，如上所述，通常的办法，都是将陶瓷粉末和烧结助剂尽可能均匀地混 合起来，再填入模具中进行预压制。但是由于粉末流动性和填充性的问题，粉末在填入模具并受力被压制成型的过程中，粉末的堆砌程度是有差异的；而理想的生坯，其各个部位的形貌都应该是相对均匀的。以制备YAG-YAG:Ce荧光粉或Ce:YAG-YAG:Ce荧光粉时MgO作为烧结助剂的情况为例进行说明。理想的情况如图1所示，YAG或YAG:Ce相颗粒分布在YAG:Ce荧光粉颗粒的周围，MgO均匀地分布在他们之间。但是在实际的生坯中，其内部结构会更多地出现如图2那样的结构；这是由于粉末在模具中受压移动时，受到压力不一致、颗粒间摩擦力不均匀和颗粒流动性不一致的影响，颗粒之间会形成如图2中的空隙。由于这些空隙的存在，通常的生坯在常压或真空烧结过程中无法通过充分的物质转移来填充空隙，空隙最后会变成封闭的气孔或连通的孔隙，影响材料的性能。
用于解决问题的方案
为解决上述问题，本发明提供一种发光陶瓷复合材料的制备方法，其特征在于，所述方法包括以下步骤：
将包含荧光粉和用于封装荧光粉的封装材料以及任选的烧结助剂a的生坯浸润于烧结助剂b的前体溶液中，并将经过浸润的生坯煅烧以使烧结助剂b的前体转变为烧结助剂b的浸润-煅烧步骤；
将煅烧之后的生坯进行常压烧结或真空烧结，从而获得发光陶瓷复合材料的烧结步骤。
根据本发明所述的发光陶瓷复合材料的制备方法，其中烧结助剂的总量为荧光粉和封装材料总质量的0.1～5％，优选0.5％～1.5％。
根据本发明所述的发光陶瓷复合材料的制备方法，其中烧结助剂b的前体溶液的浓度为0.01～10M，优选0.1M～10M，更优选0.1～1M。
根据本发明所述的发光陶瓷复合材料的制备方法，其中该生坯浸入烧结助剂的浸润时间为10min～120min，优选30min～90min，更优选40min～60min， 和/或，煅烧温度为200～500℃，优选300～500℃，更优选350～450℃。
根据本发明所述的发光陶瓷复合材料的制备方法，其中以上浸润-煅烧步骤可重复进行1～5次，优选1～3次。
根据本发明所述的发光陶瓷复合材料的制备方法，其进一步包括生坯的制备步骤，该步骤包括将包含荧光粉和用于封装荧光粉的封装材料以及任选的烧结助剂a的混合粉末进行球磨、干燥、过筛、压制，从而获得生坯。
根据本发明所述的发光陶瓷复合材料的制备方法，其中烧结助剂a和b独立地为MgO、SiO2、CaF2、BaF2中的一种以上。
根据本发明所述的发光陶瓷复合材料的制备方法，其中烧结助剂b的前体为烧结助剂的无机盐或醇盐。
本发明还提供一种发光陶瓷复合材料，其特征在于，其包括荧光粉、用于封装所述荧光粉的封装材料和烧结助剂。
其中，该所述发光陶瓷复合材料的相对密度为94％以上。
其中，所述封装材料的颗粒均匀分布于所述荧光粉的颗粒周围，所述烧结助剂分布于所述封装材料的晶界。
其中，发光陶瓷复合材料中烧结助剂的总量为荧光粉和封装材料总质量的0.1～5％，优选0.5％～1.5％。其中，烧结助剂的总量为烧结助剂a和b质量之和。
其中，烧结助剂a和b独立地为MgO、SiO2、CaF2、BaF2中的一种以上。
其中，封装材料为YAG、YAG:Ce或Al2O3中的一种以上。
发明的效果
在本发明的发光陶瓷复合材料的制备方法中，通过将预压制好的生坯浸入烧结助剂的前体溶液中，使生坯内部的空隙被烧结助剂的前体溶液填充，然后将浸润后的生坯取出烘干、煅烧，使生坯内部空隙中的烧结助剂含量获得提升，根据实际要求，生坯可多次浸润，以获得符合需求的助剂含量。经过浸润-煅烧助剂工艺后的生坯，其内部如图2的结构会变为如图3的结构； 由图2和图3可见，在空隙周围助剂(以MgO为例)的含量增加，由此在常压烧结或真空烧结过程中空隙中的液相会更显著，可以促进空隙周围的颗粒进行物质转移，有利于消除气孔，提高生坯烧结后的相对密度。因此，本发明不需要采用设备复杂、生产环境要求严格、模具材料要求高、能源消耗大、生产效率较低、生产成本高的热压烧结方式，通过采用坯体液相浸润法，改良了烧结助剂的添加方式，在常压烧结或真空烧结条件下即制得了空隙较少、相对密度较高且光学性能更加优异的发光陶瓷复合材料。
附图说明
图1为生坯内部分布均匀的各相粉末颗粒示意图。
图2为生坯内部分布不均匀的各相粉末颗粒示意图。
图3为浸润-煅烧后生坯内部各相粉末颗粒分布示意图。
图4为实施例1中制备的样品与比较例1中制备的样品的发射光谱图。
图5为发光陶瓷复合材料的一种实施方式的制备步骤。
图6为发光陶瓷复合材料的另一种实施方式的制备步骤。
具体实施方式
以下通过具体实施方案更加详细地说明本发明发光陶瓷复合材料的制备方法的具体步骤。
如图5所示，本发明的发光陶瓷复合材料的制备方法包括如下步骤：
S：1，生坯的制备步骤；
S：2，浸润-煅烧步骤；
S：4，烧结步骤。
在其它一些实施方式中，如图6所示，步骤S：4之前还包括步骤：
S：3：压片步骤。
以上步骤的具体说明如下所述。
S：1，生坯的制备步骤本发明中，生坯通过将包含荧光粉、用于封装荧光粉的封装材料以及任选的烧结助剂a的混合粉末进行球磨、干燥、过筛、压制的步骤而制得。
具体地，将包含荧光粉、用于封装荧光粉的封装材料以及任选的烧结助剂a的混合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，不再使用任何分散剂，用超低磨失率的氧化锆球进行球磨。球磨时间可根据需要选择，因此不特别限定，但通常为1～120min，优选为30～50min。如果球磨时间过长，容易损坏荧光粉的晶粒表面形态，影响发光性能。
球磨结束后，然后干燥以获得干粉。优选采用真空恒温干燥，干燥温度可为40～120℃，优选50～100℃，干燥时间可为1h～12h，优选4～8h。之后，过80目、150目、200目筛，得到高流动性的原料粉末。
然后，将获得的原料粉末进行压制，然后脱模，从而获得生坯。压制的方法不特别限定，可使用常规的压制方法如冷等静压法等进行。压制的压力通常在5～200MPa、优选15～100MPa压力下。如果压力太小，会导致孔隙较多较大，影响最终烧结成品的致密度。
当生坯中仅包含荧光粉和用于封装荧光粉的封装材料(以下简称为“封装材料”)时，将两种粉末混合即可。并且，荧光粉与封装材料的重量比为1∶0.1～0.1∶1，优选1∶1。
当生坯中包含荧光粉、封装材料和烧结助剂a时，通常将预先制得的封装材料和烧结助剂a的混合粉末与荧光粉末混合。并且，烧结助剂a与荧光粉和封装材料的总质量比为(0.01～5)∶100，优选(0.05～1)∶100。
荧光粉不特别限定，可以是任意耐1300度以上高温的商用荧光粉。通常可使用的荧光粉的例子包括YAG:RE、LuAG:RE、YGG:RE、GGG:RE和LuGG:RE，其中RE为选自Ce、Pr、Eu、Nd、Sm、Gd、Yb、Ho、Tm、Dy和Er中的元素。封装材料与烧结助剂a的混合粉末通过将封装材料的悬浊液 与烧结助剂a的前体的溶液(以下称为“溶液a”)混合，然后加入沉淀剂以使它们共沉淀，之后进行离心分离、洗涤、干燥、煅烧和冷却而获得。或者，也可以通过将封装材料与烧结助剂a直接混合球磨制得。
关于封装材料的悬浊液的制备方法不特别限定，只要能够将其分散即可。例如，可采用以下方法：配制1～3质量％的PEG水溶液；将50克的封装材料与500毫升PEG水溶液混合；然后超声1～3h后备用。超声是为了破坏颗粒之间的二次团聚，使粉末在溶液中尽可能地分散。
以下进一步说明烧结助剂a的前体的溶液即溶液a的制备方法。烧结助剂a的前体可为烧结助剂的水溶性无机盐或醇盐。当烧结助剂a的前体为水溶性金属无机盐时，以使烧结助剂a的前体与封装材料的重量比为所需的比例称取适量烧结助剂a的前体并配制成适宜浓度的金属无机盐的水溶液即可。
待封装材料的悬浊液和溶液a配制完成后，将两者优选以5∶1的体积比混合，得到混合悬浮液，放置于磁力搅拌器之上不断搅拌，温度设置为20～80℃，优选40～60℃，转速为100～300r/m，优选170～250r/m。以碳酸氢铵作为沉淀剂，配成约0.01～0.1mol/L的水溶液，缓慢滴入被不断搅拌的混合悬浮液，直到将混合悬浮液的PH值控制在8～10左右，优选为9～9.5。保持该PH值，继续搅拌1～5h、优选2～3h，从而获得共沉淀的复合粉体悬浮液。合适的PH值对于封装材料超细粉体颗粒的分散和解絮凝非常重要。进一步地，本发明中YAG、YAG:Ce或Al2O3中的至少一种均可根据实际需要作为封装材料。
将悬浮液离心分离，对获得的粉体进行水洗2～8次、优选3～5次，然后在50～150℃、优选50～100℃真空干燥1～10小时、优选1～5小时。将获得的干粉在200～500℃、优选300～400℃下煅烧以去除杂质，保温1～5h、优选2～3h，之后随炉空冷，从而得到封装材料与烧结助剂a的混合粉末。
当烧结助剂a的前体为醇盐时，采用能够使醇盐成为溶胶的方法。例如，可采用以下配制方法：以使烧结助剂a的前体与封装材料的质量比为所需的比例称取适量烧结助剂a的前体，并配制所需浓度的烧结助剂a的前体的乙醇 溶液；向该乙醇溶液中，缓慢滴加氨水溶液(即氨水和去离子水的混合溶液，其中水与醇盐的摩尔比为n水/n醇盐＝(3～4)/1)，调节pH值为9.0～9.5，经过12h的陈化，制得溶胶溶液。需要说明的是，其中水与醇盐的比例应当以醇盐至少能够部分水解为宜，以便制得所需要的溶胶溶液。示例性的，如：TEOS(正硅酸乙酯)完全水解需要的水与醇盐的摩尔比至少为n水/n醇盐＝4/1；需要形成相对稳定的溶胶体系则水与醇盐的摩尔比n水/n醇盐应等于小于4/1。
待封装材料的悬浊液和醇盐溶胶溶液a配制完成后，将两者优选以5∶1的体积比混合，得到混合悬浮液，放置于磁力搅拌器之上不断搅拌，温度设置为20～80℃，优选40～60℃，转速为100～300r/m，优选170～250r/m。然后，在120℃度下进行干燥1～10小时、优选1～5小时。将获得的干粉在200～500℃、优选300～400℃下煅烧以去除杂质，保温1～5h、优选2～3h，之后随炉空冷，从而得到封装材料与醇盐烧结助剂a的混合粉末。
配制溶液a时，按照烧结助剂a与封装材料的质量比为(0.01～2)∶100、优选(0.05～1)∶100的比例配制。溶液a的浓度可为0.01～1M，优选0.01M～0.1M，更优选0.01M～0.05M。
本发明中，封装材料的例子包括石榴石以及稀土元素掺杂的石榴石，具体地，可包括YAG、LuAG、YGG、GGG、LuGG、YAG:RE、LuAG:RE、YGG:RE、GGG:RE和LuGG:RE，其中RE为选自Ce、Pr、Eu、Nd、Sm、Gd、Yb、Ho、Tm、Dy和Er中的元素。
本发明中，烧结助剂a不特别限定，可采用本领域常用的烧结助剂。例如，烧结助剂a可为MgO、SiO2、CaF2、BaF2中的一种以上。其中，用作MgO前体的镁无机盐的例子包括Mg(NO3)2·6H2O、MgCl2·6H2O、MgSO4·7H2O等水溶性镁盐。用作MgO前体的镁醇盐的例子包括乙醇镁、异丙醇镁、叔丁醇镁等。用作SiO2前体的醇盐的例子包括正硅酸甲酯、正硅酸乙酯、正硅酸丙酯、正硅酸丁酯等。其中，正硅酸乙酯是优选的。
S：2，浸润-煅烧步骤
本发明的浸润-煅烧步骤为将包含荧光粉和用于封装荧光粉的封装材料以及任选的烧结助剂a的生坯浸润于烧结助剂b的前体溶液(以下称为“溶液b”)中，并将经过浸润的生坯煅烧以使烧结助剂b的前体转变为烧结助剂b的步骤。
将生坯浸润入溶液b中时，溶液液面要没过生坯样品的顶部。浸润时间没有特别限定，通常为10min～120min，优选30min～90min，更优选40min～60min。
浸润完成后，将生坯取出、烘干，然后进行煅烧，使主要附着在生坯内部空隙中的烧结助剂b的前体转变为烧结助剂b的颗粒。
烘干温度没有特别限定，通常可为50～80℃。煅烧温度和煅烧时间根据不同的烧结助剂而不同，但通常煅烧温度可为200～500℃，优选300～500℃，更优选350～450℃，煅烧时间可为1～5h，优选2h～3h。需要说明的是，烘干也可以同煅烧一起进行，即选择合适的升温曲线直接进行煅烧。
本发明中，浸润-煅烧工艺可根据需要重复多次，优选1～5次，更优选1～3次。需要注意的是，每一次都必须煅烧以使烧结助剂前体转化为烧结助剂颗粒。
关于浸润液即溶液b的制备，与上述溶液a的制备完全相同。溶液b的浓度可为0.01～10M，优选0.1～10M，更优选0.1～1M。
另外，溶液a和溶液b中的烧结助剂前体的含量可以相等，也可以不相等，并且两种溶液的浓度也可以相同或不同。优选溶液b的浓度是溶液a的5～20倍，优选5～10倍。因为溶液a是用来共沉淀均匀添加助剂的，浓度要相对较低以利于均匀沉淀；溶液b是用来浸润的，浓度可以偏高。溶液a中的烧结助剂前体会全部进入生坯，溶液b中的烧结助剂前体只会小部分进入生坯，生坯样品中的总烧结助剂含量可通过此原则来计算。
取浸润烧结助剂b溶液前干坯质量为m；取浸润后烧结助剂b溶液后，再 煅烧完成后的坯片质量为M；那么所述的烧结助剂b最终添加量为(M-m)；而烧结助剂a的添加量是在压制干坯前已经确定的，总烧结助剂为烧结助剂a和烧结助剂b的总和。同时，烧结助剂b的含量与①浸润时间、②助剂溶液b的浓度、③坯片的体积及表面积、④坯片内部的疏松程度有关；其中前三个因素可以精确控制；第四个因素是通过坯片制作是对粉体施加的压力和粉体颗粒自身的形态等因素决定，能在一定范围内得到控制。因此，在发光陶瓷复合材料中的总烧结助剂的含量能够较为精确的控制在一定范围内。
另外，本发明中，烧结助剂b也不特别限定，可采用本领域常用的烧结助剂，例如，可为MgO、SiO2、CaF2、BaF2中的一种以上。并且，烧结助剂b可与烧结助剂a相同。
S：3，压片步骤
将经过浸润-煅烧步骤的生坯在较大压力下进行压片。压片方式优选等静压；压力范围为100～300MPa，优选为180～220MPa。可以理解，经过浸润-煅烧步骤的生坯进一步的在较大压力下的压片能够进一步降低生坯的孔隙率，提高发光陶瓷复合材料成品的致密度。当然，压片的方式还可以为干压成型等压片方式，压力范围为100～300MPa。可以理解，该步骤仅为优选地实施步骤，在一些具体的实施方案中可以不包括该步骤。
S：4，烧结步骤
将经过浸润-煅烧工艺或压片步骤的生坯样品，放入烧结炉，在真空或氮气/氮氢气气氛下进行烧结，从而获得发光陶瓷复合材料即荧光粉-封装材料-烧结助剂复合材料。
烧结温度和烧结时间根据不同的封装材料、烧结助剂和荧光粉而不同，但通常烧结温度为1450～1700℃，优选1500～1600℃，烧结时间为1～10h，优选2～4h。
本发明的发光陶瓷复合材料的制备方法中，通过液相浸润的方法添加烧 结助剂，在常压烧结或真空烧结过程中提高了原料的流动性，空隙中的液相会更显著，可以促进空隙周围的颗粒进行物质转移，有利于消除气孔，由此减小了最终产品的空隙率，提高生坯烧结后的相对密度，并改善了发光陶瓷复合材料的光学性能。
本发明还提供一种发光陶瓷复合材料，其通过上述的本发明的方法制得。本发明的发光陶瓷复合材料的特征在于，其包括荧光粉、用于封装所述荧光粉的封装材料和烧结助剂。其中，该发光陶瓷复合材料的相对密度为94％以上。
其中，封装材料的颗粒均匀分布于荧光粉的颗粒周围，烧结助剂分布于封装材料的晶界。
其中，发光陶瓷复合材料中烧结助剂的总量为荧光粉和封装材料总质量的0.1～5％，优选0.5％～1.5％。其中，烧结助剂的总量为烧结助剂a和b质量之和。
其中，烧结助剂a和b独立地为MgO、SiO2、CaF2、BaF2中的一种以上。
其中，封装材料为YAG、YAG:Ce或Al2O3中的一种以上。
如图3所示，在空隙中助剂的含量增加，在常压烧结或真空烧结过程中空隙中的液相会更显著，可以促进空隙周围的颗粒进行物质转移，有利于消除气孔，提高生坯烧结后的相对密度。由此，使得本发明的发光陶瓷复合材料的空隙较少、相对密度较大，并因此具有更加优异的发光性能。
烧结助剂的作用是能在较低的温度下产生液相，降低了晶粒的表面能和增加了晶界的迁移速率，为气孔的排出提供了更多的晶界通道，抑制了晶粒的异常生长，减缓了晶粒连续生长，为气孔的排出提供了充裕的时间。但是对于烧结助剂的加入量必须严格控制，加入量过多时，会在陶瓷中形成第二相，而影响陶瓷的透过率和发光效率。
以下通过实施例进一步详细说明本发明，但本发明不限于以下实施例。
实施例1
配制1质量％的PEG水溶液，将50克的作为封装材料的通过共沉淀法制备的YAG纳米粉末与500毫升PEG水溶液混合。将YAG粉体悬浊液超声3h后备用。
称取25.64克(0.1mol)的Mg(NO3)2·6H2O，配制成1000毫升浓度为0.1M的水溶液。此溶液即为溶液a。
将500毫升YAG粉体悬浊液与100毫升溶液a混合，以使作为烧结助剂a的MgO与作为封装材料的YAG纳米粉体的质量比为0.8∶100的比例，得到混合悬浮液，放置于磁力搅拌器之上不断搅拌，温度设置为40℃，转速为170r/m。
以碳酸氢铵作为沉淀剂，配成约0.1mol/L的水溶液，缓慢滴入被不断搅拌的混合悬浮液，直到将混合悬浮液的PH值控制在9左右。保持该PH值，继续搅拌2h，从而获得共沉淀的复合粉体悬浮液。
将悬浮液离心分离，对获得的粉体进行水洗3次，然后在100℃真空干燥5小时。
获得的干粉在300℃下煅烧以去除杂质，保温2h，之后随炉空冷，得到YAG-MgO混合粉末。
称取50克的YAG-MgO混合粉末，50克的YAG:Ce荧光粉，将两种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，不再使用任何分散剂，用超低磨失率的氧化锆球进行球磨，球磨时间为30min。
球磨球磨结束后，在温度120℃下真空恒温干燥1h以获得干粉，之后过80目、150目、200目筛，得到高流动性的原料粉。称取0.5克原料粉末装入钢模中，在100MPa压力下进行预压制，脱模后获得生坯。
称取25.64克(0.1mol)的Mg(NO3)2·6H2O，配制成浓度为0.1M的水溶液。此溶液即为溶液b。
将0.5克生坯浸润于10毫升溶液b中，以使溶液液面没过生坯样品的顶部。浸润时间为60min，然后将浸润后的生坯取出，80℃烘干后，进行450℃的煅烧，使主要附着在生坯内部空隙中可溶性的硝酸镁转变为不可溶于水的氧化镁。
浸润工艺可根据需要重复多次，但每一次都必须煅烧以使硝酸镁转化。此实施例中重复浸润-煅烧工艺2次。
将经过浸润工艺的生坯样品，放入烧结炉，在真空或氮气/氮氢气气氛下进行烧结，烧结温度为1600℃，保温时间为4h。烧结完成后，获得发光陶瓷复合材料YAG:Ce荧光粉-YAG-MgO。
实施例2
除了将实施例1中的YAG粉体原料换成YAG:Ce的粉体材料，其它工艺参数和方案均与实施例1中相同，从而获得发光陶瓷复合材料YAG:Ce荧光粉-YAG:Ce-MgO。
实施例3
称取2.083克(0.01mol)的TEOS(正硅酸乙酯)，配制成浓度为0.01M的乙醇溶液，缓慢滴加氨水，调pH值为约9.5，经过12h的陈化，制得二氧化硅溶胶，标为溶液b。
称取50克的YAG相纳米粉末，50克的YAG:Ce荧光粉，将两种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，不再使用任何分散剂，用超低磨失率的氧化锆球进行球磨，球磨时间为30min。
球磨球磨结束后，采用真空恒温干燥获得干粉，之后过80目、150目、200目筛，得到高流动性的原料粉。称取0.5克原料粉末装入钢模中，在100MPa压力下进行预压制，脱模后获得生坯。
将0.5克生坯浸润入10毫升溶液b中，以使溶液液面没过生坯样品的顶部。浸润时间为90min，然后将浸润后的生坯取出，80℃烘干后，进行400℃的煅烧，使主要附着在生坯内部空隙中充满二氧化硅溶胶。浸润工艺可根据需要重复多次，但每一次都必须煅烧以使二氧化硅溶胶转化为二氧化硅颗粒。本实施例重复浸润-煅烧工艺3次。
将经过浸润工艺的生坯样品，放入烧结炉，在真空或氮气/氮氢气气氛下进行烧结，烧结温度为1500℃，保温时间为6h。烧结完成后，获得发光陶 瓷复合材料YAG:Ce荧光粉-YAG-SiO2。
实施例4
除了将实施例3中的YAG粉体原料换成YAG:Ce的粉体材料之外，其它工艺参数和方案均与实施例3中相同，从而获得发光陶瓷复合材料YAG:Ce荧光粉-YAG:Ce-SiO2。
实施例5
除了溶液b如下所述制备之外，其它工艺参数和方案均与实施例1中相同，从而获得光陶瓷复合材料YAG:Ce荧光粉-YAG-MgO-SiO2。
称取20.833克(0.1mol)的TEOS(正硅酸乙酯)，配制成浓度为0.1M的乙醇溶液，缓慢滴加11.52g的去离子水和0.9gHNO3，调pH值为约9.5，经过12h的陈化，制得二氧化硅溶胶，标为溶液b。
实施例6
除了将实施例5中的YAG粉体原料换成YAG:Ce的粉体材料之外，其它工艺参数和方案均与实施例5中相同，从而获得发光陶瓷复合材料YAG:Ce荧光粉-YAG:C-MgO-SiO2。
实施例7
除了将实施例1中溶液b的浓度变为1M之外，其它工艺参数和方案均与实施例1中相同，从而获得发光陶瓷复合材料YAG:Ce荧光粉-YAG-MgO。
实施例8
除了将实施例1中溶液b的浓度变为10M之外，其它工艺参数和方案均与实施例1中相同，从而获得发光陶瓷复合材料YAG:Ce荧光粉-YAG-MgO。
比较例1
除了将溶液a和溶液b都与YAG粉体悬浊液混合并且不进行浸润工艺之外，以与实施例1相同的方式制备比较例1的作为普通样品的发光陶瓷复合材料。
以下描述实施例和比较例中获得的发光陶瓷复合材料的物理性质和光 学性能的表征。
(1)密度的测试
本发明中，通过使用阿基米德排水法测试样品的密度。具体如下所述。
在温度约25℃下，先用精度为0.0001的天平称出样品的质量m(g)；再将盛有水的烧杯放置在天平上，并将天平归零；用细线吊着待测样品，将样品浸没在水中，不要碰烧杯底和壁，得到天平读数，该数正好等于待测陶瓷的体积v(ml)；然后通过下式计算样品的测量密度：测量密度＝m/v(单位g/cm3)。
样品的相对密度＝测量密度/理论密度×100％
(2)光学性能的测试
下表2中的光学性能使用QY-2000积分球光谱仪系统(由Orient KOJI制作)，在激发蓝光的光功率为50mw的条件下测试。
将本发明实施例1至5制得的坯体浸润样品和比较例1中制得的普通样品的测量密度以及相对密度的结果示于表1中。实施例1中制得的坯体浸润样品与比较例1中制得的普通样品的光学性能的结果示于表2中，并且它们的发射光谱示于图4中。
表1
Figure PCTCN2017103432-appb-000001
表2
Figure PCTCN2017103432-appb-000002
发光内效率IE＝激发光光功率/(总的蓝光光功率-剩余蓝光光功率)；
输出光效EFF＝光通量(lm)/参与激发的激发光光功率(w)；
蓝光吸收率＝(总的蓝光光功率-剩余蓝光光功率)/总的蓝光光功率。
由表1所示可知，通过本发明的方法制备得到的坯体浸润样品的密度和相对密度均高于普通样品，由此证明通过本发明的方法烧结助剂的含量增加，并因此提高了所得发光陶瓷复合材料的致密度。
由表2所示可知，通过本发明的方法制备得到的坯体浸润样品的发光内效率、EFF、蓝光吸收率等均高于普通样品。另外，如图4中所示，采用坯体浸润法制备的样品相对于比较例1制备的样品，在发射光谱上体现出，前者的光谱发射强度更强，峰值更好，在同一测试系统下，表现出的发光效率更高。由此说明，通过本发明的方法制备的发光陶瓷复合材料的光学性能与普通样品相比得到了提高。
虽然已参考示例性实施方案对本申请进行了详细说明，但应理解本发明不限于此。对于所属技术领域的技术人员来说，在不脱离本发明构思的前提下进行的改变或改进都应当视为属于本发明的保护范围。

Claims (10)

  1. 一种发光陶瓷复合材料的制备方法，其特征在于，所述方法包括以下步骤：
    将包含荧光粉和用于封装所述荧光粉的封装材料以及任选的烧结助剂a的生坯浸润于烧结助剂b的前体溶液中，并将经过浸润的生坯煅烧以使烧结助剂b的前体转变为烧结助剂b的浸润-煅烧步骤；
    将煅烧之后的生坯进行常压烧结或真空烧结，从而获得发光陶瓷复合材料的烧结步骤。
  2. 根据权利要求1所述的发光陶瓷复合材料的制备方法，其中烧结助剂的总量为所述荧光粉和所述封装材料总质量的0.1～5％。
  3. 根据权利要求1或2所述的发光陶瓷复合材料的制备方法，其中烧结助剂b的前体溶液的浓度为0.01～10M。
  4. 根据权利要求1所述的发光陶瓷复合材料的制备方法，其中浸润时间为10min～120min，和/或，煅烧温度为200～500℃。
  5. 根据权利要求1所述的发光陶瓷复合材料的制备方法，其中所述浸润-煅烧步骤进行1～5次。
  6. 根据权利要求1所述的发光陶瓷复合材料的制备方法，其进一步包括生坯的制备步骤，该步骤包括将包含所述荧光粉和用于封装所述荧光粉的封装材料以及任选的烧结助剂a的混合粉末进行球磨、干燥、过筛、压制，从而获得生坯。
  7. 根据权利要求1所述的发光陶瓷复合材料的制备方法，其中烧结助剂a和b独立地为MgO、SiO2、CaF2、BaF2中的一种以上。
  8. 根据权利要求1所述的制备方法，其中烧结助剂b的前体为烧结助剂的无机盐或醇盐。
  9. 一种发光陶瓷复合材料，其特征在于：其包括荧光粉、用于封装所述荧光粉的封装材料和烧结助剂，并且所述发光陶瓷复合材料的相对密度为94％ 以上。
  10. 根据权利要求9所述的发光陶瓷复合材料，其特征在于：所述封装材料的颗粒均匀分布于所述荧光粉的颗粒周围，所述烧结助剂分布于所述封装材料的晶界。
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