CN116655366A - Low-temperature solid-phase synthesis method of L/B-site co-doped yttrium aluminum garnet powder - Google Patents
Low-temperature solid-phase synthesis method of L/B-site co-doped yttrium aluminum garnet powder Download PDFInfo
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- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 title claims abstract description 32
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Abstract
The invention discloses a low-temperature solid-phase synthesis method of L/B co-doped yttrium aluminum garnet powder, which comprises the steps of firstly treating raw materials, ball milling and sanding, and refining all the raw materials to nano-scale, thereby creating conditions for subsequent low-temperature sintering. In the sintering and phase forming process of YAG powder, a ball milling and grinding combined mode is adopted to realize the improvement of the fine granularity and uniformity of the powder and promote the solid phase reaction, and the diffusion time of doped ions in the YAG matrix is prolonged due to low sintering temperature and low heating rate, so that the full solid solution is obtained, the occupation of the doped ions in the YAG crystal lattice is controllable, and the obtained (Y) 1‑x L x ) 3 (Al 1‑y B y ) 5 O 12 (0<x<1；0<y<1) The powder has the advantages of single garnet structure, high purity, uniform components, accurate stoichiometric ratio and controllable occupation of doped ions.
Description
Technical Field
The invention relates to a compound preparation technology, in particular to a large-scale preparation technology for multi-element doping of oxide ceramic powder.
Background
Yttrium aluminum garnet (Y) 3 Al 5 O 12 YAG) is used as an artificial compound, has stable chemical property, excellent optical property and high-temperature mechanical property, and has wide application in the fields of fluorescent powder, laser medium, thermal barrier coating and the like.
YAG belongs to a cubic crystal system and has a chemical general formula L 3 B 2 (AO 4 ) 3 (L, A, B each represents 3 lattice positions), wherein Y 3+ At a position of 8O 2- Coordinated dodecahedron L lattice site, al 3+ Respectively at 6O 2- Coordinated octahedral B sites and 4O 2- The coordinated tetrahedral A lattice site, therefore, the YAG unit cell can be regarded as a connection network of dodecahedron, octahedron and tetrahedron, has very good structural compatibility, and is easy to introduce cations with larger ionic radius range for doping substitution, thereby changing the physical properties of the material: introduction of Ce 3+ 、Eu 3+ Doping can enhance the fluorescence scintillation performance of YAG material, nd 3+ 、Yb 3+ Doping can improve the laser performance of YAG transparent ceramics and Er 3+ 、Fe 3+ Doping can reduce the thermal conductivity of YAG ceramics and improve the thermal expansion coefficient.
For example, in the beginning of the 70 th century of the 20 th century, researchers found that when Ce-doped YAG was excited by visible light, intense yellow fluorescence was emitted, and Dy, eu, and Tb-doped YAG phosphors were developed. In 1995, a high-quality neodymium-doped YAG transparent ceramic was prepared by Krosaki company in Japan, and effective laser oscillation was realized for the first time, and an Nd-YAG solid laser with laser output power as high as 67kW was developed in the United states. Padture et al 1997, study Y 3 Al x Fe 5-x O 12 (x= 0,0.7,1.4,5.0) ceramic thermal conductivity, some garnet materials were found to have high thermal conductivity as low as 2.4W/m·k, suggesting the possibility of YAG material application as a thermal barrier coating.
However, the occupation of the dopant ions in the YAG lattice is critical to the impact of the material properties. Taking thermo-physical properties as an example, er 3+ Y instead of L-lattice of YAG dodecahedron 3+ When Y having low thermal conductivity is obtained 2 ErAl 5 O 12 Ceramics (1.8W/mK, 1000 ℃ C.) but have no improvement in thermal expansion coefficient, still 8.63X10 at 1157 ℃ C.) -6 K -1 The method comprises the steps of carrying out a first treatment on the surface of the When Yb 3+ Al for substituting YAG octahedral B lattice site 3+ When the material has a thermal conductivity at room temperature lower than that of pure YAG, about 2.11W/mK, and a thermal expansion coefficient obviously improved, and the thermal expansion coefficient is more than 10 multiplied by 10 at 800 DEG C -6 K -1 . Therefore, the lattice occupation of doped ions has a remarkable influence on the thermal physical properties of YAG, the thermal conductivity of YAG can be reduced to different degrees by the L-site dodecahedron doping and the B-site octahedral doping, and the improvement of the thermal expansion coefficient of the material can be more easily obtained by the B-site octahedral doping, so that the L-site and B-site codoping is the optimal scheme for effectively improving the physical properties of the yttrium aluminum garnet material.
On the other hand, since YAG can be regarded as a composite oxide of yttrium oxide and aluminum oxide, the phase region of YAG is a line, i.e. it is possible to form it with the elements in such a way that precise metering ratios are required, and at the same time stringent demands are made on the temperature of the synthesis. Therefore, the selection of the preparation method and the regulation of the proportion of each element are important for the smooth synthesis of the doped L/B-site co-doped YAG.
At present, the methods for preparing yttrium aluminum garnet powder materials at home and abroad mainly comprise a high-temperature solid phase method, a liquid phase precipitation method, a hydrothermal synthesis method, a sol-gel method and the like.
For example, liquid phase precipitation method powder is easy to agglomerate, and due to different sensitivity of different cations to pH value, successive precipitation is easy to generate, so that powder components are unevenly distributed; the hydrothermal synthesis method needs to react under the conditions of high temperature and high pressure, has higher requirements on equipment and environment, has low yield and poor purity, and is not easy for large-scale production; the sol-gel method can obtain YAG powder at a relatively low temperature, but citric acid, triethanolamine and other complexing agents are often required to be added, so that N or C and other impurity elements are necessarily introduced to influence the purity of the final YAG product, and particle agglomeration can be formed in the drying and roasting processes, so that the YAG powder with uniform dispersion is difficult to form; high temperature solid phaseYAG synthesized by the method tends to have calcination temperature above 1600 ℃ and causes large powder particles, uneven chemical components and easy YAM (Y) 4 Al 2 O 9 ) And YAP (YAlO) 3 ) And the mixed phase has high energy consumption and high cost.
The YAG powder material prepared by the method is mainly concentrated in researching L-bit doping, and because the B-bit space is smaller than the L-bit space, the doping is not easy to disturb the phase formation, and impurities appear. Therefore, a large blank still exists in the preparation of the L/B co-doped YAG powder material at present.
Therefore, the L/B co-doped YAG powder with uniform component distribution, accurate and controllable doping elements and low production cost and the preparation method thereof are developed, and have important significance for research and application of YAG materials.
Disclosure of Invention
The invention aims to provide a low-temperature solid phase synthesis method capable of realizing large-scale preparation of high-purity and impurity-free yttrium aluminum garnet powder. The method is particularly suitable for preparing L/B co-doped yttrium aluminum garnet powder.
The technical scheme of the invention is as follows.
A low-temperature solid phase synthesis method of L/B co-doped yttrium aluminum garnet powder comprises the following steps:
s1, Y 2 O 3 Compound of L-site doping element, al (OH) 3 And B-site doped element compounds are used as raw materials, and ball milling is carried out respectively;
s2, grinding the ball-milled raw materials in the step S1, and drying to obtain ultrafine powder of four raw materials;
s3, mixing and ball milling the ultrafine powder of the four raw materials obtained in the step S2 according to the proportion of each element in the product, and drying, grinding and sieving the mixture after finishing;
s4, sintering the undersize product in the S3 at 1100-1300 ℃ to obtain the L/B co-doped yttrium aluminum garnet powder.
According to the scheme disclosed by the invention, firstly, raw materials are treated, so that conditions are created for low-temperature sintering; and then mixing the processed raw materials, sintering the YAG powder into a phase, and realizing controllable occupation of doped ions in YAG crystal lattices at a lower temperature and a heating rate.
Preferably, the L-site doping element is Er, gd, sc, ce, yb or Nd, and the B-site doping element is Fe, mg, ti, ca or Mn.
Further preferably, the compound of the L-site doping element is Er 2 O 3 、Gd 2 O 3 、Sc 2 O 3 、CeO 2 、Yb 2 O 3 Or Nd 2 O 3 The raw material of the B-site doping element is Fe 2 O 3 、MgO、TiO 2 、CaCO 3 Or MnCO 3 。
Preferably, the ball mill in S1 uses water as a dispersant.
Specifically, the solid content of rare earth oxide is less than 40% when ball milling is carried out, the solid content of metal oxide is less than 30% when ball milling is carried out, and the solid content of hydroxide and carbonate is less than 20% when ball milling is carried out.
Preferably, the sanding in S2 is performed first at 2300rpm for 1h, then at 2500rpm for 1h, and finally at 2700rpm for 1h. Through comparison of different rotating speeds and time, the obtained material is thinner under the condition, the sanding treatment time is proper, and the sanding parameter is a preferable sanding parameter with the characteristics of economy and high efficiency.
Further preferably, during the sanding of S2, a poly (meth) acrylate amine is added as a dispersant. And the addition amount of the dispersing agent is different for different raw materials.
Specifically, for rare earth oxide raw materials, the addition amount of the dispersing agent is not more than 4 wt%o; for the metal oxide raw material, the addition amount of the dispersing agent is not more than 1wt%; for hydroxide and carbonate materials, the dispersant is added in an amount of not more than 2wt%
Preferably, in S3, the method according to (Y 1-x L x ) 3 (Al 1-y B y ) 5 O 12 (0<x<1；0<y<1) Mixing the superfine powder of the four raw materials.
Preferably, the mixing in the step S3 is ball-milled, absolute ethyl alcohol is added, and the mass ratio of the raw materials to the absolute ethyl alcohol is 1:2.
Preferably, the drying in S3 is carried out by placing the material in a beaker, sealing with a film with air holes, and drying at constant temperature of 70-90 ℃. For example, the mouth of the beaker can be sealed by a film, and a plurality of small holes can be punched in the film by a knife. Preferably, the screening in S3 is by a 80-200 mesh screen.
Preferably, the sintering in S4 is performed by heating to 1000 ℃ at 5 ℃/min, then heating to 1100-1300 ℃ at 2 ℃/min, preserving heat for 3-5h, and finally cooling at 100 ℃/h.
According to the scheme disclosed by the invention, firstly, raw materials are treated, and the raw materials are ground for multiple times. The sanding process is one of the outstanding characteristics of the invention, all raw materials are thinned to nano-scale, and conditions are created for subsequent low-temperature sintering. In the treatment process, except the raw materials and the dispersing agent, other substances are not generated, the dispersing agent, namely the polymethyl acrylate amine, can be removed by calcination, does not need washing, does not generate waste liquid, is beneficial to environmental protection, water is easy to evaporate, absolute ethyl alcohol is easy to volatilize, and no impurities remain, so that the obtained yttrium aluminum garnet ceramic powder has high purity and no impurity phase.
In the sintering phase process of YAG powder, a ball milling and grinding sieving combined mode is adopted to realize the fine granularity and uniformity of the powder; the hydroxide or carbonic acid with higher reactivity (Al (OH) 3 、MnCO 3 、CaCO 3 ) The preparation method can be used for replacing oxide raw materials in the traditional preparation method, can promote solid-phase reaction, has no other material loss in the reaction process, and can obtain a product with accurate stoichiometric ratio only by calculating the raw material ratio; by reducing the temperature rising speed of the sintering temperature, optimizing the sintering process and prolonging the diffusion time of the doped ions in the YAG matrix, the full solid solution is obtained, and the occupation of the doped ions in the YAG crystal lattice is controllable.
According to the technical proposal of the invention, no component segregation or loss exists in the powder treatment and solid phase synthesis process, no impurity is introduced, and the obtained (Y) 1-x L x ) 3 (Al 1-y B y ) 5 O 12 (0<x<1；0<y<1) The powder has a single garnet structureHas the advantages of high purity, uniform components, accurate stoichiometric ratio and controllable occupation of doped ions.
The sand grinding technology introduced in the invention is a physical method for preparing ultrafine powder, and the powder is crushed mainly by a ball milling medium in the high-speed running process. In particular, the raw material powder is subjected to sand grinding, so that the particle size is uniform and fine, the specific surface area is high, the reaction activity is high, and the low-temperature phase formation of the yttrium aluminum garnet powder is easy to realize in the solid phase reaction process.
In the invention, after ball milling, secondary grinding and sieving are carried out, which is beneficial to the miniaturization and homogenization of the granularity of the powder, further reduces the solid phase synthesis reaction temperature, and can improve the component uniformity of the mixed powder to obtain the L/B co-doped YAG powder with uniform components.
Finally, compared with the traditional high-temperature solid-phase reaction of yttrium aluminum garnet powder, the sintering temperature of the invention is greatly reduced, and the maximum sintering temperature is only 1300 ℃. The traditional method is that the powder is obtained by sintering at a high temperature of above 1600 ℃, the heating speed is high and is about 10-20 ℃/min, and the phenomena of coarse powder particles and uneven component distribution are easy to occur. According to the invention, by reducing the temperature rising speed of the sintering temperature, especially the temperature rising speed in the high temperature stage of more than 1000 ℃, the reaction diffusion time can be prolonged, the full solid solution of doped ions in the YAG matrix is realized, the L/B co-doped YAG powder with controllable lattice occupation is obtained, and the production cost is greatly reduced.
Drawings
FIG. 1 is a flow chart of a low temperature solid phase synthesis method of L/B co-doped yttrium aluminum garnet powder in example 1;
FIG. 2 is an XRD pattern of the L/B co-doped yttrium aluminum garnet powder obtained in examples 1-5;
FIG. 3 is an SEM image of L/B-site co-doped yttrium aluminum garnet powder obtained in example 1;
FIG. 4 is an EDS diagram of the L/B site co-doped yttrium aluminum garnet powder obtained in example 1.
Detailed Description
The invention is illustrated and described by the following detailed description of the invention for better explaining the invention.
Example 1
Preparation of L/B-site co-doped yttrium aluminum garnet powder (Y) according to the procedure described in FIG. 1 0.4 Er 0.6 ) 3 (Al 0.8 Fe 0.2 ) 5 O 12 The specific steps are as follows.
S1, Y with chemical purity more than or equal to 99.99 percent 2 O 3 、Er 2 O 3 、Al(OH) 3 、Fe 2 O 3 The powder is respectively placed in a polyurethane ball milling tank, and deionized water is added as a dispersing agent. Wherein Y is 2 O 3 Powder and Er 2 O 3 The mass ratio of the powder to the water is 1:1.5; al (OH) 3 The mass ratio of the powder to the water is 1:4; fe (Fe) 2 O 3 The mass ratio of the powder to the water is 3:7. The polyurethane ball milling tank is placed on a tank milling ball mill, ball milling is carried out for 24 hours at the speed of 150r/min, so as to reach the feeding granularity requirement of the sand mill as the ball milling end point, and prevent coarse particles from blocking the pipeline.
S2, after ball milling is completed, pouring slurry obtained by ball milling into a sand mill, respectively grinding the raw materials for 1 hour under the conditions of rotation speed of 2300r/min, 2500r/min and 2700r/min, and meanwhile, dropwise adding the polymethyl acrylate amine dispersant according to a proportion. Wherein Y is 2 O 3 Powder and Er 2 O 3 Adding 4 wt%o of dispersing agent into the powder; al (OH) 3 Adding 2wt% of dispersing agent into the powder; fe (Fe) 2 O 3 1wt% of dispersing agent is added into the powder. After the sanding is finished, the slurry is poured into a stainless steel tray, and then is taken into an oven to be dried for 12 hours at 90 ℃ to obtain superfine raw material powder with uniform particle size.
S3, Y is 2 O 3 、Er 2 O 3 、Al(OH) 3 、Fe 2 O 3 Mixing superfine raw material powder in a molar ratio of 6:9:40:5, placing in a nylon ball milling tank, and adding absolute ethyl alcohol as raw materialThe mass ratio of the dispersant to the material is 2:1. The nylon ball milling pot was placed in a planetary ball mill for ball milling for 24 hours. After ball milling, pouring the materials into a beaker, sealing the mouth of the beaker by using a film, stamping a plurality of small holes by using a knife, and putting the beaker into an electrothermal constant-temperature blast drying oven for drying for 12 hours, wherein the temperature of the drying oven is 80 ℃. The dried powder was ground and then sieved with an 80 mesh sieve.
S4, pouring the sieved powder into a crucible, and placing the crucible in a box-type resistance furnace for sintering into a phase. The sintering temperature is 1300 ℃, the heat preservation time is 3 hours, the specific heating program is that the temperature is raised at a speed of 100 ℃/h after the temperature is lower than 1000 ℃ and is raised at a speed of 5 ℃/min and is lowered at a speed of 2 ℃/min after the heat preservation is finished.
The obtained L/B-site co-doped yttrium aluminum garnet powder (Y) 0.4 Er 0.6 ) 3 (Al 0.8 Fe 0.2 ) 5 O 12 The XRD pattern of the obtained powder is shown as figure 2, and the XRD diffraction pattern of the obtained powder is shown as a single garnet structure, and has no impurity phase, so that Er and Fe are completely dissolved in the YAG crystal lattice.
The obtained L/B-site co-doped yttrium aluminum garnet powder (Y) 0.4 Er 0.6 ) 3 (Al 0.8 Fe 0.2 ) 5 O 12 SEM and EDS images of (a) are shown in fig. 3-4. Wherein the atomic percentages of Y, er, al, fe, O elements are 6.06%, 9.07%, 20.14%, 4.81%, 59.92% respectively, which are close to the atomic ratio relationship 6:9:20:5:60 of the powder Y, er, al, fe, O, indicating that (Y) prepared by the method 0.4 Er 0.6 ) 3 (Al 0.8 Fe 0.2 ) 5 O 12 The powder has uniform components and accurate stoichiometric ratio.
Examples 2 to 10
Different L-site and B-site doped elements and raw material proportions are replaced, and yttrium aluminum garnet powder doped with different L-site and B-site elements is prepared according to the same preparation method of the embodiment 1, and the specific table is as follows. Wherein the proportion of the raw materials is Y 2 O 3 Doping raw material at L position, al (OH) 3 The mole ratio of the four raw materials of the B-site doping raw materials.
The XRD diffraction patterns of examples 2-5 are shown in figure 2, and the obtained materials are all confirmed to be of a single garnet structure and have no impurity phase.
Claims (10)
1. The low-temperature solid phase synthesis method of the L/B-site co-doped yttrium aluminum garnet powder is characterized by comprising the following steps of:
s1, Y 2 O 3 Compound of L-site doping element, al (OH) 3 And B-site doped element compounds are used as raw materials, and ball milling is carried out respectively;
s2, sanding and drying the raw materials subjected to ball milling in the step S1 to obtain four ultrafine powder of the raw materials;
s3, mixing and ball milling the four superfine powder of the raw materials obtained in the step S2 according to the proportion of each element in the product, and drying, grinding and sieving the mixture after finishing;
and S4, sintering the undersize product in the step S3 at 1100-1300 ℃ to obtain the L/B co-doped yttrium aluminum garnet powder.
2. The low temperature solid phase synthesis method of L/B co-doped yttrium aluminum garnet powder according to claim 1, wherein the L-site doping element is Er, gd, sc, ce, yb or Nd, and the B-site doping element is Fe, mg, ti, ca or Mn.
3. The low-temperature solid phase synthesis method of L/B-site co-doped yttrium aluminum garnet powder according to claim 1 or 2, wherein the compound of the L-site doped element is Er 2 O 3 、Gd 2 O 3 、Sc 2 O 3 、CeO 2 、Yb 2 O 3 Or Nd 2 O 3 The compound of the B-site doping element is Fe 2 O 3 、MgO、TiO 2 、CaCO 3 Or MnCO 3 。
4. The low temperature solid phase synthesis method of L/B co-doped yttrium aluminum garnet powder according to claim 1, wherein the ball milling in S1 uses water as a dispersant, wherein the solid content of rare earth oxide is less than 40% when the ball milling is performed, the solid content of metal oxide is less than 30% when the ball milling is performed, and the solid content of hydroxide and carbonate is less than 20% when the ball milling is performed.
5. The method for low-temperature solid phase synthesis of L/B-site co-doped yttrium aluminum garnet powder according to claim 1, wherein said sanding in S2 is performed first at 2300rpm for 1h, then at 2500rpm for 1h, and finally at 2700rpm for 1h.
6. The low temperature solid phase synthesis method of L/B co-doped yttrium aluminum garnet powder according to claim 1, wherein in S2, poly (methyl acrylate) amine is added as a dispersant during sanding, wherein the addition amount of the dispersant is not more than 4 wt% for rare earth oxide, not more than 1wt% for metal oxide, and not more than 2wt% for hydroxide and carbonate.
7. The method for low-temperature solid phase synthesis of L/B-site co-doped yttrium aluminum garnet powder according to claim 1, wherein S3 is a compound according to (Y 1-x L x ) 3 (Al 1-y B y ) 5 O 12 (0<x<1；0<y<1) Mixing four ultrafine powder of the raw materials, adding absolute ethyl alcohol during mixing and ball milling, wherein the mass ratio of the raw materials to the absolute ethyl alcohol is 1:2.
8. The method for low-temperature solid phase synthesis of L/B co-doped yttrium aluminum garnet powder according to claim 1, wherein in S3, the drying is to put the materials into a beaker, seal the materials with a film with air holes, and then dry the materials at a constant temperature of 70-90 ℃.
9. The method for low temperature solid phase synthesis of L/B co-doped yttrium aluminum garnet powder according to claim 1, wherein in S3, the sieving is through a 80-200 mesh sieve.
10. The method for low-temperature solid phase synthesis of L/B co-doped yttrium aluminum garnet powder according to claim 1, wherein in S4, the sintering is performed by heating to 1000 ℃ at 5 ℃/min, then heating to 1100-1300 ℃ at 2 ℃/min, preserving heat for 3-5h, and finally cooling at 100 ℃/h.
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