CN111252799A - Preparation of YAG Ce by containerless solidification3+Method for mixing amorphous material with aluminum nitride - Google Patents
Preparation of YAG Ce by containerless solidification3+Method for mixing amorphous material with aluminum nitride Download PDFInfo
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Abstract
The invention relates to a method for preparing YAG Ce by container-free solidification3+The method for mixing the amorphous material with the aluminum nitride comprises the following steps: preparing YAG with different proportions: ce3+And the mixture of aluminum nitride powder, the tablet is pressed and then crushed into blocks, the blocks are put into a laser suspension furnace, the size of air flow and the heating power of laser are adjusted, and the powder is melted and suspended to form stable suspension liquid drops; after the stable suspension liquid drop is heated for a period of time, the laser generation switch is closed, the heating power of the laser is rapidly reduced to zero, and the suspension liquid drop is rapidly cooled to form colorless and transparent spherical amorphous. In the rapid solidification and cooling process of the liquid drops, the liquid drops do not contact with the wall of the container, so that impurities are prevented from being introduced, heterogeneous nucleation of the liquid in the cooling process can be prevented, and amorphous formation is promoted. The invention adopts aluminum nitride and YAG：Ce3+The amorphous prepared by mixing the powder has good thermal conductivity of aluminum nitride, and is beneficial to solving the phenomena of light decay and device aging of the white light LED caused by poor heat dissipation.
Description
The technical field is as follows:
the invention belongs to the technical field of amorphous material preparation methods and solid-state lighting, and particularly relates to a method for preparing YAG (yttrium aluminum garnet) Ce by containerless solidification3+And aluminum nitride mixed amorphous material.
Background art:
yttrium Aluminum Garnet (YAG) has excellent optical, mechanical and thermal properties. Has high transmittance in infrared, visible and ultraviolet bands, and is widely used for manufacturing matrix materials and laser materials of fluorescent powder. Wherein, YAG: ce3+Has excellent yellow luminous performance, and can be combined with blue light emitted by InGaN to prepare white light LEDs (WLEDs). This is also a widely commercially used method of preparing white LEDs at present. White LEDs are widely used in the solid state lighting field due to their high luminous intensity, long lifetime, and capability of being miniaturized. The current LED lamp mainly adopts the following technical scheme that YAG: ce3+The fluorescent powder and the epoxy resin are mixed and coated on the surface of an InGaN LED chip to manufacture a white LED, however, the LED emits light to generate a large amount of heat, and the epoxy resin has poor heat conduction performance, so that the device is in a high-temperature state to generate the phenomena of light decay and device aging. Thus, on the original basis, we began to look at YAG: ce3+Aluminum nitride is added to the powder to improve heat dissipation performance.
Aluminum nitride is an atomic crystal with good thermal conductivity and small thermal expansion coefficient. Aluminum nitride has a higher thermal conductivity than alumina. Therefore, aluminum nitride and YAG: ce3+The powder is mixed, so that the heat conducting performance of the material can be further improved.
An amorphous material represented by glass is a very common material in our daily life. The amorphous has short-range order, long-range disorder and isotropic structural characteristics, so that the amorphous has special physical properties, chemical properties and optical properties.
In the forming process of the amorphous material, the viscosity is improved due to the influence of factors such as too high cooling speed, pressure influence or particle addition and the like, a crystal structure with orderly arranged atoms cannot be formed, and substances do not nucleate and grow to form amorphous. Therefore, the key to forming an amorphous is to prevent nucleation growth of the crystal. Under the existing preparation conditions, most of amorphous is prepared by heating crystals in a container and then rapidly cooling, and in the cooling process, heterogeneous nucleation is caused by contact with the container wall, so that the formation of the amorphous is influenced.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and provides YAG-Ce3+An amorphous aluminum nitride material and a container-free solidification preparation method thereof. YAG: ce3+The powder and aluminum nitride were mixed to prepare an amorphous body, and a colorless amorphous body having a diameter of 1 to 2mm was successfully prepared.
In order to achieve the purpose, the invention adopts the following technical scheme:
preparation of YAG Ce by containerless solidification3+The method for mixing the amorphous material with the aluminum nitride comprises the following steps:
step 1: mixing of materials
The weight ratio of YAG: ce3+Powder: aluminum nitride powder ═ (70-90): (10-30), mixing the two uniformly, tabletting the mixed powder firstly and then crushing the powder into a block sample.
Step 2: laser heating treatment:
placing the block sample in a nozzle of a laser suspension furnace, introducing air flow, wherein the pressure of the originally introduced air flow is 0.1KPa, increasing the air flow to the air pressure of 0.26-0.5KPa at a constant speed within 14-30s (within the time period that the laser heating power is increased to 1120W), introducing air, and simultaneously starting laser heating, specifically, increasing the laser heating power to 1120W at the speed of 40-80W/s, and increasing the laser heating power to 1200-1520W at the speed of 10-30W/s; during the laser heating power is increased from 1120W to 1200-1520W, the air pressure of the air flow is kept at 0.26-0.5KPa, so that the powder is melted and suspended to form stable suspended liquid drops;
and step 3: YAG to Ce3+Preparing a mixed aluminum nitride amorphous material:
and keeping the air pressure of the air flow at 0.26-0.5KPa, stabilizing the laser heating power at 1200-1520W, continuously heating the stable suspension liquid drops for 15-30s, and providing energy for the thermal motion of particles in the sample to ensure that the particles fully reach a disordered state. Closing the laser generation switch, cooling the suspension liquid drop to room temperature along with the furnace to form colorless transparent spherical amorphous, namely YAG: Ce3+An amorphous material of aluminum nitride is mixed.
In the step 1, YAG: ce3+The mixing ratio of (1) to (2) is 99:1, the thickness of the block sample is 1mm, and the diameter of the martensite is 2-3 mm.
In the step 1, the mixing mode is ball milling mixing, and the specific process is as follows:
(1) weighing YAG in a mass ratio: ce3+Adding anhydrous ethanol which is not metered by the mixed powder into commercial powder of the aluminum nitride, and carrying out ball milling at the ball milling speed of 30r/min for 8-10h, wherein the mass ratio of the zirconia balls to the raw materials is 5:1, the mass ratio of the zirconia balls to the medium balls is 1:3: 6;
(2) drying the ball-milled product, and removing absolute ethyl alcohol to obtain mixed powder;
in the step 1, the tabletting pressure is 2 MPa.
In the step 2, when the pressure of the airflow is increased from 0.1KPa to 0.26-0.5KPa and the laser heating power is increased from 0 to 1120W, the block sample is free from sticking to the furnace, so that stable suspension is realized; and in the process that the air flow pressure is kept at 0.26-0.5KPa, and the laser heating power is increased from 1120W to 1200-1520W, the massive sample is gradually melted, stably suspended and gradually melted to become a sphere, and a stable suspended liquid drop is formed.
In the step 2, the gas flow component is rare gas, so that the blocky sample is blown and suspended, and meanwhile, the gas flow component is used as protective gas to prevent aluminum nitride from being oxidized in the laser heating process.
In the step 2, the rare gas is argon.
In the step 3, the step of processing the image,YAG preparation: ce3+The mixed aluminum nitride amorphous material has the diameter of 1-2mm and the thermal conductivity of 19.676-34.794w/m x k. Same volume of material, YAG: ce3+The higher the doping amount, the higher the luminous intensity under the excitation of blue light.
In the step 3, YAG is added to Ce3+Of a two-phase composite of mixed aluminum nitride, YAG: Ce3+The aluminum nitride is a continuous phase and is a dispersed phase, the volume fraction of the continuous phase is 0.6234-0.8646, and the volume fraction of the dispersed phase is 0.1354-0.3766.
The invention has the beneficial effects that:
by adopting the technical scheme of the invention, the YAG powder is prepared by mixing the raw materials of the original YAG: ce3+Aluminum nitride with good heat conductivity is added into the powder, so that the heat conductivity of the mixed material is improved, and the high-performance white light LED device is more convenient to manufacture. Meanwhile, the preparation method without container solidification adopted in the preparation process ensures that the liquid substance does not contact with the container wall in the cooling process to cause heterogeneous nucleation, thereby being beneficial to the formation of amorphous. The containerless fabrication also ensures that no impurities are introduced, so that higher quality amorphization can be obtained. In addition, the invention also has the characteristics of simple operation and strong practicability.
Description of the drawings:
FIG. 1 is a YAG-Ce alloy prepared by the containerless solidification technique of example 1 of the present invention3+Macro photo of mixed aluminum nitride amorphous material;
FIG. 2 is a schematic diagram of the preparation of YAG to Ce by the containerless solidification technique of example 1 of the present invention3+A method flow chart of mixing aluminum nitride amorphous material;
FIG. 3 is a schematic diagram of the preparation of YAG to Ce by the containerless solidification technique of example 1 of the present invention3+YAG-Ce in process of mixing aluminum nitride amorphous material3+A flow chart of a block sample prepared by uniformly mixing the aluminum nitride powder and the aluminum nitride powder;
FIG. 4 shows the preparation of YAG to Ce by the containerless solidification technique of example 1 of the present invention3+XRD pattern of mixed aluminum nitride amorphous material;
FIG. 5 is a schematic diagram of the preparation of YAG to Ce by the containerless solidification technique of example 1 of the present invention3+(ii) a thermogram of the mixed aluminum nitride amorphous material;
FIG. 6 is a schematic diagram of the preparation of YAG to Ce by the containerless solidification technique of example 1 of the present invention3+Excitation and emission spectra of the mixed aluminum nitride amorphous material;
FIG. 7 is a schematic diagram of the preparation of YAG to Ce by the containerless solidification technique of example 2 of the invention3+XRD pattern of mixed aluminum nitride amorphous material.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
In the following examples:
the laser name adopted in the laser heating process: double bundle CO2Laser, model: ti100W, the air jet caliber is 1.5 mm;
YAG：Ce3+the mixing ratio of (1) to (99), the thickness of the block sample is 1mm, and the diameter of the martensite is 2-3 mm.
Example 1
Preparation of YAG Ce by containerless solidification3+The method for mixing the amorphous material with the aluminum nitride is shown in a flow chart of fig. 2 and comprises the following steps:
step 1: mixing of materials
The weight ratio of YAG: ce3+Powder: aluminum nitride powder 90: 10, ball-milling and mixing the two evenly, YAG: Ce3+The flow chart of the method for uniformly mixing aluminum nitride powder and making the mixture into blocks is shown in figure 3, and the specific process comprises the following steps:
(1) weighing YAG in a mass ratio: ce3+And commercial powder of aluminum nitride, adding absolute ethyl alcohol which is not metered by the mixed powder for ball milling, wherein the ball milling speed is 30r/min, and the ball milling time is 8-10h, whereinThe mass ratio of the zirconia balls to the raw materials is 5:1, the mass ratio of the zirconia balls to the medium balls to the large balls is 1:3: 6;
(2) drying the ball-milled product, and removing absolute ethyl alcohol to obtain mixed powder;
(3) tabletting the mixed powder under 2MPa, maintaining the pressure for 1min, and pulverizing into block sample with thickness of 1mm and Martin diameter of 2.5-3 mm.
Step 2: laser heating treatment:
the pressure of an original introduced airflow is 0.1KPa, the airflow is raised at a constant speed until the air pressure is 0.5KPa, the block sample is placed in a laser suspension furnace nozzle, and the size of the airflow and the heating power of laser are adjusted in the laser suspension furnace, so that the powder block is melted and suspended to form stable suspension liquid drops; specifically, argon gas flow is introduced, the blocky sample is blown up, the pressure of the originally introduced gas flow is 0.1KPa, the gas flow is uniformly increased to the gas pressure of 0.5KPa within 28s (within the time period that the laser heating power is increased to 1120W), the laser heating is started while the gas flow is introduced, specifically, the laser heating power is increased to 1120W at the rate of 40W/s, and then the laser heating power is increased to 1520W at the rate of 10W/s; during the process of increasing the laser heating power from 1120W to 1520W, the gas flow is kept at the gas pressure of 0.5KPa, so that the powder is melted and suspended to form stable suspended liquid drops, wherein:
argon gas flow is used for preventing aluminum nitride from being oxidized in the laser heating process, when the gas flow pressure is increased from 0.1KPa to 0.5KPa, and meanwhile, the laser heating power is increased from 0 to 1120W, the block sample is free from furnace sticking, and stable suspension is realized; when the air pressure of the air flow is kept at 0.5KPa and the laser heating power is increased to 1520W from 1120W, the blocky sample is gradually melted and becomes a sphere to form a stable suspension drop;
and step 3: YAG to Ce3+Preparing a mixed aluminum nitride amorphous material:
keeping the air pressure of the air flow at 0.5KPa, stabilizing the laser heating power at 1520W, continuing to heat the stable suspension liquid drop for 30s, turning off the laser generation switch to rapidly reduce the laser heating power to zero, rapidly cooling the suspension liquid drop to room temperature along with the furnace to form colorless transparent spherical amorphous, i.e. colorless transparent spherical amorphousIs YAG to Ce3+Mixed amorphous aluminium nitride material with thermal conductivity of 19.676w/m × k, YAG: Ce3+Of a two-phase composite of mixed aluminum nitride, YAG: Ce3+The aluminum nitride is a continuous phase and a dispersed phase, the volume fraction of the continuous phase is 0.8646, and the volume fraction of the dispersed phase is 0.1354; the absence of an alumina phase, a macroscopic photograph thereof as shown in FIG. 1, a diameter of 1 to 1.5mm, an XRD pattern as shown in FIG. 4, an excitation and emission spectrum as shown in FIG. 6, and a thermogram thereof as shown in FIG. 5, and it can be seen from an amorphous DSC curve that the glass transition temperature Tg (879 ℃ C.), the initial crystallization temperature Tx (950 ℃ C.) and the crystallization peak temperature Tp (968 ℃ C.). The supercooled liquid phase width Δ T, i.e., the difference between Tg and Tx (Δ T — Tg), is an important index for determining the ability to form an amorphous phase from a kinetic point of view, and the larger Δ T, the wider the crystallization-inhibiting temperature range existing in the liquid phase, and the easier the material is to form an amorphous phase. As can be seen, Δ T is 71 ℃, which is less than 100 ℃, indicating that it is difficult to make the mixture amorphous using conventional melt quenching techniques.
By adopting the preparation process of the embodiment, the laser heating power is high, the speed is high, and the YAG: ce3+And the aluminum nitride powder block rapidly obtains high-temperature melting, YAG: Ce3+The melting and rapid cooling solidification process of the mixed powder block with the alumina is carried out in the air and is not contacted with the wall of the container, thereby avoiding the heterogeneous nucleation phenomenon generated in the cooling process and promoting the mixed powder block to form amorphous. Meanwhile, the parameters in the process are controlled within a specific range, so that the sample is prevented from contacting with the wall of the container, other impurities are avoided, and the YAG-Ce-rich yttrium aluminum garnet (YAG-Ce) is kept3+And purity of aluminum nitride mixed amorphous material.
Comparative examples 1 to 1
The same process as that of example 1 was adopted, except that aluminum nitride in the raw material was replaced with alumina of the same content, the power was increased to 1560W at the same rate of temperature increase in the secondary power increase, the prepared product was an amorphous material, and the amorphous material was detected to have a dispersed phase volume fraction of 0.1265 and a thermal conductivity of 15.968W/m × k; the delta T was 71 ℃ by thermal analysis.
Comparative examples 1 to 2
The same procedure as in example 1 was followed, except that the alumina content in the raw material was adjusted to 35%, and the product was obtained as yellow opaque crystals with irregular spheres and pits on the surface.
Example 2
Preparation of YAG Ce by containerless solidification3+The method for mixing the amorphous material with the aluminum nitride comprises the following steps:
step 1: mixing of materials
The weight ratio of YAG: ce3+Powder: aluminum nitride powder 80: and 20, ball-milling and uniformly mixing the two, wherein the specific process is as follows:
(1) weighing YAG in a mass ratio: ce3+Adding anhydrous ethanol which is not metered by the mixed powder into commercial powder of the aluminum nitride, and carrying out ball milling at the ball milling speed of 30r/min for 8-10h, wherein the mass ratio of the zirconia balls to the raw materials is 5:1, the mass ratio of the zirconia balls to the medium balls is 1:3: 6;
(2) drying the ball-milled product, and removing absolute ethyl alcohol to obtain mixed powder;
(3) tabletting the mixed powder under 2MPa, maintaining the pressure for 1min, and pulverizing into block sample with thickness of 1mm and Martin diameter of 2-2.5 mm.
Step 2: laser heating treatment:
the pressure of an original introduced airflow is 0.1KPa, the airflow is raised at a constant speed until the air pressure is 0.38KPa, the block sample is placed in a laser suspension furnace nozzle, and the size of the airflow and the heating power of laser are adjusted in the laser suspension furnace, so that the powder block is melted and suspended to form stable suspension liquid drops; specifically, argon gas flow is introduced, the blocky sample is blown up, the pressure of the originally introduced gas flow is 0.1KPa, the gas flow is uniformly increased to the air pressure of 0.38KPa in the time period that the laser heating power is increased to 1120W, the laser heating is started simultaneously when the gas flow is introduced, specifically, the laser heating power is increased to 1120W at the rate of 60W/s, and then the laser heating power is increased to 1360W at the rate of 20W/s; during the process of increasing the laser heating power from 1120W to 1360W, the gas flow maintains the gas pressure at 0.38KPa, so that the powder is melted and suspended to form stable suspended liquid drops, wherein:
argon gas flow is used for preventing aluminum nitride from being oxidized in the laser heating process, when the gas flow pressure is increased from 0.1KPa to 0.38KPa, and meanwhile, the laser heating power is increased from 0 to 1120W, the block sample is free from furnace sticking, and stable suspension is realized; when the air pressure of the air flow is kept at 0.38Pa and the laser heating power is increased from 1120W to 1360W, the blocky sample is gradually melted and becomes a sphere to form a stable suspension drop;
and step 3: YAG to Ce3+Preparing a mixed aluminum nitride amorphous material:
keeping the air pressure of the air flow at 0.38KPa, stabilizing the laser heating power at 1360W, continuing to heat the stable suspension liquid drop for 23s, turning off the laser generation switch to rapidly reduce the laser heating power to zero, rapidly cooling the suspension liquid drop along with the furnace to room temperature to form colorless transparent spherical amorphous YAG, Ce3+Mixed amorphous aluminium nitride material with thermal conductivity of 26.485w/m × k, YAG: Ce3+Of a two-phase composite of mixed aluminum nitride, YAG: Ce3+The aluminum nitride is a continuous phase and a dispersed phase, the volume fraction of the continuous phase is 0.7394, and the volume fraction of the dispersed phase is 0.2606; the amorphous material prepared in the embodiment has no alumina phase and the diameter of 1.5-2mm, and the XRD pattern of the amorphous material is shown in figure 7 through detection, and is the same as that of the amorphous material prepared in the embodiment 1, namely the peak of steamed bread, and the amorphous material is verified; through thermal analysis, the glass transition temperature Tg (871 ℃), the initial crystallization temperature Tx (946 ℃) and the crystallization peak temperature Tp (969 ℃), and the delta T is 75 ℃; the detection shows that the excitation wavelength peak value and the emission wavelength peak value are the same as those in the embodiment 1, namely the excitation wavelength peak value and the emission wavelength peak value are not influenced on the basis of being made of amorphous materials under different proportions.
Comparative example 2
The same process as that of example 2 was adopted, except that aluminum nitride in the raw material was replaced with alumina of the same content, power was increased to 1440W at the same rate of temperature increase in the secondary power increase, and the prepared product was an amorphous material, which was detected to have a dispersed phase volume fraction of 0.2457 and a thermal conductivity of 17.999W/m × k; the delta T was 70 ℃ by thermal analysis.
Example 3
Preparation of YAG Ce by containerless solidification3+The method for mixing the amorphous material with the aluminum nitride comprises the following steps:
step 1: mixing of materials
The weight ratio of YAG: ce3+Powder: 70 parts of aluminum nitride powder: 30, ball-milling and uniformly mixing the two, wherein the specific process is as follows:
(1) weighing YAG in a mass ratio: ce3+Adding anhydrous ethanol which is not metered by the mixed powder into commercial powder of the aluminum nitride, and carrying out ball milling at the ball milling speed of 30r/min for 8-10h, wherein the mass ratio of the zirconia balls to the raw materials is 5:1, the mass ratio of the zirconia balls to the medium balls is 1:3: 6;
(2) drying the ball-milled product, and removing absolute ethyl alcohol to obtain mixed powder;
(3) tabletting the mixed powder under 2MPa, maintaining the pressure for 1min, and pulverizing into block sample with thickness of 1mm and Martin diameter of 2-2.5 mm.
Step 2: laser heating treatment:
the pressure of an original introduced airflow is 0.1KPa, the airflow is raised at a constant speed until the air pressure is 0.26KPa, the block sample is placed in a laser suspension furnace nozzle, and the size of the airflow and the heating power of laser are adjusted in the laser suspension furnace, so that the powder block is melted and suspended to form stable suspension liquid drops; specifically, argon gas flow is introduced, the blocky sample is blown up, the pressure of the originally introduced gas flow is 0.1KPa, the gas flow is uniformly increased to the air pressure of 0.26KPa within the time period that the laser heating power is increased to 1120W, the laser heating is started simultaneously when the gas flow is introduced, specifically, the laser heating power is increased to 1120W at the rate of 80W/s, and then the laser heating power is increased to 1200W at the rate of 30W/s; during the process of increasing the laser heating power from 1120W to 1200W, the gas flow maintains the gas pressure at 0.26KPa, so that the powder is melted and suspended to form stable suspended liquid drops, wherein:
argon gas flow is used for preventing aluminum nitride from being oxidized in the laser heating process, when the gas flow pressure is increased from 0.1KPa to 0.26KPa, and meanwhile, the laser heating power is increased from 0 to 1120W, the block sample is free from furnace sticking, and stable suspension is realized; when the air pressure of the air flow is kept at 0.26KPa and the laser heating power is increased to 1200W from 1120W, the massive sample is gradually melted and becomes a sphere to form a stable suspension drop;
and step 3: YAG to Ce3+Preparing a mixed aluminum nitride amorphous material:
keeping the air pressure of the air flow at 0.26KPa, stabilizing the laser heating power at 1200W, continuing to heat the stable suspension liquid drop for 30-60s, turning off the laser generation switch to rapidly reduce the laser heating power to zero, rapidly cooling the suspension liquid drop to room temperature along with the furnace to form colorless transparent spherical amorphous YAG, Ce3+Mixed amorphous aluminium nitride material with thermal conductivity of 34.794w/m × k, YAG: Ce3+Of a two-phase composite of mixed aluminum nitride, YAG: Ce3+The aluminum nitride is a continuous phase and a dispersed phase, the volume fraction of the continuous phase is 0.6234, and the volume fraction of the dispersed phase is 0.3766; the amorphous material prepared in the embodiment has no alumina phase and the diameter of 1-1.5mm, and the XRD pattern of the amorphous material is the same as that of the amorphous material prepared in the embodiment 1 through detection, and is a steamed bread peak, and the amorphous material is verified; through thermal analysis, the glass transition temperature Tg (852 ℃), the initial crystallization temperature Tx (925 ℃) and the crystallization peak temperature Tp (952 ℃), and delta T is 73 ℃; the detection shows that the excitation wavelength peak value and the emission wavelength peak value are the same as those in the embodiment 1, namely the excitation wavelength peak value and the emission wavelength peak value are not influenced on the basis of being made of amorphous materials under different proportions.
Comparative example 3
The same process as that of example 3 was adopted, except that aluminum nitride in the raw material was replaced with alumina of the same content, the power was increased to 1360W at the same rate of temperature increase in the secondary power increase, and the prepared product was an amorphous material, which was detected to have a dispersed phase fraction of 0.3583 in volume fraction and a thermal conductivity of 20.098W/m × k; the delta T was 69 ℃ by thermal analysis.
Example 4
Preparation of YAG Ce by containerless solidification3+The method for mixing the amorphous material with the aluminum nitride comprises the following steps:
step 1: mixing of materials
The weight ratio of YAG: ce3+Powder: aluminum nitride powder77: and 23, ball-milling and uniformly mixing the two, wherein the specific process is as follows:
(1) weighing YAG in a mass ratio: ce3+Adding anhydrous ethanol which is not metered by the mixed powder into commercial powder of the aluminum nitride, and carrying out ball milling at the ball milling speed of 30r/min for 8-10h, wherein the mass ratio of the zirconia balls to the raw materials is 5:1, the mass ratio of the zirconia balls to the medium balls is 1:3: 6;
(2) drying the ball-milled product, and removing absolute ethyl alcohol to obtain mixed powder;
(3) tabletting the mixed powder under 2MPa, maintaining the pressure for 1min, and pulverizing into block sample with thickness of 1mm and Martin diameter of 2-2.5 mm.
Step 2: laser heating treatment:
the pressure of an original introduced airflow is 0.1KPa, the airflow is raised at a constant speed until the air pressure is 0.35KPa, the block sample is placed in a laser suspension furnace nozzle, and the size of the airflow and the heating power of laser are adjusted in the laser suspension furnace, so that the powder block is melted and suspended to form stable suspension liquid drops; specifically, argon gas flow is introduced, the blocky sample is blown up, the pressure of the originally introduced gas flow is 0.1KPa, the gas flow is uniformly increased to the gas pressure of 0.35KPa within 14-30s (within the time period that the laser heating power is increased to 1120W), the laser heating is started while the gas is introduced, specifically, the laser heating power is increased to 1120W at the rate of 70W/s, and then the laser heating power is increased to 1280W at the rate of 20W/s; during the process that the laser heating power is increased from 1120W to 1280W, the gas flow maintains the gas pressure to be 0.35KPa, so that the powder is melted and suspended to form stable suspended liquid drops, wherein:
argon gas flow is used for preventing aluminum nitride from being oxidized in the laser heating process, when the gas flow pressure is increased from 0.1KPa to 0.35KPa, and meanwhile, the laser heating power is increased from 0 to 1120W, the block sample is free from furnace sticking, and stable suspension is realized; when the air pressure of the air flow is kept at 0.35KPa and the laser heating power is increased from 1120W to 1280W, the massive sample is gradually melted and becomes a sphere to form a stable suspension drop;
and step 3: YAG to Ce3+Preparing a mixed aluminum nitride amorphous material:
keeping the air pressure of the air flow at 0.35KPa, stabilizing the laser heating power at 1280W, continuing to heat the stable suspension liquid drop for 30-60s, turning off the laser generation switch to rapidly reduce the laser heating power to zero, rapidly cooling the suspension liquid drop to room temperature along with the furnace to form colorless transparent spherical amorphous YAG, Ce3+Mixed amorphous aluminium nitride material with thermal conductivity of 28.298w/m × k, YAG: Ce3+Of a two-phase composite of mixed aluminum nitride, YAG: Ce3+The aluminum nitride is a continuous phase and a dispersed phase, the volume fraction of the continuous phase is 0.7037, and the volume fraction of the dispersed phase is 0.2963; the amorphous material prepared in the embodiment has no alumina phase and the diameter of 1-1.5mm, and the XRD pattern of the amorphous material is the same as that of the amorphous material prepared in the embodiment 1 through detection, and is a steamed bread peak, and the amorphous material is verified; the glass transition temperature Tg (859 ℃), the initial crystallization temperature Tx (926 ℃) and the crystallization peak temperature Tp (965 ℃) of the sample are analyzed thermally, at 67 ℃; the detection shows that the excitation wavelength peak value and the emission wavelength peak value are the same as those in the embodiment 1, namely the excitation wavelength peak value and the emission wavelength peak value are not influenced on the basis of being made of amorphous materials under different proportions.
Comparative example 4
The same process as that of example 4 was adopted, except that aluminum nitride in the raw material was replaced with alumina of the same content, power was increased to 1400W at the same rate of temperature increase in the secondary power increase, and the prepared product was an amorphous material, which was detected to have a dispersed phase volume fraction of 0.2801 and a thermal conductivity of 18.621W/m × k; the delta T was 70 ℃ by thermal analysis.
Example 5
Preparation of YAG Ce by containerless solidification3+The method for mixing the amorphous material with the aluminum nitride comprises the following steps:
step 1: mixing of materials
The weight ratio of YAG: ce3+Powder: aluminum nitride powder 85: and 15, ball-milling and uniformly mixing the two, wherein the specific process is as follows:
(1) weighing YAG in a mass ratio: ce3+And commercial powder of aluminum nitride, adding absolute ethyl alcohol which is not metered by the mixed powder for ball milling, wherein the ball milling rotating speed is 30r/min,the ball milling time is 8-10h, wherein the mass ratio of the zirconia balls to the raw materials is 5:1, the mass ratio of the zirconia balls to the medium balls to the large balls is 1:3: 6;
(2) drying the ball-milled product, and removing absolute ethyl alcohol to obtain mixed powder;
(3) tabletting the mixed powder under 2MPa, maintaining the pressure for 1min, and pulverizing into block sample with thickness of 1mm and Martin diameter of 2.5-3 mm.
Step 2: laser heating treatment:
the pressure of an original introduced airflow is 0.1KPa, the airflow is raised at a constant speed until the air pressure is 0.44KPa, the block sample is placed in a laser suspension furnace nozzle, and the size of the airflow and the heating power of laser are adjusted in the laser suspension furnace, so that the powder block is melted and suspended to form stable suspension liquid drops; specifically, argon gas flow is introduced, the blocky sample is blown up, the pressure of the originally introduced gas flow is 0.1KPa, the gas flow is uniformly increased to the air pressure of 0.44KPa within the time period that the laser heating power is increased to 1120W, the laser heating is started simultaneously when the gas flow is introduced, specifically, the laser heating power is increased to 1120W at the speed of 50W/s, and then the laser heating power is increased to 1400W at the speed of 20W/s; during the laser heating power is increased from 1120W to 1400W, the gas flow maintains the gas pressure at 0.44KPa, so that the powder is melted and suspended to form stable suspended liquid drops, wherein:
argon gas flow is used for preventing aluminum nitride from being oxidized in the laser heating process, when the gas flow pressure is increased from 0.1KPa to 0.44KPa, and meanwhile, the laser heating power is increased from 0 to 1120W, the block sample is free from furnace sticking, and stable suspension is realized; when the air pressure of the air flow is kept at 0.44KPa and the laser heating power is increased from 1120W to 1400W, the massive sample is gradually melted and becomes a sphere to form a stable suspension drop;
and step 3: YAG to Ce3+Preparing a mixed aluminum nitride amorphous material:
keeping the air pressure of the air flow at 0.44KPa, stabilizing the laser heating power at 1400W, continuing to heat the stable suspension liquid drop for 30-60s, turning off the laser generation switch to rapidly reduce the laser heating power to zero, and rapidly cooling the suspension liquid drop to room temperature along with the furnace to formColorless transparent spherical amorphous, namely YAG Ce3+Mixed amorphous aluminium nitride material with thermal conductivity of 22.919w/m × k, YAG: Ce3+Of a two-phase composite of mixed aluminum nitride, YAG: Ce3+The aluminum nitride is a continuous phase and a dispersed phase, the volume fraction of the continuous phase is 0.8008, and the volume fraction of the dispersed phase is 0.1992; the amorphous material prepared in the embodiment has no alumina phase and the diameter of 1.5-2mm, and the XRD pattern of the amorphous material is the same as that of the amorphous material prepared in the embodiment 1 through detection, and is a steamed bread peak, and the amorphous material is verified; by thermal analysis, Δ T is clearly less than 100 ℃; the detection shows that the excitation wavelength peak value and the emission wavelength peak value are the same as those in the embodiment 1, namely the excitation wavelength peak value and the emission wavelength peak value are not influenced on the basis of being made of amorphous materials under different proportions.
Comparative example 5
The same process as that of example 5 was adopted, except that aluminum nitride in the raw material was replaced with alumina of the same content, power was increased to 1520W at the same rate of temperature increase in the secondary power increase, and the prepared product was an amorphous material, which was detected to have a dispersed phase volume fraction of 0.1869 and a thermal conductivity of 16.974W/m × k; and the delta T difference is less than 100 degrees through thermal analysis.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical results:
the heat conductivity coefficient of the amorphous crystal prepared by taking the aluminum nitride as the disperse phase is obviously greater than that of the amorphous crystal prepared by taking the aluminum oxide as the disperse phase, and the increase amplitude of the heat conductivity coefficient is increased along with the increase of the mass fraction of the disperse phase.
Further, YAG and Ce with different mass fractions are adopted3+And the aluminum nitride powder is uniformly mixed to prepare the LED material with better heat resistance, and the material is in an amorphous state.
The container-free solidification technology is adopted to prepare the amorphous, so that the problems of heterogeneous nucleation and impurity introduction caused by the contact of the material and the container wall in the cooling process are solved, and the amorphous is favorably formed and the purity of the product is kept. Good thermal conductivity of aluminum nitride and YAG to Ce3+In combination, aluminum nitride has good thermal conductivity, which helps to solve the problem of white light LEDThe light decay and the device aging caused by poor heat dissipation. The method provides an idea for solving the heat dissipation problem of the white light LED.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. Preparation of YAG Ce by containerless solidification3+The method for mixing the amorphous material with the aluminum nitride is characterized by comprising the following steps of:
step 1: mixing of materials
The weight ratio of YAG: ce3+Powder: aluminum nitride powder ═ (70-90): (10-30), uniformly mixing the two, tabletting the mixed powder, and then crushing the powder into a block sample;
step 2: laser heating treatment:
placing the block sample in a nozzle of a laser suspension furnace, introducing air flow, wherein the pressure of the originally introduced air flow is 0.1KPa, increasing the air flow to the air pressure of 0.26-0.5KPa at a constant speed within 14-30s (within the time period that the laser heating power is increased to 1120W), introducing air, and simultaneously starting laser heating, specifically, increasing the laser heating power to 1120W at the speed of 40-80W/s, and increasing the laser heating power to 1200-1520W at the speed of 10-30W/s; during the laser heating power is increased from 1120W to 1200-1520W, the air pressure of the air flow is kept at 0.26-0.5KPa, so that the powder is melted and suspended to form stable suspended liquid drops;
and step 3: YAG to Ce3+Preparing a mixed aluminum nitride amorphous material:
keeping the air pressure of the air flow at 0.26-0.5KPa, stabilizing the laser heating power at 1200-1520W, continuously heating the stable suspension liquid drops for 15-30s, and providing energy for the thermal motion of particles in the sample to ensure that the particles fully reach a disordered state; closing the laser generation switch, cooling the suspension liquid drop to room temperature along with the furnace to form colorless transparent spherical amorphous, namely YAG: Ce3+An amorphous material of aluminum nitride is mixed.
2. Ce prepared by containerless solidification as claimed in claim 13+The method for mixing the amorphous material with the aluminum nitride is characterized in that in the step 1, YAG: ce3+The mixing ratio of (1) to (2) is 99:1, the thickness of the block sample is 1mm, and the diameter of the martensite is 2-3 mm.
3. Ce prepared by containerless solidification as claimed in claim 13+The method for mixing the amorphous material with the aluminum nitride is characterized in that in the step 1, the mixing mode is ball milling mixing, and the specific process is as follows:
(1) weighing YAG in a mass ratio: ce3+And aluminum nitride powder, adding absolute ethyl alcohol for ball milling, wherein the ball milling speed is 30r/min, the ball milling time is 8-10h, the mass ratio of the zirconia balls to the raw materials is 5:1, and the mass ratio of the zirconia balls to the medium balls to the small balls is 1:3: 6;
(2) and drying the ball-milled product, and removing the absolute ethyl alcohol to obtain mixed powder.
4. Ce prepared by containerless solidification as claimed in claim 13+The method for mixing the amorphous material with the aluminum nitride is characterized in that in the step 2, in the process that the airflow pressure is increased from 0.1KPa to 0.26-0.5KPa, and the laser heating power is increased from 0 to 1120W, the block sample has no furnace sticking condition, so that stable suspension is realized; and in the process that the air flow pressure is kept at 0.26-0.5KPa, and the laser heating power is increased from 1120W to 1200-1520W, the massive sample is gradually melted, stably suspended and gradually melted to become a sphere, and a stable suspended liquid drop is formed.
5. Ce prepared by containerless solidification as claimed in claim 13+The method for mixing the amorphous material with the aluminum nitride is characterized in that in the step 2, the gas flow component is rare gas, so that the blocky sample is blown and suspended, and meanwhile, the gas flow component is used as protective gas to prevent the aluminum nitride from being oxidized in the laser heating process.
6. Ce prepared by containerless solidification as claimed in claim 13+And aluminum nitride mixed amorphous material, characterized in that, in the step 3, the YAG prepared: ce3+The mixed aluminum nitride amorphous material has the diameter of 1-2mm and the thermal conductivity of 19.676-34.794w/m x k.
7. Ce prepared by containerless solidification as claimed in claim 13+The method for mixing the amorphous material with the aluminum nitride is characterized in that in the step 3, YAG (yttrium aluminum garnet) and Ce (yttrium aluminum nitride) are mixed3+Of a two-phase composite of mixed aluminum nitride, YAG: Ce3+The aluminum nitride is a continuous phase and is a dispersed phase, the volume fraction of the continuous phase is 0.6234-0.8646, and the volume fraction of the dispersed phase is 0.1354-0.3766.
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