CN116178004A - Rare earth gradual change doped transparent ceramic and preparation method thereof - Google Patents
Rare earth gradual change doped transparent ceramic and preparation method thereof Download PDFInfo
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- B33Y10/00—Processes of additive manufacturing
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Abstract
The invention relates to rare earth gradual change doped transparent ceramic and a preparation method thereof. The preparation method comprises the following steps: preparing non-rare earth doped ceramic slurry and rare earth doped ceramic slurry respectively; respectively adding two kinds of ceramic slurry into two feeding needle cylinders of a mixing device of a direct ink writing printer, setting and controlling the feeding rate of the two kinds of slurry and the rotating speed of a mixing shaft in a mixing cavity by combining an online mixing technology and a feeding control program, so that the two kinds of slurry are uniformly mixed in the mixing cavity, extruding the mixed slurry from a discharge hole, and realizing continuous change of rare earth ion components in the extruded slurry by combining the feeding program and the mixing program; obtaining a rare earth gradual change doped transparent ceramic biscuit through a direct ink writing 3D printing process; and (3) performing glue discharging, vacuum sintering, hot isostatic pressing sintering, annealing and polishing treatment on the rare earth graded doped transparent ceramic biscuit to obtain the rare earth graded doped transparent ceramic.
Description
Technical Field
The invention belongs to the technical field of ceramic preparation, and particularly relates to rare earth graded doped transparent ceramic and a preparation method thereof.
Background
The solid-state laser has the advantages of compact structure, high output power, convenient use and the like, and is widely applied to industrial production, military weapons and scientific research. As a major component of the laser, the laser gain medium material determines the performance of the laser to a great extent, and the conventional laser gain medium material is laser glass or laser single crystal. The advantages of transparent ceramics over single crystals and glass are mainly: (1) The segregation coefficient has smaller restriction on transparent ceramics than single crystals, and is easy to realize high-concentration and uniform doping; (2) Transparent ceramics are easier to realize the preparation of large-size and complex shapes; (3) Transparent ceramics are easier to realize multi-layer composite structure design and multifunction.
Whether used in laser weapons or scientific research, higher laser power, laser efficiency and beam quality are the primary targets for further laser development, and the biggest problem that constrains the further development of high power lasers is thermal. Thermal effects of the laser gain medium during operation include thermal focusing, stress-induced biaxial focusing, and stress-induced birefringence. These thermal effects severely affect the beam quality of the output beam, limiting the power of the laser. These thermal effects can even lead to cracking of the gain medium at high average power pumping.
For a uniformly doped gain medium, the pump power density gradually decreases from the two ends of the doped region to the center of the doped region, resulting in uneven internal heat distribution and easy generation of serious heat effects. Graded doping structures are considered ideal forms for reducing thermal effects and increasing pump power density. In the case of a high power pump, heat can be uniformly distributed in the material, and heat accumulation at the end face can be suppressed, so that the high power pump is an ideal gain medium for high-beam quality laser output.
At present, the preparation method of the transparent ceramic with the gradient doping structure mainly comprises two modes of dry pressing and tape casting. The dry pressing forming is to lay down the powder with different rare earth doping concentration layer by layer, after each layer of powder is laid down, the powder is flattened by a mould, and after the laying down is finished, the biscuit is pressed by a larger pressure and is subjected to cold isostatic pressing to prepare. In 2008, ikesu prepared nine layers of gradient doped YAG/0.5-3.6at.% Nd: YAG/YAG composite structural ceramics (Nat. Photonics,2008, 2:721-727) by dry pressing and vacuum sintering techniques, YAG was yttrium aluminum garnet crystal. The tape casting requires ceramic powder with different doping concentrations to prepare ceramic slurry, and the prepared single-component adhesive tapes are stacked and laminated to obtain the multi-layer multi-component composite structural ceramic. In 2010, kupp et al prepared three-stage YAG/0.25at.% Er to YAG/0.5at.% Er to YAG laser ceramic rods (J. Mater. Res.,2010, 25:476-483) using casting, vacuum sintering and hot isostatic pressing sintering. However, both of the above methods require preparation of a plurality of ceramic powders with different doping concentrations, and even further preparation of slurry, the flow is complicated and a lot of time is consumed. In addition, the rare earth doping concentration of the gain medium prepared by dry pressing and tape casting is changed stepwise, so that the real continuous change of the rare earth ion concentration cannot be realized.
In recent years, direct ink writing technology has been increasingly used in the field of transparent ceramic preparation. And (3) establishing a three-dimensional model of a required formed sample through a computer, further processing the model into a movement path of a discharging needle head, and stacking the slurry layer by layer to obtain a ceramic biscuit. Tang Fei et al prepared a transparent ceramic (CN 109761608 a) in a rod-like composite structure by direct ink writing in combination with double barrel forming, but the air pressure control slurry employed was not only unstable in flow rate, but also unable to control the feed ratio precisely for slurries of different rheology. In addition, effective mixing of the two slurries cannot be achieved by means of the nozzle cavity at the very front end alone, which can lead to uneven distribution of the components in the prepared biscuit.
Disclosure of Invention
Aiming at the problems that the rare earth doping concentration is distributed stepwise, the continuous change of the rare earth ion concentration cannot be realized, the types of powder required to be prepared are more and the like in the preparation of the rare earth graded doped transparent ceramic in the prior art, the invention provides a preparation method of the rare earth graded doped transparent ceramic based on direct ink writing.
In a first aspect, the invention provides a method for preparing rare earth graded doped transparent ceramics, which comprises the following steps:
(1) Preparing non-rare earth doped ceramic slurry and rare earth doped ceramic slurry respectively;
(2) Respectively adding two kinds of ceramic slurry into two feeding needle cylinders of a mixing device of a direct ink writing printer, and removing air in the slurry; the mixing device comprises a mixing cavity, wherein two feeding holes are symmetrically arranged in the middle of the periphery, and a discharging hole is arranged at the lower part of the mixing cavity; the outlet of the needle cylinder after the slurry is deaerated is respectively connected with two feed inlets of the mixing cavity in a sealing way, a piston is arranged at one end of the inlet of the needle cylinder, and the rate of the ceramic slurry entering the mixing cavity is controlled by the cooperation of the piston and a syringe pump which is positioned at the axis of the needle cylinder and is parallel to the axis; setting and controlling the feeding rate of the two slurries and the rotating speed of a mixing shaft in a mixing cavity by combining an online mixing technology and a feeding control program, so that the two slurries are uniformly mixed in the mixing cavity; extruding the mixed slurry from the discharge port, and realizing continuous change of rare earth ion components in the extruded slurry by combining a feeding procedure and a mixing procedure; obtaining a rare earth gradual change doped transparent ceramic biscuit through a direct ink writing 3D printing process;
(3) And performing glue discharging, vacuum sintering, hot isostatic pressing sintering, annealing and polishing treatment on the rare earth graded doped transparent ceramic biscuit to obtain the rare earth graded doped transparent ceramic.
Preferably, the preparation process of the non-rare earth doped ceramic slurry and the rare earth doped ceramic slurry comprises the following steps: respectively weighing raw material powder according to the stoichiometric ratio of the non-rare earth doped ceramic to the rare earth doped ceramic, adding a solvent and a dispersing agent, and mixing to obtain a slurry mixture with the solid content of 48-52 vol%; and then adding a thickener to obtain the non-rare earth doped ceramic slurry and the rare earth doped ceramic slurry.
Preferably, the non-rare earth doped ceramic is yttrium aluminum garnet Y 3 Al 5 O 12 Ceramic, said Y 3 Al 5 O 12 The raw material powder of the ceramics is Al 2 O 3 And Y 2 O 3 ；
The rare earth doped ceramic is rare earth doped yttrium aluminum garnet Y 3 Al 5 O 12 Ceramic, the rare earth is doped with Y 3 Al 5 O 12 The raw material powder of the ceramic is rare earth oxide and Al 2 O 3 And Y 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the rare earth oxide may be one of oxides of neodymium Nd, ytterbium Yb, erbium Er, or thulium Tm.
Preferably, the dispersing agent is at least one of polyacrylic acid, ammonium polyacrylate and ammonium polymethacrylate; the thickener is at least one selected from hydroxyethyl cellulose, hydroxypropyl cellulose, 2-hydroxyethyl methylcellulose and 2-hydroxypropyl methylcellulose.
Preferably, the sum of the feeding rates of the two ceramic slurries is controlled to be 0.1-10 mL/min; the rotating speed of the mixing shaft is 200-600 rpm.
Preferably, the glue discharging is performed in an air atmosphere, the glue discharging temperature is 600-800 ℃, and the heat preservation time is 6-10 hours.
Preferably, the vacuum sintering process comprises the following steps: heating to 1600-1700 ℃ at the speed of 2-10 ℃/min, and preserving heat for 6-15 h.
Preferably, the temperature of the hot isostatic pressing sintering is 1600-1700 ℃, and the heat preservation time is 2-6 h.
Preferably, the annealing process is as follows: under the air atmosphere, the green body after hot isostatic pressing sintering is kept at 1300-1400 ℃ for 10-20 h; then cooling to 200-1000 ℃ at a speed of 2-5 ℃/min, and then cooling with a furnace.
In a second aspect, the invention provides a rare earth graded doped transparent ceramic obtained by the preparation method, wherein the transmittance of the rare earth graded doped transparent ceramic in the wavelength range of 400-1100nm reaches 80-84%, and the change range of the rare earth doping concentration is 0.1-10at%.
Advantageous effects
The preparation method provided by the invention combines the autonomously designed mixing device and the matched control program with the direct ink writing equipment, can regulate and control the proportion between the two slurries in the printing process so as to control the components of the extruded slurry, is simple and easy to operate, combines the on-line mixing technology with the direct ink writing technology, and can realize the preparation of the rare earth gradual change doped transparent ceramic in the true sense only by preparing the two ceramic slurries.
Drawings
FIG. 1 is a schematic diagram of a mixing device used in the present invention;
FIG. 2 is a graph showing the cross-sectional profile of Yb element in the extrusion line of the head of a mixing shaft at different rotation speeds;
FIG. 3 shows samples (left) and Y of HIP sintered YAG transparent ceramic body prepared in example 1 2.991 Yb 0.009 Al 5 O 12 Transparent ceramic green body sample (right);
FIG. 4 is example 2Y 2.991 Yb 0.009 Al 5 O 12 Adding red dye into the ceramic slurry to obtain an optical image of the ytterbium ion graded doped transparent ceramic biscuit;
FIG. 5 is an optical image of a transparent ceramic body doped with graded ytterbium ions after hot isostatic pressing sintering in example 2;
FIG. 6 is a graph showing ytterbium ion concentration distribution on a cross section of a transparent ceramic sample prepared by direct ink writing and dry pressing in example 2;
FIG. 7 is example 4Y 2.991 Nd 0.009 Al 5 O 12 Adding red dye into the ceramic slurry to obtain an optical image of the neodymium ion graded doped transparent ceramic biscuit;
FIG. 8 is an optical image of a neodymium ion graded doped transparent ceramic body after annealing in example 4;
reference numerals:
1. 1,2, a coupler, 3, a motor, 4, a mixing cavity, 5, 2,6, a discharge port, 7 and a feed inlet 1,
8. and a feed inlet 2.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
As shown in fig. 1, a mixing device used for preparing the rare earth graded doped transparent ceramic comprises: a material mixing cavity 4 with a material inlet 7 and a material inlet 8 symmetrically arranged in the middle of the periphery and a material outlet 6 arranged at the lower part; the two injectors are connected with the feed inlet 7 and the feed inlet 8 in a sealing way through a needle cylinder outlet and a plug, and a piston is arranged at one end of a needle cylinder inlet of the injector and is matched with the injection pumps 1 and 5 which are positioned at the axis of the needle cylinder and are parallel to the axis through the piston; and the mixer is arranged inside the mixing cavity 4 and is connected with the coupler 2 and the motor 3 which are positioned outside the mixing cavity 4 so as to stir the slurry.
In the invention, firstly, non-rare earth doped ceramic slurry M and rare earth doped ceramic slurry RE which are applicable to direct ink writing molding are prepared, wherein M is the rare earth doped ceramic slurry; then, the mixing device is utilized to control and regulate the feeding rate of two ceramic slurries and the rotating speed of a mixing shaft by combining with an online mixing technology program, so that the continuous change of rare earth ion components in the extruded slurry is realized; then, writing 3D printing by direct ink to form a rare earth gradual change doped transparent ceramic biscuit; then, the ceramic biscuit is placed in a constant temperature and humidity environment to be slowly dried; and performing glue discharging, vacuum sintering, hot isostatic pressing sintering, annealing and polishing treatment to obtain the rare earth graded doped transparent ceramic.
The method for preparing rare earth graded doped transparent ceramics based on direct ink writing, which can include the following steps, is exemplarily described in detail below.
(1) The ceramic paste for direct ink writing is prepared. The ceramic slurry comprises non-rare earth doped ceramic slurry M and rare earth doped ceramic slurry RE: M. Respectively weighing raw material powder of the non-rare earth doped ceramic and the rare earth doped ceramic according to the stoichiometric proportion of the non-rare earth doped ceramic and the rare earth doped ceramic, and then respectively adding a solvent and a dispersing agent into the raw material powder for ball milling and mixing to obtain a slurry mixture with the solid content of 48-52 vol%; and then, adding a thickening agent into the slurry mixture and uniformly mixing to obtain the rare earth-doped ceramic slurry and the rare earth-doped ceramic slurry for direct ink writing.
Wherein the non-rare earth doped ceramic can be yttrium aluminum garnet Y 3 Al 5 O 12 (YAG) ceramic, said Y 3 Al 5 O 12 The raw material powder of the ceramics is Al 2 O 3 And Y 2 O 3 . The rare earth doped ceramic can be rare earth doped yttrium aluminum garnet Y 3 Al 5 O 12 Ceramic, the rare earth is doped with Y 3 Al 5 O 12 The raw material powder of the ceramic is rare earth oxide and Al 2 O 3 And Y 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the rare earth oxide may be one of oxides of neodymium Nd, ytterbium Yb, erbium Er, or thulium Tm.
The solvent may be deionized water.
The dispersing agent can be at least one of polyacrylic acid, ammonium polyacrylate and ammonium polymethacrylate. The addition amount of the dispersing agent can be controlled to be 0.45-0.80 wt% based on 100wt% of the total mass of the ceramic raw material powder. The dispersing agent can ionize to generate negatively charged groups and simultaneously anchor the negatively charged groups on the surfaces of the raw material powder particles after being dissolved in a solvent, so that the ceramic particles and the dispersing agent anchored on the ceramic particles have electronegativity in the whole structure, and the ceramic particles are mutually repelled by means of electrostatic repulsive force to prevent particle agglomeration, thereby effectively improving the solid content of a slurry mixture.
The dispersant is too low in content, ceramic particles have small mutual repulsive interaction, and the agglomeration of the ceramic particles is easy to cause higher viscosity of the slurry; when the content of the dispersant is too high, supersaturation adsorption occurs on the surface of the ceramic particles, and excessive dispersant is released in the solvent, so that the effect of the generated compression double electric layer can promote the reduction of electrostatic repulsive force among the particles, and the viscosity of the slurry can be increased. In addition, the high-molecular dispersing agent can be removed in the later glue discharging process, and the dispersing agent cannot be easily cleaned due to the too high content of the dispersing agent.
The rotational speed of ball-milling mixing can be controlled to be 200-300rpm, the ball-milling time can be 0.5-2h, the grinding balls can be alumina grinding balls with the diameter of 3mm or 5mm, and the mass ratio of the total mass of raw material powder to the grinding balls can be 0.4-0.8.
The solids content of the ceramic slurry determines the ceramic greenbody density. The ceramic slurry has too low solid content, which can cause too low density of ceramic biscuit to reduce the strength of the biscuit, is easy to deform and crack in the subsequent drying and degreasing processes, and is unfavorable for the subsequent sintering densification process. Too high a solids content of the ceramic paste may result in a paste that is too viscous to be used for direct ink writing.
The thickener may be cellulose thickener, preferably at least one of hydroxyethyl cellulose, hydroxypropyl cellulose, 2-hydroxyethyl methylcellulose, and 2-hydroxypropyl methylcellulose. The addition amount of the thickener can be controlled to be 0.4-0.55 wt% based on 100wt% of the total mass of the ceramic raw material powder.
The printability and printing effect of the ceramic slurry can be better improved by adding the cellulose thickener, so that the slurry cannot collapse in the printing process, and the ceramic slurry has certain shape retention. The thickener content is too low, the slurry shape retention is insufficient, the extruded slurry is easy to flow, and the necessary morphology structure cannot be maintained; too high a thickener content can result in increased viscosity of the slurry and difficulty in smooth extrusion from the needle.
(2) And 3D printing a rare earth gradient doped transparent ceramic biscuit. Taking the rare earth-doped ceramic slurry and the rare earth-doped ceramic slurry which are prepared in the step (1) and used for direct ink writing, respectively transferring the ceramic slurry and the rare earth-doped ceramic slurry into two feeding needle cylinders in the mixing device, placing a piston at the inlet end of the needle cylinder, sealing the outlet end by a plug, and exhausting air in the slurry under the condition of vacuum centrifugation; then, the two needle cylinder outlets after degassing are respectively connected with two feed inlets of the mixing cavity in a sealing way, the inlet end of the needle cylinder, on which a piston is arranged, is respectively matched with two injection pumps, and is propelled by a screw rod of the injection pump, so that the joint of the needle cylinder and the mixing cavity and the piston end are controlled to be free from leakage; setting and controlling the respective feeding rates of the two slurries and the rotating speed of a mixing shaft by combining an online mixing technology and a feeding control program; then, firstly starting a mixing shaft motor, then starting an injection pump and a mixing program, and fully and uniformly mixing the two slurries in a mixing cavity; extruding the mixed slurry from a discharge port at the lower end of the mixing cavity, and realizing continuous change of rare earth ion components in the extruded slurry by combining a feeding procedure and a mixing procedure; obtaining a ceramic biscuit sample through a direct ink writing 3D printing process; and (5) drying to obtain the rare earth gradual doped transparent ceramic biscuit.
The feeding mode adopted by the invention is that the injection pump pushes the piston to extrude the slurry, and the two injection pumps are mutually independent. Therefore, the chemical composition of the slurry can be extruded according to the requirement in the control program, and the feeding speed (flow) of the two injection pumps is set so as to control the proportion of the two slurries, thereby realizing the regulation and control of the components of the slurry after mixing. In addition, the setting method can control the proportion of the two slurries at any time in the printing process, realizes the real-time change of the slurry components after mixing, and achieves the purpose of gradual change of the rare earth ion components.
In an alternative embodiment, the sum of the feeding rates of the two ceramic slurries can be controlled to be 0.1-10 mL/min; the rotation speed of the mixing shaft can be 200-600 rpm. The sum of the feeding rates of the two ceramic slurries is namely total volume flow, the total volume flow is matched with the 3D printing speed, the inner diameter of the needle head and the size of the sample, the gap between the extruded slurries cannot be filled by the total volume flow, the needle head is caused to scratch the slurries when the total volume flow is too high, the slurry molding is not facilitated, and the stacking state of the biscuit in the 3D printing process can be further controlled by controlling the feeding rate of the slurry. Meanwhile, the rotating speed of the mixing shaft also can influence the uniformity of mixing of two kinds of slurry, the too low rotating speed can lead to uneven mixing of the slurry, the too high rotating speed can lead to a large amount of heat generation of the system to accelerate the drying speed of the slurry, the needle head is easy to be blocked, and the too high rotating speed can lead to generation of grinding scraps, so that impurities are introduced.
The technological parameters of the direct ink writing 3D printing can be as follows: the printing speed is 3-5mm/s, the inner diameter of the needle head is 0.62-0.84mm, the printing line distance is 0.95-1.25mm, and the printing layer thickness is 0.6-0.8mm. In some embodiments, a three-dimensional drawing software can be adopted to design a three-dimensional model of the rare earth graded doped transparent ceramic, then the three-dimensional model is imported into auxiliary software to generate a path planning file for controlling a needle moving route in 3D printing, and the needle is used for controlling continuous change of rare earth ion components by combining an online mixing technology and a feeding program while printing slurry under the path planning, so that the rare earth graded doped transparent ceramic biscuit is finally obtained.
The ceramic biscuit sample is dried in a constant temperature and humidity environment, the drying temperature can be 20-25 ℃, the relative humidity can be 50-85%, and the drying time can be 24-72h; preferably, the drying temperature is 25 ℃, the relative humidity is 80%, and the drying time is 72 hours.
(3) And preparing the rare earth graded doped transparent ceramic. Discharging glue from the rare earth graded doped transparent ceramic biscuit prepared in the step (2); and then sequentially carrying out vacuum sintering, hot isostatic pressing sintering, annealing and polishing treatment to obtain the rare earth graded doped transparent ceramic.
The glue discharging can be performed in air atmosphere, the glue discharging temperature can be 600-800 ℃, and the heat preservation time is 6-10 h. Residual moisture in the ceramic biscuit and organic matters introduced in the forming process can be removed through glue discharging. The adhesive discharging temperature is too low, so that organic matters in the ceramic cannot be removed completely; the high glue discharging temperature can lead to the reduction of the sintering activity of ceramic particles and influence the subsequent high-temperature sintering treatment process.
The vacuum sintering process can be as follows: heating to 1600-1700 ℃ at the speed of 2-10 ℃/min, and preserving heat for 6-15 h.
The temperature of the hot isostatic pressing sintering can be 1600-1700 ℃, and is preferably 1650 ℃; the holding time is 2-6h, preferably 2h.
The annealing process may be: under the air atmosphere, the green body after hot isostatic pressing sintering is kept at 1300-1400 ℃ for 10-20 h; then cooling to 200-1000 ℃ at a speed of 2-5 ℃/min, and then cooling with a furnace. The annealing process can reduce the residual stress in the ceramic body and stabilize the ceramic size.
The transmittance of the rare earth graded doped transparent ceramic obtained by the preparation method provided by the invention in the wavelength range of 400-1100nm can reach 80-84%. The rare earth doping concentration variation range of the rare earth graded doped transparent ceramic can be 0.1-10at%.
According to the preparation method provided by the invention, only undoped rare earth ceramic slurry and rare earth doped ceramic slurry are required to be prepared, the mixing equipment with special structural design is combined with the direct ink writing 3D printing equipment, and corresponding control programs are designed in a matched manner to accurately adjust the feeding rate of the two slurries and the rotating speed of the mixing shaft, so that the real-time change of the rare earth doping concentration in the ceramic biscuit forming process is realized, and finally the transparent ceramic with the real continuous change of the rare earth doping concentration is prepared. Meanwhile, after the ceramic biscuit is subjected to glue discharging, heat treatment (vacuum sintering, hot isostatic pressing sintering and annealing) and mechanical processing (polishing), the optical quality is good, the rare earth doping concentration is continuously changed, and compared with the bulk doped transparent ceramic, the ceramic biscuit has better heat management capability.
The present invention will be described in more detail by way of examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
(1) The ceramic paste for direct ink writing is prepared.
Y 3 Al 5 O 12 And (3) preparing ceramic slurry. According to Y 3 Al 5 O 12 Is respectively weighed 35.6864g (0.35 mol) of aluminum oxide Al 2 O 3 And 47.4201g (0.21 mol) of yttrium oxide Y 2 O 3 Adding 18.26mL of deionized water and 0.499g (0.6 wt%) of dispersant ammonium polyacrylate, and performing ball milling and mixing to obtain a slurry mixture with the solid content of 50 vol%; then, to the0.457g (0.55 wt%) of hydroxyethyl cellulose was added to the slurry mixture and mixed uniformly to obtain Y for direct ink writing 3 Al 5 O 12 Ceramic slurry.
Y 2.982 Yb 0.018 Al 5 O 12 And (3) preparing ceramic slurry. According to Y 2.982 Yb 0.018 Al 5 O 12 Is respectively weighed 35.6864g (0.35 mol) of aluminum oxide Al 2 O 3 47.1355g (0.20874 mol) of yttrium oxide Y 2 O 3 And 0.4965g (0.00126 mol) ytterbium oxide Yb 2 O 3 Adding 18.31mL of deionized water and 0.375g (0.45 wt%) of dispersant ammonium polyacrylate into the powder, and performing ball milling and mixing to obtain a slurry mixture with the solid content of 50 vol%; then, 0.458g (0.55 wt%) of hydroxyethyl cellulose was added to the slurry mixture and mixed uniformly to obtain Y for direct ink writing 2.982 Yb 0.018 Al 5 O 12 Ceramic slurry.
(2) And 3D printing a ceramic biscuit. Taking the direct ink writing Y prepared in the step (1) 3 Al 5 O 12 Ceramic slurry and Y 2.982 Yb 0.018 Al 5 O 12 Ceramic slurry is respectively filled into two feeding needle cylinders in the mixing device, a piston is arranged at the inlet end of the needle cylinder, the outlet end of the needle cylinder is sealed by a plug, and air in the slurry is discharged under the condition of vacuum centrifugation; then, the two needle cylinder outlets after degassing are respectively connected with two feed inlets of the mixing cavity in a sealing way, the inlet end of the needle cylinder, on which a piston is arranged, is respectively matched with two injection pumps, and the joint of the needle cylinder and the mixing cavity and the piston end are controlled to be free from leakage; combining an online mixing technology and a feeding control program, setting the total feeding rate of the two slurries to be 0.2mL/min and the rotating speed of a mixing shaft to be 300rpm; then, firstly starting the mixing shaft motor, and then starting the injection pump and the mixing program: first, set Y 3 Al 5 O 12 The feeding amount of the ceramic slurry is 0.2mL/min, Y 2.982 Yb 0.018 Al 5 O 12 The feeding amount of the ceramic slurry is 0, and a YAG ceramic biscuit sample is prepared; then, Y is 3 Al 5 O 12 Ceramic slurry and Y 2.982 Yb 0.018 Al 5 O 12 Ceramic slurry feed rates were all set at 0.1mL/min to prepare Y 2.991 Yb 0.009 Al 5 O 12 A ceramic biscuit sample; and (3) respectively placing the two ceramic biscuit samples in a constant temperature and humidity environment with the temperature of 25 ℃ and the relative humidity of 80%, and slowly drying to obtain the ceramic biscuit.
(3) And (5) preparing transparent ceramics. Maintaining the temperature of the ceramic biscuit prepared in the step (2) at 800 ℃ for 6 hours for removing glue, and removing residual moisture in the biscuit and organic matters introduced in the forming process; then, preserving the temperature of the ceramic biscuit subjected to glue discharge at 1700 ℃ for 6 hours at a heating rate of 5 ℃/min, and carrying out vacuum sintering; then, the sintered body after vacuum sintering is heat-preserved for 2 hours at 1650 ℃ for hot isostatic pressing sintering; then, the blank after the hot isostatic pressing sintering is kept at 1400 ℃ for 10 hours, cooled to 500 ℃ at the speed of 5 ℃/min, and then cooled along with the furnace; finally, the YAG transparent ceramic sample and Y are obtained through double-sided polishing 2.991 Yb 0.009 Al 5 O 12 Transparent ceramic samples.
FIG. 2 is a graph showing the cross-sectional profile of Yb elements in a pin extrusion line at different rotational speeds for a mixing shaft. As can be seen from the graph, when the rotation speed is 0, ytterbium element is distributed on one side only; when the rotation speed is increased to 300rpm, ytterbium element is uniformly distributed on the section.
FIG. 3 shows samples (left) and Y of HIP sintered YAG transparent ceramic body prepared in example 1 2.991 Yb 0.009 Al 5 O 12 Transparent ceramic green body sample (right). As can be seen from the figure, the transparent ceramics of both components have a high transmittance after the hot isostatic pressing treatment.
Example 2
(1) The ceramic paste for direct ink writing is prepared.
Y 3 Al 5 O 12 And (3) preparing ceramic slurry. According to Y 3 Al 5 O 12 Is respectively weighed 35.6864g (0.35 mol) of aluminum oxide Al 2 O 3 And 47.4201g (0.21 mol) of yttrium oxide Y 2 O 3 Powder, 18.26mL of deionized water and 0.499g (0.6 wt%) of dispersant ammonium polyacrylate were addedBall milling and mixing to obtain a slurry mixture with a solid content of 50 vol%; then, 0.457g (0.55 wt%) of hydroxyethyl cellulose was added to the slurry mixture and mixed uniformly to obtain Y for direct ink writing 3 Al 5 O 12 Ceramic slurry;
Y 2.991 Yb 0.009 Al 5 O 12 and (3) preparing ceramic slurry. According to Y 2.991 Yb 0.009 Al 5 O 12 Is respectively weighed 35.6864g (0.35 mol) of aluminum oxide Al 2 O 3 47.2778g (0.20937 mol) of yttrium oxide Y 2 O 3 And 0.2483g (0.00063 mol) ytterbium oxide Yb 2 O 3 Adding 18.29mL of deionized water and 0.666g (0.8 wt%) of dispersant ammonium polyacrylate, and performing ball milling and mixing to obtain a slurry mixture with the solid content of 50 vol%; then, 0.416g (0.5 wt%) of hydroxyethyl cellulose was added to the slurry mixture and mixed uniformly to obtain Y for direct ink writing 2.991 Yb 0.009 Al 5 O 12 Ceramic slurry.
(2) And 3D printing a rare earth gradient doped transparent ceramic biscuit. Taking the direct ink writing Y prepared in the step (1) 3 Al 5 O 12 Ceramic slurry and Y 2.991 Yb 0.009 Al 5 O 12 Ceramic slurry is respectively filled into two feeding needle cylinders in the mixing device, a piston is arranged at the inlet end of the needle cylinder, the outlet end of the needle cylinder is sealed by a plug, and air in the slurry is discharged under the condition of vacuum centrifugation; then, the two needle cylinder outlets after degassing are respectively connected with two feed inlets of the mixing cavity in a sealing way, the inlet end of the needle cylinder, on which a piston is arranged, is respectively matched with two injection pumps, and the joint of the needle cylinder and the mixing cavity and the piston end are controlled to be free from leakage; combining an online mixing technology and a feeding control program, setting the total feeding rate of the two slurries to be 0.2mL/min and the rotating speed of a mixing shaft to be 300rpm; then, firstly starting the mixing shaft motor, and then starting the injection pump and the mixing program: first, set Y 3 Al 5 O 12 The feeding amount of the ceramic slurry is 0.2mL/min, Y 2.991 Yb 0.009 Al 5 O 12 The feeding amount of the ceramic slurry is 0; at the beginning of printing, Y 3 Al 5 O 12 The feed rate of the ceramic slurry is gradually reduced from 0.2mL/min to 0, Y 2.991 Yb 0.009 Al 5 O 12 The ceramic slurry feed rate was gradually increased from 0 to 0.2mL/min; in Y 2.991 Yb 0.009 Al 5 O 12 After the ceramic slurry feed rate increased to 0.2mL/min, it was gradually reduced to 0, and Y 3 Al 5 O 12 Gradually increasing the feeding rate of the ceramic slurry from 0 to 0.2mL/min to prepare an ytterbium ion gradual-change doped transparent ceramic biscuit sample; and slowly drying the biscuit sample in a constant temperature and humidity environment with the temperature of 25 ℃ and the relative humidity of 80%, and obtaining the ytterbium ion gradual-change doped transparent ceramic biscuit.
(3) Preparing a rare earth gradient doped transparent ceramic biscuit by a dry pressing method.
Y 3 Al 5 O 12 And (3) preparing ceramic powder. According to Y 3 Al 5 O 12 According to the stoichiometric ratio of (1) respectively weighing 35.6864g of alumina and 47.4201g of yttrium oxide powder, adding alcohol and alumina grinding balls, and mixing for 24 hours at the rotating speed of 250 rpm; then, drying the mixture after ball milling at 60 ℃; sieving the dried powder in a 100-mesh screen for 3 times to obtain the Y 3 Al 5 O 12 Ceramic powder.
Y 2.9955 Yb 0.0045 Al 5 O 12 And Y 2.991 Yb 0.009 Al 5 O 12 And (3) preparing ceramic powder. Preparation method referring to Y above 3 Al 5 O 12 The preparation method of the ceramic powder is mainly characterized in that: (1) Y is Y 2.9955 Yb 0.0045 Al 5 O 12 The raw materials for preparation are 35.6864g of alumina, 47.3489g of yttrium oxide and 0.1241g of ytterbium oxide powder; (2) Y is Y 2.991 Yb 0.009 Al 5 O 12 The raw materials for preparation of (1) are 35.6864g of alumina, 47.2778g of yttrium oxide and 0.2483g of ytterbium oxide powder.
And (5) dry pressing and forming. First, 0.9. 0.9gY was added to the mold 3 Al 5 O 12 Ceramic powder, shaking, adding 0.9. 0.9gY 2.9955 Yb 0.0045 Al 5 O 12 The ceramic powder is leveled and vibrated, and the method is usedSequentially adding 0.9 part 0.9gY 2.991 Yb 0.009 Al 5 O 12 Ceramic powder, 0.9. 0.9gY 2.9955 Yb 0.0045 Al 5 O 12 Ceramic powder and 0.9. 0.9gY 3 Al 5 O 12 Ceramic powder, and finally pressing and forming under the pressure of 15 MPa; and (3) carrying out cold isostatic pressing treatment on the block body after compression molding under the pressure of 200MPa to obtain the rare earth gradient doped transparent ceramic biscuit.
(4) And preparing the rare earth doped transparent ceramic. The rare earth gradient doped transparent ceramic biscuit prepared in the step (2) and the rare earth gradient doped transparent ceramic biscuit prepared in the step (3) by a dry pressing method are insulated for 6 hours at 800 ℃ for glue discharging, and residual moisture in the biscuit and organic matters introduced in the forming process are removed; then, the ceramic biscuit after glue discharging is subjected to vacuum sintering at 1700 ℃ for 6 hours at a heating rate of 2 ℃/min; then, the sintered body after vacuum sintering is heat-preserved for 2 hours at 1650 ℃ for hot isostatic pressing sintering; then, the blank after the hot isostatic pressing sintering is kept at 1400 ℃ for 10 hours, cooled to 500 ℃ at the speed of 5 ℃/min, and then cooled along with the furnace; finally, the ytterbium ion doped transparent ceramic sample is obtained through double-sided polishing.
FIG. 4 is example 2Y 2.991 Yb 0.009 Al 5 O 12 And adding a red dye into the ceramic slurry to obtain an optical image of the ytterbium ion graded doped transparent ceramic biscuit. As can be seen from the figure, the green body is red in the middle, and gradually transits to white from the upper end to the lower end, which means that the concentration of doped ions is high in the middle, and gradually decreases to 0 from the upper end to the lower end.
Fig. 5 is an optical image of a transparent ceramic body doped with graded ytterbium ions after hot isostatic pressing sintering in example 2. As can be seen from the figure, ytterbium ions are sintered under a reducing atmosphere to appear green. The vacuum sintering is in an anoxic environment, the +3-valent ytterbium ions become +2-valent after sintering in the environment, the natural light is green, and the YAG transparent ceramic sintered in the anoxic environment generates oxygen vacancies, so the YAG transparent ceramic is gray black.
FIG. 6 is a graph showing ytterbium ion concentration profiles on a cross section of a transparent ceramic sample prepared by direct ink writing and dry pressing in example 2. As can be seen from the graph, the ytterbium ion concentration of the transparent ceramic sample prepared by direct ink writing gradually increases to the maximum value and then gradually decreases, while the ytterbium ion concentration of the transparent ceramic sample prepared by the dry pressing method shows abrupt increase and decrease, and each layer concentration has a certain fluctuation, which may be due to interference between different component powders at the time of dry pressing.
Example 3
(1) The ceramic paste for direct ink writing is prepared.
Y 3 Al 5 O 12 And (3) preparing ceramic slurry. Referring to example 2, the main difference is that: 16.85mL of deionized water was added and the slurry mixture had a solids content of 52vol.%.
Y 2.955 Yb 0.045 Al 5 O 12 And (3) preparing ceramic slurry. According to Y 2.955 Yb 0.045 Al 5 O 12 Is respectively weighed 35.6864g (0.35 mol) of aluminum oxide Al 2 O 3 46.7088g (0.20685 mol) of yttrium oxide Y 2 O 3 And 1.2413g (0.00315 mol) ytterbium oxide Yb 2 O 3 Adding 16.97mL of deionized water and 0.502g (0.6 wt%) of dispersant ammonium polyacrylate, and performing ball milling and mixing to obtain a slurry mixture with the solid content of 52 vol%; then, 0.418g (0.5 wt%) of hydroxyethyl cellulose was added to the slurry mixture and mixed uniformly to obtain Y for direct ink writing 2.955 Yb 0.045 Al 5 O 12 Ceramic slurry.
(2) And 3D printing a rare earth gradient doped transparent ceramic biscuit. Referring to example 2, the main difference is that: taking the direct ink writing Y prepared in the step (1) 3 Al 5 O 12 Ceramic slurry and Y 2.955 Yb 0.045 Al 5 O 12 Ceramic slurry, setting the total feeding rate of the two slurries to be 0.3mL/min; first, set Y 3 Al 5 O 12 The feeding amount of the ceramic slurry is 0.3mL/min, Y 2.955 Yb 0.045 Al 5 O 12 The feeding amount of the ceramic slurry is 0; at the beginning of printing, Y 3 Al 5 O 12 The ceramic slurry feed rate was gradually increased from 0.3mL/minReduced to 0, Y 2.955 Yb 0.045 Al 5 O 12 The ceramic slurry feed rate was gradually increased from 0 to 0.3mL/min.
(3) And preparing the rare earth graded doped transparent ceramic. Referring to example 2, the main difference is that: the glue discharging temperature is 700 ℃, and the heat preservation time is 8 hours; the temperature of the vacuum sintering was 1660 ℃.
Example 4
(1) The ceramic paste for direct ink writing is prepared.
Y 3 Al 5 O 12 And (3) preparing ceramic slurry. Referring to example 2, the main difference is that: the addition content of the dispersing agent is 0.55wt%;
Y 2.991 Nd 0.009 Al 5 O 12 and (3) preparing ceramic slurry. According to Y 2.991 Nd 0.009 Al 5 O 12 Is respectively weighed 35.6864g (0.35 mol) of aluminum oxide Al 2 O 3 47.2778g (0.20937 mol) of yttrium oxide Y 2 O 3 And 0.2120g (0.00063 mol) of neodymium oxide Nd 2 O 3 Adding 18.29mL of deionized water and 0.665g (0.8 wt%) of dispersant ammonium polyacrylate, and performing ball milling and mixing to obtain a slurry mixture with a solid content of 50 vol%; then, 0.333g (0.4 wt%) of hydroxyethyl cellulose was added to the slurry mixture and mixed uniformly to obtain Y for direct ink writing 2.991 Nd 0.009 Al 5 O 12 Ceramic slurry.
(2) And 3D printing a rare earth gradient doped transparent ceramic biscuit. Referring to example 2, the main difference is that: taking the direct ink writing Y prepared in the step (1) 3 Al 5 O 12 Ceramic slurry and Y 2.991 Nd 0.009 Al 5 O 12 The ceramic slurry, the feeding rate control mode of the two slurries is as follows: first, set Y 3 Al 5 O 12 The feeding amount of the ceramic slurry is 0.2mL/min, Y 2.991 Nd 0.009 Al 5 O 12 The feeding amount of the ceramic slurry is 0; at the beginning of printing, Y 3 Al 5 O 12 The feed rate of the ceramic slurry is gradually reduced from 0.2mL/min to 0, Y 2.991 Nd 0.009 Al 5 O 12 The ceramic slurry feed rate was gradually increased from 0 to 0.2mL/min.
(3) And preparing the rare earth graded doped transparent ceramic. Referring to example 2, the main difference is that: the glue discharging temperature is 600 ℃, and the heat preservation time is 10 hours; the temperature of vacuum sintering is 1680 ℃; the soak temperature for annealing was 1350 ℃.
FIG. 7 is example 4Y 2.991 Nd 0.009 Al 5 O 12 And adding red dye into the ceramic slurry to obtain an optical image of the neodymium ion graded doped transparent ceramic biscuit. As can be seen from the figure, the green body progressively deepens from left to right, indicating a progressive increase in dopant ion concentration from left to right.
Fig. 8 is an optical image of a neodymium ion graded doped transparent ceramic body after annealing in example 4. As can be seen from the figure, the annealed neodymium ion graded doped transparent ceramic has higher transmittance.
Example 5
(1) The ceramic paste for direct ink writing is prepared.
Y 3 Al 5 O 12 And (3) preparing ceramic slurry. Referring to example 2, the main difference is that: the deionized water was added in an amount of 19.78mL, the slurry mixture had a solids content of 48vol.%;
Y 2.982 Yb 0.018 Al 5 O 12 and (3) preparing ceramic slurry. According to Y 2.982 Yb 0.018 Al 5 O 12 Is respectively weighed 35.6864g (0.35 mol) of aluminum oxide Al 2 O 3 47.1355g (0.20874 mol) of yttrium oxide Y 2 O 3 And 0.4965g (0.00126 mol) ytterbium oxide Yb 2 O 3 Adding 19.84mL of deionized water and 0.500g (0.6 wt%) of dispersant ammonium polyacrylate, and performing ball milling and mixing to obtain a slurry mixture with the solid content of 48 vol%; then, 0.333g (0.4 wt%) of hydroxyethyl cellulose was added to the slurry mixture and mixed uniformly to obtain Y for direct ink writing 2.982 Yb 0.018 Al 5 O 12 Ceramic slurry.
(2) And 3D printing a rare earth gradient doped transparent ceramic biscuit. With reference to example 2, mainlyThe difference is that: taking the direct ink writing Y prepared in the step (1) 3 Al 5 O 12 Ceramic slurry and Y 2.982 Yb 0.018 Al 5 O 12 Ceramic slurry, setting the total feeding rate of the two slurries to be 0.3mL/min; first, set Y 3 Al 5 O 12 The feeding amount of the ceramic slurry is 0.3mL/min, Y 2.982 Yb 0.018 Al 5 O 12 The feeding amount of the ceramic slurry is 0; at the beginning of printing, Y 3 Al 5 O 12 The feed rate of the ceramic slurry is gradually reduced from 0.3mL/min to 0, Y 2.982 Yb 0.018 Al 5 O 12 The ceramic slurry feed rate was gradually increased from 0 to 0.3mL/min.
(3) And preparing the rare earth graded doped transparent ceramic. Referring to example 2, the main difference is that: the vacuum sintering temperature was 1670 ℃.
Claims (10)
1. The preparation method of the rare earth graded doped transparent ceramic is characterized by comprising the following steps of:
(1) Preparing non-rare earth doped ceramic slurry and rare earth doped ceramic slurry respectively;
(2) Respectively adding two kinds of ceramic slurry into two feeding needle cylinders of a mixing device of a direct ink writing printer, and removing air in the slurry; the mixing device comprises a mixing cavity, wherein two feeding holes are symmetrically arranged in the middle of the periphery, and a discharging hole is arranged at the lower part of the mixing cavity; the outlet of the needle cylinder after the slurry is deaerated is respectively connected with two feed inlets of the mixing cavity in a sealing way, a piston is arranged at one end of the inlet of the needle cylinder, and the rate of the ceramic slurry entering the mixing cavity is controlled by the cooperation of the piston and a syringe pump which is positioned at the axis of the needle cylinder and is parallel to the axis; setting and controlling the feeding rate of the two slurries and the rotating speed of a mixing shaft in a mixing cavity by combining an online mixing technology and a feeding control program, so that the two slurries are uniformly mixed in the mixing cavity; extruding the mixed slurry from the discharge port, and realizing continuous change of rare earth ion components in the extruded slurry by combining a feeding procedure and a mixing procedure; obtaining a rare earth gradual change doped transparent ceramic biscuit through a direct ink writing 3D printing process;
(3) And performing glue discharging, vacuum sintering, hot isostatic pressing sintering, annealing and polishing treatment on the rare earth graded doped transparent ceramic biscuit to obtain the rare earth graded doped transparent ceramic.
2. The preparation method according to claim 1, wherein the preparation process of the non-rare earth doped ceramic slurry and the rare earth doped ceramic slurry comprises the following steps: respectively weighing raw material powder according to the stoichiometric ratio of the non-rare earth doped ceramic to the rare earth doped ceramic, adding a solvent and a dispersing agent, and mixing to obtain a slurry mixture with the solid content of 48-52 vol%; and then adding a thickener to obtain the non-rare earth doped ceramic slurry and the rare earth doped ceramic slurry.
3. The method of claim 1 or 2, wherein the non-rare earth doped ceramic is yttrium aluminum garnet Y 3 Al 5 O 12 Ceramic, said Y 3 Al 5 O 12 The raw material powder of the ceramics is Al 2 O 3 And Y 2 O 3 ；
The rare earth doped ceramic is rare earth doped yttrium aluminum garnet Y 3 Al 5 O 12 Ceramic, the rare earth is doped with Y 3 Al 5 O 12 The raw material powder of the ceramic is rare earth oxide and Al 2 O 3 And Y 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the rare earth oxide may be one of oxides of neodymium Nd, ytterbium Yb, erbium Er, or thulium Tm.
4. A method according to any one of claims 1 to 3, wherein the dispersant is at least one of polyacrylic acid, ammonium polyacrylate, ammonium polymethacrylate; the thickener is at least one selected from hydroxyethyl cellulose, hydroxypropyl cellulose, 2-hydroxyethyl methylcellulose and 2-hydroxypropyl methylcellulose.
5. The method according to any one of claims 1 to 4, wherein the sum of the feeding rates of the two ceramic slurries is controlled to be 0.1 to 10mL/min; the rotating speed of the mixing shaft is 200-600 rpm.
6. The preparation method according to any one of claims 1 to 5, wherein the discharging of the gel is performed in an air atmosphere at a temperature of 600 to 800 ℃ for a time of 6 to 10 hours.
7. The method according to any one of claims 1 to 6, wherein the vacuum sintering process is: heating to 1600-1700 ℃ at the speed of 2-10 ℃/min, and preserving heat for 6-15 h.
8. The method according to any one of claims 1-7, wherein the hot isostatic pressing sintering temperature is 1600-1700 ℃ and the holding time is 2-6 h.
9. The method of any one of claims 1-8, wherein the annealing process is: under the air atmosphere, the green body after hot isostatic pressing sintering is kept at 1300-1400 ℃ for 10-20 h; then cooling to 200-1000 ℃ at a speed of 2-5 ℃/min, and then cooling with a furnace.
10. A rare earth graded doped transparent ceramic obtained by the preparation method according to any one of claims 1 to 9, wherein the transmittance of the rare earth graded doped transparent ceramic in the wavelength range of 400 to 1100nm reaches 80 to 84%, and the variation range of the rare earth doping concentration is 0.1 to 10at%.
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