CN112521148A - Erbium/yttrium-doped zirconia transparent ceramic and preparation method and application thereof - Google Patents

Erbium/yttrium-doped zirconia transparent ceramic and preparation method and application thereof Download PDF

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CN112521148A
CN112521148A CN202011518989.7A CN202011518989A CN112521148A CN 112521148 A CN112521148 A CN 112521148A CN 202011518989 A CN202011518989 A CN 202011518989A CN 112521148 A CN112521148 A CN 112521148A
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erbium
yttrium
equal
transparent ceramic
doped zirconia
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CN112521148B (en
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雷若姗
王焕平
李明辉
田颖
徐时清
杨清华
华有杰
黄飞飞
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China Jiliang University Shangyu Advanced Research Institute Co Ltd
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Abstract

The invention belongs to the technical field of transparent ceramics, and particularly relates to erbium/yttrium-doped zirconia transparent ceramic and a preparation method and application thereof. The invention provides a preparation method of erbium/yttrium doped zirconia transparent ceramic, which comprises the following steps: chemical composition of (Zr)1‑x‑yErxYy)O2Carrying out cold isostatic pressing on the nano rods to obtain biscuit; wherein x is more than or equal to 0.005 and less than or equal to 0.01, and y is more than or equal to 0.06 and less than or equal to 0.09; and sintering the biscuit to obtain the erbium/yttrium-doped zirconia transparent ceramic, wherein the sintering temperature is 500-600 ℃, and the pressure is 4-6 GPa. The invention can improve the compactness of the erbium/yttrium doped zirconia transparent ceramic by sintering under the conditions of medium temperature and high pressure to obtainThe erbium/yttrium-doped zirconia transparent ceramic with higher optical transmittance in both visible light wave band and near infrared light wave band is obtained.

Description

Erbium/yttrium-doped zirconia transparent ceramic and preparation method and application thereof
Technical Field
The invention belongs to the technical field of transparent ceramics, and particularly relates to erbium/yttrium-doped zirconia transparent ceramic and a preparation method and application thereof.
Background
With yttrium oxide (Y)2O3) Cubic phase ZrO as a stabiliser2Transparent ceramics (YSZ) are widely used because of their unique optical properties. For example: the YSZ transparent ceramic has high refractive index, so that the focal length of the lens can be effectively reduced when the YSZ transparent ceramic is used for an optical lens, and the development requirement of miniaturization of modern optical devices is met; meanwhile, the YSZ transparent ceramic has lower absorptivity to mid-infrared wave bands and higher hardness, and can be used for infrared window materials; in addition, the rare earth element doped YSZ transparent ceramic has lower phonon energy (about 430-500 cm)-1) And moisture absorption resistance, so rare earth ions (Er) are added into YSZ3+、Tm3+、Nd3+) Can be used as luminescent ceramics or laser ceramics. However, the application of the existing YSZ transparent ceramic in the fields of laser materials, lighting materials and fluorescence sensing materials is limited due to the lower visible light transmittance of the existing YSZ transparent ceramic.
As early as the eighties of the last century, Tsukuma et al first reported the use of TiO2As a sintering aid, the YSZ transparent ceramic is prepared after sintering at 1630 ℃ for 7h, hot isostatic pressing at 1500 ℃ and 100MPa for 0.5h, and finally annealing at 1200 ℃, but the ceramic has high transmittance in the visible light and near infrared light wave bands (J.Mater.Sci.Lett.1986,5: 1143-. 2012, Lei et al reported glycine-nitrate-elevation viaPreparing YSZ nano powder by an energy ball milling method, sintering for 5min at 1200-1350 ℃ by a discharge plasma sintering method to prepare YSZ transparent ceramic, but the transmittance of the YSZ transparent ceramic in a visible light range is low (<30%) (Ceramics International 2012,38: 23-28). In 2019, Dash et al prepared YSZ transparent ceramics by spark plasma sintering at 1100 ℃ followed by hot isostatic pressing at 1100 ℃, but with a linear transmittance of less than 50% in the visible wavelength range (j.eur.center.soc.2019, 39: 1428-. The existing preparation method of YSZ transparent ceramics mainly comprises a spark plasma sintering method, a hot isostatic pressing method or a combination of the two methods. Although the density of the transparent ceramic can be improved by combining the spark plasma sintering method and the hot isostatic pressing method in the prior art, the visible light transmittance of the transparent ceramic is improved. However, the light transmittance of the YSZ transparent ceramic prepared by the method is difficult to meet the requirements of the fields of laser materials, lighting materials and fluorescent sensing materials on the light transmittance of the transparent ceramic.
Disclosure of Invention
In view of this, the invention provides an erbium/yttrium-doped zirconia transparent ceramic and a preparation method and application thereof, and the erbium/yttrium-doped zirconia transparent ceramic prepared by the preparation method provided by the invention has high optical transmittance in a visible light band and a near infrared light band.
The invention provides a preparation method of erbium/yttrium doped zirconia transparent ceramic, which comprises the following steps:
chemical composition of (Zr)1-x-yErxYy)O2Carrying out cold isostatic pressing on the nano rods to obtain biscuit; wherein x is more than or equal to 0.005 and less than or equal to 0.01, and y is more than or equal to 0.06 and less than or equal to 0.09;
and sintering the biscuit to obtain the erbium/yttrium-doped zirconia transparent ceramic, wherein the sintering temperature is 500-600 ℃, and the pressure is 4-6 GPa.
Preferably, the pressure of the cold isostatic pressing is 200-400 MPa, and the time is 1-5 min.
Preferably, the cold isostatic pressing further comprises, before the cold isostatic pressing: to the chemical composition of (Zr)1-x-yErxYy)O2Removing impurities from the nano-rods, wherein the chemical composition of the impurities is (Zr)1-x-yErxYy)O2Carrying out vacuum heat treatment on the nano rods;
the vacuum degree of the vacuum heat treatment is 10-2～10-4Pa, the temperature is 600-800 ℃, and the time is 2-3 h; the heating rate from the temperature rise to the vacuum heat treatment temperature is 2-5 ℃/min.
Preferably, the chemical composition is (Zr)1-x-yErxYy)O2The phase of the nanorod is a cubic phase, the diameter of the nanorod is 16-20 nm, the length of the nanorod is 170-200 nm, and the length-diameter ratio of the nanorod is 8.5-10: 1.
Preferably, the chemical composition is (Zr)1-x-yErxYy)O2The preparation method of the nano rod comprises the following steps:
ZrOCl2·8H2O, strong base and water are firstly mixed and then subjected to hydrothermal reaction to obtain Zr (OH)4；
Zr (OH)4Erbium salt, yttrium salt, water, medium-chain fatty acid and nonpolar organic solvent are secondly mixed and then subjected to solvothermal reaction to obtain the chemical composition (Zr)1-x-yErxYy)O2The nano-rod of (4);
said Zr (OH)4The molar ratio of Er in the erbium salt to Y in the yttrium salt is (1-x-Y) x: Y, wherein x is more than or equal to 0.005 and less than or equal to 0.01, and Y is more than or equal to 0.06 and less than or equal to 0.09.
Preferably, the temperature of the hydrothermal reaction is 130-160 ℃, and the time is 3-5 h;
the temperature of the solvothermal reaction is 200-230 ℃, and the time is 40-55 h.
Preferably, the medium chain fatty acids include C8 fatty acids or C10 fatty acids;
preferably, the non-polar organic solvent comprises n-heptane, toluene or n-decane.
The invention also provides the erbium/yttrium doped zirconia transparent ceramic prepared by the preparation method in the technical scheme, and the chemical composition of the erbium/yttrium doped zirconia transparent ceramic is (Zr)1-x-yErxYy)O2(ii) a Wherein x is more than or equal to 0.005 and less than or equal to 0.01, and y is more than or equal to 0.06 and less than or equal to 0.09; the density of the erbium/yttrium-doped zirconia transparent ceramic is 99.5-99.9%.
The invention also provides the application of the erbium/yttrium doped zirconia transparent ceramic in the technical scheme in the fields of laser materials, lighting materials and fluorescence sensing materials.
The invention provides a preparation method of erbium/yttrium doped zirconia transparent ceramic, which comprises the following steps: chemical composition of (Zr)1-x-yErxYy)O2Carrying out cold isostatic pressing on the nano rods to obtain biscuit; wherein x is more than or equal to 0.005 and less than or equal to 0.01, and y is more than or equal to 0.06 and less than or equal to 0.09; and sintering the biscuit to obtain the erbium/yttrium-doped zirconia transparent ceramic, wherein the sintering temperature is 500-600 ℃, and the pressure is 4-6 GPa. The invention can sinter (Zr) under high pressure1-x-yErxYy)O2Crushing and refining the nano-rods into superfine equiaxial nano-particles, and rearranging the nano-particles to promote the density of the transparent ceramic to be rapidly increased; meanwhile, the ultrafine equiaxial nano-particles can be softened by sintering at 500-600 ℃, and deformation, grain boundary sliding, grain rotation and atomic diffusion are generated under the action of high pressure, so that the compactness of the transparent ceramic is further improved, residual air holes in the ceramic are reduced, light scattering is avoided, and the erbium/yttrium-doped zirconia transparent ceramic with high optical transmittance in a visible light wave band and a near infrared light wave band is obtained.
The invention also provides the erbium/yttrium doped zirconia transparent ceramic prepared by the preparation method in the technical scheme, and the chemical composition of the erbium/yttrium doped zirconia transparent ceramic is (Zr)1-x-yErxYy)O2(ii) a Wherein x is more than or equal to 0.005 and less than or equal to 0.01, and y is more than or equal to 0.06 and less than or equal to 0.09. In the present invention, Y as a stabilizer enables ZrO in the transparent ceramic2Maintaining a cubic phase; the Er is used as a luminescence activator, so that the transparent ceramic can emit light under the excitation of laser. The results of the examples show that the erbium/yttrium-doped zirconia transparent ceramic provided by the invention has an optical transmittance of 60-63% in the visible light band and an optical transmittance of 72-73% in the near infrared band.
Drawings
FIG. 1 shows (Zr) obtained in example 10.905Er0.005Y0.09)O2TEM image of nanorods;
FIG. 2 is an XRD spectrum of the erbium/yttrium doped zirconia transparent ceramic prepared in example 1;
FIG. 3 is a TEM image of the erbium/yttrium-doped zirconia transparent ceramic prepared in example 1;
fig. 4 is a transmission spectrum of the erbium/yttrium-doped zirconia transparent ceramic prepared in example 1 in a visible light band and a near-infrared light band, wherein a picture at the upper left corner is a photo of a real object of the erbium/yttrium-doped zirconia transparent ceramic prepared in example 1 after double-sided polishing treatment on white paper containing writing;
FIG. 5 is a luminescence spectrum of the erbium/yttrium-doped zirconia transparent ceramic prepared in example 1 under excitation of 980nm laser.
Detailed Description
The invention provides a preparation method of erbium/yttrium doped zirconia transparent ceramic, which comprises the following steps:
chemical composition of (Zr)1-x-yErxYy)O2Carrying out cold isostatic pressing on the nano rods to obtain biscuit; wherein x is more than or equal to 0.005 and less than or equal to 0.01, and y is more than or equal to 0.06 and less than or equal to 0.09;
and sintering the biscuit to obtain the erbium/yttrium-doped zirconia transparent ceramic, wherein the sintering temperature is 500-600 ℃, and the pressure is 4-6 GPa.
The chemical composition of the invention is (Zr)1-x-yErxYy)O2Carrying out cold isostatic pressing on the nano rods to obtain biscuit; wherein x is more than or equal to 0.005 and less than or equal to 0.01, and y is more than or equal to 0.06 and less than or equal to 0.09. In the present invention, x may be specifically 0.005 or 0.01; said y may in particular be 0.06 or 0.09.
In the present invention, the chemical composition is (Zr)1-x-yErxYy)O2The method for preparing the nanorod preferably comprises the following steps:
ZrOCl2·8H2Mixing O, strong base and waterThen hydrothermal reaction is carried out to obtain Zr (OH)4；
Zr (OH)4Erbium salt, yttrium salt, water, medium-chain fatty acid and nonpolar organic solvent are secondly mixed and then subjected to solvothermal reaction to obtain the chemical composition (Zr)1-x-yErxYy)O2The nanorod of (1).
ZrOCl is used as a catalyst2·8H2O, strong base and water are firstly mixed and then subjected to hydrothermal reaction to obtain Zr (OH)4. In the present invention, the strong base preferably comprises NaOH or KOH, more preferably NaOH; the purity of the strong base is preferably above 99.9%, more preferably 99.9%; in the invention, the ZrOCl2·8H2The purity of O is preferably 99.9% or more, more preferably 99.9%. In the present invention, the water is preferably distilled water. In the present invention, the first mixing preferably includes the steps of:
ZrOCl2·8H2Dissolving O in part of water to obtain zirconium oxychloride solution;
dissolving strong base in the rest water to obtain strong base solution;
and dropwise adding the strong base solution into the zirconium oxychloride solution, and stirring.
ZrOCl is used as a catalyst2·8H2Dissolving O in part of water to obtain zirconium oxychloride solution. In the invention, the molar concentration of the zirconium oxychloride solution is preferably 0.08-0.12 mol/L, and more preferably 0.1 mol/L.
The invention dissolves the strong base in the residual water to obtain the strong base solution. In the invention, the molar concentration of the strong alkali solution is preferably 0.4-0.5 mol/L.
After the zirconium oxychloride solution and the strong alkali solution are obtained, the strong alkali solution is dripped into the zirconium oxychloride solution and then stirred. In the invention, ZrOCl in the zirconium oxychloride solution2And the molar ratio of the strong base in the strong base solution is preferably 1: 0.9-1.3, and more preferably 1: 1-1.1. The volume of the strong alkali solution and the zirconium oxychloride solution is not particularly limited, so long as ZrOCl can be satisfied2And strong base. In thatIn the invention, the dripping speed is preferably 40-90 drops/min, and more preferably 50-60 drops/min. In the invention, the rotation speed of the stirring is preferably 300-600 r/min, and more preferably 400-500 r/min; the time is preferably 28-32 min, and more preferably 30 min.
In the invention, the temperature of the hydrothermal reaction is preferably 130-160 ℃, and more preferably 140-150 ℃; the time is preferably 3 to 5 hours, and more preferably 4 to 4.5 hours. In the present invention, the hydrothermal reaction is preferably carried out in a high-pressure reaction vessel lined with polytetrafluoroethylene.
In the present invention, it is preferable to cool the hydrothermal reaction product to room temperature after the hydrothermal reaction, and the cooling method is not particularly limited as long as the hydrothermal reaction product can be cooled to room temperature. The hydrothermal reaction product is preferably subjected to solid-liquid separation in the present invention. The solid-liquid separation method is not particularly limited, and the solid-liquid separation can be achieved. In an embodiment of the invention, the solid-liquid separation is preferably centrifugation.
After solid-liquid separation, the solid obtained by solid-liquid separation is preferably subjected to impurity removal, and the impurity removal preferably comprises the following steps: dispersing the solid in water, centrifuging, and removing supernatant; dispersing the precipitate obtained by centrifugation in ethanol, centrifuging, and removing the supernatant; and repeating the dispersion centrifugation in water and the dispersion centrifugation in ethanol for 4-6 times. In the present invention, the water is preferably distilled water; the ethanol is preferably anhydrous ethanol. In the invention, the rotation speed of the centrifugation is preferably 5000-8000 r/min, and more preferably 5500-6000 r/min; the time is preferably 5 to 10min, and more preferably 6 to 8 min.
Obtaining Zr (OH)4Then, the invention adds Zr (OH)4Erbium salt, yttrium salt, water, medium-chain fatty acid and nonpolar organic solvent are secondly mixed and then subjected to solvothermal reaction to obtain the chemical composition (Zr)1-x-yErxYy)O2The nanorod of (1). In the present invention, the erbium salt is preferably Er (NO)3)3·5H2O; the yttrium salt is preferably Y (NO)3)3·6H2And O. In the present invention, the water is preferably distilled water. In the present inventionIn the present invention, the medium-chain fatty acid preferably includes a C8 fatty acid or a C10 fatty acid. In the present invention, the nonpolar organic solvent preferably includes n-heptane (n-C)7H16) Toluene or n-decane (n-C)10H22) More preferably n-heptane or n-decane. In the present invention, the Zr (OH)4The molar ratio of erbium salt to yttrium salt is preferably (1-x-y) x: y, wherein x is more than or equal to 0.005 and less than or equal to 0.01, and y is more than or equal to 0.06 and less than or equal to 0.09. In an embodiment of the present invention, the Zr (OH)4The molar ratio of erbium salt to yttrium salt is specifically 0.905:0.005:0.09 or 0.93:0.01: 0.06. In the present invention, the second mixing preferably comprises the steps of:
zr (OH)4Dispersing in a first portion of water to obtain Zr (OH)4A dispersion liquid;
dissolving erbium salt in the second part of water to obtain erbium salt solution;
dissolving yttrium salt in the third part of water to obtain yttrium salt solution;
dissolving medium-chain fatty acid in a nonpolar organic solvent to obtain a fatty acid organic solution;
mixing the erbium salt solution, yttrium salt solution and Zr (OH)4Thirdly mixing the dispersion liquid to obtain a primary solution to be reacted;
and carrying out fourth mixing on the primary solution to be reacted and the fatty acid organic solution.
The invention takes Zr (OH)4Dispersing in a first portion of water to obtain Zr (OH)4And (3) dispersing the mixture. In the present invention, the water is preferably distilled water; said Zr (OH)4The volume ratio of the amount of the substance(s) to water is preferably 1 to 2mol:8L, more preferably 1.3 to 1.7mol: 8L.
The invention dissolves erbium salt in the second part of water to obtain erbium salt solution. In the invention, the molar concentration of the erbium salt solution is preferably 0.4-0.6 mol/L, and more preferably 0.5 mol/L. In the present invention, Er in the erbium salt3+Is a luminescent activator.
Dissolving yttrium salt in third part of water to obtain yttrium salt solution. In the invention, the molar concentration of the yttrium salt solution is preferably 0.4-0.6 mol/L, and more preferably 0.5 mol/L. In the present inventionIn the above formula, Y in the yttrium salt3+As stabilizer, ZrO in transparent ceramics2The matrix remains in cubic phase.
The invention dissolves medium-chain fatty acid in a nonpolar organic solvent to obtain a fatty acid organic solution. In the invention, the volume ratio of the mass of the medium-chain fatty acid to the volume of the nonpolar organic solvent is preferably 1g (13-16) mL, and more preferably 1g (14-15) mL. In the invention, the dissolving of the medium-chain fatty acid in the nonpolar organic solvent is preferably carried out under the condition of stirring, and the rotating speed of the stirring is preferably 300-600 r/min, and more preferably 450-550 r/min; the time is preferably 20 to 90min, and more preferably 30 to 60 min.
Obtaining Zr (OH)4After the dispersion, the erbium salt solution and the yttrium salt solution are dispersed, the invention mixes the erbium salt solution, the yttrium salt solution and Zr (OH)4And carrying out third mixing on the dispersion liquid to obtain a primary solution to be reacted. In the present invention, the third mixing preferably includes the steps of: dropping erbium salt solution and yttrium salt solution to Zr (OH)4The dispersion was stirred. In the present invention, the dropping is preferably performed by sequentially dropping an erbium salt solution and an yttrium salt solution to Zr (OH)4In the dispersion, or simultaneously dripping erbium salt solution and yttrium salt solution into Zr (OH)4In the dispersion. In the invention, the dripping speed is preferably 40-70 drops/min, and more preferably 55-65 drops/min. The present invention is directed to said Zr (OH)4The volumes of the dispersion, erbium salt solution and yttrium salt solution are not particularly limited as long as Zr (OH) is satisfied4The mole ratio of erbium salt and yttrium salt. In the invention, the rotation speed of the stirring is preferably 500-800 r/min, and more preferably 600-700 r/min; the time is preferably 25 to 35min, and more preferably 30 min.
After the fatty acid organic solution and the primary solution to be reacted are obtained, the primary solution to be reacted and the fatty acid organic solution are mixed for the fourth time. In the present invention, the volume ratio of the fatty acid organic solution to the primary reaction solution is preferably (3:4) to (9:10), more preferably (3.2:4) to (21: 25). In the invention, the fourth mixing is preferably to drop the fatty acid organic solution into the primary solution to be reacted, and the dropping speed is preferably 50-70 drops/min, and more preferably 55-60 drops/min. In the invention, the fourth mixing is preferably carried out under the condition of stirring, and the rotating speed of the stirring is preferably 300-600 r/min, and more preferably 450-550 r/min; the time is preferably 30-60 min, and more preferably 30 min.
In the present invention, the solvothermal reaction is preferably in an autoclave. In the invention, the temperature of the solvothermal reaction is preferably 200-230 ℃, and more preferably 210-220 ℃; the time is 40-55 h, preferably 45-50 h.
The product of the solvothermal reaction is preferably cooled to room temperature in the present invention, and the cooling method is not particularly limited as long as it can be cooled to room temperature. The present invention preferably subjects the solvothermal reaction product to solid-liquid separation. The solid-liquid separation method is not particularly limited, and the solid-liquid separation can be achieved. In an embodiment of the invention, the solid-liquid separation is preferably centrifugation.
After solid-liquid separation, the invention sequentially washes and centrifuges the solid obtained by solid-liquid separation. In the present invention, the cleaning solvent is preferably ethanol or propanol. In the present invention, the washing and centrifuging preferably comprises the steps of: dispersing the solid in ethanol, centrifuging, removing supernatant, dispersing the centrifuged precipitate in propanol, centrifuging, and removing supernatant; and repeating the dispersion and centrifugation in the ethanol and the dispersion and centrifugation in the propanol for 3-5 times. In the invention, the rotation speed of the centrifugation is preferably 5000-8000 r/min, and more preferably 5000-6000 r/min; the time is preferably 5 to 7min, and more preferably 6 min. In the present invention, the number of repetitions is preferably 3 to 5, and more preferably 4. According to the invention, the precipitate obtained by centrifugal separation is preferably dried, wherein the drying temperature is preferably 40-60 ℃, and more preferably 45-55 ℃; the time is preferably 20 to 24 hours, and more preferably 22 to 23 hours.
In the present invention, the hydrothermal reaction is carried out in an alkaline environment in favor of Zr (OH)4The nucleation clusters grow up, thereby obtaining Zr (OH) with larger grain size4This is advantageous in promoting Zr (OH)4ZrO obtained after cluster decomposition reaction2Nucleation ofGrowth, i.e. the Zr (OH)4The size of the cluster is directly related to ZrO2Nanocrystal size and morphology are related. In the present invention, the decomposition reaction equation is shown in formula 1:
Zr(OH)4→ZrO2+2H2o is represented by the formula 1.
In the present invention, the medium-chain fatty acid is at ZrO2Selective adsorption of nano crystal surface to obtain ZrO2The { -111} and {111} crystal planes grow rapidly and form rods along the { -111} and {111} crystal planes.
In the present invention, the chemical composition is (Zr)1-x-yErxYy)O2The phase of the nanorod is preferably cubic, the diameter of the nanorod is preferably 16-20 nm, and more preferably 17-19 nm; the length is preferably 170-200 nm, more preferably 180-190 nm; the aspect ratio is preferably 8.5-10: 1, and more preferably 9-9.5: 1.
In the present invention, the cold isostatic pressing preferably further comprises, before the cold isostatic pressing: to the chemical composition of (Zr)1-x-yErxYy)O2Preferably, the chemical composition of the impurity removal is (Zr)1-x-yErxYy)O2Carrying out vacuum heat treatment on the nano rods; the degree of vacuum of the vacuum heat treatment is preferably 10-2～10-4Pa, more preferably 10-3～10-4Pa; the temperature is preferably 600-800 ℃, and more preferably 650-700 ℃; the time is preferably 2-3 h, and more preferably 2.5 h. In the present invention, the rate of temperature rise from the temperature rise to the vacuum heat treatment temperature is preferably 2 to 5 ℃/min, and more preferably 3 to 4 ℃/min. In the present invention, the vacuum heat treatment preferably removes impurities attached to the surface of the nanorods. In the invention, the impurities are medium-chain fatty acids or non-polar organic solvents remained on the surface of the nano-rod.
In the present invention, the cold isostatic pressing preferably loads the nanorods into a mold, which is preferably a high strength steel mold. The shape and the size of the die and the biscuit are not specially limited, and the die and the biscuit can be selected according to the requirement. In the invention, the pressure of the cold isostatic pressing is preferably 200-400 MPa, and more preferably 300-350 MPa; the time is preferably 1 to 5min, and more preferably 2 to 3 min.
After a biscuit is obtained, sintering the biscuit to obtain the erbium/yttrium doped zirconia transparent ceramic, wherein the sintering temperature is 500-600 ℃, and preferably 540-560 ℃; the pressure is 4-6 GPa, preferably 4.5-5.5 GPa; the time is preferably 3 to 5 hours, and more preferably 4 to 4.5 hours. In the invention, the heating rate of heating to the sintering temperature is preferably 1.8-2.2 ℃/min, and more preferably 2 ℃/min. In the present invention, the sintered product is preferably cooled to room temperature after the sintering; in the present invention, the cooling is preferably furnace cooling.
The invention preferably grinds and polishes the cooled transparent ceramic in sequence. The present invention is not particularly limited to the above-mentioned finish grinding and polishing, and may be carried out in a manner conventional in the art.
The preparation method provided by the invention can be used for sintering at a lower temperature, and compared with the traditional preparation method, the preparation method has the advantages that the production cost is reduced and the preparation period is shortened; meanwhile, the preparation method provided by the invention does not need to add a sintering aid, effectively avoids the generation of second-phase impurities, keeps the zirconium dioxide in a cubic-phase structure in the sintering process, and is favorable for improving the transparency of the erbium/yttrium-doped zirconium oxide transparent ceramic.
The invention also provides the erbium/yttrium doped zirconia transparent ceramic prepared by the preparation method in the technical scheme, and the chemical composition of the erbium/yttrium doped zirconia transparent ceramic is (Zr)1-x-yErxYy)O2(ii) a Wherein x is more than or equal to 0.005 and less than or equal to 0.01, and y is more than or equal to 0.06 and less than or equal to 0.09; the density of the erbium/yttrium doped zirconia transparent ceramic is 99.5-99.9%, preferably 99.8-99.9%. In the invention, the chemical composition of the erbium/yttrium-doped zirconia transparent ceramic is specifically (Er)0.01Y0.06Zr0.93)O2Or (Er)0.005Y0.09Zr0.905)O2. In the invention, the thickness of the erbium/yttrium doped zirconia transparent ceramic is preferably 0.5-1 mm.
The invention also provides the application of the erbium/yttrium doped zirconia transparent ceramic in the technical scheme in the fields of laser materials, lighting materials and fluorescence sensing materials.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
2.9168g of ZrOCl2·8H2Dissolving O in 90.51mL of distilled water to obtain a zirconium oxychloride solution with the molar concentration of 0.1 mol/L;
dissolving 20g of NaOH in 1000mL of distilled water to obtain a NaOH solution with the molar concentration of 0.5 mol/L;
dripping 18.1mL of NaOH solution into 90.51mL of zirconium oxychloride solution at the rate of 60 drops/min, stirring at the rotating speed of 400r/min for 30min, transferring the solution into a polytetrafluoroethylene high-pressure reaction kettle serving as an inner liner, and carrying out hydrothermal reaction at 160 ℃ for 3 h; naturally cooling a product of the hydrothermal reaction to room temperature, and centrifuging to remove a supernatant; dispersing the precipitate obtained by centrifugation in distilled water, and centrifuging for 8min at a rotation speed of 5000 r/min; removing distilled water, dispersing the centrifuged precipitate in ethanol, and centrifuging at 5000r/min for 8 min; repeating the above washing and centrifuging for 5 times, and removing the solvent to obtain Zr (OH)4；
2.270g of Zr (OH)4Dispersed in 36.2mL of distilled water to obtain Zr (OH)4A dispersion liquid; 5.5412g Er (NO)3)3·5H2O was dissolved in 25mL of distilled water to obtain Er (NO) with a molar concentration of 0.5mol/L3)3A solution; 3.5382gY (NO)3)3·6H2O was dissolved in 25mL of distilled water to prepare Y (NO) having a molar concentration of 0.5mol/L3)3A solution;
add 0.1mL Er (NO)3)3Solutions and 1.8mLY (NO)3)3The solution was dropped into the flask at a rate of 55 drops/min to 36.2mLZr (OH)4Stirring the dispersion liquid for 30min at the rotating speed of 600r/min to obtain a primary solution to be reacted;
2g C10 fatty acid was dissolved in 32mL of n-C7H16Stirring at 550r/min for 30min, and stirring at 6Dripping the solution into the primary solution to be reacted at the speed of 0 drop/min, stirring the solution for 1h at the rotating speed of 550r/min, transferring the solution into a high-pressure reaction kettle, carrying out solvothermal reaction for 50h at the temperature of 200 ℃, cooling the solution to room temperature along with a furnace, and centrifuging the solution to remove supernatant; dispersing the precipitate obtained by centrifugation in ethanol, and centrifuging for 6min at the rotation speed of 5000 r/min; dispersing the precipitate obtained by centrifugation in propanol, and centrifuging for 6min at a rotation speed of 5000 r/min; repeating the steps of dispersing in ethanol, centrifuging, dispersing in propanol and centrifuging for 4 times; drying the precipitate obtained by final centrifugation at 55 deg.C for 22h to obtain (Er)0.005Y0.09Zr0.905)O2Nanorods (average length 170nm, average diameter 18 nm);
will (Er)0.005Y0.09Zr0.905)O2After the nano-rods are loaded into a high-strength steel die, the vacuum degree is 10-3Heating to 800 ℃ at the speed of 5 ℃/min under the condition of Pa, carrying out vacuum heat treatment for 2h, and carrying out cold isostatic pressing at the pressure of 200MPa for 3min to obtain a biscuit with the diameter of about 10 mm; heating the biscuit to 600 ℃ at the speed of 2 ℃/min, and sintering for 3h under the pressure of 6 GPa; after furnace cooling, the sintered product was subjected to finish grinding and polishing to obtain an (Er) sheet having a thickness of about 0.5mm0.005Y0.09Zr0.905)O2A transparent ceramic.
Example 2
2.9974g of ZrOCl2·8H2Dissolving O in 93.02mL of distilled water to obtain a zirconium oxychloride solution with the molar concentration of 0.1 mol/L;
dissolving 20g of NaOH in 1000mL of distilled water to obtain a NaOH solution with the molar concentration of 0.5 mol/L;
dripping 23.25mL of NaOH solution into 93.02mL of zirconium oxychloride solution at the speed of 50 drops/min, stirring for 30min at the rotating speed of 500r/min, transferring the solution to a polytetrafluoroethylene high-pressure reaction kettle serving as an inner liner, and carrying out hydrothermal reaction for 5h at the temperature of 130 ℃; naturally cooling a product of the hydrothermal reaction to room temperature, and centrifuging to remove a supernatant; dispersing the precipitate obtained by centrifugation in distilled water, and centrifuging for 6min at a rotating speed of 6000 r/min; removing distilled water, dispersing the centrifuged precipitate in ethanol, and centrifuging at 6000r/min for 6 min; repeating the above cleaningCentrifuging for 5 times, and removing the solvent to obtain Zr (OH)4；
2.33g of Zr (OH)4Dispersed in 28mL of distilled water to obtain Zr (OH)4A dispersion liquid; 5.5412g Er (NO)3)3·5H2O was dissolved in 25mL of distilled water to obtain Er (NO) with a molar concentration of 0.5mol/L3)3A solution; 3.5382gY (NO)3)3·6H2O was dissolved in 25mL of distilled water to prepare Y (NO) having a molar concentration of 0.5mol/L3)3A solution;
add 0.2mL Er (NO)3)3Solutions and 1.2mLY (NO)3)3The solution was dropped into 28mL of Zr (OH) at a rate of 65 drops/min4Stirring the dispersion liquid for 30min at the rotating speed of 700r/min to obtain a primary solution to be reacted;
2g C8 fatty acid was dissolved in 26mL of n-C10H22After stirring for 60min at the rotating speed of 450r/min, dripping the solution into the primary solution to be reacted at the speed of 50 drops/min, stirring for 1h at the rotating speed of 450r/min, transferring the solution into a high-pressure reaction kettle, carrying out solvothermal reaction for 40h at the temperature of 230 ℃, cooling to room temperature along with a furnace, and centrifuging to remove supernatant; dispersing the precipitate obtained by centrifugation in ethanol, and centrifuging at 6000r/min for 6 min; dispersing the precipitate obtained by centrifugation in propanol, and centrifuging at 6000r/min for 6 min; repeating the steps of dispersing in ethanol, centrifuging, dispersing in propanol and centrifuging for 4 times; drying the precipitate obtained by final centrifugation at 45 deg.C for 23h to obtain (Er)0.01Y0.06Zr0.93)O2Nanorods (average length 190nm, average diameter 20 nm);
will (Er)0.01Y0.06Zr0.93)O2After the nano-rods are loaded into a high-strength steel die, the vacuum degree is 10-4Heating to 600 ℃ at the speed of 2 ℃/min under the condition of Pa, carrying out vacuum heat treatment for 3h, and carrying out cold isostatic pressing under the pressure of 400MPa for 1min to obtain a biscuit with the diameter of about 10 mm; heating the biscuit to 500 ℃ at the speed of 2 ℃/min, and sintering for 5h under the pressure of 4 GPa; after furnace cooling, the sintered product is finely ground and polished to obtain a thickness of about 0.5mm of (Er)0.01Y0.06Zr0.93)O2A transparent ceramic.
Comparative example 1
At 9 mol% Y2O3-ZrO2(9YSZ) powder and Er2O3The powder is used as a raw material, and 0.05mmol of Er is added2O3Ball-milling 9.95mmol of 9YSZ and 40mL of absolute ethyl alcohol in a planetary ball mill for 4 hours, then presintering at 1050 ℃ for 2 hours, cooling the presintering product to room temperature, sieving with a 200-mesh sieve after grinding, collecting undersize, putting the undersize into a mold, cold-pressing and molding for 30 seconds, and then carrying out cold isostatic pressing under the pressure of 250MPa to obtain a biscuit; keeping the biscuit at 1700 ℃ for 6h, and annealing at 1200 ℃ for 2h to obtain (Er)0.005Y0.09Zr0.905)O2A ceramic.
Test example
TEM observation is performed on the nanorods prepared in example 1 to obtain a TEM image, which is shown in FIG. 1. As shown in FIG. 1, the nanorods prepared in example 1 have good dispersibility and no significant agglomeration.
The transparent erbium/yttrium-doped zirconia ceramic prepared in example 1 was subjected to XRD detection, and an XRD spectrum was obtained, as shown in fig. 2. FIG. 2 shows that ZrO in the nanorod obtained in example2The phase of (A) is pure cubic phase, Er3+And Y3+The ions being completely solid-soluble in ZrO2In the matrix.
TEM observation was performed on the erbium/yttrium-doped zirconia transparent ceramic prepared in example 1 to obtain a TEM image, which is shown in fig. 3. As can be seen from FIG. 3, the grain size of the erbium/yttrium-doped zirconia transparent ceramic is 20-30 nm, and the erbium/yttrium-doped zirconia transparent ceramic has no obvious pores and has high density.
The light transmittance of the erbium/yttrium-doped zirconia transparent ceramic prepared in example 1 in the visible light band and the near-infrared light band is detected by a fluorescence absorption spectrum test, and a transmission spectrum is obtained, as shown in fig. 4. In FIG. 4, the absorption peaks with central peaks respectively at 409nm, 455nm, 491nm, 524nm, 549nm, 657nm, 974nm and 1531nm are derived from Er3+4f-4f electronic transitions of the ions. From FIG. 4, it can be seen that the erbium/yttrium doped oxygen prepared in example 1The zirconium oxide transparent ceramic has an optical transmittance of 63% in a visible light wave band and a transmittance of 73% or more in a near-infrared light wave band; it can be seen that the erbium/yttrium-doped zirconia transparent ceramic prepared in example 1 has a good optical transmittance in the visible light band.
The picture at the upper left corner of fig. 4 is a real photograph of the erbium/yttrium-doped zirconia transparent ceramic prepared in example 1 after double-sided polishing treatment, according to the invention, the erbium/yttrium-doped zirconia transparent ceramic subjected to double-sided polishing treatment is placed on white paper with writing, and the writing can be clearly seen through the erbium/yttrium-doped zirconia transparent ceramic subjected to double-sided polishing treatment, which indicates that the erbium/yttrium-doped zirconia transparent ceramic has higher transparency.
The transparent ceramics prepared in example 2 and comparative example 1 were measured for their transmittances in the visible light wavelength band and near infrared light wavelength band according to the above-mentioned methods, and the results are shown in table 1.
TABLE 1 light transmittance of transparent ceramics prepared in examples 1 and 2 and comparative example 1
Figure BDA0002848899000000121
The erbium/yttrium-doped zirconia transparent ceramic prepared in example 1 was subjected to fluorescence detection, and a luminescence spectrum was obtained under excitation of 980nm laser, as shown in fig. 5. As can be seen from FIG. 5, under the excitation of 980nm laser, the erbium/yttrium-doped zirconia transparent ceramic prepared in example 1 has a plurality of emission peaks in the range of 1400-1600 nm, wherein the strongest peak is at 1532 nm.
The erbium/yttrium-doped zirconia transparent ceramic prepared in example 2 was subjected to fluorescence detection, and the result was consistent with the result of example 1.
The transparent ceramic prepared in the comparative example 1 is subjected to fluorescence detection, and the luminous intensity under the excitation of 980nm is smaller than that of the erbium/yttrium-doped zirconia transparent ceramic in the example 1.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.

Claims (10)

1. A preparation method of erbium/yttrium-doped zirconia transparent ceramic comprises the following steps:
chemical composition of (Zr)1-x-yErxYy)O2Carrying out cold isostatic pressing on the nano rods to obtain biscuit; wherein x is more than or equal to 0.005 and less than or equal to 0.01, and y is more than or equal to 0.06 and less than or equal to 0.09;
and sintering the biscuit to obtain the erbium/yttrium-doped zirconia transparent ceramic, wherein the sintering temperature is 500-600 ℃, and the pressure is 4-6 GPa.
2. The method according to claim 1, wherein the cold isostatic pressing is performed at a pressure of 200 to 400MPa for a period of 1 to 5 min.
3. The method of manufacturing according to claim 1 or 2, further comprising, before the cold isostatic pressing: to the chemical composition of (Zr)1-x-yErxYy)O2Removing impurities from the nano-rods, wherein the chemical composition of the impurities is (Zr)1-x-yErxYy)O2Carrying out vacuum heat treatment on the nano rods;
the vacuum degree of the vacuum heat treatment is 10-2～10-4Pa, the temperature is 600-800 ℃, and the time is 2-3 h; the heating rate from the temperature rise to the vacuum heat treatment temperature is 2-5 ℃/min.
4. The method according to claim 1, wherein the chemical composition is (Zr)1-x-yErxYy)O2The phase of the nanorod is a cubic phase, the diameter of the nanorod is 16-20 nm, the length of the nanorod is 170-200 nm, and the length-diameter ratio of the nanorod is 8.5-10: 1.
5. The production method according to claim 1 or 4, wherein the chemical composition is (Zr)1-x-yErxYy)O2The preparation method of the nano rod comprises the following steps:
ZrOCl2·8H2O, strong base and water are firstly mixed and then subjected to hydrothermal reaction to obtain Zr (OH)4；
Zr (OH)4Erbium salt, yttrium salt, water, medium-chain fatty acid and nonpolar organic solvent are secondly mixed and then subjected to solvothermal reaction to obtain the chemical composition (Zr)1-x-yErxYy)O2The nano-rod of (4);
said Zr (OH)4The molar ratio of Er in the erbium salt to Y in the yttrium salt is (1-x-Y) x: Y, wherein x is more than or equal to 0.005 and less than or equal to 0.01, and Y is more than or equal to 0.06 and less than or equal to 0.09.
6. The preparation method according to claim 5, wherein the temperature of the hydrothermal reaction is 130-160 ℃ and the time is 3-5 h;
the temperature of the solvothermal reaction is 200-230 ℃, and the time is 40-55 h.
7. The method of claim 5, wherein the medium-chain fatty acid comprises a C8 fatty acid or a C10 fatty acid.
8. The method of claim 5, wherein the non-polar organic solvent comprises n-heptane, toluene, or n-decane.
9. An erbium/yttrium-doped zirconia transparent ceramic prepared by the preparation method of any one of claims 1 to 8, wherein the chemical composition of the erbium/yttrium-doped zirconia transparent ceramic is (Zr)1-x-yErxYy)O2(ii) a Wherein x is more than or equal to 0.005 and less than or equal to 0.01, and y is more than or equal to 0.06 and less than or equal to 0.09; the density of the erbium/yttrium-doped zirconia transparent ceramic is 99.5-99.9%.
10. The use of the erbium/yttrium-doped zirconia transparent ceramic according to claim 9 in the fields of laser materials, lighting materials and fluorescence sensing materials.
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