CN107619280B - Preparation method of layered calcium fluoride transparent ceramic - Google Patents
Preparation method of layered calcium fluoride transparent ceramic Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 125
- 229910001634 calcium fluoride Inorganic materials 0.000 title claims abstract description 59
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 65
- 239000011858 nanopowder Substances 0.000 claims abstract description 40
- 238000005245 sintering Methods 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 27
- 239000010439 graphite Substances 0.000 claims abstract description 27
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- 238000003825 pressing Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000007731 hot pressing Methods 0.000 claims abstract description 17
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- 239000010410 layer Substances 0.000 claims description 25
- 238000000227 grinding Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011698 potassium fluoride Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
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- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
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- 238000010030 laminating Methods 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
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- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
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Abstract
The invention discloses a preparation method of layered calcium fluoride transparent ceramic, which comprises the following steps: 1) CaF synthesis by using commercial chemical reagents as raw materials2With Ca1‑xRExF2+xNano powder, wherein RE is a doped element; 2) carrying out dry pressing molding on the nano powder synthesized in the step 1) to obtain a ceramic blank with a laminated structure; 3) putting the ceramic blank with the layered structure obtained in the step 2) into a graphite mould with a proper diameter, separating the mould from the ceramic blank by using graphite paper, and putting the graphite mould into a vacuum hot pressing furnace for pressure sintering; 4) and after sintering, taking out the ceramic, and performing double-sided polishing treatment to obtain the calcium fluoride transparent ceramic material with a layered structure. Compared with the existing prepared homogeneous component single-structure calcium fluoride transparent ceramic material, the invention provides a method for preparing the layered calcium fluoride transparent ceramic by combining dry pressing molding with vacuum hot pressing sintering technology, which has simple process and low cost.
Description
Technical Field
The invention relates to the field of transparent ceramic preparation, in particular to CaF with the particle size of less than 100 nm2With Ca1-xRExF2+xThe method for preparing the calcium fluoride transparent ceramic with the laminated structure by using the powder as a raw material and adopting the dry pressing molding and the vacuum hot pressing sintering technology.
Background
The all-solid-state laser has the advantages of small volume, high efficiency, good stability, long service life and the like, is one of important development directions in the field of laser application, and has important application in the fields of material processing, national defense engineering, scientific research and the like. The gain medium is one of the core components of the all-solid-state laser, and in the working process, the gain medium can generate heat, so that the temperature of the medium is increased, a series of thermal effects including a thermal lens effect, thermal birefringence, a temperature gradient effect, thermal stress and the like are caused, the operation of the laser is adversely affected, and the quality of a light beam output by the laser is seriously reduced.
The heat effect of the gain medium is partially caused by the uneven absorption of the pumping energy by the medium, and the vicinity of the incident end surface has higher temperature and temperature gradient during working. In recent years, researchers have proven that the laser gain medium is subjected to a layered structure design, so that the doping concentration of active ions is changed in a gradient manner, the heat conduction capability of the medium can be improved, and heat dissipation is promoted, thereby reducing the heat effect generated by the gain medium during working. The preparation of such a gain medium with a layered structure has to be achieved by means of certain shaping techniques. Since Ikesue et al realized laser output using Nd: YAG transparent ceramics as a medium in 1995, transparent ceramics have been rapidly developed due to their advantages of short preparation period, high doping concentration, easy realization of large-size and composite structure preparation, and the like. Compared with dielectric materials such as single crystal and the like, the transparent ceramic material can obtain layered structures with various configurations through different forming processes. Dry pressing, also known as compression molding, is a process in which powder is filled into a mold and pressed into a desired compact shape by unidirectional or bidirectional pressurization. Dry-pressing has the advantages of simple operation, high efficiency, higher density of the obtained product, low cost and the like, is suitable for forming transparent ceramics with a laminated structure with small size and simple shape, and is applied to laminated oxide transparent ceramics (see the documents J. Li, Y. Wu, Y. Pan, et al. Laminar-structured YAG/Nd: YAG/YAG transmissive ceramics for solid-state lasers, int. J. Appl. Ceram. Technol. 5 (2008) 360-364.).
In transparent ceramics, CaF2The rare earth doped luminescent material is a substrate material with excellent comprehensive performance, has a wide transmission wavelength range, low phonon energy and low refractive index, is very suitable for being used as a rare earth doped substrate material, and can fully exert good luminescent performance of rare earth elements. In 2009, there was a report on the preparation of Yb/CaF from nano-powder as a raw material2Transparent ceramics (see document P. Aubry, A. Bensalah, P. Gredin, et al. Synthesis and optical characteristics of Yb-doped CaF)2ceramics, Opt. mater, 31 (2009), 750-753). Since then, the researchersThe calcium fluoride transparent ceramics doped with different elements are prepared. However, at present, calcium fluoride transparent ceramics are all single structures with uniformly distributed components, and no literature report of calcium fluoride transparent ceramics with a layered structure is found.
Disclosure of Invention
The invention provides a preparation method of calcium fluoride transparent ceramic with a laminated structure, which is simple in process and low in cost and is prepared by combining dry pressing molding with vacuum hot pressing sintering.
The purpose of the invention is realized as follows:
a preparation method of layered calcium fluoride transparent ceramic comprises the following specific steps:
1) and (3) synthesis of nano powder: the method is characterized in that a CaF-containing reagent is synthesized in an aqueous solution by taking commercially available nitrate and potassium fluoride reagents as raw materials2With Ca1-xRExF2+xSuspension of the particles, drying and grinding the suspension after centrifugation-washing to obtain CaF2With Ca1-xRExF2+xNano powder;
2) preparing a layered ceramic blank: weighing the nano powder synthesized in the step 1) according to the set gradient layer component and thickness, and then sequentially carrying out dry pressing and forming to obtain a ceramic blank with a laminated structure in a laminated laminating manner;
3) sintering of the layered transparent ceramic: filling the ceramic blank with the layered structure prepared in the step 2) into a graphite mold, and putting the graphite mold into a vacuum hot-pressing furnace for pressure sintering;
4) ceramic sample treatment: and 3) after the sintering process is finished, taking out the ceramic and polishing to obtain the calcium fluoride transparent ceramic with the layered structure.
The CaF synthesized in the step 1)2With Ca1-xRExF2+xThe particle size of the powder is less than 100 nm, and the doped RE is one of cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and yttrium.
The number of the ceramic blank layers in the step 2) is 3-11, and the single-layer thickness is 0.2-1 mm.
The unidirectional pressure applied to each gradient layer in the step 2) is respectively 5 MPa to 20 MPa, and the pressure maintaining time is respectively 10min to 30 min.
The sintering process conditions in the step 3) are as follows: the heating rate is 5 ℃/min to 15 ℃/min, the sintering temperature is 700 ℃ to 900 ℃, the pressure is 20 MPa to 60 MPa, and the heat preservation time is 1 h to 5 h.
Has the positive and beneficial effects that: 1. the invention uses artificially synthesized CaF2With Ca1-xRExF2+xPreparing calcium fluoride transparent ceramic with a laminated structure by using nano powder as a raw material and adopting a dry pressing molding and vacuum hot pressing sintering technology, wherein the calcium fluoride transparent ceramic is developed from a single structure to the laminated structure; 2. the invention adopts the dry pressing molding and the vacuum hot pressing sintering technology to prepare the layered calcium fluoride transparent ceramic, and has simple process and low cost; 3. the layered calcium fluoride transparent ceramic prepared by the invention has high density and good transparency.
Description of the drawings:
FIG. 1 shows Ca with different doping concentrations1-xYxF2+xA picture of the shape of the nano powder, wherein a is doped 3%, and b is doped 7%;
FIG. 2 is a schematic view of a process for obtaining a layered ceramic body by dry pressing;
FIG. 3 is a picture of a prepared layered calcium fluoride transparent ceramic sample;
fig. 4 is a microstructure of the different layers in the ceramic sample, where a is doped 3% and b is doped 7%.
The specific implementation scheme is as follows:
for a better understanding of the present invention, the following detailed description of the preferred embodiments is given in conjunction with the accompanying drawings, which should not be taken to limit the scope of the present invention. Rather, these examples are provided to explain and illustrate the principles and practical application of the present invention so as to enable others skilled in the art to understand the present invention and make certain desired modifications. Unless otherwise specified, various raw materials and other consumables used in the present invention can be purchased from the market.
A preparation method of layered calcium fluoride transparent ceramic comprises the following specific steps:
1) and (3) synthesis of nano powder: the method is characterized in that a CaF-containing reagent is synthesized in an aqueous solution by taking commercially available nitrate and potassium fluoride reagents as raw materials2With Ca1-xRExF2+xSuspension of the particles, drying and grinding the suspension after centrifugation-washing to obtain CaF2With Ca1-xRExF2+xNano powder;
2) preparing a layered ceramic blank: weighing the nano powder synthesized in the step 1) according to the set gradient layer component and thickness, and then sequentially carrying out dry pressing and forming to obtain a ceramic blank with a laminated structure in a laminated laminating manner;
3) sintering of the layered transparent ceramic: filling the ceramic blank with the layered structure prepared in the step 2) into a graphite mold, and putting the graphite mold into a vacuum hot-pressing furnace for pressure sintering;
4) ceramic sample treatment: and 3) after the sintering process is finished, taking out the ceramic and polishing to obtain the calcium fluoride transparent ceramic with the layered structure.
The CaF synthesized in the step 1)2With Ca1-xRExF2+xThe particle size of the powder is less than 100 nm, and the doped RE is one of cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and yttrium.
The number of the ceramic blank layers in the step 2) is 3-11, and the single-layer thickness is 0.2-1 mm.
The unidirectional pressure applied to each gradient layer in the step 2) is respectively 5 MPa to 20 MPa, and the pressure maintaining time is respectively 10min to 30 min.
The sintering process conditions in the step 3) are as follows: the heating rate is 5 ℃/min to 15 ℃/min, the sintering temperature is 700 ℃ to 900 ℃, the pressure is 20 MPa to 60 MPa, and the heat preservation time is 1 h to 5 h.
Example 1
1）Ca1-xYxF2+xAnd (3) synthesis of nano powder: with commercially available Ca (NO)3)2、Y(NO3)3And KF as raw materials, synthesizingCa1- xYxF2+xCentrifuging, washing, drying and grinding the nano powder to obtain Ca1-xYxF2+xA powder, wherein x =0.03 and 0.07;
2) preparing a layered calcium fluoride ceramic blank: weigh 0.8g Ca0.97Y0.03F2.03And (3) filling the nano powder into a steel die with the diameter of 16 mm, applying the pressure of 20 MPa to the steel die, and maintaining the pressure for 10 min. Then, 0.6g of Ca was charged into the same mold0.93Y0.07F2.07And (3) applying 20 MPa pressure to the steel die by using the nano powder, and keeping the pressure for 10 min. Weigh again 0.8g Ca0.97Y0.03F2.03Loading the nano powder into a steel die, applying pressure of 20 MPa to the steel die, and maintaining the pressure for 10min to obtain a yttrium-doped calcium fluoride ceramic blank with 3 layers;
3) sintering of the layered transparent ceramic: loading the layered calcium fluoride ceramic blank obtained in the step 2) into a graphite mold, isolating the mold from the ceramic blank by using graphite paper, then placing the loaded graphite mold into a vacuum hot pressing furnace, heating to 900 ℃ at the speed of 10 ℃/min, then applying pressure of 30 MPa, and keeping the temperature for 3 h;
4) treating the layered transparent ceramic: and after sintering, taking out the layered ceramic sample, sequentially selecting different types of sand paper to carry out double-sided grinding on the ceramic sample, and then carrying out double-sided polishing on the ceramic sample by using diamond polishing solution on an automatic polishing machine to obtain the yttrium-doped calcium fluoride transparent ceramic with 3 layers.
Respectively Ca as shown in FIG. 10.97Y0.03F2.03With Ca0.93Y0.07F2.07The shape of the nano powder; FIG. 2 is a schematic view of a process for preparing a layered ceramic body; FIG. 3 shows that the prepared layered calcium fluoride transparent ceramic sample can clearly distinguish characters under the ceramic sample; FIG. 4 is a microstructure of the different component layers of the transparent ceramic sample.
Example 2
1）Ca1-xYxF2+xAnd (3) synthesis of nano powder: with commercially available Ca (NO)3)2、Y(NO3)3And KF is used as a raw material to synthesize Ca1- xYxF2+xCentrifuging, washing, drying and grinding the nano powder to obtain Ca1-xYxF2+xA powder, wherein x =0 and 0.03;
2) preparing a layered calcium fluoride ceramic blank: weigh 0.8g CaF2And (3) filling the nano powder into a steel die with the diameter of 16 mm, applying the pressure of 20 MPa to the steel die, and maintaining the pressure for 10 min. Then, 0.6g of Ca was charged into the same mold0.97Y0.03F2.03And (3) applying 20 MPa pressure to the steel die by using the nano powder, and keeping the pressure for 10 min. Weigh again 0.8g CaF2Loading the nano powder into a steel die, applying pressure of 20 MPa to the steel die, and maintaining the pressure for 10min to obtain a calcium fluoride ceramic blank with 3 layers;
3) sintering of the layered transparent ceramic: loading the layered calcium fluoride ceramic blank obtained in the step 2) into a graphite mold, isolating the mold from the ceramic blank by using graphite paper, then placing the loaded graphite mold into a vacuum hot pressing furnace, heating to 900 ℃ at the speed of 15 ℃/min, then applying pressure of 60 MPa, and keeping the temperature for 5 h;
4) treating the layered transparent ceramic: and after sintering, taking out the layered ceramic sample, sequentially selecting different types of sand paper to carry out double-sided grinding on the ceramic sample, and then carrying out double-sided polishing on the ceramic sample by using diamond polishing solution on an automatic polishing machine to obtain the calcium fluoride transparent ceramic with 3 layers.
Example 3
1）Ca1-xYbxF2+xAnd (3) synthesis of nano powder: with commercially available Ca (NO)3)2、Yb(NO3)3And KF as raw materials to synthesize Ca1- xYbxF2+xCentrifuging, washing, drying and grinding the nano powder to obtain Ca1-xYbxF2+xA powder, wherein x =0.03 and 0.07;
2) preparing a layered calcium fluoride ceramic blank: weigh 0.8g Ca0.97Yb0.03F2.03Loading the nanometer powder into a steel mold with diameter of 16 mm, applying pressure of 5 MPa to the steel mold, maintaining the pressure for 30min, and loading into the same mold0.6g of Ca was charged0.93Yb0.07F2.07Applying 5 MPa pressure to the steel die, maintaining the pressure for 30min, and weighing 0.8g Ca again0.97Yb0.03F2.03Loading the nano powder into a steel die, applying pressure of 5 MPa to the steel die, and maintaining the pressure for 30min to obtain an ytterbium-doped calcium fluoride ceramic blank with 3 layers;
3) sintering of the layered transparent ceramic: loading the layered calcium fluoride ceramic blank obtained in the step 2) into a graphite mold, isolating the mold from the ceramic blank by using graphite paper, then placing the loaded graphite mold into a vacuum hot pressing furnace, heating to 800 ℃ at the speed of 15 ℃/min, then applying the pressure of 60 MPa, and keeping the temperature for 1 h;
4) treating the layered transparent ceramic: and after sintering, taking out the layered ceramic sample, sequentially selecting different types of sand paper to carry out double-sided polishing on the ceramic sample, and then carrying out double-sided polishing on the ceramic sample by using diamond polishing solution on an automatic polishing machine to obtain the ytterbium-doped calcium fluoride transparent ceramic with 3 layers.
Example 4
1）Ca1-xErxF2+xAnd (3) synthesis of nano powder: with commercially available Ca (NO)3)2、Er(NO3)3And KF as raw materials to synthesize Ca1- xErxF2+xCentrifuging, washing, drying and grinding the nano powder to obtain Ca1-xErxF2+xA powder, wherein x =0.03 and 0.07; (ii) a
2) Preparing a layered calcium fluoride ceramic blank: weigh 0.8g Ca0.97Er0.03F2.03And (3) filling the nano powder into a steel die with the diameter of 16 mm, applying the pressure of 10 MPa to the steel die, and maintaining the pressure for 20 min. Then, 0.6g of Ca was charged into the same mold0.93Er0.07F2.07And (3) applying 10 MPa pressure to the steel die by using the nano powder, and maintaining the pressure for 20 min. Weigh again 0.8g Ca0.97Er0.03F2.03Loading the nano powder into a steel die, applying 10 MPa of pressure to the steel die, and maintaining the pressure for 20 min to obtain an erbium-doped calcium fluoride ceramic blank with 3 layers;
3) sintering of the layered transparent ceramic: loading the layered calcium fluoride ceramic blank obtained in the step 2) into a graphite mold, isolating the mold from the ceramic blank by using graphite paper, then placing the loaded graphite mold into a vacuum hot pressing furnace, heating to 800 ℃ at the speed of 10 ℃/min, then applying pressure of 30 MPa, and keeping the temperature for 2 h;
4) treating the layered transparent ceramic: and after sintering, taking out the layered ceramic sample, sequentially selecting different types of sand paper to carry out double-sided grinding on the ceramic sample, and then carrying out double-sided polishing on the ceramic sample by using diamond polishing solution on an automatic polishing machine to obtain the erbium-doped calcium fluoride transparent ceramic with 3 layers.
Example 5
1）Ca1-xYxF2+xAnd (3) synthesis of nano powder: with commercially available Ca (NO)3)2、Y(NO3)3And KF as raw materials to synthesize Ca1- xYxF2+xCentrifuging, washing, drying and grinding the nano powder to obtain Ca1-xYxF2+xA powder, wherein x =0.03, 0.05 and 0.07;
2) preparing a layered calcium fluoride ceramic blank: 0.8g of Ca was sequentially charged into a steel mold having a diameter of 16 mm0.97Y0.03F2.03、0.6g Ca0.95Y0.05F2.05、0.6g Ca0.93Y0.07F2.07、0.6g Ca0.95Y0.05F2.05And 0.8g Ca0.97Y0.03F2.03After each layer of nano powder is added, respectively applying 5 MPa pressure to a steel die, and keeping the pressure for 30min to finally obtain a yttrium-doped calcium fluoride ceramic blank with 5 layers;
3) sintering of the layered transparent ceramic: loading the layered calcium fluoride ceramic blank obtained in the step 2) into a graphite mold, isolating the mold from the ceramic blank by using graphite paper, then placing the loaded graphite mold into a vacuum hot pressing furnace, heating to 800 ℃ at the speed of 5 ℃/min, then applying pressure of 30 MPa, and keeping the temperature for 3 h;
4) treating the layered transparent ceramic: and after sintering, taking out the layered ceramic sample, sequentially selecting different types of sand paper to carry out double-sided grinding on the ceramic sample, and then carrying out double-sided polishing on the ceramic sample by using diamond polishing solution on an automatic polishing machine to obtain the yttrium-doped calcium fluoride transparent ceramic with 5 layers.
Example 6
1）Ca1-xYxF2+xAnd (3) synthesis of nano powder: with commercially available Ca (NO)3)2、Y(NO3)3And KF as raw materials to synthesize Ca1- xYxF2+xCentrifuging, washing, drying and grinding the nano powder to obtain Ca1-xYxF2+xA powder, wherein x =0.03, 0.04, 0.05, 0.07, 0.1, and 0.12;
2) preparing a layered calcium fluoride ceramic blank: 0.4g Ca was charged into a steel mold having a diameter of 16 mm in sequence0.97Y0.03F2.03、0.3g Ca0.96Y0.04F2.04、0.3g Ca0.95Y0.05F2.05、0.3g Ca0.93Y0.07F2.07、0.3g Ca0.9Y0.1F2.1、0.3g Ca0.88Y0.12F2.12、0.3g Ca0.9Y0.1F2.1、0.3g Ca0.93Y0.07F2.07、0.3g Ca0.95Y0.05F2.05、0.3g Ca0.96Y0.04F2.04、0.4g Ca0.97Y0.03F2.03After adding each layer of nano powder, respectively applying 10 MPa pressure to a steel die, and keeping the pressure for 30min to finally obtain an yttrium-doped calcium fluoride ceramic blank with 11 layers;
3) sintering of the layered transparent ceramic: loading the layered calcium fluoride ceramic blank obtained in the step 2) into a graphite mold, isolating the mold from the ceramic blank by using graphite paper, then placing the loaded graphite mold into a vacuum hot pressing furnace, heating to 700 ℃ at the speed of 15 ℃/min, then applying the pressure of 20 MPa, and keeping the temperature for 5 h;
4) treating the layered transparent ceramic: and after sintering, taking out the layered ceramic sample, sequentially selecting different types of sand paper to carry out double-sided grinding on the ceramic sample, and then carrying out double-sided polishing on the ceramic sample by using diamond polishing solution on an automatic polishing machine to obtain the yttrium-doped calcium fluoride transparent ceramic with 11 layers.
Finally, it should be noted that the above description is only a preferred embodiment of the present invention, and is only used to explain the technical solutions of the present invention in further detail. Numerous insubstantial modifications and adaptations of the present invention will now occur to those skilled in the art based on the teachings herein.
The invention uses artificially synthesized CaF2With Ca1-xRExF2+xPreparing calcium fluoride transparent ceramic with a laminated structure by using nano powder as a raw material and adopting a dry pressing molding and vacuum hot pressing sintering technology, wherein the calcium fluoride transparent ceramic is developed from a single structure to the laminated structure; the invention adopts the dry pressing molding and the vacuum hot pressing sintering technology to prepare the layered calcium fluoride transparent ceramic, and has simple process and low cost; the layered calcium fluoride transparent ceramic prepared by the invention has high density and good transparency.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (1)
1. A preparation method of layered calcium fluoride transparent ceramic comprises the following specific steps:
1) and (3) synthesis of nano powder: the method is characterized in that a CaF-containing reagent is synthesized in an aqueous solution by taking commercially available nitrate and potassium fluoride reagents as raw materials2And Ca1-xRExF2+xSuspension of the particles, drying and grinding the suspension after centrifugation-washing to obtain CaF2With Ca1-xRExF2+xNano powder;
2) preparing a layered ceramic blank: weighing the nano powder synthesized in the step 1) according to the set gradient layer component and thickness, and then sequentially carrying out dry pressing and forming to obtain a ceramic blank with a laminated structure in a laminated laminating manner;
3) sintering of the layered transparent ceramic: filling the ceramic blank with the layered structure prepared in the step 2) into a graphite mold, and putting the graphite mold into a vacuum hot-pressing furnace for pressure sintering;
4) ceramic sample treatment: step 3), after the sintering process is finished, taking out the ceramic and polishing the ceramic to obtain the calcium fluoride transparent ceramic with a laminated structure;
the CaF synthesized in the step 1)2With Ca1-xRExF2+xThe particle size of the powder is less than 100 nm, and the doped RE is one of cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and yttrium;
the number of the ceramic blank layers in the step 2) is 3-11, and the single-layer thickness is 0.2-1 mm;
the unidirectional pressure applied to each gradient layer in the step 2) is respectively 5 MPa to 20 MPa, and the pressure maintaining time is respectively 10min to 30 min;
the sintering process conditions in the step 3) are as follows: the heating rate is 5 ℃/min to 15 ℃/min, the sintering temperature is 700 ℃ to 900 ℃, the pressure is 20 MPa to 60 MPa, and the heat preservation time is 1 h to 5 h.
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| CN113956043B (en) * | 2021-11-29 | 2023-02-10 | 中国科学院上海光学精密机械研究所 | Fluoride infrared complex phase transparent ceramic and preparation method thereof |
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| CN102126857A (en) * | 2011-01-31 | 2011-07-20 | 武汉理工大学 | Method for preparing transparent calcium fluoride ceramic |
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| CN102126858A (en) * | 2011-01-31 | 2011-07-20 | 武汉理工大学 | Preparation method of erbium ion-doped calcium fluoride laser transparent ceramic material |
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