CN116514537A - Preparation method of high-light-transmittance magnesia-alumina spinel transparent ceramic - Google Patents
Preparation method of high-light-transmittance magnesia-alumina spinel transparent ceramic Download PDFInfo
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- CN116514537A CN116514537A CN202211364895.8A CN202211364895A CN116514537A CN 116514537 A CN116514537 A CN 116514537A CN 202211364895 A CN202211364895 A CN 202211364895A CN 116514537 A CN116514537 A CN 116514537A
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- Prior art keywords
- sintering
- magnesia
- calcium fluoride
- alumina spinel
- transmittance
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- 239000000919 ceramic Substances 0.000 title claims abstract description 71
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 69
- 239000011029 spinel Substances 0.000 title claims abstract description 69
- 238000002834 transmittance Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000005245 sintering Methods 0.000 claims abstract description 81
- 239000000843 powder Substances 0.000 claims abstract description 59
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 46
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 46
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000011777 magnesium Substances 0.000 claims abstract description 21
- 235000015895 biscuits Nutrition 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 8
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 36
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 31
- 239000000395 magnesium oxide Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 14
- 238000001513 hot isostatic pressing Methods 0.000 claims description 14
- 238000001272 pressureless sintering Methods 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 238000007569 slipcasting Methods 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 238000000498 ball milling Methods 0.000 description 16
- 230000003287 optical effect Effects 0.000 description 15
- 239000002002 slurry Substances 0.000 description 12
- 238000005498 polishing Methods 0.000 description 11
- 238000000227 grinding Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000002609 medium Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000009694 cold isostatic pressing Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- -1 oxygen ions Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910020068 MgAl Inorganic materials 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
- C04B35/443—Magnesium aluminate spinel
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Abstract
The invention relates to a preparation method of high-light-transmittance magnesia-alumina spinel transparent ceramic. The preparation method of the high-light-transmittance magnesia-alumina spinel transparent ceramic comprises the following steps: taking an aluminum source and an Mg source as raw materials, weighing the raw materials according to an aluminum-magnesium ratio, adding calcium fluoride as a sintering aid, mixing, forming to obtain a biscuit, and finally sintering to prepare the high-light-transmittance magnesia-alumina spinel transparent ceramic; the calcium fluoride is at least one selected from calcium fluoride powder and calcium fluoride single crystal particles; the chemical formula of the magnesia-alumina spinel transparent ceramic is MgO 2 O 3 ，1≤n≤2.5。
Description
Technical Field
The invention relates to a preparation method of magnesia-alumina spinel transparent ceramic, belonging to the field of transparent ceramic.
Background
Magnesia alumina spinel transparent ceramics have received much attention since the advent of their excellent optical and mechanical properties. Magnesia alumina spinel belongs to a cubic crystal system, has optical isotropy, has a light transmission range covering ultraviolet to mid-infrared wave bands, and has excellent mechanical properties such as: high hardness, high flexural strength, etc. In addition, the magnesia-alumina spinel has the characteristics of low density, wear resistance, chemical resistance, sand erosion resistance, rain erosion resistance and the like, and is widely applied to the fields of dual purposes of armies and civilians such as transparent armor, infrared guide head fairings, high-temperature observation windows, precise instrument windows and the like.
The difficulty in preparing transparent magnesia-alumina spinel ceramics is mainly focused on the difficult sintering densification caused by the slow diffusion speed of close-packed oxygen ions, however, the preparation of the magnesia-alumina spinel ceramics with high optical quality requires that the porosity in a sample is lower than 100ppm and the pore size is lower than 40nm, so that the transparent magnesia-alumina spinel ceramics are prepared by adopting an extreme mode of combining high temperature with high pressure and the like, which provides great challenges for sintering equipment. In order to reduce the sintering temperature, the sintering is carried out at present mainly by adding suitable sintering aids, such as LiF, caO, B 2 O 3 、Y 2 O 3 Etc. Among them, liF is the most mature sintering aid at present, and has been applied to the preparation of large-size magnesia-alumina spinel transparent ceramics. The LiF has the advantages of having the functions of liquid phase sintering and increasing defect concentration, and promoting the densification process jointly through the two modes. In addition, liF also has the function of removing impurities in the raw material powder. However, the crystal grains caused by LiF sintering aid are abnormally grown and combined with MgAl 2 O 4 LiAlO produced by reaction 2 The second phase causes grain boundary microcracks and the like to reduce the mechanical properties of the ceramic, which severely limits the application of the magnesia-alumina spinel transparent ceramic as a protective material. In addition, liF is characterized by low melting point and low boiling point, and is usually combined with hot press sintering, however, hot press sinteringThe graphite mold used for sintering contaminates the sample, and although the addition of LiF can act as a decarbonization, it cannot be eradicated, resulting in a final sample that still turns black. In addition, uneven volatilization of LiF can cause differential sintering, and a sample after sintering has a fog center, so that the optical quality of the sample is affected, and the preparation of a large-size magnesia-alumina spinel transparent ceramic sample is severely limited.
CaO is another sintering aid commonly used for preparing magnesia-alumina spinel transparent ceramics, and has the advantage that CaO can be mixed with MgAl 2 O 4 The reaction generates calcium aluminate with low melting point, and in the heating process, the calcium aluminate is melted to form liquid phase to promote sintering, so that the sintering temperature can be remarkably reduced by about 100 ℃, and the transmittance of a sample in an ultraviolet band can be improved. However, the use of CaO as a sintering aid requires a strict control of the hot isostatic pressing sintering temperature, and too high a temperature may reduce the optical quality of the ceramic sample. In addition, at high temperatures, secondary phase deposition of the radioactive calcium aluminate can result, affecting the uniformity of the microstructure.
At present, several commonly used sintering aids cannot meet the requirement of preparing large-size and high-optical-quality magnesia-alumina spinel transparent ceramics, and in order to get rid of the dependence on LiF sintering aids, the exploration of a new sintering aid system is important for practical application.
Disclosure of Invention
Therefore, the invention aims to provide a preparation method of magnesia-alumina spinel transparent ceramic with simple flow, and the chemical formula of the magnesia-alumina spinel transparent ceramic is MgO and nAL 2 O 3 N is more than or equal to 1 and less than or equal to 2.5. The invention selects high-purity magnesium and aluminum sources (magnesium and aluminum oxides or magnesium and aluminum hydroxides) or magnesia-alumina spinel commercial powder with wide sources as raw materials, adopts the sintering additive calcium fluoride which can be melted into liquid phase at high temperature, and fully wets the particle surfaces through the liquid phase formed in the sintering temperature rising process, promotes the rearrangement of particles, reduces the sintering temperature, promotes the discharge of nano pores, prevents abnormal growth of crystal grains, and prepares the magnesia-alumina spinel transparent ceramic with high optical quality.
In one aspect, the invention provides a preparation method of high-light-transmittance magnesia-alumina spinel transparent ceramic, which comprisesThe chemical formula of the magnesia-alumina spinel transparent ceramic is MgO. NAL 2 O 3 ，1≤n≤2.5；
The preparation method of the high-light-transmittance magnesia-alumina spinel transparent ceramic comprises the following steps: taking an aluminum source and an Mg source as raw materials, weighing the raw materials according to an aluminum-magnesium ratio, adding calcium fluoride as a sintering aid, mixing, forming to obtain a biscuit, and finally sintering to prepare the high-light-transmittance magnesia-alumina spinel transparent ceramic; the calcium fluoride is at least one selected from calcium fluoride powder and calcium fluoride single crystal particles. The invention has the following points: by CaF 2 The auxiliary agent can be melted into a liquid phase at high temperature, the surface of particles is fully wetted by the liquid phase formed in the sintering temperature rising process, the particle rearrangement is promoted, the sintering temperature is reduced, the discharge of nano pores is promoted, the abnormal growth of crystal grains is prevented, and the magnesia-alumina spinel transparent ceramic with high optical quality is prepared, and belongs to the field of transparent ceramics.
Preferably, the aluminum source and the magnesium source are at least one of aluminum, magnesium oxide/hydroxide or magnesium aluminum spinel powder. In the present invention, the aluminum source is an oxide/hydroxide of aluminum. The magnesium source is an oxide/hydroxide of magnesium. The aluminum source and the magnesium source can also be magnesia-alumina spinel powder.
Preferably, the oxide of aluminum Al 2 O 3 The purity of the powder is more than or equal to 99.9 percent, and the grain diameter is 50-1000 nm; the purity of MgO powder of magnesium oxide is more than or equal to 99.9%, and the grain diameter is 100-1000 nm.
Preferably, the hydroxide of aluminum Al (OH) 3 The purity of the product is more than or equal to 99.9 percent, and the grain diameter is 10 to 20 mu m; magnesium hydroxide Mg (OH) 2 The purity of the powder is more than or equal to 99.9 percent, and the grain diameter is 5-7 mu m.
On the other hand, the invention provides a preparation method of high-light-transmittance magnesia-alumina spinel transparent ceramic, wherein the chemical formula of the magnesia-alumina spinel transparent ceramic is MgO (nAL) 2 O 3 ，1≤n≤2.5；
The preparation method of the high-light-transmittance magnesia-alumina spinel transparent ceramic comprises the following steps: adopting magnesia-alumina spinel MgO. NAL 2 O 3 Adding calcium fluoride as sintering aid into the powder as raw material, mixing, shaping to obtain biscuit, and finalSintering to prepare high-light-transmittance magnesia-alumina spinel transparent ceramic; the calcium fluoride is at least one selected from calcium fluoride powder and calcium fluoride single crystal particles.
Preferably, the purity of the magnesia-alumina spinel powder is more than or equal to 99.9 percent, and the grain diameter is 50-500 nm.
Preferably, the particle size of the calcium fluoride powder is 100-1000 nm, and the particle size of the calcium fluoride single crystal particles is 100-300 μm.
Preferably, the mass concentration of the sintering aid is 100-5000 ppm, preferably 100-3000 ppm;
preferably, when the sintering aid is calcium fluoride powder, the mass concentration is 500-2000 ppm;
preferably, when the sintering aid is calcium fluoride single crystal particles, the mass concentration is 500 to 3000ppm. The calcium fluoride powder is generally referred to as calcium fluoride polycrystalline powder unless otherwise specified in the present invention.
Preferably, the forming mode is dry forming or wet forming, the dry forming comprises dry pressing forming or/and cold isostatic pressing forming, and the wet forming comprises slip casting and coagulation casting.
Preferably, the molded biscuit is pre-sintered before sintering;
the presintering is pressureless sintering, comprising: the pressureless sintering temperature is 1400-1700 ℃, and the sintering atmosphere is one of air or vacuum;
preferably, a pressureless sintering process is adopted in an air atmosphere, the sintering temperature is 1400-1600 ℃, and the heat preservation time is 3-6 hours;
preferably, the sintering temperature of the pressureless sintering process is 1500-1700 ℃ under vacuum atmosphere, and the temperature is kept for 4-6 hours.
Preferably, when the biscuit contains the binder, the biscuit is firstly subjected to glue discharging treatment and then is subjected to presintering; the temperature of the glue discharging treatment is 600-800 ℃ and the heat preservation time is 3-6 hours, so as to discharge organic matters.
Preferably, the sintering mode is hot isostatic pressing sintering; the technological parameters of the hot isostatic pressing sintering are as follows: the sintering temperature is 1500-1700 ℃; the heat preservation time is 1 to 6 hours; the pressurizing medium is argon or nitrogen, and the pressure is 120-200 MPa.
The beneficial effects are that:
the preparation method provided by the invention can realize low-temperature sintering of the magnesia-alumina spinel transparent ceramic, prepare the magnesia-alumina spinel transparent ceramic with high optical quality, and the transmittance of a sample (5 mm thick) subjected to double-sided polishing in a near infrared region (760-1100 nm) can reach 87%, so that the theoretical transmittance of the magnesia-alumina spinel is realized, the transmittance at a visible light wave band of 400nm can reach more than 82%, and the requirements on the optical and mechanical properties of the magnesia-alumina spinel transparent ceramic in the fields of optical guide head fairings, transparent armor and the like can be met. In addition, compared with the prior art, the preparation method has the advantages of simple flow, easy control of material components, low cost and the like.
Drawings
FIG. 1 is a physical photograph of a magnesia-alumina spinel transparent ceramic sample having a thickness of 5mm after grinding and double-sided polishing of the sample prepared in example 1;
FIG. 2 is a graph showing the transmittance of a sample of magnesia-alumina spinel transparent ceramic with a thickness of 5mm after grinding and double-sided polishing, prepared in example 1;
FIG. 3 is a graph showing the transmittance of a sample of magnesia-alumina spinel transparent ceramic with a thickness of 5mm after grinding and double-sided polishing of the sample prepared in example 2;
FIG. 4 is a graph showing the transmittance of a sample of magnesia-alumina spinel transparent ceramic with a thickness of 5mm after grinding and double-sided polishing, prepared in example 3;
FIG. 5 is a photograph of a transparent ceramic sample of magnesia-alumina spinel 5mm thick after grinding and double-sided polishing of the sample prepared in example 4;
FIG. 6 is a graph showing the transmittance of a sample of magnesia-alumina spinel transparent ceramic with a thickness of 5mm after grinding and double-sided polishing, prepared in example 5;
FIG. 7 is a graph showing the transmittance of a sample of magnesia-alumina spinel transparent ceramic with a thickness of 5mm after grinding and double-sided polishing, which was prepared in comparative example 1.
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.
In the invention, magnesia-alumina spinel transparent ceramics with different aluminum-magnesium ratios are prepared by taking commercial high-purity magnesium sources and aluminum sources (including but not limited to oxides or hydroxides of magnesium and aluminum) or high-purity magnesia-alumina spinel commercial powder as raw materials and adding sintering aids calcium fluoride (including but not limited to calcium fluoride powder or calcium fluoride single crystal particles). The main process flow of the method comprises three steps of raw material powder mixing, powder forming and densification. Firstly weighing magnesium source, aluminum source or magnesia-alumina spinel commercial powder and sintering aid according to the proportion of the required sample, uniformly mixing and deagglomerating the powder by wet ball milling, obtaining a ceramic biscuit by dry/wet forming (including but not limited to dry press forming, slip casting and the like), then pre-sintering the ceramic biscuit to remove open pores, and combining hot isostatic pressing sintering to remove residual closed pores, thereby obtaining the ceramic sample with optical permeability.
The following exemplifies a method for preparing the magnesia-alumina spinel transparent ceramic of the present invention.
Powder mixing and deagglomeration: the commercial powder of magnesium source, aluminum source or magnesium aluminate spinel and sintering aid are weighed according to proportion (if adopting wet forming process, proper amount of dispersing agent and curing agent are added when preparing slurry), deionized water/absolute ethyl alcohol is used as dispersing medium, high-purity alumina ball-milling beads are used as ball-milling medium for uniform mixing. The mixing mode is planetary ball milling, the ball milling process is 200-300 rpm, and the ball milling is carried out for 10-12 hours. The mixing mode comprises, but is not limited to, planetary ball milling mixing, and is applicable to the invention in all modes capable of realizing uniform mixing of raw materials. If the powder treatment capacity is too large, all equipment (such as stirring mill, sand mill and the like) capable of realizing deagglomeration and uniform mixing of the powder are suitable for the invention. High-purity oxides of aluminum and magnesium are used as raw materials, al 2 O 3 The purity of the powder is more than or equal to 99.9%, the grain diameter is 50-1000 nm, the purity of MgO powder is more than or equal to 99.9%, and the grain diameter is 100-1000 nm. High-purity hydroxides of aluminum and magnesium are used as raw materials, and Al (OH) 3 The purity of the product is more than or equal to 99.9 percent, and the grain diameter is 10 to the upper20μm。Mg(OH) 2 The purity of the powder is more than or equal to 99.9 percent, and the grain diameter is 5-7 mu m. The high-purity magnesia alumina spinel commercial powder is adopted, the purity of the powder is more than or equal to 99.9 percent, and the grain diameter is 20-500 nm. The mass concentration of the added calcium fluoride sintering aid is 100-5000 ppm, preferably 100-3000 ppm. Preferably, when the sintering aid is calcium fluoride powder, the mass concentration is 500-2000 ppm, and the particle size of the calcium fluoride powder is 100-500 nm. If the calcium fluoride powder is added in a higher amount, a second phase is more likely to be generated during sintering, and the optical quality of the transparent ceramic sample is further affected. Preferably, when the sintering aid is calcium fluoride single crystal particles, the mass concentration is 500-3000 ppm, and the single crystal calcium fluoride particle size is 0.1-0.3 mm. If the amount of calcium fluoride single crystal particles added is too high, a second phase is easily generated similarly to the case of adding calcium fluoride powder, thereby affecting the optical quality of the transparent ceramic sample.
And (3) forming: and a dry/wet forming process is adopted to obtain the ceramic biscuit. When the forming process is dry forming, the slurry is required to be dried, the drying condition is 50-60 ℃ for 8-12 hours, and the slurry is sieved by a 100-mesh sieve. And (3) adopting a dry isostatic pressing mode or/and a cold isostatic pressing mode to press and mold the powder. Drying the treated slurry by adopting dry press molding and cold isostatic press molding, sieving the slurry with a 100-mesh sieve, calcining the slurry at 600-800 ℃ for 4-6 hours to remove residual organic impurities, filling the treated raw material powder into a mold, and maintaining the pressure for 1-3 minutes under the pressure of 10-20 MPa for dry press molding. And (3) carrying out cold isostatic pressing treatment on the dried biscuit, wherein the pressure is 200MPa, and the pressure maintaining time is 5-10 minutes. The molding process is wet molding, including but not limited to injection molding, slip casting, and the like. By adopting the injection molding process, 0.3 to 2.0 weight percent of dispersing agent (CE 64 or Dolapix) and 0.2 to 0.3 weight percent of gel curing agent (ISOBAM AF600 or ISOBAM 104) are added when preparing the slurry, the solid content of the slurry is 35 to 56 volume percent, the slurry is cured and dried at room temperature, and the temperature is kept at 600 to 800 ℃ for 3 to 6 hours to discharge organic substances, thus obtaining the biscuit with higher strength.
And (3) presintering the ceramic biscuit, and completely discharging the ceramic biscuit out of the open pores to obtain a presintered body. The presintering process comprises the following steps: and (3) pressureless sintering at 1400-1700 ℃ in one of air and vacuum. Preferably, the sintering temperature of the pressureless sintering process is 1400-1600 ℃ and the heat preservation time is 3-6 hours under the air atmosphere, and the relative density of the obtained sintered body is not less than 96%. Preferably, the sintering temperature of the pressureless sintering process is 1500-1700 ℃ under vacuum atmosphere, and the temperature is kept for 4-6 hours.
And (5) sintering by hot isostatic pressing. And sintering the pre-sintered body by hot isostatic pressing. The hot isostatic pressing sintering process comprises the following steps: the sintering temperature is 1500-1700 ℃, the heat preservation time is 1-6 hours, the pressurizing medium is argon or nitrogen, and the pressure is 120-200 MPa.
The sample after the hot isostatic pressing sintering is preferably annealed. And polishing to obtain the magnesia-alumina spinel transparent ceramic. Wherein the annealing treatment temperature can be 1100-1350 ℃ and the time is 6-30 hours, and the atmosphere is air or oxygen atmosphere.
The transmittance of the magnesia-alumina spinel transparent ceramic with the thickness of 5mm and polished on both sides, prepared by the invention, in a near infrared region (760-1100 nm) can reach 87%, so that the transmittance reaches theoretical transmittance, and the transmittance at the 400nm position of a visible light wave band can reach more than 82%. In addition, the method has simple manufacturing flow, can realize the preparation of magnesia-alumina spinel transparent ceramics with complex shapes, and meets the application requirements of the material in the fields of transparent armor, spacecraft optical guide head fairings, optical windows and the like. In addition, the sintering aid system selected by the preparation method can obviously reduce the sintering temperature of the magnesia-alumina spinel transparent ceramic and reduce the production cost.
The present invention will be further illustrated by the following 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) According to MgO to Al 2 O 3 Molar of (2)MgO and Al are respectively weighed according to the ratio of 1:1 2 O 3 Powder, namely weighing calcium fluoride powder with the mass concentration of 500ppm, placing the powder into a ball milling tank, taking absolute ethyl alcohol as a dispersion medium, taking high-purity alumina ball milling beads as a ball milling medium, ball milling for 12 hours at the rotating speed of 200-300 rpm/min, placing the ball milling slurry into a 60 ℃ oven for drying for 12 hours, sieving the dried powder by a 100-mesh sieve, placing the sieved powder into a muffle furnace, and calcining the powder at 800 ℃ for 6 hours to remove residual alcohol and organic impurities;
(2) Weighing 3g of the calcined powder, putting the powder into a die with the diameter of 20mm, and performing dry pressing molding on the powder at 20MPa by adopting a double-sided pressurizing mode and maintaining the pressure for 1 minute. Cold isostatic pressing is adopted to the preformed biscuit at 200MPa, and the density of the biscuit is more than 40% under the pressure maintaining condition for 5 minutes;
(3) Placing the biscuit in a muffle furnace to presintered for 3 hours at 1500 ℃, and removing open pores in the air atmosphere to obtain a presintered sample with the relative density of more than 96%;
(4) Carrying out hot isostatic pressing sintering on the pre-sintered sample, wherein the sintering atmosphere is argon, the pressure is 200MPa, the sintering temperature is 1550 ℃, and the heat preservation time is 3 hours;
(5) And grinding and double-sided polishing the sample subjected to the hot isostatic pressing sintering until the thickness is 5mm.
FIG. 1 is a sample obtained by the method of example 1, wherein the sample is subjected to double-sided polishing treatment, has a thickness of 5mm, and has good light transmittance in the visible light range and no macroscopic defect. FIG. 2 is a graph showing the linear transmittance of the transparent ceramics with the thickness of 5mm prepared by the method in the embodiment 1, the transmittance of the sample in the near infrared band (760-1100 nm) can reach more than 87%, the theoretical transmittance is realized, the linear transmittance at the visible light band 400nm can reach more than 82%, and the transmittance is higher.
Example 2:
the procedure for the preparation of the high light transmittance magnesia-alumina spinel transparent ceramic of this example 2 is similar to that of example 1, except that: the addition amount of the nano calcium fluoride powder is 2000ppm, and the presintering temperature is 1455 ℃.
FIG. 3 is a graph showing the linear transmittance of the transparent ceramics with the thickness of 5mm prepared by the method in the embodiment 2, wherein the transmittance of the sample in the near infrared band (760-1100 nm) can reach 87%, the theoretical transmittance is realized, and the linear transmittance in the visible light band at 400nm can reach more than 78%.
Example 3:
the preparation procedure was similar to example 1, except that: mgO-Al 2 O 3 The molar ratio of (2) is 1:1.5, the addition amount of the sintering aid is 2000ppm, and the presintering temperature is 1485 ℃.
FIG. 4 is a graph showing the linear transmittance of the transparent ceramics with the thickness of 5mm obtained by the method described in the present example 3, wherein the transmittance of the sample in the near infrared band (760-1100 nm) can reach more than 85%, the transmittance approaches to the theoretical transmittance, and the linear transmittance in the visible light band at 400nm can reach 76%.
Example 4:
the preparation procedure was similar to example 1, except that: presintering in vacuum atmosphere, wherein the presintering temperature is 1550 ℃; the sintering temperature of the hot isostatic pressing is 1600 ℃; the post-hiped samples were annealed at 1300 ℃ for 10 hours in an air atmosphere.
FIG. 5 is a photograph of a transparent ceramic with a thickness of 5mm obtained by the method described in example 4, wherein no defects are visible in the sample, the transmittance in the near infrared band (760-1100 nm) can reach 84%, and the transmittance in the visible band at 400nm can reach 75.2%.
Example 5:
(1) 0.5 weight percent of dispersing agent (CE 64) and 0.3 weight percent of gel curing agent (ISOBAM 600 AF) are weighed according to the proportion and dissolved in deionized water, commercial powder of the magnesium aluminate spinel is weighed, then calcium fluoride powder with the mass concentration of 500ppm is weighed and placed in a ball milling tank, deionized water is taken as a dispersing medium, high-purity alumina ball milling beads are taken as a ball milling medium, and slurry with the solid content of 45Vol% is prepared. Ball milling for 12 hours at a rotating speed of 200-300 rpm/min, pouring the slurry into a mould after uniform mixing, performing crosslinking reaction in-situ curing, demoulding, drying at room temperature, and calcining in a muffle furnace at 800 ℃ for 6 hours to remove residual alcohol and organic impurities;
(2) The above green compacts were placed in a muffle furnace and pre-sintered at 1475 ℃ for 3 hours, in an air atmosphere, and after removing the open pores, the hot isostatic pressing sintering system was similar to that of example 1.
FIG. 6 is a graph showing the linear transmittance of the transparent ceramics with the thickness of 5mm obtained by the method described in the present example 5, the transmittance (760-1100 nm) of the sample in the near infrared band can reach more than 85%, the transmittance approaches to the theoretical transmittance, and the linear transmittance at 400nm in the visible band can reach 75%.
Comparative example 1:
the preparation procedure was similar to example 1, except that: no sintering aid is added; . FIG. 7 is a graph showing the linear transmittance of the transparent ceramics of 5mm thickness obtained in comparative example 1, wherein the transmittance of the sample in the near infrared band (760 to 1100 nm) can reach 84% or more, and the linear transmittance in the visible light band at 400nm can reach 75%, and the transmittance is lower.
Claims (11)
1. A preparation method of high-light-transmittance magnesia-alumina spinel transparent ceramic is characterized in that the chemical formula of the magnesia-alumina spinel transparent ceramic is MgO 2 O 3 ，1≤n≤2.5；
The preparation method of the high-light-transmittance magnesia-alumina spinel transparent ceramic comprises the following steps: taking an aluminum source and an Mg source as raw materials, weighing the raw materials according to an aluminum-magnesium ratio, adding calcium fluoride as a sintering aid, mixing, forming to obtain a biscuit, and finally sintering to prepare the high-light-transmittance magnesia-alumina spinel transparent ceramic; the calcium fluoride is at least one selected from calcium fluoride powder and calcium fluoride single crystal particles.
2. The method of claim 1, wherein the aluminum source, magnesium source is at least one of aluminum, magnesium oxide/hydroxide, or magnesium aluminum spinel powder.
3. The preparation method according to claim 2, wherein the aluminum oxide Al 2 O 3 The purity of the powder is more than or equal to 99.9 percent, and the grain diameter is 50-1000 nm; the purity of MgO powder of magnesium oxide is more than or equal to 99.9%, and the grain diameter is 100-1000 nm;
aluminum hydroxide Al (OH) 3 The purity of the product is more than or equal to 99.9 percent, and the grain diameter is 10 to 20 mu m; magnesium hydroxide Mg (OH) 2 The purity of the powder is more than or equal to 99.9 percent, and the grain diameter is 5-7 mu m.
4. A preparation method of high-light-transmittance magnesia-alumina spinel transparent ceramic is characterized in that the chemical formula of the magnesia-alumina spinel transparent ceramic is MgO 2 O 3 ，1≤n≤2.5；
The preparation method of the high-light-transmittance magnesia-alumina spinel transparent ceramic comprises the following steps: adopting magnesia-alumina spinel MgO. NAL 2 O 3 Adding calcium fluoride as a sintering aid into the powder serving as a raw material, mixing, forming to obtain a biscuit, and finally sintering to prepare the high-light-transmittance magnesia-alumina spinel transparent ceramic; the calcium fluoride is at least one selected from calcium fluoride powder and calcium fluoride single crystal particles.
5. The preparation method of claim 4, wherein the magnesia-alumina spinel powder has a purity of 99.9% or more and a particle size of 20-500 nm.
6. The method according to any one of claims 1 to 5, wherein the particle size of the calcium fluoride powder is 100 to 1000nm, and the particle size of the calcium fluoride single crystal particles is 100 μm to 300 μm.
7. The preparation method according to any one of claims 1 to 6, wherein the mass concentration of the calcium fluoride burn is 100 to 5000ppm, preferably 100 to 3000ppm;
preferably, when the sintering aid is calcium fluoride powder, the mass concentration is 500-2000 ppm;
preferably, when the sintering aid is calcium fluoride single crystal particles, the mass concentration is 500 to 3000ppm.
8. The method according to any one of claims 1 to 7, wherein the dry forming comprises dry press forming or/and cold isostatic press forming, or the wet forming comprises slip casting or slip casting.
9. The method of manufacturing according to claims 1-8, wherein the shaped green body is pre-sintered prior to sintering;
the presintering is pressureless sintering, comprising: the pressureless sintering temperature is 1400-1700 ℃, and the sintering atmosphere is one of air or vacuum;
preferably, in the air atmosphere, adopting a pressureless sintering process, wherein the sintering temperature is 1400-1600 ℃, the heat preservation time is 3-6 hours, and the relative density of the obtained sintered body is controlled to be not lower than 96%;
preferably, the sintering temperature of the pressureless sintering process is 1500-1700 ℃ under vacuum atmosphere, the temperature is kept for 4-6 hours, and the relative density of the obtained sintered body is controlled to be not lower than 96%.
10. The method according to claim 9, wherein when the biscuit contains a binder, the biscuit is subjected to a paste ejection treatment and then to a pre-sintering;
the temperature of the glue discharging treatment is 600-800 ℃ and the heat preservation time is 3-6 hours, so as to discharge organic matters.
11. The method of any one of claims 1-10, wherein the sintering is performed by hot isostatic pressing; the technological parameters of the hot isostatic pressing sintering are as follows: the sintering temperature is 1500-1700 ℃; the heat preservation time is 1 to 6 hours; the pressurizing medium is argon or nitrogen, and the pressure is 120-200 MPa.
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| CN101269951A (en) * | 2008-04-15 | 2008-09-24 | 清华大学 | Supergravity assisted non-equilibrium preparation method of alumina-based transparent ceramic material |
| CN105377792A (en) * | 2013-05-13 | 2016-03-02 | 凯得力法国公司 | Spinel forming refractory compositions, their method of production and use thereof |
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| CN109790075A (en) * | 2016-10-05 | 2019-05-21 | 信越化学工业株式会社 | The manufacturing method of transparent spinel sintered body, optical component and transparent spinel sintered body |
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