CN102336570A - Preparation method of semi-transparent Ca<2+> doped SiAlON composite ceramic material and product prepared by using same - Google Patents
Preparation method of semi-transparent Ca<2+> doped SiAlON composite ceramic material and product prepared by using same Download PDFInfo
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Abstract
The invention relates to a preparation method of a semi-transparent Ca<2+> doped SiAlON composite ceramic material and a product prepared by using the same. The method comprises the following steps: mixing alpha-Si3N4, AlN, alpha-Al2O3 and CaCO3 which are selected according to a stoichiometric ratio in a general formula Cam/2Si(12-m-n)Al(m+n)OnN(16-n) so as to obtain a mixture A, wherein m is larger than or equal to 0.8 and less than or equal to 1.6, and n is larger than or equal to 1.0 and less than or equal to 2.0; then adding a mixture B to be mixed with the mixture A, wherein the mixture B is a mixture of AlN and alpha-Si3N4, the weight of the mixture B is 10-40wt% that of the mixture A, and the weight ratio of alpha-Si3N4 to AlN in the mixture B is (0-5):1; carrying ball milling, drying, screening with a 100-mesh sieve, sintering with a hot-press sintering or discharge plasma sintering method so as to obtain a sintering body; and cutting, grinding, polishing to form a mirror surface, so as to obtain the semi-transparent Ca<2+> doped SiAlON composite ceramic material. In the preparation method provided by the invention, a heat discharge plasma sintering method can be adopted, the hot-press sintering method can also be adopted, and sintering process is simple, has strong repeatability and low sintering temperature and is widely applied; and the prepared semi-transparent Ca<2+> doped SiAlON composite ceramic material has good infrared transmission performance and fracture toughness.
Description
Technical field
The present invention relates to translucent Ca
2+Ion doping SiAlO
NPreparing method of diphase ceramic material and products thereof belongs to the translucent ceramic material preparation field.
Background technology
Stupalith is being played the part of very important role usually because of having Chang Zuowei such as mechanical property and high-temperature stability structured material preferably in various fields such as Aeronautics and Astronautics, metallurgy, machineries.Along with the progress and development of science and technology, on the one hand increasingly high requirement has been proposed for the own institute of stupalith inherent mechanical property etc.; Also require material to possess 26S Proteasome Structure and Function property simultaneously on the other hand.At present, the structure of stupalith and function integration have become a new important development direction.Crystalline ceramics or semitransparent ceramics then are typical case's representatives of structure and function integration stupalith.Through lot of domestic and foreign scholar's effort, the transparent or semitransparent pottery of having reported at present has: Y
2O
3(CN1562886), YAG (CN1562880), MgAl
2O
4[J. Am. Ceram. Soc., 2,010 93 9 2656 ~ 66], Al
2O
3[Acta. Mater., 2,010 58 4527 ~ 35], AlN (Japanese ceramic industry association will, Vol. 93, and No. 9,1985, pp517-522; JP1199036A), AlON (US4686070A), MgO-Y
2O
3[J. Am. Ceram. Soc., 2010,93 11 3535-38] etc.
Compare with the transparent or semitransparent oxide ceramics of having reported, α-SiAlON pottery has more excellent heat-shock resistance and higher characteristics such as hardness; Compare with existing transparent or semitransparent nitride ceramics, α-SiAlON pottery has characteristics such as better oxidation-resistance, intensity and erosion resistance.α-SiAlON is α-Si
3N
4Sosoloid, with Si
3N
4Pottery is different to be, and the oxide stabilizer of being added (like CaO, MgO, Y
2O
3) at high temperature form instantaneous liquid phase with the oxide compound of silicon nitride surface and promote densification, these liquid phases progressively get at holding stage can play the effect that purifies crystal boundary in the lattice.α-SiAlON pottery is studied as structured material always and is used for a long time, and the light transmission of α-SiAlON just obtains paying attention to gradually up to date.Wherein by Nd
3+[J. Eur. Ceram. Soc., 19,2349-57 (1997)], Lu
3+[J. Am. Ceram. Soc., 2,004 87 4 714 ~ 716], Gd
3+[J. Am. Ceram. Soc., 87 [4] 730-32 (2004)], Yb
3+[Mater. Lett., 62,4535-38 (2008)], Y
3+The stable translucent α-SiAlON stupalith of [Mater. Lett., 58,1985-88 (2004)] plasma all has the research report.Yet, on the one hand, because the HMP of rare earth oxide makes the sintering temperature of these α-SiAlON higher (generally above 1800 ℃); On the other hand, because the out-shell electron of rare earth ion excites generation transition down at the incident light of specific wavelength mostly, thereby cause α-SiAlON to absorb, and then influence its optical transmittance in the selection of infrared band.In fact, alkali or alkaline earth metal ion Li
+, Mg
2+And Ca
2+Also use always as stabilizing ion and prepare α-SiAlON pottery.At present, adopt the discharge plasma sintering to prepare a kind of Mg of mixing
2+SiAlON semitransparent ceramics [J. Am. Ceram. Soc., 90 [5] 1647-49 (2007)], although it has avoided the infrared band absorption, sintering temperature is still higher.Mix Li and adopt the discharge plasma flash sintering method under relatively low temperature, to prepare equally
+α-SiAlON pottery [J. Am. Ceram. Soc., 93 [11] 3549-51 (2010)], but lower (3.0 MPam only of its fracture toughness property
1/2) and comparatively harsh to processing condition.Relative Li
+And Mg
2+Adulterated SiAlON pottery, Ca
2+Doped alpha-SiAlON realizes densification more easily, and sintering process is required lower (just can realize densification fully like pressureless sintering).And only by single ion Ca
2+The semitransparent ceramics of doped alpha-SiAlON does not at home and abroad also appear in the newspapers.In addition, because single-phase α-fracture toughness property of SiAlON pottery is generally lower, therefore preparation is to lead and the SiAlON complex phase semitransparent ceramics that contains other column crystals has more practical significance with α-SiAlON.
Summary of the invention
Technical problem to be solved by this invention provides translucent Ca
2+Preparing method of doping SiAlON diphase ceramic material and products thereof.The present invention can adopt hot pressed sintering or discharge plasma sintering, and technology is simple, and repeatable strong, sintering temperature is low, can realize suitability for industrialized production in batches.The stupalith that makes is complete fine and close translucent Ca
2+Doping SiAlON diphase ceramic material has excellent infrared light transmission performance and fracture toughness property.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is:
Translucent Ca
2+The preparation method of doping SiAlON diphase ceramic material is characterized in that it comprises the steps:
(1) according to general formula Ca
M/2Si
12-m-nAl
M+nO
nN
16-n, wherein the stoichiometric ratio of 0.8≤m≤1.6,1.0≤n≤2.0 is chosen α-Si
3N
4, AlN, α-Al
2O
3And CaCO
3, mix, obtain mixture A, add mixture B then, mix, described mixture B is AlN and α-Si
3N
4Mixture, wherein: the weight of mixture B is 10 ~ 40wt% of mixture A weight, α-Si among the mixture B
3N
4With the weight ratio of AlN be 0 ~ 5:1;
(2) mixture that step (1) is obtained is dispersion medium with the absolute ethyl alcohol, and ball milling at least 24 hours gets slurry;
(3) the slurry rotary evaporation that step (2) is obtained is dry, and vacuum-drying 24h at least grinds then, crosses 100 mesh sieves, obtains screen underflow;
(4) screen underflow after step (3) is sieved adopts hot pressed sintering or discharge plasma sintering method to carry out sintering, and described hot pressed sintering is that screen underflow is put into hot-pressed sintering furnace, is not less than 30MPa and N at sintering pressure
2Protection down is warming up to 950 ~ 1050 ℃ of insulation 10 ~ 60min with the temperature rise rate of 5 ~ 30 ℃/min, and the temperature rise rate with 5 ~ 20 ℃/min was warming up to 1600 ~ 1850 ℃ of sintering 0.5 ~ 2 hour then, and furnace cooling obtains sintered compact; Described discharge plasma sintering is that screen underflow is put into the discharge plasma sintering stove, is not less than 30MPa and N at sintering pressure
2Protection down is warming up to 950 ~ 1050 ℃ of insulation 1 ~ 2min with the temperature rise rate of 50 ~ 500 ℃/min, and the temperature rise rate with 50 ~ 500 ℃/min rises to 1600 ~ 1850 ℃ of insulation 0 ~ 20min then, and furnace cooling obtains sintered compact;
(5) sintered compact that step (4) is obtained cuts, grinds, is polished to minute surface, obtains translucent Ca
2+Ion doping SiAlON diphase ceramic material.
Press such scheme, the ball milling described in the step (2) is with Si
3N
4Ball is a ball-milling medium, and ball-to-powder weight ratio is 4:1.
Press such scheme, said α-Si
3N
4Oxygen level≤1.6wt%, median size≤0.2 μ m.
Press such scheme, oxygen level≤1.0wt% of said AlN, median size≤0.8 μ m.
Press such scheme, said α-Al
2O
3Purity purity>99.5%, median size≤500nm.
Press such scheme, said CaCO
3Purity purity>99.5%, median size≤500nm.
Press such scheme, said N
2N under the protection
2Pressure is 0.01 ~ 0.1MPa.
Principle of the present invention is: through Si
3N
4-AlN-Al
2O
3Composition points in-CaO phasor design α-SiAlON plane, also extra on this basis interpolation AlN and Si
3N
4Mixture, total composition points is positioned under α-SiAlON plane, help reducing the intergranular glass content, thereby reduce glassy phase scattering of light.
Useful result of the present invention: 1, the present invention can adopt hot discharge plasma sintering, also can adopt hot pressed sintering to prepare translucent Ca
2+Doping SiAlON diphase ceramic material, technology is simple, and is repeatable strong, widely applicable, sintering temperature low (can be low to moderate 1600 ℃); 2, prepared fine and close translucent Ca
2+Stablize the SiAlON diphase ceramic material and have good infrared transmission performance and fracture toughness property, this translucent Ca
2+Stablize the SiAlON diphase ceramic material and can reach 62%, and can to regulate its fracture toughness property through design of components be 4-5.6MPam at infrared band 1.0-5.0 μ m maximum transmission
1/2
Description of drawings
Fig. 1 is prepared translucent Ca in the embodiment of the invention 1
2+Stablize the XRD spectra of SiAlON diphase ceramic material;
Fig. 2 is prepared translucent Ca in the embodiment of the invention 1
2+Stablize the stereoscan photograph of SiAlON diphase ceramic material;
Fig. 3 is prepared translucent Ca in the embodiment of the invention 1
2+Stablize the straight line transmitance of SiAlON diphase ceramic material;
Fig. 4 is prepared translucent Ca in the embodiment of the invention 1
2+Stablize the effect photo of SiAlON diphase ceramic material.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with accompanying drawing and embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
With oxygen level is α-Si of 1.5 wt%
3N
4, oxygen level is the AlN of 1.0 wt%, α-Al
2O
3, CaCO
3Be raw material, according to Ca
M/2Si
12-m-nAl
M+nO
nN
16-n(m=0.8, stoichiometric ratio n=1.0) is chosen α-Si that gross weight is 50g
3N
4, AlN, α-Al
2O
3, CaCO
3Raw material mixes, and in this mixture extra adding 5g AlN, above-mentioned raw materials is mixed in Plastic Bottle, with Si
3N
4Ball is a ball-milling medium, and ball material mass ratio is 4:1, adds the 400ml absolute ethyl alcohol, and roller ball mill 24 hours gets slurry; With slurry 60 ℃ of rotation evaporates to dryness in Rotary Evaporators, put into vacuum drying oven vacuum-drying 24h at least then, take out again, grind 20min, cross 100 mesh sieves, get screen underflow; With the diameter of packing into of the screen underflow after sieving is in the graphite jig of 48mm, puts into hot-pressed sintering furnace then, at N
2Protection and sintering pressure are under the condition of 30MPa, said N
2Pressure is 0.1MPa, rises to 950 ℃ of insulation 10min with the temperature rise rate of 30 ℃/min, and the temperature rise rate with 5 ℃/min rises to 1600 ℃ then, and heat preservation sintering 1 hour is again with the stove naturally cooling; Cooled sintered compact is obtained translucent Ca after grinding, polishing
2+Doping SiAlON ceramic body (see figure 4).
The translucent Ca that present embodiment is obtained
2+Doping SiAlON diphase ceramic material carries out XRD test (see figure 1), and Fig. 1 explanation: prepared material is mainly Ca-α-SiAlON, also contains a spot of β-SiAlON and AlN polytype 21R.
Carry out SEM test (see figure 2), Fig. 2 explanation: prepared material is mainly equiax crystal, and homogeneous grain size also contains the less column crystal of a small amount of length-to-diameter ratio.
Carry out straight line transmission measurement (see figure 3), Fig. 3 explanation: prepared material has higher transmittance near infrared region, and the sample that the 0.5mm for preparing is thick is 50% at the infrared band maximum transmission, and adopting pressing in method to record fracture toughness property is 5.0 MPam
1/2
Embodiment 2:
With oxygen level is α-Si of 1.5 wt%
3N
4, oxygen level is the AlN of 1.0 wt%, α-Al
2O
3, CaCO
3Be raw material, according to Ca
M/2Si
12-m-nAl
M+nO
nN
16-n(m=0.8, stoichiometric ratio n=1.0) is chosen α-Si that gross weight is 50g
3N
4, AlN, α-Al
2O
3, CaCO
3Raw material, and in this mixture extra adding 20g AlN, above-mentioned raw materials is mixed in Plastic Bottle, with Si
3N
4Ball is a ball-milling medium, and ball-to-powder weight ratio is 4:1, adds the 400ml absolute ethyl alcohol, and roller ball mill 24 hours gets slurry; With slurry 60 ℃ of rotation evaporates to dryness in Rotary Evaporators, put into vacuum drying oven vacuum-drying 24h at least then, take out again, grind 20min, cross 100 mesh sieves, get screen underflow; With the diameter of packing into of the screen underflow after sieving is in the graphite jig of 48mm, puts into hot-pressed sintering furnace then, at N
2Protection and sintering pressure are under the condition of 30MPa, said N
2Pressure is 0.05MPa, rises to 950 ℃ of insulation 10min with the temperature rise rate of 30 ℃/min, and the temperature rise rate with 5 ℃/min rises to 1600 ℃ then, and heat preservation sintering 1 hour is again with the stove naturally cooling; Cooled sintered compact is obtained translucent Ca after grinding, polishing
2+Doping SiAlON ceramic body.
Through measuring, ceramic block also contains a spot of β-SiAlON and AlN polytype 21R for being mainly Ca-α-SiAlON.The sample that the 0.5mm for preparing is thick is 62% at the infrared band maximum transmission, and adopting pressing in method to record fracture toughness property is 4.8MPam
1/2
Embodiment 3:
With oxygen level is α-Si of 1.5 wt%
3N
4, oxygen level is the AlN of 1.0 wt%, α-Al
2O
3, CaCO
3Be raw material, according to Ca
M/2Si
12-m-nAl
M+nO
nN
16-n(m=1.6, stoichiometric ratio n=2.0) is chosen α-Si that gross weight is 50g
3N
4, AlN, α-Al
2O
3, CaCO
3Raw material, and in this mixture extra adding 16g α-Si
3N
4Mixture with 4g AlN mixes above-mentioned raw materials in Plastic Bottle, with Si
3N
4Ball is a ball-milling medium, and ball-to-powder weight ratio is 4:1, adds the 400ml absolute ethyl alcohol, and roller ball mill 24 hours gets slurry; With slurry 60 ℃ of rotation evaporates to dryness in Rotary Evaporators, put into vacuum drying oven vacuum-drying 24h at least then, take out again, grind 20min, cross 100 mesh sieves, get screen underflow; With the diameter of packing into of the screen underflow after sieving is in the graphite jig of 48mm, puts into hot-pressed sintering furnace then, at N
2Protection and sintering pressure are under the condition of 30MPa, said N
2Pressure is 0.01MPa, rises to 950 ℃ of insulation 10min with the temperature rise rate of 30 ℃/min, and the temperature rise rate with 5 ℃/min rises to 1600 ℃ then, and heat preservation sintering 1 hour is again with the stove naturally cooling; Cooled sintered compact is obtained translucent Ca after grinding, polishing
2+Stablize the SiAlON ceramic body.
Through measuring, ceramic block also contains a spot of β-SiAlON and AlN polytype 12H for being mainly Ca-α-SiAlON.The thick sample of 0.5mm of preparation is 43% at the infrared band maximum transmission, and adopting pressing in method to record fracture toughness property is 4.0MPam
1/2
Embodiment 4:
With oxygen level is α-Si of 1.5 wt%
3N
4, oxygen level is the AlN of 1.0 wt%, α-Al
2O
3, CaCO
3Be raw material, according to Ca
M/2Si
12-m-nAl
M+nO
nN
16-n(m=1.0, stoichiometric ratio n=1.5) is chosen α-Si that gross weight is 50g
3N
4, AlN, α-Al
2O
3, CaCO
3Raw material, and in this mixture extra adding 10g α-Si
3N
4Mixture with 10g AlN mixes above-mentioned raw materials in Plastic Bottle, with Si
3N
4Ball is a ball-milling medium, and ball-to-powder weight ratio is 4:1, adds the 400ml absolute ethyl alcohol, and roller ball mill 24 hours gets slurry; With slurry 60 ℃ of rotation evaporates to dryness in Rotary Evaporators, put into vacuum drying oven vacuum-drying 24h at least then, take out again, grind 20min, cross 100 mesh sieves, get screen underflow; With the diameter of packing into of the screen underflow after sieving is in the graphite jig of 48mm, puts into hot-pressed sintering furnace then, at N
2Protection and sintering pressure are under the condition of 30MPa, said N
2Pressure is 0.1MPa, rises to 950 ℃ of insulation 60min with the temperature rise rate of 10 ℃/min, and the temperature rise rate with 5 ℃/min rises to 1850 ℃ then, and heat preservation sintering 1 hour is again with the stove naturally cooling; Cooled sintered compact is obtained translucent Ca after grinding, polishing
2+Doping SiAlON ceramic body.
Through measuring, ceramic block also contains a spot of AlN polytype for being mainly Ca-α-SiAlON.The sample that the 0.5mm for preparing is thick is 45% at the infrared band maximum transmission, and adopting pressing in method to record fracture toughness property is 4.5MPam
1/2
Embodiment 5:
With oxygen level is α-Si of 1.5 wt%
3N
4, oxygen level is the AlN of 1.0 wt%, α-Al
2O
3, CaCO
3Be raw material, according to Ca
M/2Si
12-m-nAl
M+nO
nN
16-n(m=1.6, stoichiometric ratio n=2.0) is chosen α-Si that gross weight is 50g
3N
4, AlN, α-Al
2O
3, CaCO
3Raw material, and in this mixture extra adding 7.5g α-Si
3N
4Mixture with 7.5g AlN mixes above-mentioned raw materials in Plastic Bottle, with Si
3N
4Ball is a ball-milling medium, and ball-to-powder weight ratio is 4:1, adds the 400ml absolute ethyl alcohol, and roller ball mill 24 hours gets slurry; With slurry 60 ℃ of rotation evaporates to dryness in Rotary Evaporators, put into vacuum drying oven vacuum-drying 24h at least then, take out again, grind 20min, cross 100 mesh sieves, get screen underflow; With the diameter of packing into of the screen underflow after sieving is in the graphite jig of 48mm, puts into hot-pressed sintering furnace then, at N
2Protection and sintering pressure are under the condition of 30MPa, said N
2Pressure is 0.1MPa, rises to 950 ℃ of insulation 30min with the temperature rise rate of 20 ℃/min, and the temperature rise rate with 10 ℃/min rises to 1700 ℃ then, and heat preservation sintering 1 hour is again with the stove naturally cooling; Cooled sintered compact is obtained translucent Ca after grinding, polishing
2+Doping SiAlON ceramic body.
Through measuring, ceramic block also contains a spot of β-SiAlON and AlN polytype 8H for being mainly Ca-α-SiAlON.The thick sample of 0.5mm of preparation is 34% at the infrared band maximum transmission, and adopting pressing in method to record fracture toughness property is 5.6MPam
1/2
Embodiment 6:
With oxygen level is α-Si of 1.5 wt%
3N
4, oxygen level is the AlN of 1.0 wt%, α-Al
2O
3, CaCO
3Be raw material, according to Ca
M/2Si
12-m-nAl
M+nO
nN
16-n(m=1.2, stoichiometric ratio n=1.5) is chosen α-Si that gross weight is 50g
3N
4, AlN, α-Al
2O
3, CaCO
3Raw material, and in this mixture extra adding 10g α-Si
3N
4Mixture with 5g AlN mixes above-mentioned raw materials in Plastic Bottle, with Si
3N
4Ball is a ball-milling medium, and ball-to-powder weight ratio is 4:1, adds the 400ml absolute ethyl alcohol, and roller ball mill 24 hours gets slurry; With slurry 60 ℃ of rotation evaporates to dryness in Rotary Evaporators, put into vacuum drying oven vacuum-drying 24h at least then, take out again, grind 20min, cross 100 mesh sieves, get screen underflow; With the diameter of packing into of the screen underflow after sieving is in the graphite jig of 48mm, puts into hot-pressed sintering furnace then, at N
2Protection and sintering pressure are under the condition of 30MPa, said N
2Pressure is 0.1MPa, rises to 950 ℃ of insulation 10min with the temperature rise rate of 30 ℃/min, and the temperature rise rate with 20 ℃/min rises to 1700 ℃ then, and heat preservation sintering 1 hour is again with the stove naturally cooling; Cooled sintered compact is obtained translucent Ca after grinding, polishing
2+Stablize the SiAlON ceramic body.
Through measuring, ceramic block also contains a spot of β-SiAlON and AlN polytype 8H for being mainly Ca-α-SiAlON.The thick sample of 0.5mm of preparation is 57% at the infrared band maximum transmission, and adopting pressing in method to record fracture toughness property is 5.1MPam
1/2
Embodiment 7:
With oxygen level is α-Si of 1.5 wt%
3N
4, oxygen level is the AlN of 1.0 wt%, α-Al
2O
3, CaCO
3Be raw material, according to Ca
M/2Si
12-m-nAl
M+nO
nN
16-n(m=1.2, stoichiometric ratio n=1.5) is chosen α-Si that gross weight is 50g
3N
4, AlN, α-Al
2O
3, CaCO
3Raw material, and in this mixture extra adding 15g α-Si
3N
4Mixture with 5g AlN mixes above-mentioned raw materials in Plastic Bottle, with Si
3N
4Ball is a ball-milling medium, and ball-to-powder weight ratio is 4:1, adds the 400ml absolute ethyl alcohol, and roller ball mill 24 hours gets slurry; With slurry 60 ℃ of rotation evaporates to dryness in Rotary Evaporators, put into vacuum drying oven vacuum-drying 24h at least then, take out again, grind 20min, cross 100 mesh sieves, get screen underflow; With the diameter of packing into of the screen underflow after sieving is in the graphite jig of 48mm, puts into hot-pressed sintering furnace then, at N
2Protection and sintering pressure are under the condition of 30MPa, said N
2Pressure is 0.1MPa, rises to 950 ℃ of insulation 30min with the temperature rise rate of 20 ℃/min, and the temperature rise rate with 10 ℃/min rises to 1700 ℃ then, and heat preservation sintering 2 hours is again with the stove naturally cooling; Cooled sintered compact is obtained translucent Ca after grinding, polishing
2+Doping SiAlON ceramic body.
Through measuring, ceramic block also contains a spot of β-SiAlON and AlN polytype 21R for being mainly Ca-α-SiAlON.The thick sample of 0.5mm of preparation is 50% at the infrared band maximum transmission, and adopting pressing in method to record fracture toughness property is 4.6MPam
1/2
Embodiment 8:
With oxygen level is α-Si of 1.5 wt%
3N
4, oxygen level is the AlN of 1.0 wt%, α-Al
2O
3, CaCO
3Be raw material, according to Ca
M/2Si
12-m-nAl
M+nO
nN
16-n(m=1.2, stoichiometric ratio n=1.5) is chosen α-Si that gross weight is 50g
3N
4, AlN, α-Al
2O
3, CaCO
3Raw material, and in this mixture extra adding 1.5g α-Si
3N
4Mixture with 13.5 g AlN mixes above-mentioned raw materials in Plastic Bottle, with Si
3N
4Ball is a ball-milling medium, and ball-to-powder weight ratio is 4:1, adds the 400ml absolute ethyl alcohol, and roller ball mill 24 hours gets slurry; With slurry 60 ℃ of rotation evaporates to dryness in Rotary Evaporators, put into vacuum drying oven vacuum-drying 24h at least then, take out again, grind 20min, cross 100 mesh sieves, get screen underflow; With the diameter of packing into of the screen underflow after sieving is in the graphite jig of 48mm, puts into hot-pressed sintering furnace then, at N
2Protection and sintering pressure are under the condition of 10MPa, said N
2Pressure is 0.1MPa, rises to 1050 ℃ of insulation 30min with the temperature rise rate of 20 ℃/min, and the temperature rise rate with 15 ℃/min rises to 1700 ℃ then, and heat preservation sintering 2 hours is again with the stove naturally cooling; Cooled sintered compact is obtained translucent Ca after grinding, polishing
2+Doping SiAlON ceramic body.
Through measuring, ceramic block also contains a spot of β-SiAlON and AlN polytype 21R for being mainly Ca-α-SiAlON.The thick sample of 0.5mm of preparation is 47% at the infrared band maximum transmission, and adopting pressing in method to record fracture toughness property is 4.8MPam
1/2
Embodiment 9:
With oxygen level is α-Si of 1.5 wt%
3N
4, oxygen level is the AlN of 1.0 wt%, α-Al
2O
3, CaCO
3Be raw material, according to Ca
M/2Si
12-m-nAl
M+nO
nN
16-n(m=1.2, stoichiometric ratio n=1.5) is chosen α-Si that gross weight is 50g
3N
4, AlN, α-Al
2O
3, CaCO
3Raw material, and in this mixture extra adding 10g α-Si
3N
4Mixture with 5g AlN mixes above-mentioned raw materials in Plastic Bottle, with Si
3N
4Ball is a ball-milling medium, and ball-to-powder weight ratio is 4:1, adds the 400ml absolute ethyl alcohol, and roller ball mill 24 hours gets slurry; With slurry 60 ℃ of rotation evaporates to dryness in Rotary Evaporators, put into vacuum drying oven vacuum-drying 24h at least then, take out again, grind 20min, cross 100 mesh sieves, get screen underflow; With the diameter of packing into of the screen underflow after sieving is in the graphite jig of 20mm, puts into the discharge plasma sintering stove then, at N
2Protection and sintering pressure are under the condition of 30MPa, said N
2Pressure is 0.01MPa, is warming up to 1050 ℃ of insulation 1min with the temperature rise rate of 50 ℃/min, and the temperature rise rate with 50 ℃/min is warming up to 1850 ℃ then, at once with the stove naturally cooling; Cooled sintered compact is obtained translucent Ca after grinding, polishing
2+Doping SiAlON ceramic body.
Through measuring, ceramic block also contains a spot of β-SiAlON and AlN polytype 21R for being mainly Ca-α-SiAlON.The thick sample of 0.5mm of preparation is 46% at the infrared band maximum transmission, and adopting pressing in method to record fracture toughness property is 4.8MPam
1/2
Embodiment 10:
With oxygen level is α-Si of 1.5 wt%
3N
4, oxygen level is the AlN of 1.0 wt%, α-Al
2O
3, CaCO
3Be raw material, according to Ca
M/2Si
12-m-nAl
M+nO
nN
16-n(m=1.2, stoichiometric ratio n=1.5) is chosen α-Si that gross weight is 50g
3N
4, AlN, α-Al
2O
3, CaCO
3Raw material, and in this mixture extra adding 15g α-Si
3N
4Mixture with 5g AlN mixes above-mentioned raw materials in Plastic Bottle, with Si
3N
4Ball is a ball-milling medium, and ball-to-powder weight ratio is 4:1, adds the 400ml absolute ethyl alcohol, and roller ball mill 24 hours gets slurry; With slurry 60 ℃ of rotation evaporates to dryness in Rotary Evaporators, put into vacuum drying oven vacuum-drying 24h at least then, take out again, grind 20min, cross 100 mesh sieves, get screen underflow; With the diameter of packing into of the screen underflow after sieving is in the graphite jig of 20mm, puts into the discharge plasma sintering stove then, at N
2Protection and sintering pressure are under the condition of 30MPa, said N
2Pressure is 0.05MPa, is warming up to 950 ℃ of insulation 1min with the temperature rise rate of 200 ℃/min, and the temperature rise rate with 300 ℃/min is warming up to 1600 ℃ of sintering 10min then, again with the stove naturally cooling; Cooled sintered compact is obtained translucent Ca after grinding, polishing
2+Doping SiAlON ceramic body.
Through measuring, ceramic block also contains a spot of β-SiAlON and AlN polytype 21R for being mainly Ca-α-SiAlON.The thick sample of 0.5mm of preparation is 51% at the infrared band maximum transmission, and adopting pressing in method to record fracture toughness property is 5.0MPam
1/2
Embodiment 11:
With oxygen level is α-Si of 1.5 wt%
3N
4, oxygen level is the AlN of 1.0 wt%, α-Al
2O
3, CaCO
3Be raw material, according to Ca
M/2Si
12-m-nAl
M+nO
nN
16-n(m=1.2, stoichiometric ratio n=1.5) is chosen α-Si that gross weight is 50g
3N
4, AlN, α-Al
2O
3, CaCO
3Raw material, and in this mixture extra adding 1.5g α-Si
3N
4Mixture with 13.5 g AlN mixes above-mentioned raw materials in Plastic Bottle, with Si
3N
4Ball is a ball-milling medium, and ball-to-powder weight ratio is 4:1, adds the 400ml absolute ethyl alcohol, and roller ball mill 24 hours gets slurry; With slurry 60 ℃ of rotation evaporates to dryness in Rotary Evaporators, put into vacuum drying oven vacuum-drying 24h at least then, take out again, grind 20min, cross 100 mesh sieves, get screen underflow; With the diameter of packing into of the screen underflow after sieving is in the graphite jig of 20mm, puts into the discharge plasma sintering stove then, at N
2Protection and sintering pressure are under the condition of 10MPa, said N
2Pressure is 0.1MPa, is warming up to 1000 ℃ of insulation 1min with the temperature rise rate of 500 ℃/min, and the temperature rise rate with 500 ℃/min is warming up to 1750 ℃ of sintering 20min then, again with the stove naturally cooling; Cooled sintered compact is obtained translucent Ca after grinding, polishing
2+Doping SiAlON ceramic body.
Through measuring, ceramic block also contains a spot of β-SiAlON and AlN polytype 21R for being mainly Ca-α-SiAlON.The thick sample of 0.5mm of preparation is 62% at the infrared band maximum transmission, and adopting pressing in method to record fracture toughness property is 4.0MPam
1/2
The concrete consumption of each raw material sees the following form 1 among the foregoing description 1-11:
Raw material consumption among each embodiment of table 1
| Embodiment | Si 3N 4Raw material/g | AlN raw material/g | Al 2O 3Raw material/g | CaCO
3Raw material/ |
| 1，2 | 41.6 | 6.2 | 0.2 | 2.0 |
| 3，5 | 33.3 | 10.8 | 2.1 | 3.8 |
| 4 | 38.4 | 7.7 | 1.5 | 2.4 |
| 6-11 | 37.6 | 8.6 | 1.2 | 2.6 |
Claims (8)
1. translucent Ca
2+The preparation method of doping SiAlON diphase ceramic material is characterized in that it comprises the steps:
(1) according to general formula Ca
M/2Si
12-m-nAl
M+nO
nN
16-n, wherein the stoichiometric ratio of 0.8≤m≤1.6,1.0≤n≤2.0 is chosen α-Si
3N
4, AlN, α-Al
2O
3And CaCO
3, mix, obtain mixture A, add mixture B then, mix, described mixture B is AlN and α-Si
3N
4Mixture, wherein: the weight of mixture B is 10 ~ 40 wt% of mixture A weight, α-Si among the mixture B
3N
4With the weight ratio of AlN be 0 ~ 5:1;
(2) mixture that step (1) is obtained is dispersion medium with the absolute ethyl alcohol, and ball milling at least 24 hours gets slurry;
(3) the slurry rotary evaporation that step (2) is obtained is dry, and vacuum-drying 24h at least grinds then, crosses 100 mesh sieves, obtains screen underflow;
(4) screen underflow after step (3) is sieved adopts hot pressed sintering or discharge plasma sintering method to carry out sintering, and described hot pressed sintering is that screen underflow is put into hot-pressed sintering furnace, is not less than 30MPa and N at sintering pressure
2Protection down is warming up to 950 ~ 1050 ℃ of insulation 10 ~ 60min with the temperature rise rate of 5 ~ 30 ℃/min, and the temperature rise rate with 5 ~ 20 ℃/min was warming up to 1600 ~ 1850 ℃ of sintering 0.5 ~ 2 hour then, and furnace cooling obtains sintered compact; Described discharge plasma sintering is that screen underflow is put into the discharge plasma sintering stove, is not less than 30MPa and N at sintering pressure
2Protection down is warming up to 950 ~ 1050 ℃ of insulation 1 ~ 2min with the temperature rise rate of 50 ~ 500 ℃/min, and the temperature rise rate with 50 ~ 500 ℃/min is warming up to 1600 ~ 1850 ℃ then, sintering 0 ~ 20min, and furnace cooling obtains sintered compact;
(5) sintered compact that step (4) is obtained cuts, grinds, is polished to minute surface, obtains translucent Ca
2+Ion doping SiAlON diphase ceramic material.
2. translucent Ca according to claim 1
2+The preparation method of doping SiAlON diphase ceramic material is characterized in that: the ball milling described in the step (2) is with Si
3N
4Ball is a ball-milling medium, and ball-to-powder weight ratio is 4:1.
3. translucent Ca according to claim 1
2+The preparation method of doping SiAlON diphase ceramic material is characterized in that: said α-Si
3N
4Oxygen level≤1.6wt%, median size≤0.2 μ m.
4. translucent Ca according to claim 1
2+The preparation method of doping SiAlON diphase ceramic material is characterized in that: oxygen level≤1.0wt% of said AlN, median size≤0.8 μ m.
5. translucent Ca according to claim 1
2+The preparation method of doping SiAlON diphase ceramic material is characterized in that: said α-Al
2O
3Purity purity>99.5%, median size≤500nm.
6. translucent Ca according to claim 1
2+The preparation method of doping SiAlON diphase ceramic material is characterized in that: said CaCO
3Purity purity>99.5%, median size≤500nm.
7. translucent Ca according to claim 1
2+The preparation method of doping SiAlON diphase ceramic material is characterized in that: said N
2N under the protection
2Pressure is 0.01 ~ 0.1MPa.
8. translucent Ca
2+Doping SiAlON diphase ceramic material is characterized in that: it is translucent Ca according to claim 1
2+The preparation method of doping SiAlON diphase ceramic material prepares.
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| CN104829236A (en) * | 2015-04-14 | 2015-08-12 | 苏州工业园区晶冠瓷材料科技有限公司 | Preparation method of SiAlON transparent ceramic phosphor |
| CN109020558A (en) * | 2018-09-07 | 2018-12-18 | 安徽理工大学 | A kind of high-power warm white solid-state lighting SiAlON fluorescent transparent ceramics and preparation method thereof |
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| CN101269970A (en) * | 2008-05-14 | 2008-09-24 | 哈尔滨工业大学 | Alpha--sialon ceramic doping composite rare earth and preparation method thereof |
| CN101851098A (en) * | 2010-05-18 | 2010-10-06 | 武汉理工大学 | Method for fast preparing translucent Li-alpha-SiAlON ceramic material |
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| CN101851098A (en) * | 2010-05-18 | 2010-10-06 | 武汉理工大学 | Method for fast preparing translucent Li-alpha-SiAlON ceramic material |
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| CN104829236A (en) * | 2015-04-14 | 2015-08-12 | 苏州工业园区晶冠瓷材料科技有限公司 | Preparation method of SiAlON transparent ceramic phosphor |
| CN109020558A (en) * | 2018-09-07 | 2018-12-18 | 安徽理工大学 | A kind of high-power warm white solid-state lighting SiAlON fluorescent transparent ceramics and preparation method thereof |
| CN109020558B (en) * | 2018-09-07 | 2021-11-12 | 安徽理工大学 | SiAlON fluorescent transparent ceramic for high-power warm white light solid-state lighting and preparation method thereof |
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