CN1228273C - Semi-transparent hard Sailong ceramics and its preparation - Google Patents

Semi-transparent hard Sailong ceramics and its preparation Download PDF

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CN1228273C
CN1228273C CN 02160735 CN02160735A CN1228273C CN 1228273 C CN1228273 C CN 1228273C CN 02160735 CN02160735 CN 02160735 CN 02160735 A CN02160735 A CN 02160735A CN 1228273 C CN1228273 C CN 1228273C
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oxide
ceramic material
sialon
transparent hard
sialon ceramic
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CN1424284A (en
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刘茜
归林华
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Abstract

The present invention relates to a semitransparent hard sialon ceramic material and a making method thereof, which belongs to the field of ceramics. The present invention is characterized in that the composition general formula of the sialon ceramic is MxNySi(12-m-n)Al(m+n)OnN(16-n), wherein M is either Ca or Sr, N comprises one of Y, Nd, Dy and Yb or any combination of (Y+Nd), (Y+Dy) and (Y+Yb), X is larger than 0 and smaller than 0.75, 2X+3Y equals to m, m is larger than 1.0 and smaller than 2.5, and n is larger than 0.9 and smaller than 2.0. The sialon ceramic material is made by uniaxial hot pressing, and the method comprises two stages of temperature rise and heat preservation, wherein the final hot pressing temperature is from 1550 to 1850 DEG C, the pressure is from 0.8 to 40Mpa, and the temperature is preserved for 30 to 120 minutes; a sintered sample has uniform light transmission and can be made with large size.

Description

Semi-transparent hard Sialon ceramic material and preparation method thereof
Technical field
The present invention relates to grand (Sialon) stupalith of a kind of semi-transparent hard match and preparation method thereof, relating to a kind of composition general formula or rather is M xN ySi 12-m-nAl M+nO nN 16-nGrand (Sialon) stupalith of a kind of semi-transparent hard match and preparation method thereof.Belong to the crystalline ceramics field.
Background technology
The grand Sialon of match was found in the synthetic product by Japan and Britain scientist first in early 1970s.Sialon is the transliteration of silicon (Si), aluminium (Al), oxygen (O) and 4 symbols of element combinations of nitrogen (N), its basic structural unit be (Si, Al) (O, N) 4Tetrahedron.α-Sialon and beta-Sialon be respectively have different crystal forms in the Sialon family two kinds of things mutually.
α-Sialon is α-Si 3N 4Sosoloid, can be abbreviated as α ', its structure and α-Si 3N 4Similar, chemical general formula is Me xSi 12-m-nAl M+nO nN 16-n(x≤2), wherein Me is Li 1+, Mg 2+, Ca 2+, Y 3+Or rare earth ion.The characteristics of α-Sialon phase are to have very high hardness and good heat-shock resistance, oxidation-resistance.Single-phase α-Sialon is difficult to be obtained, and often makes α '+β ' composite diphase material.Such material has been used to make the abrading-ball of ceramic bearing, wear ring and sand mill.
Beta-Sialon is β-Si 3N 4Sosoloid, be abbreviated as β ', its chemical general formula is Si 6-zAl zO zN 8-z(0＜z＜4.2), wherein z N replaced by O, and z Si replaced by Al simultaneously, thereby forms sosoloid and keep electric neutrality, do not form the point defect of any room or calking.Such material has high strength and high tenacity and sintering character preferably because of it, is used widely in industry, mainly as the point of a knife of cutting tool.
As for crystalline ceramics, by General Principle, the preparation more options of translucent ceramic material have optically isotropic cubic or equiax crystal section bar material, and need to use superfine powder, become high ceramic of compact body through hot pressing or HIP sintering again.With the development of powder technology and sintering technology, the development of non-oxidized substance semitransparent ceramics and exploitation also had report repeatly but in recent years.For example can be used as the existing many reports of transparent six side AlN pottery that radiator element, substrate and bag divide closure material.But the report of relevant Sialon crystalline ceramics is very few, if can be made into transparent or semitransparently, and this can enlarge its Application Areas undoubtedly.Day in 1999 disclosure special permission spy opens and discloses a kind of translucent Sialon sintered compact and preparation method thereof on the flat 11-343173.The composition general formula of related Sialon sintered compact is typical beta-Sialon: Si 6-zAl zO zN 8-z, z＜1.0 wherein.Its tissue of sintered body be the crystal boundary formed of Sialon principal crystalline phase and the oxide compound that contains yttrium or oxynitride mutually.Four-point bending intensity under the sample room temperature is greater than 1000MPa; Flexural strength under 1200 ℃ is greater than 600MPa.This Sialon preparation methods is greater than 10m in specific surface area 2Adding the 4-6wt% specific surface area in the Sialon matter powder of/g is 20m 2The Y that/g is above 2O 3Powder, normal pressure-sintered prior to 1650-1800 ℃ under the flowing nitrogen atmosphere behind dry-pressing formed or casting, be incubated 1-3 hour; Under the 150-190MPa nitrogen pressure, hip treatment under 1600-1700 ℃ of temperature makes the Sialon stupalith with light transmission, comes down to the beta-Sialon crystalline ceramics then.Obviously, the shortcoming that the patented technology of the disclosure special permission exists is that (1) use waits the static pressure treatment process after normal pressure-sintered again, technical sophistication, and to the equipment requirements height, preparation cost is corresponding higher; (2) only describe made sample and had light transmission under the visible light condition, both do not expressed transmitance, do not indicated the size of Sialon sample again.
Summary of the invention
The object of the present invention is to provide a kind of composition general formula to be: M xN ySi 12-m-nAl M+nO nN 16-n... Sialon transparent material (1).In the formula, M is a kind of among Ca or the Sr, N comprise a kind of among Y, Nd, Dy or the Yb or (Y+Nd), (Y+Dy) and any combination (Y+Yb); And 0.05 〉=x＞0,0.83＞y＞0.33 is arranged, 2x+3y=m, 2.0＞n＞0.9.
In fact, the expression formula Me of general formula (1) and α-Sialon xSi 12-m-nAl M+nO nN 16-nBe consistent, its only changes on component to some extent, make Me in α-Sialon component become valence mumber be 2 and valence mumber be two kinds of elements of 3 (M, N) compound, and the mol ratio of the two meets the relational expression of 2X+3Y=m.In phasor, form to select to drop on and draw ... the zone in (Fig. 1).
Semi-transparent hard Sialon ceramic material provided by the invention, concrete composition is:
(1) Ca 0.05(Y, Dy) 0.77Si 8.49Al 3.51O 1.1N 14.9, i.e. x=0.05, y=0.77, m=2.41, n=1.10;
(2) Sr 0.05(Y, Yb) 0.61Si 8.67Al 3.33O 1.4N 14.6, i.e. x=0.05, y=0.61, m=1.93, n=1.4.
Another object of the present invention provides the preparation method of a kind of general formula for the transparent Sialon pottery of (1).Concrete preparation process is: (1) is with a kind of or (yttrium oxide+Neodymium trioxide), (yttrium oxide+dysprosium oxide) in a kind of and yttrium oxide, Neodymium trioxide, dysprosium oxide or the ytterbium oxide in silicon nitride, aluminium nitride, aluminum oxide, calcium oxide or the strontium oxide, the arbitrary combination in (yttrium oxide+ytterbium oxide), press the component ratio batching of general formula (1), wet mixing, after drying, the granulation, hot pressed sintering.The ratio of grinding media to material of wet mixing is specially: powder: abrading-ball (Si 3N 4): ethanol=1 (g): 5 (g): 5 (ml), drying is carried out under 80-90 ℃ of condition, and granulation, sieve (80 order) are made the powder with certain flowability.(2) hot pressed sintering is that this mixed powder is filled in the graphite jig, under 0.8-40MPa mechanical pressure and 1500-1800 ℃ of temperature, carries out hot uniaxial pressing in flowing nitrogen atmosphere.At first sample is heated to 850-1250 ℃, and kept 30-60 minute, and then be heated to the highest sintering temperature 1500-1800 ℃, and kept 30-120 minute, then furnace cooling with 5-10 ℃/minute heat-up rate with 3-8 ℃/minute heat-up rate.Through said process, can make the semi-transparent hard Sialon ceramic material.
The overall dimension of Zhi Bei translucent Sialon ceramics sample is 70mm as stated above.Advantage of the present invention is conspicuous:
(1) raw material that uses is commercial goods chemical pure raw material;
(2) sintering process of Cai Yonging is general heat pressing process, need not hot isostatic apparatus, thereby cost descends greatly.
(3) the sintered sample printing opacity is even, can be made into the large size sample.
Description of drawings
Fig. 1 is that the concrete compositional range of sialon material provided by the invention (is used ... the zone of expression).
Fig. 2 is the audio-visual picture of transparent Sialon ceramics sample provided by the invention.
The sample size on the left side is diameter 70mm, thick 1mm; The sample size on the right side is diameter 25mm, thick 0.5mm.
Embodiment
Further illustrate substantive distinguishing features of the present invention and marked improvement by following specific embodiment and Comparative Examples.But the present invention only limits to described embodiment by no means.
Embodiment 1: with silicon nitride, and aluminium nitride, aluminum oxide, calcium oxide, yttrium oxide, dysprosium oxide raw material are pressed x=0.05, and y=0.77, m=2.41, n=1.10 are mixed with and consist of Ca 0.05(Y, Dy) 0.77Si 8.49Al 3.51O 1.1N 14.9Compound.Employing is ball milling blended method in ethanol medium, wherein powder: abrading-ball (Si 3N 4): ethanol=1 (g): 5 (g): 5 (ml), wet mixing is closed powder and be used for hot pressed sintering after 85 ℃ of dryings, granulation (80 order).This mixed powder is filled in the graphite jig, under 30MPa mechanical pressure and 1680 ℃ of temperature, in flowing nitrogen atmosphere, carries out hot uniaxial pressing, and kept 70 minutes, then furnace cooling.Through said process, can make the semi-transparent hard Sialon ceramic material.Concrete temperature rise rate is to be heated to 1150 ℃ with 5 ℃ of/minute heat-up rates earlier, is incubated 45 minutes, is warming up to 1680 ℃ with 8 ℃ of/minute speed again after the heating, sintering and insulation.
Embodiment 2
With silicon nitride, aluminium nitride, aluminum oxide, strontium oxide, yttrium oxide, ytterbium oxide raw material are pressed x=0.05, and y=0.61, m=1.93, n=1.4 are mixed with and consist of Sr 0.05(Y, Yb) 0.61Si 8.67Al 3.33O 1.4N 14.6Compound.Employing is ball milling blended method in ethanol medium, wherein powder: abrading-ball (Si 3N 4): ethanol=1 (g): 5 (g): 5 (ml), wet mixing is used for hot pressed sintering after closing powder drying, granulation.This mixed powder is filled in the graphite jig, under 20MPa mechanical pressure and 1740 ℃ of temperature, in flowing nitrogen atmosphere, carries out hot uniaxial pressing, and kept 80 minutes, then furnace cooling.Through said process, can make the semi-transparent hard Sialon ceramic material.All the other are with embodiment 1.
The major control factor of semi-transparent hard Sialon ceramic material preparation is to form and sintering process, is illustrated below by Comparative Examples.
Comparative Examples 1: with silicon nitride, aluminium nitride, aluminum oxide, calcium oxide, Neodymium trioxide raw material are pressed x=0.01, and y=0.33, m=1.01, n=1.7 are mixed with and consist of Ca 0.01Nd 0.33Si 9.29Al 2.71O 1.7N 14.3Compound.All the other processing modes are with embodiment 1.This mixed powder is filled in the graphite jig, under 30MPa mechanical pressure and 1800 ℃ of temperature, in flowing nitrogen atmosphere, carries out hot uniaxial pressing, and kept 45 minutes, then furnace cooling.The hard Sialon ceramic material that obtains through said process does not have light transmission.
Comparative Examples 2: with silicon nitride, aluminium nitride, aluminum oxide, strontium oxide, ytterbium oxide raw material are pressed x=0.01, and y=0.33, m=1.01, n=1.7 are mixed with and consist of Sr 0.01Yb 0.33Si 9.29Al 2.71O 1.7N 14.3Compound.All the other processing modes are with embodiment 1.This mixed powder is filled in the graphite jig, under 0.8-30MPa mechanical pressure and 1800 ℃ of temperature, in flowing nitrogen atmosphere, carries out hot uniaxial pressing, and kept 45 minutes, then furnace cooling.The hard Sialon ceramic material that obtains through said process does not have light transmission.
Comparative Examples 3: with silicon nitride, aluminium nitride, aluminum oxide, the dysprosium oxide raw material is pressed x=0, and y=0.35, m=1.05, n=1.7 are mixed with and consist of Dy 0.35Si 9.25Al 2.75O 1.7N 14.3Compound.All the other processing modes are with embodiment 1.This mixed powder is filled in the graphite jig, under 0.8-30MPa mechanical pressure and 1750 ℃ of temperature, in flowing nitrogen atmosphere, carries out hot uniaxial pressing, and kept 45 minutes, then furnace cooling.The hard Sialon ceramic material that obtains through said process does not have light transmission.
Relative embodiment 1,2, the oxides additive that adds in the Comparative Examples 1,2,3 is few, although corresponding raising sintering temperature, sample does not still present light transmission.
Embodiment and Comparative Examples be particular sheet relatively
Alkaline-earth oxide Rare earth oxide The stoicheiometry formula Sintering temperature (℃) Soaking time (m) Hot pressing pressure (MPa) Performance characterization
Light transmission Hardness (GPa)
Embodiment 1 CaO Y 2O 3 Dy 2O 3 Ca 0.05(Y，Dy) 0.77 Si 8.49Al 3.51O 1.1N 14.9 1680 70 30 Have 15
2 SrO Y 2O 3 Yb 2O 3 Sr 0.05(Y，Yb) 0.61 Si 8.67Al 3.33O 1.4N 14.6 1740 80 40 Have 18
Comparative Examples 1 CaO Nd 2O 3 Ca 0.01Nd 0.33 Si 9.29Al 2.71O 1.7N 14.3 1800 45 30 Do not have 17
2 SrO Yb 2O 3 Sr 0.01Yb 0.33 Si 9.29Al 2.71O 1.7N 14.3 1800 45 30 Do not have 21
3 ---- Dy 2O 3 Dy 0.35Si 9.25Al 2.75O 1.7N 14.3 1750 45 30 Do not have 19

Claims (5)

1, a kind of semi-transparent hard Sialon ceramic material, it is characterized in that forming general formula is M xN ySi 12-m-nAl M+nO nN 16-n, M is a kind of among Ca or the Sr in the formula, N comprises a kind of or Y+Nd, Y+Dy among Y, Nd, Dy or the Yb and any combination among the Y+Yb, and 0.05 〉=x＞0,0.83＞y＞0.33,2x+3y=m, 2.0＞n＞0.9.
2, by the described semi-transparent hard Sialon ceramic material of claim 1, it is characterized in that consisting of Ca 0.05(Y, Dy) 0. 77Si 8.49Al 3.51O 1.1N 14.9, i.e. x=0.05, y=0.77, m=2.41, n=1.10.
3, by the described semi-transparent hard Sialon ceramic material of claim 1, it is characterized in that consisting of Sr 0.05(Y, Yb) 0.61Si 8.67Al 3.33O 1.4N 14.6, i.e. x=0.05, y=0.61, m=1.93, n=1.4.
4, the method for preparation a kind of semi-transparent hard Sialon ceramic material as claimed in claim 1 comprises batching, wet mixing, drying, granulation and hot pressed sintering, it is characterized in that:
(1) with silicon nitride, aluminium nitride, aluminum oxide, a kind of in calcium oxide or the strontium oxide, and yttrium oxide, Neodymium trioxide, a kind of or yttrium oxide+Neodymium trioxide in dysprosium oxide or the ytterbium oxide, yttrium oxide+dysprosium oxide, yttrium oxide+ytterbium oxide are pressed M xN ySi 12-m-nAl M+nO nN 16-nGeneral formula component ratio batching, 0.05 〉=x in the formula＞0,0.83＞y＞0.33,2x+3y=m, 2.0＞n＞0.9;
(2) wet mixing condition is a powder: abrading-ball: ethanol=1g: 5g: 5ml;
(3) drying conditions 80-90 ℃;
(4) hot pressed sintering is that powder is filled in the graphite jig, hot uniaxial pressing under 0.8-40MPa pressure and 1500-1850 ℃ of temperature current downflow nitrogen.
5, press the preparation method of the described semi-transparent hard Sialon ceramic material of claim 4, its hot pressed sintering at first is heated to 850-1250 ℃ with 3-8 ℃/minute heat-up rate with sample, and kept 30-60 minute, and then be heated to the highest sintering temperature 1500-1800 ℃ with 5-10 ℃/minute heat-up rate, and kept furnace cooling then 30-120 minute.
CN 02160735 2002-12-27 2002-12-27 Semi-transparent hard Sailong ceramics and its preparation Expired - Fee Related CN1228273C (en)

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Publication number Priority date Publication date Assignee Title
CN1317231C (en) * 2005-08-11 2007-05-23 武汉理工大学 Semitransparent silicon nitride ceramics and its preparation method
CN100418924C (en) * 2007-04-27 2008-09-17 北京科技大学 Method for preparing Ca-alpha-SiAlON material using iron selection tailings
CN104829236B (en) * 2015-04-14 2017-06-16 苏州工业园区晶冠瓷材料科技有限公司 Preparation method of SiAlON transparent ceramic phosphor
CN105330295A (en) * 2015-09-29 2016-02-17 洛阳暖盈电子技术有限公司 Y-alpha Sialon method transparent ceramic preparation method
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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