CN1569745A - Process for self-propagating synthesis of alpha-sialon powder with stable rare earth ion - Google Patents
Process for self-propagating synthesis of alpha-sialon powder with stable rare earth ion Download PDFInfo
- Publication number
- CN1569745A CN1569745A CN 200410015999 CN200410015999A CN1569745A CN 1569745 A CN1569745 A CN 1569745A CN 200410015999 CN200410015999 CN 200410015999 CN 200410015999 A CN200410015999 A CN 200410015999A CN 1569745 A CN1569745 A CN 1569745A
- Authority
- CN
- China
- Prior art keywords
- powder
- sialon
- rare earth
- ball
- earth ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention relates to a process for self-propagating synthesis of alpha-sialon powder with stable rare earth ion by using mass percent no less than 99.0% of silicon nitride Si3N4 powder, aluminium nitride (AlN) powder, rare-earth oxide (RE2O3, RE=Ce, Pr and Eu) and yttrium oxide (Y2O3), and mass percent no less then 98.0% of aluminium (Al) and silicon (Si) powder as raw material, using alpha-Sialon general formula Re[x]Si[12-(m+n)]Al[m+n]O[n]N[16-n] as parameter for batching, wherein m=2n=3x, x=0.3-0.6, RE is doped by any one of Ce, Pr or Eu or by different proportion for composite doping with element Y.
Description
Technical field
The present invention relates to be the stable A Erfasailong of a kind of rare earth ion (powder of α-Sialon) spread synthetic method certainly.More precisely provide a kind of with silicon nitride (Si
3N
4), aluminium nitride (AlN), rare earth oxide (RE
2O
3) and yttrium oxide (Y
2O
3), aluminium powder (Al) and silica flour (Si) be main raw material, (preparation method of powder of α-Sialon) belongs to the preparation field of nitrogen based ceramic powder body by the synthetic light rare earth ion stabilized A Erfasailong of self-propagating high-temperature burning process.
Background technology
Sialon is Si
3N
4Sosoloid, at first propose in 1972 by people such as people such as K.H.Jack and Y.Oyama.Corresponding to Si
3N
4α-and β-two kind of variant, the sosoloid of two kinds of structures of Sialon is called α-Sialon and beta-Sialon.Because the Sialon pottery has high strength, high rigidity, wear-resistant, corrosion-resistant, characteristics such as anti-thermal shock and high-temperature stability and using in high temperature, corrosive atmospheres such as metallurgy, chemical industry, its high strength, high rigidity can also play a role in mechanical industry as cutter and bearing etc.With regard to α-Sialon and beta-Sialon pottery, characteristics are separately arranged again.α-Sialon pottery has very high hardness, but its toughness is lower, thereby is restricted on using; Though the beta-Sialon pottery has low slightly hardness, has obtained popularization because of its toughness is higher.Therefore, can come the microstructure of control material to reach the purpose of the over-all properties of optimizing material by certain technology, increase its toughness such as pattern, bring into play α-Sialon and beta-Sialon over-all properties mutually by forming α-Sialon/ beta-Sialon complex phase ceramic by control α-Sialon crystal grain.
Ce is thought in research in the past
3+Owing to can not enter the room in α-Sialon lattice too greatly.People such as C.M.Wang in recent years
(C.M.Wang, M.Mitomo, F.F.Xu, N.Hirosaki and Y.Bando, " Synthesis of Ceriom α-sialon with nuclei addition, " J.Am.Ceram.Soc, 84[6] 1389-91 (2001))Y α-the Sialon that adds 1wt% has synthesized Ce α-Sialon as crystal seed with plasma reactive sintering (PAS) technology.They think that the formation of Ce α-Sialon is what to be subjected in the lip-deep one-tenth nuclear control of the α that has existed-Sialon phase, because can not form Ce α-Sialon phase when not adding crystal seed.And Z.J.Shen
(Z.Shen and M.Nygren, " Implications of kinetically promoted formation of metastable α-Sialon phases, " J.Eur.Cearm Soc., 21611-15 (2001))Research work Deng human plasma sintering (SPS) prepared Ce α-Sialon shows that α-Sialon is the principal crystalline phase in the sintered compact mutually.They think that the reason that Ce α-Sialon forms is that plasma sintering is the process of a rapid temperature rise and drop.Heat up fast and make Ce
3+Can enter α-Sialon lattice, cooling fast makes the Ce that enters α-Sialon lattice
3+Be suppressed in the lattice, and such Ce α-Sialon is metastable mutually.In view of heat up fast and cooling aspect the similarity of SHS and SPS, we have synthesized the stable Sialon powder of light rare earth ion Ce with the self-propagating high-temperature combustion synthesis process.
Although the report of more research to Ce α-Sialon material is arranged in recent years, but seldom to the research of Pr and Eu α-Sialon material.Reported the half-full or full up trivalent rare earth ions of some 4f tracks, for example Yb
3+, Eu
3+And Sm
3+, at Si
3N
4Be reduced into divalent ion easily in the sintering process of base pottery.Though Eu
3+Ionic radius be 0.095nm, compare Nd
3+Ionic radius little, can enter α-Sialon lattice, still, Eu
2+Ionic radius but than Nd
3+Much bigger, be 0.116nm, can not enter α-Sialon lattice.People such as Z.J.Shen (
Z.Shen and M.Nygren, " Implications of kinetically promoted formation of metastable α-Sialon phases, " J.Eur.Cearm.Soc., 21611-15 (2001))Synthesized Eu α-Sialon material with SPS technology, contained α-Sialon in the material, beta-Sialon and P-be (EuSi mutually
9Al
19ON
31), and be principal crystalline phase with α-Sialon.People such as R.J.Xie (
R.J.Xie, M.Mitomo, K.Uheda, F.F.Xu and Y.Akimune, " Preparation and luminescence spectra of calcium-and Rare-earth (R=Eu; Tb and Pr)-codoped α-sialon ceramics, " J.Am.Ceram.Soc., 85 [5] 1229-34 (2002))Synthesized Eu with heat pressing process
2O
3/ Pr
2O
3With the stable α-Sialon material of CaO compound ion.In that (Eu, Ca) in α-Sialon system, during less than 70at.%, can obtain with α-Sialon is the material of principal crystalline phase at Eu/Ca, wherein also contains the β-Si of trace
3N
4Perhaps beta-Sialon phase, and in that (Pr, Ca) in α-Sialon system, when Pr/Ca=50at.%, α-Sialon is a principal crystalline phase, also has a spot of β to generate mutually.Therefore, we have also synthesized rare earth ion Pr and the stable Sialon powder of Eu with the self-propagating high-temperature combustion synthesis process.
Summary of the invention
The object of the present invention is to provide the stable A Erfasailong of a kind of rare earth ion (powder of α-Sialon) spread synthetic method certainly.
The objective of the invention is to implement: use existing RE by following manner
2O
3-Si
3N
4-AlN-Al
2O
3The knowledge of α in the multicomponent system-Sialon phase plane is not less than 99% silicon nitride (Si with mass percent
3N
4), aluminium nitride (AlN), rare earth oxide (RE
2O
3) and yttrium oxide (Y
2O
3) and mass percent is not less than 98% aluminium powder (Al) and silica flour (Si) is a main raw material, by the ion stabilized A Erfasailong of the self-propagating high-temperature burning process synthesizing rare-earth (powder of α-Sialon).
Specifically:
(1) according to existing Ln
2O
3-Si
3N
4-AlN-Al
2O
3The knowledge of α in the multicomponent system-Sialon phase plane is with α-Sialon general formula R E
xSi
12-(m+n)Al
M+nO
nN
16-nIn x, m, n for selecting the parameter of component point, m=2n=3x, x=0.3~0.6.RE be among Ce, Pr and the Eu any independent doping or with Y composite mixed by different ratios.
(2) raw material: comprise that mass percent is not less than 99% silicon nitride powder, aluminum nitride powder, rareearth oxidate powder and mass percent and is not less than 98% silica flour and aluminium powder.After the composition proportioning weighing according to above-mentioned (1), in plastics pot, be dispersion medium with the dehydrated alcohol, Si
3N
4Ball is that ball-milling medium mixed 24 hours, after the oven dry of taking-up slurry, sieves through 55 eye mesh screens.
(3) powder is synthetic: the powder that mixes is put in the plumbago crucible, at shop, top layer layer of metal detonator Ti powder, the tungsten filament or the molybdenum filament of coiled spring-like are imbedded in the powder, and energising heating tungsten filament, the Ti powder that ignites, and cause the spontaneous of entire reaction and carry out.
(4) the blocky powder of synthetic is broken, in oxidation aluminium pot or agate jar, be dispersion medium with the dehydrated alcohol, Si
3N
4Ball is a ball-milling medium at ball milling 20-30 on the single-phase ball mill hour or on the high speed planetary ball mill ball milling 3-5 hour, take out the slurry oven dry after, sieve through 55 eye mesh screens.
Advantage of the present invention is:
(1) synthesis technique of powder and equipment are simple; React very rapid, reaction time is short; React spontaneous carrying out, need extra power hardly, cost is low.
(2) the content height of α in the synthetic powder-Sialon phase, the synthetic powder is metastable, has certain activity, helps sintering.
(3) at Ce, when Pr or Eu element and Y element are composite mixed, can be by regulating Ce in the starting raw material, the ratio of Pr or Eu element and Y element is regulated and control the phase composite of synthetic powder.Composite mixed and definite its ratio that the embodiment of the invention has exemplified Ce and Y was respectively 4: 1,3: 2 or 1: 1.In fact suitable equally to Pr involved in the present invention and Eu, and ratio also is not limited only to listed ratio, as long as in the X=0.3-0.6 scope, three kinds of elements and Y element can be regulated the phase composite of α-Sialon powder with this by the complete or corresponding α-Sialon of any ratio.
Description of drawings
XRD figure spectrum (a) Eu of the different α of Fig. 1-sialon component, the adulterated α of Pr and Ce-sialon component (b) (Eu, Y), (Pr, Y), (Ce, Y) adulterated α-sialon component (among the figure:, α ', O β ', Λ Ce
2Si
6O
3N
8, BS-phase, 7 AlN-polytypoids)
The EDS collection of illustrative plates (right side) of α-Sialon crystal grain in the pattern (left side) of Fig. 2 synthetic powder and the corresponding powder, among the figure, (a) Eu α-sialon (c) Pr α-sialon (e) Ce α-sialon
Fig. 3 is from spreading synthetic (Ce, Y) XRD figure of α-Sialon powder spectrum (a) Ce0.5Y0 (b) Ce0.4Y0.1 (c) Ce0.3Y0.2 (d) Ce0.25Y0.25
Embodiment
Embodiment 1 usefulness cerium oxide is made stablizer, and being not less than 99% silicon nitride powder, aluminum nitride powder, cerium oxide powder and mass percent with mass percent, to be not less than 98% silica flour and aluminium powder be raw material.General formula R E at α-Sialon
xSi
12-(m+n)Al
M+nO
nN
16-nIn x, m, n be respectively m=2n=3x, x=0.3~0.6.The powder that proportioning is good is a dispersion medium with the dehydrated alcohol in plastics pot, Si
3N
4Ball is that ball-milling medium mixed 24 hours, after the oven dry of taking-up slurry, sieves through 55 eye mesh screens.The powder that mixes is put in the plumbago crucible, at shop, top layer one deck Ti powder, the tungsten filament of spring-like imbedded in the powder, and energising heating tungsten filament, the Ti powder that ignites, and cause the spontaneous of entire reaction and carry out.Then the blocky powder of synthetic being broken into pieces, is dispersion medium with the dehydrated alcohol in oxidation aluminium pot or agate jar, Si
3N
4Ball is a ball-milling medium at ball milling 20-30 on the single-phase ball mill hour or on the high speed planetary ball mill ball milling 3-5 hour, take out the slurry oven dry after, sieve through 55 eye mesh screens.The XRD figure spectrum of synthetic powder, microstructure and corresponding EDS collection of illustrative plates are respectively as depicted in figs. 1 and 2.
Embodiment 3 usefulness europium sesquioxides are made stablizer, according to method synthetic powder, the preparation pottery of embodiment 1.The XRD figure spectrum of synthetic powder and microstructure are respectively as depicted in figs. 1 and 2.
Embodiment 4 adopt a kind of and yttrium oxide in cerium oxide, Praseodymium trioxide and the europium sesquioxides according to 1: 1 ratio as one package stabilizer, according to embodiment 1 method synthetic powder, the XRD figure of synthetic powder is composed as shown in Figure 1.
Embodiment 5 adopts cerium oxide and yttrium oxide as one package stabilizer, and changes its ratio, and according to embodiment 1 method synthetic powder, the XRD figure of synthetic powder is composed as shown in Figure 3.
Claims (5)
- The stable A Erfasailong powder of a rare earth ion spread synthetic method certainly, it is characterized in that:(1) with α-Sialon general formula R E xSi 12-(m+n)Al M+nO nN 16-nIn x, m, n prepare burden for the parameter of selecting component point, m=2n=3x wherein, x=0.3~0.6, RE is Ce among Ce, Pr or the En, any independent doping among Pr or the Eu or composite mixed with different ratios with Y;(2) powder of batch mixes after evenly places plumbago crucible, at shop, top layer layer of metal Ti detonator, tungsten filament or molybdenum filament imbedded powder, and initiation reaction is spontaneous to be carried out, and obtains blocky powder, and powder forms through disintegrating process.
- By the stable A Erfasailong powder of the described a kind of rare earth ion of claim 1 spread synthetic method certainly, it is characterized in that selecting for use mass percent to be not less than 99.0% silicon nitride (Si 3N 4) powder, aluminium nitride (AlN) powder, rare earth oxide (RE 2O 3) and yttrium oxide (Y 2O 3) and mass percent to be not less than 98.0% aluminium powder (Al) and silica flour (Si) be raw material, in plastics pot, be dispersion medium after the weighing, with the different Si of diameter with the dehydrated alcohol 3N 4Ball is that the ball-milling medium ball milling takes out oven dry and sieves through 55 mesh sieve orders after 24 hours.
- By the stable A Erfasailong powder of the described a kind of rare earth ion of claim 1 spread synthetic method certainly, it is characterized in that the block powder of self-propagating high-temperature after synthetic is dispersion medium with the dehydrated alcohol in aluminum oxide or agate jar, with the different Si of diameter 3N 4Ball is ball-milling medium at ball milling 20-30 on the single-phase ball mill hour or took out oven dry and sieve through 55 mesh sieve orders after ball milling 3-5 on the high speed planetary ball mill hour.
- By the stable A Erfasailong powder of the described a kind of rare earth ion of claim 1 spread synthetic method certainly, it is characterized in that general formula R E xSi 12-(m+n)Al M+nO nN 16-nIn X=0.5, any and Y's is composite mixed among Rare-Earth Ce, Pr or the En, the ratio of any rare earth of Ce, Pr or En and Y was respectively 4: 1,3: 2,1: 1.
- By the stable A Erfasailong powder of the described a kind of rare earth ion of claim 1 spread synthetic method certainly, it is characterized in that tungsten filament or molybdenum filament coiled spring-like.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 200410015999 CN1239432C (en) | 2004-01-19 | 2004-01-19 | Process for self-propagating synthesis of alpha-sialon powder with stable rare earth ion |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 200410015999 CN1239432C (en) | 2004-01-19 | 2004-01-19 | Process for self-propagating synthesis of alpha-sialon powder with stable rare earth ion |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1569745A true CN1569745A (en) | 2005-01-26 |
CN1239432C CN1239432C (en) | 2006-02-01 |
Family
ID=34478682
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN 200410015999 Expired - Fee Related CN1239432C (en) | 2004-01-19 | 2004-01-19 | Process for self-propagating synthesis of alpha-sialon powder with stable rare earth ion |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1239432C (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101146890B (en) * | 2005-03-22 | 2011-06-01 | 独立行政法人物质·材料研究机构 | Fluorescent substance, process for producing the same, and luminescent device |
CN101146891B (en) * | 2005-03-22 | 2011-06-08 | 独立行政法人物质·材料研究机构 | Phosphor and process for producing the same |
CN103601500A (en) * | 2013-10-28 | 2014-02-26 | 株洲钻石切削刀具股份有限公司 | SiAlON ceramic containing crystalline phase Y4SiAlO8N, and preparation method and application thereof |
CN109400176A (en) * | 2018-09-27 | 2019-03-01 | 广东工业大学 | A kind of high-performance silicon nitride ceramics and its preparation method and application |
-
2004
- 2004-01-19 CN CN 200410015999 patent/CN1239432C/en not_active Expired - Fee Related
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101146890B (en) * | 2005-03-22 | 2011-06-01 | 独立行政法人物质·材料研究机构 | Fluorescent substance, process for producing the same, and luminescent device |
CN101146891B (en) * | 2005-03-22 | 2011-06-08 | 独立行政法人物质·材料研究机构 | Phosphor and process for producing the same |
CN102226085B (en) * | 2005-03-22 | 2014-07-30 | 独立行政法人物质·材料研究机构 | Process for producing phosphor |
CN103601500A (en) * | 2013-10-28 | 2014-02-26 | 株洲钻石切削刀具股份有限公司 | SiAlON ceramic containing crystalline phase Y4SiAlO8N, and preparation method and application thereof |
CN103601500B (en) * | 2013-10-28 | 2015-07-22 | 株洲钻石切削刀具股份有限公司 | SiAlON ceramic containing crystalline phase Y4SiAlO8N, and preparation method and application thereof |
CN109400176A (en) * | 2018-09-27 | 2019-03-01 | 广东工业大学 | A kind of high-performance silicon nitride ceramics and its preparation method and application |
Also Published As
Publication number | Publication date |
---|---|
CN1239432C (en) | 2006-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Tang et al. | The characterization of Ce/Pr-doped YAG phosphor ceramic for the white LEDs | |
CN101133001B (en) | Siaion ceramic and method of making the same | |
CN100590171C (en) | Alpha-sialon, alpha-sialon phosphor and method for producing same | |
KR100984822B1 (en) | Phosphor and process for producing the same | |
KR101483657B1 (en) | Light emitting device comprising a multiphase sialon-based ceramic material | |
KR102062950B1 (en) | Acid nitride phosphor powder and method for producing same | |
Suehiro et al. | Powder synthesis of Y-α-SiAlON and its potential as a phosphor host | |
CN104736664B (en) | Wavelength convert parts and use its light-emitting device | |
CN1239432C (en) | Process for self-propagating synthesis of alpha-sialon powder with stable rare earth ion | |
KR20080061314A (en) | Ceramic material and cutting tools made thereof for applications demanding good notch wear resistance | |
Hirosaki et al. | Phase relationships in the Si3N4–SiO2–Lu2O3 system | |
EP1414580B1 (en) | Multication doped alpha-beta sialon ceramics | |
RU2613994C1 (en) | Method for producing alloyed yttrium aluminium garnet | |
CN1157347C (en) | Low cost process of synthesizing sialon ceramic powder | |
Zhao et al. | Effect of phase structure evolution on thermal expansion and toughness of (Nd1-xScx) 2Zr2O7 (x= 0, 0.025, 0.05, 0.075, 0.1) ceramics | |
US7294596B2 (en) | Sintered ceramic material with improved properties and method for its manufacturing | |
Aminaka et al. | Effect of rare-earth oxide additives on transparency and fluorescence of α-SiAlON ceramics | |
JP2007161942A (en) | Inorganic compound, manufacturing method thereof, luminous composition, luminous article and light-emitting device | |
Zhu et al. | Synthesis and photoluminescence of blue-emitting 15R-sialon: Eu2+ phosphors | |
Gan et al. | Photoluminescence properties of Ca–α-SiAlON: Ce3+ phosphors as function of composition and microstructure | |
CN100336886C (en) | Nitrogen oxide fluorescent material and preparation method thereof | |
Naga et al. | Fabrication, microstructure and properties of hot-pressed Nd: YAG ceramics | |
Yamada et al. | Development of SiAlON-from mechanical to optical applications | |
CN1260178C (en) | Alpha sialon ceramic materials with high infrared transmittance and method for preparing same | |
WO1998032711A1 (en) | Gas pressure sintered silicon nitride having high strength and stress rupture resistance |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060201 Termination date: 20100219 |