CN1521141A - Process for preparation of self-spread high-temperature synthesizing low cost alpha-sialon powder - Google Patents
Process for preparation of self-spread high-temperature synthesizing low cost alpha-sialon powder Download PDFInfo
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- CN1521141A CN1521141A CNA031154204A CN03115420A CN1521141A CN 1521141 A CN1521141 A CN 1521141A CN A031154204 A CNA031154204 A CN A031154204A CN 03115420 A CN03115420 A CN 03115420A CN 1521141 A CN1521141 A CN 1521141A
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Abstract
The present invention is high-temperature self-spreading process of synthesizing alpha-Sialon powder at low cost and belongs to the field of the superfine non-oxide powder preparation. Metallic silicon, metallic aluminum powder, slag or some natural mineral or their mixture and Sialon powder in certain proportion are mixed and nitrogen in 3-15 MPa is led in to prepare alpha-Sialon powder. The said process features no need of pressing block in advance, reaction completed in a vertical annular or disc container of carbon felt, the addition of Sialon additive as crystal seed and diluent, low cost, low impurity content in the reaction system and loose combustion product.
Description
Technical field
What the present invention relates to is the method for synthetic α-Sai Long (Sialon) powder of a kind of low cost.A kind of more precisely is main raw material with metallurgical slag or some natural mineral or their mixture, metallic silicon power and metallic aluminium powder, by the method for self-propagating high-temperature technology synthetic powder.Belong to non-oxidized substance superfine powder preparation field.
Background technology
Sialon is the silicon-nitride-based ceramic that recent two decades grows up, has high-temperature stability, high strength, wear-resistant, performances such as corrosion-resistant and anti-thermal shock, α-Sialon compares with beta-Sialon, have higher hardness and wear resistance, intensity and toughness are then a little less than beta-Sialon, and owing to dissolved in metallic element, therefore also has electroconductibility, α-the Sialon that adds some rare earth element also has new optical property, this pottery has relative higher transparency, and present certain color, and, therefore can obtain many new application because it has photoelectric properties and favorable mechanical and thermal characteristics simultaneously.The production cost of the normal pressure-sintered method of α-Sialon is 1/5～1/10 of a beta-Sialon.In recent years, the Sialon stupalith is mainly used in grinding medium, metal is cut several aspects such as tool, bearing, engine and turbine material, be suitable for especially under high temperature, corrosive atmospheres such as metallurgy, chemical industry using and mechanical industry in play a role.Along with industrial expansion, the Sialon pottery will have application prospect widely.Therefore, countries in the world are at Si
3N
4Dropped into a large amount of scientific research strengths on the base Sialon pottery.Development through decades, the existing raising by a relatively large margin of the high temperature of Sialon pottery and room-temperature mechanical property, yet its application still is restricted, and its reason is that mainly high cost makes it be difficult to base oneself upon, and can only be applied to some high-quality precision and sophisticated technology fields on a small quantity on common business market.Production cost analysis from the Sialon pottery, find that cost of material is to cause a higher important factor of Sialon pottery cost, because existing preparation Sialon raw material that powder adopts need be with highly purified silicon nitride and high additive, as AlN and rare earth oxide etc.Therefore, reduce cost and keep its excellent properties, just become the important directions of Sialon pottery Application and Development from now on.
Synthetic (SHS) technology of self propagating high temperature is the modern technique of the nearest efficient flourishing ceramic powder that grew up in two, 30 years, thereby it guarantees that by the heat release burning of self between the reactant is synthetic reaction continues to carry out, whole process needs the external world that any energy is provided hardly, and in tens seconds, finish reaction, thereby be a kind of method of the synthetic powder that receives much attention, have advantages such as technology is simple, energy consumption is low, product purity is high, less investment.Adopt this technology to synthesize some Sialon powders, " a kind of preparation method of ceramics powder (CN1055279C) " as people's inventions such as Iron and Steel Research Geueral Inst Korea Spro of portion of China Metallurgical Industry celebrate joyously adds aluminium powder and silicon oxide or aluminum oxide or adds aluminium nitride and aluminum oxide in silica flour, adopt the synthetic beta-Sialon powder of self propagating high temperature synthetic technology." a kind of method of low-cost synthesizing sialon ceramic powder " (application number 01126758.5) of people such as the Chen Weiwu of Shanghai Silicate Inst., Chinese Academy of Sciences invention, be in silica flour, aluminium powder, silicon nitride or Sialon powder, to add aluminum nitride powder and industrial waste, as a large amount of clays that exist of slag, slag, flyash or nature, by adopting energy-efficient self propagating high temperature synthesis technique to obtain single-phase cheaply α-Sialon powder, but silicon nitride and aluminium nitride cost are higher.Can the inventor propose cancel silicon nitride and aluminium nitride in the preparation process of α-Sialon powder, simultaneously do not use alcohol to be dispersion medium, omit complicated procedures of forming such as raw material stoving processing, thereby further save the energy, really reach the purpose of low-cost synthetic α-Sialon powder.
Summary of the invention
The object of the present invention is to provide the method for a kind of low-cost synthesized high-performance α-Sai Long (Sialon) powder.
The objective of the invention is to implement by following manner.Promptly use existing Ln, Ca, Mg, Al, O, N multicomponent system facies relationship knowledge, utilize slag or some natural mineral or their mixture to be raw material, by adding metallic silicon power, aluminium powder and the grand powder of the technology of the present invention synthetic match, prepare low cost alpha-Sialon powder in conjunction with the self propagating high temperature synthesis technique.
Specifically:
(1) α-Sai Long is the formula M with α-Sialon
xSi
12-(m+n)Al
M+nO
nN
16-nIn x, m, n value as the significant parameter of design α-cold grand powder, when M is Nd, Sm, Gd, Dy, Y, Yb or their composite granule, common 0.33＜x＜0.67, m=3x, m=2n; When M is Ca, 0.4＜x＜1.4, m=2n=2x, according to the chemical constitution of slag or some natural mineral and respective metal element the single phase region of corresponding α-Sialon, determine the chemical expression of synthetic α-Sialon and the composition proportioning of desired raw material.
(2) raw material, comprise metallic silicon power (purity 99%-99.5%, particle size range is 0.3 μ m～150 μ m), metallic aluminium powder (94%～99.5%, particle size range is 0.3 μ m～50 μ m), slag or some natural mineral (particle size range is 0.5 μ m～40 μ m) and synthetic Sialon powder of the present invention, design according to the Sialon component, mixed by 5-50: 5-30: 5-30: 5-60 is prepared burden, form the proportioning weighing by above-mentioned α-Sialon after, with Sialon ball or Si
3N
4Ball or Al
2O
3Ball or steel ball or sintered carbide ball or synthetic glass ball or their mixture or other ball-milling medium are at Sialon or Si
3N
4Or in the ball milling bucket of corundum or nylon or plastics ball milling bucket or other material, do to mix 2 hours-48 hours, take out, manually or adopt the mechanical vibration mode to sieve through 15 orders-300 eye mesh screen.
(3) silica flour, aluminium powder, slag or some natural mineral or their mixture and synthetic Sialon powder of the present invention are mixed by a certain percentage after, the raw pine that mixes is loaded in the upright ring-type tube or disc shaped container of carbon felt, be positioned in the self propagating high temperature synthetic furnace, the high pressure nitrogen pressure of reaction is 3Mpa-15Mpa, synthetic through the igniting self propagating high temperature in high pressure vessel then, can generate required Sialon powder in stove or in the air behind the naturally cooling.
(4) described slag or some natural mineral comprise metallurgical slag, fine coal ashes, Wingdale, rare-earth mineral or their mixture.
Advantage of the present invention is:
The large-scale production of the synthetic Sialon of self propagating high temperature, maximum difficulty are to reduce the cost of raw material and reduce production process.The objective of the invention is to utilize the self propagating high temperature synthetic method, by changing its processing parameter, provide a kind of easy, quick, energy-conservation, prepare the method for α-Sai Long (Sialon) powder efficiently, cheaply.The advantage that the present invention is had except " a kind of method of low-cost synthesizing sialon ceramic powder " (application number 01126758.5) (as efficient, that energy consumption is low, form that variation range is wide, low to ingredient requirement, equipment is simple etc.), also have following characteristics:
The first, only adopt the grand powder of silica flour, aluminium powder, slag or some natural mineral or their mixture and synthetic of the present invention match, and the aluminium nitride that replaces the required silicon nitride of raw material with the self propagating high temperature synthesizing silicon nitride and the aluminium nitride of silica flour and aluminium powder.
Second, the main raw material that the present invention adopts is metallic silicon power, metallic aluminium powder and slag or some natural mineral or their mixture, granularity is respectively 0.3 μ m-150 μ m, 0.3 μ m-50 μ m and 0.3 μ m-40 μ m, and the size range of broad can effectively reduce cost.
The 3rd, adopt synthetic α-Sialon of the present invention as starting raw material, both can be used as crystal seed, can be used as thinner again, slow down the speed of response of SHS, and reduce the system foreign matter content.
The 4th, in raw material mixing process, do not adopt complicated procedures of forming such as wet-milling, oven dry, only adopt dry mixing process, thereby can reduce production costs effectively.
The 5th, with the 3-15Mpa high pressure nitrogen as nitridation source, for nitrogenize furnishes ample material.
The 6th, high pressure vessel provided by the invention does not have particular requirement, only be reactant and additive behind the uniform mixing or behind the uniform mixing of reactant own, be placed in the upright ring-type tube or disc shaped container of carbon felt, their shape figure respectively as shown in Figure 1, 2.
The 7th, range of application of the present invention is wide, be not limited to utilize slag or some day mineral prepare α-Sai Long (Sialon) powder, and and can utilize the starting material that the element (comprising metal ion and oxygen) that can enter Sialon can be provided, obtain α-Sai Long (Sialon) powder.
Further illustrate progress of invention essence and innovative point of the present invention below by embodiment.
Description of drawings
Fig. 1 is the XRD figure of embodiment 6 synthetic powders provided by the invention.
Fig. 2 is the upright ring-type tube of the carbon felt that adopts among the embodiment 1-5 provided by the invention.
Fig. 3 is the disc shaped container of the carbon felt of employing among the embodiment 6 provided by the invention.
Wherein, among the figure:
1-tungsten filament heating element, 2-priming mixture, 3-reactant
4-carbon felt container
Fig. 1 is upright ring-type, and Fig. 2 is a disc shaped container.
Embodiment
With certain Steel Plant's blast furnace slag, metallic silicon power, aluminium powder is raw material, and 5% technology synthetic Sialon powder of the present invention, considers the chemical constitution (table 1) of slag, and the component of α-Sialon is pressed Ca
0.71Mg
0.23Si
9.18Al
2.82O
0.94N
15.06Design, in the nylon bucket, make medium by this component confected materials with silicon nitride ball, dried bastard mill is after 48 hours, pine is loaded in the upright ring-type tube (shown in Figure 2) of carbon felt of external diameter φ 60mm * internal diameter φ 55mm * high φ 60mm, put into the self propagating high temperature synthetic furnace, charge into the high pressure nitrogen (purity 99.99%) of 15Mpa after vacuumizing, synthetic atmosphere is high pressure nitrogen, self-propagating combustion after lighting a fire promptly gets the Sialon powder behind the naturally cooling.The powder that synthesizes is single-phase α-Sialon through XRD determining, wherein α-Sialon through EDS be determined as (Ca, Mg)-α-Sialon.The Sialon powder as crystal seed and thinner that adds in the reactant makes combustion reactions complete, and product is easily broken.
The chemical constitution of certain steel mill's blast-furnace slag of table 1
| Component | ?CaO | ?SiO 2 | ?A1 2O 3 | ?MgO | ?Fe 2O 3 | MnO | ?Tio 2 | ?SO 3 | ?K 2O | Na 2O | ?F -1 | Cl -1 |
| Wt％ | ?39.76 | ?34.48 | ?14.04 | ?9.18 | ?0.52 | 0.09 | ?0.83 | ?1.36 | ?0.25 | 0.31 | ?0.58 | 0.27 |
| Mol/100g | ?0.71 | ?0.57 | ?0.14 | ?0.23 | ?＜0.01 | ＜0.01 | ?0.01 | ?0.02 | ?＜0.01 | ＜0.01 | ?0.03 | ＜0.01 |
Adopt embodiment 1 same process, just use limestone powder (CaCO instead
3＞98wt%) replacing blast-furnace slag, it and metallic silicon power, aluminium powder and 15% synthetic Sialon powder of the present invention are made raw material, and the component of Ca-α-Sialon is pressed Ca
0.8Si
8.8Al
3.2O
1.6N
14.4Design, by the synthetic Ca-α-Sialon of self-propagating high-temperature technology, the powder that synthesizes is single-phase Ca-α-Sialon through XRD determining.
Adopt embodiment 1 same process, just use white stone transporting powder instead and replace blast-furnace slag, it and metallic silicon power, aluminium powder and 30% synthetic Sialon powder of the present invention are made raw material, the component design of Ca-α-Sialon changes in whole C a-α-Sialon phase region, by self-propagating high-temperature technology all can synthesize (Ca, Mg)-α-Sialon.Specifically, press M
xSi
12-3xAl
3xAl
3xO
2xN
16-2xThe component design appoints in 0.4＜x＜1.4 to get a bit to get final product.Beta-Sialon is pressed the amount design of silicon and aluminium.All the other conditions comprise all with embodiment 1, all obtained (Ca, Mg)-α-Sialon powder.
Embodiment 4
Adopt embodiment 1 same process, just use xenotime powder (Y instead
2O
3Content 61.4wt%) replaces blast-furnace slag, it and metallic silicon power, aluminium powder and 40% synthetic Sialon powder of the present invention are made raw material, the component design of Y-α-Sialon changes in whole Y-α-Sialon phase region, all can synthesize Y-α-Sialon by self-propagating high-temperature technology.Specifically, press Y
xSi
12-3xAl
3xO
xO
2N
16-xThe component design appoints in 0.33＜x＜0.67 to get a bit to get final product.All the other conditions are all with embodiment 1, and by the synthetic Y-α-Sialon of self-propagating high-temperature technology, the powder that synthesizes is single-phase through XRD determining, Y-α-Sialon.
Embodiment 5
Adopt embodiment 1 same process, just use distinctive heavy rare earths ionic absorption ore deposit, China south instead and (contain Y
2O
351.5%, Nd
2O
310%, Dy
2O
35.8%, Sm
2O
34.5%) powder replaces blast-furnace slag, it and metallic silicon power, aluminium powder and 50% synthetic Sialon powder of the present invention are made raw material, (Y, Nd, Dy, Sm)-design of the component of α-Sialonr changes in whole Y-α-Sialon phase region, takes into account the α-Sialon phase region of other rare earth element, all can synthesize (Y by self-propagating high-temperature technology, Nd, Dy, Sm, Gd)-α-Sialon.Specifically, press Y
xSi
12-3xAl
3xO
xO
2N
16-xThe component design appoints in 0.33＜x＜0.67 to get a bit to get final product.All the other conditions all with embodiment 1, have all obtained (Y, Nd, Dy, Sm Gd)-α-Sialon powder.
Embodiment 6
Adopt embodiment 1 same process, just the powder that mixes is loaded in the disc shaped container (Fig. 2) of carbon felt, other condition is with embodiment 1, and what synthesize is single-phase α-Sialon through XRD determining, and XRD result as shown in Figure 1.
Claims (6)
1, the self-propagating high temperature synthesis preparation method of a kind of low cost alpha-Sai Long powder, α-Sai Long is the formula M with α-Sialon
xSi
12-(m+n)Al
M+nO
nN
16-nIn x, m, n value as the significant parameter of design α-cold grand powder, when M is Nd, Sm, Gd, Dy, Y, Yb or their composite granule, 0.33＜x＜0.67, m=3x, m=2n; When M is Ca, 0.4＜x＜1.4, m=2n=2x is characterized in that:
(1) metallic silicon power, metallic aluminium powder, slag or some natural mineral or their mixture and synthetic of the present invention α-Sai Long powder are pressed the mixed batching that 5-50: 5-30: 5-30: 5-60 is pressed in α-Sialon component design; Certainly spread synthetic Si with silica flour and aluminium powder
3N
4, AlN replaces required Si in the batching
3N
4And AlN;
(2) in ball grinding cylinder, did mixed 2-48 hour, take out after screen cloth sieves;
(3) powder that mixes is loaded in the container of carbon felt, is placed in the self propagating high temperature stove again, and igniting high temperature is synthetic, and nitrogen pressure is 3-15Mpa, synthetic back naturally cooling in stove or in the air.
2, press the self-propagating high temperature synthesis preparation method of the described low cost alpha of claim 1-Sai Long powder, the purity 95%-99.5% that it is characterized in that described silica flour, through the footpath scope is 0.3 μ m～150 μ m, the purity 94%～99.5% of aluminium powder, particle size range is 0.3 μ m～50 μ m, slag or some natural mineral particle size range are 0.5 μ m～40 μ m, and the particle size range of Sialon is 0.3 μ m～40 μ m.
3, by the self-propagating high temperature synthesis preparation method of the described low cost alpha of claim 1-Sai Long powder, it is characterized in that described slag or some natural mineral comprise metallurgical slag, fine coal ashes, Wingdale, rare-earth mineral or their mixture.
4,, it is characterized in that it is with Sialon ball or Si that the batching back is done mixed by the self-propagating high temperature synthesis preparation method of the described low cost alpha of claim 1-Sai Long powder
3N
4Ball or Buddha's warrior attendant ball or sintered carbide ball or synthetic glass ball or other ball-milling medium or their mixture are at Sialon or Si
3N
4Or in the ball grinding cylinder of corundum or nylon or baton round mill tube or other material.
5,, it is characterized in that doing and mix after the 10-300 order sieves is manually or the mechanical vibration mode by the self-propagating high temperature synthesis preparation method of claim 1 or 4 described low cost alpha-Sai Long powders.
6,, it is characterized in that doing the powder that mixes and pack in the upright ring-type tube or disc shaped container of carbon felt by the self-propagating high temperature synthesis preparation method of the described low cost alpha of claim 1-Sai Long powder.
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| CN100391899C CN100391899C (en) | 2008-06-04 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101607821B (en) * | 2009-07-13 | 2011-11-09 | 西安建筑科技大学 | Method for utilizing gasifier slag to synthesize Ca-alpha-Sialon |
| CN101144015B (en) * | 2006-09-14 | 2012-06-13 | 晶元光电股份有限公司 | Method for preparing fluorescent material |
| CN102617151A (en) * | 2012-03-30 | 2012-08-01 | 中国科学院唐山高新技术研究与转化中心 | Sialon ceramic powder and preparation method thereof |
| 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 |
| CN107986767A (en) * | 2017-11-24 | 2018-05-04 | 南昌航空大学 | A kind of CRN method synthesis long column shape α-Sialon fine grains and preparation method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055279C (en) * | 1997-05-13 | 2000-08-09 | 冶金工业部钢铁研究总院 | Method for preparing ceramic powder |
| CN1157347C (en) * | 2001-09-14 | 2004-07-14 | 中国科学院上海硅酸盐研究所 | Low cost process of synthesizing sialon ceramic powder |
-
2003
- 2003-02-14 CN CNB031154204A patent/CN100391899C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101144015B (en) * | 2006-09-14 | 2012-06-13 | 晶元光电股份有限公司 | Method for preparing fluorescent material |
| CN101607821B (en) * | 2009-07-13 | 2011-11-09 | 西安建筑科技大学 | Method for utilizing gasifier slag to synthesize Ca-alpha-Sialon |
| CN102617151A (en) * | 2012-03-30 | 2012-08-01 | 中国科学院唐山高新技术研究与转化中心 | Sialon ceramic powder and preparation method thereof |
| 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 |
| CN107986767A (en) * | 2017-11-24 | 2018-05-04 | 南昌航空大学 | A kind of CRN method synthesis long column shape α-Sialon fine grains and preparation method |
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