CN1355150A - Process for preparing composite microcrystal alumina ceramics with high P/C ratio - Google Patents
Process for preparing composite microcrystal alumina ceramics with high P/C ratio Download PDFInfo
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- CN1355150A CN1355150A CN 00123336 CN00123336A CN1355150A CN 1355150 A CN1355150 A CN 1355150A CN 00123336 CN00123336 CN 00123336 CN 00123336 A CN00123336 A CN 00123336A CN 1355150 A CN1355150 A CN 1355150A
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Abstract
A composite microcrystal alumina ceramic is prepared from nanometer Si-based powder (average grain diameter D50=15-30 nm as reinforcing phase through ultrasonic dispersing in absolute alcohol or distilled water, proportionally mixing it with alpha-Al2O3 powder and MgO powder, then mixing with matrix powder alpha Al2O3 and MgO powder (D50=0.3-0.5nm) in ball mill, ball grinding for 1-10 hr, shaping, and sintering. It can be used for antiwear part, cutting tool, or crucible with the advantages of high performance and reliability.
Description
The present invention relates to the preparation of alumina-based nano composite ceramics, a kind of technology of preparing of the compound micro-crystalline ceramic of aluminum oxide of high-performance and low-cost is provided especially.
Aluminum oxide is most widely used engineering structure pottery.Yet with regard to 95 porcelain with the most use, its intensity is on the low side, is 250～350MPa; Fracture toughness property is also on the low side, only is 2～3Mpa.m
1/2Its heat shock resistance temperature only is 275 ℃.Therefore improve its intensity, toughness and reliability are the targets that people pursue always.
Adopt the second phase nano powder, nanometer β-SiC especially, Si
3N
4, three kinds of nm-class Si-base powders of Si/C/N are the effective ways that realize this target.In these three kinds of nm-class Si-base powders, current the most frequently used be the nano SiC powder.Owing to relate to Si more than 1600 ℃
3N
4Part is decomposed and Si
3N
4With Al
2O
3Reaction, and these two all discharge gas and hinder densified sintering product and make degradation, so Si
3N
4, the Si/C/N nano powder all is of little use.
Alumina-based nano composite ceramics especially aluminum oxide-silicon carbide-nano composite ceramic is a kind of high-performance alumina composite ceramic that develops rapidly the beginning of the nineties, its essential characteristic is that matrix powder (aluminum oxide powder) is time micropowder, and wild phase nm-class Si-base powder average particle diameter D
50＜300nm.The adding of the nanometer second phase particle, refinement alumina grain (being generally less than 10um), make weave construction more even, the size and the quantity of defective reduce, reliability is improved.Simultaneously, the nanoparticle that is positioned at crystal boundary all plays the highly malleablized effect with the nanoparticle that is positioned at the aluminum oxide intracrystalline to alumina-ceramic.The highly malleablized of microcrystalline structure and pottery, make Standpoint of Ceramic Wear-resisting Function can and creep-resistant property significantly improve, in process of lapping even plastic deformation of metal also occurs being similar to.The compound micro-crystalline ceramic of this alumina base has a extensive future, and except will substituting 95 traditional porcelain, even may substitute cemented carbide part etc., will be used for wearing piece, cutter material, crucible under a lot of occasions etc. in large quantities.
SiC, Si
3N
4Or the adding of Si/C/N nanoparticle, though the performance of alumina-ceramic is increased substantially, also in sintering process, seriously hinder simultaneously the densification process of alumina-ceramic, improved about 200 ℃ before making sintering temperature not add nano powder.Therefore, in order to obtain fine and close sintered compact, when adopting pressureless sintering, holding temperature is generally at 1700～1850 ℃.This makes the cost that burns till of pottery improve greatly undoubtedly, makes this pottery be difficult to carry out suitability for industrialized production.Even the employing hot-pressing sintering technique still needs to carry out under 1600～1700 ℃ high temperature.The technology of preparation " aluminum oxide-nm-class Si-base powder " nano composite ceramic generally adopts hot-pressing sintering method at present, from breadboard result, has obtained success.But hot-pressing sintering method still fails to realize industrialization at present, can obtain high performance pottery though reason is exactly a hot pressed sintering under lower temperature, and its mould is made complicated, production efficiency is low, the cost height is not suitable for preparing complex-shaped part, and its application is restricted.
For fear of many unfavorable factors that hot pressed sintering brought, there is the scholar on the basis of pressureless sintering, to carry out the hot isostatic pressing subsequent disposal abroad.The main purpose of this method is exactly the density of the alumina-based nano composite ceramics that further improves pressureless sintering and obtained, reduces the defective of material, further improves the Performance And Reliability of pottery.Though utilize HIP sintering subsequent disposal technology can more easily obtain complex-shaped ceramic part, but the HIP sintering aftertreatment also still has the problem that an equipment is extremely expensive and be difficult to carry out scale operation.
So preferable approach is to adopt pressureless sintering (or carrying out gas pressure sintering after the pressureless sintering again), by the design of reasonable component design and processes, realizes pressureless sintering under lower temperature, obtains one reasonably, satisfies the results of property of industrial requirement.
Be to provide a kind of mechanical property height, good reliability, the preparation method of the compound micro-crystalline ceramic of aluminum oxide that cost is low order of the present invention.
The invention provides a kind of preparation method of composite microcrystal alumina ceramics with high P/C ratio, it is characterized in that:
With median size D
50The nm-class Si-base powder of=15～30nm is as wild phase, in dehydrated alcohol or distilled water, carry out ultra-sonic dispersion after, with median size D
50Matrix powder α-Al of=0.2～0.5um
2O
3Be mixed in the agitating ball mill with the MgO powder, the ball milling time is 1～10 hour; Nm-class Si-base powder is selected from β-SiC nano powder, Si
3N
4One or more of nano powder, Si/C/N nanometer, add-on are 1～13vol%, α-Al
2O
3The add-on of powder is 85～98vol%, and the add-on of MgO powder is 0.3～3vol%;
The slip that is obtained is dried in vacuum drying oven and is crossed 50～100 mesh sieve, cold isostatic compaction under 200Mpa then after 8～20 hours;
The gained shaping blank is at 1500～1650 ℃ of sintering, and temperature rise rate is 5～15 ℃/min, and soaking time is 1～4 hour.
When nano powder is β-SiC nano powder or Si/C/N nano powder, carry out pressureless sintering at 1550～1650 ℃ among the present invention, protective atmosphere is hydrogen or argon gas; When nano powder is Si
3N
4During nano powder, carry out earlier pressureless sintering under 1550～1570 ℃, gas pressure sintering is carried out at 1600～1650 ℃ in the back, and pressure is 60～80Mpa, and protective atmosphere is nitrogen in the sintering process.
Matrix powder α-Al of the present invention
2O
3Best purity 〉=99.5%; When carrying out stirring ball-milling, solvent is preferably distilled water; Matrix used powder α-Al
2O
3The median size of powder is preferably between 0.3～0.4um, and content is preferably between 90～96vol%; When carrying out stirring ball-milling after various raw materials mix, the time of stirring ball-milling is preferably 2～7 hours.
Can obtain the sintered compact relative density by technology of preparing of the present invention and reach 98.5%, bending strength is 450～550Mpa, and toughness is 4.5～6.7Mpa.m
1/2, Vickers' hardness is 11～17Gpa, and the heat shock resistance temperature reaches 480～520 ℃, and average grain size is the composite microcrystal alumina ceramics with high P/C ratio of 0.8～2um.
The test of bending strength is carried out according to the three-point bending resistance strength test method among standard GB/T 14390-93; Fracture toughness property adopts the pressing in method test, and load is 5Kg, and the hold-time is 10～15 seconds; The heat shock resistance temperature is tested by standard GB/T 16536-1996.
The innovative point of technology of preparing of the present invention is as follows:
1. median size D
50The nm-class Si-base powder of=10～30nm is all thinner than general used nm-class Si-base powder.Such nano powder particle is easy to enter the aluminum oxide intracrystalline in sintering process, form substructure, and a part then is positioned at crystal boundary.Can realize that so just intracrystalline and crystal boundary strengthen the effect with malleableize simultaneously, very effective to the mechanical property that improves pottery.
2. intensity that should pottery reaches 450～550Mpa; Toughness is up to 4.5～6.7Mpa.m
1/2, be 2～3 times of common alumina-ceramic; Its heat shock resistance temperature is also up to 480～520 ℃, far above 275 ℃ of common single-phase alumina-ceramic.This ceramic intensity, especially toughness and thermal shock resistance are the highest level of present domestic pressureless sintering alumina composite ceramic.Its fracture apperance (SEM) is seen Fig. 1.
3. should pottery be microcrystalline structure's structure, median size be 0.8～2um.This is the important assurance of the good over-all properties of the compound micro-crystalline ceramic of described aluminum oxide.Therefore this pottery also has good processing properties.Machined surface roughness is little, even also viscous deformation can occur.Its Wear Mechanism is only alumina grain then and peels off singly for elder generation begins to peel off from the substructure of intracrystalline.Accompanying drawing 2,3 is the friction surface of itself and the tungsten pottery after to mill.Therefore good combination property that should pottery, the reliability height is suitable for doing high-temperature wearable spare etc.
4. add in the alumina-ceramic and generally behind the nm-class Si-base powder particle adopt 1600 ℃～1700 ℃ hot-pressing sintering technique or the non-pressure sintering technology more than 1700 ℃ (nano powder is Si
3N
4Shi Ze is gas pressure sintering).
In a word, the preparation method of the compound micro-crystalline ceramic of aluminum oxide provided by the invention still can obtain good ceramic over-all properties in 1550～1650 ℃ non-pressure sintering technology (or after the pressureless sintering gas pressure sintering) again, and sintered density reaches 98.5% theoretical density.Therefore cost is lower, can make the ceramic member of different shape complexity, is easy to very much suitability for industrialized production.
Below by embodiment in detail the present invention is described in detail.
Accompanying drawing 1 is the fracture apperance (SEM) of the compound micro-crystalline ceramic of aluminum oxide
Accompanying drawing 2 is the compound micro-crystalline ceramic of aluminum oxide and the tungsten friction surface after to mill.
Accompanying drawing 3 is the compound micro-crystalline ceramic of aluminum oxide and the tungsten friction surface after to mill.
Embodiment 1
The median size D of starting raw material: β-SiC nano powder
50=20nm, add-on is 3vol% or 5vol% or 10vol%.MgO is the analytical pure chemical reagent, and add-on is 1vol%.All the other are α-Al
2O
3Powder, D
50=0.37um.
β-SiC nano powder carries out in dehydrated alcohol behind the ultra-sonic dispersion and MgO powder, α-Al
2O
3Powder mixes, stirring ball-milling 4 hours.The slip that is obtained is dried in vacuum drying oven and is crossed the sub-granulation of 55 mesh sieves after 12 hours.Make composite granule cold isostatic compaction under the pressure of 200Mpa of grain.Pressureless sintering is carried out in molybdenum wire furnace, adopts hydrogen to make protection atmosphere, and temperature rise rate is 10 ℃/min, and holding temperature is 1650 ℃, soaking time 2 hours.
The performance of the composite microcrystal alumina ceramics with high P/C ratio that is obtained sees Table 1.
Comparative example 1
Do not add β-SiC nano powder, other conditions are with embodiment 1.
The results of property of the pottery that is obtained sees Table 1.
Table 1
| Thin SiC powder/vol% | Relative density/% | Median size/um | Bending strength/Mpa | Fracture toughness property/Mpa.m 1/2 | Microhardness/Gpa | Heat-shock resistance/℃ |
| ????3 | ???98.8 | ????1.7 | ????467 | ????6.1 | ????11.9 | ??490 |
| ????5 | ???98.6 | ????1.5 | ????489 | ????6.7 | ????11.6 | ??510 |
| ????10 | ???98.5 | ????0.8 | ????453 | ????5.6 | ????12.8 | ??480 |
| Comparative Examples 1 | ???99.3 | ????19 | ????339 | ????3.3 | ????18.6 | ??280 |
Embodiment 2
The median size D of β-SiC nano powder
50=15nm, add-on is 3vol%.α-Al
2O
3The median size D of powder
50=0.50um.Solvent is a distilled water.Slip exsiccant time in vacuum drying oven is 20 hours.Holding temperature is 1600 ℃ during sintering, and protective atmosphere is an argon gas.Other processing condition together
Embodiment 1.
The performance of the composite microcrystal alumina ceramics with high P/C ratio that is obtained sees Table 2.
Comparative example 2
Do not add β-SiC nano powder, other processing condition are with embodiment 2.
The results of property of the pottery that is obtained sees Table 2.
Comparative example 3
Solvent is a dehydrated alcohol, and other processing condition are with embodiment 2.
The results of property of the pottery that is obtained sees Table 2.
Table 2
| Relative density/% | Median size/um | Bending strength/Mpa | Fracture toughness property/Mpa.m 1/2 | Microhardness/Gpa | Heat-shock resistance/℃ | |
| Embodiment 2 | ??98.6 | ??1.2 | ??481 | ??5.7 | ??12.5 | ??500 |
| Comparative Examples 2 | ??98.9 | ??14 | ??313 | ??2.9 | ??18.3 | ??260 |
| Comparative Examples 3 | ??98.5 | ??1.4 | ??461 | ??4.9 | ??12.7 | ??480 |
Embodiment 3
Used nano powder is the Si/C/N composite powder, median size D
50=15nm.Other conditions are with embodiment 1.
The performance of the composite microcrystal alumina ceramics with high P/C ratio that is obtained sees Table 3.
Comparative Examples 4
Do not add nanometer Si/C/N composite powder, other conditions are with embodiment 3.
The results of property of the pottery that is obtained sees Table 3.
Table 3
| Thin Si/C/N powder/vol% | Relative density/% | Median size/um | Bending strength/Mpa | Fracture toughness property/Mpa.m 1/2 | Microhardness/Gpa | Heat-shock resistance/℃ |
| ????3 | ??98.6 | ????2.0 | ??452 | ??5.6 | ??13.8 | ??480 |
| ????5 | ??98.6 | ????2.0 | ??458 | ??6.0 | ??13.1 | ??480 |
| ????10 | ??98.5 | ????1.5 | ??450 | ??4.5 | ??11.7 | ??480 |
| Comparative Examples 4 | ??99.3 | ????19 | ??339 | ??3.3 | ??18.6 | ??280 |
Embodiment 4
Used nano powder is the Si/C/N composite powder, median size D
50=15nm.MgO powder add-on is 2.0vol%.85 mesh sieve are crossed in slip dry back in vacuum drying oven.Other conditions are with embodiment 2.
The performance of the composite microcrystal alumina ceramics with high P/C ratio that is obtained sees Table 4.
Table 4
| Relative density/% | Median size/um | Bending strength/Mpa | Fracture toughness property/Mpa.m 1/2 | Microhardness/Gpa | Heat-shock resistance/℃ |
| ?98.5 | ?1.7 | ?454 | ?5.4 | ?13.2 | ?480 |
Embodiment 5
Used nano powder is Si
3N
4Nano powder.The stirring ball-milling time is 2 hours or 5 hours or 10 hours.Sintering process: carry out earlier pressureless sintering under 1560 ℃, gas pressure sintering is carried out at 1650 ℃ in the back, and pressure is 70Mpa.Pressureless sintering and gas pressure sintering all carry out in the gas pressure sintering stove, and protective atmosphere is nitrogen, and soaking time is 2 hours, and temperature rise rate is 10 ℃/min.Other processing condition are with embodiment 2.
The performance of the composite microcrystal alumina ceramics with high P/C ratio that is obtained sees Table 5.
Table 5
| Ball milling time/hour | Relative density/% | Median size/um | Bending strength/Mpa | Fracture toughness property/Mpa.m 1/2 | Microhardness/Gpa | Heat-shock resistance/℃ |
| ?2 | ?98.7 | ?1.5 | ?513 | ?6.3 | ?16.3 | ?490 |
| ?5 | ?98.7 | ?1.5 | ?538 | ?6.5 | ?15.4 | ?510 |
| ?10 | ?98.6 | ?2.0 | ?483 | ?5.4 | ?13.4 | ?480 |
Claims (7)
1, a kind of preparation method of composite microcrystal alumina ceramics with high P/C ratio is characterized in that:
With median size D
50The nm-class Si-base powder of=15～30nm is as wild phase, in dehydrated alcohol or distilled water, carry out ultra-sonic dispersion after, with median size D
50Matrix powder α-Al of=0.2～0.5um
2O
3Be mixed in the agitating ball mill with the MgO powder, the ball milling time is 1～10 hour; Nm-class Si-base powder is selected from β-SiC nano powder, Si
3N
4One or more of nano powder, Si/C/N nanometer, add-on are 1～13vol%, α-Al
2O
3The add-on of powder is 85～98vol%, and the add-on of MgO powder is 0.3～3vol%;
The slip that is obtained is dried in vacuum drying oven and is crossed 50～100 mesh sieve, cold isostatic compaction under 200Mpa then after 8～20 hours;
The gained shaping blank is at 1500～1650 ℃ of sintering, and temperature rise rate is 5～15 ℃/min, and soaking time is 1～4 hour.
2, by the preparation method of the described composite microcrystal alumina ceramics with high P/C ratio of claim 1, it is characterized in that: when nano powder is β-SiC nano powder or Si/C/N nano powder, carry out pressureless sintering at 1550～1650 ℃, protective atmosphere is hydrogen or argon gas.
3, by the preparation method of the described composite microcrystal alumina ceramics with high P/C ratio of claim 1, it is characterized in that: when nano powder is Si
3N
4During nano powder, carry out earlier pressureless sintering under 1550～1570 ℃, gas pressure sintering is carried out at 1600～1650 ℃ in the back, and pressure is 60～80Mpa, and protective atmosphere is nitrogen in the sintering process.
4, by the preparation method of the described composite microcrystal alumina ceramics with high P/C ratio of claim 1, it is characterized in that: described matrix powder α-Al
2O
3Purity 〉=99.5%.
5, by the preparation method of claim 1,2 or 3 described composite microcrystal alumina ceramics with high P/C ratio, it is characterized in that: when carrying out stirring ball-milling, solvent is a distilled water.
6, by the preparation method of claim 1,2 or 3 described composite microcrystal alumina ceramics with high P/C ratio, it is characterized in that: matrix used powder α-Al
2O
3The median size of powder is between 0.3～0.4um, and content is between 90～96vol%.
7, according to the preparation method of claim 1,2 or 3 described composite microcrystal alumina ceramics with high P/C ratio, it is characterized in that: when carrying out stirring ball-milling after various raw materials mix, the time of stirring ball-milling is 2～7 hours.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100455353C (en) * | 2007-03-09 | 2009-01-28 | 湖南泰鑫瓷业有限公司 | Production of ceramic carrier for nanometer reinforced catalyst |
| CN101555142B (en) * | 2009-05-15 | 2012-02-01 | 山东硅苑新材料科技股份有限公司 | Preparation method of nanosized silicon carbide toughened aluminum oxide bulletproof ceramic |
| CN102677166A (en) * | 2012-06-08 | 2012-09-19 | 常州天合光能有限公司 | Method for manufacturing gradient crucible for polycrystalline silicon ingot casting |
| CN107363736A (en) * | 2017-07-31 | 2017-11-21 | 河南绿添和节能环保科技有限公司 | A kind of high density micro-crystalline ceramic abrasive body and preparation method thereof |
| CN108147794A (en) * | 2018-02-08 | 2018-06-12 | 洛阳中伟环保科技有限公司 | A kind of preparation method of high strength ceramic material |
-
2000
- 2000-11-29 CN CNB00123336XA patent/CN1151994C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100455353C (en) * | 2007-03-09 | 2009-01-28 | 湖南泰鑫瓷业有限公司 | Production of ceramic carrier for nanometer reinforced catalyst |
| CN101555142B (en) * | 2009-05-15 | 2012-02-01 | 山东硅苑新材料科技股份有限公司 | Preparation method of nanosized silicon carbide toughened aluminum oxide bulletproof ceramic |
| CN102677166A (en) * | 2012-06-08 | 2012-09-19 | 常州天合光能有限公司 | Method for manufacturing gradient crucible for polycrystalline silicon ingot casting |
| CN102677166B (en) * | 2012-06-08 | 2015-06-03 | 常州天合光能有限公司 | Method for manufacturing gradient crucible for polycrystalline silicon ingot casting |
| CN107363736A (en) * | 2017-07-31 | 2017-11-21 | 河南绿添和节能环保科技有限公司 | A kind of high density micro-crystalline ceramic abrasive body and preparation method thereof |
| CN107363736B (en) * | 2017-07-31 | 2019-06-07 | 河南绿添和节能环保科技有限公司 | A kind of high density micro-crystalline ceramic abrasive body and preparation method thereof |
| CN108147794A (en) * | 2018-02-08 | 2018-06-12 | 洛阳中伟环保科技有限公司 | A kind of preparation method of high strength ceramic material |
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| Publication number | Publication date |
|---|---|
| CN1151994C (en) | 2004-06-02 |
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