CN1270944A - Sialon ceramic material for bearing ball and its preparation - Google Patents

Sialon ceramic material for bearing ball and its preparation Download PDF

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CN1270944A
CN1270944A CN 00115005 CN00115005A CN1270944A CN 1270944 A CN1270944 A CN 1270944A CN 00115005 CN00115005 CN 00115005 CN 00115005 A CN00115005 A CN 00115005A CN 1270944 A CN1270944 A CN 1270944A
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phase
sintering
sialon
bearing ball
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CN1143837C (en
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张宝林
庄汉锐
李文兰
徐素英
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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

Through specific formulation and sintering process, the present invention obtains a kind of material comprising Alpha-sialon phase and Beta-phase Si3N4, B phase Y2SiAlO3N, N phase Y5(SiO4)3N, small amount of YAG phase 3Y2PO3.5Al2O3, and glass phase. The present invention adopts a three-stage temperature-maintaining sintering process and in its second and third stages, nitrogen pressure inside the furnace is maintained under 0.15-0.22 MPa and 1.0-5.0 MPa respectively to prevent high-temperature decomposition. Bearing ball produced with the said ceramic material has a crushing load not lower than 45% that of a steel bearing ball in the same size, a Vickers hardness greater than 16.5 GPa and a porosity in polished surface smaller than 0.25 (by volume ratio).

Description

Be used for Sialon ceramic material of bearing ball and preparation method thereof
The present invention relates to Sai Long (sialon) stupalith and preparation method thereof, particularly can be used for Sialon ceramic material of bearing ball and preparation method thereof.Belong to silicon nitride (Si 3N 4) the sill field.
Sialon is Si 3N 4Sosoloid, at first propose in 1978 by scientist, two kinds of plasmodiums of α-sialon and β-sialon are arranged.The Sialon material has high rigidity, high-intensity characteristics, thereby be extremely rising abrasion-proof structure stupalith.
β-sialon molecular formula is Si 6-ZAl ZO ZN 8-ZBe by β-Si 3N 4Middle Z Si-N key obtains after being replaced by Z Al-O key; α-sialon molecular formula is Me xSi 12-(m+n)Al M+nO nN 16-n, be α-Si 3N 4Middle n Si-N key obtained after m Si-N key replaced by m Al-N key simultaneously by n Al-O key, and the electricity price imbalance that a back replacement causes compensates by introducing x atoms metal Me.When atoms metal Me is Y element, x=m/3.Y -α/βSialon generally presses different ratios blended Si by thermal treatment 3N 4, AlN, Al 2O 3And Y 2O 3Powder is synthetic.The sialon ceramic of compact can adopt hot pressing (HP), not have and press (PLS), air pressure (GPS) and hot isotatic pressing sintering methods such as (HIP) to obtain.Some intermediate phase: YAG, nitrogenous melilith, nitrogenated silicon hydrochlorate, 12H, 21R and β appear in the Sialon sintering process 60Equate.The formation of these intermediate phase has reduced the transition liquid-phase amount, and sintering is produced bigger influence, and therefore, promptly sintering condition should be to sintering process and the big influence of the final density generation of product stage by stage for the middle heat-retaining condition in the sintering process.By design solid solution capacity and sintering process, certain mechanical property that obtains wanting and microstructural Sialon stupalith can satisfy the excellent comprehensive performance of ceramic bearing ball demand.
In the structural ceramics, silicon nitride ceramics has higher fracture toughness property, good anti-rolling contact fatigue characteristic and spalling failure pattern, and be applied to field of bearings, particularly be used for making bearing ball and roller.R.L. " silicon nitride bearing ball with high fatigue life " (CN 1143944A) of Ye Keli invention introduced the preparation technology of the silicon nitride material that is used for bearing, and this material has long rolling contact fatigue life.But generally to adopt expensive hot isostatic pressing (HIP) sintering process to obtain, and the hardness of material be not very high (<15.6GPa).The sialon material that " composite ceramics and the preparation method " of people such as Wang Peiling invention (CN1142478A) prepares has very high hardness and hot strength, but not mentioned material grains size, after two stage sintering and long heat treatment, crystal grain is very easily grown up until about 10 microns in the material, toughness of material can be higher, but may discomfort be fit to do the bearing ball material.Silicon nitride bearings material has the spalling failure pattern in the application and the course of processing, crystal grain is usually extracted and taken place, and excessive crystal grain can reduce working accuracy and work-ing life.
The object of the present invention is to provide a kind of sialon material that is used for bearing ball and preparation method thereof, the sialon material that is used for bearing that it provides has high rigidity, high crush strength and low porosity, particularly material is micro-is made up of less crystal grain (within the size of microcrystal 0.3-3 micron of 95% quantity), and is suitable for mass production.
At first, the main raw material of the present invention's employing is Si 3N 4(α phase 〉=90wt%, 0.36 micron of median size, oxygen level 1.8wt%), AlN (0.93 micron of median size, oxygen level 1.57wt%, nitrogen content 32.5wt%), Al 2O 3(purity>99.9%) and Y 2O 3(purity>99.9%) powder.AlN content is at 6~11wt%, 8~9wt% better, Al 2O 3Content is at 1.5~4.5wt%, 3~3.5wt% better, Y 2O 3Content is at 5~9wt%, 7~7.9wt% better, Si 3N 4Content is promptly joined the needed amount of sufficient 100wt%.
Secondly, adopt no pressure, air pressure or HIP sintering, adopt performance/cost better than high gas pressure sintering.Sintering process at sialon is the reaction sintering process of a complexity, and the present invention adopts three sections unique heat preservation sintering methods, 1710~1830 ℃ of fs, is incubated 0.5~2 hour; 1790~1910 ℃ of subordinate phase are incubated 0.5~2.5 hour; 1830~1950 ℃ of phase IIIs, be incubated 0.5~5 hour.Decompose in order to control high-temperature sample, remain on 0.15~0.22MPa, remain on 1.0~5.0MPa at phase III sintering nitrogen pressure in furnace at subordinate phase sintering nitrogen pressure in furnace.The benefit of this sintering schedule is: when being incubated under about 1750 ℃ not high not low temperature of fs temperature, and a large amount of tiny α-sialon crystal grain and β phase Si 3N 4Crystal grain forms, subordinate phase and fs temperature head are not more than 80 ℃, the temperature head that the most important thing is phase III and subordinate phase is not more than 40 ℃, temperature head can not be too big, and the temperature of fs and subordinate phase can not be too low, can not be lower than 1710 ℃ and 1790 ℃ (seeing embodiment 4 for details) respectively.In conjunction with prescription provided by the invention, make α-sialon crystal grain both make at high temperature and also do not grow up unusually, and β phase Si 3N 4Crystal grain is under the steric effect restriction of α-sialon crystal grain, and crystal grain is not grown up yet, and in the high-temperature sintering process of phase III, owing to there is not the restriction of excessive crystal grain stretching, sample can continue to shrink fine and close, final sample density height, and pore is few, and crystal grain is little.Sample imbedded consist of Si 3N 4: AlN: BN=8.2: the burying in the powder of 0.8: 1 (weight ratio).Sample and bury powder and all place plumbago crucible.The stove temperature rise rate is 10 ℃/minute, and rate of temperature fall ℃ is 18 ℃/minute from high temperature to 1300.Decompose in order to control high-temperature sample, remain on 0.15~0.22MPa at subordinate phase sintering nitrogen pressure in furnace, the phase III nitrogen pressure remains on 1.0~5.0MPa.
By the Sialon ceramic material that is used for bearing ball that component provided by the invention and prepared go out, match grand, β phase Si mutually by α 3N 4, B phase (Y 2SiAlO 5N), H phase (Y 5(SiO 4) 3N), reach a small amount of YAG (3Y 2O 35Al 2O 3) and the glassy phase composition, the grand phase content of α match is in 25~45wt% scope.The size of microcrystal of 95% quantity is in 0.3~3 micron, greater than 5 microns crystal grain quantity<1%.Material void content≤0.2%, and crystal grain such as is at the axle shape.
The present invention has following advantage:
(1) by pointed prescription and sintering process, the α-sialon that can obtain α-sialon content 25wt%~45wt% and β be Si mutually 3N 4Matrix material, bring into play this two phase material strong point separately, material hardness is higher, Vickers' hardness is greater than 16.5GPa, fracture toughness property and bending strength are all higher under the room temperature simultaneously, are respectively: K IC: 5.5~6.2MPam 1/2And 607~756MPa.
(2) the tiny axle shape such as be of the microstructure of material particularly is made up of the small grains of 0.3~3 micron of the size of microcrystal of 95% quantity.This material is suitable for doing bearing materials, particularly the bearing ball material.The crushing load of the bearing ball of this material preparation is higher, and this mainly has benefited from waiting axle shape crystal grain.
Further illustrate the advantage and the novel part of invention below by embodiment.
The Si of embodiment 1 405 grams 3N 4Powder (α phase 〉=90wt%, 0.36 micron of median size, oxygen level 1.8wt%), the AlN (0.93 micron of median size, oxygen level 1.57wt%, nitrogen content 32.5wt%) of 40 grams, the Y of 38 grams 2O 3The Al of (purity>99.9%) and 17 grams 2O 3(purity>99.9%).Add 500 milliliters of ethanol, 1000 gram diameters are 10 millimeters silicon nitride bead, and 10.1 gram PVB mixed 20 hours in the silicon nitride tube.After the oven dry, the unidirectional strip that is pressed into 5mm * 5mm * 50mm that adds, isostatic cool pressing further increases biscuit density under 250MPa pressure again.
Sintering is to carry out in the graphite heater stove, and sample is imbedded and consisted of Si 3N 4: AlN: BN=8.2: the burying in the powder of 0.8: 1 (weight ratio).Sample and bury powder and all place plumbago crucible.The stove temperature rise rate is 10 ℃/minute, and rate of temperature fall ℃ is 18 ℃/minute from high temperature to 1300.Adopt three sections heat preservation sintering methods, sample was incubated in the fs: 1770 ℃, and 1 hour; Subordinate phase: 1850 ℃, 1.5 hours; Phase III: 1880 ℃, 3 hours.Decompose in order to control high-temperature sample, remain on 0.18MPa, remain on 1.2MPa at phase III sintering nitrogen pressure in furnace at subordinate phase sintering nitrogen pressure in furnace.
Behind the sample sintering, the surface grinds off about thickness 0.5mm, and with Archimedes's water soaking method measuring density, X-ray diffraction method carries out facies analysis.After the polishing sample corrodes, use the scanning electron microscopic observation pattern in fusion NaOH.
Fine and close sample attrition process becomes bending strength strip 3 * 4 * 35mm 3, measure bending strength with three-point bending method, span 30mm.Load 10kg measures microhardness down, measures crack length and calculates fracture toughness property.
Material α-sialon content is 39wt%, and intensity is 659MPa.Crystal boundary is mainly B phase (Y mutually 2SiAlO 5N), H phase (Y 5(SiO 4) 3N), a small amount of YAG phase (3Y 2O 35Al 2O 3) and glassy phase, its X-ray diffractogram is as shown in Figure 1.Among the figure 1: β phase Si 3N 4, 2: α-sialon, 3:B phase, 4:YAG phase, 5:H phase.
Prescription and sintering process that embodiment 2 adopts similarly to Example 1, the sample shape of overmolding is not that diameter is the ball-type sample of 8mm.Nitrogen pressure in furnace is 0.16MPa during the subordinate phase insulation, and the phase III nitrogen pressure in furnace is 3MPa.Behind the sintering, sample rate is 3.3 gram/mm 3, after the ball polishing, adopt ball-ball that the ball crushing of platen press test is loaded and be 9.7KN, be 45.6% of unidimensional bearing steel ball.Ball is cut back tangent plane polishing, and the observation void content is<0.2vol%.Microhardness 17.6GPa on the tangent plane, fracture toughness property K IC: 5.7MPam 1/2In fused NaOH corrosion back scanning electron microscopic observation pattern mutually as shown in Figure 2, the size of microcrystal of 95% quantity and is and waits the axle shape in 0.3~3 micron, helps it as bearing ball usefulness, can improve ultimate compression strength and minimizing pore.
(as the YAG with 10wt% is sintering aid for the SiAlON ceramic bearing ball of method for preparing and general gas Pressure Sintered Silicon Nitride; 1900 ℃ of sintering 2 hours; then 1940 ℃ of sintering 2 hours, the highest 1.2MPa nitrogen protection atmosphere) the ceramic bearing ball performance relatively has advantage as shown in table 1.
Table 1
Performance Embodiment 2 General gas Pressure Sintered Silicon Nitride
Microhardness (GPa) ????17.3 ????13.2
Crushing strength/unidimensional bearing steel ball crushing strength ????>45% ????≤30%
>5 microns crystal grain quantity ????<1% ????>10%
The grand raw material of embodiment 3 matches consists of 81.2wt%Si 3N 4(Ube newly product company is produced, UBE, E10), 8.1wt%AlN, 4.2wt%Al 2O 3And 6.5wt%Y 2O 3Adding is with the ethanol and the PVB of embodiment 1 ratio, is that 10 millimeters silicon nitride bead is the mix grinding medium with diameter, mixes 20 hours in the silicon nitride bucket.After the oven dry, dry-pressing and isostatic pressing sample shape are that diameter is the ball of 8mm and the strip of 5mm * 5mm * 50mm.
Sintering process contains the α phase sialon of 29wt% with embodiment 1 in the material.The material breaking tenacity is 692MPa, Vickers' hardness 17.3GPa, and ball polishing tangent plane is observed void content<0.2vol% under 100 times of opticmicroscopes.
The grand raw material of embodiment 4 matches is formed with embodiment 1 and embodiment 2, and moulding process of the same race is shaped to ball-type or strip, sintering buries powder, stove and temperature rise rate also with embodiment 1 and embodiment 2, and sintering schedule changes into: sample was incubated in the fs: 1680 ℃, and 1 hour; Subordinate phase: 1780 ℃, 1.5 hours; Phase III: 1900 ℃, 3 hours.Decompose in order to control high-temperature sample, remain on 0.18MPa, remain on 1.2MPa at phase III sintering nitrogen pressure in furnace at subordinate phase sintering nitrogen pressure in furnace.Because each holding stage temperature difference is bigger, and preceding two phase temperature are on the low side, take place to grow up unusually at phase III crystal grain, occur a large amount of crystal grain greater than 3 microns in the material microstructure, as shown in Figure 3.The buttressing effect influence that excessive crystal grain produces is final fine and close, and ball polishing tangent plane is observed void content>0.5vol% under 100 times of opticmicroscopes.This illustrates that prescription of the present invention must just can reach desired performance in conjunction with sintering process of the present invention.
SiAlON ceramic of the present invention can be used for (but being not limited to) ceramic bearing ball or roller, also can be used for other wear parts, as ceramic cutter, ceramic sand jet etc.

Claims (5)

1. a sintering that is used for bearing ball is matched grand (sialon) stupalith, mainly by α-sialon phase, β-Si 3N 4Phase composite.It is characterized in that:
(1) it is by α-sialon phase, the β-Si of 25~45wt% 3N 4Phase, B phase (Y 2SiAlO 5N), H phase (Y 5(SiO 4) 3N), a small amount of YAG phase (3Y 2O 35Al 2O 3) and the glassy phase composition;
(2) the material microstructure is formed tiny and is and waits a shape, and the size of microcrystal of 95% quantity is in 0.3~3 micron, greater than 5 microns crystal grain quantity<1%.
2, by the described preparation method who is used for the sintering Sialon ceramic material of bearing ball of claim 1, it is characterized in that:
(1) main raw material of Cai Yonging is Si 3N 4, AlN, Al 2O 3And Y 2O 3Powder, AlN content be at 6~11wt%, Al 2O 3Content is at 1.5~4.5wt%, Y 2O 3Content is at 5~9wt%, Si 3N 4Content is promptly joined the needed amount of sufficient 100wt%;
(2) adopt three sections heat preservation sintering methods,, be incubated 0.5~2 hour 1710~1830 ℃ of fs; 1790~1910 ℃ of subordinate phase, 0.5~2.5 hour; 1830~1950 ℃ of phase IIIs, 0.5~5 hour.Subordinate phase and fs temperature head are not more than 80 ℃, and phase III and subordinate phase temperature head are not more than 40 ℃; And remain on 0.15~0.22MPa at subordinate phase sintering nitrogen pressure in furnace, remain on 1.0~5.0MPa at phase III sintering nitrogen pressure in furnace.
3, by the preparation method of claim 2, be to imbed to consist of Si in the sample sintering process 3N 4: AlN: BN=8.2: the burying in the powder of 0.8: 1 (weight ratio).
By the described sintering Sialon ceramic material that is used for bearing ball of claim 1, it is characterized in that 4, the crushing load is not less than 45% of unidimensional bearing steel ball.
5, by the described sintering Sialon ceramic material that is used for bearing ball of claim 1, can be used for ceramic bearing ball or wear parts such as roller and ceramic cutter, ceramic sand jet.
CNB001150057A 2000-03-21 2000-03-21 Sialon ceramic material for bearing ball and its preparation Expired - Fee Related CN1143837C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1316173C (en) * 2004-12-24 2007-05-16 上海汽车股份有限公司 Method of making oil-containing bearing block through powdered metallurgy
CN101688558B (en) * 2007-06-27 2012-12-19 Ntn株式会社 Rolling member, rolling bearing and process for manufacturing rolling member
CN102135131B (en) * 2006-12-20 2013-03-13 Ntn株式会社 Hub unit
CN107001157A (en) * 2014-12-12 2017-08-01 陶瓷技术有限责任公司 α/β match with improved sintering activity and high rim-intensity is grand
CN108863399A (en) * 2018-07-26 2018-11-23 深圳市东川技术研究有限公司 Match the sintering process of grand electric heating new material

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1316173C (en) * 2004-12-24 2007-05-16 上海汽车股份有限公司 Method of making oil-containing bearing block through powdered metallurgy
CN102135131B (en) * 2006-12-20 2013-03-13 Ntn株式会社 Hub unit
CN101688558B (en) * 2007-06-27 2012-12-19 Ntn株式会社 Rolling member, rolling bearing and process for manufacturing rolling member
CN107001157A (en) * 2014-12-12 2017-08-01 陶瓷技术有限责任公司 α/β match with improved sintering activity and high rim-intensity is grand
CN108863399A (en) * 2018-07-26 2018-11-23 深圳市东川技术研究有限公司 Match the sintering process of grand electric heating new material

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