CN104498755B - A kind of preparation method of Ultra-fine Grained high heat stability boron carbide ceramics material - Google Patents
A kind of preparation method of Ultra-fine Grained high heat stability boron carbide ceramics material Download PDFInfo
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Abstract
The preparation method of a kind of thin brilliant high heat stability boron carbide material, the present invention first passes through the superfine boron carbide powder that boron carbide powder ball milling and classification of sedimentation obtain below particle diameter 1 μm；Then coprecipitation is utilized will to prepare B4C and rare earth oxide La2O3/Pr2O3Even dispersion composite powder, its middle rare earth is boron carbide material grain growth inhibitor；Then obtain B by mechanical attrition method4C 0.5～5%Ni3Al/Fe3Al 2～10%La2O3/Pr2O3Composite powder, wherein Ni3Al/Fe3Al boron carbide is toughener；Finally use hot pressing/discharge plasma sintering (SPS) technology, under suitable temperature with sintering time, shape thin brilliant high heat stability boron carbide ceramics material.It is an advantage of the invention that the fine crystalline carbon boron material of preparation has high hardness, low coefficient of friction, high-wearing feature, high thermal structure stability, it is possible to act on high performance gyroscope bearing material and use.
Description
Technical field
The present invention relates to the preparation method of a kind of Ultra-fine Grained high heat stability boron carbide material, be specifically related to a kind of boron carbide ceramics material toughness reinforcing containing rare earth grain growth inhibitor and intermetallic aluminide.
Background technology
(molecular formula is B to boron carbide4C, has another name called boron carbide, usually dark gray powder), its fusing point 2350 DEG C and have ultrahigh hardness, is the third hard material known after diamond, cubic boron nitride, and its Mohs' hardness is 9.3.Can be applicable to the grinding of hard material based on above-mentioned advantage powder boron carbide, grind, hole and polish；And owing to the feature boron carbides such as its acid corrosion-resistant performance is good, density is low are also used as the ceramic coating of warship and helicopter.
A kind of extremely important application of boron carbide is then used as the bearing material of gyroscope dynamic pressure motor.In the inertial guidance system of the carriers such as aircraft, naval vessel, guided missile, aerospace craft, the basic function of gyroscope is used to sensitive angular displacement and the sensor of angular velocity.Boron carbide is used as air-suspension gyroscope bearing and starts from 700 series gyros of nineteen sixty-five Britain Smith Instrument Corporation, instead of the 300 series of balls bearing rate gyroscopes of the said firm.Fine and close boron carbide has the hot pressing ceramic material of good physical chemical characteristic, and hardness is only second to diamond, and weight ratio aluminum is light, has good wear resistence and frictional property, and the bearing being made up of boron carbide is widely used for for many years on the gyroscope of Smith's industrial group.
During boron carbide aero dynamic bearing steady operation, " suspension " is in gas, and frictional resistance and abrasion are the least, but when starting and stop, it is secondary that boron carbide bearing and boron carbide axle sleeve form a set of slip self-friction.At present there is a techniques below difficult problem in boron carbide bearing material:
(1) requirement of boron carbide gyroscope bearing boron carbide ceramics is thin crystalline substance, wear-resisting, high thermal stability, but traditional method preparation technology at present, adds pressureless sintering or the hot pressed sintering of additive, and sintering process crystal grain is grown up, more than 3 μm, cause fracture toughness, hardness, wear no resistance performance；
(2) macrocrystalline boron self-friction coefficient is big, motor will be caused can not to start under specified startup voltage, it is the key hindering its start and stop life-span: the abrasion of macrocrystalline boron self-friction pair is big, cause axle and the change of axle sleeve fit-up gap, the performance of gas dynamic pressure film can be changed, affect the precision of gyroscope.
(3) even if improving sintering process to obtain fine crystalline carbon boron material, crystal grain ＜ 2 μm, when boron carbide uses as hot-end component, may proceed to cause crystal grain to be grown up as frictional heat heats up, causing degradation.
Summary of the invention
For the deficiency in above-mentioned boron carbide material preparation process, the present invention provides a kind of Ultra-fine Grained high heat stability boron carbide material and preparation method
Boron carbide ceramics composition is: B4C-Ni3Al/Fe3Al-La2O3/Pr2O3.Effect: Ni3Al/Fe3Al intermetallic Fe-Al compound shows the shortcoming of a kind of black brittleness at low temperatures, but under the high temperature conditions, intermetallic Fe-Al compound then presents the highest intensity, oozes miscellaneous a certain amount of Ni in boron carbide matrix3Al/Fe3Al, is possible not only to the material working environment of the localized hyperthermia that adaptation occurs because of boron carbide frictional heat, and can be good at increasing B4The toughness of C pottery；La2O3/Pr2O3: grain growth inhibitor, it is positioned at boron carbide grain boundary, reduces crystal boundary energy, inhibiting grain growth.
Preparation method:
(1) with the B of granularity≤20 μm4C ceramics is raw material, utilizes high-energy ball milling to refine boron carbide powder, it is thus achieved that relatively thin boron carbide powder granule, and recycling sedimentation chooses the superfine boron carbide powder of below wherein 1 μm；
(2) solution coprecipitation prepares La2O3/Pr2O3Cladding B4C composite powder；
(4) Ni is added3Al or Fe3Al powder prepares B4C-Ni3Al/Fe3Al-La2O3/Pr2O3Composite powder, ball milling；
(5) boron carbide ceramics material is prepared in pressure sintering (hot pressing or SPS).
Concrete steps and parameter prepared by Ultra-fine Grained high heat stability boron carbide are as follows:
A, first choose≤the B of 20 μm4C powder, as material powder, is placed on ball milling in planetary ball mill with the ratio of grinding media to material of 10-20:1, with 200-400 turn/the rotating speed ball milling 50-100h of min after take out.
B, then sedimentation is utilized to obtain the superfine boron carbide powder granule of below 1 μm, sedimentation chooses the principle of varigrained powder particle: the microfine solid particle termin al velocity degree V0 in fluid media (medium) and its particle size diameter d square is directly proportional, and therefore can determine its granularity by measuring the terminal velocity of granule.Owing to the boron carbide particles of required separation is the powder after high-energy ball milling, its particle size range is less, therefore use and the specific operation process of the sedimentation superfine boron carbide granule that separates 1 μm uses container high for 1-2m (glass container is optimal, because the speed of observable sedimentation in infall process, to control the amount of the powder particle added), sedimentation use water or ethanol as disperse medium.After boron carbide particles natural subsidence in media as well is completely uniform, extracting container upper strata suspension, dry, i.e. obtain the boron carbide superfines granule of 1 μm.
C, utilize coprecipitation by above-mentioned B4C powder and La2O3/Pr2O3Make La2O3/Pr2O3Cladding B4C powder, La2O3/Pr2O3The mode being added in matrix as grain growth inhibitor can directly affect its effect acted on.By B4C and mass fraction 0.5-5%La2O3/Pr2O3Add in same alcoholic solution, and (effect of activator is so that B to add the phosphoric acid solution activator of 1-5%4C powder surface adsorption strengthens), stand 10-20h after stirring, in precipitation process, due to the activation of phosphoric acid solution, La2O3/Pr2O3It is adsorbed in B4C Surface forms unstable cladding powder and gradually at solution bottom deposit.Take out alcohol washes after having deposited completely, drying obtains stable cladding powder.
D. above-mentioned La is taken2O3/Pr2O3Cladding B4C powder and the Ni of mass fraction 2-10%3Al/Fe3Al powder mixes, and obtains B after high-energy ball milling4C-Ni3Al/Fe3Al-La2O3/Pr2O3Composite powder, ball milling uses planetary type ball-milling, and rotational speed of ball-mill 200-40 turns/min, Ball-milling Time 20-100h.
E. above-mentioned B is taken4C-Ni3Al/Fe3Al-La2O3/Pr2O3Composite powder uses hot pressing/discharge plasma sintering (SPS), sintering temperature 1300-1900 DEG C, sintering pressure 20-50Mpa, temperature retention time 5-60min.
Miscellaneous a certain amount of Ni is oozed in boron carbide matrix3Al/Fe3Al, is possible not only to the material working environment of the localized hyperthermia that adaptation occurs because of boron carbide frictional heat, and can be good at increasing B4The toughness of C pottery；La2O3/Pr2O3: grain growth inhibitor, it is positioned at boron carbide grain boundary, reduces crystal boundary energy, inhibiting grain growth.
The invention have the advantage that
(1) add rare earth oxide can grow up by inhibition of sintering crystal grain, thin brilliant (crystal grain ＜ 1 μm), the boron carbide bearing material of high heat stability can be prepared；
(2) add rare earth oxide and can also improve thermal structure stability when boron carbide ceramics material at high temperature uses, keep grained material characteristic；
(3) Ni is added3Al/Fe3Al can improve the obdurability of boron carbide material, improves serviceability；
(4) the fine crystalline carbon boron material prepared has high hardness, low coefficient of friction, high-wearing feature, it is possible to acts on high performance gyroscope bearing material and uses.
Detailed description of the invention
Method in conjunction with the present invention, it is provided that following instance:
Embodiment 1
First the B of 20 μm is chosen4C powder 50g, weighs the rigid ball (ball requires size distributed uniform) of 500g, then the ball milling speed ball milling 50h with 200 turns/min with the ratio of grinding media to material of 10:1；Second step is by the B after ball milling4C powder particle is placed in the container that 1m is high (filling the water of 90% in container), extracting container upper strata suspension after being completely dispersed uniformly, dries the B obtained about 1 μm4C powder particle；3rd step is by B4C and mass fraction 1%La2O3Add in same alcoholic solution, and add 1% phosphoric acid solution activator, after stirring stand 10h, after deposit completely take out alcohol washes, drying obtain stable cladding powder.4th step takes above-mentioned La2O3/Pr2O3Cladding B4C powder and the Fe of mass fraction 2%3Al powder mixes, and obtains B after high-energy ball milling4C+ Fe3Al
+La2O3Composite powder, ball milling uses planetary type ball-milling, 200 turns/min of rotational speed of ball-mill, Ball-milling Time 20h.Take the above-mentioned B of 20g4C+ Fe3Al+La2O3Composite powder uses discharge plasma sintering, sintering temperature 1900 DEG C, sintering pressure 20Mpa, and programming rate uses 100K/min to be rapidly heated, temperature retention time 5min.Take out after cooling completely and obtain causing close to complete fine and close, the boron carbide product of crystal grain small stable.
Embodiment 2
First the B of 20 μm is chosen4C powder 40g, weighs the rigid ball (ball requires size distributed uniform) of 400g, then the ball milling speed ball milling 70h with 300 turns/min with the ratio of grinding media to material of 10:1；Second step is by the B after ball milling4C powder particle is placed in the container that 1m is high (filling the water of 90% in container), extracting container upper strata suspension after being completely dispersed uniformly, dries the B obtained about 1 μm4C powder particle；3rd step is by B4C and mass fraction 2%Pr2O3Add in same alcoholic solution, and add 3% phosphoric acid solution activator, after stirring stand 15h, after deposit completely take out alcohol washes, drying obtain stable cladding powder.4th step takes above-mentioned La2O3/Pr2O3Cladding B4C powder and the Fe of mass fraction 5%3Al powder mixes, and obtains B after high-energy ball milling4C+Fe3Al
+La2O3Composite powder, ball milling uses planetary type ball-milling, 300 turns/min of rotational speed of ball-mill, Ball-milling Time 40h.Take the above-mentioned B of 20g4C+Fe3Al+Pr2O3Composite powder uses hot pressed sintering, sintering temperature 2100 DEG C, sintering pressure 30Mpa, and programming rate uses 100K/min to be rapidly heated, temperature retention time 10min.Take out after cooling completely and obtain close to complete fine and close, the boron carbide product of crystal grain more small stable.
Embodiment 3
First the B of 15 μm is chosen4C powder 50g, weighs the rigid ball (ball requires size distributed uniform) of 1000g, then the ball milling speed ball milling 100h with 400 turns/min with the ratio of grinding media to material of 20:1；B4C powder particle after ball milling is placed in the high container of 1m and (fills the water of 90% in container) by second step, extracting container upper strata suspension after being completely dispersed uniformly, dries the B obtained about 1 μm4C powder particle；3rd step is by B4C and mass fraction 3%La2O3Add in same alcoholic solution, and add 5% phosphoric acid solution activator, after stirring stand 20h, after deposit completely take out alcohol washes, drying obtain stable cladding powder.4th step takes above-mentioned La2O3Cladding B4C powder and the Fe of mass fraction 8%3Al powder mixes, and obtains B after high-energy ball milling4C+ Fe3Al
+La2O3Composite powder, ball milling uses planetary type ball-milling, 400 turns/min of rotational speed of ball-mill, Ball-milling Time 60h.Take the above-mentioned B of 20g4C+ Fe3Al
+La2O3Composite powder uses discharge plasma sintering (SPS), sintering temperature 1950 DEG C, sintering pressure 40Mpa, and programming rate uses 100K/min to be rapidly heated, temperature retention time 8min.Take out after cooling completely and obtain close to complete fine and close, the boron carbide product of crystal grain small stable.
Embodiment 4
First the B of 20 μm is chosen4C powder 40g, weighs the rigid ball (ball requires size distributed uniform) of 800g, then the ball milling speed ball milling 100h with 300 turns/min with the ratio of grinding media to material of 20:1；Second step is by the B after ball milling4C powder particle is placed in the container that 1m is high (filling the water of 90% in container), extracting container upper strata suspension after being completely dispersed uniformly, dries the B obtained about 1 μm4C powder particle；3rd step is by B4C and mass fraction 4%La2O3Add in same alcoholic solution, and add 3% phosphoric acid solution activator, after stirring stand 15h, after deposit completely take out alcohol washes, drying obtain stable cladding powder.4th step takes above-mentioned La2O3Cladding B4C powder and the Ni of mass fraction 5%3Al powder mixes, and obtains B after high-energy ball milling4C+ Ni3Al+La2O3Composite powder, ball milling uses planetary type ball-milling, 300 turns/min of rotational speed of ball-mill, Ball-milling Time 80h.Take the above-mentioned B of 20g4C+Ni3Al+La2O3Composite powder uses discharge plasma sintering, sintering temperature 2100 DEG C, sintering pressure 30Mpa, and programming rate uses 100K/min to be rapidly heated, temperature retention time 40min.Take out after cooling completely and obtain nearly full densification, the boron carbide product of the tiny high stable of crystal grain.
Embodiment 5
First the B of 20 μm is chosen4C powder 50g, weighs the rigid ball (ball requires size distributed uniform) of 1000g, then the ball milling speed ball milling 100h with 400 turns/min with the ratio of grinding media to material of 20:1；Second step is by the B after ball milling4C powder particle is placed in the container that 1m is high (filling the water of 90% in container), extracting container upper strata suspension after being completely dispersed uniformly, dries the B obtained about 1 μm4C powder particle；3rd step is by B4C and mass fraction 1%Pr2O3Add in same alcoholic solution, and add 5% phosphoric acid solution activator, after stirring stand 20h, after deposit completely take out alcohol washes, drying obtain stable cladding powder.4th step takes above-mentioned Pr2O3Cladding B4C powder and the Ni of mass fraction 10%3Al powder mixes, and obtains B after high-energy ball milling4C+ Ni3Al
+Pr2O3Composite powder, ball milling uses planetary type ball-milling, 400 turns/min of rotational speed of ball-mill, Ball-milling Time 100h.Take the above-mentioned B of 20g4C+Ni3Al+Pr2O3Composite powder uses discharge plasma sintering, sintering temperature 2050 DEG C, sintering pressure 40Mpa, and programming rate uses 150K/min to be rapidly heated, temperature retention time 6min.Take out after cooling completely and obtain nearly full densification, the boron carbide product of the tiny high stable of crystal grain.
Claims (1)
1. the preparation method of one kind thin brilliant high heat stability boron carbide material, it is characterised in that comprise the steps:
(1)≤the B of 20 μm is first chosen4C powder, as material powder, is placed on ball milling in planetary ball mill with the ratio of grinding media to material of 10-20:1, with 200-400 turn/the rotating speed ball milling 50-100h of min after take out and obtain boron carbide particles；
(2) sedimentation is utilized to obtain the superfine boron carbide powder of below 1 μm: sedimentation to use water or ethanol as disperse medium, the boron carbide particles natural subsidence in media as well obtained until step (1) completely uniformly after, extracting container upper strata suspension, dry, i.e. obtain the boron carbide superfines granule of below 1 μm；
(3) utilize coprecipitation by above-mentioned B4C powder and La2O3/Pr2O3Make La2O3/Pr2O3Cladding B4C powder: by the B of preparation in step (2)4C and mass fraction 0.5-5%La2O3/Pr2O3Add in same alcoholic solution, and add the phosphoric acid solution activator of 1-5%, stand 10-20h after stirring, in precipitation process, due to the activation of phosphoric acid solution, La2O3/Pr2O3It is adsorbed in B4C Surface forms unstable cladding powder and gradually at solution bottom deposit；Take out alcohol washes after having deposited completely, drying obtains stable cladding powder；
(4) above-mentioned La is taken2O3/Pr2O3Cladding B4C powder and the Ni of mass fraction 2-10%3Al/Fe3Al powder mixes, and obtains B after high-energy ball milling4C-Ni3Al/Fe3Al-La2O3/Pr2O3Composite powder, ball milling uses planetary type ball-milling, and rotational speed of ball-mill 200-400 turns/min, Ball-milling Time 20-100h；
(5) by above-mentioned B4C-Ni3Al/Fe3Al-La2O3/Pr2O3Composite powder uses hot pressing/discharge plasma sintering, sintering temperature 1300-1900 DEG C, sintering pressure 20-50MPa, temperature retention time 5-60min, shapes thin brilliant high heat stability boron carbide ceramics material.
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| CN105543609B (en) * | 2015-12-21 | 2017-11-24 | 中南大学 | A kind of boron carbide-based composite material containing zirconium and preparation method thereof |
| CN106854080B (en) * | 2016-11-15 | 2020-10-30 | 中南大学 | Preparation method for reducing sintering temperature of compact superfine crystal boron carbide ceramic material |
| CN108546129A (en) * | 2018-04-18 | 2018-09-18 | 中国科学院兰州化学物理研究所 | A kind of preparation method of High-Purity Molybdenum aluminium boron ceramic material |
| CN110028321B (en) * | 2019-05-31 | 2022-08-05 | 中南大学 | Energy-saving preparation method of high-performance pure boron carbide ceramic material and pure boron carbide ceramic material |
| CN111057927B (en) * | 2019-12-11 | 2021-03-30 | 中南大学 | Low-temperature high-strength and high-toughness boron carbide material and preparation method and application thereof |
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| CN101265108A (en) * | 2008-04-16 | 2008-09-17 | 哈尔滨工业大学 | Boride-silicon carbide-boron carbide ternary ceramic-base composite material and preparation method thereof |
| CN101269967A (en) * | 2008-05-13 | 2008-09-24 | 武汉理工大学 | Method for preparing boron carbide ceramic |
| CN103572087A (en) * | 2013-11-25 | 2014-02-12 | 武汉理工大学 | Preparation method of boron carbide particle enhanced aluminum-based composite material |
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| WO2012170069A1 (en) * | 2010-12-28 | 2012-12-13 | WILEY, Charles, Schenck | Boron carbide based materials and process for the fabrication thereof |
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| CN101265108A (en) * | 2008-04-16 | 2008-09-17 | 哈尔滨工业大学 | Boride-silicon carbide-boron carbide ternary ceramic-base composite material and preparation method thereof |
| CN101269967A (en) * | 2008-05-13 | 2008-09-24 | 武汉理工大学 | Method for preparing boron carbide ceramic |
| CN103572087A (en) * | 2013-11-25 | 2014-02-12 | 武汉理工大学 | Preparation method of boron carbide particle enhanced aluminum-based composite material |
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