CN108298996A - A kind of method of boron nitride nano-tube flexible silicon nitride ceramic and its product of preparation - Google Patents

A kind of method of boron nitride nano-tube flexible silicon nitride ceramic and its product of preparation Download PDF

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CN108298996A
CN108298996A CN201810030536.6A CN201810030536A CN108298996A CN 108298996 A CN108298996 A CN 108298996A CN 201810030536 A CN201810030536 A CN 201810030536A CN 108298996 A CN108298996 A CN 108298996A
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tube
boron nitride
nitride nano
raw material
silicon nitride
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骆丽杰
陈拥军
李天峰
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Hainan University
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Abstract

An embodiment of the present invention provides a kind of methods of boron nitride nano-tube flexible silicon nitride ceramic, including：(1) raw material is weighed, based on the gross mass of the raw material, the raw material includes：88.8 90% alpha silicon nitride, 0.1 1.2% boron nitride nano-tube, 2 8% aluminium oxide, 2 8% gadolinium oxide；(2) by after other raw material ball milling specified times in addition to boron nitride nano-tube, then boron nitride nano-tube is added and continues ball milling, mixed slurry will be arrived；(3) mixed slurry is fitted into after drying, sieving in mold, carries out hot pressed sintering in an inert atmosphere.The method of boron nitride nano-tube flexible silicon nitride ceramic provided by the invention is mutually introduced into silicon nitride matrix using boron nitride nano-tube as toughening, considerably improves the fracture toughness of silicon nitride ceramics.

Description

A kind of method of boron nitride nano-tube flexible silicon nitride ceramic and its product of preparation
Technical field
The present invention relates to boron nitride ceramics preparing technical fields, more particularly to a kind of boron nitride nano-tube flexible silicon nitride The method of ceramics and its product of preparation.
Background technology
In silicon nitride structure, the chemical bond of nitrogen-atoms and silicon atom is very strong, therefore silicon nitride ceramics has hardness high, resistance to The advantages that good, good thermal shock of mill property, good chemical stability, it is widely used in the fields such as machinery, chemical industry, aerospace.But It is big that silicon nitride ceramics still has the shortcomings that ceramic material shares a brittleness.Therefore, the toughness for how improving silicon nitride ceramics, according to It is so one of the hot spot of ceramic material research.
The method for toughening of ceramic material includes phase toughness, whisker and particle toughening, fiber toughening, nano wire and nanotube Toughening etc..But phase transformation, whisker and particle toughening effect are not particularly evident, the opertions engineering of fiber toughening is complex, together When product consistency it is poor, it is carbon nanotube toughening that application is more at present.It is made due to the high-temperature oxydation of carbon nanotube Using with certain limitation, and the fracture toughness of the silicon nitride ceramics of carbon nanotube toughening is generally 8.5MPam1/2 (referring to E.L.Corral, J.Cesarano III, A.Shyam, E.Lara-Curzio, N.Bell, J.Stuecker, N.Perry,M.D.Prima,Z.Munir,J.Garay,and E.V.Barrera,Engineered nanostructures for multifunctional single-walled carbon nanotube reinforced ailicon nitride Nanocomposites, J.Am.Ceram.Soc.91 (2008) 3129-3137.), toughening effect is limited.
Invention content
Boron nitride nano-tube is a kind of structure and the very much like monodimension nanometer material of carbon nanotube, boron nitride nano-tube with Carbon nanotube-sample has excellent mechanical property, and Young's modulus is in 0.7-0.9TPa ranges.In terms of thermal property, it is theoretical and Experimental result all proves that the thermal conductivity of boron nitride nano-tube is suitable with carbon nanotube.In addition, boron nitride nano-tube compares carbon nanometer There is pipe better thermal stability and chemical stability, oxidation resistance temperature may be up to 900 DEG C, and far above carbon nanotube, (it is aoxidized Temperature is 400-500 DEG C).Inventor is by being extensively studied, it has unexpectedly been found that, although the structure of boron nitride nano-tube and carbon are received Mitron is very much like, but the effect of its flexible silicon nitride ceramic is but unexpectedly substantially better than carbon nanotube；Based on this, originally Invention provides a kind of method of boron nitride nano-tube flexible silicon nitride ceramic and its product of preparation, to overcome carbon nanotube to increase The ineffective problem of tough silicon nitride ceramics.
Specific technical solution is as follows：
Present invention firstly provides a kind of methods of boron nitride nano-tube flexible silicon nitride ceramic, including：
(1) raw material is weighed, based on the gross mass of the raw material, the raw material includes：The α-siliconnitride of 88.8-90%, The boron nitride nano-tube of 0.1-1.2%, the aluminium oxide of 2-8%, the gadolinium oxide of 2-8%；
(2) by after other raw material ball milling specified times in addition to boron nitride nano-tube, then by boron nitride nano-tube be added after Continuous ball milling, will arrive mixed slurry；
(3) mixed slurry is fitted into after drying, sieving in mold, carries out hot pressed sintering in an inert atmosphere.
In some preferred embodiments of the present invention, the raw material includes：The α-siliconnitride of 88.8-89.4%, 0.6- 1.2% boron nitride nano-tube, 6% aluminium oxide, 4% gadolinium oxide；Preferably, the raw material includes：89.2-89.4%'s α-siliconnitride, the boron nitride nano-tube of 0.6-0.8%, 6% aluminium oxide, 4% gadolinium oxide.
In some preferred embodiments of the present invention, the average grain diameter of α-siliconnitride is 600-800nm, and aluminium oxide is put down Equal grain size is 200-400nm, and the average grain diameter of gadolinium oxide is 400nm.
In some preferred embodiments of the present invention, step (2) is specially：By other originals in addition to boron nitride nano-tube After pellet is ground 8-10 hours, then boron nitride nano-tube is added and continues ball milling 0.5-1 hour.
The present invention some preferred embodiments in, the inert atmosphere in step (3) in nitrogen, argon gas at least It is a kind of.
In some preferred embodiments of the present invention, the hot-pressing sintering technique parameter in step (3) includes：With 16-25 DEG C/min heating rate be warming up to 1200 DEG C, then with 5-15 DEG C/min of heating rate to 1750-1800 DEG C, heat-insulation pressure keeping 0.5-1 hours, the pressure of hot pressed sintering was 30-40MPa.
In some preferred embodiments of the present invention, after step (3) hot pressed sintering, then release naturally cools to Room temperature.
In some preferred embodiments of the present invention, after cooling is complete, rubbing down working process is carried out to products obtained therefrom.
In some preferred embodiments of the present invention, the boron nitride nano-tube is made by following methods：
By FeCl3Dissolving in ethanol, is then added unformed boron powder mixing, boron powder mixed liquor is obtained, wherein unformed Boron powder and FeCl3Molar ratio be 1：(0.03-0.07)；
The boron powder mixed liquor is evaporated at 40-60 DEG C, ethyl alcohol is removed, obtains boron nitride nano-tube precursor；
Boron nitride nano-tube precursor is warming up to 1200-1250 DEG C in ammonia reaction atmosphere, is kept for 3-7 hours, ammonia Flow velocity is 30-60mL/ minutes；
It is cooling in nitrogen atmosphere.
The present invention also provides boron nitride nano-tube flexible silicon nitride ceramics prepared by method above-mentioned.
The method of boron nitride nano-tube flexible silicon nitride ceramic provided by the invention, using boron nitride nano-tube as toughening phase It is introduced into silicon nitride matrix, considerably improves the fracture toughness of silicon nitride ceramics.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with Obtain other attached drawings according to these attached drawings.
Fig. 1 is the XRD diagram of boron nitride nano-tube flexible silicon nitride ceramic prepared by embodiment 3.
Specific implementation mode
A kind of method of boron nitride nano-tube flexible silicon nitride ceramic, this method using boron nitride nano-tube as toughening phase, with α-siliconnitride forms boron nitride ceramics matrix, and aluminium oxide and gadolinium oxide is added as sintering aid, prepares boron nitride nano-tube increasing Tough boron nitride ceramic material, this method may include：
(1) raw material is weighed, based on the gross mass of the raw material, the raw material is calculated in mass percent, including：88.8- 90% α-siliconnitride, the boron nitride nano-tube of 0.1-1.2%, the aluminium oxide of 2-8%, the gadolinium oxide of 2-8%；
(2) by after other raw material ball milling specified times in addition to boron nitride nano-tube, then by boron nitride nano-tube be added after Continuous ball milling, will arrive mixed slurry；
(3) mixed slurry is fitted into after drying, sieving in mold, carries out hot pressed sintering in an inert atmosphere.
α-siliconnitride (silicon nitride of α crystalline phases), aluminium oxide and gadolinium oxide of the present invention, may be used this field Prepare the convenient source of silicon nitride ceramics, such as commercial alumina powder (Alpha-alumina) and gadolinium oxide powder etc..These raw materials It can be bought by commercial sources, the present invention is at this to its source without limiting.
In certain specific embodiments of the invention, the average grain diameter of α-siliconnitride is 600-800nm, and aluminium oxide is put down Equal grain size is 200-400nm, and the average grain diameter of gadolinium oxide is 400nm.
In certain specific embodiments of the invention, based on the gross mass of the raw material, the raw material is with quality percentage Number meter, including：The α-siliconnitride of 88.8-89.4%, the boron nitride nano-tube of 0.6-1.2%, 6% aluminium oxide, 4% oxidation Gadolinium.Preferably, the raw material includes：The α-siliconnitride of 89.2-89.4%, the boron nitride nano-tube of 0.6-0.8%, 6% oxygen Change aluminium, 4% gadolinium oxide.
For step (2), first by other raw material ball millings in addition to boron nitride nano-tube, boron nitride nano-tube addition is added Continue ball milling, can both prevent boron nitride nano-tube broken by prolonged grinding；It can ensure boron nitride nanometer again Pipe is uniformly mixed with other raw material components.
Step (2) uses wet ball grinding technique, and in some embodiments, step (2) is specially：Boron nitride will be removed Other raw material ball millings outside nanotube are after 8-10 hours, then boron nitride nano-tube is added and continues ball milling 0.5-1 hour.More have Body can using silicon nitride ball as ball-milling medium, using isopropanol as decentralized medium when wet ball grinding.
In certain specific embodiments of the invention, the inert atmosphere in step (3) can be in nitrogen, argon gas It is at least one；Consider cost, preferably nitrogen.
The present invention uses hot-pressing sintering technique, hot pressed sintering to have been widely used for manufacturing fine and close ceramics at a lower temperature And promote the isometric growth of ceramic crystalline grain.
In certain specific embodiments of the invention, the hot-pressing sintering technique parameter in step (3) is：With 16-25 DEG C/ Minute, preferably 20 DEG C/min of heating rate is warming up to 1200 DEG C, then with 5-15 DEG C/min, preferably 10 DEG C/min Heating rate is to 1750-1800 DEG C, after being warming up to 1750-1800 DEG C, heat-insulation pressure keeping 0.5-1 hours, and the pressure of hot pressed sintering For 30-40MPa.The temperature that α → β phase transformations occur for silicon nitride is 1400 DEG C.Therefore be warming up to before 1200 DEG C, faster liter can be used Wen Su, such as preferably 20 DEG C/min, 1200-1800 DEG C of stage, the more slow heating rate of use, such as preferably 10 DEG C/min, be conducive to the perfect growth of crystal grain.
In certain specific embodiments of the invention, after step (3) hot pressed sintering, then release naturally cools to Room temperature (such as 25 DEG C).In certain specific embodiments of the invention, after cooling is complete, rubbing down is carried out to products obtained therefrom and is added Work processing.
Various known boron nitride nano-tubes may be used to realize in boron nitride nano-tube used in toughening of the present invention.Preferably Document may be used in ground：An Pan,Yongjun Chen.Large-scale fabrication of boron nitride nanotubes with high purity via solid-state reaction method,Nanoscale Research Letters,2014,9:The boron nitride nano-tube that 555 (document is incorporated by herein by quoting it) are reported is come toughening. Boron nitride nano-tube in the document is Bamboo-shaped, and major diameter is relatively high, and specific surface area bigger, toughening effect is more preferably；It is specifically closed It is as follows at method：
By FeCl3Dissolving in ethanol, is then added unformed boron powder mixing, boron powder mixed liquor is obtained, wherein unformed Boron powder and FeCl3Molar ratio be 1：(0.03-0.07)；
The boron powder mixed liquor is evaporated at 40-60 DEG C, ethyl alcohol is removed, obtains boron nitride nano-tube precursor；
Boron nitride nano-tube precursor is warming up to 1200-1250 DEG C in ammonia reaction atmosphere, is kept for 3-7 hours, ammonia Flow velocity is 30-60mL/ minutes；
It is cooling in nitrogen atmosphere.
The method of boron nitride nano-tube flexible silicon nitride ceramic provided by the invention, the equipment used is simple, easy to operate, It is safe, pollution-free, stable preparation process, production efficiency height.Prepared silicon nitride ceramics toughening effect is apparent, and fracture is tough Property can reach 10.4MPam1/2, 22.3% is at most improved than carbon nanotube flexible silicon nitride ceramic, than pure silicon nitride ceramics At most improve 44.4%.
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
Firstly, it is necessary to explanation, each raw material and relevant device used in following embodiment, unless there are specified otherwise, It can be obtained by commercial sources.
The preparation of 1 packed boron-nitride bamboo-like nano-tubes of embodiment
The method that bibliography is recorded prepares packed boron-nitride bamboo-like nano-tubes, and for the toughening as following embodiment Material；Specific preparation process is as follows：
By FeCl3·6H2O is dissolved in absolute ethyl alcohol, and unformed boron powder is then added, and obtains boron powder mixed liquor, wherein Unformed boron powder and FeCl3·6H2The molar ratio of O is 1：0.05.Stirred in water bath 2 hours by boron powder mixed liquor at 40 DEG C To evaporate solvent, until starchiness, then gained paste mixture is dried at 55 DEG C thoroughly to remove absolute ethyl alcohol, obtain Boron nitride nano-tube precursor.Boron nitride nano-tube precursor is fitted into the aluminium oxide porcelain boat for being placed in tube furnace center, to tube furnace In be passed through ammonia to remove the residual air in tube furnace.In ammonia reaction atmosphere, by diamond heating to 1200 DEG C, and protect It holds 5 hours；In the process, ammonia flow velocity is 50mL/ minutes.Finally by tube furnace under the protection of nitrogen atmosphere (nitrogen stream) Naturally cool to environment temperature.
The preparation of 2 boron nitride nano-tube flexible silicon nitride ceramic of embodiment
Weigh the α-siliconnitride of 21.456g with electronic balance, the aluminium oxide of 1.44g, the gadolinium oxide of 0.96g and 0.144g's Boron nitride nano-tube.It will pour into agate jar except the material of boron nitride nano-tube dress, using silicon nitride ball as ball-milling medium, use Isopropanol does decentralized medium, and ball milling adds the boron nitride nano-tube continuation for weighing up quality after 8 hours on planetary ball mill Ball milling 1 hour.The slurry mixed is dried at 100 DEG C, crosses 100 mesh standard sieves.The sieving materials for weighing certain mass are packed into directly It is placed in hot pressing furnace in the graphite jig that diameter is 42mm, in N2Under atmosphere protection, 1200 DEG C are warming up to 20 DEG C/min, then with 10 DEG C/min is warming up to 1750 DEG C, pressurize 40MPa, heat-insulation pressure keeping 0.5 hour, then then release naturally cools to room temperature.Optionally Ground by gained ceramics after grinding and polishing, then is machined, such as grinding, cutting means obtain finished product, for testing.
The preparation of 3 boron nitride nano-tube flexible silicon nitride ceramic of embodiment
The silicon nitride of 21.408g, the aluminium oxide of 1.44g, the gadolinium oxide of 0.96g and the nitrogen of 0.192g are weighed with electronic balance Change boron nanotube.It will be poured into agate jar except the material of boron nitride nano-tube dress, using silicon nitride ball as ball-milling medium, use is different Propyl alcohol does decentralized medium, and ball milling adds the boron nitride nano-tube continuation ball for weighing up quality after 9 hours on planetary ball mill Mill 1 hour.The slurry mixed is dried at 100 DEG C, crosses 100 mesh standard sieves.The sieving materials for weighing certain mass are packed into diameter To be placed in hot pressing furnace in the graphite jig of 42mm, in N2Under atmosphere protection, 1200 DEG C are warming up to 20 DEG C/min of rate, 1750 DEG C are warming up to 10 DEG C/min of rate again, pressurize 35MPa, heat-insulation pressure keeping 1 hour, then release, then natural cooling To room temperature.Optionally, it by gained ceramics after grinding and polishing, then is machined, such as grinding, cutting means obtain finished product, For testing.
The preparation of 4 boron nitride nano-tube flexible silicon nitride ceramic of embodiment
The silicon nitride of 21.312g, the aluminium oxide of 1.44g, the gadolinium oxide of 0.96g and the nitrogen of 0.288g are weighed with electronic balance Change boron nanotube.It will be poured into agate jar except the material of boron nitride nano-tube dress, using silicon nitride ball as ball-milling medium, use is different Propyl alcohol does decentralized medium, and ball milling adds the boron nitride nano-tube continuation for weighing up quality after 10 hours on planetary ball mill Ball milling 0.5 hour.The slurry mixed is dried at 100 DEG C, crosses 100 mesh standard sieves.The sieving materials for weighing certain mass are packed into It is placed in hot pressing furnace in the graphite jig of a diameter of 42mm, in N2Under atmosphere protection, 1200 are warming up to 20 DEG C/min of rate DEG C, then 1800 DEG C are warming up to 10 DEG C/min of rate, pressurize 30MPa, heat-insulation pressure keeping 1 hour, and then release is then natural It is cooled to room temperature.Optionally, it by gained ceramics after grinding and polishing, then is machined, such as grinding, cutting means are obtained into Product, for testing.
The preparation (non-toughening) of comparative example 1 pure silicon nitride ceramics
The silicon nitride of 21.6g, the aluminium oxide of 1.44g, the gadolinium oxide of 0.96g are weighed with electronic balance.Mixture dress is fallen Enter in agate jar, using silicon nitride ball as ball-milling medium, decentralized medium is done with isopropanol, ball milling 10 on planetary ball mill Hour.The slurry mixed is dried at 100 DEG C, crosses 100 mesh standard sieves.The sieving materials loading for weighing certain mass is a diameter of It is placed in hot pressing furnace in the graphite jig of 42mm, in N2Under atmosphere protection, 1200 DEG C are warming up to 20 DEG C/min of rate, then 1750 DEG C are warming up to 10 DEG C/min of rate, pressurize 35MPa, heat-insulation pressure keeping 1 hour, then then release naturally cools to Room temperature.Optionally, it by gained ceramics after grinding and polishing, then is machined, such as grinding, cutting means obtain finished product, use In test.
Characterization
To the silicon nitride ceramics progress X-ray diffraction characterization of boron nitride nano-tube toughening prepared by embodiment 3, (D8 Advance type polycrystal X ray diffractometers (XRD), test condition：Cu targets, pipe press 40kV, pipe stream 30mA), the results are shown in Figure 1, As can be seen from Figure 1 the composite ceramics principal crystalline phase being sintered is beta-silicon nitride (JCPDS No.33-1160), diffraction maximum is sharp, Regular, diffracted intensity is larger, and grain development is good after illustrating sintering.Meanwhile there are not α-Si3N4Characteristic peak, boron nitride receives The addition of mitron is to the no inhibiting effect of the transformation of α-siliconnitride to beta-silicon nitride.
Performance test
Purity nitrogen prepared by the silicon nitride ceramics and comparative example 1 of the boron nitride nano-tube toughening prepared by testing example 2-4 The relative density and fracture toughness of SiClx ceramics, test method are as follows：
(1) relative density of sample is the theoretical density of the bulk density divided by sample with sample, the theoretical density of sample It can be calculated according to raw material proportioning and each raw material theoretical density of itself, bulk density is measured with Archimedes method, is calculated Formula is：
Wherein：m1It is completely dried rear aerial quality, m for sample23h is boiled for sample boiling, is subsequently cooled to room Temperature, it is quiet put for 24 hours after, the quality to suspend in water, m3To take out sample from water, with clean tissue paper gently by specimen surface Water is wiped, aerial quality；ρwFor density (0.9970g/cm of the water under room temperature (25 DEG C)3 )；The relative density of each sample It is shown in Table 1.
(2) fracture toughness of sample is measured with Single edge notch beam, by gained sample after grinding and polishing, reprocessing At the test bars of height × width x length=2mm × 4mm × 25mm, chamfering is carried out along sample long side direction to the arris of sample, with Stress concentration phenomenon is influenced and reduced caused by eliminating mechanical processing trauma as much as possible, improves the accuracy of measurement data.It surveys Testing bar is under the conditions of 0.05mm/min loading velocities, span 16mm, until sample broke, carries out fracture toughness test.Test It the results are shown in Table 1.
Table 1
Embodiment 2 Embodiment 3 Embodiment 4 Comparative example 1
Relative density/% 97.8 97.1 95.9 99.4
Fracture toughness/MPam1/2 9.6 10.4 8.8 7.2
As can be seen from Table 1, the present invention uses boron nitride nano-tube flexible silicon nitride ceramic, can significantly improve ceramics Fracture toughness, fracture toughness is at most than pure silicon nitride ceramic (comparative example 1) 44.4%.
In addition, the silicon nitride of the silicon nitride ceramics and existing carbon nanotube toughening using aspect toughening provided by the invention Fracture toughness (the 8.5MPam of ceramics1/2) compare, fracture toughness is improved, and at most can be improved 22.3%.
Example 3 illustrates boron nitride nano-tube and silicon nitride circle in the embodiment relative to example 2,4, fracture toughness highest Face has stronger combination, the reinforcing effect that can more play that can more promote beta-silicon nitride long column shape to develop, convenient for giving full play to column The toughening effect of shape crystalline substance.But when boron nitride nano-tube is excessive, boron nitride nano-tube is reunited, and can be produced in intrinsic silicon Part holes and defect, relative density decline, and performance is caused to decline.
The production of method to a kind of boron nitride nano-tube flexible silicon nitride ceramic provided by the present invention and its preparation above Product are described in detail.Principle and implementation of the present invention are described for specific embodiment used herein, with The explanation of upper embodiment is merely used to help understand the method and its central idea of the present invention.It should be pointed out that for this field For those of ordinary skill, without departing from the principle of the present invention, can with several improvements and modifications are made to the present invention, These improvement and modification also fall into the protection of the claims in the present invention.

Claims (10)

1. a kind of method of boron nitride nano-tube flexible silicon nitride ceramic, which is characterized in that including：
(1) raw material is weighed, based on the gross mass of the raw material, the raw material includes：The α-siliconnitride of 88.8-90%, 0.1- 1.2% boron nitride nano-tube, the aluminium oxide of 2-8%, the gadolinium oxide of 2-8%；
(2) by after other raw material ball milling specified times in addition to boron nitride nano-tube, then boron nitride nano-tube is added and continues ball Mill, will arrive mixed slurry；
(3) mixed slurry is fitted into after drying, sieving in mold, carries out hot pressed sintering in an inert atmosphere.
2. the method as described in claim 1, which is characterized in that the raw material includes：The α-siliconnitride of 88.8-89.4%, The boron nitride nano-tube of 0.6-1.2%, 6% aluminium oxide, 4% gadolinium oxide；Preferably, the raw material includes：89.2- 89.4% α-siliconnitride, the boron nitride nano-tube of 0.6-0.8%, 6% aluminium oxide, 4% gadolinium oxide.
3. the method as described in claim 1, which is characterized in that the average grain diameter of α-siliconnitride is 600-800nm, aluminium oxide Average grain diameter is 200-400nm, and the average grain diameter of gadolinium oxide is 400nm.
4. the method as described in claim 1, which is characterized in that step (2) is specially：It will be other in addition to boron nitride nano-tube After raw material ball milling 8-10 hours, then boron nitride nano-tube is added and continues ball milling 0.5-1 hour.
5. the method as described in claim 1, which is characterized in that the inert atmosphere in step (3) in nitrogen, argon gas extremely Few one kind.
6. the method as described in claim 1, which is characterized in that the hot-pressing sintering technique parameter in step (3) includes：With 16- 25 DEG C/min of heating rate is warming up to 1200 DEG C, then with 5-15 DEG C/min of heating rate to 1750-1800 DEG C, and heat preservation is protected The pressure of pressure 0.5-1 hours, hot pressed sintering is 30-40MPa.
7. the method as described in claim 1, which is characterized in that after step (3) hot pressed sintering, release, then natural cooling To room temperature.
8. the method for claim 7, which is characterized in that after cooling is complete, carried out at rubbing down processing to products obtained therefrom Reason.
9. the method as described in any one of claim 1-8, which is characterized in that the boron nitride nano-tube is by following methods system ：
By FeCl3Dissolving in ethanol, is then added the mixing of unformed boron powder, obtains boron powder mixed liquor, wherein unformed boron powder with FeCl3Molar ratio be 1：(0.03-0.07)；
The boron powder mixed liquor is evaporated at 40-60 DEG C, ethyl alcohol is removed, obtains boron nitride nano-tube precursor；
Boron nitride nano-tube precursor is warming up to 1200-1250 DEG C in ammonia reaction atmosphere, is kept for 3-7 hours, ammonia flow velocity It is 30-60mL/ minutes；
It is cooling in nitrogen atmosphere.
10. boron nitride nano-tube flexible silicon nitride ceramic prepared by method as claimed in any one of claims 1-9 wherein.
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