CN107540382A - A kind of boron nitride continuous fiber and its preparation technology and application - Google Patents
A kind of boron nitride continuous fiber and its preparation technology and application Download PDFInfo
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- CN107540382A CN107540382A CN201710711873.7A CN201710711873A CN107540382A CN 107540382 A CN107540382 A CN 107540382A CN 201710711873 A CN201710711873 A CN 201710711873A CN 107540382 A CN107540382 A CN 107540382A
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Abstract
The invention discloses a kind of boron nitride continuous fiber and its preparation technology and application, comprise the following steps：Raw material, into forerunner's fiber, carries out low temperature nitride reaction, high temperature hot-stretch, finally carries out protective coating and obtain finished product, the melting, wire drawing are automatic charging, continuous wire drawing afterwards by melting, wire drawing.By the way that batch (-type) of the prior art is melted, wire drawing is automatic charging, continuous wire drawing, and discrete by product diameter is reduced to less than 7% by original 12%, and wire drawing is uniform.
Description
Technical field
The invention belongs to inorfil technical field, and in particular to a kind of boron nitride continuous fiber and its preparation technology are with answering
With.
Background technology
With the development of the technologies such as weapon hypersonic, long endurance and precise guidance, guided missile is hit by a bullet body surface in flight course
The Aerodynamic Heating total amount that face is born is increasing, in order to ensure that weapon aerodynamic configuration and electromagnetic transmission signal are normal, to antenna
The ablation property of cover material, electric property etc. propose rigors.Existing available quartz-ceramics, quartz fibre composite wood
Material, silicon nitride ceramics are difficult to meet more than 2000 DEG C of long-time high state requirement, and BN fibers increase in current material system
Strong nitride ceramic composites are the optimal candidate materials of the high temperature wave-transparent material under more high state.Boron nitride fiber has high temperature resistant
(inert atmosphere 3000K, oxygen atmosphere 1123K), resistant to chemical etching, dielectric properties are excellent, electrical insulating property is good and with other materials
Excellent combination property, the boron-nitride fibre composites such as the material preferable chemical compatibility in interface can be used as resistance to overtemperature ablation material
Material, high temperature wave-transparent material, battery diaphragm material and neutron absorber material etc..BN fiber reinforcements nitride ceramic composites can meet
The demand of 2500 DEG C of use above environment.
It is compound to strengthen ceramic high-temperature resistant anti-yaw damper wave transparent to boron nitride fiber for domestic multiple weapon models since " 13 "
Material proposes active demand, it is desirable to breaks through key technology prepared by boron nitride continuous fiber as early as possible, realizes prepare with scale.
The development of domestic and international boron nitride fiber has had the time of decades, but because its preparation technology is complicated, needs to break through
Key technology be related to overall process from precursor preparation, low temperature nitride, high-temperature ammonolysis technique and equipment, thus make slow progress.Mountain
Eastern industrial ceramics studying and designing institute took the lead in having carried out at home in 1976 prepares BN continuous fibers using presoma conversion method
Research, by the tackling key problem of nearly 30 years by the research to preparation technology and microstructure fiber, has been prepared high performance, high
The boron nitride continuous fiber of yield, be it is domestic it is currently the only can mass prepare the unit of boron nitride fiber.
The Chinese patent of Application No. 90107561.2 discloses a kind of boron nitride fiber preparation technology and its equipment, article
" the thermodynamics of reactions dynamics research that boron nitride fiber is prepared using chemical transformation ", this two all describe in the prior art
The preparation method of boron nitride fiber, but the above-mentioned following shortcoming of prior art generally existing：(1) initial melt temperature of boric acid
It is higher, waste the energy；(2) dispersion of fibre diameter is higher；(3) fracture in continuous fiber preparation process is easily occurred in；
(4) large-scale continuous production of continuity fiber is limited；(5) coating acts on unobvious in terms of strength retrogression is prevented, exists
Accounting weight is larger in the fibre, and solidification is slower, and the fiber after drying is inconvenient to unwind, the shortcomings of coating removal difficulty.
The content of the invention
In view of drawbacks described above of the prior art or deficiency, it is expected that providing one kind is suitable to industrialization large-scale production boron nitride
The scheme of continuous fiber.
In a first aspect, the embodiment of the present application provides a kind of preparation technology of boron nitride continuous fiber, comprise the following steps：
Raw material, into forerunner's fiber, carries out low temperature nitride reaction, high temperature hot-stretch, finally carries out protective coating afterwards by melting, wire drawing
Finished product is obtained, the melting, wire drawing are automatic charging, continuous wire drawing.
Further：The raw material is the mixture of boron oxide and rare earth, preferably：The mass parts of the boric acid and rare earth
Counting ratio is：90-100：0-10.
Further：The high temperature hot-stretch is continuous fiber folding and unfolding silk heat treatment mode.
Further：The wire drawing is to go out a diameter of 5-7 microns according to glass fibre process drawing, and 150-250 is (preferably：
200) forerunner's fiber of root/beam, by forerunner's fiber after plying into 0.5-1.5K (preferably：Boron oxide synnema 1K), then by n
Boron nitride synnema described in beam (preferably 3,4,5 beams) is twisted and plied.
Further：Temperature in the low temperature nitride reaction is that scope is RT~1000 DEG C, and ammonia total flow is 2m3/
h。
Further：Treatment temperature in the high temperature hot-stretch：1600~1900 DEG C, nitrogen total flow 3m3/ h, traction
Rate 1~3%.
Further：The coating, it is mixed by the raw material of following masses number：Tetraethyl orthosilicate 15-30 parts are organic
Solvent 8-20 parts, more preferably：The organic solvent is ketone, ester, alkane or alcohol, preferably：The organic solvent is ethanol, positive 12
One or more of alkane, butyl acetate or acetone.
Further：The coated weight of the coating is less than 1%, and drying temperature is 100 DEG C.
Second aspect, the embodiment of the present application additionally provide a kind of preparation technology by above-mentioned boron nitride continuous fiber and are prepared into
The boron nitride continuous fiber arrived.
Further：The BN contents of the boron nitride continuous fiber>99%, bulk density>1.8g/cm3, tensile strength
800~1000MPa, 60~80GPa of stretch modulus, 7~8um of fibre diameter, length>500m.
The third aspect, the embodiment of the present application additionally provide what is be prepared by the preparation technology of above-mentioned boron nitride continuous fiber
Boron nitride continuous fiber is as the ablator of resistance to overtemperature, high temperature wave-transparent material, battery diaphragm material and neutron absorber material
Using.
Beneficial effect：
The technical scheme for the boron nitride continuous fiber preparation technology that the embodiment of the present application provides, by will be of the prior art
Batch (-type) melting, wire drawing are improved to automatic charging, continuous wire drawing, so that the discrete of product diameter is reduced to by original 12%
Less than 7%, and wire drawing is uniform.
The embodiment of the present application adds rare earth when melting boric acid, reduces the initial melt temperature of boric acid, it is initially melted
Melt temperature and be reduced to 700 DEG C or so by 1000 DEG C or so, reduce energy resource consumption, reduce cost.
The embodiment of the present application by the processing mode of forerunner's fibre bundle of original doubling twisting integral manner, be changed to plying,
Twisting is separated and independently performed, and fiber substantially increases the intensity of synnema per Shu Zengjia.
Original filament-wound heat treatment mode is changed to continous way folding and unfolding silk heat treatment mode by the embodiment of the present application, fine
Wound form heat treatment mode is tieed up by the length of roller and the limitation of rugosity, is difficult to realize continuous long stapled continuous industry life
Production, and the method for the embodiment of the present application has broken away from the limitation of roller, realizes industrialized production.
The coating coated fiber of the embodiment of the present application, improves fibre strength retention rate, while solves BN fibers and certain
Interface wet ability and consistency problem between a little matrices of composite materials, the curing of coatings time is short, only needs 80-120 DEG C of low temperature, 5-
60s can rapid curing, the embodiment of the present application coating only needs high-temperature process, and it is convenient to remove, simple and efficient, after BN fibers it is equal
Even, fiber interface is apparent, and fiber is not easy adhesion, has good pliability, can freely be wound on the pole of different-diameter.
Embodiment
In order to be better understood by technical scheme, the present invention is made furtherly with reference to specific embodiment
It is bright.
Embodiment 1
Using 98% (weight) acid reagent+2% (weight) rare-earth yttrium as raw material, it is put into material fiber drawing furnace and melts, initially
Melt temperature is arranged to 700 DEG C, founds out glass melt and flows at material fiber drawing furnace bushing, then, according to glass fibre
Process drawing goes out 6 microns of diameter, the boric oxide fibre of 200/beam, fiber is turned into 1K boron oxide synnema after plying, so
It is afterwards that 4 beam boron nitride synnemas are twisted and plied, afterwards, nitridation reaction is carried out in continuous nitride stove, at 800 DEG C, be passed through ammonia, ammonia
Gas total flow 2m3/ h, drawing by high temperature nitridation reaction is carried out in continuous high temperature stretches nitriding furnace, passes through the control of folding and unfolding silk equipment
Realize continuous processing of the fiber in a nitrogen atmosphere in heat-treatment furnace, treatment temperature：At 1800 DEG C, nitrogen total flow 3m3/ h, leads
Rate 2% is stretched, afterwards, organic silicon fiber protective coating is coated, coating amount 1%, it is fine to obtain continuous boron nitride through 100 DEG C of drying
Dimension, the organic silicon fibrous protective layer, is mixed by the raw material of following masses number：23 parts of tetraethyl orthosilicate, ethanol 15
Part.
Embodiment 2
Using 90% (weight) acid reagent+10% (weight) rare earth neodymium as raw material, it is put into material fiber drawing furnace and melts, initially
Melt temperature is arranged to 700 DEG C, founds out glass melt and flows at material fiber drawing furnace bushing, then, according to glass fibre
Process drawing goes out 7 microns of diameter, the boric oxide fibre of 200/beam, and fiber is turned into 0.5K boron oxide synnema after plying,
Then it is the boron nitride synnema of 3 beams is twisted and plied, afterwards, nitridation reaction is carried out in continuous nitride stove, at 950 DEG C, be passed through ammonia
Gas, ammonia total flow 2m3/ h, drawing by high temperature nitridation reaction is carried out in continuous high temperature stretches nitriding furnace, passes through folding and unfolding silk equipment
Control realize continuous processing of the fiber in a nitrogen atmosphere in heat-treatment furnace, treatment temperature：At 1900 DEG C, nitrogen total flow
3m3/ h, degree of draft 3%, afterwards, organic silicon fiber protective coating is coated, coating amount 1%, is obtained through 100 DEG C of drying continuous
Boron nitride fiber, the organic silicon fibrous protective layer, is mixed by the raw material of following masses number：Tetraethyl orthosilicate 15
Part, ethanol, n-dodecane, butyl acetate mix 10 parts.
Embodiment 3
Using 95% (weight) acid reagent+5% (weight) cerium as raw material, it is put into material fiber drawing furnace and melts, initially
Melt temperature is arranged to 700 DEG C, founds out glass melt and flows at material fiber drawing furnace bushing, then, according to glass fibre
Process drawing goes out 5 microns of diameter, the boric oxide fibre of 200/beam, and fiber is turned into 1.5K boron oxide synnema after plying,
Then it is the boron nitride synnema of 5 beams is twisted and plied, afterwards, nitridation reaction is carried out in continuous nitride stove, in RT (room temperatures：Room
Temperature), it is passed through ammonia, ammonia total flow 2m3/ h, drawing by high temperature nitridation is carried out in continuous high temperature stretches nitriding furnace
Reaction, continuous processing of the fiber in a nitrogen atmosphere in heat-treatment furnace, treatment temperature are realized by the control of folding and unfolding silk equipment：
1600 DEG C, nitrogen total flow 3m3/ h, degree of draft 1%, afterwards, coat organic silicon fiber protective coating, coating amount 1%, warp
100 DEG C of drying obtain continuous boron nitride fiber, the organic silicon fibrous protective layer, are mixed by the raw material of following masses number
It is made：29 parts of 30 parts of tetraethyl orthosilicate, butyl acetate or acetone.
Embodiment 4
Using 93% (weight) acid reagent+7% (weight) Rare Earth Lanthanum as raw material, it is put into material fiber drawing furnace and melts, initially
Melt temperature is arranged to 700 DEG C, founds out glass melt and flows at material fiber drawing furnace bushing, then, according to glass fibre
Process drawing goes out 7 microns of diameter, the boric oxide fibre of 200/beam, fiber is turned into 1K boron oxide synnema after plying, so
It is afterwards that 4 beam boron nitride synnemas are twisted and plied, afterwards, nitridation reaction is carried out in continuous nitride stove, at 500 DEG C, be passed through ammonia, ammonia
Gas total flow 2m3/ h, drawing by high temperature nitridation reaction is carried out in continuous high temperature stretches nitriding furnace, passes through the control of folding and unfolding silk equipment
Realize continuous processing of the fiber in a nitrogen atmosphere in heat-treatment furnace, treatment temperature：At 1700 DEG C, nitrogen total flow 3m3/ h, leads
Rate 2% is stretched, afterwards, organic silicon fiber protective coating is coated, coating amount 1%, it is fine to obtain continuous boron nitride through 100 DEG C of drying
Dimension, the organic silicon fibrous protective layer, is mixed by the raw material of following masses number：15 parts of tetraethyl orthosilicate, positive 12
Alkane, butyl acetate, 8 parts of acetone mixture.
Embodiment 5
Using 98% (weight) acid reagent+2% (weight) cerium as raw material, it is put into material fiber drawing furnace and melts, initially
Melt temperature is arranged to 700 DEG C, founds out glass melt and flows at material fiber drawing furnace bushing, then, according to glass fibre
Process drawing goes out 7 microns of diameter, the boric oxide fibre of 200/beam, fiber is turned into 1K boron oxide synnema after plying, so
It is afterwards that 5 beam boron nitride synnemas are twisted and plied, afterwards, nitridation reaction is carried out in continuous nitride stove, at 700 DEG C, be passed through ammonia, ammonia
Gas total flow 2m3/ h, drawing by high temperature nitridation reaction is carried out in continuous high temperature stretches nitriding furnace, passes through the control of folding and unfolding silk equipment
Realize continuous processing of the fiber in a nitrogen atmosphere in heat-treatment furnace, treatment temperature：At 1900 DEG C, nitrogen total flow 3m3/ h, leads
Rate 3% is stretched, afterwards, organic silicon fiber protective coating is coated, coating amount 1%, it is fine to obtain continuous boron nitride through 100 DEG C of drying
Dimension, the organic silicon fibrous protective layer, is mixed by the raw material of following masses number：25 parts of tetraethyl orthosilicate, positive 12
16 parts of alkane.
Above description is only the preferred embodiment of the application and the explanation to institute's application technology principle.People in the art
Member should be appreciated that invention scope involved in the application, however it is not limited to the technology that the particular combination of above-mentioned technical characteristic forms
Scheme, while should also cover in the case where not departing from the inventive concept, carried out by above-mentioned technical characteristic or its equivalent feature
The other technical schemes for being combined and being formed.Such as features described above has similar work(with (but not limited to) disclosed herein
The technical scheme that the technical characteristic of energy is replaced mutually and formed.
Claims (10)
1. a kind of preparation technology of boron nitride continuous fiber, it is characterized in that：Comprise the following steps：Raw material by melting, wire drawing into
Forerunner's fiber, low temperature nitride reaction is carried out afterwards, high temperature hot-stretch, protective coating is finally carried out and obtains finished product, the melting, drawing
Silk is automatic charging, continuous wire drawing.
2. preparation technology as claimed in claim 1, it is characterized in that：The raw material is the mixture of boron oxide and rare earth.
3. preparation technology as claimed in claim 1, it is characterized in that：The high temperature hot-stretch is at continuous fiber folding and unfolding silk heat
Reason mode.
4. preparation technology as claimed in claim 1, it is characterized in that：The wire drawing is to go out diameter according to glass fibre process drawing
For 5-7 microns, forerunner's fiber of 150-250 roots/beam, by forerunner's fiber after plying into 0.5-1.5K boron oxide synnema, so
It is afterwards that the boron nitride synnema described in n beams is twisted and plied.
5. preparation technology as claimed in claim 1, it is characterized in that：Temperature in low temperature nitride reaction be scope be RT~
1000 DEG C, ammonia total flow is 2m3/h。
6. preparation technology as claimed in claim 1, it is characterized in that：Treatment temperature in the high temperature hot-stretch：1600~
1900 DEG C, nitrogen total flow 3m3/ h, traction rate 1~3%.
7. preparation technology as claimed in claim 1, it is characterized in that：The coating, system is mixed by the raw material of following masses number
Into：Tetraethyl orthosilicate 15-30 parts, organic solvent 8-20 parts, more preferably：The organic solvent is ketone, ester, alkane or alcohol, preferably：
The organic solvent is one or more of ethanol, n-dodecane, butyl acetate or acetone.
8. preparation technology as claimed in claim 1, it is characterized in that：The coated weight of the coating is less than 1%, and drying temperature is
100℃。
9. the boron nitride continuous fiber being prepared by any described preparation technologies of claim 1-8.
10. the boron nitride continuous fiber being prepared by any described preparation technologies of claim 1-8 is as resistance to overtemperature ablation
The application of material, high temperature wave-transparent material, battery diaphragm material and neutron absorber material.
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| CN201710711873.7A CN107540382B (en) | 2017-08-18 | 2017-08-18 | Boron nitride continuous fiber and preparation process and application thereof |
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Cited By (2)
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| CN115611635A (en) * | 2022-12-14 | 2023-01-17 | 山东工业陶瓷研究设计院有限公司 | Boron nitride fiber and preparation method and application thereof |
| CN115613163A (en) * | 2022-12-06 | 2023-01-17 | 山东工业陶瓷研究设计院有限公司 | Decarburization method of boron nitride precursor fiber |
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| CN115613163A (en) * | 2022-12-06 | 2023-01-17 | 山东工业陶瓷研究设计院有限公司 | Decarburization method of boron nitride precursor fiber |
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