CN103952796B - A kind of preparation method of silicon nitrogen boron continuous ceramic fiber - Google Patents
A kind of preparation method of silicon nitrogen boron continuous ceramic fiber Download PDFInfo
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Abstract
A preparation method for silicon nitrogen boron continuous ceramic fiber, comprises the following steps: (1) nitrogenize decarburization; (2) borax treatment; (3) high temperature burns till, and obtains silicon nitrogen boron continuous ceramic fiber.The present invention adds boron element and prepares silicon nitrogen boron fibre in silicon nitride fiber, and technique is simple compared with existing silicon boron nitrogen fiber, and low cost of manufacture, utilizes the production equipment of silicon nitride fiber just can implement, be easy to industrialization.
Description
Technical field
The invention belongs to high performance ceramic material field, especially relate to a kind of preparation method of silicon nitrogen boron continuous ceramic fiber.
Background technology
Silicon nitride fiber is a kind of high-temperature structural material of function admirable, the premium properties such as there is high strength, high tenacity, high heat conductance, high-insulativity, erosion resistant, heat shock resistance, non-oxidizability, thermal coefficient of expansion is low, density is low, being mainly used in Metal Substrate, the reinforcing material of ceramic matric composite and the preparation of heat resistant functional composites, is one of the ideal material of aerospace field, automobile engine high temperature resistant component.The preparation method of silicon nitride fiber mainly contains: silicon nitride ceramics polymer-derived method and polycarbosilane fiber nitriding.
The silicon nitride fiber adopting precursor pyrolysis and hot pressing to prepare, with the difference of preceramic polymer synthetic route, has different compositions, Structure and Properties.General organochlorosilane is carried out ammonia solution or aminolysis obtains polysilazane, or obtain polysilazane by the reaction of organosilazanes, then burn till the obtained silicon nitride fiber of process through spinning, non-fusible, high temperature.DowCorning company of the U.S., Japanese East Asia fuel corporation are the Typical Representatives of silicon nitride ceramics polymer-derived method.DowCorning company of the U.S. is with hydrogenation polysilazane (Hydridopolysilazane, referred to as HPZ) be precursor, can obtain by melt spinning the HPZ precursor that diameter is 15 ~ 20 μm, be exposed in polyfunctional chlorosilane atmosphere, cure treatment can be realized fast.Then HPZ fusion-free fibre is placed in high temperature furnace and processes 1200 DEG C of just obtained silicon nitride fibers at High Purity Nitrogen air-flow.East Asia fuel corporation of Japan is with Perhydropolysilazane (Perhydropolysilazane, referred to as PHS) be pioneer, PHS precursor is obtained by dry spinning, PHS precursor is directly heated to 1100 ~ 1200 DEG C in inert atmosphere or high-purity ammonia atmosphere, in high pure nitrogen, process 1400 DEG C again, just obtain silicon nitride fiber.But the silicon nitride ceramics precursor obtained is because its Si-N chemical bond is extremely easily hydrolyzed and is oxidized, to moisture and air very responsive, require that precursor synthesis, spinning and the technical process such as non-fusible all must completely cut off air, moisture and water, cause silicon nitride fiber complex process equipment, technical difficulty is large, and cost is high.Therefore above-mentioned three kinds of fibers all do not carry out suitability for industrialized production.
Nitriding is the common method preparing nitride ceramics, and such as boron nitride fiber is prepared in boric oxide fibre nitrogenize, and silicon boron nitrogen pottery etc. is prepared in the nitrogenize of silicon boron nitrogen carbon precursor.Japan Atomic Energy Research Institute is with Polycarbosilane (polycarbosilane, referred to as PCS) be precursor, PCS fiber is prepared through melt spinning, realized non-fusible by electron beam irradiation, silicon nitride fiber (called after Sinber) (RadiationPhysicsandChemistry.1999,51 (9): 575-581) has been prepared by the nitrogenize under high-purity ammonia atmosphere and high-temperature process.Domestic, the National University of Defense technology adopts similar method to prepare silicon nitride fiber (Wang get Yin, the UV absorber of continuous SiC fiber and SiNO fiber, National University of Defense Technology Ph.D. Dissertation, 2011; JournalofNon-CrystallineSolids2012,358:3338 – 3341; MaterialsandDesign2013,43:258 – 263).Prepare silicon nitride fiber by PCS fiber Direct-Nitridation, easily realize suitability for industrialized production, relative to silicon nitride ceramics precursor method, there is obvious technical advantage and cost advantage.
Research shows, silicon nitrogen boron fibre has higher resistance to elevated temperatures than silicon nitride fiber, has lower dielectric constant, can be used for the critical component such as antenna house and antenna windows of high-speed aircraft.The preparation method of the silicon nitrogen boron fibre reported at present has two kinds: dry spinning and melt spinning method.Toray company is reacted by Perhydropolysilazane and trimethylborate, obtains PVDF hollow fiber membrane, and product is white powder, less than 500 DEG C not meltings, and by dry spinning, in high-purity ammonia, nitrogenize obtains SiBNO fiber further, fibre density 2.4gcm
-3, intensity 2.5GPa, modulus 180GPa, serviceability temperature can reach 1600 DEG C of (J.Mater.Sci.1994,29,2238-2244; J.Mater.Sci.1995,30,410-416).But the fiber continuous length prepared by dry spinning is limited, be unfavorable for preparing silicon nitrogen boron continuous fibers.The domestic National University of Defense technology take PVDF hollow fiber membrane as precursor, burns till that to prepare silicon nitrogen boron continuous fibers (be 200710035734.3 see application number through melt spinning, non-fusible, nitrogenize and high temperature; 200710035733.9; 200810031252.5; 200810031253.X Chinese patent application).It (is 200710170513.7 see application number that Donghua University adopts similar approach to prepare silicon nitrogen boron fibre; 201110410000.5 Chinese patent application).But in these methods, because polymerized boron silazane precursor itself is containing a large amount of B-N and Si-N chemical bonds, extremely responsive to air, moisture and water etc., need complicated process equipment and strict environmental requirement, cost is also very high.
Therefore, explore that technology and equipment is simple, silicon nitrogen boron continuous ceramic fiber preparation method that cost is low, to promoting the application of continuous fibers, to promote high-performance composite materials development significant.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, and provide a kind of technique and device therefor simply, low cost of manufacture, does not need the preparation method of the silicon nitrogen boron continuous ceramic fiber of anhydrous and oxygen-free environment.
The technical solution adopted for the present invention to solve the technical problems is, a kind of preparation method of silicon nitrogen boron continuous ceramic fiber, comprises the following steps:
(1) nitrogenize decarburization: non-fusible polycarbosilane fiber is placed in high-temperature atmosphere furnace, pass into after vacuumizing high pure nitrogen and in triplicate after, at ammonia atmosphere, or ammonia and nitrogen or/and argon gas mixed atmosphere under, 400-1000 DEG C is warming up to by the speed of 50-300 DEG C/h, carry out nitrogenize decarburization, insulation 1-4h;
Described ammonia and nitrogen or/and argon gas mixed atmosphere in, ammonia gas volume concentrations >=10%;
Utilize ammonia and fusion-free fibre to react and form nitride fiber, containing a large amount of Si-NHx structures in nitride fiber;
(2) borax treatment: be evacuated to furnace pressure≤30Pa, pass into BCl
3gas, or BCl
3gas and nitrogen are or/and the mist of argon gas, and the flow of described gas is after 5-30L/min, 0.5-3h, is again evacuated to furnace pressure≤30Pa, again passes into the ammonia that flow is 1-10L/min, reaction 1-2h;
Described BCl
3gas and nitrogen or/and argon gas mist in, BCl
3void fraction>=10%;
Utilize the Si-NHx structural response in boron chloride and nitride fiber, form Si-N-B structure, with high-purity ammonia, unnecessary B-Cl reaction is consumed further;
(3) high temperature burns till: stop passing into ammonia, change nitrogen or argon gas that through-current capacity is 5-25L/min, continues to be warming up to 1200-1500 DEG C and at maximum temperature insulation 0.1 ~ 3h, obtain silicon nitrogen boron continuous ceramic fiber with the speed of 20-200 DEG C/h.
Further, in step (1), under ammonia atmosphere, be warming up to 600-900 DEG C by the speed of 60-180 DEG C/h, carry out nitrogenize decarburization, insulation 2-3h.
Further, in step (2), BCl is passed into
3the time of gas is 1-2h.
Further, in step (3), continue to be warming up to 1200-1500 DEG C with the speed of 80-150 DEG C/h and be incubated 1-2h in maximum temperature.
Further, purity >=99.99% of described ammonia.
Further, described BCl
3purity>=99.9% of gas.
Further, purity >=99.99% of described nitrogen or argon gas.
The non-fusible polycarbosilane fiber preparation of raw material of the present invention: Polycarbosilane (PCS) is obtained polycarbosilane fiber by melt spinning, by polycarbosilane fiber at chemical atmosphere, crosslinking Treatment is carried out under the condition of electron beam irradiation or high-energy ray irradiation, fiber can not be melted in subsequent high temperature processing procedure, namely non-fusible PCS fiber is obtained, concrete steps are as follows: raw material organosilicon polymer is placed in reactor, after repeatedly vacuumizing and filling high-purity inert atmosphere, be heated to 400-500 DEG C and carry out cracking, crude product filters after organic solvent dissolution, be heated to 300-400 DEG C again and carry out decompression distillation except desolventizing and a small amount of lower-molecular substance, Polycarbosilane PCS is obtained after cooling.Above-mentioned Polycarbosilane PCS is placed in the molten cylinder of melt spinning device, under high-purity inert atmosphere protection, is heated to 280-380 DEG C, after its fine melt uniformly melt; at 250-320 DEG C; under 0.1-0.8MPa pressure, carry out melt spinning with 200-600m/min speed, obtain continuous P CS fiber.Take one of the following two kinds method to produce PCS fusion-free fibre: (a) above-mentioned PCS fiber is placed in cure treatment device vacuumize fill high pure nitrogen and in triplicate after, pass into the reactive atmosphere containing multiple bond, 300-450 DEG C is heated to by 10-30 DEG C/min programming rate, and in this temperature process after 1-6 hour, obtained fusion-free fibre; B above-mentioned continuous P CS fiber is placed in electron beam irradiation by (), irradiation dose reaches 5-20MGy and annealing in process, obtained fusion-free fibre (see ZL201210138279.0).
The preparation method of the silicon nitrogen boron continuous ceramic fiber of the present invention, comprises the following steps:
In the present invention, non-fusible PCS fiber nitrogenize decarburization forms a large amount of Si-NHx, utilizes the chemical reaction of boron chloride and NH to introduce boron element, then eliminates unnecessary B-Cl chemical bond with high-purity ammonia, and further high temperature burns till prepares silicon nitrogen boron continuous ceramic fiber.
The present invention compared with prior art, has following positive effect:
(1) the present invention introduces boron element after non-fusible PCS nitrogenize, and compared with existing polymerized boron silazane precursor method, do not need synthesis, spinning, the anhydrous and oxygen-free environment such as non-fusible, equipment requirement is lower, and technology controlling and process is more prone to;
(2) the present invention adopts boron chloride and ammonia process successively after nitriding process, directly can carry out in nitriding process equipment, not need extra process equipment;
(3) the present invention adds boron element and prepares silicon nitrogen boron fibre in silicon nitride fiber, and technique is simple compared with existing silicon boron nitrogen fiber, and low cost of manufacture, utilizes the production equipment of silicon nitride fiber just can implement, be easy to industrialization.
Accompanying drawing explanation
Fig. 1 is the photomacrograph figure of the silicon nitrogen boron continuous ceramic fiber of the present invention;
Fig. 2 is the SEM microscopic appearance figure of the silicon nitrogen boron continuous ceramic fiber of the present invention;
Fig. 3 is EDS spectrogram and the element composition diagram on the silicon nitrogen boron continuous ceramic fiber surface of the present invention.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.The present invention includes but be not limited to following examples.
Reference example
The non-fusible polycarbosilane fiber preparation (with reference to ZL201210138279.0) of raw material of the present invention: raw material organosilicon polymer is placed in reactor, after repeatedly vacuumizing and filling high-purity inert atmosphere, be heated to 500 DEG C and carry out cracking, crude product filters after organic solvent dissolution, be heated to 400 DEG C again and carry out decompression distillation except desolventizing and a small amount of lower-molecular substance, after cooling, obtain Polycarbosilane PCS.Above-mentioned Polycarbosilane PCS is placed in the molten cylinder of melt spinning device, under high-purity inert atmosphere protection, is heated to 380 DEG C, after its fine melt uniformly melt; at 320 DEG C; under 0.2MPa pressure, carry out melt spinning with 200m/min speed, obtain continuous P CS fiber.Above-mentioned PCS fiber is placed in cure treatment device vacuumize fill high pure nitrogen and in triplicate after, pass into the reactive atmosphere containing multiple bond, be heated to 300 DEG C by 30 DEG C/min programming rate, and in this temperature process after 6 hours, obtained fusion-free fibre.
The purity of the ammonia used in each embodiment all>=99.99%, BCl
3all>=99.9%, the purity of nitrogen and argon gas all>=99.99% for the purity of gas.
Embodiment 1
The present embodiment comprises the following steps:
(1) nitrogenize decarburization: obtained non-fusible PCS fiber is placed in high-temperature atmosphere furnace, passes into nitrogen and in triplicate, under ammonia atmosphere, is warming up to 1000 DEG C by the speed of 300 DEG C/h after vacuumizing, insulation 1h;
(2) borax treatment: being evacuated to furnace pressure is 30Pa, then passes into the gaseous mixture of boron trichloride gas and nitrogen, BCl in described gaseous mixture
3void fraction is 10%, and mixed gas flow is that to be evacuated to furnace pressure after 30L/min, 3h be 30Pa, then passes into the unnecessary B-Cl key of ammonia cancellation with 2L/min, reaction 1h;
(3) high temperature burns till: stop passing into ammonia, pass into nitrogen, continue to be warming up to 1300 DEG C with the programming rate of 100 DEG C/h, isothermal holding 2 hours, obtain silicon nitrogen boron continuous ceramic fiber with the flow of 20L/min.
The present embodiment gained silicon nitrogen boron ceramic fibre diameter is 11.5 μm, and tensile strength is 1.6GPa, and Young's modulus is 98GPa, and fiber oxygen content is 1.8wt%, and nitrogen content is 35.5wt%, Boron contents 0.85wt%, and resistivity is 1.1 × 10
8Ω cm, dielectric constant is 3.82.
Embodiment 2
The present embodiment comprises the following steps:
(1) nitrogenize decarburization: obtained non-fusible PCS fiber is placed in high-temperature atmosphere furnace, pass into nitrogen after vacuumizing and in triplicate after, under the gaseous mixture atmosphere of ammonia and nitrogen, be warming up to 900 DEG C by the speed of 100 DEG C/h, carry out nitrogenize decarburization, insulation 1h;
In the gaseous mixture of described ammonia and nitrogen, ammonia gas volume concentrations is 50%;
(2) borax treatment: being evacuated to furnace pressure is 28Pa, then passes into the gaseous mixture of boron chloride and nitrogen, in described gaseous mixture, BCl
3void fraction is 25%, and mixed gas flow is after 20L/min, 0.5h, and being again evacuated to furnace pressure is 30Pa, then passes into the unnecessary B-Cl key of ammonia cancellation with 2L/min, reaction 2h;
(3) high temperature burns till: stop passing into ammonia, pass into argon gas, continue to be warming up to 1400 DEG C with the programming rate of 200 DEG C/h, isothermal holding 2 hours, obtain silicon nitrogen boron ceramic fibre with the flow of 10L/min.
The present embodiment gained silicon nitrogen boron ceramic fibre fibre diameter is 12.2 μm, and tensile strength is 1.4GPa, and Young's modulus is 110GPa, and fiber oxygen content is 0.8wt%, and nitrogen content is 36.7wt%, Boron contents 0.95wt%, and resistivity is 2.5 × 10
8Ω cm, dielectric constant is 4.15.
Embodiment 3
The present embodiment comprises the following steps:
(1) nitrogenize decarburization: obtained non-fusible PCS fiber is placed in high-temperature atmosphere furnace, pass into nitrogen after vacuumizing and in triplicate after, under the mixed atmosphere of ammonia and nitrogen, be warming up to 800 DEG C by the speed of 150 DEG C/h, carry out nitrogenize decarburization, insulation 2h;
In the gaseous mixture of described ammonia and nitrogen, ammonia gas volume concentrations is 70%;
(2) borax treatment: being evacuated to furnace pressure is 28Pa, then passes into the gaseous mixture of boron chloride and nitrogen, in described gaseous mixture, BCl
3void fraction is 60%, and flow 10L/min is evacuated to furnace pressure 28Pa after 1h, then passes into the unnecessary B-Cl key of high-purity ammonia cancellation with 5L/min, reaction 1h;
(3) high temperature burns till: stop passing into ammonia, pass into nitrogen, continue to be warming up to 1200 DEG C with the programming rate of 150 DEG C/h, isothermal holding 2 hours, obtain silicon nitrogen boron ceramic fibre with the flow of 25L/min.
The present embodiment gained silicon nitrogen boron ceramic fibre fibre diameter is 11.8 μm, and tensile strength is 1.5GPa, and Young's modulus is 97GPa, and fiber oxygen content is 1.3wt%, and nitrogen content is 35.2wt%, Boron contents 0.78wt%, and resistivity is 1.6 × 10
8Ω cm, dielectric constant is 3.89.
Embodiment 4
The present embodiment comprises the following steps:
(1) nitrogenize decarburization: obtained non-fusible PCS fiber is placed in high-temperature atmosphere furnace, pass into high pure nitrogen after vacuumizing and in triplicate after, under the mixed atmosphere of ammonia and nitrogen, be warming up to 700 DEG C by the speed of 260 DEG C/h, carry out nitrogenize decarburization, insulation 1h;
In the gaseous mixture of described ammonia and nitrogen, ammonia gas volume concentrations is 80%;
(2) borax treatment: being evacuated to furnace pressure is 25Pa, then passes into the gaseous mixture of boron chloride and nitrogen, in described gaseous mixture, BCl
3void fraction is 80%, flow 5L/min, after 2h, is evacuated to furnace pressure 25Pa, then passes into the unnecessary B-Cl key of ammonia cancellation with 8L/min, reaction 1h;
(3) high temperature burns till: stop passing into ammonia, pass into argon gas, continue to be warming up to 1300 DEG C with the programming rate of 80 DEG C/h, isothermal holding 3 hours, obtain silicon nitrogen boron ceramic fibre with the flow of 20L/min.
The present embodiment gained silicon nitrogen boron ceramic fibre fibre diameter is 12.0 μm, and tensile strength is 1.3GPa, and Young's modulus is 121GPa, and fiber oxygen content is 2.1wt%, and nitrogen content is 34.2wt%, Boron contents 0.72wt%, and resistivity is 1.0 × 10
8Ω cm, dielectric constant is 3.71.
Embodiment 5
The present embodiment comprises the following steps:
(1) nitrogenize decarburization: obtained non-fusible PCS fiber is placed in high-temperature atmosphere furnace, pass into high pure nitrogen after vacuumizing and in triplicate after, under the gaseous mixture of ammonia and argon gas, be warming up to 600 DEG C by the speed of 300 DEG C/h, carry out nitrogenize decarburization, insulation 2h;
In the gaseous mixture of described ammonia and argon gas, ammonia gas volume concentrations is 50%;
(2) borax treatment: be evacuated to furnace pressure 30Pa, then passes into 100% boron trichloride gas, flow 5L/min, after 1h, is evacuated to furnace pressure 30Pa, then passes into the unnecessary B-Cl key of ammonia cancellation with 10L/min, reaction 2h;
(3) high temperature burns till: stop passing into ammonia, pass into nitrogen, continue to be warming up to 1500 DEG C with the programming rate of 200 DEG C/h, isothermal holding 0.5 hour, obtain silicon nitrogen boron ceramic fibre with the flow of 10L/min.
The present embodiment gained silicon nitrogen boron ceramic fibre fibre diameter is 12.3 μm, and tensile strength is 1.6GPa, and Young's modulus is 108GPa, and fiber oxygen content is 1.1wt%, and nitrogen content is 35.9wt%, Boron contents 0.91wt%, and resistivity is 1.7 × 10
8Ω cm, dielectric constant is 4.15.
Embodiment 6
The present embodiment comprises the following steps:
(1) nitrogenize decarburization: obtained non-fusible PCS fiber is placed in high-temperature atmosphere furnace, pass into nitrogen after vacuumizing and in triplicate after, under the gaseous mixture of ammonia and nitrogen, be warming up to 500 DEG C by the speed of 50 DEG C/h, carry out nitrogenize decarburization, insulation 3h;
In the gaseous mixture of described ammonia and nitrogen, ammonia gas volume concentrations is 20%;
(2) borax treatment: be evacuated to furnace pressure 30Pa, then passes into the gaseous mixture of boron chloride and nitrogen, in described gaseous mixture, and BCl
3void fraction is 40%, flow 15L/min, and being evacuated to furnace pressure after 2h is 30Pa, then passes into the unnecessary B-Cl key of ammonia cancellation with 1L/min, reaction 2h;
(3) high temperature burns till: stop passing into ammonia, pass into argon gas, continue to be warming up to 1250 DEG C with the programming rate of 50 DEG C/h, isothermal holding 3 hours, obtain silicon nitrogen boron ceramic fibre with the flow of 5L/min.
The present embodiment gained silicon nitrogen boron ceramic fibre fibre diameter is 11.2 μm, and tensile strength is 1.5GPa, and Young's modulus is 101GPa, and fiber oxygen content is 1.0wt%, and nitrogen content is 35.1wt%, Boron contents 0.80wt%, and resistivity is 1.6 × 10
8Ω cm, dielectric constant is 4.19.
Claims (7)
1. a preparation method for silicon nitrogen boron continuous ceramic fiber, is characterized in that, comprise the following steps:
(1) nitrogenize decarburization: non-fusible polycarbosilane fiber is placed in high-temperature atmosphere furnace, pass into after vacuumizing high pure nitrogen and in triplicate after, at ammonia atmosphere, or ammonia and nitrogen or/and argon gas mixed atmosphere under, 400-1000 DEG C is warming up to by the speed of 50-300 DEG C/h, carry out nitrogenize decarburization, insulation
1-4h;
Described ammonia and nitrogen or/and argon gas mixed atmosphere in, ammonia gas volume concentrations >=10%;
(2) borax treatment: be evacuated to furnace pressure≤30Pa, pass into BCl
3gas, or BCl
3gas and nitrogen are or/and the mist of argon gas, and the flow of described gas is after 5-30L/min, 0.5-3h, is again evacuated to furnace pressure≤30Pa, again passes into the ammonia that flow is 1-10L/min, reaction 1-2h;
Described BCl
3with nitrogen or/and in the mist of argon gas, BCl
3void fraction>=10%;
(3) high temperature burns till: stop passing into ammonia, changing through-current capacity is
5-25L/min'snitrogen or argon gas, continue to be warming up to 1200-1500 DEG C with the speed of 20-200 DEG C/h and at maximum temperature insulation 0.1 ~ 3h, obtain silicon nitrogen boron continuous ceramic fiber.
2. the preparation method of silicon nitrogen boron continuous ceramic fiber according to claim 1, is characterized in that, in step (1), be warming up under ammonia atmosphere by the speed of 60-180 DEG C/h
600-900 DEG C, carry out nitrogenize decarburization, insulation
2-3h.
3. the preparation method of silicon nitrogen boron continuous ceramic fiber according to claim 1 and 2, is characterized in that, in step (2), pass into BCl
3the time of gas is 1-2h.
4. the preparation method of silicon nitrogen boron continuous ceramic fiber according to claim 1 and 2, is characterized in that, in step (3), continues to be warming up to 1200-1500 DEG C and be incubated in maximum temperature with the speed of 80-150 DEG C/h
1-2h.
5. the preparation method of silicon nitrogen boron continuous ceramic fiber according to claim 1 and 2, is characterized in that, purity >=99.99% of described ammonia.
6. the preparation method of silicon nitrogen boron continuous ceramic fiber according to claim 1 and 2, is characterized in that, described BCl
3purity>=99.9% of gas.
7. the preparation method of silicon nitrogen boron continuous ceramic fiber according to claim 1 and 2, is characterized in that, purity >=99.99% of described nitrogen or argon gas.
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| CN103952796A (en) | 2014-07-30 |
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