CN101269969A - Method for preparing nitride ceramic fibre - Google Patents
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- CN101269969A CN101269969A CNA200810031253XA CN200810031253A CN101269969A CN 101269969 A CN101269969 A CN 101269969A CN A200810031253X A CNA200810031253X A CN A200810031253XA CN 200810031253 A CN200810031253 A CN 200810031253A CN 101269969 A CN101269969 A CN 101269969A
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Abstract
The present invention provides a preparation method of nitrogen ceramic fiber. In the preparation method, the halides of the target element and small molecules disilazane are used as starting materials and are mixed according to a certain ratio; the temperature is raised to be between 125 and 500 DEG C and is maintained for 2 to 30 hours; after the temperature is lowered, the mixture is processed through vacuum distillation and is cooled to be at the room temperature; thus the nitrogen ceramics precursor of the target element can be prepared; the nitrogen ceramics precursor is fused for spinning to prepare the precursor fiber of nitride that is not treated through fusing; the non-molten fiber is dispersed at high temperature; after the fiber is cooled, the product of nitride ceramic fiber can be prepared. The preparation method has the advantages of low costs of raw materials, reliable source, higher synthetic yield, simple process and one-step preparation of the precursor. The efficiency is high and the preparation method is conducive to the integrative operation of spinning, non-melting treatment and sintering of the precursor.
Description
Technical field
The present invention relates to a kind of preparation method of nitride ceramic fibre, particularly relate to a kind of method for preparing the multicomponent nitride ceramic fiber by the organic nitrogen compound polymkeric substance by the high temperature pyrolysis conversion.
Background technology
Nitride ceramic fibre, have high thermal conductivity, low-expansion coefficient and characteristics such as high temperature resistant, be a kind of ceramic fiber of excellent combination property, in Aeronautics and Astronautics, weapons, naval vessels etc. need the field of high strength, high-modulus, high temperature resistant, anti-oxidant, heat-shock resistance, high temperature and creep resistance material, have important application prospects with the matrix material of its preparation.
At present, the preparation of multicomponent nitride ceramic fiber mainly concentrates on silica-based nitride ceramic fibers such as SiCN, SiBNC etc.For the preparation of these ceramic fibers, mainly adopt Stainless Steel via Precursor Pyrolysis, from the synthetic route angle of precursor, the Stainless Steel via Precursor Pyrolysis of nitride ceramic fibre can be divided into polymkeric substance route and monomer route.
The polymkeric substance route is meant and with boron-containing compound polysilazane etc. is contained the polymer modification of Si-N key and obtain the SiBNC precursor.Modification obtains the SiBNC ceramic fiber precursor to hydrogenation polysilazane (HPZ) with the derivative of borine or borazine as Sneddon etc., obtain SiBNC fiber (Chem.Mater. by high temperature sintering in melt-spinning, non-melt processed, the nitrogen again, 1993,5:547; Chem.Mater., 1995,7:2203; Chem.Mater., 1997,9:2218).Trimethyl borate B (OCH such as Funayama
3)
3Modification perhydro polysilazane obtains ceramic precursor, again by dry-spinning, final N
2In Pintsch process obtain the SiBON fiber (J.Mater.Sci., 1994,29:2238).Tashiro etc. obtain poly-metal oxygen silazane precursor by metal alkyl oxide modifying silazane, have obtained SiMON (C) (M is a metallic element) ceramic fiber (US 5032551) by spinning, non-melt processed, Pintsch process then.In the ceramic precursor that this route obtains, element distributes and is difficult to reach the even of atom, molecular level, and when at high temperature being on active service with its ceramic fiber of making, easily generation separates and lost efficacy.
The monomer route is the at first synthetic monomer that contains Si, B, N, four kinds of elements of C, and this monomer often is called as single source precursor (Single Source Precursor), makes the precursor polymerization of single source then by rights, can obtain the SiBNC ceramic precursor.Burn till by melt-spinning, non-melt processed and high temperature then, can obtain SiBNC ceramic fiber (J.Mater.Chem., 2005,15,289; Science, 285,30; 699).The The Nomenclature Composition and Structure of Complexes feature that the precursor that this approach obtains has often can remain in the target ceramic product.As (Science, 285:699 such as Jansen; US 5834388; US 5885519; US 5968859; US 7297649B2) be starting raw material with hexamethyldisilazane, halosilanes, boron trichloride etc., at first at low temperatures through polystep reaction, synthetic single source precursor, obtain solvable fusile polymerized boron silazane precursor by vacuum heat treatment after making the precursor polymerization of single source by aminolysis reaction then, again through melt-spinning, N
2Middle sintering obtains the SiBNC ceramic fiber.Takeda (US5041515) etc. utilizes two kinds of halosilanes, halogenated titanium and hexamethyldisilazane reactions of containing different backbone structures, has prepared poly-titanium carbon silazane precursor, has obtained the SiTiCN ceramic fiber through melt-spinning, non-melt processed and Pintsch process.
Above-mentioned preparation method's process complexity, cost is higher relatively, is unfavorable for applying.
Summary of the invention
The objective of the invention is to overcome the above-mentioned defective of prior art, provide a kind of operation steps simple, the method for preparing nitride ceramic fibre that production cost is lower.
The objective of the invention is to be achieved through the following technical solutions: halogenide, small molecules disilazane with object element are starting raw material, after mixing according to a certain ratio, be warming up to 125-500 ℃, and under this temperature, be incubated 2-30 hour, cooling back underpressure distillation, be cooled to room temperature and promptly obtain containing the nitride ceramic precursor of object element, nitride ceramic precursor is carried out melt-spinning, obtain nitride precursor precursor, precursor is carried out not melt processed, then fusion-free fibre is carried out Pintsch process, promptly get the nitride ceramic fibre product after the cooling.
Specifically comprise following operation steps:
(1) halogenide with object element is dissolved in the organic solvent, simultaneously, will be with the reactor of stirring, dropping, water distilling apparatus to vacuumize, fill drying nitrogen repeatedly at least three times, to get rid of air and moisture wherein;
(2) with the halogenide of object element and small molecules disilazane by 1: the mol ratio of 3-30 adds in the reactor in the mode that drips, the stirring while dripping;
The halid molecular formula of described object element is as follows:
R
1 a-bMX
b
Wherein, M is an object element, M=Si, Al, B, Zr, Ta, Hf, Cr, Nb, Ge, V, W, Fe or Ti; X is halogens (preferred X=Cl); R
1Organic groups such as=H, methyl, ethyl, propyl group, butyl or phenyl (preferred R
1=methyl or ethyl); A is that the maximum of object element is closed valence state, b=1,2,3 or 4 (preferred b=2,3 or 4), and a-b 〉=0;
Described small molecules disilazane is the alkyl silyl disilazane, and its general molecular formula is:
(R
2 3Si)
2NR
3
R wherein
2Organic groups such as=H, methyl, ethyl, propyl group, butyl or phenyl (preferred R
2=methyl); R
3Organic groups such as=H, methyl, ethyl, propyl group, butyl or phenyl (preferred R
3=H or methyl), but when the halogenide of object element be TiCl
4Or when being the halid mixture of Si halogenide, B, R
3≠ H;
(3) reactor is heated to 125-500 ℃ (preferred 200-350 ℃) after dropwising, and insulation 2-30 hour (preferred 8-16 hour) under this temperature;
(4) temperature of reactor is reduced to room temperature-350 ℃ (preferred 100-300 ℃), underpressure distillation 0.2-2 hour (preferred 0.5-1 hour) reduced to room temperature with system and can be obtained nitride ceramic precursor under this temperature;
Described halogenide and small molecules disilazane add in the reactor in the mode that drips: 1. elder generation adds to the halogenide of object element in the reactor, adds the small molecules disilazane by the mode that drips then; Or 2. earlier the small molecules disilazane is added in the reactor, add different halogenide in reactor by the mode that drips then;
(5) (4) step gained nitride ceramic precursor is placed melt spinning device, after heating is higher than 30-80 ℃ of its softening temperature and carries out deaeration and handle under nitrogen protection, in 120-300 ℃ (preferred 150-240 ℃), 2-7 * 10
5Pa (preferred 3-6 * 10
5Pa) under the pressure, carry out melt-spinning, make the precursor that diameter is 8-15 μ m with 50-500m/min (preferred 100-300m/min) speed;
(6) (5) step gained nitride ceramic precursor precursor is placed not melting vessel,, be warming up to and be lower than 5 ℃-25 ℃ of precursor softening temperatures, feed BCl while lead to nitrogen then with the air in the drying nitrogen displacement container
3Or halosilanes gas 5-120 minute (preferred 30-60 minute), and then feed ammonia or water vapor, promptly obtain fusion-free fibre;
(7) in the High Temperature Furnaces Heating Apparatus of inert atmosphere or reactive atmosphere, the nitride ceramic precursor fusion-free fibre is warming up to 800-1300 ℃ (preferred 1000-1100 ℃) by the heat-up rate of 100-200 ℃/hr, and 1-6 hour (preferred 2-4 hour) handled in insulation under this temperature;
Described inert atmosphere is argon gas, nitrogen or helium, and described reactive atmosphere is ammonia or hydrogen;
(8) (7) step gained fiber temperature rise rate by 200-800 ℃/hr in inert atmosphere is risen to 1300-1800 ℃ (preferred 1400-1600 ℃), and insulation 1/12-4 hour (preferred 0.3-1 hour) under this temperature, be cooled to room temperature and promptly obtain Si-M-N-(C) ceramic fiber.
The nitride ceramic fibre that the present invention makes except that containing object element, also have Si, N or (with) C is elementary composition.
The present invention compares with existing method, and following positively effect is arranged: the raw materials cost of 1. selecting for use is cheap, and is from the horse's mouth, and higher synthetic yield is arranged; 2. select the preparation method of halogenide and small molecules disilazane cocondensation for use, technology is simple, can finish the preparation of precursor by single step reaction; 3. the not melt processed of precursor precursor adopts the crosslinked method of chemical gas phase, and the efficient height is convenient to the institutional operation with spinning, non-melt processed and the sintering process of precursor.
Embodiment
Embodiment 1:SiAlNC fiber production example 1.
(1) dichloro methyl silane, aluminum chloride are dissolved in the dimethylbenzene, simultaneously, will have in the there-necked flask reactor of 250ml of stirring, dropping, water distilling apparatus and vacuumize, fill drying nitrogen repeatedly at least three times, to get rid of air and moisture wherein; (2) get dichloro methyl silane 0.15mol, aluminum chloride 0.15mol is to the there-necked flask of drying nitrogen protection, getting hexamethyldisilazane 0.9mol again is injected in the constant pressure funnel, hexamethyldisilazane is added in the mixed solution of dichloro methyl silane and aluminum chloride in the mode that drips, stirs while dripping; (3) dropwise after, with the speed of 0.5 ℃/mi n reactor is warming up to 280 ℃, insulation is 10 hours under this temperature; (4) temperature of reactor is reduced to 150 ℃, underpressure distillation 0.5 hour naturally cools to room temperature, promptly obtains solid-state poly-aluminium silazane precursor 12.2g; (5) precursor with (4) step gained places melt spinning device, after heating is higher than 50 ℃ of its softening temperatures and carries out deaeration and handle under nitrogen protection, at 205 ℃, 4 * 10
5Under the Pa pressure, carry out melt-spinning with 350m/min speed, good spinning property, making diameter is the nitride precursor silk of 15.3 μ m; (6) the poly-aluminium silazane precursor that (5) step was made places not melt processed stove, by being warming up to 102 ℃, feeds HSiCl again in nitrogen atmosphere
3Gas 15min feeds the about 15min of steam subsequently, and the fiber weightening finish is not 11.23wt% after the melt processed; (7) fusion-free fibre is placed High Temperature Furnaces Heating Apparatus, under inert atmosphere protection, be warming up to 1100 ℃ by the heat-up rate of 150 ℃/hr, insulation was handled 2 hours; (8) (7) step gained fiber temperature rise rate by 300 ℃/hr in inert atmosphere is risen to 1400 ℃, and under this temperature, be incubated 0.5 hour, be cooled to room temperature and promptly make the Si-Al-N-C fiber.Fibre diameter is 11.3 μ m, and tensile strength is 1.45GPa.
Embodiment 2:SiAlNC fiber production example 2.
(1) aluminum chloride is dissolved in the toluene, simultaneously, will has in the there-necked flask reactor of 250ml of stirring, dropping, water distilling apparatus and vacuumize, fill drying nitrogen repeatedly at least three times, to get rid of air and moisture wherein; (2) get in the there-necked flask that aluminum chloride 0.15mol is added to drying nitrogen protection, get hexamethyldisilazane 0.6mol again and be added in the constant pressure funnel, then hexamethyldisilazane is added in the aluminum trichloride solution stirring in the mode that drips while dripping; (3) dropwise after, with the speed of 0.5 ℃/min reactor is warming up to 300 ℃, 290 ℃ of insulations 8 hours; (4) reactor is cooled to 105 ℃, underpressure distillation 0.5 hour promptly obtains poly-aluminium silazane precursor 19.2g.(5) the poly-aluminium silazane precursor of (4) step gained is placed melt spinning device, after heating is higher than 45 ℃ of its softening temperatures and carries out deaeration and handle under nitrogen protection, at 187 ℃, 5 * 10
5Under the Pa pressure, carry out melt-spinning with 350m/min speed, good spinning property makes the precursor that diameter is 15.6 μ m; (6) precursor that (5) step was made places not melt processed stove, by being warming up to 90 ℃, feeds SiCl again in nitrogen atmosphere
4Gas 15min feeds the about 15min of steam subsequently, and the fiber weightening finish is not 13.6wt% after the melt processed; (7) fusion-free fibre is placed High Temperature Furnaces Heating Apparatus, under inert atmosphere protection, be warming up to 1000 ℃ by the heat-up rate of 100 ℃/hr, insulation was handled 3 hours; (8) (7) step gained fiber temperature rise rate by 300 ℃/hr in inert atmosphere is risen to 1400 ℃, and under this temperature, be incubated 0.5 hour, be cooled to room temperature and make the Si-Al-N-C fiber.Fibre diameter is 12.2 μ m, and tensile strength is 1.26GPa.
Embodiment 3:SiBAlNC fiber production example 1.
(1) boron trichloride, aluminum chloride are dissolved in the normal hexane, simultaneously, will have in the there-necked flask reactor of 250ml of stirring, dropping, water distilling apparatus and vacuumize, fill drying nitrogen repeatedly at least three times, to get rid of air and moisture wherein; (2) get boron trichloride 0.15mol, aluminum chloride 0.3mol successively is added in the there-necked flask of drying nitrogen protection, get heptamethyldisilazane 0.6mol again and add in the constant pressure funnel, heptamethyldisilazane is added in preceding two kinds of monomeric mixed solutions in the mode that drips, stir while dripping; (3) dropwise after, with the speed of 0.5 ℃/min reactor is warming up to 320 ℃, insulation is 12 hours under this temperature; (4) temperature of reactor is reduced to 165 ℃, underpressure distillation naturally cooled to room temperature after 0.5 hour, promptly obtained solid-state poly-silicon boron aluminium alkane precursor 14.6g; (5) (4) step gained precursor is placed melt spinning device, after heating is higher than 40 ℃ of its softening temperatures and carries out deaeration and handle under nitrogen protection, at 207 ℃, 3 * 10
5Under the Pa pressure, carry out melt-spinning with 300m/min speed, making diameter is the aluminium borosilicate azane precursor of 16.3 μ m; (6) the poly-aluminium borosilicate azane precursor that (5) step was made places not melt processed stove, is warming up to 90 ℃ in nitrogen atmosphere, feeds BCl while lead to nitrogen then
360 minutes, and then after feeding ammonia 15min, reduce to room temperature, promptly obtain fusion-free fibre, the fiber weightening finish is not 9.87wt% after the melt processed; (7) fusion-free fibre is placed High Temperature Furnaces Heating Apparatus, under drying nitrogen protection, be warming up to 1200 ℃, insulation processing 2 hours by the heat-up rate of 150 ℃/hr; (8) (7) step gained fiber temperature rise rate by 400 ℃/hr in inert atmosphere is risen to 1500 ℃, and under this temperature, be incubated 1 hour, be cooled to room temperature and make the Si-Al-B-N-C fiber.Fibre diameter is 13.2 μ m, and tensile strength is 1.28GPa.
Embodiment 4:SiBAlNC fiber production example 2.
(1) trichlorosilane, boron trichloride, methylaluminum dichloride are dissolved in the toluene, simultaneously, to have in the there-necked flask reactor of 250ml of stirring, dropping, water distilling apparatus and vacuumize, fill drying nitrogen repeatedly at least three times, to get rid of air and moisture wherein; (2) get trichlorosilane 0.15mol, boron trichloride 0.15mol, methylaluminum dichloride successively is added in the there-necked flask of drying nitrogen protection, getting heptamethyldisilazane 1.5mol again is added in the constant pressure funnel, heptamethyldisilazane is added in the mixed solution of trichlorosilane, boron trichloride, methylaluminum dichloride in the mode that drips, stirs while dripping; (3) dropwise after, with the speed of 0.3 ℃/min reactor is warming up to 305 ℃, insulation is 14 hours under this temperature; (4) reactor is cooled to 182 ℃, underpressure distillation 1 hour promptly obtains solid-state poly-boron aluminium silazane precursor 10.8g after being cooled to room temperature; (5) (4) step gained precursor is placed melt spinning device, after heating is higher than 60 ℃ of its softening temperatures and carries out deaeration and handle under nitrogen protection, at 198 ℃, 5 * 10
5Under the Pa pressure, carry out melt-spinning with 200m/min speed, good spinning property makes the precursor that diameter is 15 μ m; (6) the poly-boron aluminium silazane precursor that (5) step was made places not melt processed stove, by being warming up to 93 ℃, feeds HSiCl again in nitrogen atmosphere
3Gas 15min feeds the about 15min of steam subsequently, and the fiber weightening finish is not 9.65wt% after the melt processed; (7) fusion-free fibre is placed High Temperature Furnaces Heating Apparatus, under inert atmosphere protection, be warming up to 1000 ℃ by the heat-up rate of 100 ℃/hr, insulation was handled 2 hours; (8) (7) step gained fiber temperature rise rate by 500 ℃/hr in inert atmosphere is risen to 1450 ℃, and under this temperature, be incubated 0.5 hour, be cooled to room temperature and make the Si-B-Al-N-C fiber.Fibre diameter is 12.3 μ m, and tensile strength is 1.6GPa.
Embodiment 5:SiTiAlNC fiber production example
(1) titanium tetrachloride, aluminum chloride are dissolved in the chloroform, simultaneously, will have in the there-necked flask reactor of 250ml of stirring, dropping, water distilling apparatus and vacuumize, fill drying nitrogen repeatedly at least three times, to get rid of air and moisture wherein; (2) get titanium tetrachloride 0.1mol, aluminum chloride 0.15mol successively is added in the there-necked flask of drying nitrogen protection, getting hexamethyldisilazane 0.6mol then is added in the constant pressure funnel, hexamethyldisilazane is mixed in the mixed solution of titanium tetrachloride and aluminum chloride in the mode that drips, stirs while dripping; (3) dropwise after, with the speed of 0.5 ℃/min reactor is warming up to 310 ℃, insulation is 12 hours under this temperature; (4) reactor is cooled to 160 ℃, underpressure distillation 0.5 hour is chilled to room temperature, promptly obtains solid-state poly-titanium aluminium silazane precursor 18.9g.(5) (4) step gained precursor is placed melt spinning device, after heating is higher than 50 ℃ of its softening temperatures and carries out deaeration and handle under nitrogen protection, at 187 ℃, 5 * 10
5Under the Pa pressure, carry out melt-spinning with 300m/min speed, making diameter is the poly-titanium aluminium silazane precursor of 16.3 μ m; (6) precursor that (5) step was made places not melt processed stove, is warming up to 100 ℃ in nitrogen atmosphere, feeds HSiCl while lead to nitrogen then
330 minutes, and then after feeding ammonia 15min, reduce to room temperature, promptly obtain fusion-free fibre, the fiber weightening finish is not 11.26wt% after the melt processed; (7) fusion-free fibre is placed High Temperature Furnaces Heating Apparatus, under drying nitrogen protection, be warming up to 1100 ℃, insulation processing 2 hours by the heat-up rate of 150 ℃/hr; (8) (7) step gained fiber temperature rise rate by 500 ℃/hr in inert atmosphere is risen to 1600 ℃, and under this temperature, be incubated 0.5 hour; (8) (7) step gained fiber temperature rise rate by 300 ℃/hr in inert atmosphere is risen to 1600 ℃, and under this temperature, be incubated 0.5 hour, be cooled to room temperature and make the Si-Ti-Al-N-C fiber.Fibre diameter is 13.1 μ m, and tensile strength is 1.15GPa.
Embodiment 6:SiZrNAlC fiber production example
(1) tetrabormated zirconium, aluminum chloride are dissolved in the toluene, simultaneously, will have in the there-necked flask reactor of 250ml of stirring, dropping, water distilling apparatus and vacuumize, fill drying nitrogen repeatedly at least three times, to get rid of air and moisture wherein; (2) get tetrabormated zirconium 0.15mol, aluminum chloride 0.15mol is added in the there-necked flask of drying nitrogen protection, getting heptamethyldisilazane 1.5mol again is added in the constant pressure funnel, then heptamethyldisilazane is added in the solution of tetrabormated zirconium and aluminum chloride in the mode that drips, stirs while dripping; (3) dropwise after, with the speed of 0.5 ℃/min reactor is warming up to 330 ℃, 330 ℃ of insulations 15 hours; (4) reactor is reduced to 195 ℃, underpressure distillation 1 hour promptly obtains solid-state poly-zirconium aluminium silazane precursor 20.8g.(5) (4) step gained precursor is placed melt spinning device, after heating is higher than 50 ℃ of its softening temperatures and carries out deaeration and handle under nitrogen protection, at 225 ℃, 4 * 10
5Under the Pa pressure, carry out melt-spinning, make the precursor that diameter is 15.6 μ m with 300m/min speed; (6) precursor that (5) step was made places not melt processed stove, is warming up to 110 ℃ in nitrogen atmosphere, feeds H while lead to nitrogen then
2SiCl
260 minutes, and then after feeding ammonia 15min, reduce to room temperature, promptly obtain fusion-free fibre, the fiber weightening finish is not 8.9wt% after the melt processed; (7) the 6th step gained fusion-free fibre is placed High Temperature Furnaces Heating Apparatus, under the drying nitrogen protection, be warming up to 1100 ℃, insulation processing 2 hours by the heat-up rate of 150 ℃/hr; (8) (7) step gained fiber temperature rise rate by 300 ℃/hr in inert atmosphere is risen to 1400 ℃, and under this temperature, be incubated 0.5 hour, be cooled to room temperature and make the Si-Zr-N-Al-C fiber.Fibre diameter is 12.7 μ m, and tensile strength is 1.35GPa.
Embodiment 7:SiTiBNC fiber production example
(1) titanium tetrachloride, boron trichloride are dissolved in the dimethylbenzene, simultaneously, will have in the there-necked flask reactor of 250ml of stirring, dropping, water distilling apparatus and vacuumize, fill drying nitrogen repeatedly at least three times, to get rid of air and moisture wherein; (2) get titanium tetrachloride 0.15mol, boron trichloride 0.15mol is added in the there-necked flask of drying nitrogen protection, getting N-ethyl hexamethyldisilazane 1.2mol again is added in the constant pressure funnel, then N-ethyl hexamethyldisilazane is added in the solution of titanium tetrachloride and boron trichloride in the mode that drips, stirs while dripping; (3) dropwise after, with the speed of 0.5 ℃/min reactor is warming up to 320 ℃, insulation is 15 hours under this temperature; (4) reactor is reduced to 195 ℃, underpressure distillation 1 hour promptly obtains solid-state poly-titanium borosilicate azane precursor 19.8g.(5) the poly-titanium borosilicate azane precursor of (4) step gained is placed melt spinning device, after heating is higher than 40 ℃ of its softening temperatures and carries out deaeration and handle under nitrogen protection, at 215 ℃, 4.5 * 10
5Under the Pa pressure, carry out melt-spinning with 300m/min speed, making diameter is the poly-titanium borosilicate azane precursor of 15.6 μ m; (6) precursor that (5) step was made places not melt processed stove, is warming up to 100 ℃ in nitrogen atmosphere, feeds BCl while lead to nitrogen then
360 minutes, and then after feeding ammonia 15min, reduce to room temperature, promptly obtain fusion-free fibre, the fiber weightening finish is not 11.9wt% after the melt processed; (7) fusion-free fibre is placed High Temperature Furnaces Heating Apparatus, under drying nitrogen protection, be warming up to 1100 ℃, insulation processing 2 hours by the heat-up rate of 150 ℃/hr; (8) (7) step gained fiber temperature rise rate by 300 ℃/hr in inert atmosphere is risen to 1400 ℃, and under this temperature, be incubated 0.5 hour, be cooled to room temperature and make the Si-Ti-B-N-C fiber.Fibre diameter is 12.7 μ m, and tensile strength is 1.13GPa.
Embodiment 8:SiTaBNC fiber production example
(1) four tantalum chlorides, boron trichloride, silicon tetrachloride are dissolved in the toluene, simultaneously, will have in the there-necked flask reactor of 250ml of stirring, dropping, water distilling apparatus and vacuumize, fill drying nitrogen repeatedly at least three times, to get rid of air and moisture wherein; (2) get in the there-necked flask that hexamethyldisilazane 1.5mol is added to drying nitrogen protection, get four tantalum chloride 0.15mol again, boron trichloride 0.15mol, silicon tetrachloride 0.15mol are added in the constant pressure funnel, then above-mentioned three kinds of muriatic mixtures are added in the hexamethyldisilazane in the mode that drips, stir while dripping; (3) dropwise after, with the speed of 0.5 ℃/min reactor is warming up to 300 ℃, insulation is 12 hours under this temperature; (4) reactor is reduced to 165 ℃, underpressure distillation 1 hour promptly obtains solid-state poly-tantalum borosilicate azane precursor 23.6g.(5) (4) step gained precursor is placed melt spinning device, after heating is higher than 50 ℃ of its softening temperatures and carries out deaeration and handle under nitrogen protection, at 195 ℃, 4 * 10
5Under the Pa pressure, carry out melt-spinning, make the precursor that diameter is 14.6 μ m with 300m/min speed; (6) precursor that (5) step was made places not melt processed stove, is warming up to 70 ℃ in nitrogen atmosphere, feeds BCl while lead to nitrogen then
360 minutes, and then after feeding ammonia 15min, reduce to room temperature, promptly obtain fusion-free fibre, the fiber weightening finish is not 12.3wt% after the melt processed; (7) fusion-free fibre is placed High Temperature Furnaces Heating Apparatus, under drying nitrogen protection, be warming up to 1100 ℃, insulation processing 2 hours by the heat-up rate of 150 ℃/hr; (8) (7) step gained fiber temperature rise rate by 300 ℃/hr in inert atmosphere is risen to 1400 ℃, and under this temperature, be incubated 0.5 hour, be cooled to room temperature and make the Si-Ta-B-N-C fiber.Fibre diameter is 12.2 μ m, and tensile strength is 1.06GPa.
Embodiment 9:SiAlN fiber production example
Fusion-free fibre among the embodiment 1 is placed High Temperature Furnaces Heating Apparatus, under ammonia atmosphere and inert atmosphere mixed atmosphere, be warming up to 1000 ℃ by the heat-up rate of 150 ℃/hr, insulation was handled 2 hours; Gained fiber temperature rise rate by 600 ℃/hr in inert atmosphere is risen to 1600 ℃, and be cooled to room temperature in insulation under this temperature after 0.5 hour and make the Si-Al-N fiber.Fibre diameter is 10.1 μ m, and tensile strength is 1.21GPa.
Embodiment 10:SiBAlN fiber production example
Fusion-free fibre among the embodiment 3 is placed High Temperature Furnaces Heating Apparatus, under ammonia atmosphere and inert atmosphere mixed atmosphere, be warming up to 1000 ℃ by the heat-up rate of 100 ℃/hr, insulation was handled 2 hours; Fiber temperature rise rate by 700 ℃/hr in inert atmosphere is risen to 1400 ℃, and be cooled to room temperature in insulation under this temperature after 1 hour and make the Si-B-Al-N fiber.Fibre diameter is 10.9 μ m, and tensile strength is 1.03GPa.
Claims (8)
1, a kind of preparation method of nitride ceramic fibre is characterized in that, comprises the steps:
(1) in the halogenide dissolving organic solvent with object element, simultaneously, will be with the reactor of stirring, dropping, water distilling apparatus to vacuumize, fill drying nitrogen repeatedly at least three times;
(2) with the halogenide of object element and small molecules disilazane by 1: the mol ratio of 3-30 adds in the reactor in the mode that drips, the stirring while dripping;
The halid molecular formula of described object element is as follows:
R
1 a-bMX
b
Wherein, M is an object element, M=Si, Al, B, Zr, Ta, Hf, Cr, Nb, Ge, V, W, Fe or Ti; X is a halogens; R
1=H, methyl, ethyl, propyl group, butyl or phenyl; A is that the maximum of object element is closed valence state, b=1,2,3 or 4, and a-b 〉=0;
Described small molecules disilazane is the alkyl silyl disilazane, and its general molecular formula is:
(R
2 3Si)
2NR
3
R wherein
2=H, methyl, ethyl, propyl group, butyl or phenyl; R
3=H, methyl, ethyl, propyl group, butyl or phenyl, but when the halogenide of object element be TiCl
4Or when being the halid mixture of Si halogenide, B, R
3≠ H;
(3) reactor is heated to 125-500 ℃ after dropwising, and insulation 2-30 hour under this temperature;
(4) temperature of reactor is reduced to room temperature-350 ℃, under this temperature underpressure distillation 0.2-2 hour, system is reduced to room temperature can obtain nitride ceramic precursor;
Described halogenide and small molecules disilazane add in the reactor in the mode that drips: 1. elder generation adds to the halide solution of object element in the reactor, adds the small molecules disilazane by the mode that drips then; Or 2. earlier the small molecules disilazane is added in the reactor, add different halogenide in reactor by the mode that drips then;
(5) (4) step gained nitride precursor is placed melt spinning device, after under nitrogen protection, being heated above 30-80 ℃ of its softening temperature and carrying out deaeration and handle, at 120-300 ℃, 2-7 * 10
5Under the Pa pressure, carry out melt-spinning, make the precursor that diameter is 8-15 μ m with 50-500m/min speed;
(6) (5) step gained precursor is placed not melting vessel,, be warming up to and be lower than 5 ℃-25 ℃ of precursor softening temperatures, feed BCl while lead to nitrogen then with the air in the drying nitrogen displacement container
3Or halosilanes gas 5-120 minute, feed ammonia or water vapor again, promptly obtain fusion-free fibre;
(7) in the High Temperature Furnaces Heating Apparatus of inert atmosphere or reactive atmosphere, fusion-free fibre is warming up to 800-1300 ℃ by the heat-up rate of 100-200 ℃/hr, and insulation was handled 1-6 hour under this temperature;
Described inert atmosphere is argon gas, nitrogen or helium, and described reactive atmosphere is ammonia or hydrogen;
(8) (7) step gained fiber temperature rise rate by 200-800 ℃/hr in inert atmosphere is risen to 1300-1800 ℃, and under this temperature, be incubated 1/12-4 hour, be cooled to room temperature, promptly obtain Si-M-N-(C) ceramic fiber.
2, the preparation method of nitride ceramic fibre according to claim 1 is characterized in that, in described (2) step, described halogens is Cl.
3, the preparation method of nitride ceramic fibre according to claim 1 and 2 is characterized in that, in described (3) step, after dropwising reactor is heated to 200-350 ℃, and is incubated 8-16 hour under this temperature.
4, the preparation method of nitride ceramic fibre according to claim 1 and 2 is characterized in that, in described (4) step, temperature of reactor is reduced to 100-300 ℃, under this temperature underpressure distillation 0.5-1 hour.
5, the preparation method of nitride ceramic fibre according to claim 1 and 2 is characterized in that, in described (5) step, described spinning temperature is 150-240 ℃, and pressure is 3-6 * 10
5Pa, speed is 100-300m/min.
6, the preparation method of nitride ceramic fibre according to claim 1 and 2 is characterized in that, described (6) step, described feeding nitrogen and BCl
3Or the time of halosilanes gas is 30-60 minute.
7, the preparation method of nitride ceramic fibre according to claim 1 and 2 is characterized in that, in described (7) step, fusion-free fibre is warming up to 1000-1100 ℃, and insulation is handled 2-4 hour under this temperature.
8, the preparation method of nitride ceramic fibre according to claim 1 and 2 is characterized in that, in described (8) step, (7) step gained fiber is risen to 1400-1600 ℃ in inert atmosphere, and be incubated 0.3-1 hour under this temperature.
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