CN102515771A - Continuous preparation method of silicon boron nitrogen-based ceramic fiber - Google Patents
Continuous preparation method of silicon boron nitrogen-based ceramic fiber Download PDFInfo
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- CN102515771A CN102515771A CN2011104100005A CN201110410000A CN102515771A CN 102515771 A CN102515771 A CN 102515771A CN 2011104100005 A CN2011104100005 A CN 2011104100005A CN 201110410000 A CN201110410000 A CN 201110410000A CN 102515771 A CN102515771 A CN 102515771A
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Abstract
The invention relates to a continuous preparation method of a silicon boron nitrogen-based ceramic fiber, which comprises the following steps 1) melt spinning a precursor polymer polyborosilazane by insulating air under the temperature of 120-250 DEG C to obtain the precursor polymer fiber; 2) putting the precursor polymer fiber in a cracking furnace, introducing mixed gas, heating with 0.5-5 DEG Cmin to 200-350 DEG C and insulating for 2-10 hours to obtain the crosslinked fusion-free fiber; 3) under the condition that the above mixed gas is introduced, continuously heating with 0.5-5 DEG Cmin to 400-1000 DEG C and insulating for 2-10 hours, and heating with 0.5-5 DEG Cmin to 1200-1700 DEG C and insulating for 2-10 hours to obtain the product. The precursor polymer nascent fiber can effectively inhibit the introduction of oxygen element and enhance the anti-oxidation performance of inorganic ceramic fiber, the cost of the raw material is low, the process is stable and easy to adjust, and the method of the invention is suitable for large scale production.
Description
Technical field
The invention belongs to the preparation field of ceramic fiber, particularly a kind of preparation method of continuous silicone boron nitrogen base ceramic fibre.
Background technology
Silicon boron nitrogen base pottery is develop rapidly and the type material that is born of needs and the missilery of modern war; Silicon boron nitride-based ceramic material has that working temperature height, high temperature ablation rate are low, stable performance, nonhygroscopic, intensity is high and advantage such as wave, can satisfy the request for utilization of high Mach number guided missile.But stupalith has a fatal shortcoming---fragility, has had a lot of scholar's research methods to solve this universally acknowledged problem, finds that finally fiber is an efficient and simple method as strengthening body.Therefore the research of silicon boron-nitrogen ceramic fibre becomes key.Silicon nitrogen boron ceramic fiber has had Si concurrently
3N
4The advantage of the high-temperature stability of the HS of fiber and BN fiber has wave penetrate capability simultaneously, therefore is expected to become candidate's strongthener of high temperature wave-penetrating composite material of new generation.So important a kind of material has received international concern, mainly adopts the precursor polymer conversion method to prepare silicon nitrogen boron ceramic fiber at present in the world.External main research and development mechanism comprises Japanese Shin Etsu chemical company and east industry fuel corporation, German Bayer company, Univ Bonn Germany, Lyons, France university, Massachusetts Institute Technology, the University of Pennsylvania, Donghua University, the National University of Defense technology etc.Research institution has all reported the preparation of SiBNC ceramic fiber mostly, and the report of SiBN ceramic fiber preparation only has the M.Jasen of the general institute of German horse to propose a kind of preparation route, but does not show material object; Also there is the relevant report of SiBN ceramic fiber in the domestic National University of Defense technology, but only limits to laboratory scale short fiber preparation.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of continuous silicone boron nitrogen base ceramic fibre; The precursor polymer nascent fibre of this method gained is preparation under protection of inert gas; Effectively suppress the introducing of oxygen element, improved the antioxidant property of inorganic ceramic fiber; Raw materials cost is low, process stabilizing and be easy to the adjustment, adapt to very much large-scale production.
The preparation method of a kind of continuous silicone boron nitrogen base ceramic fibre of the present invention comprises:
(1) precursor polymer is gathered silicon nitrogen borine and under 120-250 ℃ of secluding air and moisture, carry out melt-spinning, get the precursor polymer fiber;
(2) the not melt processed and the de-carbon thereof of precursor polymer fiber: above-mentioned precursor polymer fiber is put into pyrolyzer; Feed the mixed gas that 100-1000ml/min is made up of reactive gas and rare gas element; Be warming up to 200-350 ℃ of insulation 2-10h with 0.5-5 ℃/min, obtain crosslinked fusion-free fibre;
(3) the preliminary inorganicization transformation and inorganicization of Pintsch process of precursor polymer fiber: under the situation that feeds above-mentioned mixed gas; Continuation is warming up to 400 ℃～1000 ℃ insulation 2-10h with 0.5-5 ℃/min; Be warming up to 1200 ℃～1700 ℃ insulation 2-10h with 0.5-5 ℃/min at last, get the continuous silicone nitrogen boron ceramic fiber of carbon content≤1.0%.
In the said step (1) during melt-spinning winding speed be 50-1000m/min.
Reactive gas in the said step (2) is ammonia, BCl
3Or DCMS, rare gas element is nitrogen or argon gas, the volume ratio of reactive gas and rare gas element is 5: 95-95: 5.
The receipts silk speed of fiber is 0.1-100mm/min in said step (2) and (3).
Beneficial effect
(1) the precursor polymer nascent fibre that makes of the present invention cracking to 1600 ℃ under ammonia atmosphere can make that carbon content is lower than 0.1%, has wave penetrate capability;
(2) the precursor polymer nascent fibre of gained of the present invention is preparation under protection of inert gas, has effectively suppressed the introducing of oxygen element, has improved the antioxidant property of inorganic ceramic fiber;
(3) raw materials cost of the present invention is low, process stabilizing and be easy to the adjustment, adapt to very much large-scale production.
Description of drawings
Fig. 1 is the nascent fibre (left side) and ceramic fiber (right side) the SEM photo of the embodiment of the invention 2, and scale is respectively 50 μ m and 20 μ m;
Fig. 2 is the XRD photo of the embodiment of the invention 3.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Precursor polymer is gathered silicon nitrogen borine (PBSZ) secluding air and moisture carries out melt-spinning, and spinning temperature is 130 ℃, and winding speed is 200m/min; The precursor polymer fiber is put into the continuous cracking stove, feed ammonia and nitrogen volume ratio and be 70: 30 mixed gas, rise to 280 ℃ with the heat-up rate of 0.5 ℃/min, be incubated 2 hours, carry out not melt processed, a receipts speed is 0.6mm/min; Fusion-free fibre is further put into continuous high temperature understand stove, feed ammonia and nitrogen volume ratio and be 70: 30 mixed gas, rise to 600 ℃ with the heat-up rate of 0.5 ℃/min; Be incubated 3 hours and begin inorganicization transformation, continue to rise to 1000 ℃, be incubated 4 hours with the heat-up rate of 2 ℃/min; Heat-up rate with 1 ℃/min rises to 1600 ℃ again; Insulation 2h reduces to room temperature, obtains successive SiNB ceramic fiber.C% is 0.1% (seeing table 1) in this ceramic fiber, can be in air 1500 ℃ of heatproofs, heatproof is 1700 ℃ in the nitrogen.
Table 1 ceramic fiber is elementary composition
| Si％ | B％ | N％ | C％ | H％ | O％ |
| 43.80 | 13.45 | 38.20 | 0.10 | 2.00 | 2.45 |
Embodiment 2
Precursor polymer is gathered silicon nitrogen borine (PBSZ) secluding air and moisture carries out melt-spinning, and spinning temperature is 150 ℃, and winding speed is 200m/min; The precursor polymer fiber is put into the continuous cracking stove, feed ammonia and nitrogen volume ratio and be 90: 10 mixed gas, rise to 280 ℃ with the heat-up rate of 1 ℃/min, be incubated 2 hours, carry out not melt processed, a receipts speed is 0.6mm/min; Fusion-free fibre is further put into continuous high temperature understand stove, feed ammonia and nitrogen volume ratio and be 80: 20 mixed gas, rise to 600 ℃ with the heat-up rate of 2 ℃/min; Be incubated 4 hours and begin inorganicization transformation, continue to rise to 1000 ℃, be incubated 5 hours with the heat-up rate of 1.5 ℃/min; Heat-up rate with 3 ℃/min rises to 1600 ℃ again; Insulation 6h reduces to room temperature, obtains successive SiNB ceramic fiber.C% is 0.05% in this ceramic fiber, can be in air 1500 ℃ of heatproofs, heatproof is 1700 ℃ in the nitrogen.
Precursor polymer is gathered silicon nitrogen borine (PBSZ) secluding air and moisture carries out melt-spinning, and spinning temperature is 250 ℃, and winding speed is 800m/min; The precursor polymer fiber is put into the continuous cracking stove, feed ammonia and nitrogen volume ratio and be 50: 50 mixed gas, rise to 280 ℃ with the heat-up rate of 0.5 ℃/min, be incubated 3 hours, carry out not melt processed, a receipts speed is 0.6mm/min; Fusion-free fibre is further put into continuous high temperature understand stove, feed ammonia and nitrogen volume ratio and be 50: 50 mixed gas, rise to 600 ℃ with the heat-up rate of 1 ℃/min; Be incubated 3 hours and begin inorganicization transformation, continue to rise to 1000 ℃, be incubated 2 hours with the heat-up rate of 0.5～5 ℃/min; Heat-up rate with 5 ℃/min rises to 1600 ℃ again; Insulation 8h reduces to room temperature, obtains successive SiNB ceramic fiber.C% is 1.0% in this ceramic fiber, can be in air 1500 ℃ of heatproofs, heatproof is 1700 ℃ in the nitrogen.
Embodiment 4
Precursor polymer is gathered silicon nitrogen borine (PBSZ) secluding air and moisture carries out melt-spinning, and spinning temperature is 350 ℃, and winding speed is 600m/min; The precursor polymer fiber is put into the continuous cracking stove, feed ammonia and nitrogen volume ratio and be 40: 60 mixed gas, rise to 280 ℃ with the heat-up rate of 0.5 ℃/min, be incubated 2 hours, carry out not melt processed, a receipts speed is 0.6mm/min; Fusion-free fibre is further put into continuous high temperature understand stove, feed ammonia and nitrogen volume ratio and be 40: 60 mixed gas, rise to 600 ℃ with the heat-up rate of 0.5 ℃/min; Be incubated 3 hours and begin inorganicization transformation, continue to rise to 1000 ℃, be incubated 2 hours with the heat-up rate of 1 ℃/min; Heat-up rate with 3 ℃/min rises to 1600 ℃ again; Insulation 2h reduces to room temperature, obtains successive SiNB ceramic fiber.C% is 0.8% in this ceramic fiber, can be in air 1500 ℃ of heatproofs, heatproof is 1700 ℃ in the nitrogen.
Claims (4)
1. the preparation method of a continuous silicone boron nitrogen base ceramic fibre comprises:
(1) precursor polymer is gathered silicon nitrogen borine and under 120-250 ℃ of secluding air and moisture, carry out melt-spinning, get the precursor polymer fiber;
(2) above-mentioned precursor polymer fiber is put into pyrolyzer, feed the mixed gas that 100-1000ml/min is made up of reactive gas and rare gas element, be warming up to 200-350 ℃ of insulation 2-10h, obtain crosslinked fusion-free fibre with 0.5-5 ℃/min;
(3) under the situation that feeds above-mentioned mixed gas; Continuation is warming up to 400 ℃～1000 ℃ insulation 2-10h with 0.5-5 ℃/min; Be warming up to 1200 ℃～1700 ℃ insulation 2-10h with 0.5-5 ℃/min at last, get the continuous silicone nitrogen boron ceramic fiber of carbon content≤1.0%.
2. the preparation method of a kind of continuous silicone boron nitrogen base ceramic fibre according to claim 1 is characterized in that: in the said step (1) during melt-spinning winding speed be 50-1000m/min.
3. the preparation method of a kind of continuous silicone boron nitrogen base ceramic fibre according to claim 1 is characterized in that: the reactive gas in the said step (2) is ammonia, BCl
3Or DCMS, rare gas element is nitrogen or argon gas, the volume ratio of reactive gas and rare gas element is 5: 95-95: 5.
4. the preparation method of a kind of continuous silicone boron nitrogen base ceramic fibre according to claim 1 is characterized in that: the receipts silk speed of fiber is 0.1-100mm/min in said step (2) and (3).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106835359A (en) * | 2017-02-06 | 2017-06-13 | 厦门大学 | A kind of preparation method of the silicon nitrogen carbon ceramic fibers of graded |
| CN106995947A (en) * | 2017-05-02 | 2017-08-01 | 中国人民解放军国防科学技术大学 | The gradual decarbonization method of nitride fiber |
| CN110952170A (en) * | 2019-12-25 | 2020-04-03 | 中国人民解放军国防科技大学 | Nitride fiber thermal crosslinking assisted atmosphere non-melting method |
| CN114875524A (en) * | 2022-06-24 | 2022-08-09 | 中国人民解放军国防科技大学 | Continuous SiBN fiber and preparation method and application thereof |
| CN115124371A (en) * | 2022-06-24 | 2022-09-30 | 中国人民解放军国防科技大学 | SiBN fiber with high elastic modulus as well as preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913877A (en) * | 2010-08-13 | 2010-12-15 | 东华大学 | Method for preparing borosilazane ceramic fiber precursor |
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- 2011-12-09 CN CN2011104100005A patent/CN102515771A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101913877A (en) * | 2010-08-13 | 2010-12-15 | 东华大学 | Method for preparing borosilazane ceramic fiber precursor |
Non-Patent Citations (2)
| Title |
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| PETER GREIL: "Active-Filler-Controlled Pyrolysis of Preceramic Polymers", 《J.AM.CREAM.SOC.》 * |
| 袁佳等: "SiBN(C)陶瓷纤维先驱体的表征及熔融纺丝", 《合成纤维工业》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106835359A (en) * | 2017-02-06 | 2017-06-13 | 厦门大学 | A kind of preparation method of the silicon nitrogen carbon ceramic fibers of graded |
| CN106995947A (en) * | 2017-05-02 | 2017-08-01 | 中国人民解放军国防科学技术大学 | The gradual decarbonization method of nitride fiber |
| CN110952170A (en) * | 2019-12-25 | 2020-04-03 | 中国人民解放军国防科技大学 | Nitride fiber thermal crosslinking assisted atmosphere non-melting method |
| CN110952170B (en) * | 2019-12-25 | 2022-04-19 | 中国人民解放军国防科技大学 | Nitride fiber thermal crosslinking assisted atmosphere non-melting method |
| CN114875524A (en) * | 2022-06-24 | 2022-08-09 | 中国人民解放军国防科技大学 | Continuous SiBN fiber and preparation method and application thereof |
| CN115124371A (en) * | 2022-06-24 | 2022-09-30 | 中国人民解放军国防科技大学 | SiBN fiber with high elastic modulus as well as preparation method and application thereof |
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Application publication date: 20120627 |