CN102659086B - Preparation method of silicon nitride nanometer fiber felt - Google Patents

Preparation method of silicon nitride nanometer fiber felt Download PDF

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Publication number
CN102659086B
CN102659086B CN201210135940.2A CN201210135940A CN102659086B CN 102659086 B CN102659086 B CN 102659086B CN 201210135940 A CN201210135940 A CN 201210135940A CN 102659086 B CN102659086 B CN 102659086B
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silicon nitride
preparation
reaktionsofen
fibrefelt
nitride nano
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CN102659086A (en
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邵长伟
宋永才
谢征芳
简科
王浩
王军
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National University of Defense Technology
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National University of Defense Technology
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Abstract

The invention relates to a preparation method of a silicon nitride nanometer fiber felt. The preparation method comprises the following steps of: 1) selecting, cleaning and drying a graphite substrate; 2) putting polymers containing Si-C bonds and the graphite substrate in a reaction furnace; 3) pumping the air of the reaction furnace till the internal pressure is below 100Pa; 4) feeding nitrogen or ammonia into the reaction furnace; 5) feeding NH3 or mixed gas of NH3 and inert gas into the reaction furnace, increasing the temperature to 500 DEG C to 1400 DEG C and maintaining the temperature for 0.4 to 3 hours; 6) stopping feeding the NH3 or the mixed gas of the NH3 and the inert gas, feeding nitrogen or hermetically closing the furnace and cooling with the furnace; and 7) when the temperature of the reaction furnace is decreased to be below 100 DEG C, taking out the graphite substrate to obtain the silicon nitride nanometer fiber felt. The preparation method of the silicon nitride nanometer fiber felt has the advantages that the raw materials are easy to obtain, the process is simple and easy to control, the synthesis temperature is low, the cost is low, the yield is high and the large-scale production is easy to realize.

Description

A kind of preparation method of silicon nitride nano fibrefelt
Technical field
The present invention relates to a kind of preparation method of silicon nitride nano fibrefelt.
Background technology
Silicon nitride (Si 3n 4) nanofiber is good semiconductor material, is the ideal material of preparing high-temperature nano device and high performance composite, has extraordinary application prospect.
At present, develop multiple silicon nitride nano fiber preparation method, comprised the thermal decomposition method of silicon-dioxide carbothermic method, silica flour direct nitridation method, combustion synthesis method, silicoorganic compound ammonolysis process, chemical Vapor deposition process, silicon-containing polymer etc.
Although silicon nitride nano fiber has excellent physical and chemical performance, it is easily reunited, is difficult to weave, and has restricted its practical application.Based on the multidirectional nanofiber silicon nitride fiber felt forming of arranging, can provide crucial strongthener for matrix material.
CN101838886A discloses a kind of silicon nitride nanometer non-weaving fabric and preparation method thereof on 09 22nd, 2010, the method is used sol-gel method to prepare amorphous Si-B-O-C composite granule presoma, and then silicon nitride nanometer non-weaving fabric is prepared in nitrogenize in high-temperature atmosphere sintering oven, but its operational path is long, and cost is high.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, provides that a kind of processing unit is simple without catalyzer, and cost is low, the preparation method of the silicon nitride nano fibrefelt of suitable complicated shape and large-scale production.
The technical scheme that the present invention solves its technical problem employing is that a kind of preparation method of silicon nitride nano fibrefelt, comprises the following steps:
(1) graphite cake, graphite flake or the graphite paper of choosing desired shape are substrate, by washed with de-ionized water, dry or dry, for subsequent use;
(2) graphite substrate of processing by the polymkeric substance containing Si-C key with through step (1) is put into Reaktionsofen;
The described polymkeric substance containing Si-C key can be polysilane, Polycarbosilane or poly-silicon-carbon alkane, wherein preferred Polycarbosilane;
(3) use vacuum pump that Reaktionsofen internal pressure is evacuated to 100Pa following (preferably 20Pa is following);
(4) in Reaktionsofen, lead to nitrogen or ammonia, to pressure 0.1-0.5MPa;
(5) in Reaktionsofen, lead to NH 3or NH 3with the gas mixture of inert atmosphere, control flow at the preferred 150/h-250L/h of 30L/h-400L/h(), while being warming up to 500-1400 DEG C (preferably 1000-1300 DEG C), be incubated 0.4-3 hour (preferably 0.5-1 hour);
Heat-up rate be the preferred 180-300 of 100-350 DEG C/h(DEG C/h);
Described inert atmosphere can be N 2, Ar or the preferred N of He( 2);
Described NH 3in the gas mixture of inert atmosphere, preferably NH 3the mixed atmosphere of volumetric concentration>=50%;
(6) stop passing into NH 3or NH 3with the gas mixture of inert atmosphere, then change logical nitrogen or airtight body of heater, furnace cooling;
(7) in the time that Reaktionsofen temperature drops to below 100 DEG C, take out graphite substrate.
The present invention taking polysilane, Polycarbosilane or poly-silicon-carbon alkane and this class of adulterating containing the polymkeric substance of Si-C key as raw material, with NH 3or NH 3with N 2, Ar or He etc. gas mixture be nitriding atmosphere, NH 3siliceous small molecules generation gas-phase chemical reaction with the polymer unwinds release containing Si-C key, generate silazane, and generate small molecules alkane to eliminate uncombined carbon, silazane deposition growing on graphite substrate forms nano silicon nitride silica fibre, nano silicon nitride silica fibre spreads on graphite substrate voluntarily, forms silicon nitride nano fibrefelt.Gained fibrefelt thickness is generally 0.2-5mm, and wherein the diameter of silicon nitride nano fiber is generally 50-200nm.
The present invention is by controlling NH 3the factor such as concentration, flow and polymer cracking temperature program(me), scission reaction time, can obtain the nano silicon nitride silica fibre of big area, Complex Different Shape structure.
Show by SEM, EDX, XRD analysis, product is silicon nitride nano fibrefelt.
It is raw material that the present invention adopts ripe Industrial products, and common gas-protecting sintering stove, does not need catalyzer, does not need the equipment of complex and expensive, and technique is simple, is easy to control, and cost is low, and output is high, easily accomplishes scale production.
Brief description of the drawings
Fig. 1 is the typical outside drawing of embodiment 1 gained nano-silicon nitride fibrefelt;
Fig. 2 is the typical SEM figure of embodiment 1 gained nano silicon nitride silica fibre;
Fig. 3 is the typical EDX figure of embodiment 1 gained nano silicon nitride silica fibre.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
The present embodiment comprises the following steps:
(1) choosing graphite paper is substrate, by washed with de-ionized water, dries, stand-by;
(2) graphite paper of processing by 50 grams of Polycarbosilanes with through step (1) is put into Reaktionsofen;
(3) use vacuum pump that Reaktionsofen internal pressure is evacuated to 50Pa;
(4) in Reaktionsofen, lead to nitrogen to pressure 0.2MPa;
(5) in Reaktionsofen, change logical NH 3, control flow at 300L/h, start to heat up by 5 DEG C/min, in the time that Reaktionsofen temperature reaches 1300 DEG C, be incubated 2 hours;
(6) stop passing into NH 3, airtight body of heater, furnace cooling;
(7) in the time that Reaktionsofen temperature drops to 50 DEG C, take out graphite paper, 27 grams of products.
The present embodiment gained nano-silicon nitride fibrefelt, its exterior appearance is as shown in Figure 1; Its microscopic appearance as shown in Figure 2; Survey with EDX that it is elementary composition, as shown in Figure 3, as shown in Figure 3, nano silicon nitride silica fibre is mainly made up of Si, N result.
Embodiment 2
The present embodiment comprises the following steps:
(1) choosing graphite paper is substrate, by washed with de-ionized water, dries, stand-by;
(2) graphite paper of processing by 50 grams of polysilanes with through step (1) is put into Reaktionsofen;
(3) use vacuum pump that Reaktionsofen internal pressure is evacuated to 20Pa;
(4) in Reaktionsofen, lead to ammonia to pressure 0.1MPa;
(5) in Reaktionsofen, change the gas mixture that leads to 90% volume ammonia and 10% volume nitrogen, control flow at 200L/h, start to heat up by 3 DEG C/min, in the time that Reaktionsofen temperature rises to 1300 DEG C, be incubated 2 hours;
(6) stop passing into the gas mixture of 90% volume ammonia and 10% volume nitrogen, airtight body of heater, furnace cooling;
(7) in the time that Reaktionsofen temperature drops to 60 DEG C, take out graphite paper, obtain 23 grams of nanofiber mats.
Embodiment 3
The present embodiment comprises the following steps:
(1) choosing graphite paper is substrate, by washed with de-ionized water, dries, stand-by;
(2) graphite paper of processing by 50 grams of Polycarbosilanes with through step (1) is put into Reaktionsofen;
(3) use vacuum pump that Reaktionsofen internal pressure is evacuated to 15Pa;
(4) in Reaktionsofen, lead to ammonia to pressure 0.15MPa;
(5) in Reaktionsofen, continue to pass into NH 3, control flow at 200L/h, start to heat up by 3 DEG C/min, in the time that Reaktionsofen temperature reaches 1200 DEG C, be incubated 3 hours;
(6) stop passing into NH 3, airtight body of heater, furnace cooling;
(7) in the time that Reaktionsofen temperature drops to 50 DEG C, take out graphite paper, obtain 24 grams of products.
Embodiment 4
The present embodiment comprises the following steps:
(1) choosing graphite cake is substrate, by washed with de-ionized water, dries, stand-by;
(2) graphite cake of processing by 50 grams of Polycarbosilanes with through step (1) is put into Reaktionsofen;
(3) use vacuum pump that Reaktionsofen internal pressure is evacuated to 10Pa;
(4) in Reaktionsofen, lead to ammonia to pressure 0.1MPa;
(5) in Reaktionsofen, continue logical NH 3, control flow at 200L/h, start to heat up by 3 DEG C/min, in the time that Reaktionsofen temperature reaches 1250 DEG C, be incubated 3 hours;
(6) stop passing into NH 3, airtight body of heater, furnace cooling;
(7) in the time that Reaktionsofen temperature drops to 80 DEG C, take out graphite cake, obtain 26 grams of products.
Embodiment 5
The present embodiment comprises the following steps:
(1) choosing graphite cake is substrate, by washed with de-ionized water, dries, stand-by;
(2) graphite cake of processing by 50 grams of Polycarbosilanes with through step (1) is put into Reaktionsofen;
(3) use vacuum pump that Reaktionsofen internal pressure is evacuated to 50Pa;
(4) in Reaktionsofen, lead to nitrogen to pressure 0.1MPa;
(5) in Reaktionsofen, change the gas mixture that leads to 60% volume ammonia and 40% volume argon gas, control flow at 300L/h, start to heat up by 3 DEG C/min, in the time that Reaktionsofen temperature reaches 1250 DEG C, be incubated 3 hours;
(6) stop passing into the gas mixture of 60% volume ammonia and 40% volume argon gas, airtight body of heater, furnace cooling;
(7) in the time that Reaktionsofen temperature drops to 100 DEG C, take out graphite cake, obtain 21 grams of products.
Embodiment 6
The present embodiment comprises the following steps:
(1) choosing graphite flake is substrate, by washed with de-ionized water, dries, stand-by;
(2) graphite flake of processing by 50 grams of Polycarbosilanes with through step (1) is put into Reaktionsofen;
(3) use vacuum pump that Reaktionsofen internal pressure is evacuated to 20Pa;
(4) in Reaktionsofen, lead to nitrogen to pressure 0.1MPa;
(5) to the gas mixture of logical 70% volume ammonia and 30% volume argon gas in Reaktionsofen, control flow at 350L/h, start to heat up by 5 DEG C/min, in the time that Reaktionsofen temperature reaches 1250 DEG C, be incubated 1 hour;
(6) stop passing into the gas mixture of 70% volume ammonia and 30% volume argon gas, airtight body of heater, furnace cooling;
(7) in the time that Reaktionsofen temperature drops to 80 DEG C, take out graphite flake, obtain 22 grams of products.

Claims (8)

1. a preparation method for silicon nitride nano fibrefelt, is characterized in that, comprises the following steps:
(1) graphite cake, graphite flake or the graphite paper of choosing desired shape are substrate, by washed with de-ionized water, dry or dry, for subsequent use;
(2) graphite substrate of processing by the polymkeric substance containing Si-C key with through step (1) is put into Reaktionsofen;
(3) use vacuum pump that Reaktionsofen internal pressure is evacuated to below 100Pa;
(4) in Reaktionsofen, lead to nitrogen or ammonia, to pressure 0.1-0.5MPa;
(5) in Reaktionsofen, lead to NH 3or NH 3with the gas mixture of inert atmosphere, control flow at 30L/h-400L/h, while being warming up to 500-1400 DEG C, insulation 0.4-3 hour; Heat-up rate is 100-350 DEG C/h;
(6) stop passing into NH 3or NH 3with the gas mixture of inert atmosphere, then change logical nitrogen or airtight body of heater, furnace cooling;
(7) in the time that Reaktionsofen temperature drops to below 100 DEG C, take out graphite substrate.
2. the preparation method of silicon nitride nano fibrefelt according to claim 1, is characterized in that, in step (2), the described polymkeric substance containing Si-C key is polysilane or poly-silicon-carbon alkane.
3. the preparation method of silicon nitride nano fibrefelt according to claim 1, is characterized in that, in step (2), the described polymkeric substance containing Si-C key is Polycarbosilane.
4. according to the preparation method of the silicon nitride nano fibrefelt described in claim 1 or 2 or 3, it is characterized in that, in step (3), use vacuum pump that furnace pressure is evacuated to below 20Pa.
5. according to the preparation method of the silicon nitride nano fibrefelt described in claim 1 or 2 or 3, it is characterized in that, in step (5), described inert atmosphere is argon gas or helium.
6. according to the preparation method of the silicon nitride nano fibrefelt described in claim 1 or 2 or 3, it is characterized in that, in step (5), described inert atmosphere is N 2.
7. according to the preparation method of the silicon nitride nano fibrefelt described in claim 1 or 2 or 3, it is characterized in that, in step (5), described NH 3with the gas mixture of inert atmosphere be NH 3the mixed atmosphere of volumetric concentration>=50%.
8. according to the preparation method of the silicon nitride nano fibrefelt described in claim 1 or 2 or 3, it is characterized in that, in step (5), in Reaktionsofen, lead to NH 3or NH 3with the gas mixture of inert atmosphere, control flow at 150/h-250L/h, be warming up to 1000-1300 DEG C, insulation 0.5-1 hour; Heat-up rate is 180-300 DEG C/h.
CN201210135940.2A 2012-05-04 2012-05-04 Preparation method of silicon nitride nanometer fiber felt Expired - Fee Related CN102659086B (en)

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CN105752952B (en) * 2016-01-28 2017-08-25 哈尔滨工业大学 A kind of method for preparing overlength beta-silicon nitride nanowire in porous body or powder shaped carborundum Polycarbosilane surface in situ and ex situ

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US5093096A (en) * 1987-03-20 1992-03-03 Japan Atomic Energy Research Institute High purity and high strength inorganic silicon nitride continuous fiber and a method of producing the same

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JPS61295298A (en) * 1985-06-21 1986-12-26 Nippon Carbon Co Ltd Preparation of silicon nitride
ES2006119A6 (en) * 1988-03-24 1989-04-01 Union Explosivos Rio Tinto Process for the preparation of silicon nitride.
JP2006066884A (en) * 2004-07-27 2006-03-09 Tokyo Electron Ltd Deposition method, deposition device and storage medium

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Publication number Priority date Publication date Assignee Title
US5093096A (en) * 1987-03-20 1992-03-03 Japan Atomic Energy Research Institute High purity and high strength inorganic silicon nitride continuous fiber and a method of producing the same

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