CN112624766B - Preparation method of silicon nitride @ silicon carbide @ boron nitride composite fiber felt - Google Patents
Preparation method of silicon nitride @ silicon carbide @ boron nitride composite fiber felt Download PDFInfo
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Abstract
A preparation method of a silicon nitride @ silicon carbide @ boron nitride composite fiber felt relates to a preparation method of a composite fiber felt. The invention aims to solve the problem that the use temperature of the existing ceramic fiber material is lower than 1200 ℃. The preparation method comprises the following steps: mono, Si3N4Preparing a fiber felt; secondly, wrapping a carbon layer; III, Si3N4Preparing a @ SiC fibrofelt; and fourthly, loading the BN layer. The preparation method is used for preparing the silicon nitride @ silicon carbide @ boron nitride composite fiber felt.
Description
Technical Field
The invention relates to a preparation method of a composite fiber felt.
Background
The ceramic fiber felt is used as a light and flexible refractory fiber heat insulation material commonly used at present, has excellent heat insulation performance, and plays an important role in promoting rapid development in the fields of aviation, aerospace, metallurgy, chemical industry, energy and the like. High temperature resistant ceramic fiber materials are considered to be the most promising materials for use in harsh high temperature environments. The service temperature of the ceramic fiber in the international market under the aerobic environment is generally lower than 1200 ℃, and in order to meet the development requirement of future equipment, the development of a novel high-temperature resistant ceramic fiber material is urgently needed. Currently, SiC and Si are commonly used in ultra-high temperature environments3N4Ceramic fiber, wherein the service temperature of the two ceramic materials under the air atmosphere is not higher than 1200 ℃. The service temperature of the ceramic fiber in the international market under the aerobic environment is generally lower than 1200 ℃, and in order to meet the development requirement of future equipment, the development of novel high-temperature resistant ceramic fiber is urgently neededAnd (5) a fiber material.
Disclosure of Invention
The invention provides a preparation method of a silicon nitride @ silicon carbide @ boron nitride composite fiber felt, aiming at solving the problem that the use temperature of the existing ceramic fiber material is lower than 1200 ℃.
A preparation method of a silicon nitride @ silicon carbide @ boron nitride composite fiber felt is completed according to the following steps:
mono, Si3N4Preparing a fiber felt:
laying reaction silicon source powder at the bottom of a graphite crucible to obtain a reaction silicon source layer, then covering a carbon fiber felt on the surface of the reaction silicon source layer, putting the graphite crucible which is not covered with a graphite crucible cover and contains reactants into a tubular furnace, introducing nitrogen as reaction gas at the flow rate of 60-160 mL/min, heating to 1500-1700 ℃ at the heating rate of 1-10 ℃/min, carrying out sintering reaction for 90-240 min at the reaction temperature of 1500-1700 ℃, and naturally cooling to room temperature after the reaction is finished to obtain Si3N4A fiber mat;
the mass ratio of the reaction silicon source powder to the carbon fiber felt is 1 (1-8);
secondly, coating a carbon layer:
mixing Si3N4Soaking the fiber felt in a carbon precursor solution for 12-48 h, drying to obtain a soaked felt, placing the soaked felt in a tubular furnace, heating to 600-1000 ℃ at a heating rate of 5-10 ℃/min under the protection of nitrogen, preserving the heat for 120-480 min at the temperature of 600-1000 ℃, then reducing the temperature to 300-500 ℃ at a cooling rate of 5-10 ℃/min, and naturally cooling along with the furnace to obtain Si coating the C layer3N4A fiber mat;
the concentration of the carbon precursor solution is 0.5-2 mol/L;
III, Si3N4Preparation of @ SiC fiber felt:
laying silicon source powder at the bottom of a graphite crucible to obtain a silicon source layer, and then wrapping Si of the C layer3N4Fiber feltCovering the surface of the silicon source layer, covering a graphite crucible cover, putting the graphite crucible containing reactants into a tube furnace, heating to 1400-1700 ℃ at the heating rate of 1-2.5 ℃/min by taking argon as protective gas, carrying out sintering reaction for 120-360 min at the reaction temperature of 1400-1700 ℃, and naturally cooling to room temperature after the reaction is finished to obtain Si3N4@ SiC fiber felt;
the silicon source powder and Si coating the C layer3N4The mass ratio of the fiber felt is 1 (1-6);
fourthly, loading of the BN layer:
dissolving boron source and nitrogen source in methanol/deionized water solution to obtain impregnation solution, and adding Si3N4Soaking the @ SiC fibrofelt in the impregnation liquid, performing ultrasonic treatment for 0.5 to 5 hours under the condition that the power is 35 to 50W, performing drying treatment after ultrasonic treatment, then placing the fibrofelt in a tubular furnace, heating the fibrofelt to 1500 to 1800 ℃ at the heating rate of 5 to 10 ℃/min under the nitrogen atmosphere, preserving the heat for 2 to 6 hours under the temperature of 1500 to 1800 ℃, and cooling the fibrofelt along with the furnace to obtain the Si3N4@ SiC @ BN composite fiber felt;
the concentration of the boron source in the dipping solution is 0.1-2 mol/L; the concentration of the nitrogen source in the impregnation liquid is 0.1-1 mol/L; the mass percentage of the methanol in the impregnation liquid is 5-20%.
The invention has the beneficial effects that:
the invention develops Si with strong operability and wide industrialization prospect3N4A preparation method of the @ SiC @ BN composite fiber felt is characterized in that a silicon carbide layer is wrapped on the surface of the composite fiber felt by a method of generating silicon nitride fibers on the basis of an original template carbon fiber felt and then carrying out further carbon thermal reduction of a loaded carbon source, and finally, a BN layer is wrapped. BN, SiC, Si3N4The layers are respectively wrapped layer by layer, and the synergistic effect of the unique structure plays a critical role in high-temperature stability. This microstructural characteristic allows the multicomponent composite fiber mat to maintain ultra-high temperature stability. This structural design can maintain the stability of the multi-element ceramic fiber from three aspects: aerobic atmosphereSi unstable under3N4The fiber is positioned at the innermost layer of the gradient fiber and is shielded and blocked by three elements at the outer layer on the atomic scale; the element B is positioned on the outer surface layer, so that high-temperature stability is facilitated; and the Si-C bond formed by the mutual bonding of the intermediate layers on the atomic scale is used as a transition layer due to the unique heat conduction performance of the intermediate layers.
The method is simple, and each component of the obtained fiber felt is tightly combined. Si prepared by the invention3N4The heat conductivity of the @ SiC @ BN composite fiber felt is only 0.09W/m.K at normal temperature, the temperature is increased to 1600 ℃ in high-purity air, the quality is not reduced, and the high-temperature stability is good. The Si is3N4The @ SiC @ BN composite fiber felt has good high-temperature-resistant heat-insulating property and good application prospect in the high-temperature application fields of aviation, aerospace, metallurgy, chemical industry and the like.
The invention relates to a preparation method of a silicon nitride @ silicon carbide @ boron nitride composite fiber felt.
Drawings
FIG. 1 shows Si prepared in one step three of the example3N4A microstructure diagram of the @ SiC fibrofelt;
FIG. 2 shows Si prepared in example one3N4A micro-topography of the @ SiC @ BN composite fiber felt;
FIG. 3 is a chart of EDS elements for region A of FIG. 2;
FIG. 4 shows Si prepared in example one3N4High temperature thermal weight loss curve of @ SiC @ BN fibrofelt.
Detailed Description
The first embodiment is as follows: the embodiment of the invention relates to a preparation method of a silicon nitride @ silicon carbide @ boron nitride composite fiber felt, which is completed according to the following steps:
mono, Si3N4Preparing a fiber felt:
laying reaction silicon source powder at the bottom of a graphite crucible to obtain a reaction silicon source layer, then covering a carbon fiber felt on the surface of the reaction silicon source layer, putting the graphite crucible which is not covered with a graphite crucible cover and contains reactants into a tubular furnace, introducing nitrogen as reaction gas at the flow rate of 60-160 mL/min, and raising the pressure of the reaction gasHeating to 1500-1700 ℃ at a temperature rate of 1-10 ℃/min, carrying out sintering reaction for 90-240 min at a reaction temperature of 1500-1700 ℃, and naturally cooling to room temperature after the reaction is finished to obtain Si3N4A fiber mat;
the mass ratio of the reaction silicon source powder to the carbon fiber felt is 1 (1-8);
secondly, coating a carbon layer:
mixing Si3N4Soaking the fiber felt in a carbon precursor solution for 12-48 h, drying to obtain a soaked felt, placing the soaked felt in a tubular furnace, heating to 600-1000 ℃ at a heating rate of 5-10 ℃/min under the protection of nitrogen, preserving the heat for 120-480 min at the temperature of 600-1000 ℃, then reducing the temperature to 300-500 ℃ at a cooling rate of 5-10 ℃/min, and naturally cooling along with the furnace to obtain Si coating the C layer3N4A fiber mat;
the concentration of the carbon precursor solution is 0.5-2 mol/L;
III, Si3N4Preparation of @ SiC fiber felt:
laying silicon source powder at the bottom of a graphite crucible to obtain a silicon source layer, and then wrapping Si of the C layer3N4Covering a fibrofelt on the surface of the silicon source layer, covering a graphite crucible cover, putting the graphite crucible containing reactants into a tubular furnace, heating to 1400-1700 ℃ at the heating rate of 1-2.5 ℃/min by taking argon as protective gas, carrying out sintering reaction for 120-360 min at the reaction temperature of 1400-1700 ℃, and naturally cooling to room temperature after the reaction is finished to obtain Si3N4@ SiC fiber felt;
the silicon source powder and Si coating the C layer3N4The mass ratio of the fiber felt is 1 (1-6);
fourthly, loading of the BN layer:
dissolving boron source and nitrogen source in methanol/deionized water solution to obtain impregnation solution, and adding Si3N4The @ SiC fiber felt is immersed in the immersion liquid, under the condition that the power is 35W-50W,ultrasonic treatment for 0.5-5 h, drying after ultrasonic treatment, then placing in a tube furnace, heating to 1500-1800 ℃ at a heating rate of 5-10 ℃/min in a nitrogen atmosphere, keeping the temperature at 1500-1800 ℃ for 2-6 h, and furnace cooling to obtain Si3N4@ SiC @ BN composite fiber felt;
the concentration of the boron source in the dipping solution is 0.1-2 mol/L; the concentration of the nitrogen source in the impregnation liquid is 0.1-1 mol/L; the mass percentage of the methanol in the impregnation liquid is 5-20%.
The beneficial effects of the embodiment are as follows:
the embodiment develops the Si with strong operability and wide industrialization prospect3N4A preparation method of the @ SiC @ BN composite fiber felt is characterized in that a silicon carbide layer is wrapped on the surface of the composite fiber felt by a method of generating silicon nitride fibers on the basis of an original template carbon fiber felt and then carrying out further carbon thermal reduction of a loaded carbon source, and finally, a BN layer is wrapped. BN, SiC, Si3N4The layers are respectively wrapped layer by layer, and the synergistic effect of the unique structure plays a critical role in high-temperature stability. This microstructural characteristic allows the multicomponent composite fiber mat to maintain ultra-high temperature stability. This structural design can maintain the stability of the multi-element ceramic fiber from three aspects: [ unstable Si in oxygen atmosphere3N4The fiber is positioned at the innermost layer of the gradient fiber and is shielded and blocked by three elements at the outer layer on the atomic scale; the element B is positioned on the outer surface layer, so that high-temperature stability is facilitated; and the Si-C bond formed by the mutual bonding of the intermediate layers on the atomic scale is used as a transition layer due to the unique heat conduction performance of the intermediate layers.
The method of the embodiment is simple, and each component of the obtained fiber felt is tightly combined. Si prepared in the present embodiment3N4The heat conductivity of the @ SiC @ BN composite fiber felt is only 0.09W/m.K at normal temperature, the temperature is increased to 1600 ℃ in high-purity air, the quality is not reduced, and the high-temperature stability is good. The Si is3N4The @ SiC @ BN composite fiber felt has good high-temperature-resistant heat-insulating property and good high-temperature application fields of aviation, aerospace, metallurgy, chemical industry and the likeThe application prospect of (1).
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the carbon fiber felt in the step one is 400g/m of unit mass2～1000g/m2The carbon fiber felt of (1); the thickness of the carbon fiber felt in the step one is 3 mm-10 mm. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: the reaction silicon source powder in the first step is a mixture of silicon dioxide powder and silicon powder in a molar ratio of 1 (1-6). The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the drying in the second step is drying for 6 to 12 hours under the condition that the treatment temperature is 60 to 160 ℃. The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and the precursor solution in the second step is sucrose solution, glucose solution, starch solution, polyacrylonitrile solution or phenolic resin solution. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and the silicon source powder in the third step is a mixture of silicon dioxide powder and silicon powder in a molar ratio of 1 (1-6). The rest is the same as the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the drying treatment in the fourth step is drying for 6 to 12 hours at the treatment temperature of 60 to 160 ℃. The others are the same as the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the concentration of the boron source in the impregnating solution in the fourth step is 1 mol/L-2 mol/L; the concentration of the nitrogen source in the steeping liquor in the fourth step is 0.5-1 mol/L; the mass percent of the methanol in the steeping liquor in the fourth step is 10-20%. The rest is the same as the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: the boron source in the fourth step is boric acid, boron oxide or borax. The other points are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: the nitrogen source in the fourth step is urea, ammonium nitrate or melamine. The other points are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a preparation method of a silicon nitride @ silicon carbide @ boron nitride composite fiber felt is completed according to the following steps:
mono, Si3N4Preparing a fiber felt:
laying reaction silicon source powder at the bottom of a graphite crucible to obtain a reaction silicon source layer, then covering a carbon fiber felt on the surface of the reaction silicon source layer, putting the graphite crucible which is not covered with a graphite crucible cover and contains reactants into a tubular furnace, introducing nitrogen as reaction gas at the flow rate of 60mL/min, heating to 1500 ℃ at the heating rate of 2.5 ℃/min, carrying out sintering reaction for 2h under the condition that the reaction temperature is 1500 ℃, naturally cooling to room temperature after the reaction is finished to obtain Si3N4A fiber mat;
the mass ratio of the reaction silicon source powder to the carbon fiber felt is 1: 4;
secondly, coating a carbon layer:
mixing Si3N4Soaking the fiber felt in a carbon precursor solution for 24h, drying to obtain a soaked felt, placing the soaked felt in a tubular furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, keeping the temperature for 120min at the temperature of 800 ℃, then cooling to 300 ℃ at a cooling rate of 10 ℃/min, and naturally cooling with the furnace to obtain Si coated with the C layer3N4A fiber mat;
the concentration of the carbon precursor solution is 1 mol/L;
III, Si3N4Preparation of @ SiC fiber felt:
laying silicon source powder at the bottom of a graphite crucible to obtain a silicon source layer, and then wrapping Si of the C layer3N4Covering a fibrofelt on the surface of the silicon source layer, covering a graphite crucible cover, putting the graphite crucible containing reactants into a tubular furnace, heating to 1500 ℃ at the heating rate of 2.5 ℃/min by taking argon as protective gas, sintering and reacting for 120min at the reaction temperature of 1500 ℃, and naturally cooling to room temperature after the reaction is finished to obtain Si3N4@ SiC fiber felt;
the silicon source powder and Si coating the C layer3N4The mass ratio of the fiber felt is 1: 1;
fourthly, loading of the BN layer:
dissolving boron source and nitrogen source in methanol/deionized water solution to obtain impregnation solution, and adding Si3N4Soaking the @ SiC fibrofelt in the impregnation liquid, carrying out ultrasonic treatment for 0.5h under the condition that the power is 35W, carrying out drying treatment after ultrasonic treatment, then placing the fibrofelt in a tube furnace, heating the fibrofelt to 1600 ℃ under the nitrogen atmosphere at the heating rate of 5 ℃/min, keeping the temperature for 3h under the condition that the temperature is 1600 ℃, and carrying out furnace cooling to obtain the Si-based composite material3N4@ SiC @ BN composite fiber felt;
the concentration of the boron source in the impregnating solution is 1 mol/L; the concentration of the nitrogen source in the impregnation liquid is 1 mol/L; the mass percentage of the methanol in the impregnation liquid is 10%.
The unit mass of the carbon fiber felt in the step one is 750g/m2The carbon fiber felt of (1). The thickness of the carbon fiber felt in the step one is 5 mm.
The reaction silicon source powder in the first step is a mixture of silicon dioxide powder and silicon powder in a molar ratio of 1: 1.
The purity of the nitrogen in the first step is 99.99%.
The drying in the second step is drying for 10 hours under the condition that the treatment temperature is 80 ℃.
And the precursor solution in the second step is a sucrose solution.
The silicon source powder in the third step is a mixture of silicon dioxide powder and silicon powder with a molar ratio of 1: 1.
The purity of the argon in the third step is 99.99 percent.
The drying treatment in the fourth step is drying for 8 hours at the treatment temperature of 85 ℃.
The boron source in step four is boric acid.
The nitrogen source in the fourth step is urea.
FIG. 1 shows Si prepared in one step three of the example3N4A microstructure diagram of the @ SiC fibrofelt; as can be seen, the surface of the prepared silicon nitride fiber is successfully wrapped with a silicon carbide layer, and the thickness of the silicon carbide layer is about 2 microns.
FIG. 2 shows Si prepared in example one3N4A micro-topography of the @ SiC @ BN composite fiber felt; as can be seen from the figure, a layer of BN layered structure is loaded after the boron source is dipped and the high-temperature sintering reaction is carried out under the nitrogen, and the thickness is 1 micron.
FIG. 3 is a chart of EDS elements for region A of FIG. 2; as can be seen from the figure, the side surface of the prepared fiber felt with four elements of Si, B, C and N shows that the Si is present3N4And (3) preparing the @ SiC @ BN composite fiber felt.
Si prepared for example one3N4The thermal conductivity of the @ SiC @ BN composite fiber felt is tested, and the thermal conductivity of the composite fiber felt is only 0.09W/m.K at normal temperature. The thermal conductivity is significantly lower than that of a large number of porous ceramic structures, and is a candidate for an excellent heat-proof and heat-insulating material.
FIG. 4 shows Si prepared in example one3N4According to the high-temperature thermal weight loss curve of the @ SiC @ BN fibrofelt, the test atmosphere is high-purity air, the quality is not reduced when the temperature is increased to 1600 ℃, and the high-temperature stability is better.
Claims (9)
1. A preparation method of a silicon nitride @ silicon carbide @ boron nitride composite fiber felt is characterized by comprising the following steps:
mono, Si3N4Preparing a fiber felt:
laying reaction silicon source powder at the bottom of a graphite crucible to obtain a reaction silicon source layer, then covering a carbon fiber felt on the surface of the reaction silicon source layer, putting the graphite crucible which is not covered with a graphite crucible cover and contains reactants into a tubular furnace, introducing nitrogen as reaction gas at the flow rate of 60-160 mL/min, heating to 1500-1700 ℃ at the heating rate of 1-10 ℃/min, carrying out sintering reaction for 90-240 min at the reaction temperature of 1500-1700 ℃, and naturally cooling to room temperature after the reaction is finished to obtain Si3N4A fiber mat;
the mass ratio of the reaction silicon source powder to the carbon fiber felt is 1 (1-8);
secondly, coating a carbon layer:
mixing Si3N4Soaking the fiber felt in a carbon precursor solution for 12-48 h, drying to obtain a soaked felt, placing the soaked felt in a tubular furnace, heating to 600-1000 ℃ at a heating rate of 5-10 ℃/min under the protection of nitrogen, preserving the heat for 120-480 min at the temperature of 600-1000 ℃, then reducing the temperature to 300-500 ℃ at a cooling rate of 5-10 ℃/min, and naturally cooling along with the furnace to obtain Si coating the C layer3N4A fiber mat;
the concentration of the carbon precursor solution is 0.5-2 mol/L;
III, Si3N4Preparation of @ SiC fiber felt:
laying silicon source powder at the bottom of a graphite crucible to obtain a silicon source layer, and then wrapping Si of the C layer3N4Covering a fibrofelt on the surface of the silicon source layer, covering a graphite crucible cover, putting the graphite crucible containing reactants into a tubular furnace, heating to 1400-1700 ℃ at the heating rate of 1-2.5 ℃/min by taking argon as protective gas, carrying out sintering reaction for 120-360 min at the reaction temperature of 1400-1700 ℃, and naturally cooling to room temperature after the reaction is finished to obtain Si3N4@ SiC fiber felt;
the silicon source powder and Si coating the C layer3N4The mass ratio of the fiber felt is 1:(1～6)；
Fourthly, loading of the BN layer:
dissolving boron source and nitrogen source in methanol/deionized water solution to obtain impregnation solution, and adding Si3N4Soaking the @ SiC fibrofelt in the impregnation liquid, performing ultrasonic treatment for 0.5 to 5 hours under the condition that the power is 35 to 50W, performing drying treatment after ultrasonic treatment, then placing the fibrofelt in a tubular furnace, heating the fibrofelt to 1500 to 1800 ℃ at the heating rate of 5 to 10 ℃/min under the nitrogen atmosphere, preserving the heat for 2 to 6 hours under the temperature of 1500 to 1800 ℃, and cooling the fibrofelt along with the furnace to obtain the Si3N4@ SiC @ BN composite fiber felt;
the concentration of the boron source in the impregnating solution is 1 mol/L; the concentration of the nitrogen source in the impregnation liquid is 1 mol/L; the mass percentage of the methanol in the impregnation liquid is 5-20%.
2. The method for preparing the silicon nitride @ silicon carbide @ boron nitride composite fiber felt according to claim 1, wherein the carbon fiber felt in the first step is 400g/m in unit mass2～1000g/m2The carbon fiber felt of (1); the thickness of the carbon fiber felt in the step one is 3 mm-10 mm.
3. The preparation method of the silicon nitride @ silicon carbide @ boron nitride composite fibrofelt according to claim 1, wherein the reaction silicon source powder in the first step is a mixture of silicon dioxide powder and silicon powder in a molar ratio of 1 (1-6).
4. The preparation method of the silicon nitride @ silicon carbide @ boron nitride composite fiber felt according to claim 1, wherein the drying in the second step is drying for 6 to 12 hours at a treatment temperature of 60 to 160 ℃.
5. The method for preparing the silicon nitride @ silicon carbide @ boron nitride composite fiber felt according to claim 1, wherein the precursor solution in the second step is a sucrose solution, a glucose solution, a starch solution, a polyacrylonitrile solution or a phenolic resin solution.
6. The preparation method of the silicon nitride @ silicon carbide @ boron nitride composite fibrofelt according to claim 1, wherein the silicon source powder in the third step is a mixture of silicon dioxide powder and silicon powder in a molar ratio of 1 (1-6).
7. The preparation method of the silicon nitride @ silicon carbide @ boron nitride composite fibrofelt according to claim 1, wherein the drying treatment in the fourth step is drying for 6 to 12 hours at a treatment temperature of 60 to 160 ℃.
8. The method of claim 1, wherein in step four said boron source is boric acid, boron oxide, or borax.
9. The preparation method of the silicon nitride @ silicon carbide @ boron nitride composite fiber felt according to claim 1, wherein the nitrogen source in the fourth step is urea, ammonium nitrate or melamine.
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