CN104016685A - Method for synthesizing carbon nano tube modified ultra-high temperature ceramic hybrid powder in situ - Google Patents
Method for synthesizing carbon nano tube modified ultra-high temperature ceramic hybrid powder in situ Download PDFInfo
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- CN104016685A CN104016685A CN201410283089.7A CN201410283089A CN104016685A CN 104016685 A CN104016685 A CN 104016685A CN 201410283089 A CN201410283089 A CN 201410283089A CN 104016685 A CN104016685 A CN 104016685A
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Abstract
The invention relates to a method for synthesizing carbon nano tube modified ultra-high temperature ceramic hybrid powder in situ, and the method can be used for solving the problem of agglomeration of carbon nano tubes when carbon nano tube modified ultra-high temperature ceramic is prepared in the prior art. The method for synthesizing the carbon nano tube modified ultra-high temperature ceramic hybrid powder in situ comprises the following steps: 1, sufficiently dispersing a catalyst in an organic polymer precursor to obtain mixed powder; 2, putting the mixed powder obtained in the step 1 into a square mold of which the upper part is open, heating in a tube furnace for cracking till the complete vitrification temperature of the organic polymer precursor is 1,450-1,550 DEG C, and carrying out heat preservation for 0.5-2 hours; 3, naturally cooling the heated and cracked mixed powder obtained in the step 2 to 20-25 DEG C, thus obtaining the carbon nano tube modified ultra-high temperature ceramic hybrid powder. The method is applicable in the technical field of structural ceramics, especially carbon nano tube modified ultra-high temperature ceramics.
Description
Technical field
A kind of method that the present invention relates to carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder, belongs to structural ceramics technical field.
Background technology
Carbon nanotube has excellent mechanical property, electric property and thermal property.The toughness that carbon nanotube improves hard brittle material has outstanding effect, and the carbon nanotube being incorporated in pottery can significantly improve by bridging effect the mechanical property of material.But carbon nanotube has very large length-to-diameter ratio, easily reunite, during for the preparation of the matrix material of carbon nano-tube modification, be difficult to fully disperse in matrix, especially in granular powder.
The method of preparing carbon nanotube of report mainly contains chemical Vapor deposition process, arc discharge method and laser ablation method etc. at present.Chemical Vapor deposition process is higher to equipment requirements, and investment is large; It is harsh that laser ablation method is prepared the required condition of carbon nanotube; Arc process has simple and quick feature, but the carbon nanotube defect that this method is produced is more, and productive rate is lower and be difficult to purifying, is not suitable for batch production.
For preparing carbon nano-tube modification superhigh temperature ceramics, adopt aforesaid method to obtain after carbon nanotube, can run into a technical barrier, it is exactly the problem how carbon nanotube fully disperses in matrix, because carbon nanotube has very large length-to-diameter ratio, easily reunite, during for the preparation of the matrix material of carbon nano-tube modification, be difficult to fully disperse in matrix, especially in granular powder.Adopt the method for growth in situ can well solve the scattering problem of carbon nanotube at ceramic particle surface in situ carbon nano-tube.
Summary of the invention
The present invention is existing while preparing carbon nano-tube modification superhigh temperature ceramics in order to solve, and carbon nanotube exists the problem of reuniting, and proposes a kind of method of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder.
A method for carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder, carry out according to the following steps:
One, by catalyst n i (NO
3)
2.6H
2o is well dispersed in the preceramic organosilicon polymer body of boracic by the mode of grinding and containing the mixed powder that obtains three in the preceramic organosilicon polymer body of zirconium, wherein the preceramic organosilicon polymer body of boracic is 2,4,6-, tri--methylamino-boron azine, and molecular formula is (NHCH
3)
3b
3n
3h
3, containing the preceramic organosilicon polymer body of zirconium, be [(C
4h
8o) Zr (acac)
2]
n, n=110～120, the mol ratio of B:Zr is (1～4): 1, catalyst n i (NO
3)
2.6H
2o and boracic and containing the ratio of the weight of the preceramic organosilicon polymer body of zirconium, be 1:(50～200);
Two, mixed powder step 1 being obtained is placed in the mould of open topped, heating pyrolyze in tube furnace, the temperature rise rate of first take is warmed up to 950 ℃～1050 ℃ by diamond heating as 4 ℃/min～6 ℃/min, take again temperature rise rate as 1 ℃/min～3 ℃/min by diamond heating to 1450 ℃～1550 ℃ of the complete ceramic temperature of preceramic organosilicon polymer body, soaking time is 0.5h～2h, in heating pyrolyze process, adopt rare gas element as shielding gas;
Three, the mixed powder after heating pyrolyze step 2 being obtained, cools to 20 ℃～25 ℃ naturally, obtains carbon nano-tube modification superhigh temperature ceramics hydridization powder.
Reaction mechanism of the present invention: the gas of emitting during the cracking of polymeric preceramic body has CO, CO
2, CH
4, NH
4, NO
2, H
2o etc., the CO that wherein cracking of polymeric preceramic body is emitted, CH
4, CO
2be the main carbon source of carbon nano tube growth, other products are along with the rising of temperature is deviate from from matrix with the form of gas, thereby obtain carbon nano-tube modification superhigh temperature ceramics hydridization powder.
The forming process of carbon nanotube: carbonaceous gas CO, CH
4, CO
2at catalyst surface, resolve into containing carbon part with not containing carbon part, containing catalyzed dose of dissolving of carbon part, containing carbon part, be not separated, owing to providing carbon source containing constantly catalyzed dose of dissolving of carbon part, in the bottom of catalyzer, carbon nanotube is constantly separated out growth.
The present invention includes following beneficial effect:
1, in the carbon nano-tube modification superhigh temperature ceramics hydridization powder that prepared by employing the inventive method, carbon nanotube is evenly distributed, and does not have agglomeration to occur;
2, adopt the inventive method to prepare carbon nanotube structure complete, have no mechanical damage, defect is few, and quality product is high;
3, the inventive method equipment used is simple, invests littlely, and can manufacture carbon nano-tube modification superhigh temperature ceramics hydridization powder.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the carbon nano-tube modification superhigh temperature ceramics hydridization powder of embodiment six preparations;
Fig. 2 is the XRD figure of the carbon nano-tube modification superhigh temperature ceramics hydridization powder of embodiment six preparations.
Embodiment
Embodiment one: a kind of method of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder, carry out according to the following steps:
One, by catalyst n i (NO
3)
2.6H
2o is well dispersed in the preceramic organosilicon polymer body of boracic by the mode of grinding and containing the mixed powder that obtains three in the preceramic organosilicon polymer body of zirconium, wherein the preceramic organosilicon polymer body of boracic is 2,4,6-, tri--methylamino-boron azine, and molecular formula is (NHCH
3)
3b
3n
3h
3, containing the preceramic organosilicon polymer body of zirconium, be [(C
4h
8o) Zr (acac)
2]
n, n=110～120, the mol ratio of B:Zr is (1～4): 1, catalyst n i (NO
3)
2.6H
2o and boracic and containing the ratio of the weight of the preceramic organosilicon polymer body of zirconium, be 1:(50～200);
Two, mixed powder step 1 being obtained is placed in the mould of open topped, heating pyrolyze in tube furnace, the temperature rise rate of first take is warmed up to 950 ℃～1050 ℃ by diamond heating as 4 ℃/min～6 ℃/min, take again temperature rise rate as 1 ℃/min～3 ℃/min by diamond heating to 1450 ℃～1550 ℃ of the complete ceramic temperature of preceramic organosilicon polymer body, soaking time is 0.5h～2h, in heating pyrolyze process, adopt rare gas element as shielding gas;
Three, the mixed powder after heating pyrolyze step 2 being obtained, cools to 20 ℃～25 ℃ naturally, obtains carbon nano-tube modification superhigh temperature ceramics hydridization powder.
Embodiment two: present embodiment is different from embodiment one: in step 1, the mol ratio of B:Zr is (2～3): 1, catalyst n i (NO
3)
2.6H
2o and boracic and containing the ratio of the weight of the preceramic organosilicon polymer body of zirconium, be 1:(100～150).Other step and parameter are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one: in step 1, the mol ratio of B:Zr is 2.5:1, catalyst n i (NO
3)
2.6H
2o and boracic and be 1:125 containing the ratio of the weight of the preceramic organosilicon polymer body of zirconium.Other step and parameter are identical with embodiment one.
Embodiment four: present embodiment is different from one of embodiment one to three: the temperature rise rate of first take in step 2 is warmed up to 1000 ℃ by diamond heating as 5 ℃/min, take again temperature rise rate as 2 ℃/min by diamond heating to 1480 ℃～1520 ℃ of the complete ceramic temperature of preceramic organosilicon polymer body, soaking time is 1h～2h.Other step and parameter are identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to three: the temperature rise rate of first take in step 2 is warmed up to 1000 ℃ by diamond heating as 5 ℃/min, take again temperature rise rate as 2 ℃/min by diamond heating to 1500 ℃ of the complete ceramic temperature of preceramic organosilicon polymer body, soaking time is 2h.Other step and parameter are identical with one of embodiment one to three.
Embodiment six: a kind of method of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder
A method for carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder, carry out according to the following steps:
1, by weight, be 0.5g catalyst n i (NO
3)
2.6H
2o is well dispersed in the preceramic organosilicon polymer body of boracic by the mode of grinding and containing the mixed powder that obtains three in the preceramic organosilicon polymer body of zirconium, wherein the preceramic organosilicon polymer body of boracic is 2,4,6-, tri--methylamino-boron azine, and molecular formula is (NHCH
3)
3b
3n
3h
3, containing the preceramic organosilicon polymer body of zirconium, be [(C
4h
8o) Zr (acac)
2]
n, n=110～120, the mol ratio of B:Zr is 1:1, the preceramic organosilicon polymer body of boracic and be 100g containing the preceramic organosilicon polymer body gross weight of zirconium;
2, mixed powder step 1 being obtained is placed in the mould of square open topped, heating pyrolyze in tube furnace, the temperature rise rate of first take is warmed up to 1000 ℃ by diamond heating as 5 ℃/min, take again temperature rise rate as 2 ℃/min by diamond heating to 1500 ℃ of the complete ceramic temperature of preceramic organosilicon polymer body, soaking time is 2h, in heating pyrolyze process, adopt argon gas as shielding gas;
3, the mixed powder after heating pyrolyze step 2 being obtained, cools to 25 ℃ naturally, obtains carbon nanotube-zirconium boride 99.5004323A8ure-zirconium white pyroceramic hydridization powder.
Fig. 1 is the SEM figure of the carbon nano-tube modification superhigh temperature ceramics hydridization powder of embodiment six preparations, and Fig. 2 is the XRD figure of the carbon nano-tube modification superhigh temperature ceramics hydridization powder of embodiment six preparations.
As can be seen from Figure 1: in figure, thin rope is carbon nanotube, and as can be seen from Figure 1 carbon nanotube, without reunion, is evenly dispersed in superhigh temperature ceramics hydridization powder.
As can be seen from Figure 2: the composition of hydridization powder is zirconium boride 99.5004323A8ure, zirconium white and carbon.
Therefore can draw such conclusion: in carbon nano-tube modification superhigh temperature ceramics hydridization powder prepared by employing the inventive method, carbon nanotube is evenly distributed, not have agglomeration to occur, carbon nanotube is very complete, and defect is few, and quality is high, has reached desired result; The product generating is carbon nanotube-zirconium boride 99.5004323A8ure-Zircite superhigh temperature pottery hydridization powder.
Embodiment seven:
1, by weight, be 1g catalyst n i (NO
3)
2.6H
2o is well dispersed in the preceramic organosilicon polymer body of boracic by the mode of grinding and containing the mixed powder that obtains three in the preceramic organosilicon polymer body of zirconium, wherein the preceramic organosilicon polymer body of boracic is 2,4,6-, tri--methylamino-boron azine, and molecular formula is (NHCH
3)
3b
3n
3h
3, containing the preceramic organosilicon polymer body of zirconium, be [(C
4h
8o) Zr (acac)
2]
n, n=110～120, the mol ratio of B:Zr is 4:1, the preceramic organosilicon polymer body of boracic and be 50g containing the preceramic organosilicon polymer body gross weight of zirconium;
2, mixed powder step 1 being obtained is placed in the mould of square open topped, heating pyrolyze in tube furnace, the temperature rise rate of first take is warmed up to 950 ℃ by diamond heating as 4 ℃/min, take again temperature rise rate as 1 ℃/min by diamond heating to 1450 ℃ of the complete ceramic temperature of preceramic organosilicon polymer body, soaking time is 1h, in heating pyrolyze process, adopt argon gas as shielding gas;
3, the mixed powder after heating pyrolyze step 2 being obtained, cools to 25 ℃ naturally, obtains carbon nanotube-zirconium boride 99.5004323A8ure-Zircite superhigh temperature pottery hydridization powder.
The composition of hydridization powder is zirconium boride 99.5004323A8ure, zirconium white and carbon.
The superhigh temperature ceramics hydridization powder containing graphene oxide and carbon nanotube that this experiment is obtained carries out electron-microscope scanning, and carbon nanotube is filament shape, therein dispersed, without reuniting.
Embodiment seven:
1, by weight, be 1g catalyst n i (NO
3)
2.6H
2o is well dispersed in the preceramic organosilicon polymer body of boracic by the mode of grinding and containing the mixed powder that obtains three in the preceramic organosilicon polymer body of zirconium, wherein the preceramic organosilicon polymer body of boracic is 2,4,6-, tri--methylamino-boron azine, and molecular formula is (NHCH
3)
3b
3n
3h
3, containing the preceramic organosilicon polymer body of zirconium, be [(C
4h
8o) Zr (acac)
2]
n, n=110～120, the mol ratio of B:Zr is 2:1, the preceramic organosilicon polymer body of boracic and be 100g containing the preceramic organosilicon polymer body gross weight of zirconium;
2, mixed powder step 1 being obtained is placed in the mould of square open topped, heating pyrolyze in tube furnace, the temperature rise rate of first take is warmed up to 1050 ℃ by diamond heating as 6 ℃/min, take again temperature rise rate as 3 ℃/min by diamond heating to 1550 ℃ of the complete ceramic temperature of preceramic organosilicon polymer body, soaking time is 0.5h, in heating pyrolyze process, adopt argon gas as shielding gas;
3, the mixed powder after heating pyrolyze step 2 being obtained, cools to 25 ℃ naturally, obtains carbon nanotube-zirconium boride 99.5004323A8ure-zirconium white pyroceramic hydridization powder.
The composition of hydridization powder is zirconium boride 99.5004323A8ure, zirconium white and carbon.
The superhigh temperature ceramics hydridization powder containing graphene oxide and carbon nanotube that this experiment is obtained carries out electron-microscope scanning, and carbon nanotube is filament shape, therein dispersed, without reuniting.
Claims (10)
1. a method for carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder, is characterized in that carrying out according to the following steps:
One, by catalyzer, boracic preceramic organosilicon polymer body, containing zirconium preceramic organosilicon polymer body, mix after grinding distribution;
Two, be then placed in the mould of open topped, heating pyrolyze under the protection of rare gas element, cools to 20 ℃～25 ℃ naturally, obtains carbon nano-tube modification superhigh temperature ceramics hydridization powder.
2. the method for a kind of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder according to claim 1, is characterized in that boracic preceramic organosilicon polymer body in step 1, containing zirconium preceramic organosilicon polymer body, by the mol ratio of B:Zr, is (1～4): 1 proportioning is mixed.
3. the method for a kind of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder according to claim 1, the weight that it is characterized in that catalyzer in step 1 and boracic preceramic organosilicon polymer body and containing the ratio of zirconium preceramic organosilicon polymer body gross weight, be 1:(50～200).
4. the method for a kind of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder described in 1 as requested, is characterized in that in step 1, catalyzer is Ni (NO
3)
2.6H
2o.
5. the method for a kind of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder described in 1 as requested, is characterized in that in step 1, boracic preceramic organosilicon polymer body is 2,4,6-, tri--methylamino-boron azine, and molecular formula is (NHCH
3)
3b
3n
3h
3.
6. the method for a kind of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder described in 1 as requested, is characterized in that in step 1 being [(C containing zirconium preceramic organosilicon polymer body
4h
8o) Zr (acac)
2]
n, n=110～120.
7. the method for a kind of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder described in 1 as requested, is characterized in that in step 2, rare gas element is argon gas, neon or helium.
8. the method for a kind of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder described in 1 as requested, while it is characterized in that in step 2 heating pyrolyze, the mould of open topped is placed in tube furnace.
9. the method for a kind of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder described in 1 as requested, it is characterized in that in step 2 first take in heating pyrolyze process that temperature rise rate is warmed up to 950 ℃～1050 ℃ by diamond heating as 4 ℃/min～6 ℃/min, take temperature rise rate as 1 ℃/min～3 ℃/min is by diamond heating to 1450 ℃～1550 ℃ of the complete ceramic temperature of preceramic organosilicon polymer body again, and soaking time is 0.5h～2h.
10. the method for a kind of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder described in 1 as requested, it is characterized in that in step 2 first take in heating pyrolyze process that temperature rise rate is warmed up to 1000 ℃ by diamond heating as 5 ℃/min, take again temperature rise rate as 2 ℃/min by diamond heating to 1500 ℃ of the complete ceramic temperature of preceramic organosilicon polymer body, soaking time is 2h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725031A (en) * | 2015-03-16 | 2015-06-24 | 上海交通大学 | Method for growing carbon nano fibers on ceramic hollow microsphere surface in situ |
| CN106518120A (en) * | 2016-10-27 | 2017-03-22 | 哈尔滨工业大学 | Preparing method and application of carbon fiber-carbon nanotube composite toughened ZrC ceramic composite material |
| CN115196987A (en) * | 2022-06-02 | 2022-10-18 | 航天材料及工艺研究所 | Carbon nano tube/fiber multi-scale reinforced ceramic matrix composite material and preparation method thereof |
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2014
- 2014-06-23 CN CN201410283089.7A patent/CN104016685B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725031A (en) * | 2015-03-16 | 2015-06-24 | 上海交通大学 | Method for growing carbon nano fibers on ceramic hollow microsphere surface in situ |
| CN106518120A (en) * | 2016-10-27 | 2017-03-22 | 哈尔滨工业大学 | Preparing method and application of carbon fiber-carbon nanotube composite toughened ZrC ceramic composite material |
| CN106518120B (en) * | 2016-10-27 | 2019-06-11 | 哈尔滨工业大学 | A kind of preparation method and application of carbon fiber-carbon nanotube composite toughening ZrC ceramic composite |
| CN115196987A (en) * | 2022-06-02 | 2022-10-18 | 航天材料及工艺研究所 | Carbon nano tube/fiber multi-scale reinforced ceramic matrix composite material and preparation method thereof |
| CN115196987B (en) * | 2022-06-02 | 2023-09-29 | 航天材料及工艺研究所 | Carbon nano tube/fiber multi-scale reinforced ceramic matrix composite material and preparation method thereof |
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