CN104016685B - 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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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
The present invention relates to a kind of method of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder, belong 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 be incorporated in pottery can significantly improve the mechanical property of material by bridging effect.But carbon nanotube has very large length-to-diameter ratio, easily reunites, during matrix material for the preparation of carbon nano-tube modification, be difficult to fully disperse in the base, especially in granular powder.
The method preparing carbon nanotube of current report mainly contains chemical Vapor deposition process, arc discharge method and laser ablation method etc.Chemical Vapor deposition process is higher to equipment requirements, and investment is large; It is harsh that laser ablation method prepares condition needed for 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, after adopting aforesaid method to obtain carbon nanotube, a technical barrier can be run into, it is exactly the problem how carbon nanotube fully disperses in the base, because carbon nanotube has very large length-to-diameter ratio, easily reunite, during matrix material for the preparation of carbon nano-tube modification, be difficult to fully disperse in the base, 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 be in order to solve existing prepare carbon nano-tube modification superhigh temperature ceramics time, there is the problem of reuniting in carbon nanotube, 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 obtains the mixed powder of three containing in the preceramic organosilicon polymer body of zirconium, wherein the preceramic organosilicon polymer body of boracic is 2,4,6-, tri--methylamino-boron azine, molecular formula is (NHCH
3)
3b
3n
3h
3, the preceramic organosilicon polymer body containing zirconium is [(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 is 1:(50 ~ 200 with boracic and the ratio containing the weight of the preceramic organosilicon polymer body of zirconium);
Two, the mixed powder that step one obtains is placed in the mould of open topped, heating pyrolyze in tube furnace, first with temperature rise rate be 4 DEG C/diamond heating is warmed up to 950 DEG C ~ 1050 DEG C by min ~ 6 DEG C/min, again with temperature rise rate be 1 DEG C/min ~ 3 DEG C/min by diamond heating to the complete ceramming temperature of preceramic organosilicon polymer body 1450 DEG C ~ 1550 DEG C, 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 obtained, Temperature fall, to 20 DEG C ~ 25 DEG C, namely obtains carbon nano-tube modification superhigh temperature ceramics hydridization powder.
Reaction mechanism of the present invention: the gas of releasing during polymer precursor cracking has CO, CO
2, CH
4, NH
4, NO
2, H
2o etc., the CO of wherein polymer precursor cracking releasing, CH
4, CO
2be the primary carbon source of carbon nano tube growth, other products are deviate from from matrix with the form of gas along with the rising of temperature, thus obtain carbon nano-tube modification superhigh temperature ceramics hydridization powder.
The forming process of carbon nanotube: carbonaceous gas CO, CH
4, CO
2resolve into containing carbon part with not containing carbon part at catalyst surface, containing the dissolving of catalyzed dose of carbon part, be not separated containing carbon part, owing to providing carbon source containing carbon part constantly catalyzed dose of dissolving, in the bottom of catalyzer, carbon nanotube constantly separates out growth.
The present invention includes following beneficial effect:
1, in the carbon nano-tube modification superhigh temperature ceramics hydridization powder adopting the inventive method to prepare, 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 little, and can manufacture carbon nano-tube modification superhigh temperature ceramics hydridization powder.
Accompanying drawing explanation
Fig. 1 is the SEM figure of carbon nano-tube modification superhigh temperature ceramics hydridization powder prepared by embodiment six;
Fig. 2 is the XRD figure of carbon nano-tube modification superhigh temperature ceramics hydridization powder prepared by embodiment six.
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 obtains the mixed powder of three containing in the preceramic organosilicon polymer body of zirconium, wherein the preceramic organosilicon polymer body of boracic is 2,4,6-, tri--methylamino-boron azine, molecular formula is (NHCH
3)
3b
3n
3h
3, the preceramic organosilicon polymer body containing zirconium is [(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 is 1:(50 ~ 200 with boracic and the ratio containing the weight of the preceramic organosilicon polymer body of zirconium);
Two, the mixed powder that step one obtains is placed in the mould of open topped, heating pyrolyze in tube furnace, first with temperature rise rate be 4 DEG C/diamond heating is warmed up to 950 DEG C ~ 1050 DEG C by min ~ 6 DEG C/min, again with temperature rise rate be 1 DEG C/min ~ 3 DEG C/min by diamond heating to the complete ceramming temperature of preceramic organosilicon polymer body 1450 DEG C ~ 1550 DEG C, 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 obtained, Temperature fall, to 20 DEG C ~ 25 DEG C, namely obtains carbon nano-tube modification superhigh temperature ceramics hydridization powder.
Embodiment two: present embodiment and embodiment one unlike: in step one, the mol ratio of B:Zr is (2 ~ 3): 1, catalyst n i (NO
3)
2.6H
2o is 1:(100 ~ 150 with boracic and the ratio containing the weight of the preceramic organosilicon polymer body of zirconium).Other step and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment one unlike: in step one, the mol ratio of B:Zr is 2.5:1, catalyst n i (NO
3)
2.6H
2o is 1:125 with boracic and the ratio containing the weight of the preceramic organosilicon polymer body of zirconium.Other step and parameter identical with embodiment one.
Embodiment four: one of present embodiment and embodiment one to three unlike: be first that diamond heating is warmed up to 1000 DEG C by 5 DEG C/min with temperature rise rate in step 2, again with temperature rise rate be 2 DEG C/min by diamond heating to the complete ceramming temperature of preceramic organosilicon polymer body 1480 DEG C ~ 1520 DEG C, soaking time is 1h ~ 2h.Other step and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to three unlike: be first that diamond heating is warmed up to 1000 DEG C by 5 DEG C/min with temperature rise rate in step 2, again with temperature rise rate be 2 DEG C/min by diamond heating to the complete ceramming temperature of preceramic organosilicon polymer body 1500 DEG C, soaking time is 2h.Other step and parameter 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 obtains the mixed powder of three containing in the preceramic organosilicon polymer body of zirconium, wherein the preceramic organosilicon polymer body of boracic is 2,4,6-, tri--methylamino-boron azine, molecular formula is (NHCH
3)
3b
3n
3h
3, the preceramic organosilicon polymer body containing zirconium is [(C
4h
8o) Zr (acac)
2]
n, n=110 ~ 120, the mol ratio of B:Zr is 1:1, and the preceramic organosilicon polymer body of boracic and the preceramic organosilicon polymer body gross weight containing zirconium are 100g;
2, the mixed powder that step 1 obtains is placed in the mould of square open topped, heating pyrolyze in tube furnace, first is that diamond heating is warmed up to 1000 DEG C by 5 DEG C/min with temperature rise rate, again with temperature rise rate be 2 DEG C/min by diamond heating to the complete ceramming temperature of preceramic organosilicon polymer body 1500 DEG C, soaking time is 2h, in heating pyrolyze process, adopt argon gas as shielding gas;
3, the mixed powder after heating pyrolyze step 2 obtained, Temperature fall, to 25 DEG C, namely obtains carbon nanotube-zirconium boride 99.5004323A8ure-zirconium white pyroceramic hydridization powder.
Fig. 1 is the SEM figure of carbon nano-tube modification superhigh temperature ceramics hydridization powder prepared by embodiment six, and Fig. 2 is the XRD figure of carbon nano-tube modification superhigh temperature ceramics hydridization powder prepared by embodiment six.
As can be seen from Figure 1: in figure, filamentous substance is carbon nanotube, as can be seen from Figure 1 carbon nanotube soilless sticking, be 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 such conclusion can be drawn: in the carbon nano-tube modification superhigh temperature ceramics hydridization powder adopting the inventive method to prepare, carbon nanotube is evenly distributed, and do not have agglomeration to occur, carbon nanotube is very complete, and defect is few, and quality is high, reaches desired result; The product generated is carbon nanotube-zirconium boride 99.5004323A8ure-Zircite superhigh temperature ceramic hybrid 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 obtains the mixed powder of three containing in the preceramic organosilicon polymer body of zirconium, wherein the preceramic organosilicon polymer body of boracic is 2,4,6-, tri--methylamino-boron azine, molecular formula is (NHCH
3)
3b
3n
3h
3, the preceramic organosilicon polymer body containing zirconium is [(C
4h
8o) Zr (acac)
2]
n, n=110 ~ 120, the mol ratio of B:Zr is 4:1, and the preceramic organosilicon polymer body of boracic and the preceramic organosilicon polymer body gross weight containing zirconium are 50g;
2, the mixed powder that step 1 obtains is placed in the mould of square open topped, heating pyrolyze in tube furnace, first is that diamond heating is warmed up to 950 DEG C by 4 DEG C/min with temperature rise rate, again with temperature rise rate be 1 DEG C/min by diamond heating to the complete ceramming temperature of preceramic organosilicon polymer body 1450 DEG C, soaking time is 1h, in heating pyrolyze process, adopt argon gas as shielding gas;
3, the mixed powder after heating pyrolyze step 2 obtained, Temperature fall, to 25 DEG C, namely obtains carbon nanotube-zirconium boride 99.5004323A8ure-Zircite superhigh temperature ceramic hybrid powder.
The composition of hydridization powder is zirconium boride 99.5004323A8ure, zirconium white and carbon.
Carry out electron-microscope scanning to the superhigh temperature ceramics hydridization powder containing graphene oxide and carbon nanotube that this experiment obtains, carbon nanotube is filament shape, wherein dispersed, soilless sticking.
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 obtains the mixed powder of three containing in the preceramic organosilicon polymer body of zirconium, wherein the preceramic organosilicon polymer body of boracic is 2,4,6-, tri--methylamino-boron azine, molecular formula is (NHCH
3)
3b
3n
3h
3, the preceramic organosilicon polymer body containing zirconium is [(C
4h
8o) Zr (acac)
2]
n, n=110 ~ 120, the mol ratio of B:Zr is 2:1, and the preceramic organosilicon polymer body of boracic and the preceramic organosilicon polymer body gross weight containing zirconium are 100g;
2, the mixed powder that step 1 obtains is placed in the mould of square open topped, heating pyrolyze in tube furnace, first is that diamond heating is warmed up to 1050 DEG C by 6 DEG C/min with temperature rise rate, again with temperature rise rate be 3 DEG C/min by diamond heating to the complete ceramming temperature of preceramic organosilicon polymer body 1550 DEG C, soaking time is 0.5h, in heating pyrolyze process, adopt argon gas as shielding gas;
3, the mixed powder after heating pyrolyze step 2 obtained, Temperature fall, to 25 DEG C, namely 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.
Carry out electron-microscope scanning to the superhigh temperature ceramics hydridization powder containing graphene oxide and carbon nanotube that this experiment obtains, carbon nanotube is filament shape, wherein dispersed, soilless sticking.
Claims (8)
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 mixing after grinding distribution;
Two, be then placed in the mould of open topped, heating pyrolyze under the protection of rare gas element, Temperature fall, to 20 DEG C ~ 25 DEG C, namely obtains carbon nano-tube modification superhigh temperature ceramics hydridization powder;
Wherein, in step one, boracic preceramic organosilicon polymer body is 2,4,6-, tri--methylamino-boron azine, and molecular formula is (NHCH
3)
3b
3n
3h
3, containing zirconium preceramic organosilicon polymer body in step one is [(C
4h
8o) Zr (acac)
2]
n, n=110 ~ 120.
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 one, is (1 ~ 4) containing zirconium preceramic organosilicon polymer body by the mol ratio of B:Zr: the proportioning of 1 mixes.
3. 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 the weight of catalyzer in step one is 1:(50 ~ 200 with boracic preceramic organosilicon polymer body and the ratio containing zirconium preceramic organosilicon polymer body gross weight).
4. the method for a kind of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder as requested described in 1, is characterized in that in step one, 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 as requested described in 1, is characterized in that in step 2, rare gas element is argon gas, neon or helium.
6. the method for a kind of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder as requested described in 1, when it is characterized in that heating pyrolyze in step 2, the mould of open topped is placed in tube furnace.
7. the method for a kind of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder as requested described in 1, to it is characterized in that in step 2 in heating pyrolyze process first with temperature rise rate be 4 DEG C/diamond heating is warmed up to 950 DEG C ~ 1050 DEG C by min ~ 6 DEG C/min, again with temperature rise rate be 1 DEG C/min ~ 3 DEG C/min by diamond heating to the complete ceramming temperature of preceramic organosilicon polymer body 1450 DEG C ~ 1550 DEG C, soaking time is 0.5h ~ 2h.
8. the method for a kind of carbon nano-tube in situ modification superhigh temperature ceramics hydridization powder as requested described in 1, it is characterized in that first in heating pyrolyze process in step 2 is that diamond heating is warmed up to 1000 DEG C by 5 DEG C/min with temperature rise rate, again with temperature rise rate be 2 DEG C/min by diamond heating to the complete ceramming temperature of preceramic organosilicon polymer body 1500 DEG C, soaking time is 2h.
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| 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 |
| 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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