CN106518120B - A kind of preparation method and application of carbon fiber-carbon nanotube composite toughening ZrC ceramic composite - Google Patents
A kind of preparation method and application of carbon fiber-carbon nanotube composite toughening ZrC ceramic composite Download PDFInfo
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- CN106518120B CN106518120B CN201610975323.1A CN201610975323A CN106518120B CN 106518120 B CN106518120 B CN 106518120B CN 201610975323 A CN201610975323 A CN 201610975323A CN 106518120 B CN106518120 B CN 106518120B
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Abstract
A kind of preparation method and application of carbon fiber-carbon nanotube composite toughening ZrC ceramic composite, is related to a kind of preparation method and application of ZrC ceramic composite.It is the problem that ZrC based ultra-high temperature ceramic material intensity to be solved is low, fracture toughness is poor.Method: the one, pretreatment of carbon fiber 3 D weaving body；Two, the load of carbon fiber surface metallic catalyst；Three, carbon fiber-carbon nanotube composite reinforcement preparation；Four, the preparation of CF-CNTs/ZrC ceramic matric composite.The porosity of ceramic matric composite of the present invention is 74%~81%, and density is 0.61~1.17g/cm3, there is the characteristic of porous light, compressive strength can reach 23.64MPa, and fracture toughness can reach 4.63MPam1/2.The present invention is used for field of compound material.
Description
Technical field
The present invention relates to a kind of preparation method and applications of ZrC ceramic composite.
Background technique
There is an urgent need to the superhigh temperature composite materials of high reliability for development hypersonic aircraft and scramjet engine.It wants
It asks composite material to be not only able to bear extra high temperature, also there is excellent mechanical property.ZrC based ultra-high temperature ceramics antioxygen
Change, anti-ablation ability are prominent, but brittleness is big, and fracture toughness is low.Currently, ceramics are used as matrix using carbon fiber as reinforcement
Ceramic matric composite (Ceramic Matrix Composites, CMC) with height than strong, Gao Bimo, high temperature resistant and anti-ablation
The characteristics of haveing excellent performance causes the attention of each industrially developed country, and wherein continuous carbon fibre toughening ceramic based composites most draw
People gazes at.Continuous carbon fibre toughening ceramic based composites can not only keep ceramic matrix low bulk, high temperature resistant and resistance to ablation
The advantages of, while using the advantage of carbon fiber high-strength high-ductility, the big disadvantage of ceramic material brittleness is compensated for well, is finally made
Composite material has excellent mechanics, thermal property, guarantees its reliability in harsh high-temperature oxidation environment.
The preparation method of existing carbon fiber-reinforced ZrC ceramic composite, such as the infiltration of chemical vapour deposition technique, melt
Method etc. is with preparation process is complicated, at high cost, the production cycle is long, it is difficult to prepare a systems such as the tiny ZrC of even tissue, crystal grain
Lieque point.
Summary of the invention
The problem that the present invention is to solve ZrC based ultra-high temperature ceramic material intensity is low, fracture toughness is poor, while in order to overcome
Complicated, at high cost, the production cycle the is long insufficient problem of existing carbon fiber-reinforced ZrC ceramic composite preparing technique process,
A kind of preparation method and application of carbon fiber-carbon nanotube composite toughening ZrC ceramic composite is provided.
The preparation method of carbon fiber-carbon nanotube (CF-CNTs) composite toughening ZrC ceramic composite of the present invention, is pressed
Following steps carry out:
One, needle-penetrating three-dimensional carbon fibrage body the pretreatment of carbon fiber 3 D weaving body: is cut into 15 × 15 × 35mm
The cubic block of specification；It uses temperature for 70~90 DEG C of 24~48h of acetone reflux, the carbon fiber knitted body after acetone treatment is set
Be dry 12 in 70 DEG C of thermostatic drying chamber in temperature~for 24 hours；Will the dry carbon fiber completed be placed in mass fraction be 65%~
In 75% concentrated nitric acid, 1~7h is impregnated under room temperature, is washed carbon fiber to neutrality using deionized water, being placed in temperature is
Dry 24~36h, obtains pretreated carbon fiber knitted body in 120 DEG C of thermostatic drying chamber；
Two, the load of carbon fiber surface metallic catalyst: with magnesium-yttrium-transition metal salt Ni (NO3)2、Co(NO3)2Or Fe (NO3)3
For solute, acetone is solvent, and compound concentration is the solution of 0.01~0.09mol/L, and the pretreated carbon fiber of step 1 is woven
Body is put into solution, impregnates 8~12h under room temperature, take out be placed on temperature be dry 12 in 70 DEG C of thermostatic drying chamber~
For 24 hours, the carbon fiber for being loaded with metallic catalyst is obtained；
Three, the preparation of carbon fiber-carbon nanotube (CF-CNTs) composite reinforcement: using chemical vapor deposition (CVD) in carbon
Fiber surface grows CNTs, detailed process are as follows: the carbon fiber for being loaded with metallic catalyst is placed in tube furnace, in nitrogen atmosphere
Under be warming up to 500 DEG C, keep the temperature 1h, H be passed through with the flow velocity of 40sccm2, continue to keep the temperature 0.5h, be continuously heating to 700~900 later
DEG C, it is passed through ethyl alcohol, ethyl alcohol and N2Injection flow be respectively 10mL/h and 150sccm, react 40~160min, obtain CF-
CNTs composite reinforcement；
Four, the preparation of CF-CNTs/ZrC ceramic matric composite: ZrC ceramic precursor powder is dissolved in dimethylbenzene and is matched
The ZrC ceramic setter liquid solution that mass fraction is 66.7% is produced, is added in the CF-CNTs composite reinforcement that step 3 obtains,
It is fully immersed in CF-CNTs composite reinforcement in ZrC ceramic setter liquid solution；It is then placed into vacuum infiltration reaction kettle,
Pressure is evacuated to close to 0Pa, impregnates 20~60min；Sample is placed in the thermostatic drying chamber that temperature is 120 DEG C after the completion
Curing process, curing time 12h；Sample is placed in pyrolysis furnace after the completion of solidification, is passed through at room temperature into pyrolysis furnace high-purity
Ar keeps 30min, temperature is increased to 1000 DEG C from room temperature with the heating rate of 15 DEG C/min under high-purity Ar atmosphere, heat preservation
30min then raises the temperature to 1400~1600 DEG C with the heating rate of 10 DEG C/min, keeps the temperature 1h, protects later in Ar atmosphere
It is naturally cooling to room temperature under shield and completes cracking, obtains CF-CNTs/ZrC ceramic composite.
The powder of ZrC ceramic precursor described in step 4 the preparation method comprises the following steps: under room temperature, mechanical agitation, with
ZrCl4For zirconium source, Zr (OC is generated with ethanol synthesis2H5)4.Then 1,4-butanediol and acetylacetone,2,4-pentanedione is added, reacts and depressurizes steaming
Solvent therein is removed in distillation, finally obtains orange-red ZrC ceramic precursor powder.
Above-mentioned carbon fiber-carbon nanotube (CF-CNTs) composite toughening ZrC ceramic composite as a kind of Strengthening and Toughening,
High temperature resistant, high reliability thermally protective materials can be used for preparing hypersonic aircraft nose cone and engine thermal end pieces.
Since carbon fiber has the good characteristics such as low-density, high intensity, high-modulus, high temperature resistant, resist chemical, carbon
Fibre-reinforced ultrahigh temperature ceramic composite also has high-intensitive, high tenacity mechanical property accordingly, is provided simultaneously with super
The fire-resistant oxidation resistant performance of refractory ceramics matrix.The quality of interface performance directly affects compound between carbon fiber and ceramic matrix
The mechanical property of material.Only when between carbon fiber and ZrC ceramic matrix have interface binding power appropriate, basis material ability
Effectively transmitting extraneous load, plays fiber reinforced effect.The present invention prepares CF- by growing CNTs in carbon fiber surface
The multi-level composite reinforcement of CNTs, effectively increases the specific surface area of CF, increases interface shearing between CF and ZrC ceramic matrix
Intensity improves interface performance, has a very important significance to the Strengthening and Toughening of ZrC based composite ceramic material.
Beneficial effects of the present invention:
1, carbon fiber-carbon nanotube (CF-CNTs) composite toughening ZrC ceramic composite prepared by the present invention uses
Chemical vapour deposition technique grows CNTs in the carbon fiber surface for being loaded with catalyst, realizes effectively connecting between CF and CNTs
Connect, significantly increase the interface binding power between CF and ZrC ceramic matrix, guarantee ZrC ceramic matrix and CF-CNTs reinforcement it
Between load effective transmitting, given full play to the toughening effect of CF.
2, carbon fiber-carbon nanotube (CF-CNTs) composite toughening ZrC ceramic composite produced by the present invention, hole
Rate is 74%~81%, and density is 0.61~1.17g/cm3, the characteristic with porous light, composite material is branch with CF-CNTs
Support bone frame, the ZrC ceramics obtained using cracking are partially filled with the hole of CF-CNTs skeleton as filler, simultaneously as the surface CF
The porosity of composite material can be substantially improved in the presence of CNTs structure, reduce the density of composite material.
3, the present invention is using the ZrC ceramics of high temperature resistance excellent (fusing point is up to 3540 DEG C) as basis material, with CF-CNTs
" micro--to receive " multi-level composite reinforcement is activeness and quietness phase, and the CF-CNTs/ZrC composite material of preparation has more excellent power
Learn performance.CF-CNTs/ZrC composite material compressive strength prepared by the present invention can reach 23.64MPa, and fracture toughness can reach
4.63MPa·m1/2。
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) map of CF-CNTs/ZrC composite material prepared by Examples 1 to 4；
Fig. 2 is the surface Scanning Electron microscope photo of CF-CNTs/ZrC composite material prepared by embodiment 4；
Fig. 3 is the section scanning electron microscope photo of CF-CNTs/ZrC composite material prepared by embodiment 4；
Fig. 4 is the compressive strength test result of CF-CNTs/ZrC composite material prepared by embodiment 4.
Specific embodiment
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment
Any combination.
Specific embodiment 1: present embodiment carbon fiber-carbon nanotube composite toughening ZrC ceramic composite system
Preparation Method sequentially includes the following steps:
One, needle-penetrating three-dimensional carbon fibrage body the pretreatment of carbon fiber 3 D weaving body: is cut into cubic block；Using temperature
24~48h of acetone reflux that degree is 70~90 DEG C is dry by the carbon fiber knitted body after acetone treatment；By the dry carbon fiber completed
Dimension is placed in the concentrated nitric acid that mass fraction is 65%~75%, impregnates 1~7h under room temperature, using deionized water by carbon fiber
Washing to neutrality, drying obtains pretreated carbon fiber knitted body；
Two, the load of carbon fiber surface metallic catalyst: using magnesium-yttrium-transition metal salt as solute, acetone is solvent, is prepared dense
Degree is the solution of 0.01~0.09mol/L, and the pretreated carbon fiber knitted body of step 1 is put into solution, is soaked under room temperature
8~12h is steeped, it is dry after taking-up, obtain the carbon fiber for being loaded with metallic catalyst；
Three, it carbon fiber-carbon nanotube composite reinforcement preparation: is grown using chemical vapor deposition in carbon fiber surface
CNTs obtains CF-CNTs composite reinforcement；
Four, the preparation of CF-CNTs/ZrC ceramic matric composite: ZrC ceramic precursor powder is dissolved in dimethylbenzene and is matched
ZrC ceramic setter liquid solution is produced, is added in the CF-CNTs composite reinforcement that step 3 obtains, makes CF-CNTs composite reinforcement
It is fully immersed in ZrC ceramic setter liquid solution, is then placed into vacuum infiltration reaction kettle, being evacuated to pressure is 0Pa, leaching
20~60min of stain；It is curing process in 120 DEG C of thermostatic drying chamber that sample, which is placed in temperature, after the completion, curing time 12h,
Sample is placed in pyrolysis furnace after the completion of solidification and is cracked, CF-CNTs/ZrC ceramic composite is obtained.
Needle-penetrating three-dimensional carbon fibrage body described in step 1 is to be commercially available.The ZrC ceramic precursor powder can be with
It is commercially available.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: it is dried for the first time in step 1
Specially be placed in temperature be dry 12 in 70 DEG C of thermostatic drying chamber~for 24 hours.It is other same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that: second in step 1
Dry is specially dry 24~36h in the thermostatic drying chamber for being placed in temperature and being 120 DEG C.Other and specific embodiment one or two-phase
Together.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: in step 1
3~5h is impregnated under room temperature.It is other identical as one of specific embodiment one to three.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: institute in step 2
Stating magnesium-yttrium-transition metal salt is Ni (NO3)2、Co(NO3)2Or Fe (NO3)3.It is other identical as one of specific embodiment one to four.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five: matching in step 2
Concentration processed is the solution of 0.03~0.07mol/L.It is other identical as one of specific embodiment one to five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to five: matching in step 2
Concentration processed is the solution of 0.05mol/L.It is other identical as one of specific embodiment one to five.
Specific embodiment 8: unlike one of present embodiment and specific embodiment one to seven: institute in step 2
State it is dry for be placed in the thermostatic drying chamber that temperature is 70 DEG C dry 12~for 24 hours.One of other and specific embodiment one to seven
It is identical.
Specific embodiment 9: unlike one of present embodiment and specific embodiment one to eight: being adopted in step 3
The detailed process of CNTs is grown in carbon fiber surface with chemical vapor deposition are as follows: be placed in the carbon fiber for being loaded with metallic catalyst
In tube furnace, it is warming up to 500 DEG C in a nitrogen atmosphere, keeps the temperature 1h, H is passed through with the flow velocity of 40sccm2, continue to keep the temperature 0.5h, it
After be continuously heating to 700~900 DEG C, be passed through ethyl alcohol, ethyl alcohol and N2Injection flow be respectively 10mL/h and 150sccm, reaction
40~160min obtains CF-CNTs composite reinforcement.It is other identical as one of specific embodiment one to eight.
Specific embodiment 10: unlike one of present embodiment and specific embodiment one to nine: institute in step 4
The mass fraction for stating ZrC ceramic setter liquid solution is 60%~70%.It is other identical as one of specific embodiment one to nine.
Specific embodiment 11: unlike one of present embodiment and specific embodiment one to ten: in step 4
Dip time is 40min.It is other identical as one of specific embodiment one to ten.
Specific embodiment 12: present embodiment is unlike specific embodiment one to one of 11: step 4
Middle cracking specifically comprises the processes of: be passed through at room temperature into pyrolysis furnace high-purity Ar keep 30min, under high-purity Ar atmosphere with 15 DEG C/
Temperature is increased to 1000 DEG C from room temperature by the heating rate of min, keeps the temperature 30min, then will be warm with the heating rate of 10 DEG C/min
Degree is increased to 1300~1600 DEG C, keeps the temperature 1h, is naturally cooling to room temperature under Ar atmosphere protection later and completes cracking.Other and tool
Body embodiment one to one of 11 is identical.
Elaborate below to the embodiment of the present invention, following embodiment under the premise of the technical scheme of the present invention into
Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities
Apply example.
Embodiment 1: the present embodiment carbon fiber-carbon nanotube (CF-CNTs) composite toughening ZrC ceramic composite system
Preparation Method sequentially includes the following steps:
One, needle-penetrating three-dimensional carbon fibrage body the pretreatment of carbon fiber 3 D weaving body: is cut into 15 × 15 × 35mm
The cubic block of specification；Use temperature for 70 DEG C of acetone reflux 48h, the carbon fiber knitted body after acetone treatment, which is placed in temperature, is
Dry 12h in 70 DEG C of thermostatic drying chamber；The dry carbon fiber completed is placed in the concentrated nitric acid that concentration is 65%, room temperature condition
Lower immersion 1h is washed carbon fiber to neutrality using deionized water, is placed in the thermostatic drying chamber that temperature is 120 DEG C and is dried for 24 hours,
Obtain the carbon fiber that pretreatment is completed；
Two, the load of carbon fiber surface metallic catalyst: with magnesium-yttrium-transition metal salt Ni (NO3)2For solute, acetone is solvent,
Compound concentration is the solution of 0.01mol/L, the carbon fiber knitted body that step 1 pretreatment is completed is put into solution, room temperature condition
Lower immersion 12h takes out and is placed on dry 12h in the thermostatic drying chamber that temperature is 70 DEG C；
Three, the preparation of carbon fiber-carbon nanotube (CF-CNTs) composite reinforcement: chemical vapor deposition (CVD) technology is used
CNTs is grown in carbon fiber surface, detailed process is the carbon fiber for being loaded with metallic catalyst to be placed in tube furnace, in nitrogen
It is warming up to 500 DEG C under atmosphere, keeps the temperature 1h, H is passed through with the flow velocity of 40sccm2, continue to keep the temperature 0.5h, be continuously heating to 900 later
DEG C, ethyl alcohol, ethyl alcohol and N are passed through after temperature reaches2Injection flow be respectively 10mL/h and 150sccm, the reaction time is
40min obtains CF-CNTs；
Four, the preparation of CF-CNTs/ZrC ceramic matric composite: ZrC ceramic precursor is dissolved in dimethylbenzene and is made
The beaker of the CF-CNTs composite reinforcement obtained equipped with step 3 is added in the ceramic setter liquid solution that mass fraction is 66.7%
In, it is fully immersed in CF-CNTs block in precursor solution；Beaker is placed in vacuum infiltration reaction kettle, is evacuated to
Pressure impregnates 20min close to 0Pa；Sample is placed in curing process 12h in the thermostatic drying chamber that temperature is 120 DEG C after the completion；
Sample is placed in pyrolysis furnace after the completion of solidification, high-purity Ar is passed through into pyrolysis furnace at room temperature and keeps 30min, in high-purity Ar atmosphere
Under with the heating rate of 15 DEG C/min temperature is increased to 1000 DEG C from room temperature, 30min is kept the temperature, then with the heating of 10 DEG C/min
Rate raises the temperature to 1600 DEG C, keeps the temperature 1h, is naturally cooling to room temperature under Ar atmosphere protection later and completes cracking, obtains
CF-CNTs/ZrC ceramic composite.
Embodiment 2: the present embodiment carbon fiber-carbon nanotube (CF-CNTs) composite toughening ZrC ceramic composite system
Preparation Method sequentially includes the following steps:
One, needle-penetrating three-dimensional carbon fibrage body the pretreatment of carbon fiber 3 D weaving body: is cut into 15 × 15 × 35mm
The cubic block of specification；Use temperature for 80 DEG C of acetone reflux 48h, the carbon fiber knitted body after acetone treatment, which is placed in temperature, is
It is dried for 24 hours in 70 DEG C of thermostatic drying chamber；The dry carbon fiber completed is placed in the concentrated nitric acid that concentration is 70%, room temperature condition
Lower immersion 3h is washed carbon fiber to neutrality using deionized water, is placed in the thermostatic drying chamber that temperature is 120 DEG C and is dried for 24 hours,
Obtain the carbon fiber that pretreatment is completed；
Two, the load of carbon fiber surface metallic catalyst: with magnesium-yttrium-transition metal salt Co (NO3)2For solute, acetone is solvent,
Compound concentration is the solution of 0.05mol/L, the carbon fiber knitted body that step 1 pretreatment is completed is put into solution, room temperature condition
Lower immersion 10h takes out to be placed in the thermostatic drying chamber that temperature is 70 DEG C and dry for 24 hours；
Three, the preparation of carbon fiber-carbon nanotube (CF-CNTs) composite reinforcement: chemical vapor deposition (CVD) technology is used
CNTs is grown in carbon fiber surface, detailed process is the carbon fiber for being loaded with metallic catalyst to be placed in tube furnace, in nitrogen
It is warming up to 500 DEG C under atmosphere, keeps the temperature 1h, H is passed through with the flow velocity of 40sccm2, continue to keep the temperature 0.5h, be continuously heating to 800 later
DEG C, ethyl alcohol, ethyl alcohol and N are passed through after temperature reaches2Injection flow be respectively 10mL/h and 150sccm, the reaction time is
80min obtains CF-CNTs；
Four, the preparation of CF-CNTs/ZrC ceramic matric composite: ZrC ceramic precursor is dissolved in dimethylbenzene and is made
The beaker of the CF-CNTs composite reinforcement obtained equipped with step 3 is added in the ceramic setter liquid solution that mass fraction is 66.7%
In, it is fully immersed in CF-CNTs block in precursor solution；Beaker is placed in vacuum infiltration reaction kettle, is evacuated to
Pressure impregnates 40min close to 0Pa；Sample is placed in curing process 12h in the thermostatic drying chamber that temperature is 120 DEG C after the completion；
Sample is placed in pyrolysis furnace after the completion of solidification, high-purity Ar is passed through into pyrolysis furnace at room temperature and keeps 30min, in high-purity Ar atmosphere
Under with the heating rate of 15 DEG C/min temperature is increased to 1000 DEG C from room temperature, 30min is kept the temperature, then with the heating of 10 DEG C/min
Rate raises the temperature to 1500 DEG C, keeps the temperature 1h, is naturally cooling to room temperature under Ar atmosphere protection later and completes cracking, obtains
CF-CNTs/ZrC ceramic composite.
Embodiment 3: the present embodiment carbon fiber-carbon nanotube (CF-CNTs) composite toughening ZrC ceramic composite system
Preparation Method sequentially includes the following steps:
One, needle-penetrating three-dimensional carbon fibrage body the pretreatment of carbon fiber 3 D weaving body: is cut into 15 × 15 × 35mm
The cubic block of specification；For 24 hours using acetone reflux at a temperature of 90 °C, the carbon fiber knitted body after acetone treatment is placed in temperature is
Dry 12h in 70 DEG C of thermostatic drying chamber；The dry carbon fiber completed is placed in the concentrated nitric acid that concentration is 75%, room temperature condition
Lower immersion 5h is washed carbon fiber to neutrality using deionized water, is placed in dry 36h in the thermostatic drying chamber that temperature is 120 DEG C,
Obtain the carbon fiber that pretreatment is completed；
Two, the load of carbon fiber surface metallic catalyst: with magnesium-yttrium-transition metal salt Fe (NO3)3For solute, acetone is solvent,
Compound concentration is the solution of 0.09mol/L, the carbon fiber knitted body that step 1 pretreatment is completed is put into solution, room temperature condition
Lower immersion 8h takes out and is placed on dry 12h in the thermostatic drying chamber that temperature is 70 DEG C；
Three, the preparation of carbon fiber-carbon nanotube (CF-CNTs) composite reinforcement: chemical vapor deposition (CVD) technology is used
CNTs is grown in carbon fiber surface, detailed process is the carbon fiber for being loaded with metallic catalyst to be placed in tube furnace, in nitrogen
It is warming up to 500 DEG C under atmosphere, keeps the temperature 1h, H is passed through with the flow velocity of 40sccm2, continue to keep the temperature 0.5h, be continuously heating to 700 later
DEG C, ethyl alcohol, ethyl alcohol and N are passed through after temperature reaches2Injection flow be respectively 10mL/h and 150sccm, the reaction time is
120min obtains CF-CNTs；
Four, the preparation of CF-CNTs/ZrC ceramic matric composite: ZrC ceramic precursor is dissolved in dimethylbenzene and is made
The beaker of the CF-CNTs composite reinforcement obtained equipped with step 3 is added in the ceramic setter liquid solution that mass fraction is 66.7%
In, it is fully immersed in CF-CNTs block in precursor solution；Beaker is placed in vacuum infiltration reaction kettle, is evacuated to
Pressure impregnates 60min close to 0Pa；Sample is placed in curing process 12h in the thermostatic drying chamber that temperature is 120 DEG C after the completion；
Sample is placed in pyrolysis furnace after the completion of solidification, high-purity Ar is passed through into pyrolysis furnace at room temperature and keeps 30min, in high-purity Ar atmosphere
Under with the heating rate of 15 DEG C/min temperature is increased to 1000 DEG C from room temperature, 30min is kept the temperature, then with the heating of 10 DEG C/min
Rate raises the temperature to 1400 DEG C, keeps the temperature 1h, is naturally cooling to room temperature under Ar atmosphere protection later and completes cracking, obtains
CF-CNTs/ZrC ceramic composite.
Embodiment 4: the present embodiment carbon fiber-carbon nanotube (CF-CNTs) composite toughening ZrC ceramic composite system
Preparation Method sequentially includes the following steps:
One, needle-penetrating three-dimensional carbon fibrage body the pretreatment of carbon fiber 3 D weaving body: is cut into 15 × 15 × 35mm
The cubic block of specification；Use temperature for 70 DEG C of acetone reflux 48h, the carbon fiber knitted body after acetone treatment, which is placed in temperature, is
It is dried for 24 hours in 70 DEG C of thermostatic drying chamber；The dry carbon fiber completed is placed in the concentrated nitric acid that concentration is 65%, room temperature condition
Lower immersion 7h is washed carbon fiber to neutrality using deionized water, is placed in dry 36h in the thermostatic drying chamber that temperature is 120 DEG C,
Obtain the carbon fiber that pretreatment is completed；
Two, the load of carbon fiber surface metallic catalyst: with magnesium-yttrium-transition metal salt Ni (NO3)2For solute, acetone is solvent,
Compound concentration is the solution of 0.05mol/L, the carbon fiber knitted body that step 1 pretreatment is completed is put into solution, room temperature condition
Lower immersion 10h takes out to be placed in the thermostatic drying chamber that temperature is 70 DEG C and dry for 24 hours；
Three, the preparation of carbon fiber-carbon nanotube (CF-CNTs) composite reinforcement: chemical vapor deposition (CVD) technology is used
CNTs is grown in carbon fiber surface, detailed process is the carbon fiber for being loaded with metallic catalyst to be placed in tube furnace, in nitrogen
It is warming up to 500 DEG C under atmosphere, keeps the temperature 1h, H is passed through with the flow velocity of 40sccm2, continue to keep the temperature 0.5h, be continuously heating to 800 later
DEG C, ethyl alcohol, ethyl alcohol and N are passed through after temperature reaches2Injection flow be respectively 10mL/h and 150sccm, the reaction time is
160min obtains CF-CNTs；
Four, the preparation of CF-CNTs/ZrC ceramic matric composite: ZrC ceramic precursor is dissolved in dimethylbenzene and is made
The beaker of the CF-CNTs composite reinforcement obtained equipped with step 3 is added in the ceramic setter liquid solution that mass fraction is 66.7%
In, it is fully immersed in CF-CNTs block in precursor solution；Beaker is placed in vacuum infiltration reaction kettle, is evacuated to
Pressure impregnates 40min close to 0Pa；Sample is placed in curing process 12h in the thermostatic drying chamber that temperature is 120 DEG C after the completion；
Sample is placed in pyrolysis furnace after the completion of solidification, high-purity Ar is passed through into pyrolysis furnace at room temperature and keeps 30min, in high-purity Ar atmosphere
Under with the heating rate of 15 DEG C/min temperature is increased to 1000 DEG C from room temperature, 30min is kept the temperature, then with the heating of 10 DEG C/min
Rate raises the temperature to 1600 DEG C, keeps the temperature 1h, is naturally cooling to room temperature under Ar atmosphere protection later and completes cracking, obtains
CF-CNTs/ZrC ceramic composite.
Fig. 1 is X-ray diffraction (XRD) map of the CF-CNTs/ZrC composite material of Examples 1 to 4 preparation.★ table in figure
Show ZrC, ▲ indicate m-ZrO2, ● indicate t-ZrO2。
As seen from Figure 1, when cracking temperature is 1300 DEG C, pyrolysis product contains a small amount of m-ZrO2With a large amount of t-
ZrO2, when cracking temperature is 1400 DEG C, pyrolysis product is completely converted into t-ZrO2, when cracking temperature is increased to 1500 DEG C, split
Start ZrC phase occur in solution product, but contains a small amount of t-ZrO simultaneously2, when cracking temperature is increased to 1600 DEG C, cracking is produced
The good ZrC of all crystallinity of object.
Fig. 2 is the surface Scanning Electron microscope photo of CF-CNTs/ZrC composite material prepared by embodiment 4.
Fig. 3 is the section scanning electron microscope photo of CF-CNTs/ZrC composite material prepared by embodiment 4.
ZrC ceramics are evenly coated at the surface CF-CNTs it can be seen from Fig. 2 and Fig. 3, and exposed CF- is not observed in material
The presence of CNTs, the presence of CF surface C NTs significantly enhance the interface cohesion between CF and ZrC ceramic matrix, it is ensured that ZrC pottery
Effective transmitting of load between porcelain basal body and CF-CNTs reinforcement.Meanwhile infiltration pyrolysis cycle-index appropriate, both realized
Effective cladding of CF-CNTs outer layer ZrC ceramics, in turn ensures the higher porosity of composite material, maintains lower density.
Fig. 4 is the compressive strength test result of CF-CNTs/ZrC composite material prepared by embodiment 4,Indicate CF/ZrC
Z,Indicate CF-CNTs/ZrC Z,Indicate CF/ZrC XY,Indicate CF-CNTs/ZrC XY.Wherein CF/ZrC Z table
Show the compressive strength in CF/ZrC ceramic matric composite Z-direction, CF-CNTs/ZrC Z indicates that CF-CNTs/ZrC ceramic base is multiple
Compressive strength in condensation material Z-direction, CF/ZrC XY indicate the compressive strength on the direction CF/ZrC ceramic matric composite XY,
CF-CNTs/ZrC XY indicates the compressive strength on the direction CF-CNTs/ZrC ceramic matric composite XY.
As seen from Figure 4, with the increase of infiltration pyrolysis cycle-index, the compressive strength of composite material is gradually increased；
No matter in Z-direction or the direction XY, the compressive strength of CF-CNTs/ZrC composite material is above CF/ZrC composite material, says
The presence of bright CF surface C NTs improves the compressive strength of composite material；When infiltration pyrolysis recycles 6 times, CF-CNTs/ZrC is multiple
The compressive strength of condensation material in z-direction can reach 23.64MPa.Fracture toughness can reach 4.63MPam1/2。
Claims (9)
1. a kind of carbon fiber-carbon nanotube composite toughening ZrC ceramic composite preparation method, it is characterised in that this method
It sequentially includes the following steps:
One, needle-penetrating three-dimensional carbon fibrage body the pretreatment of carbon fiber 3 D weaving body: is cut into cubic block；Use temperature for
70~90 DEG C of 24~48h of acetone reflux is dry by the carbon fiber knitted body after acetone treatment；The dry carbon fiber completed is set
In the concentrated nitric acid that mass fraction is 65%~75%, 1~7h is impregnated under room temperature, is washed carbon fiber using deionized water
It is dry to neutrality, obtain pretreated carbon fiber knitted body；
Two, the load of carbon fiber surface metallic catalyst: using magnesium-yttrium-transition metal salt as solute, acetone is solvent, and compound concentration is
The pretreated carbon fiber knitted body of step 1 is put into solution, impregnates 8 under room temperature by the solution of 0.01~0.09mol/L
~12h, it is dry after taking-up, obtain the carbon fiber for being loaded with metallic catalyst；
Three, carbon fiber-carbon nanotube composite reinforcement preparation: growing CNTs in carbon fiber surface using chemical vapor deposition,
Obtain CF-CNTs composite reinforcement；
Four, the preparation of CF-CNTs/ZrC ceramic matric composite: ZrC ceramic precursor powder is dissolved in dimethylbenzene and is made
ZrC ceramic setter liquid solution is added in the CF-CNTs composite reinforcement that step 3 obtains, and keeps CF-CNTs composite reinforcement whole
It is immersed in ZrC ceramic setter liquid solution, is then placed into vacuum infiltration reaction kettle, be evacuated to pressure and be close to 0Pa, soak
20~60min of stain；It is curing process in 120 DEG C of thermostatic drying chamber that sample, which is placed in temperature, after the completion, curing time 12h,
Sample is placed in pyrolysis furnace after the completion of solidification and is cracked, CF-CNTs/ZrC ceramic composite is obtained；The CF-CNTs/ZrC
The porosity of ceramic composite is 74%~81%, and density is 0.61~1.17g/cm3；
It is cracked in step 4 specifically comprises the processes of: be passed through high-purity Ar into pyrolysis furnace at room temperature and keep 30min, in high-purity Ar atmosphere
Under with the heating rate of 15 DEG C/min temperature is increased to 1000 DEG C from room temperature, 30min is kept the temperature, then with the heating of 10 DEG C/min
Rate raises the temperature to 1600 DEG C, keeps the temperature 1h, is naturally cooling to room temperature under Ar atmosphere protection later and completes cracking.
2. a kind of carbon fiber according to claim 1-carbon nanotube composite toughening ZrC ceramic composite preparation side
Method, it is characterised in that it is dry for the first time in step 1 be specially dry 12 in the thermostatic drying chamber for being placed in temperature and being 70 DEG C~for 24 hours.
3. a kind of carbon fiber according to claim 1-carbon nanotube composite toughening ZrC ceramic composite preparation side
Method, it is characterised in that in step 1 second it is dry be specially dry 24 in the thermostatic drying chamber for being placed in temperature and being 120 DEG C~
36h。
4. a kind of carbon fiber according to claim 1-carbon nanotube composite toughening ZrC ceramic composite preparation side
Method, it is characterised in that magnesium-yttrium-transition metal salt described in step 2 is Ni (NO3)2、Co(NO3)2Or Fe (NO3)3。
5. a kind of carbon fiber according to claim 1-carbon nanotube composite toughening ZrC ceramic composite preparation side
Method, it is characterised in that compound concentration is the solution of 0.05mol/L in step 2.
6. a kind of carbon fiber according to claim 1-carbon nanotube composite toughening ZrC ceramic composite preparation side
Method, it is characterised in that described in step 2 it is dry for be placed in the thermostatic drying chamber that temperature is 70 DEG C dry 12~for 24 hours.
7. a kind of carbon fiber according to claim 1-carbon nanotube composite toughening ZrC ceramic composite preparation side
Method, it is characterised in that grow the detailed process of CNTs in step 3 in carbon fiber surface using chemical vapor deposition are as follows: will load
There is the carbon fiber of metallic catalyst to be placed in tube furnace, be warming up to 500 DEG C in a nitrogen atmosphere, 1h is kept the temperature, with the stream of 40sccm
Speed is passed through H2, continue to keep the temperature 0.5h, be continuously heating to 700~900 DEG C later, be passed through ethyl alcohol, ethyl alcohol and N2Injection flow difference
For 10mL/h and 150sccm, 40~160min is reacted, CF-CNTs composite reinforcement is obtained.
8. a kind of carbon fiber according to claim 1-carbon nanotube composite toughening ZrC ceramic composite preparation side
Method, it is characterised in that the mass fraction of the liquid solution of ZrC ceramic setter described in step 4 is 60%~70%.
9. carbon fiber-carbon nanotube composite toughening ZrC ceramic composite of the method as described in claim 1 preparation is answered
With, it is characterised in that the composite material is used to prepare hypersonic aircraft nose cone and engine thermal end pieces.
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