CN108129151A - A kind of graphene/carbon SiClx nano composite structure layered ceramic and preparation method thereof - Google Patents
A kind of graphene/carbon SiClx nano composite structure layered ceramic and preparation method thereof Download PDFInfo
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Abstract
A kind of graphene/carbon SiClx nano composite structure layered ceramic and preparation method thereof is related to ceramic material preparation.1) precursor PCS (GOx) synthesis；2) graphene/carbon SiClx nano composite structure layered ceramic SiC (rGOx) preparation.Using GO, VTES, PCS as raw material, precursor PCS (GO are prepared by the method for chemical modificationx) powder, through compression molding, high temperature pyrolysis step to get fine and close graphene/carbon SiClx nano composite structure layered ceramic SiC (rGOx).Wherein VTES is because with-Si-O-key and-CH=CH2Group, can be by the new GO-VTES-PCS macromolecular structures of GO and PCS composition generations.GO, which is combined in silicon carbide ceramics, can be significantly expanded precursor crosslinking area, SiC nanocrystals is inhibited to be formed, reduce sintering temperature, solve the problems, such as that polymer-derived method prepares silicon carbide layered ceramic difficult forming, compactness difference.
Description
Technical field
The present invention relates to ceramic material preparations, make pottery more particularly, to a kind of graphene/carbon SiClx nano composite structure monolithic
Porcelain and preparation method thereof.
Background technology
Silicon carbide ceramics not only at normal temperatures have it is corrosion-resistant, wear-resistant, hardness is high, chemical stability is good, thermal expansion system
The low advantage of number, also shows excellent mechanical property, is widely used the fields such as electronics, machinery, nuclear energy, mesh at high temperature
Before can by reaction-sintered, hot pressed sintering and it is normal pressure-sintered the methods of be made.Patent ZL 200910020810.2 is open a kind of
The preparation method of silicon carbide based reinforced composite ceramic is obtained by compression molding and after 1450~1550 DEG C of progress siliconising sintering
Ceramic material with good toughness.Patent ZL 200910098377.4 discloses a kind of preparation of normal pressure-sintered carbonized ceramic
Method, using graphite powder and boron carbide powder as sintering aid, by being segmented ball milling, mist projection granulating, compression molding, stage drying etc.
It is sintered after step in the case where 2150~2200 DEG C of argon gas atmospheres are protected, has prepared the higher corrosion-resistant silicon carbide pottery of purity
Porcelain.Patent ZL 201410116797.1 discloses a kind of method that moulding by casting prepares large-scale self-bonding silicon carbide articles, using shaking
Dynamic moulding by casting technology, is burnt under 1300~1500 DEG C of inert atmosphere protections, can be applied to the industries such as steel, non-ferrous metal.
But since the strong covalent bond of silicon carbide is unfavorable for its densification, traditional preparation methods are needed in the sintered of silicon carbide ceramics
Sintering aid is added in journey or higher temperature is provided, causes to remain the impurity phase of sintering aid introducing, shadow in ceramic matrix
Ring its mechanical property, and there are production cost it is higher the problems such as.
Silicon carbide ceramics prepared by polymer-derived method is due to excellent mechanical strength, corrosion resistance, thermal-shock resistance
Energy, thermal stability and chemical stability etc. receive multi-party concern.Compared to traditional silicon carbide ceramics technology of preparing, precursor
Method flexibility ratio in terms of design and molding is high, the requirement to sintering temperature is low and does not need to addition sintering aid, has very big excellent
Gesture.The lightweight silicon carbide ceramics (amorphous, crystalline state or nanocomposite) of high-purity can be prepared by polymer-derived method, is had preparing
The ceramic component aspect for having complicated shape, structure has potential using value.Patent ZL 201010280856.0 discloses a kind of profit
With the method for the standby continuous long silicon carbide fibre of Polycarbosilane (PCS) precursor.Patent ZL 200510031775.6 is open a kind of
Using trichloromethyl silane as precursor, the technology of compact silicon carbide ceramic coating is prepared using chemical vapour deposition technique, is suitable for
The preparation in optical mirror reflecting layer.6635215 B2 of patent US disclose one kind and are mixed by Polycarbosilane and polyvinyl silane
After closing precursor impregnation carbonization silica fibre, method that sintering prepares carbon fibre reinforced silicon carbide composite material, products obtained therefrom purity
Higher, Good Heat-resistance.Patent ZL 201010152549.4 discloses the skill that a kind of polymer-derived method prepares porous silicon carbide silicon materials
Art using silicon-resin core-shell structured powder as precursor, after pressure forming, charing process and sintering processes, is prepared a kind of high
Thermal shock resistance porous silicon carbide ceramic.Although silicon carbide prepared by polymer-derived method is at low dimensional form (fiber, film, coating etc.)
Show good performance, but the preparation of the three dimensional ceramic materials such as silicon carbide layered ceramic, block ceramic, ceramic matric composite
Technology there is also some problems, such as production cost is higher, there are a large amount of SiC nanocrystals precipitated phases etc. in product, wherein making
Standby large area silicon carbide layered ceramic is difficult to molding particularly problematic.In the pyrolytic process of precursor, a large amount of gaseous state objects
Matter is sustained, and layered ceramic and block ceramic can be caused the defects of crack, stomata occur, seriously affect the consistency of product, thus
It limits polymer-derived method and prepares the application of silicon carbide ceramics industrially.In order to improve the forming ability of PRECURSOR-DERIVED CERAMICS, prepare
The silicon carbide layered ceramic that has excellent performance and applied to industrial production, the crosslinking of high molecular weight solid state precusor becomes silicon carbide pottery
Critical process prepared by porcelain.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to it provides with high rigidity, low-density, low linear shrinkage
A kind of graphene/carbon SiClx nano composite structure layered ceramic.
Another object of the present invention is to provide simple economy, can apply to a kind of industrial graphene/carbon SiClx
The preparation method of nano composite structure layered ceramic.
Graphene/carbon SiClx nano composite structure layered ceramic SiC (rGO of the present inventionx) it is by precursor PCS (GOx)
It is obtained through high temperature pyrolysis, the PCS (GOx) general structure it is as follows：
The preparation method of the graphene/carbon SiClx nano composite structure layered ceramic, includes the following steps：
1) precursor PCS (GOx) synthesis
PCS and Karstedt catalyst is dissolved in organic solvent, then graphene oxide (GO) powder is mixed into deionization
In water and ultrasonic disperse, PCS/ xylene mixtures are then added in into GO aqueous solutions, then into mixed liquor plus three ethoxy of vinyl
Base silane (VTES), is adjusted with dilute hydrochloric acid to acidity；Then by mixed solution heating water bath, magnetic agitation is carried out at the same time,
Upper liquid is taken to be evaporated under reduced pressure by Rotary Evaporators after standing, obtain black solid and ground, obtain fine precursor PCS
(GOx) powdered product, x PCS, GO mass ratio；
2) graphene/carbon SiClx nano composite structure layered ceramic SiC (rGOx) preparation
By PCS (GO obtained by step 1)x) powder is pressed into green compact, it is placed on graphite paper, under inert gas shielding
Pyrolysis, obtains graphene/carbon SiClx nano composite structure layered ceramic SiC (rGOx)；PCS generates silicon carbide by Pintsch process
(SiC), GO is burnt eventually by high temperature is reduced to redox graphene (rGO).
In step 1), the mass ratio of described PCS, GO is preferably 10 ︰ (1~5), the Karstedt catalyst, ethylene
The volume ratio of ethyl triethoxy silicane alkane (VTES) is preferably 1 ︰ (2~4)；The dosage of the dimethylbenzene is preferably 15~25ml；Institute
The dosage for stating deionized water is preferably 15~25ml；The dilute hydrochloric acid dosage is preferably 5ml, and it is preferably 2~4 to make pH value；It is described
The temperature of heating water bath is preferably 70 DEG C, and the time of heating water bath is preferably 1h；The magnetic agitation frequency is preferably 20rpm.
It is described by PCS (GO obtained by step 1) in step 2)x) powder is pressed into green compact and hydraulic press can be used by step 1) institute
Obtain PCS (GOx) powder is pressed into green compact in steel model, the hydraulic press is preferably 100MPa using dynamics；The steel die
Type diameter is preferably 10~20mm；The inert gas is preferably high purity argon, and flow control is in 150~250ml/min；Institute
It is preferably 1300~1500 DEG C to state pyrolysis temperature, heating rate 5 DEG C/min, 20~40min of soaking time.
The present invention is prepared for precursor PCS (GO using GO, VTES, PCS as raw material, by the method for chemical modificationx) powder,
By compression molding, high temperature pyrolysis, you can with fine and close graphene/carbon SiClx nano composite structure layered ceramic
SiC(rGOx).Wherein VTES is because with-Si-O-key and-CH=CH2Group, can by the new GO of GO and PCS composition generations-
VTES-PCS macromolecular structures.GO, which is combined in silicon carbide ceramics, can be significantly expanded precursor crosslinking area, inhibit SiC nanometers
The formation of crystal reduces sintering temperature, and efficiently solving polymer-derived method, to prepare silicon carbide layered ceramic difficult forming, compactness poor
The problem of.
Beneficial effects of the present invention are as follows：
(1) high molecular weight PCS (GOx) application of precursor is conducive to the molding of silicon carbide layered ceramic, it can meet multiple
The molding process requirements of silicon carbide device of miscellaneous shape design.
(2) preparation method is simple and practicable compared to traditional polymer-derived method, can be by adjusting material rate, technological parameter etc.
Obtain SiC (rGO0.1-0.5) layered ceramic, it is highly practical, promote the industrialized production that polymer-derived method prepares silicon carbide ceramics.
(3) the product hardness of synthesis is adjusted for 14~20GPa, and density is about 2.0g/cm3, linear shrinkage is about
26%.Ceramic dense is good, and performance has larger improvement compared with Conventional silicon carbide ceramics, can be applied under the conditions of Various Complex work
Device.
Description of the drawings
Fig. 1 is PCS (GO0.1) precursor (left side) and SiC (rGO0.1) graphene/carbon SiClx nano composite structure layered ceramic
(right side).
Fig. 2 is PCS, VTES, GO and green compact PCS (GO0.1)、PCS(GO0.3)、PCS(GO0.5) infrared (FTIR) spectrogram.
Abscissa in fig. 2 is wave number (cm-1)。
Fig. 3 is graphene/carbon SiClx nano composite structure layered ceramic SiC (rGO0.1)、SiC(rGO0.3)、SiC
(rGO0.5) X-ray diffraction (XRD) figure.Abscissa in figure 3 is 2 θ (°).
Fig. 4 is graphene/carbon SiClx nano composite structure layered ceramic SiC (rGO0.1)、SiC(rGO0.3)、SiC
(rGO0.5) Raman (Raman) spectrogram.Abscissa in Fig. 4 is wave number (cm-1)。
Fig. 5 is graphene/carbon SiClx nano composite structure layered ceramic SiC (rGO0.1)、SiC(rGO0.3)、SiC
(rGO0.5) hardness to the relationships of PCS/GO weight ratios.Ordinate in Figure 5 is hardness (GPa), and abscissa is PCS/GO weights
Amount ratio.
Fig. 6 is graphene/carbon SiClx nano composite structure layered ceramic SiC (rGO0.1)、SiC(rGO0.3)、SiC
(rGO0.5) density to the relationships of PCS/GO weight ratios and linear shrinkage to the relationship of PCS/GO weight ratios.A left side in Figure 5
Ordinate is density (g/cm3), right ordinate is linear shrinkage (%), and abscissa is PCS/GO weight ratios.
Specific embodiment
Said program is described further below in conjunction with specific embodiment.
Graphene/carbon SiClx nano composite structure layered ceramic SiC (rGO of the present inventionx) it is by precursor PCS (GOx)
It is obtained through high temperature pyrolysis, the PCS (GOx) general structure it is as follows：
Precursor PCS (the GOx) there is following feature in infrared (FTIR) spectrogram：In 2100cm-1Place belongs to
The peak of Si-H keys, and peak intensity increases with raw material GO contents and is reduced；In 780cm-1(belonging to Si-C keys) and 1410cm-1(return
Belong to-CH2Key) peak intensity with raw material GO contents increase and enhance；As raw material GO contents increase, in 1610cm-1It (belongs to
Aromatic ring C=C keys) and 1720cm-1The absorption intensity of (belonging to C=O keys) also enhances.Precursor PCS (the GOx) gray,
And increase with raw material GO contents, PCS (GOx) color it is deeper, closer to black.
Graphene/carbon SiClx nano composite structure layered ceramic SiC (rGO of the present inventionx) at X-ray diffraction (XRD)
There is following feature in figure：There is the peak for belonging to rGO at 2 θ=21.947 °, and increase with raw material GO contents, the raising of this peak value；2
There is the peak for belonging to β-SiC crystal at θ=35.827 °/60.141 °/71.285 °, and increase with raw material GO contents, these three peaks
Peak value be gradually reduced.The graphene/carbon SiClx nano composite structure layered ceramic SiC (rGOx) composed in Raman (Raman)
There is following feature in figure：In 1335cm-1(D peaks) and 1600cm-1There are two apparent peak at (G peaks), and as raw material GO contains
Amount increases, and D peaks are than the value (I at G peakD/IG) increase.The graphene/carbon SiClx nano composite structure layered ceramic SiC (rGOx)
It is also equipped with following feature：As raw material GO contents increase, ceramic hardness, density, linear shrinkage decline；The SiC
(rGOx) ceramic in black.
Specific preparation method embodiment is given below.
Embodiment 1
1st, the Karstedt catalyst of PCS and 0.5ml that 1g relative molecular weights are 1426g/mol are dissolved in 20ml diformazans
In benzene, clear solution is obtained；
2nd, the GO powder of 0.1g is mixed into 20ml deionized waters, subsequent ultrasonic wave disperses 30min；
3rd, PCS/ xylene mixtures are slowly added in GO aqueous solutions, then 1ml VTES is added in into mixed solution, used
5ml dilute hydrochloric acid adjusts its pH value to 2~4.
4th, mixed solution heating water bath to 70 DEG C and is kept into 1h, while magnetic agitation is carried out with the rate of 20rpm.
5th, by after the static 5min of mixed liquor in step 4, upper liquid is taken to be evaporated under reduced pressure by Rotary Evaporators, is obtained
Black solid.
6th, the black solid obtained in grinding steps 5 obtains fine PCS (GO0.1) powdered product.
7th, the PCS (GO that will be obtained in step 6 using hydraulic press0.1) powder is pressed into life in the steel model of diameter 17mm
Base is placed on graphite paper, is pyrolyzed in the case where flow is the high-purity argon gas shielded of 200ml/min, and 5 DEG C of heating rate/
Min, 1400 DEG C of pyrolysis temperature keep 30min, finally obtain SiC (rGO0.1) layered ceramic.
8th, to gained SiC (rGO in step 70.1) layered ceramic is tested for the property, its Vickers is measured by microhardness instrument
Hardness is 19.49GPa, its density is measured as 2.18g/cm according to Archimedes principle3, its linear shrinkage is obtained by calculation
It is 26.88%.
Embodiment 2
1st, PCS the and 0.5ml Karstedt catalyst that 1g relative molecular weights are 1426g/mol is dissolved in 20ml diformazans
In benzene, clear solution is obtained；
2nd, the GO powder of 0.3g is mixed into 20ml deionized waters, subsequent ultrasonic wave disperses 30min；
3rd, PCS/ xylene mixtures are slowly added in GO aqueous solutions, then 1.4ml VTES are added in into mixed solution,
Its pH value is adjusted to 2~4 with 5ml dilute hydrochloric acid.
4th, mixed solution heating water bath to 70 DEG C and is kept into 1h, while magnetic agitation is carried out with the rate of 20rpm.
5th, by after the static 5min of mixed liquor in step 4, upper liquid is taken to be evaporated under reduced pressure by Rotary Evaporators, is obtained
Black solid.
6th, the black solid obtained in grinding steps 5 obtains fine PCS (GO0.3) powdered product.
7th, the PCS (GO that will be obtained in step 6 using hydraulic press0.3) powder is pressed into life in the steel model of diameter 17mm
Base is placed on graphite paper, is pyrolyzed in the case where flow is the high-purity argon gas shielded of 200ml/min, and 5 DEG C of heating rate/
Min, 1400 DEG C of pyrolysis temperature keep 30min, finally obtain SiC (rGO0.3) layered ceramic.
8th, to gained SiC (rGO in step 70.3) layered ceramic is tested for the property, its Vickers is measured by microhardness instrument
Hardness is 15.41GPa, its density is measured as 2.01g/cm according to Archimedes principle3, its linear shrinkage is obtained by calculation
It is 25.88%.
Embodiment 3
1st, PCS the and 0.5ml Karstedt catalyst that 1g relative molecular weights are 1426g/mol is dissolved in 20ml diformazans
In benzene, clear solution is obtained；
2nd, the GO powder of 0.5g is mixed into 20ml deionized waters, subsequent ultrasonic wave disperses 30min；
3rd, PCS/ xylene mixtures are slowly added in GO aqueous solutions, then 1.8ml VTES are added in into mixed solution,
Its pH value is adjusted to 2~4 with 5ml dilute hydrochloric acid.
4th, mixed solution heating water bath to 70 DEG C and is kept into 1h, while magnetic agitation is carried out with the rate of 20rpm.
5th, by after the static 5min of mixed liquor in step 4, upper liquid is taken to be evaporated under reduced pressure by Rotary Evaporators, is obtained
Black solid.
6th, the black solid obtained in grinding steps 5 obtains fine PCS (GO0.5) powdered product.
7th, the PCS (GO that will be obtained in step 6 using hydraulic press0.5) powder is pressed into life in the steel model of diameter 17mm
Base is placed on graphite paper, is pyrolyzed in the case where flow is the high-purity argon gas shielded of 200ml/min, and 5 DEG C of heating rate/
Min, 1400 DEG C of pyrolysis temperature keep 30min, finally obtain SiC (rGO0.5) layered ceramic.
8th, to gained SiC (rGO in step 70.5) layered ceramic is tested for the property, its Vickers is measured by microhardness instrument
Hardness is 14.29GPa, its density is measured as 1.77g/cm according to Archimedes principle3, its linear shrinkage is obtained by calculation
It is 23.88%.
Fig. 1 is PCS (GO0.1) precursor (left side) and SiC (rGO0.1) graphene/carbon SiClx nano composite structure layered ceramic
(right side).
Fig. 2 is PCS, VTES, GO and green compact PCS (GO0.1)、PCS(GO0.3)、PCS(GO0.5) infrared (FTIR) spectrogram.
Abscissa in fig. 2 is wave number (cm-1)。
Fig. 3 is graphene/carbon SiClx nano composite structure layered ceramic SiC (rGO0.1)、SiC(rGO0.3)、SiC
(rGO0.5) X-ray diffraction (XRD) figure.Abscissa in figure 3 is 2 θ (°).
Fig. 4 is graphene/carbon SiClx nano composite structure layered ceramic SiC (rGO0.1)、SiC(rGO0.3)、SiC
(rGO0.5) Raman (Raman) spectrogram.Abscissa in Fig. 4 is wave number (cm-1)。
Fig. 5 is graphene/carbon SiClx nano composite structure layered ceramic SiC (rGO0.1)、SiC(rGO0.3)、SiC
(rGO0.5) hardness to the relationships of PCS/GO weight ratios.Ordinate in Figure 5 is hardness (GPa), and abscissa is PCS/GO weights
Amount ratio.
Fig. 6 is graphene/carbon SiClx nano composite structure layered ceramic SiC (rGO0.1)、SiC(rGO0.3)、SiC
(rGO0.5) density to the relationships of PCS/GO weight ratios and linear shrinkage to the relationship of PCS/GO weight ratios.A left side in Figure 5
Ordinate is density (g/cm3), right ordinate is linear shrinkage (%), and abscissa is PCS/GO weight ratios.The present invention obtains
Graphene/carbon SiClx nano composite structure layered ceramic good physical properties, physical property influenced by GO adding proportions
Less.
The present invention devise it is a kind of simply by graphene oxide-vinyltriethoxysilane-Polycarbosilane (GO-
VTES-PCS are named as PCS (GOx)) precursor high temperature pyrolysis prepares graphene/carbon SiClx nano composite structure layered ceramic
Technology.This novel process solves the problems, such as silicon carbide PRECURSOR-DERIVED CERAMICS difficult forming, can meet labyrinth design
The standby requirement of ceramic system, effectively improves the physical property of silicon carbide layered ceramic and reduces production cost, be conducive to large-scale production simultaneously
Extensive use.
Claims (10)
1. a kind of preparation method of graphene/carbon SiClx nano composite structure layered ceramic, it is characterised in that include the following steps：
1) precursor PCS (GOx) synthesis
PCS and Karstedt catalyst is dissolved in organic solvent, then GO powder is mixed into deionized water simultaneously ultrasonic disperse, with
PCS/ xylene mixtures are added in into GO aqueous solutions afterwards, then add VTES into mixed liquor, are adjusted with dilute hydrochloric acid to acidity；With
Afterwards by mixed solution heating water bath, magnetic agitation is carried out at the same time, upper liquid is taken to carry out decompression steaming by Rotary Evaporators after standing
It evaporates, obtain black solid and grinds, obtain fine precursor PCS (GOx) powdered product, x PCS, GO mass ratio；
2) graphene/carbon SiClx nano composite structure layered ceramic SiC (rGOx) preparation
By PCS (GO obtained by step 1)x) powder is pressed into green compact, it is placed on graphite paper, is pyrolyzed under inert gas shielding,
Obtain graphene/carbon SiClx nano composite structure layered ceramic SiC (rGOx)；PCS generates SiC by Pintsch process, and GO is through excessively high
Warm burn eventually is reduced to rGO.
2. a kind of preparation method of graphene/carbon SiClx nano composite structure layered ceramic as described in claim 1, feature exist
In in step 1), the mass ratio of described PCS, GO is 10 ︰ (1~5), the Karstedt catalyst, VTES volume ratio be
1 ︰ (2~4).
3. a kind of preparation method of graphene/carbon SiClx nano composite structure layered ceramic as described in claim 1, feature exist
In in step 1), the dimethylbenzene is 15~25ml；The dosage of the deionized water is 15~25ml；The dilute hydrochloric acid is used
It measures as 5ml, it is 2~4 to make pH value.
4. a kind of preparation method of graphene/carbon SiClx nano composite structure layered ceramic as described in claim 1, feature exist
In in step 1), the temperature of the heating water bath is 70 DEG C, and the time of heating water bath is 1h.
5. a kind of preparation method of graphene/carbon SiClx nano composite structure layered ceramic as described in claim 1, feature exist
In in step 1), the frequency of the magnetic agitation is 20rpm.
6. a kind of preparation method of graphene/carbon SiClx nano composite structure layered ceramic as described in claim 1, feature exist
It is described by PCS (GO obtained by step 1) in step 2)x) powder is pressed into green compact using hydraulic press by PCS obtained by step 1)
(GOx) powder is pressed into green compact in steel model.
7. a kind of preparation method of graphene/carbon SiClx nano composite structure layered ceramic as claimed in claim 6, feature exist
It is 100MPa to use dynamics in the hydraulic press；A diameter of 10~the 20mm of steel model.
8. a kind of preparation method of graphene/carbon SiClx nano composite structure layered ceramic as described in claim 1, feature exist
In in step 2), the inert gas is argon gas, and flow control is in 150~250ml/min.
9. a kind of preparation method of graphene/carbon SiClx nano composite structure layered ceramic as described in claim 1, feature exist
In in step 2), the pyrolysis temperature is 1300~1500 DEG C, heating rate 5 DEG C/min, 20~40min of soaking time.
10. stone prepared by a kind of preparation method of graphene/carbon SiClx nano composite structure layered ceramic as described in claim 1
Black alkene/nanometer silicon carbide composite construction layered ceramic.
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