CN107176604A - A kind of method that carbon materials surface in situ generates nano-carbide coating - Google Patents
A kind of method that carbon materials surface in situ generates nano-carbide coating Download PDFInfo
- Publication number
- CN107176604A CN107176604A CN201610133960.4A CN201610133960A CN107176604A CN 107176604 A CN107176604 A CN 107176604A CN 201610133960 A CN201610133960 A CN 201610133960A CN 107176604 A CN107176604 A CN 107176604A
- Authority
- CN
- China
- Prior art keywords
- carbon materials
- carbon
- coating
- carbide
- situ
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention discloses a kind of method that carbon materials surface in situ generates nano-carbide coating, belong to the technical field of material such as high-strength, superhard, wear-resisting and heat management.This method is to prepare oxide sol or gel using sol-gal process, uniformly it is coated to behind carbon materials surface, is handled after drying, sintering process, then through vacuum high-temperature, in-situ reducing carburizing reagent is realized, in-situ carbon compound nano coating is formed on carbon materials surface.Instant invention overcomes carbon materials surface free energy is low between the binding agent/matrix such as metal, ceramics and macromolecule poor compatibility, interface cohesion is bad the problems such as, the adhesion between matrix and carbon materials such as metal, ceramics and macromolecule is improved, the thermal impedance at interface between carbon materials and metal is reduced.The present invention can effectively improve the mechanics of carbon materials enhancing metal, ceramics and the composite such as macromolecule, heat conduction, conductive and wear-resisting etc. performance.
Description
Technical field
The present invention relates to the technical field of material such as high-strength, superhard, wear-resisting and heat management, and in particular to a kind of
The method that carbon materials surface in situ generates nano-carbide coating.
Background technology
Carbon possesses a variety of C-C bondings modes and crystal structure, can form the carbon of a variety of configurations and excellent combination property
Cellulosic material, such as carbon fiber, diamond, crystalline flake graphite and multi-walled carbon nanotube, with density is low, thermal expansion
The advantages of coefficient is low, intensity is high, modulus is big, especially heat conduction, electric conductivity are extremely excellent.Carbon materials is not
Only it is the important raw and processed materials in traditional industry field, is also the height that the fields such as photoelectricity, national defence and Aero-Space are representative
The grand strategy goods and materials of scientific and technological industry.
Although carbon materials possesses many excellent performances, carbon materials is generally particle or threadiness, it is difficult to single
Solely use.Composite is by the one of two or more physics combinations of substances different with chemical property
Multiphase solid material is planted, the advantage of different materials can be integrated, learnt from other's strong points to offset one's weaknesses, be the important development of Material Field
One of direction.Therefore, carbon materials is considered as the preferable reinforcement of composite.But, carbon materials with
Interface compatibility between the other materials such as metal, ceramics, carbon, macromolecule is poor, such as carbon materials and gold
Wetability, chemical stability and mechanical compatibility between category aluminium etc. are all poor.In addition, carbon materials and metal,
The heat-conducting mode of the material such as ceramics and macromolecule is also completely different, and this causes between carbon materials and other materials
Interface resistance is anti-higher, is unfavorable for giving full play to the characteristic of carbon material high heat conduction.
Research shows to be effectively improved or improve carbon materials and its carbon material surface alloying is coating modified
Compatibility between its material.At present, the coating modified technology of surface alloying is carried out to carbon materials has chemistry
Be vapor-deposited (CVD), physical vapour deposition (PVD) (PVD), the micro- evaporation plating of magnetron sputtering, vacuum, chemical plating and
Elements diffusion method etc..Wherein, the method such as PVD and magnetron sputtering is compared with suitable in the outer of smooth workpiece or material
Surface is coated, and uniform coating can not be formed in the inner surface of porous material, thus be difficult to apply to diamond,
The carbon materialses such as carbon fiber, crystalline flake graphite；It is unfavorable that the technique of chemical vapour deposition technique is complex, cost is high etc.
Factor also greatly limits its industrial applications.In addition, although Electroless Cu Plating and Ni technology very into
It is ripe, but belong to chemical inertness between Cu, Ni and carbon, it is hardly produced metallic compound, it is impossible to fundamentally solve
Certainly between the material such as carbon materials and metal the problem of poor compatibility, and the preparation work of the coating such as chemical plating Ti, Al
Skill is complicated, cost is also higher, and is easily guided into impurity element, therefore is not also used widely.
The academic journal published for 2002《Diamond and grinding materials and grinding tool engineering》" the gold of 128th 25-28 pages of phase
In the text of the relation of hard rock plating technic and using effect " one, Wang Yanhui et al. is existed using the micro- evaporation electroplating method of vacuum
Diamond surface is coated with Ti coatings, can effectively reduce the diamond drop-off rate in diamond saw blade, improves work
The efficiency and service life of tool.This method is after diamond is well mixed with the pioneer containing titanium elements, true
The principle that can be migrated under empty, hot conditions using Ti atoms in short distance, is finally deposited in diamond surface
Ti coatings.However, the thickness distribution Normal Distribution of diamond surface titanium coating in theory, i.e., apart from titanium member
The titanium coating of plain precursor more near position is thicker.In addition, the academic journal published for 2006《Diamond and abrasive material
Grinding tool engineering》" vacuum slowly vapor deposition parameters on coating quality and the diamond of 155th 17-19 pages of phase
In the text of the influence of performance " one, Zhao Yucheng et al. has inquired into influence of the temperature to diamond, finds at 1100 DEG C
Under the conditions of, too high temperature, which can increase the extension of diamond internal flaw and the expansion of Ti integuments, causes crystal cleavage
Chance, causes the impact flexibility of diamond drastically to decline.
The academic journal published for 2015《Composites Part B:Engineering》22-26 pages of volume 68
“Thermal conductivity of Cu-Zr/diamond composites produced by high
In the texts of temperature-high pressure method " one, He etc. is used under conditions of 1500 DEG C, 5GPa
Method of impregnation is prepared for diamond/Cu-Zr composites, and the thermal conductivity of composite has reached 677W/mK, this
It is mainly due to Zr elements being diffused into diamond surface and foring ZrC layers of nanoscale in Cu.
The academic journal published for 2013《Applied Surface Science》603-609 pages of volume 265
“Preparation of anti-oxidative SiC/SiO2coating on carbon fibers from
In the texts of vinyltriethoxysilane by sol-gel method " one, Xia et al. is using sol-gel process in carbon fiber
Surface is coated with SiO2Coating, and 1500 DEG C of sintering after 2 hours, are obtained under the protection of high-purity argon gas
SiC/SiO2Composite coating, research shows that the coating can effectively improve the inoxidizability of carbon fiber.The experimental program
By the use of the carbon in carbon fiber as reducing agent, but because carbon fiber has good heat endurance and is initially formed
SiC layer hinders the diffusion of carbon atom, still can not provide and fills under conditions of 2 hours even in 1500 DEG C, sintering
The free carbon atom of foot causes still to remain part SiO in coating as reducing agent and the raw material of carburizing reagent2。
The content of the invention
, should it is an object of the invention to provide a kind of method that carbon materials surface in situ generates nano-carbide coating
Method can prepare in situ on the carbon materials such as carbon fiber, diamond, crystalline flake graphite and multi-walled carbon nanotube surface
The nano-carbide coating of generation, the thickness of the coating can be controlled in 10~20nm, with cladding it is complete, apply
Layer is uniform, controllable chemical composition, simple and reliable process, with low cost, preparation temperature is low, be applied carbon material
The advantages of material damage is small, carburizing reagent is complete and has wide range of applications.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of method that carbon materials surface in situ generates nano-carbide coating, this method comprises the following steps：
(1) single or doping oxide sol or gel, its concentration are prepared using traditional sol-gel process
For 0.05~1.5 mol/L；
(2) it is carbon materials removing surface is clean；The carbon materials is carbon fiber, graphite, diamond and many
One or more in wall carbon nano tube；
(3) surface coating processing：According to coating object difference, using ultrasonic oscillation, lifting, stir or
Colloidal sol or gel are uniformly coated to carbon materials surface by the methods such as spraying；
(4) drying process：Carbon materials after the coating processing of surface is placed on to 10~80 DEG C of drying, cleaning
Processing is dried in space, the drying process time is 1 hour~mono- week；
(5) pre-sintered processing：Under the conditions of air or protective atmosphere, by by coating and the carbon after drying process
Cellulosic material is put into resistance furnace, and 240-700 DEG C, 20-300 points of insulation are warming up to the speed less than 10 DEG C/min
Clock, coating is formed on carbon materials surface；
(6) operating process of repeat step (3)-step (5), until the coating on carbon materials surface reaches
Required thickness；
(7) in-situ reducing-carburizing reagent：Carbon materials after sintering processes is put into vacuum drying oven, vacuumized
Vacuum is less than 5 × 10 in stove-1After Pa, it is warming up to 700~1450 DEG C with the speed less than 20 DEG C/min and protects
Temperature is furnace-cooled to room temperature after 2~48 hours under vacuum condition, in-situ reducing-carburizing reagent is completed, finally in carbon
Material surface obtains the nano-carbide coating of growth in situ.
In above-mentioned steps (1), the single oxide sol or gel refer to only containing titanium oxide, silica,
One kind in chromium oxide, vanadium oxide, zirconium oxide, niobium oxide, tantalum oxide, molybdenum oxide, tungsten oxide and rheium oxide
Or several colloidal sol or gel；The oxide sol or gel of the doping refer to single oxide sol (or
Gel) in the colloidal sol (or gel) that is formed after precursor of the addition as reducing agent (carbon), wherein, addition
It is 0.1 of oxide molar amount in colloidal sol or gel as the mole of carbon atom in the precursor of reducing agent (carbon)
It is the organic matters such as sucrose, polyethylene, polyvinyl alcohol as the precursor of reducing agent (carbon) to 10 times.Wherein,
It is undersaturation as the content of the precursor of reducing agent residual carbon after Pintsch process, that is, cracks the content of residual carbon
Less than the total amount of the carbon required for reduction-carburizing reagent.In addition, the addition of macromolecule organic can also improve molten
The viscosity of glue or gel, is conducive to increasing coating layer thickness, and the repeatedly process such as coating is reduced or avoided.
It is described that carbon materials removing surface is clean in above-mentioned steps (2), mainly according to carbon materials table
The residue or impurity in face, the method such as burn by pickling, alkali cleaning, organic solvent washing and/or high temperature.Carbon
The residue or impurity of material surface refer to catalyst, organic matter of carbon material surface residual etc. and production and stored up
Catalyst, the gluing of carbon fiber surface remained on pollutant introduced during depositing etc., such as multi-walled carbon nanotube
Deng.
In above-mentioned steps (7), the reducing agent used in the in-situ reducing-carburizing reagent is carbon, carbon
Source includes being applied the organic matter of doping in the carbon of object carbon materials itself and/or colloidal sol (or gel) in height
Remaining carbon is cracked under the conditions of temperature.
The composition of nano-carbide coating is generated for titanium carbide, carbon in carbon materials surface in situ using the above method
SiClx, chromium carbide, vanadium carbide, zirconium carbide, niobium carbide, ramet, molybdenum carbide, tungsten carbide and carbonization rhenium etc.
One or more (such as (Ta, Nb) C) in carbide, the thickness of nano-carbide coating is 10~20nm.
Design principle of the present invention and have the beneficial effect that：
1st, from the reaction equation of carbon reduced oxide, its reaction product is gaseous CO, and the present invention is adopted
With the method for vacuum, the CO that reaction is generated quickly is taken away, cause the concentration dramatic decrease of reaction product,
The speed of reduction reaction will be greatly improved in this, and ensure that the irreversible of reaction.
2nd, according to thermodynamic principles, the chemical reaction of carbon reduced oxide needs to exceed the just meeting of certain reaction temperature
Carry out, that is, the Gibbs free energy for must being fulfilled for reaction system declines, and Gibbs free energy is in a standard
Carry out evaluation response maximum system energy on the premise of atmospheric pressure.Under vacuum, reaction product CO is pumped phase
Externally done work when in reaction system, compared with conventional argon gas protective condition, this will substantially reduce carbon reduction-oxidation
The reaction temperature of thing.
3rd, the temperature of superelevation can cause diamond graphitization and energy cost to rise, and C-C keys are highly stable
Covalent bond, the constraint that relatively low temperature can not allow more carbon atoms to depart from C-C keys turns into free state carbon atom,
In addition the carbide lamella that carbon material surface is formed in advance can also hinder carbon atom to diffusion on the outside of coating, and these cause
Reduction and carburizing reagent between carbon materials and oxide coating can not be carried out thoroughly.The present invention is using in oxidation
Doping sucrose etc. contains carbon macromolecule in the precursor (sol-gel) of thing coating, utilizes macromolecule under hot conditions
Remaining carbon is cracked as supplementary carbon source, it is ensured that the progress of in-situ reducing-carburizing reagent.
4th, the viscosity of sol-gel is improved using the addition of macromolecule organic, is conducive to increasing coating layer thickness,
The repeatedly process such as coating is reduced or avoided.
5th, (content for cracking residual carbon is anti-less than reduction-carbonization for unsaturated state for the macromolecule carbon source of doping
The total amount of carbon that should be required), thus in the original location in reduction-carbonation reaction carbon concentration in gradient distribution,
Concentration i.e. closer to carbon materials surface carbon is higher, and the atom (i.e. oxide reduzate) being reduced can be with
To carbon material surface diffusion and and then in-situ preparation carbide.
6th, the oxide coating of sol-gel process coating constitutes for nano particle, using heredity principle, in situ
Generation carbide coating is similarly nanostructured.
7th, the inventive method can effectively solve nanocarbon/metal, carbon/ceramics, carbon/macromolecule and carbon/carbon interface it
Between poor compatibility the problem of, improve the bond strength at interface between carbon and multiple material, thermal conductivity and wear-resisting
Performance.In addition, in-situ nano carbide coating prepared by the technique can also effectively improve the antioxygen of carbon materials
Change performance.
Brief description of the drawings
Fig. 1 is the generated in-situ TiC coatings of diamond surface prepared by embodiment 1；Wherein：(a) electron scanning
The TiC coating cladding diamonds of Electronic Speculum (SEM) observation grind after pattern, (b) and (c) are respectively TiC/
The low power and high power high-resolution atomic response of diamond.
Fig. 2 is the SEM patterns of SiC coating cladding diamond broken materials prepared by embodiment 2.
Fig. 3 is the generated in-situ nanometer Cr of carbon fiber surface prepared by embodiment 33C2Coating；Wherein：(a) carbon
Fiber surface in-situ preparation nanometer Cr3C2SEM patterns after coating, the carbon fiber surface after (b) is artificially poked is applied
The SEM photograph of layer.
Embodiment
The present invention can prepare in-situ nano carbide coating on the carbon materials surface of various configuration, below by way of
The present invention is further described for embodiment.
Embodiment 1：
The coating object selected in the present embodiment is the bortz powder of 25 μm of particle diameters purchased in market, is comprised the following steps that：
(1) the present embodiment is with butyl titanate (Ti (OC4H9)4) be presoma, and using absolute ethyl alcohol, go from
Sub- water, acetylacetone,2,4-pentanedione, nitric acid (concentration is 69wt.%, analyze pure) and PEG-800 as raw material, wherein
Butyl titanate, absolute ethyl alcohol, deionized water, acetylacetone,2,4-pentanedione and PEG-800 volume ratio are
1:9:0.7:0.15:0.25；It it is first two parts by 1/3 and 2/3 point of total consumption by absolute ethyl alcohol；By deionized water and 1/3
Absolute ethyl alcohol mixing wiring solution-forming, it is the dilute of 2.5wt.% that 69wt.% nitric acid is diluted into concentration with deionized water
Nitric acid, then the pH value for adjusting solution with dust technology are made into solution A to 3.0；By the butyl titanate of weighing,
Acetylacetone,2,4-pentanedione, is slowly added in remaining 2/3 absolute ethyl alcohol, is made into B solution under rapid stirring；
Then under fast stirring, solution A is slowly dropped into B solution with buret, then instills PEG-800 and (gathered
Ethylene glycol), the TiO for the homogeneous transparent that concentration is 0.3 mol/L is obtained after stirring2Colloidal sol；What is obtained is molten
Still aging 24 hours of glue is stand-by.
(2) diamond of clean surface is poured into the colloidal sol of step (1) acquisition, after stirring, in 360rpm
Under conditions of rotating speed after centrifugal filtration 5 minutes, take out diamond and be placed in 50 DEG C of drying box processing is dried,
Drying process 48 hours.
(3) after the diamond for obtaining step (2) is put into cover and closed preferable graphite crucible, it is placed in electricity
Hinder in stove, be warming up under atmospheric environment with 5 DEG C/min speed after 350 DEG C and be incubated 1 hour, carry out pre-burning
Knot processing；
(4) finally the graphite crucible for filling diamond is put into vacuum drying oven, is evacuated to vacuum in stove and is less than
1×10-1After Pa, with 10 DEG C/min speed be warming up to 1250 DEG C and be incubated 4 hours after, stove is cold under vacuum condition
To room temperature, in-situ reducing-carburizing reagent is completed, it is final to obtain the Buddha's warrior attendant that surface is coated with in-situ nano TiC coatings
Stone.
Fig. 1 show in the present embodiment the patterns of 40~50 μm of diamond surfaces coating TiC coatings and micro-
See structure, the TiC coating tights that diamond surface is about 10nm by thickness, and diamond and TiC layer
Between be tightly combined (by SEM patterns, it is difficult to diamond initial surface and TiC coatings be distinguished, to TiC
The diamond of coating cladding, observation understands (such as Fig. 1 (a) after grinding：Black portions are conductive preferably TiC
Cleavage surface is destroyed in coating, brilliant white part for the diamond of conductive insulation)；50 are prepared for using powder metallurgic method
Vol.% diamonds/6061Al composites, performance test shows, after diamond surface coated carbide coating,
The bending strength and thermal conductivity of the composite of preparation have significantly lifting (such as table 1).
Embodiment 2：
The coating object selected in the present embodiment is 40~50 μm of diamond broken materials purchased in market, and specific steps are such as
Under：
(1) the present embodiment with tetraethyl orthosilicate (TEOS) be presoma, and using nitric acid (concentration is 69wt.%,
Analysis is pure), deionized water, absolute ethyl alcohol and sucrose be used as raw material, wherein TEOS, deionized water, anhydrous second
The mol ratio of alcohol and sucrose is 1：6：25：0.25；It is 2.5wt.% that nitric acid first is diluted into concentration with deionized water
Dust technology, then distilled water pH value is adjusted to 3 with dust technology, then the TEOS and ethanol of weighing are added to
In deionized water, airtight heating is to 70 DEG C and stirs 24 hours, then adds sucrose and stops to after being completely dissolved
Stirring, obtains the SiO that concentration is about the homogeneous transparent of 0.15 mol/L2Colloidal sol stand 48 hours it is stand-by.
(2) diamond of clean surface is poured into the SiO of step (1) acquisition2In colloidal sol, after stirring,
Under conditions of the 300rpm rotating speeds after centrifugal filtration 5 minutes, the drying box that single-crystal diamond is placed in 50 DEG C is taken out
In processing, drying process 48 hours is dried.
(3) after the diamond for obtaining step (2) is put into cover and closed preferable graphite crucible, it is placed in electricity
Hinder in stove, be warming up under atmospheric environment with 5 DEG C/min speed after 350 DEG C and be incubated 1 hour, carry out pre-burning
Knot processing；
(4) finally the graphite crucible for filling single-crystal diamond is put into vacuum drying oven, is evacuated to vacuum in stove
Less than 1 × 10-1After Pa, with 10 DEG C/min speed be warming up to 1350 DEG C and be incubated 4 hours after, vacuum condition
Under be furnace-cooled to room temperature, complete in-situ reducing-carburizing reagent, the final surface that obtains is coated with in-situ nano SiC coatings
Diamond.
As shown in Fig. 2 diamond broken material is coated completely by generated in-situ nano SiC coating, and SiC is applied
Layer is uniform, fine and close；50vol.% diamonds/6061Al composites are prepared for using powder metallurgic method, performance is surveyed
Take temperature bright, after SiC Coating, the thermal conductivity of composite is lifted (such as table 1) by a relatively large margin.
The performance characteristic of the 50vol.% diamonds of table 1/6061Al composites
Embodiment 3：
The coating object selected in the present embodiment is domestic T300 carbon fibers, is comprised the following steps that：
(1) the present embodiment is with chromic nitrate (Cr (NO3)3·9H2O) it is presoma, and uses deionized water, ammoniacal liquor
(concentration is 25wt.%), sucrose (analysis pure) and PEG-800 as raw material, wherein chromic nitrate, go from
The weight ratio of sub- water, sucrose and PEG-800 is 1：9：0.5：0.5.Under agitation, first by chromic nitrate
It is dissolved into deionized water, then is adjusted the concentration of ammoniacal liquor to 5wt.% with deionized water, the ammoniacal liquor of dilution is delayed
Slowly it is added drop-wise in chromium nitrate solution, pH is to 3.5 for adjustment, and is kept stirring for 0.5 hour formation concentration and is rubbed for 0.25
You/liter transparent and stable Cr2O3Colloidal sol, 60 DEG C of water-bath agings 1 hour under conditions of stirring, to stand 48 small
When it is stand-by.
(2) carbon fiber is put into vacuum drying oven, is evacuated to 1 × 10-1After more than Pa, it is warming up to 400 DEG C and protects
Temperature 1 hour, removes the organic binder of carbon fiber surface.
(3) it will be equipped with Cr2O3The container of colloidal sol is positioned in ultrasonic oscillation tank, then that the carbon handled well is fine
Dimension is immersed in colloidal sol, and ultrasonic oscillation draws carbon fiber from colloidal sol after 5 minutes with 1.6mm/s speed
Go out, be placed at dried and clean and dry.
(4) after the carbon fiber for obtaining step (3) is put into cover and closed preferable graphite crucible, it is placed in electricity
Hinder in stove, be warming up to 5 DEG C/min speed after 350 DEG C and be incubated 1 hour, carry out pre-sintered processing；
(5) carbon fiber for finally obtaining step (4) is put into vacuum drying oven, is evacuated to vacuum in stove and is less than
1×10-1After Pa, with 10 DEG C/min speed be warming up to 1000 DEG C and be incubated 4 hours after, stove is cold under vacuum condition
To room temperature, in-situ reducing-carburizing reagent is completed, the final surface that obtains is coated with in-situ nano Cr3C2The carbon of coating
Fiber.
As shown in figure 3, carbon fiber surface in-situ preparation nanometer Cr3C2After coating, its coating is evenly distributed, wrapped
Wrap up in tight；After artificial poke, it is observed that Cr3C2Coating layer thickness is about tens nanometers.
Claims (7)
1. a kind of method that carbon materials surface in situ generates nano-carbide coating, it is characterised in that：This method
Comprise the following steps：
(1) single or doping oxide sol or gel are prepared using sol-gel process, its concentration for 0.05~
1.5 mol/L；
(2) it is carbon materials removing surface is clean；
(3) surface coating processing：According to coating object difference, using ultrasonic oscillation, lifting, stir or
Colloidal sol or gel are uniformly coated to carbon materials surface by spraying method；
(4) drying process：Carbon materials after the coating processing of surface is placed on to 10~80 DEG C of drying, cleaning
Processing is dried in space；
(5) pre-sintered processing：Under the conditions of air or protective atmosphere, by by coating and the carbon after drying process
Cellulosic material is put into resistance furnace, and 240-700 DEG C, 20-300 points of insulation are warming up to the speed less than 10 DEG C/min
Clock, coating is formed on carbon materials surface；
(6) operating process of repeat step (3)-step (5), until the coating on carbon materials surface reaches
Required thickness；
(7) in-situ reducing-carburizing reagent：Carbon materials after pre-sintered processing is put into vacuum drying oven, takes out true
Sky to vacuum in stove is less than 5 × 10-1After Pa, 700~1450 DEG C are warming up to the speed less than 20 DEG C/min
And after being incubated 2~48 hours, room temperature is furnace-cooled under vacuum condition, in-situ reducing-carburizing reagent is completed, is finally existed
Carbon materials surface obtains the nano-carbide coating of growth in situ.
2. the method that carbon materials surface in situ according to claim 1 generates nano-carbide coating, its
It is characterised by：Single oxide sol or gel described in step (1) refer to only containing titanium oxide, silica,
One kind in chromium oxide, vanadium oxide, zirconium oxide, niobium oxide, tantalum oxide, molybdenum oxide, tungsten oxide and rheium oxide
Or the colloidal sol or gel of several compositions；The oxide sol or gel of the doping are in single oxide sol
Or added in gel after the precursor as reducing agent formed, the precursor as reducing agent added be sucrose,
Polyethylene or polyvinyl alcohol.
3. the method that carbon materials surface in situ according to claim 2 generates nano-carbide coating, its
It is characterised by：In the oxide sol or gel of the doping, carbon in the precursor as reducing agent added
The mole of atom is 0.1 to 10 times of oxide molar amount in colloidal sol or gel.
4. the method that carbon materials surface in situ according to claim 1 generates nano-carbide coating, its
It is characterised by：Carbon materials described in step (2) is in carbon fiber, graphite, diamond and multi-walled carbon nanotube
One or more.
5. carbon materials surface in situ according to claim 1 generates the Preparation Method of nano-carbide coating,
It is characterized in that：The reducing agent used described in step (7) in in-situ reducing-carburizing reagent is carbon, carbon
Source include being applied the organic matter adulterated in the carbon of object carbon materials itself and/or colloidal sol or gel in height
Remaining carbon is cracked under the conditions of temperature.
6. carbon materials surface in situ according to claim 1 generates the Preparation Method of nano-carbide coating,
It is characterized in that：The composition of the nano-carbide coating be titanium carbide, carborundum, chromium carbide, vanadium carbide,
One or more in zirconium carbide, niobium carbide, ramet, molybdenum carbide, tungsten carbide and carbonization rhenium.
7. the standby side of the carbon materials surface in situ generation nano-carbide coating according to claim 1 or 6
Method, it is characterised in that：The thickness of the nano-carbide coating is 10~20nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610133960.4A CN107176604B (en) | 2016-03-10 | 2016-03-10 | A kind of method that carbon materials surface in situ generates nano-carbide coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610133960.4A CN107176604B (en) | 2016-03-10 | 2016-03-10 | A kind of method that carbon materials surface in situ generates nano-carbide coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107176604A true CN107176604A (en) | 2017-09-19 |
| CN107176604B CN107176604B (en) | 2019-08-02 |
Family
ID=59829995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610133960.4A Active CN107176604B (en) | 2016-03-10 | 2016-03-10 | A kind of method that carbon materials surface in situ generates nano-carbide coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107176604B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217629A (en) * | 2017-12-29 | 2018-06-29 | 西安理工大学 | A kind of preparation method of the compound CNTs of surface in situ generation nano SiC |
| CN109940162A (en) * | 2019-04-30 | 2019-06-28 | 西安理工大学 | A kind of preparation method of carbide In-sltu reinforcement titanium and its alloy porous bracket |
| CN110304628A (en) * | 2019-08-12 | 2019-10-08 | 南昌航空大学 | A method of controllable nano silica is prepared in diamond surface |
| CN111732448A (en) * | 2020-06-16 | 2020-10-02 | 璨隆科技发展有限公司 | Graphite crucible and preparation method thereof |
| CN112661507A (en) * | 2021-01-11 | 2021-04-16 | 湖南省美程陶瓷科技有限公司 | Alumina ceramic material for dual-function pressure sensor and preparation method thereof |
| CN114455586A (en) * | 2022-02-22 | 2022-05-10 | 合肥工业大学 | W-shaped steel plate2Rapid preparation method of C nanoparticles |
| CN114907144A (en) * | 2022-06-06 | 2022-08-16 | 吉林联科特种石墨材料有限公司 | Method for preparing SiC-C composite high-temperature coating by one-step method |
| TWI824212B (en) * | 2020-12-18 | 2023-12-01 | 遠東科技大學 | Method for forming carbide film on surface of graphite substrate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435503A (en) * | 2002-01-28 | 2003-08-13 | 西北工业大学 | Carbide coating of enhancing carbon/copper interface binding characteristic, and process thereof |
| CN101585534A (en) * | 2009-06-18 | 2009-11-25 | 西安交通大学 | Sol-gel method-based method for preparing composite nano diamond thin films |
| CN101792331A (en) * | 2010-01-04 | 2010-08-04 | 北京科技大学 | Microwave preparation method of anti-oxidation coating made of carbon-based material |
| CN102560291A (en) * | 2010-12-17 | 2012-07-11 | 中国科学院金属研究所 | Preparation method of metal-based composite material reinforcement surface nano coating |
| CN102677031A (en) * | 2012-05-18 | 2012-09-19 | 中国科学院上海硅酸盐研究所 | Metal/carbon nano composite porous membrane and preparation method thereof |
| CN103643481A (en) * | 2013-10-24 | 2014-03-19 | 上海交通大学 | Preparation method of alumina coating layer on carbon fiber surface |
-
2016
- 2016-03-10 CN CN201610133960.4A patent/CN107176604B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435503A (en) * | 2002-01-28 | 2003-08-13 | 西北工业大学 | Carbide coating of enhancing carbon/copper interface binding characteristic, and process thereof |
| CN101585534A (en) * | 2009-06-18 | 2009-11-25 | 西安交通大学 | Sol-gel method-based method for preparing composite nano diamond thin films |
| CN101792331A (en) * | 2010-01-04 | 2010-08-04 | 北京科技大学 | Microwave preparation method of anti-oxidation coating made of carbon-based material |
| CN102560291A (en) * | 2010-12-17 | 2012-07-11 | 中国科学院金属研究所 | Preparation method of metal-based composite material reinforcement surface nano coating |
| CN102677031A (en) * | 2012-05-18 | 2012-09-19 | 中国科学院上海硅酸盐研究所 | Metal/carbon nano composite porous membrane and preparation method thereof |
| CN103643481A (en) * | 2013-10-24 | 2014-03-19 | 上海交通大学 | Preparation method of alumina coating layer on carbon fiber surface |
Non-Patent Citations (2)
| Title |
|---|
| KEDONG XIA ET AL: "Preparation of anti-oxidative SiC/SiO2 coating on carbon fibers from vinyltriethoxysilane by sol–gel method", 《APPLIED SURFACE SCIENCE》 * |
| YIPING TANG ET AL: ""Improvement of interface between Al and short carbon fibers by a-Al2O3 coatings deposited by sol–gel technology"", 《CERAMICS INTERNATIONAL》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217629A (en) * | 2017-12-29 | 2018-06-29 | 西安理工大学 | A kind of preparation method of the compound CNTs of surface in situ generation nano SiC |
| CN108217629B (en) * | 2017-12-29 | 2019-07-23 | 西安理工大学 | A kind of preparation method of the compound CNTs of surface in situ generation nano SiC |
| CN109940162A (en) * | 2019-04-30 | 2019-06-28 | 西安理工大学 | A kind of preparation method of carbide In-sltu reinforcement titanium and its alloy porous bracket |
| CN110304628A (en) * | 2019-08-12 | 2019-10-08 | 南昌航空大学 | A method of controllable nano silica is prepared in diamond surface |
| CN111732448A (en) * | 2020-06-16 | 2020-10-02 | 璨隆科技发展有限公司 | Graphite crucible and preparation method thereof |
| TWI824212B (en) * | 2020-12-18 | 2023-12-01 | 遠東科技大學 | Method for forming carbide film on surface of graphite substrate |
| CN112661507A (en) * | 2021-01-11 | 2021-04-16 | 湖南省美程陶瓷科技有限公司 | Alumina ceramic material for dual-function pressure sensor and preparation method thereof |
| CN114455586A (en) * | 2022-02-22 | 2022-05-10 | 合肥工业大学 | W-shaped steel plate2Rapid preparation method of C nanoparticles |
| CN114455586B (en) * | 2022-02-22 | 2024-03-19 | 合肥工业大学 | W (W) 2 Rapid preparation method of C nano-particles |
| CN114907144A (en) * | 2022-06-06 | 2022-08-16 | 吉林联科特种石墨材料有限公司 | Method for preparing SiC-C composite high-temperature coating by one-step method |
| CN114907144B (en) * | 2022-06-06 | 2023-04-18 | 吉林联科特种石墨材料有限公司 | Method for preparing SiC-C composite high-temperature coating by one-step method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107176604B (en) | 2019-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107176604A (en) | A kind of method that carbon materials surface in situ generates nano-carbide coating | |
| CN107032816B (en) | Silicon carbide nanowire reinforced C/C-SiC-ZrB2Preparation method of ceramic matrix composite | |
| Li et al. | Preparation of a titanium carbide coating on carbon fibre using a molten salt method | |
| US7497918B2 (en) | Method of siliciding thermostructural composite materials, and parts obtained by the method | |
| CN105506579B (en) | A kind of preparation method of graphene coated silicon carbide nanometer line | |
| CN106083116B (en) | The method that one-step method prepares SiC ceramic matrix composite material cladding tubes | |
| CN109553430A (en) | A kind of SiC with compound interfacef/ SiC ceramic based composites and preparation method thereof | |
| CN108585897B (en) | Refractory metal high-temperature oxidation-resistant Si-Mo-YSZ coating and preparation method thereof | |
| EP2470472B1 (en) | Composite materials containing aligned nanotubes and the production thereof | |
| CN110357635A (en) | A method of improving carbon-based or ceramic matric composite surface oxidation-resistant coating bond strength | |
| KR100454715B1 (en) | MoSi2-Si3N4 COMPOSITE COATING AND MANUFACTURING METHOD THEREOF | |
| Ren et al. | Influence of HfC nanowires on the growth behavior, microstructure and ablation resistance of CVD-HfC coating | |
| CN103898499A (en) | Method for preparing SiC/Al2O3 coating by using precursor conversion method | |
| CN103265331A (en) | C/SiC/Na2SiO3 antioxidative compound coating suitable for graphite material and preparation method thereof | |
| CN116332678B (en) | Method for preparing tantalum carbide coating on surface of carbon material | |
| CN110304932B (en) | Preparation method of Cf/SiC composite material with HfB2 interface | |
| CN106631161B (en) | A method of composite coating resistant to high temperature oxidation is prepared on carbon-based material surface | |
| Dong et al. | Fabrication of protective tantalum carbide coatings on carbon fibers using a molten salt method | |
| Xu et al. | High-quality SiC-HfC coating with interpenetrating structure based on a two-step low temperature molten salt method | |
| Wang et al. | Ablation behaviors and mechanism of ZrC-SiC-Si/SiC-Si double-layered coatings on C/C composite under plasma flame at 3000° C | |
| CN112299882B (en) | In-situ preparation method of HfC-based ternary carbide gradient coating on surface of carbon material | |
| CN105669231B (en) | A kind of fibre reinforced MoSi2The preparation method of SiC ceramic based composites | |
| CN107311685A (en) | The preparation method of electrophoresis and thermal evaporation techniques fabricated in situ refractory carbide nano wire | |
| Liu et al. | Research progress on tantalum carbide coatings oncarbon materials | |
| CN102560291B (en) | Preparation method of metal-based composite material reinforcement surface nano coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |