CN109468614A - A kind of surface anti-coking nano compound film and preparation method thereof - Google Patents

A kind of surface anti-coking nano compound film and preparation method thereof Download PDF

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CN109468614A
CN109468614A CN201811496605.9A CN201811496605A CN109468614A CN 109468614 A CN109468614 A CN 109468614A CN 201811496605 A CN201811496605 A CN 201811496605A CN 109468614 A CN109468614 A CN 109468614A
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film
coking
layer
tio
wall
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CN109468614B (en
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马大衍
朱昌发
刘小勇
马会民
郭金鑫
胡申林
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Xian Jiaotong University
Beijing Power Machinery Institute
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Xian Jiaotong University
Beijing Power Machinery Institute
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment

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  • Chemical Vapour Deposition (AREA)
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Abstract

The invention discloses a kind of surface anti-coking nano compound films and preparation method thereof.Inner wall using technique for atomic layer deposition in stainless steel tube deposits one layer of 50nm thickness Al2O3Film；To Al2O3Stainless steel tube after coating film treatment is annealed at 500 DEG C；Stainless steel tube after annealing deposits 200nm thickness TiO with technique for atomic layer deposition2Film.Compound structure film prepared by the present invention is with bottom Al2O3Film prevents infiltration of the carbon to matrix, as barrier layer with TiO2Film coated inner wall of the pipe surface, reduces the catalytic action of active element, to reduce pipeline carbon distribution with compound structure film.Present invention could apply to the various pipe material inner walls such as the round tube of different bores, square tube, shape tube, preparation process is simple, it is easy to accomplish.For improving the anti-coking performance of pipeline, the stability and service life for promoting engine is of great significance the present invention.

Description

A kind of surface anti-coking nano compound film and preparation method thereof
Technical field
The present invention relates to the laminated films for improving matrix surface anti-coking performance, and in particular to a kind of TiO2/Al2O3Nanometer Compound structure film and preparation method thereof can be applied to the various pipe material inner walls such as round tube, square tube, shape tube of different bores.
Background technique
The reason of engine breakdown, generally comprises two aspects: 1) the long-time abrasion of the accessories such as engine gear； 2) carbon distribution that fuel system generates.And inspection often subtle the engine failure as caused by carbon distribution；In engine operation When, the high-carbon such as fuel oil or combustion gas organic compound or mixture enter combustion chamber, pyrolysis oxidization occurs under the action of high temperature, Toughness substance is resolved into, and is adhered to the inner wall surface of engine operation.These toughness substances fire fuel and lubricating oil Burn the salt generated after the carbonaceous sediment generated, the leaded object that gasoline anti-knock agent generates, the combustion of sulfur in fuel with metal, profit The silicides such as the dust and sand that metal oxide, the air formed after metallic addition burning in lubricating oil carries, engine component mill Disfigurement at metal fillings and its compound etc. be adhered to above it, as the impurity of adherency is constantly superimposed, finally at high temperature by Layer charing, forms carbon distribution.
In current engine high-temperature fuel channel, anticoking capability mainly is improved using following several method: 1) being existed The heat sink performance for promoting fuel in fuel using the doping of element, reduces coking；2) passivating coating (example is prepared in inner wall of the pipe Such as SiO2Deng), the catalytic action of base activated element is reduced, carbon distribution is reduced, and then promotes anticoking capability.
For film anti-coking, chemical vapor deposition (CVD) process requirement is completed at 500 DEG C or more, higher temperature The damage spent to matrix is larger, and in inner wall of the pipe deposition film, cannot guarantee the quality of film layer well.Atomic layer Deposition (ALD) technology makes full use of surface saturated reaction (surface saturation reactions), has thickness control It is little to the variation of temperature and reactant flux with the stability of height.Obtained film purity, density are high, smooth, and Shape-retaining ability is high, can also realize good stepcoverage even for the vertical wide structure than up to 100:1.Most techniques of ALD can be with It is carried out in 400 DEG C of following temperature, it is possible to reduce the damage to matrix.
Chinese patent CN104498899A discloses " a kind of to inhibit metal surface carbon distribution using atomic layer deposition passivation layer Method ", wherein the passivation layer disclosed is Al2O3Layer, TiO2Layer or Al2O3/SiO2Composite construction layer, using ALD technique deposition At overall thickness is in 150nm or so, not more than 225nm.Disadvantage is that: 1) Pintsch process can not be generated Spherical carbon distribution effectively obstructs, and is only the formation speed for reducing tube wall carbon distribution to a certain extent, can not effectively avoid carbon distribution Occur, is not suitable for fuel engines high temp oil-fired metal tube operating condition；2) active atoms of carbon under high temperature is not secondly can effectively prevent Enter matrix along grain boundary, and then destroys matrix.3) for the original of the surface with certain radian, especially inner wall of the pipe Sublayer deposition still lacks further investigation, for example, for oxides coating, if atomic layer deposition state modulator is improper, Effective film layer can not be formed.
Summary of the invention
The purpose of the present invention is to provide a kind of surface anti-coking nano compound films and preparation method thereof.
In order to achieve the above objectives, the invention adopts the following technical scheme:
A kind of surface anti-coking nano compound film, the laminated film include the nanoscopic barrier being arranged on matrix surface And the nanometer anti-carbon layer on nanoscopic barrier is set.
Preferably, the nanoscopic barrier and nanometer anti-carbon layer are made of the stable material of chemical property.
Preferably, the Al that the nanoscopic barrier is selected from a thickness of 40~60nm2O3Film layer, nanometer anti-carbon layer choosing is certainly With a thickness of the TiO of 180~220nm2Film layer.
Preferably, the Al2O3Film layer is γ-Al2O3Non-crystal structure.
Preferably, the nanoscopic barrier and nanometer anti-carbon layer are successively uniform using Atomic layer deposition method, complete It is covered on matrix.
Preferably, described matrix is selected from metal (for example, stainless steel) pipeline.
Preferably, the laminated film is located at inner wall of the pipe.
The preparation method of above-mentioned surface anti-coking nano compound film, comprising the following steps:
1) nanoscopic barrier is prepared in matrix surface；
2) nanometer anti-carbon layer is prepared on nanoscopic barrier.
Preferably, the step 1) specifically includes the following steps:
The Al that a layer thickness is 40~60nm is deposited in matrix surface with Atomic layer deposition method2O3Film；To obtained Al2O3Film is made annealing treatment.
Preferably, in the step 1), in the presoma that atomic layer deposition uses, source metal be selected from halide containing aluminium, Alkoxide containing aluminium, the dione compounds containing aluminium, the organo-metallic compound (for example, trimethyl aluminium) containing aluminium, oxygen source are selected from peroxide Change hydrogen, water, atomic layer deposition reaction chamber background air pressure is 200~400mtorr, and depositing temperature is 150~300 DEG C.
Preferably, the halide containing aluminium, the alkoxide containing aluminium, the dione compounds containing aluminium, the organometallic containing aluminium The injection length of object is closed as 0.1~5s, the injection length of hydrogen peroxide or water is 0.1~1s, when carrier gas (for example, nitrogen) is rinsed Between for >=20s, cycle period is 500~1000.
Preferably, the step 2) specifically includes the following steps: with Atomic layer deposition method nanoscopic barrier (for example, The above-mentioned Al by annealing2O3Film) on preparation a layer thickness be 180~220nm TiO2Film.
Preferably, in the step 2), atomic layer deposition use presoma in, source metal be selected from titaniferous halide, The alkoxide of titaniferous, the dione compounds of titaniferous, titaniferous organo-metallic compound (for example, titanium tetraisopropylate), oxygen source was selected from Hydrogen oxide, water, atomic layer deposition reaction chamber background air pressure are 200~400mtorr, and depositing temperature is 150~250 DEG C.
Preferably, the organometallic of the halide of the titaniferous, the alkoxide of titaniferous, the dione compounds of titaniferous, titaniferous The injection length of object is closed as 0.1~5s, the injection length of hydrogen peroxide or water is 0.1~1s, when carrier gas (for example, nitrogen) is rinsed Between for >=30s, cycle period is 1500~2500.
Preferably, the condition of the annealing are as follows: in 450~550 DEG C of 20~40min of heat preservation under vacuum.
Preferably, described matrix is selected from metal (for example, stainless steel) pipeline, in the pipeline wall surface depositing Al2O3Before film, The pipeline is cleaned by ultrasonic.
Above-mentioned surface anti-coking nano compound film can reduce the carbon distribution and/or drop of inner wall of metal tube in high temperature oil transportation It is applied in low metal tube wall temperature.
The beneficial effects of the present invention are embodied in:
Nanostructure laminated film provided by the invention can be prevented effectively using carbon spread barrier layer and anti-carbon layer Carbon is penetrated into matrix, is reduced carbon distribution, is achieved the purpose that matrix anti-coking.Also, preparation process of the present invention is simple, is easy to real It is existing.The present invention improves the anti-coking performance of pipeline, promotes the stability and service life of engine for the carbon distribution of reduction pipeline It is of great significance.
Further, the present invention utilizes Al2O3And TiO2There is a higher chemical stability, heat-resisting ability is strong and atom γ-the Al that layer deposition (ALD) generates2O3For non-crystal structure, infiltration of the carbon to matrix, TiO can be effectively prevented2Film is also Solves Al2O3The film deficiency poor to the catalytic action effect for reducing active element, and improve matrix surface passivating film Smooth degree, anti-coking performance are obviously improved.
Further, the present invention utilizes technique for atomic layer deposition, and prepared nanostructure laminated film is applied to difference The quality of inner wall of the pipe film can be effectively ensured in the various pipe material inner walls such as round tube, square tube, the shape tube of bore, promote resistive connection Burnt performance.
Further, the present invention for presoma in atomic layer deposition (especially oxygen source) injection length, and deposition The multiple parameters such as background air pressure, temperature carried out it is a large amount of experiment grope, ensure that inner wall of the pipe deposit to be formed it is uniform, complete Whole, fine and close plated film.
Detailed description of the invention
Fig. 1 is atomic layer deposition apparatus；Wherein: 1-C3H9Al storage tank, 2-H2O2Storage tank, 3-C12H28O4Ti storage tank, 4- resistive heater, 5- vacuum mechanical pump, T- temperatuer detector, P- pressure detecting meter.
Fig. 2 is sample topography after coking test；Wherein: (a) Al2O3/TiO2Plated film tube, (b) non-plated film tube.
Fig. 3 is sample topography under light microscopic after coking test；Wherein: (a) Al2O3/TiO2Plated film tube, (b) non-plated film tube.
Fig. 4 is sample topography under scanning electron microscope after coking test；Wherein: (a) Al2O3/TiO2Plated film tube, (b) non-plated film Pipe.
Fig. 5 a is Al2O3/TiO2The EDS of plated film tube inner wall of the pipe to exterior line scanning C scheme.
Fig. 5 b is the EDS figure that non-plated film tube inner wall of the pipe to exterior line scans C.
Fig. 6 is Al2O3/TiO2The pattern of plated film tube coking.
Fig. 7 is Al2O3/TiO2Plated film tube and non-plated film tube wall temperature comparison diagram.
Fig. 8 is Al2O3/TiO2Composite construction transmission electron microscope picture.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
(1) the nano composite structure film design of inner wall of the pipe anti-coking performance is improved
It is found according to experiment, product existing for connector (for example, bilateral) surface of engine pipeline or the different pipelines of connection Some is that fuel oil is formed by radical reaction at high temperature to carbon, and this kind of carbon distribution is rendered as spherical shape on microcosmic, with The filiform that the active element as contained by matrix (referring specifically to the metallic matrixes such as pipeline, bilateral) (elements such as Fe, Ni and Cr) catalysis generates There are significant differences for carbon distribution.
The present invention prepares Al in matrix surface (for example, inner wall of the pipe)2O3/TiO2Nano composite structure film is realized to pipe The Passivation Treatment of road inner wall.The compound structure film is with Al2O3Film is bottom, can hinder the infiltration of carbon, protects matrix；With TiO2Film is surface layer, it is possible to reduce carbon distribution is (by TiO2Film coated is made in inner wall of the pipe surface, the catalysis for reducing active element With, and coarse tube wall is become fine and close smooth, it is not easy to adhere to).
(2) Al is prepared in inner wall of the pipe2O3/TiO2Nano composite structure film
The Al2O3/TiO2Nano composite structure film mainly uses atomic layer deposition (ALD) method to prepare, first in pipe Road inner wall depositing Al2O3Film；ALD grows Al2O3Film is island growth mode, Al2O3Film is after annealing, and lower point of high temperature The warm-up movement of son is reinforced, and the lesser island in surface starts to merge, and then surface becomes more smooth, and roughness reduces, and surface is more Add smooth.Again in Al2O3ALD deposition TiO is used on film2Film.
Using pipe range 1500mm, internal diameter 2mm, wall thickness 1mm 316 stainless steel tubes as sample cell, the Al that is prepared using ALD2O3 Film with a thickness of 50nm, TiO2Film with a thickness of 200nm.ALD equipment used as shown in Figure 1, control valve 1# in deposition Length is opened, so that the high pure nitrogen (N being connect by Trunk Line with reaction chamber left end2) storage tank provide deposition process needed for carrier gas With flushing gas, maintaining the air pressure of reaction chamber background with high pure nitrogen is 360mtorr；First presoma is trimethyl aluminium (C3H9Al), By being connected to Trunk Line and C3H9Control valve 8# and 9# control between Al storage tank 1；Second presoma is hydrogen peroxide (H2O2), By being connected to Trunk Line and H2O2Control valve 3# control between storage tank 2；Third presoma is titanium tetraisopropylate (C12H28O4Ti), by being connected to Trunk Line and C12H28O4Control valve 5# and 10# control between Ti storage tank 3.
Al2O3/TiO2The specific preparation process of nano composite structure film is as follows:
1) stainless steel tube (sample cell) is put into industrial ultrasonic machine and is cleaned up, acetone and alcohol is respectively adopted as cleaning Agent, every kind of cleaning agent cleaning are dried after ten minutes.Acetone can effectively remove grease stain and impurity in sample cell, and acetone can be with It dissolves each other with alcohol, alcohol washes can remove extra acetone, and drying can make extra alcohol volatilize.
2) stainless steel tube after ultrasonic cleaning is put into reaction chamber, the vacuum mechanical pump 5 that will be connect with reaction chamber right end It opens, reaction chamber is vacuumized, make the pressure of reaction chamber lower than 20mtorr, vacuum mechanical pump 5 is kept to open.
3) reaction chamber heating device (for example, being wound in the resistive heater 4 on the outside of reaction chamber) is opened, makes reaction chamber temperature It is maintained at 250 DEG C.
4) ALD equipment technological parameter is adjusted, the Al of 500 loop cycles is deposited2O3Film layer
Circulation: 1sec (injection) is opened referring to Fig. 1, control valve 9#, is spaced 1.5sec, then control valve 8# opens 1sec； Reaction chamber 20sec is rinsed, completes first step A1 at this time；Control valve 3# opens 0.3sec；Reaction chamber 45sec is rinsed, is completed Second step A2；Then first step A1 is reentered；
Recycled for 500 periods, wherein depositing temperature is 250 DEG C.
5) Al will be deposited with2O3The stainless steel tube of film layer is put into tubular annealing furnace, is annealed at 500 DEG C, in annealing process It is protected using argon gas, the flow of argon gas is 1sccm, vacuum degree 15Pa, keeps the temperature 30min.Furnace cooling after annealing is completed, to furnace temperature Lower than 200 DEG C, stainless steel tube is taken out.
6) stainless steel tube after making annealing treatment is reentered into the reaction chamber of ALD equipment, repeats vacuumizing for step 2)；It beats Opening drying box and keeping third forerunner temperature is 40 DEG C, and reaction chamber temperature is then maintained at 150 DEG C according to step 3).
7) ALD equipment technological parameter is adjusted, the TiO of 1500 loop cycles is deposited2Film layer
Circulation: 1.5sec is opened referring to Fig. 1, control valve 10#, is spaced 5sec, then control valve 5# opens 1.5sec (note Enter)；Reaction chamber 30sec is rinsed, completes first step B1 at this time；Control valve 3# opens 0.3sec；Reaction chamber 80sec is rinsed, Complete second step B2；Then first step B1 is reentered；
Recycled for 1500 periods, wherein depositing temperature is 150 DEG C.
Fig. 4 shows Al2O3/TiO2Nano composite structure film improves the roughness of inner wall of the pipe well, wraps up in entire Wall, the anti-coking performance of riser tubing；For the ease of observing the THIN COMPOSITE prepared under the conditions of process above under transmission electron microscope The structure of film prepares Al on matrix (silicon wafer)2O3/TiO2Nano compound film.As shown in figure 8, obviously being seen under transmission electron microscope Al on matrix out2O3And TiO2Film layer shows that Al can be prepared under the conditions of present invention process2O3/TiO2Nano compound film.
8) stainless steel tube passes through above step 1)-step 7) i.e. completion Passivation Treatment, coking survey is then carried out at high temperature Examination.
(3) inner wall of the pipe coking is tested
Using stainless steel tube as test object, it is directed to Al respectively2O3/TiO2Plated film tube (is deposited with Al2O3/TiO2Nanometer is multiple Close the stainless steel tube of structural membrane) and non-plated film light pipe, using 851-2 type fluid fuel, inside pipe wall burns at 800 DEG C of progress Heat sink experiment, burning time stablize 20 minutes.The Al shown according to fig. 22O3/TiO2Plated film inside pipe wall and non-plated film light pipe inner wall Pattern, inner wall of the pipe remains less carbon after Passivation Treatment, and color is shallower；Fig. 3 boxed area is the feelings of inner wall of the pipe carbon distribution Condition finds Al2O3/TiO2Nano composite structure film effectively reduces the carbon distribution of inner wall of the pipe, does not find the generation of Filamentous carbon, A small amount of spherical carbon is generated on the surface of film, as shown in Figure 6.Compare Fig. 5 a, Fig. 5 b, shows Al2O3/TiO2It is nano combined thin Film effectively prevents the infiltration of carbon in inner wall of the pipe to outer wall direction.
Experimental result also shows (Fig. 7), heating and 800 DEG C of insulating processes, Al2O3/TiO2Nano compound film makes tube wall temperature Degree is significantly lower than non-plated film tube.
The experimental results showed that the present invention effectively prevents fuel oil high-temp combustion outside the coking of inside pipe wall, reduction metal tube Wall temperature.
The present invention deposits one layer of passivating film (i.e. Al by the inner wall in engine pipelines2O3/TiO2Nano composite structure is thin Film), the phenomenon that carbon distribution can be significantly reduced, prevents pipeline because clogged with soot has suitable for high temp oil-fired operating condition in harsh pipe In the service life for helping improve liquid fuel motor, guarantee the steady operation of engine.The present invention can different bores round tube, The inner wall of the various tubing such as square tube, shape tube completes thin-film-coating, Al2O3And TiO2Nanometer layer is complete, it is elongated uniformly to cover Inner wall of the pipe surface.The present invention can apply in the exploitation of high-performance fuel engine oil tube.

Claims (10)

1. a kind of surface anti-coking nano compound film, it is characterised in that: the laminated film includes being arranged on matrix surface Nanoscopic barrier and the nanometer anti-carbon layer being arranged on nanoscopic barrier.
2. a kind of surface anti-coking nano compound film according to claim 1, it is characterised in that: the nanoscopic barrier choosing From the Al with a thickness of 40~60nm2O3Film layer, nanometer anti-carbon layer choosing is certainly with a thickness of the TiO of 180~220nm2Film layer.
3. a kind of surface anti-coking nano compound film according to claim 2, it is characterised in that: the Al2O3Film layer is γ-Al2O3Non-crystal structure.
4. a kind of surface anti-coking nano compound film according to claim 1, it is characterised in that: the nanoscopic barrier and Nanometer anti-carbon layer is successively uniform using Atomic layer deposition method, is completely covering on matrix.
5. a kind of surface anti-coking nano compound film according to claim 4, it is characterised in that: described matrix is selected from metal Pipeline.
6. a kind of surface anti-coking nano compound film according to claim 5, it is characterised in that: the laminated film is located at Inner wall of the pipe.
7. a kind of preparation method of anti-coking nano compound film in surface as described in claim 1, it is characterised in that: including with Lower step:
1) nanoscopic barrier is prepared in matrix surface；
2) nanometer anti-carbon layer is prepared on nanoscopic barrier.
8. preparation method according to claim 7, it is characterised in that: the step 1) is specifically includes the following steps: with original Sublayer deposition method deposits the Al that a layer thickness is 40~60nm in matrix surface2O3Film, then to Al obtained2O3Film It is made annealing treatment；The step 2) is specifically includes the following steps: with Atomic layer deposition method in the Al by annealing2O3 The TiO that a layer thickness is 180~220nm is prepared on film2Film.
9. preparation method according to claim 8, it is characterised in that: in the step 1), before atomic layer deposition uses Drive that body is halide, alkoxide, dione compounds or organo-metallic compound containing aluminium and hydrogen peroxide or water, background air pressure are 200~400mtorr, depositing temperature are 150~300 DEG C；The halide containing aluminium, alkoxide, dione compounds or organic metal The injection length of compound is 0.1~5s, and the injection length of hydrogen peroxide or water is 0.1~1s, cycle period is 500~ 1000；The condition of the annealing are as follows: in 450~550 DEG C of 20~40min of heat preservation under vacuum；In the step 2), atomic layer The presoma that uses is deposited as the halide of titaniferous, alkoxide, dione compounds or organo-metallic compound and hydrogen peroxide or water, Background air pressure is 200~400mtorr, and depositing temperature is 150~250 DEG C；Halide, alkoxide, the dione compounds of the titaniferous Or the injection length of organo-metallic compound is 0.1~5s, the injection length of hydrogen peroxide or water is 0.1~1s, cycle period It is 1500~2500.
10. a kind of anti-coking nano compound film in surface as described in claim 1 reduce inner wall of metal tube carbon distribution and/or Reduce the application in metal tube wall temperature.
CN201811496605.9A 2018-12-07 2018-12-07 Surface anti-coking nano composite film and preparation method thereof Active CN109468614B (en)

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