CN104498899A - Method for inhibiting metal surface carbon deposition by using atomic layer deposition passivation layer - Google Patents
Method for inhibiting metal surface carbon deposition by using atomic layer deposition passivation layer Download PDFInfo
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- CN104498899A CN104498899A CN201410771681.1A CN201410771681A CN104498899A CN 104498899 A CN104498899 A CN 104498899A CN 201410771681 A CN201410771681 A CN 201410771681A CN 104498899 A CN104498899 A CN 104498899A
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Abstract
The invention discloses a method for inhibiting metal surface carbon deposition. The method eliminates carbon deposition formed by the catalytic action of a metal at a high temperature and prolongs the service life of a fluid system. The method mainly comprises the following steps: (1) connecting a to-be-passivated fluid system with an atomic layer deposition system gas path; (2) carrying out atomic layer deposition of inert compound on the inner wall of the fluid system, specifically comprising the following steps: injecting a first reaction precursor into a reaction chamber; and injecting a second reaction precursor after cleaning and then cleaning; and (3) repeating the operations and acquiring the passivation layer with required thickness by controlling the number of cycle periods. The method disclosed by the invention is high in degree of automation, good in repeatability, relatively low in process and free of damage to a substrate; in the deposition process, the thickness of the thin film is precise to control, a flow passage is easily prevented from being blocked, and the method is suitable for passivation processing the flow system which is expensive in price and complex in structure.
Description
Technical field
The present invention relates to the preparation method of a kind of metallic surface anti-carbon passivation layer, can be used for all kinds of carbon distribution at high temperature transporting the fluid system of hydrocarbon compound and suppress.
Background technology
The fuel delivery line of the engines such as aviation, automobile, steamer and heat exchanger components thereof is processed by heat-resistance stainless steel or superalloy, wherein containing a large amount of Fe, Cr, Ni isoreactivity metal component.At high temperature hydrocarbon fuel generates metallic carbide (NiC fast under the katalysis of active metal component
3, Fe
3c etc.), then form carbon distribution by series reaction.Because fuel delivery line caliber is tiny, can reduce further at nozzle place, even less in engine controls part, the carbon distribution of generation easily blocks fuel delivery line, nozzle and accurate valve member and reduces heat transfer efficiency, damage metal base, causes motor performance to decline.Adopt and metallic surface carbon distribution can be suppressed to generate at method isolation Fe, Cr, Ni isoreactivity metal component of metallic surface growth inert passivation layer and the contact of fuel oil, significant to the lifting power system operational life-span.Adopt Sol-gel method can generate SiO at stainless steel-based basal surface
2deng passivating coating, in aviation kerosene Pintsch process process, play inhibition of coke formation effect (Liu Qiaomei, the preparation of stainless steel surface inertia oxide film and anticoking capability research).But Sol-gel method complicated process of preparation, poor repeatability, there is the problem of uneven thickness in passivation layer, easily comes off at high temperature under high pressure.Patent CN102154625 A discloses the method for a kind of Thermochemical Decomposition deposition Si film, improves engine surface anti-carbon performance.The shortcoming of the method is that coatings growth temperature is too high, easily causes metal base and damages and increase its difficulty realized in engineering and cost.Patent CN200710058969.4 adopts the method for coating that the zeolite molecular sieve of carried noble metal is attached to inner wall of metal tube, isolate the contact of fuel and metal pipe-wall, improve the anti-carbon performance of system, and at a certain temperature katalysis is played to fuel-pyrolysis.But the molecular sieve of acidity can generate by catalysis carbon distribution equally, causes rapid catalyst deactivation, and this technology also exists coating and easily peels off, the unmanageable shortcoming of thickness.Except above-mentioned defect, above various passivation layer preparation method lacks the accurate control to passivation layer thickness; For the fluid path of complexity, these methods very easily cause microchannel to block, and therefore should not attempt on the entity engine involved great expense or heat exchanger components.
Summary of the invention
For the shortcomings and deficiencies that prior art exists, the object of the present invention is to provide a kind of method for effectively reducing metallic surface carbon distribution.Adopt ald (Atomic Layer Deposition is called for short ALD) technology to carry out thin film deposition in metallic surface, generate even, fine and close passivation layer, and accuracy controlling is carried out to passivation layer thickness.Metallic surface after transpassivation has the advantages such as anti-carbon, high temperature resistant, corrosion-resistant, resistance to erosion.
The present invention adopts following technical scheme to be achieved:
Utilize ald passivation layer to suppress a method for metallic surface carbon distribution, the method comprises the following steps:
Step one, will treat that passive metal is connected with atomic layer deposition system gas circuit, gas directly be flowed through and treat passivating metallic surfaces;
Step 2, passes into inert carrier gas and vacuumizes in atomic layer deposition system, and regulation system reaction chamber outlet valve makes cavity pressure be in negative pressure; And making reaction chamber temperature be in specified range by heating, specified range depends on deposited material category;
Step 3, in reaction chamber, inject the first precursors containing Al, Ti, Si element, the time is t
1; Pass into inert carrier gas and rinse excessive precursors and by product, the time is t
2; In reaction chamber, inject the second precursors, the time is t
3; Pass into inert carrier gas again and rinse unreacted the second precursors and by product, the time is t
4;
Step 4, repeats the step 3 of respective cycle number, until treating that passivating metallic surfaces generates the inert passivation layer of desired thickness.
In the present invention, described in treat that passivating metallic surfaces is that all kinds of being used at high temperature stores or transport the container of hydrocarbon compound or the inwall of pipeline, comprise miniature chemical reactor, interchanger, engine and appurtenances and length-to-diameter ratio up to 10
4and there is the fluid transport circuit of various complex geometric shapes.
Negative pressure described in step 2 is within the scope of 0.1-5000Pa usually; Range of reaction temperature depends on deposited material category, is usually within the scope of 30-450 DEG C; Inert carrier gas is nitrogen, helium or argon gas.
The precursors containing Al element described in step 3 is the one in trimethyl aluminium, triethyl aluminum, aluminum ethylate or aluminum chloride; Precursors containing Ti element is the one in titanium isopropylate, trimethyl carbinol titanium, titanium chloride, four (dimethyl amido) titanium, four (ethyl-methyl amido) titanium; Precursors containing Si element is the one in silicon tetrachloride, tetraethoxy, four different hydracid silicon, three different hydracid silica methane; The second precursors is deionized water, hydrogen peroxide, oxygen, ozone or NH
3in one.
Presoma injection length t described in step 3
1, t
3scope is 1-20s, carrier gas flush time t
2, t
4scope is 5-200s.
Described passivation layer consists of Al
2o
3, TiO
2, SiO
2, or TiN in one, and the complex thin film formed by two or more above-claimed cpd alternating deposit.
The circulating cycle issue of the step 3 described in step 4 is 1-10000.
The present invention's Advantageous Effects compared with prior art:
(1) ALD passivation layer even compact, namely the passivation layer of nanoscale has good carbon distribution and suppresses effect, very little on the heat-conductive characteristic impact of metal pipe-wall;
(2) ALD passivation layer and metal base are connected firmly, and do not peel off under high temperature and fluid scouring effect;
(3) ALD process temperature is lower, does not cause damage to substrate;
(4) ALD process passivation layer thickness controls accurately, not easily causes fluid channel to block, and is applicable to involving great expense, baroque fluid system carries out passivation processing;
(5) level of automation of the present invention is high, reproducible.
Accompanying drawing explanation
Fig. 1 is atomic layer deposition system schematic diagram of the present invention.
Fig. 2 is atomic layer deposition system gas circuit and the mode of connection schematic diagram being passivated metal tubes.
Fig. 3 is the XPS spectrum figure of the metal pipe internal wall through different oxide passivation.
Fig. 4 is the device schematic diagram of fuel-pyrolysis reaction (test of carbon distribution rejection).
Fig. 5 is the SEM photo on the metallic conduit surface of unpassivated.
Fig. 6 is the SEM photo of the metallic conduit area carbon of unpassivated.
Fig. 7 is the SEM photo of the metallic conduit inside generation carbon distribution of unpassivated.
Fig. 8 is 1500 cycle ALD Al
2o
3the SEM photo of inner wall of metal tube pattern after passivation.
Fig. 9 is 2000 cycle ALD TiO
2the SEM photo of inner wall of metal tube pattern after passivation.
Figure 10 is 1750 cycle ALD Al
2o
3/ SiO
2the SEM photo of inner wall of metal tube pattern after passivation.
Figure 11 is the SEM photo of inner wall of metal tube pattern after 500 cycle ALD TiN passivation.
Figure 12 is 1500 cycle ALD Al
2o
3the SEM photo of inner wall of metal tube carbon distribution pattern after passivation.
Figure 13 is 1500 cycle ALD Al
2o
3after passivation, metal tube inside generates the SEM photo of carbon distribution.
Embodiment
Below in conjunction with drawings and Examples, technical scheme of the present invention is described further.
Gas phase atomic layer deposition system (ALD system), is developed according to reference 1 by Xi'an Inst. of Modern Chemistry.Document 1:J.W.Elam, M.D.Groner, and S.M.George.Viscous flow reactor with quartz crystalmicrobalance for thin film growth by atomic layer deposition.Rev.Sci.Instrum, 2002,73 (8): 2981-2987.System schematic is see Fig. 1.Scanning electronic microscope (FEI Quanta 600FEG SEM).Electron Energy Disperse Spectroscopy (EDS).X-ray photoelectron power spectrum (Thermo Scientific K-Alpha XPS).
Below provide specific embodiments of the invention, it should be noted that the present invention is not limited to following specific embodiment, all equivalents done on technical scheme basis all fall into protection scope of the present invention.
Embodiment 1:
The present embodiment provides a kind of method utilizing ald passivation layer to suppress metallic surface carbon distribution, and the method specifically comprises the following steps:
Step one, be 2mm by internal diameter, length is that 1100mm metal tube immerses in acetone, cleans 40min and remove oil stain and impurity under ul-trasonic irradiation, the metal tube cleaned is connected in ALD system gas circuit by stationary installation (see Fig. 2), makes air-flow in system pass through metallic conduit;
Step 2, sealed reaction chamber, passes into nitrogen and vacuumizes in atomic layer deposition system, and regulate reaction chamber outlet valve to make cavity pressure control at 133Pa, reaction chamber temperature maintains 100 DEG C;
Step 3, in reaction chamber, inject the first reaction precursor trimethyl aluminium, the time is 8s; Pass into inert carrier gas cleaning unreacted the first reaction precursor and by product, the time is 40s.The second reaction precursor H is injected in reaction chamber
2o, the time is 8s; Pass into inert carrier gas again and clean unreacted the second reaction precursor and by product, the time is 40s;
Step 4, repeats the step 3 of 250 cycle lifies.
Through experimental verification, under the reaction conditions, Al
2o
3passivation layer growth velocity
/ cycle, therefore ALD aluminium oxide passivation layer thickness 24.5nm in embodiment 1.
Utilize XPS to deposited 250 cycle ALD Al in embodiment 1
2o
3inner wall of metal tube characterize, the results are shown in Figure of description 3.As shown in Figure 3, only there is Al, O, C element signal in spectrogram, metallic element Fe, Cr, Ni do not detected, ALD Al has been described
2o
3passivation layer is complete, fine and close, 250 cycle ALD Al
2o
3(thickness is 24.5nm) gets final product the metallic element of complete shielded-plate tube inwall.
Embodiment 2:
Identical with other condition of embodiment 1, repeat the Al in 1000 cycles
2o
3ald, generating thickness at inner wall of metal tube is the passivation layer of 98nm.
Embodiment 3:
Identical with other condition of embodiment 1, repeat the Al in 2000 cycles
2o
3ald, generating thickness at inner wall of metal tube is the passivation layer of 196nm.
Embodiment 4:
Identical with other condition of embodiment 1, repeat the Al in 1500 cycles
2o
3ald, generating thickness at inner wall of metal tube is the passivation layer of 147nm.
The Electron Energy Disperse Spectroscopy (EDS) adopting scanning electronic microscope to be equipped with measures the surface-element kind of inner wall of metal tube different positions in embodiment 4, the results are shown in table 1.Because the investigation depth of EDS to metal and metal oxide reaches micron order, therefore can the element kind that contains to the metal pipe-wall that ALD passivation layer and passivation layer cover of detection by quantitative and content.The Al constituent content recorded at tube wall different positions place can reflect the homogeneity of passivation layer.As shown in table 1, the Al constituent content recorded at metal tube import, middle part, exit inwall is basically identical, proves ALD Al
2o
3passivation layer has good uniformity.
The EDAX results of table 1 embodiment 1 ~ 4 metal tube
| Constituent content (wt%) | O | Al | Fe | Ni | Cr |
| Import | 58.53 | 26.57 | 9.55 | 0.86 | 3.84 |
| Middle part | 58.32 | 26.10 | 10.51 | 0.73 | 3.88 |
| Outlet | 58.14 | 25.54 | 10.70 | 0.11 | 4.32 |
Embodiment 5:
The present embodiment provides a kind of method utilizing ald passivation layer to suppress metallic surface carbon distribution, and the method specifically comprises the following steps:
Internal diameter is 2mm by step one, and length is that 1100mm metal tube immerses in acetone, cleans 40min and removes oil stain and impurity, be connected in ALD system gas circuit by clean metal tube, make airflow passes metallic conduit by stationary installation under ul-trasonic irradiation;
Step 2, sealed reaction chamber, passes into nitrogen and vacuumizes in atomic layer deposition system, regulates reaction chamber outlet valve that cavity pressure is controlled at 133Pa, and makes reaction chamber temperature be in 150 DEG C by heating; Heat presoma titanium isopropylate to 60 DEG C simultaneously;
Step 3, injects the first precursors titanium isopropylate in reaction chamber, and the time is 8s; Pass into inert carrier gas cleaning the first precursors unreacted and by product again, the time is 40s.The second precursors H is injected in reaction chamber
2o
2, the time is 8s; Pass into inert carrier gas again and clean unreacted the second precursors and by product, the time is 40s;
Step 4, repeats the step 3 of 1500 cycle lifies.
Through experimental verification, under the reaction conditions, TiO
2passivation layer growth velocity
/ cycle, therefore TiO in embodiment 5
2passivation layer thickness 75nm.
Utilize XPS to deposited 1500 cycle ALD TiO in embodiment 5
2inner wall of metal tube characterize, the results are shown in Figure of description 3.As shown in Figure 3, only there is Ti, O, C element signal in spectrogram, metallic element Fe, Cr, Ni do not detected, ALD TiO has been described
2passivation layer is complete, fine and close, shields the metallic element of inside pipe wall completely.
Embodiment 6:
The present embodiment provides a kind of method utilizing ald passivation layer to suppress metallic surface carbon distribution, and the method specifically comprises the following steps:
First the ALD Al in 1500 cycles is carried out according to the method for embodiment 4 and condition
2o
3passivation layer deposition, then makes reaction chamber temperature be in 60 DEG C, and in reaction chamber, inject the first precursors silicon chlorides and catalyst pyridine, the time is 8s simultaneously; Pass into inert carrier gas cleaning the first precursors unreacted and by product again, the time is 40s; Inject the second precursors H in reaction chamber simultaneously
2o and catalyst pyridine, the time is 8s; Pass into inert carrier gas again and clean unreacted the second precursors and by product, the time is 40s.Repeat the ALD SiO in 250 cycles
2passivation layer deposition, obtains Al
2o
3/ SiO
2layer compound passivation.
Through experimental verification, under the reaction conditions, SiO
2passivation layer growth velocity is
/ cycle, therefore SiO in embodiment 6
2passivation layer thickness is 33nm, Al
2o
3/ SiO
2layer compound passivation total thickness is 180nm.
Utilize XPS to deposited 1500 cycle ALD Al in embodiment 6
2o
3with 250 cycle ALD SiO
2inner wall of metal tube characterize, the results are shown in Figure of description 3.As shown in Figure 3, only occurred Si, O, C element signal in spectrogram, Al metallic element Fe, Cr, Ni not detected and previously deposited, illustrates Al
2o
3/ SiO
2layer compound passivation is complete, fine and close, shields the metallic element of inside pipe wall completely.
Embodiment 7:
The present embodiment provides a kind of method utilizing ald passivation layer to suppress metallic surface carbon distribution, and the method specifically comprises the following steps:
Step one, be 2mm by internal diameter, length is that 1100mm metal tube immerses in acetone, cleans 40min and remove oil stain and impurity under ul-trasonic irradiation, the metal tube (bundle) cleaned is connected in ALD system gas circuit by stationary installation, makes airflow passes metallic conduit;
Step 2, sealed reaction chamber, passes into nitrogen and vacuumizes in atomic layer deposition system, regulates reaction chamber outlet valve that cavity pressure is controlled at 133Pa, and makes reaction chamber temperature be in 160 DEG C by heating;
Step 3, in reaction chamber, inject the first precursors four (ethyl-methyl amido) titanium, the time is 8s; Pass into inert carrier gas cleaning the first precursors unreacted and by product again, the time is 40s.The second precursors NH is injected in reaction chamber
3, the time is 8s; Pass into inert carrier gas again and clean unreacted the second precursors and by product, the time is 40s;
Step 4, repeats the step 3 of 500 cycle lifies.
Through experimental verification, under the reaction conditions, TiN passivation layer growth velocity
/ cycle, therefore TiN passivation layer thickness 225nm in embodiment 7.
Comparative example 1:
Be 2mm by internal diameter, length is that the stainless steel tube of 1100mm immerses in acetone, cleans 40min and removes oil stain and impurity, be directly used in anti-carbon performance test by clean metal tube as reference sample under ul-trasonic irradiation.
Anti-carbon performance test experiment is carried out respectively to the metal tube in embodiment 1 ~ 7 and comparative example 1.Adopt the anticoking capability of fuel-pyrolysis reaction evaluating passivation layer, experimental installation schematic diagram as shown in Figure 4.Scission reaction chooses n-dodecane as test fuel, and temperature of reactor is 750 DEG C.Along with the carrying out of reaction, carbon distribution accumulates gradually in metal tube inside, causes system on-state rate to decline, and upstream and downstream pressure difference increases.The stopped reaction when pressure reduction reaches 4MPa, utilizes the anticoking capability of the time of systems stay work and the carbon deposition quantity assessment passivation layer of tube wall attachment.Experimental results is summed up in table 2.
Table 2 embodiment 1 ~ 7 and comparative example 1 metal tube test after EDAX results
| Embodiment | Carbon deposition quantity (mg)/working time (min) | Embodiment | Carbon deposition quantity (mg)/working time (min) |
| Embodiment 1 | 184.5mg/7min | Embodiment 5 | 150.2mg/10min |
| Embodiment 2 | 169.1/11min | Embodiment 6 | 212.0mg/18min |
| Embodiment 3 | 143.6mg/16min | Embodiment 7 | 171.7mg/11min |
| Embodiment 4 | 157.2mg/17min | Comparative example 1 | 188.6mg/2min |
Under condition is carried out in fuel-pyrolysis reaction, carbon distribution can be formed by tube wall metal catalyzing effect and Pintsch process two kinds of approach.In the starting stage of reaction, carbon distribution is formed mainly through the first approach and metal catalytic effect.The carbon distribution formed by metal catalytic effect is thread, is extended to moving phase direction by tube wall, and coking speed of response is very fast, and easily retains the carbon distribution carried in moving phase, very easily causes the rapid occlusion of fluid path.Namely the main purpose of metal surface passivation is suppress the formation of this type of carbon distribution.At higher temperatures, carbon distribution also can be formed in moving phase by scission reaction.The carbon distribution formed in this way is spherical, and can be attached to tube wall formation continuous print sheet carbon film gradually, causes fluid path to block gradually.The method of tube wall passivation cannot suppress the formation of this type of carbon distribution, therefore the working hour of impossible indefinite extension system.
As can be seen from the test result in table 2, after ALD Passivation Treatment, the anticoking capability of metal tube obtains and obviously promotes, and passivation layer can make System production time extend several times.Thickness is the ALD Al of about 150nm
2o
3and thickness is the Al of about 200nm
2o
3/ SiO
2layer compound passivation has best anti-carbon effect.After passivation layer thickness reaches about 150nm, increase passivation layer thickness further limited to carbon distribution inhibition.
The pattern of SEM to part metals pipe sample inwall, ALD passivation layer and generation carbon distribution is utilized to characterize.Fig. 5 is the primary morphology of the metal pipe-wall of unpassivated; Fig. 6 is the pattern of metal pipe-wall after scission reaction of unpassivated; Fig. 7 is the carbon distribution pattern generated in the metal tube of unpassivated.SEM characterization result shows, metal tube surface is coarse, there is a large amount of fold, pore space structure.In scission reaction, under the katalysis of metal species, tube wall surface generates a large amount of thread carbon distribution; The inner carbon distribution of metal tube forms primarily of the mixture of thread carbon distribution and spherical carbon distribution.Fig. 8, Fig. 9, Figure 10, Figure 11 are respectively and adopt ALD Al
2o
3(1500 cycle), TiO
2(2000 cycle), Al
2o
3/ SiO
2(1750 cycle), and the SEM photo of inner wall of metal tube surface topography after TiN (500 cycle) passivation.Result shows, ALD passivation layer can the small geometrical structure of covering metal inside pipe wall completely, is formed firmly be connected with tube wall, thus the thoroughly contact of metal component and fuel in isolation original substrate.Figure 12,13 is for being coated with ALD Al
2o
3the carbon distribution pattern that the inner wall of metal tube of (1500 cycle) passivation layer generates in the surface topography after scission reaction and this metal tube.After scission reaction, passivation layer is still complete is attached to tube wall surface.The contact of active metal component and fuel has been isolated in existence due to passivation layer, and tube wall surface does not exist the thread carbon distribution formed by metal catalytic effect; The carbon film being attached to passivation layer surface is made up of spherical carbon distribution completely, and the carbon distribution of metal tube inside is also all made up of the spherical carbon distribution formed in scission reaction.Above characterization result proves the contact that thoroughly can completely cut off active metal component in base material and hydrocarbon fuel at the ALD passivation layer of high length-diameter ratio metal pipe internal surface deposition, at high temperature has effective restraining effect to the thread carbon distribution formed by metal catalytic effect.
Claims (12)
1. utilize ald passivation layer to suppress a method for metallic surface carbon distribution, it is characterized in that comprising the following steps:
Step one, will treat that passive metal is connected with atomic layer deposition system gas circuit, gas directly be flowed through and treat passivating metallic surfaces;
Step 2, passes into inert carrier gas and vacuumizes in atomic layer deposition system, and regulation system reaction chamber outlet valve makes cavity pressure be in negative pressure; And making reaction chamber temperature be in specified range by heating, specified range depends on deposited material category;
Step 3, in reaction chamber, inject the first precursors containing Al, Ti, Si element, the time is t
1; Pass into inert carrier gas and rinse excessive precursors and by product, the time is t
2; In reaction chamber, inject the second precursors, the time is t
3; Pass into inert carrier gas again and rinse unreacted the second precursors and by product, the time is t
4;
Step 4, repeats the step 3 of respective cycle number, until treating that passivating metallic surfaces generates the inert passivation layer of desired thickness.
2. utilize ald passivation layer to suppress the method for metallic surface carbon distribution as claimed in claim 1, it is characterized in that the inert carrier gas described in step 2 is nitrogen, helium or argon gas.
3. utilize ald passivation layer to suppress the method for metallic surface carbon distribution as claimed in claim 1, it is characterized in that the negative pressure described in step 2 is within the scope of 0.1-5000Pa.
4. utilize ald passivation layer to suppress the method for metallic surface carbon distribution as claimed in claim 1, it is characterized in that the temperature specified range described in step 2 is in 30-450 DEG C.
5. utilize ald passivation layer to suppress the method for metallic surface carbon distribution as claimed in claim 1, it is characterized in that the precursors containing Al element described in step 3 is the one in trimethyl aluminium, triethyl aluminum, aluminum ethylate or aluminum chloride.
6. utilize ald passivation layer to suppress the method for metallic surface carbon distribution as claimed in claim 1, it is characterized in that the precursors containing Ti element described in step 3 is the one in titanium isopropylate, trimethyl carbinol titanium, titanium chloride, four (dimethyl amido) titanium, four (ethyl-methyl amido) titanium.
7. utilize ald passivation layer to suppress the method for metallic surface carbon distribution as claimed in claim 1, it is characterized in that the precursors containing Si element described in step 3 is the one in silicon tetrachloride, tetraethoxy, four different hydracid silicon, three different hydracid silica methane.
8. utilize ald passivation layer to suppress the method for metallic surface carbon distribution as claimed in claim 1, it is characterized in that the second precursors described in step 3 is deionized water, hydrogen peroxide, oxygen, ozone or NH
3in one.
9. utilize ald passivation layer to suppress the method for metallic surface carbon distribution as claimed in claim 1, it is characterized in that the precursor injection length t described in step 3
1, t
3scope is 1-20s, carrier gas flush time t
2, t
4scope is 5-200s.
10. utilize ald passivation layer to suppress the method for metallic surface carbon distribution as claimed in claim 1, it is characterized in that the circulating cycle issue of the step 3 described in step 4 is 1-10000.
11. utilize ald passivation layer to suppress the method for metallic surface carbon distribution as claimed in claim 1, treat that passivating metallic surfaces is that all kinds of being used at high temperature stores or transport the container of hydrocarbon compound or the inwall of pipeline described in it is characterized in that.
12. utilize ald passivation layer to suppress the method for metallic surface carbon distribution as claimed in claim 12, it is characterized in that described container or pipeline be miniature chemical reactor, interchanger, engine and appurtenances and length-to-diameter ratio are 10
4and there is the fluid transport circuit of various complex geometric shapes.
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