CN104498899B - A kind of method that utilization ald passivation layer suppresses metal surface carbon distribution - Google Patents
A kind of method that utilization ald passivation layer suppresses metal surface carbon distribution Download PDFInfo
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Abstract
The invention discloses a kind of method of suppression metal surface carbon distribution.The carbon distribution for being acted on and being formed by metal catalytic under high temperature is this method eliminates, extends the service life of fluid system.Have main steps that：(1) fluid system to be passivated is attached with atomic layer deposition system gas circuit；(2) fluid system inwall carries out inert compound ald, concretely comprises the following steps：The first precursors is injected into reaction chamber；Second of precursors is injected after cleaning, then is cleaned；(3) circulation performs aforesaid operations, by controlling circulating cycle issue to obtain the passivation layer of required thickness.Automaticity of the present invention is high, reproducible；Process temperature is relatively low, does not cause damage to substrate；Deposition process plastics thickness control is accurate, and fluid passage obstruction is not easily caused, it is adaptable to involving great expense, baroque fluid system be passivated processing.
Description
Technical field
The present invention relates to a kind of preparation method of metal surface anti-carbon passivation layer, hydrocarbon is transported at high temperature available for all kinds of
The carbon distribution of the fluid system of class compound suppresses.
Background technology
The fuel delivery line of the engines such as aviation, automobile, steamer and its heat exchanger components is by heat-resistance stainless steel or high temperature
Alloy is processed, wherein containing a large amount of Fe, Cr, Ni isoreactivity metal components.Hydrocarbon fuel is in active metal group at high temperature
Metal carbides (NiC is quickly generated under the catalytic action divided3、Fe3C etc.), carbon distribution is then formed by series reaction.Due to
Fuel delivery line caliber is tiny, can further be reduced at nozzle, even more small in engine control system part, generation
Carbon distribution easily blocks fuel delivery line, nozzle and accurate valve member and reduces heat transfer efficiency, damages metallic substrates, causes to start
Machine hydraulic performance decline.Using method isolation Fe, Cr, Ni isoreactivity metal component and fuel oil that inert passivation layer is grown in metal surface
Contact can suppress the generation of metal surface carbon distribution, it is significant to the lifting power system operational life-span.Using Sol-gel
Method can generate SiO in stainless steel substrate surface2Deng passivating coating, inhibition of coke formation is played during aviation kerosine Pintsch process
Effect (Liu Qiaomei, the oxidation film preparation of stainless steel surfaces inertia and anticoking capability research).But Sol-gel methods preparation technology is answered
Miscellaneous, poor repeatability, the problem of passivation layer has uneven thickness easily comes off at high temperature under high pressure.Patent CN102154625 A are public
A kind of method that Thermochemical Decomposition deposits Si films has been opened, engine surface anti-carbon performance is improved.The shortcoming of this method is to apply
Layer growth temperature is too high, and easily metallic substrates are caused to damage and increased with its difficulty and cost for being realized in engineering.Patent
The zeolite molecular sieve of carried noble metal is attached to inner wall of metal tube by CN200710058969.4 using the method for coating, is isolated
Contact of the fuel with metal pipe-wall, improves the anti-carbon performance of system, and plays catalysis to fuel-pyrolysis at a certain temperature
Effect.But acid molecular sieve can equally be catalyzed carbon distribution generation, cause rapid catalyst deactivation, and the technology there is also
Coating is easily peeled off, the unmanageable shortcoming of thickness.In addition to drawbacks described above, any of the above passivation layer preparation method lacks to passivation layer
The accurate control of thickness；For complicated fluid path, these methods easily cause microchannel to block, therefore should not be high in cost
Attempted on expensive entity engine or heat exchanger components.
The content of the invention
The shortcomings and deficiencies existed for prior art, are used to effectively reduce metal it is an object of the invention to provide one kind
The method of area carbon.Using ald (Atomic Layer Deposition, abbreviation ALD) technology in metal surface
Thin film deposition, uniform, the fine and close passivation layer of generation are carried out, and accuracy controlling is carried out to passivation layer thickness.Gold after transpassivation
Metal surface has the advantages that anti-carbon, high temperature resistant, corrosion-resistant, resistance to erosion.
The present invention, which is adopted the following technical scheme that, to be achieved：
A kind of method that utilization ald passivation layer suppresses metal surface carbon distribution, this method comprises the following steps：
Step one, it will treat that passive metal is connected with atomic layer deposition system gas circuit, make gas directly through treating passive metal
Surface；
Step 2, inert carrier gas is passed through into atomic layer deposition system and is vacuumized, regulating system reaction chamber outlet valve
Cavity pressure is set to be in negative pressure；And reaction chamber temperature is in particular range by heating, particular range depends on being deposited
Material category；
Step 3, the first precursors containing Al, Ti, Si element are injected into reaction chamber, and the time is t1；It is passed through lazy
Property carrier gas rinse excessive precursors and accessory substance, the time is t2；Second of precursors is injected into reaction chamber, when
Between be t3；Inert carrier gas is passed through again and rinses unreacted second of precursors and accessory substance, and the time is t4；
Step 4, repeats the step three of respective cycle number, until the thickness needed for passivating metallic surfaces generation is treated
Inert passivation layer.
It is described to treat that passivating metallic surfaces be used to storing or transporting hydrocarbon compound at high temperature to be all kinds of in the present invention
The inwall of container or pipeline, including miniature chemical reactor, heat exchanger, engine and appurtenances and draw ratio are up to 104
And the fluid transport circuit with various complex geometric shapes.
Negative pressure described in step 2 is generally in the range of 0.1-5000Pa；Range of reaction temperature depends on what is deposited
Material category, is generally in the range of 30-450 DEG C；Inert carrier gas is nitrogen, helium or argon gas.
The precursors of the element containing Al described in step 3 are trimethyl aluminium, triethyl aluminum, aluminium ethoxide or three
One kind in aluminium chloride；The precursors of the element containing Ti are isopropyl titanate, tert-butyl alcohol titanium, titanium chloride, four (dimethyl amidos)
One kind in titanium, four (ethyl-methyl amido) titaniums；The precursors of the element containing Si are silicon tetrachloride, tetraethyl orthosilicate, four different
One kind in hydracid silicon, three different hydracid silica methane；Second precursors be deionized water, hydrogen peroxide, oxygen, ozone or
NH3In one kind.
Presoma injection length t described in step 31、t3Scope is 1-20s, carrier gas washing time t2、t4Scope is 5-
200s。
Described passivation layer composition is Al2O3、TiO2、SiO2Or one kind in TiN, and on two or more
State the complex thin film of compound alternating deposit formation.
The circulating cycle issue of the step of described in step 4 three is 1-10000.
The advantageous effects of the present invention compared with prior art：
(1) ALD passivation layers even compact, the passivation layer of nanoscale there is good carbon distribution to suppress effect, to metal
The heat-conductive characteristic influence very little of tube wall；
(2) ALD passivation layers are connected firmly with metallic substrates, are not peeled off under high temperature and fluid scouring effect；
(3) ALD process temperatures are relatively low, do not cause damage to substrate；
(4) control of ALD processes passivation layer thickness is accurate, fluid passage obstruction is not easily caused, it is adaptable to involving great expense, tying
The complicated fluid system of structure is passivated processing；
(5) automaticity of the present invention is high, reproducible.
Brief description of the drawings
Fig. 1 is atomic layer deposition system schematic diagram of the present invention.
Fig. 2 is atomic layer deposition system gas circuit and the connected mode schematic diagram for being passivated metal tubes.
Fig. 3 is the XPS spectrum figure of the metal pipe internal wall by different oxide passivations.
Fig. 4 is the schematic device that fuel-pyrolysis reacts (test of carbon distribution rejection).
Fig. 5 is the SEM photograph on unpassivated metallic conduit surface.
Fig. 6 is the SEM photograph of unpassivated metallic conduit area carbon.
Fig. 7 generates the SEM photograph of carbon distribution for unpassivated metallic conduit inside.
Fig. 8 is 1500 cycle ALD Al2O3The SEM photograph of inner wall of metal tube pattern after passivation.
Fig. 9 is 2000 cycle ALD TiO2The SEM photograph of inner wall of metal tube pattern after passivation.
Figure 10 is 1750 cycle ALD Al2O3/SiO2The SEM photograph of inner wall of metal tube pattern after passivation.
Figure 11 is the SEM photograph of inner wall of metal tube pattern after 500 cycle ALD TiN are passivated.
Figure 12 is 1500 cycle ALD Al2O3The SEM photograph of inner wall of metal tube carbon distribution pattern after passivation.
Figure 13 is 1500 cycle ALD Al2O3The SEM photograph of carbon distribution is generated after passivation inside metal tube.
Embodiment
Technical scheme is described further below in conjunction with drawings and examples.
Gas phase atomic layer deposition system (ALD system), is developed by Xi'an Inst. of Modern Chemistry according to bibliography 1.Text
Offer 1：J.W.Elam,M.D.Groner,and S.M.George.Viscous flow reactor with quartz
crystal microbalance for thin film growth by atomic layer
deposition.Rev.Sci.Instrum,2002,73(8):2981-2987.System schematic is referring to Fig. 1.Scanning electron shows
Micro mirror (FEI Quanta 600FEG SEM).Electron spectrometer (EDS).X-ray photoelectron power spectrum (Thermo Scientific
K-Alpha XPS)。
Specific embodiment of the invention given below is, it is necessary to which explanation is that the invention is not limited in implement in detail below
Example, all equivalents done on the basis of technical scheme each fall within protection scope of the present invention.
Embodiment 1：
The present embodiment provides a kind of method that utilization ald passivation layer suppresses metal surface carbon distribution, and this method is specific
Comprise the following steps：
Step one, it is 2mm by internal diameter, length is that 1100mm metal tubes are immersed in acetone, is cleaned under ul-trasonic irradiation
40min removes oil stain and impurity, and clean metal tube is connected in ALD system gas circuit by fixing device (referring to Fig. 2), made
System interior air-flow passes through metallic conduit；
Step 2, seals reaction chamber, nitrogen is passed through into atomic layer deposition system and is vacuumized, and adjusts reaction chamber outlet valve
Door makes cavity pressure control in 133Pa, and reaction chamber temperature maintains 100 DEG C；
Step 3, the first reaction precursor trimethyl aluminium is injected into reaction chamber, the time is 8s；It is passed through inert carrier gas clear
The first unreacted reaction precursor and accessory substance are washed, the time is 40s.Second of reaction precursor is injected into reaction chamber
H2O, the time is 8s；Unreacted second of the reaction precursor of inert carrier gas cleaning and accessory substance are passed through again, and the time is 40s；
Step 4, the step of repeating 250 periodicities three.
By experimental verification, under the reaction conditions, Al2O3Passivation layer growth rate/ cycle, therefore embodiment 1
Middle ALD alumina passivation layers thickness 24.5nm.
Using XPS to deposited 250 cycle ALD Al in embodiment 12O3Inner wall of metal tube characterized, as a result see
Bright book accompanying drawing 3.As shown in figure 3, only occurring in that Al, O, C element signal in spectrogram, metallic element Fe, Cr, Ni are not detected by, is said
Bright ALD Al2O3Passivation layer is complete, fine and close, 250 cycle ALD Al2O3(thickness is 24.5nm) can shield inside pipe wall completely
Metallic element.
Embodiment 2：
It is identical with the other conditions of embodiment 1, repeat the Al in 1000 cycles2O3Ald, in inner wall of metal tube life
Into the passivation layer that thickness is 98nm.
Embodiment 3：
It is identical with the other conditions of embodiment 1, repeat the Al in 2000 cycles2O3Ald, in inner wall of metal tube life
Into the passivation layer that thickness is 196nm.
Embodiment 4：
It is identical with the other conditions of embodiment 1, repeat the Al in 1500 cycles2O3Ald, in inner wall of metal tube life
Into the passivation layer that thickness is 147nm.
The electron spectrometer (EDS) being equipped with using SEM is to inner wall of metal tube diverse location in embodiment 4
Surface-element species be measured, be as a result listed in table 1.Due to EDS the investigation depth of metal and metal oxide is reached it is micro-
Meter level, therefore the element species and contain that detect that the metal pipe-wall that ALD passivation layers and passivation layer covered contains can be quantified
Amount.The Al constituent contents measured at tube wall diverse location can reflect the uniformity of passivation layer.As shown in table 1, in metal
The Al constituent contents that pipe import, middle part, exit inwall are measured are basically identical, it was demonstrated that ALD Al2O3Passivation layer has good uniformity.
The EDAX results of the metal tube of 1 embodiment of table 1~4
| 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 that utilization ald passivation layer suppresses metal surface carbon distribution, and this method is specific
Comprise the following steps：
Step one, it is 2mm by internal diameter, length is that 1100mm metal tubes are immersed in acetone, is cleaned under ul-trasonic irradiation
40min removes oil stain and impurity, and clean metal tube is connected in ALD system gas circuit by fixing device, makes airflow passes
Metallic conduit；
Step 2, seals reaction chamber, nitrogen is passed through into atomic layer deposition system and is vacuumized, and adjusts reaction chamber outlet valve
Door makes cavity pressure control reaction chamber temperature is in 150 DEG C in 133Pa, and by heating；Presoma isopropanol is heated simultaneously
Titanium is to 60 DEG C；
Step 3, the first precursors isopropyl titanate is injected into reaction chamber, and the time is 8s；Inert carrier gas is passed through again
The first unreacted precursors of cleaning and accessory substance, the time is 40s.Second of precursors is injected into reaction chamber
H2O2, the time is 8s；Inert carrier gas is passed through again and cleans unreacted second of precursors and accessory substance, and the time is 40s；
Step 4, the step of repeating 1500 periodicities three.
By experimental verification, under the reaction conditions, TiO2Passivation layer growth rateIn/cycle, therefore embodiment 5
TiO2Passivation layer thickness 75nm.
Using XPS to deposited 1500 cycle ALD TiO in embodiment 52Inner wall of metal tube characterized, as a result see
Bright book accompanying drawing 3.As shown in figure 3, only occurring in that Ti, O, C element signal in spectrogram, metallic element Fe, Cr, Ni are not detected by, is said
Bright ALD TiO2Passivation layer is complete, fine and close, and the metallic element of inside pipe wall is shielded completely.
Embodiment 6：
The present embodiment provides a kind of method that utilization ald passivation layer suppresses metal surface carbon distribution, and this method is specific
Comprise the following steps：
The method and condition for being first according to embodiment 4 carry out the ALD Al in 1500 cycles2O3Passivation layer deposition, then makes anti-
Chamber temperature is answered to be in 60 DEG C, while injecting the first precursors silicon chloride and catalyst pyridine, time into reaction chamber
For 8s；Inert carrier gas is passed through again and cleans the first unreacted precursors and accessory substance, and the time is 40s；Into reaction chamber
Second of precursors H is injected simultaneously2O and catalyst pyridine, the time are 8s；It is unreacted that inert carrier gas cleaning is passed through again
Second of precursors and accessory substance, the time are 40s.Repeat the ALD SiO in 250 cycles2Passivation layer deposition, is obtained
Al2O3/SiO2Layer compound passivation.
By experimental verification, under the reaction conditions, SiO2Passivation layer growth rate is/ cycle, therefore embodiment 6
Middle SiO2Passivation layer thickness is 33nm, Al2O3/SiO2Layer compound passivation gross thickness is 180nm.
Using XPS to deposited 1500 cycle ALD Al in embodiment 62O3With 250 cycle ALD SiO2Inner wall of metal tube
Characterized, as a result see Figure of description 3.As shown in figure 3, only occurring in that Si, O, C element signal in spectrogram, gold is not detected by
Category element of Fe, Cr, Ni and Al previously deposited, illustrates Al2O3/SiO2Layer compound passivation is complete, fine and close, and pipe is shielded completely
The metallic element of inwall.
Embodiment 7：
The present embodiment provides a kind of method that utilization ald passivation layer suppresses metal surface carbon distribution, and this method is specific
Comprise the following steps：
Step one, it is 2mm by internal diameter, length is that 1100mm metal tubes are immersed in acetone, is cleaned under ul-trasonic irradiation
40min removes oil stain and impurity, and clean metal tube (beam) is connected in ALD system gas circuit by fixing device, makes air-flow
Flow through metallic conduit；
Step 2, seals reaction chamber, nitrogen is passed through into atomic layer deposition system and is vacuumized, and adjusts reaction chamber outlet valve
Door makes cavity pressure control reaction chamber temperature is in 160 DEG C in 133Pa, and by heating；
Step 3, the first precursors four (ethyl-methyl amido) titanium is injected into reaction chamber, the time is 8s；Lead to again
Enter inert carrier gas and clean the first unreacted precursors and accessory substance, the time is 40s.Injected into reaction chamber second
Precursors NH3, the time is 8s；Inert carrier gas is passed through again cleans unreacted second of precursors and accessory substance, when
Between be 40s；
Step 4, the step of repeating 500 periodicities three.
By experimental verification, under the reaction conditions, TiN passivation layer growth ratesIn/cycle, therefore embodiment 7
TiN passivation layer thickness 225nm.
Comparative example 1：
It is 2mm by internal diameter, length is immersed in acetone for 1100mm stainless steel tube, and 40min is cleaned under ul-trasonic irradiation
Oil stain and impurity are removed, clean metal tube is directly used in anti-carbon performance test as reference sample.
Carry out anti-carbon performance test experiment respectively to the metal tube in embodiment 1~7 and comparative example 1.Split using fuel
The anticoking capability of reaction evaluating passivation layer is solved, experimental provision schematic diagram is as shown in Figure 4.Cracking reaction chooses n-dodecane conduct
Fuel is tested, temperature of reactor is 750 DEG C.With the progress of reaction, carbon distribution is gradually accumulated inside metal tube, causes system to lead
Passband declines, the increase of upstream and downstream pressure differential.Stop reaction, the time worked using systems stay and pipe when pressure difference reaches 4MPa
The carbon deposition quantity of wall attachment assesses the anticoking capability of passivation layer.Experimental results are summarised in table 2.
EDAX results after the embodiment 1~7 of table 2 and the test of the metal tube of comparative example 1
| Embodiment | Carbon deposition quantity (mg)/run time (min) | Embodiment | Carbon deposition quantity (mg)/run 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 the conditions of fuel-pyrolysis reaction is carried out, carbon distribution can pass through tube wall metal catalyzing effect and two kinds of ways of Pintsch process
Footpath is formed.In the starting stage of reaction, carbon distribution is mainly that metal catalytic is acted on and formed by the first approach.Pass through metal catalytic
The carbon distribution that effect is formed is extended in thread from tube wall to mobile phase direction, and coking reaction speed quickly, and easily retains mobile phase
The carbon distribution of middle carrying, easily causes the rapid occlusion of fluid path.The main purpose of passivation of metal surfaces is to suppress such product
The formation of carbon.At higher temperatures, carbon distribution can also be formed by cracking reaction in mobile phase.Formed in this way
Carbon distribution in spherical, and can gradually be attached to tube wall and form continuous sheet carbon film, cause fluid path gradually to block.Tube wall is blunt
The method of change can not suppress the formation of such carbon distribution, therefore the working time of impossible indefinite extension system.
The anticoking capability of metal tube obtains obvious after ALD Passivation Treatments it can be seen from the test result in table 2
Lifting, passivation layer can make System production time extend several times.Thickness is 150nm or so ALD Al2O3And thickness is
200nm or so Al2O3/SiO2Layer compound passivation has best anti-carbon effect.When passivation layer thickness reach about 150nm it
Afterwards, further increase passivation layer thickness is limited to carbon distribution inhibition.
The pattern of part metals pipe sample inwall, ALD passivation layers and generation carbon distribution is characterized using SEM.Fig. 5 is not
The primary morphology of passivated metal pipe-wall；Fig. 6 is pattern of the unpassivated metal pipe-wall after cracking reaction；Fig. 7 be
The carbon distribution pattern of generation in unpassivated metal tube.SEM characterization results show that metal tube surface is coarse, exist a large amount of folds,
Pore space structure.In cracking reaction, under metal species catalytic action, a large amount of thread carbon distributions of tube wall surface generation；In metal tube
Portion's carbon distribution is mainly made up of the mixture of thread carbon distribution and spherical carbon distribution.Fig. 8, Fig. 9, Figure 10, Figure 11 are respectively to use ALD
Al2O3(1500 cycle), TiO2(2000 cycle), Al2O3/SiO2Metal after (1750 cycle), and TiN (500 cycle) passivation
The SEM photograph of inside pipe wall surface topography.As a result show, the small geometrical knot of inner wall of metal tube can be completely covered in ALD passivation layers
Structure, firm connection is formed with tube wall, so that thoroughly contact of the metal component with fuel in isolation original substrate.Figure 12,13 are
Covered with ALD Al2O3The inner wall of metal tube of (1500 cycle) passivation layer is in the surface topography after cracking reaction and the gold
The carbon distribution pattern of generation in category pipe.After cracking reaction, passivation layer is still completely attached to tube wall surface.Due to passivation layer
In the presence of contact of the active metal component with fuel has been isolated, the thread product for being acted on and being formed by metal catalytic is not present in tube wall surface
Carbon；The carbon film for being attached to passivation layer surface is made up of spherical carbon distribution completely, and the carbon distribution inside metal tube is also all anti-by cracking
The spherical carbon distribution composition that middle should be formed.Above characterization result proves the ALD passivation layers deposited in high length-diameter ratio metal pipe internal surface
Contact of the active metal component that can thoroughly completely cut off in base material with HC fuel, at high temperature to being acted on by metal catalytic
The thread carbon distribution formed has effective inhibitory action.
Claims (8)
1. a kind of method that utilization ald passivation layer suppresses metal surface carbon distribution, it is characterised in that comprise the following steps：
Step one, will treat that passive metal is connected by fixing device with atomic layer deposition system gas circuit, pass the gas through container or
Without entering in reaction cavity inside pipeline；It is described to treat that passivating metallic surfaces be used to store or transport at high temperature to be all kinds of
The container of hydrocarbon compound or the inwall of pipeline；
Step 2, inert carrier gas is passed through into atomic layer deposition system and is vacuumized, and regulating system reaction chamber outlet valve makes chamber
Interior pressure is in negative pressure；And reaction chamber temperature is in particular range by heating, particular range depends on deposited material
Expect species；
Step 3, the first precursors containing Al, Si element are injected into reaction chamber, and the time is t1；It is passed through inert carrier gas
Excessive precursors and accessory substance are rinsed, the time is t2；Second of precursors is injected into reaction chamber, the time is
T3, second described of precursors are deionized water, hydrogen peroxide, oxygen, ozone or NH3；Inert carrier gas flushing is passed through again
Unreacted second of precursors and accessory substance, the time is t4；
Step 4, repeats the step three of respective cycle number, until treating that passivating metallic surfaces generation thickness is 150nm's
ALD Al2O3Passivation layer or the Al that thickness is 200nm2O3/SiO2Layer compound passivation, the periodicity is 1-10000.
2. suppress the method for metal surface carbon distribution using ald passivation layer as claimed in claim 1, it is characterised in that
Inert carrier gas described in step 2 is nitrogen, helium or argon gas.
3. suppress the method for metal surface carbon distribution using ald passivation layer as claimed in claim 1, it is characterised in that
Negative pressure described in step 2 is in the range of 0.1-5000Pa.
4. suppress the method for metal surface carbon distribution using ald passivation layer as claimed in claim 1, it is characterised in that
Temperature particular range described in step 2 is in the range of 30-450 DEG C.
5. suppress the method for metal surface carbon distribution using ald passivation layer as claimed in claim 1, it is characterised in that
The precursors of the element containing Al described in step 3 is in trimethyl aluminium, triethyl aluminum, aluminium ethoxide or alchlors
One kind.
6. suppress the method for metal surface carbon distribution using ald passivation layer as claimed in claim 1, it is characterised in that
The precursors of the element containing Si described in step 3 are silicon tetrachloride, tetraethyl orthosilicate, four different hydracid silicon, three different hydracid silicon
One kind in oxygen methane.
7. suppress the method for metal surface carbon distribution using ald passivation layer as claimed in claim 1, it is characterised in that
Precursor injection length t described in step 31、t3Scope is 1-20s, carrier gas washing time t2、t4Scope is 5-200s.
8. suppress the method for metal surface carbon distribution using ald passivation layer as claimed in claim 1, it is characterised in that
Described container or pipeline is miniature chemical reactor, heat exchanger, engine and appurtenances and draw ratio is 104And have
There is the fluid transport circuit of various complex geometric shapes.
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| US11794382B2 (en) * | 2019-05-16 | 2023-10-24 | Applied Materials, Inc. | Methods for depositing anti-coking protective coatings on aerospace components |
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