CN106367732B - A kind of medium temperature metal organic chemical vapor deposition TiO2-Al2O3Composite coating device and painting method - Google Patents
A kind of medium temperature metal organic chemical vapor deposition TiO2-Al2O3Composite coating device and painting method Download PDFInfo
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- CN106367732B CN106367732B CN201610841130.7A CN201610841130A CN106367732B CN 106367732 B CN106367732 B CN 106367732B CN 201610841130 A CN201610841130 A CN 201610841130A CN 106367732 B CN106367732 B CN 106367732B
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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
- C23C16/22—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
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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
- C23C16/52—Controlling or regulating the coating process
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Abstract
A kind of medium temperature metal organic chemical vapor deposition AL2O3‑TiO2Composite coating device and painting method are closed in small-sized deposition chamber interior using raw material premix, are realized in stainless steel surface, the TiO in 250-450 DEG C of temperature range using Metalorganic chemical vapor deposition method and horizontal furnace apparatus2‑Al2O3The fine and close of composite coating is co-deposited, and achievees the purpose that inhibit stainless steel surface coking carbon distribution.
Description
Technical field
The invention belongs to material surface processing and coating technology fields, are related to medium temperature metal organic chemical vapor deposition
TiO2-Al2O3 composite coatings device and painting method
Background technology
For future aircraft in high-speed flight, amount of heat is released in indoor combustion reaction of burning so that the wall of combustion chamber
Face temperature is up to 3000K, exceeds the resistance to extreme temperature of current material, and therefore, rational thermal management scheme becomes limitation high-speed flight
The key point that device further develops.Become using the method that Endothermic Hydrocarbon Fuel carries out active cooling and solves heat management at present
The potential effective scheme of problem.Hydrocarbon fuel is dynamic in engine wall surface current first before spraying into combustion chamber, passes through fuel itself
Physics heats up and high temeperature chemistry cracking reaction absorbs combustion chamber wall surface heat to cooling engine, has a clear superiority.
But Endothermic Hydrocarbon Fuel is while cracking reaction generates combustibility excellent small molecule product, due to
Fuel conduit can generally contain the metallic elements such as Fe, Ni, they are contacted with fuel high-temperature pyrolysis product can occur surface catalysis knot
Coke reaction.These cokings be attached to fuel pipe surface not only can blocking pipeline, cause pressure-drop in pipeline to increase, and can cause to pass
Heat deteriorates, and reduces the mechanical performance of fuel pipe material, the major accident of engine misses is caused when serious.Therefore, inhibit pipe
Road surfaces coking becomes urgent problem.
Inhibit Metal catalytic coke that can be realized by face coat modification technology, i.e., prepares one layer in metal base surface
Inert inorganic coating blocks the catalytic action of metal surface, to eliminate Metal catalytic coke.Currently, prepared by common coating
Technology mainly has physical vapour deposition (PVD), chemical vapor deposition, sol-gel, plasma spray technology, electrochemical coating etc..These works
Skill has been obtained for applying well in the industry, and if physical vapour deposition (PVD) is in the preparation of biomaterial, chemical vapor deposition exists
The processing of hard alloy cutter, sol-gal process catalyst production, electrochemical coating surface polishing etc. all obtain
Good application.But in view of the complexity of true cooling channel structure, there was only chemical vapor deposition method in above method
It is not only restricted to the labyrinth of sample.And traditional high temperature chemical vapor deposition can cause matrix material since depositing temperature is excessively high
Expect the structural behaviour variation of itself, and metal organic chemical vapor deposition technology can be effectively reduced depositing temperature, not change base
The body material structural behaviour of itself, but there are problem be single coating internal stress it is larger, be susceptible to coating cracking.Cause
This, by the metal organic chemical vapor deposition scheme of reasonable design, realize that medium temperature composite coating deposition possible effective solution is determined on
State problem.
TiO2-Al2O3Composite coating even compact has good heat conductivility, antioxygenic property, heat shock resistance, coking
The catalytically inactive of reaction is led with single coating the advantages that coefficient of thermal expansion, is overcome similar in basis material because of internal stress
The problem of Cracking of cause, to one of the preferred embodiment as medium temperature depositing coating.Therefore, we have by using for reference traditional metal
Chemical machine vapor deposition method is co-deposited the specific demand of coating for stainless steel surface even compact under mesophilic condition, leads to
Redesign medium temperature chemical vapor depsotition equipment is crossed, new coating process and method are developed, to finally realize cooling duct table
The coating treatment technology in face.
Invention content
Patent of the present invention is designed to provide a kind of medium temperature composite coating chemical gaseous phase co-deposition device, it is characterised in that
The device includes mixing gas tank (10), heating tape (11), quartz glass tube settling chamber (12), Horizontal electric with lower component, purifying part
Hinder stove (13) and device for absorbing tail gas (14)；
The purifying part is by sequentially connected air source (1), molecular sieve (2), discoloration silica gel (3), needle valve (4) and quality
Flowmeter (5) forms, and the air source (1) is high-purity argon gas；
There are three purifying part tools, the mass flowmenter (5) of the first purifying part by pipeline connection ball valve (6) and
Mixed gas tank (10) is connected, and the mass flowmenter (5) of the second purifying part connects Ti carrying shields (7), third purifying part by pipeline
Mass flowmenter (5) Al carrying shields (8) are connected by pipeline, Ti carrying shields (7) and Al carrying shields (8) with mixed gas tank (10) phase
Even, the other end of mixed gas tank (10) is placed in the quartz glass tube settling chamber (12) in horizontal electric resistance furnace (13) by pipeline connection
The outlet end of input end, the quartz glass tube settling chamber (12) is connected with device for absorbing tail gas (14).
Temperature control table (9) is connected on the Ti carrying shields (7), Al carrying shields (8) and horizontal electric resistance furnace (13).
Road is taken between ball valve (6) and mixed gas tank (10), the connecting line between Ti carrying shields (7) and mixed gas tank (10),
Connecting line between Al carrying shields (8) and mixed gas tank (10), mix gas tank (10) and quartz glass tube settling chamber (12) input end it
Between connecting line be placed in heating tape (11), the connecting line passes through heating tape heating and thermal insulation.
There is heating and temperature control device on the outside of the Ti carrying shields (7) and Al carrying shields (8).
The Ti carrying shields (7) and Al carrying shields (8) inlet/outlet pipe road are respectively equipped with ball valve.
The pipeline that quartz glass tube settling chamber (12) outlet end is connect with device for absorbing tail gas (14) is equipped with ball valve.
The Ti carrying shields (7) and Al carrying shields (8) connection mix gas tank (10) and mixed gas tank (10) even quartz glass tube deposition
Pipeline between room (12) input end is 4 internal diameter stainless steel tubes of 316L types Φ.
It is a kind of that stainless steel surface TiO is carried out using foregoing device2-Al2O3The method that dense coating is co-deposited, should
Method includes the following steps：
Step 1：The pretreatment of stainless steel sample：
Stain removal cleaning agent cleans the dust of stainless steel sample and fine impurity, and the scavenging period is 15-30min；
It uses mass fraction to carry out pickling for 1~3% hydrochloric acid solution, removes the oxidation film and corrosion product of sample surfaces,
The pickling time is 15-30min；
Ultrasonic cleaning 15-30min is carried out using the high deionized water of degree of purity, removes surface residual debris；
Finally it is cleaned by ultrasonic using acetone and removes degreasing and other organic substances, scavenging period is 15~30min, later
It is put into baking oven and is dried for standby at 120 DEG C, drying time 1h；
Step 2：The assembly of coating exemplar：
The stainless steel deck (21) that a width is less than quartz glass tube settling chamber (12) internal diameter is made first, in deck
The conduit (22) that a width is 2mm is opened at one short side center, it would be desirable to the stainless steel print (20) of deposition blocks in the channel,
The two is packed into quartz glass tube jointly, ensures that deck is horizontal, stainless steel sample strip be located at quartzy tube hub and
Quartz ampoule settling chamber (12) input end is connected by horizontal electric resistance furnace (13) interior constant temperature zone with mixed gas tank (10) outlet conduit, stone
The outlet end of the settling chambers Ying Guan (12) is connected with device for absorbing tail gas (14)；
Step 3：Heat up depositing operation
First by the argon gas in air source (1) after over-molecular sieve (2) and discoloration silica gel (3) filter, with the speed of 1L/min
Purge whole device 10 minutes, the air in removing device；Pass through horizontal electric resistance furnace (13) heating heated quartz glass tube deposition
Room (12), is heated to 250-450 DEG C of intended deposition temperature, and it is anti-to be passed through filtered argon gas protection gas always during heating
Only sample is aoxidized；
It opens heating tape (11) and is heated to 150 DEG C, open temperature control table (9) on Ti carrying shields (7) and Al carrying shields (8), point
It is not heated to 70 DEG C and 120 DEG C, to provide saturated vapor pressure, the saturated vapor pressure that the Ti carrying shields (7) provide is TTIP
1.2KPa, the saturated vapor pressure that the Al carrying shields (8) provide are ATSB 1.0KPa；
After all temperature rise to 250-450 DEG C of temperature, protection gas argon flow amount is adjusted to 0.4L/min, waits for flow
After stabilization, Ti carrying shields (7) and Al carrying shields (8) are opened, for argon gas as carrier gas, adjusting needle valve (4) makes the carrier gas flux of Ti carrying shields
Carrier gas flux for 0.3L/min, Al carrying shields is 0.3L/min, and carrier gas argon gas is made to reach Ti carrying shields (7) and Al carrying shields in advance
(8) at inlet valve, Ti carrying shields (7) inlet valve and outlet valve are first opened simultaneously, then opens simultaneously Al carrying shields (8) inlet valve and outlet
Valve, record reaction time started；
When reaching the predetermined time of 30-60min in the reaction time, simultaneously close off Ti carrying shields (7) and Al carrying shields (8) into
Mouth valve and outlet valve stop being passed through the metal organic precursor provided by Ti carrying shields (7) and Al carrying shields (8) to mixed gas tank (10),
After the protection gas argon gas in air source (1) is adjusted simultaneously with 1L/min purging whole devices 30min, protection gas and heating tape are closed,
Allow device Temperature fall.
Step 4：Exemplar takes out：
Horizontal electric resistance furnace (13) uses Temperature fall, waits for that temperature is reduced to room temperature, and it is heavy to be taken out from quartz glass tube settling chamber
Product exemplar, obtains required depositing Ti O2-Al2O3The sample of coating, the coating layer thickness are about 2 μm.The coating and single TiO2
Coating is compared, and surface hole defect and crack disappear, and composition coated microgranules are also relatively fine, show that the coating is comparatively dense
Stainless steel substrates are 310S stainless steel substrates.
The high deionized water of degree of purity is conductivity in step 1<10us/cm ionized waters.
Multiple empty slots can be opened up in deck short side in step 2, realize the multiple stainless steel samples of primary coating.
The metal organic precursor that Ti carrying shields (7) and Al carrying shields (8) provide in step 3 is respectively isopropyl titanate (TTIP)
With aluminium secondary butylate (ATSB).
Advantageous effect：
The beneficial effects of the invention are as follows realize stainless steel substrates surface, the TiO in 350-450 DEG C of temperature range2-Al2O3It is compound
The fine and close of coating is co-deposited, and is eliminated single coating cracking phenomena, is achieved the purpose that good inhibition surface coking carbon distribution.
Using traditional organic chemical vapor deposition thought, for elongated stainless steel substrates surface TiO2-Al2O3Composite coating
Chemical gaseous phase is co-deposited particular/special requirement and inhibits the purpose of coking, we ensure Al using ATSB/TTIP organometallic sources systems
Source supply synchronous with the sources Ti realizes that the fine and close of composite coating is co-deposited using MOCVD methods at lower deposition temperatures.Using
Horizontal chamber furnace (oven) and card slot fix the method that print stands on settling chamber vertically, and it is uneven to solve sample both sides distribution of air flow in deposition process
The problem of.Composite coating surface obtained even compact does not occur crack and (coating is made at 300 DEG C, 350 DEG C, sees Fig. 4 substantially
Middle c and d), with TiO2Single coating and Al2O3Single coating is compared, and the consistency and bond strength on surface are more preferable.
Description of the drawings
Fig. 1 is stainless steel surface TiO of the present invention2-Al2O3Composite coating chemical gaseous phase is co-deposited coating unit schematic diagram；
Fig. 2-1 is the connected mode schematic diagram of 1-310S of the present invention stainless steel sample and deck；
Fig. 2-2 is the quartz glass tube settling chamber schematic diagram of the present invention；
Fig. 3 is to prepare TiO at 350 DEG C2Single coating surface topography；
Fig. 4 is TiO prepared by present example same time different deposition temperatures2-Al2O3The surface topography of composite coating：
(a)250℃,(b)300℃,(c)350℃,(d)400℃, (e)450℃；
Fig. 5 is 350 DEG C of different sedimentation time prepares coating patterns of present example.(a1)30 min,(a2)40min,
(a3)50min,(a4)60min；
Fig. 6 changes for O, Al, Ti element in the prepares coating of present example with depositing temperature；
Fig. 7 is 350 DEG C of stainless steel substrates TiO of present example2-Al2O3The inhibition coking effect of composite coating.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.
It is insufficient the present invention be directed to existing chemical vapour deposition technique and what is provided a kind of novel be directed to stainless steel surface
TiO2-Al2O3Medium temperature composite coating chemical gaseous phase is co-deposited device and its depositing operation, its main feature is that：Inhibit surface knot to reach
The purpose of burnt carbon distribution, using chemical vapor deposition method and horizontal furnace apparatus, in stainless steel surface, in 350-450 DEG C of temperature strip
TiO is realized under part2-Al2O3The fine and close of composite coating is co-deposited.
The deposition principle of the present invention：The basic principle of the present invention is, as follows using occurring under the conditions of 350-450 DEG C of medium temperature
Chemical reaction：
Ti(OC3H7)4=TiO2+2C3H6+2HOC3H7
2Al(C4H9O)3=Al2O3+6C4H8+3H2O
Realize the TiO in substrate material surface2-Al2O3Composite coating chemical gaseous phase is co-deposited.And in order to realize in 310S
The depositing operation on stainless steel substrates surface, wherein needing to solve the problems, such as the following aspects successively：
First, settling chamber's condition of chemical vapor deposition, since deposition workpiece is elongated 310S stainless steel substrates,
In order to make the uniform applying coating of sample surfaces, stainless steel substrates are made to be located in quartz glass tube settling chamber using the deck with empty slot
Centre and axis parallel zone, ensure the even flow field of two sidewind of sample strip, make sample front and back end using higher gas flow rate
Coating layer thickness it is essentially identical.
Second, the control of reaction gas system.Chemical vapor deposition needs reaction gas to reach enough purity and aridity,
Therefore two-step purification system is used to initial reaction gas；While in order to ensure being uniformly mixed for reaction gas, reaction gas
It is pre-mixed before entering in the reaction chamber using mixed gas system.
Third, the temperature control of organic titanium, silicon source saturator.Because isopropanol state and the decomposition temperature of aluminium secondary butylate are satisfied
It is different with vapour pressure, in order to ensure the two sufficient inlet amount and proportioning, needs to set different saturator temperature, both meet
Material quantity needed for reaction is less than the decomposition temperature of metallorganic again.
4th, temperature control system.Entire reacting pipe is before entering settling chamber, using heating tape heating and thermal insulation, control
Temperature processed is at 150 DEG C or more；Entire furnace temperature system is controlled by temperature programming switch board, ensures that final heating reaches temperature
In the target temperature of setting.
5th, gas flow control.To ensure that the accuracy and repeatability of technique, entire gas flow use quality stream
Gauge is controlled.
On the basis of above each section condition is guaranteed, we are according to TiO2-Al2O3The chemical gaseous phase of composite coating
Codeposition reactions are uniformly passed through reaction gas in elongated stainless steel exemplar, and TiO finally can be achieved2-Al2O3Compound painting
The surface vapor of layer is co-deposited.And the quality of coating can be by thickness, the testing results such as elemental analysis and surface topography carry out
Analysis, and it inhibits coking behavior that can be verified by the coking of high temperature.
As shown, a kind of medium temperature composite coating chemical gaseous phase is co-deposited device, it is characterised in that the device includes following
Component, purifying part mix gas tank (10), heating tape (11), quartz glass tube settling chamber (12), horizontal electric resistance furnace (13) and tail gas
Absorption plant (14)；
The purifying part is by sequentially connected air source (1), molecular sieve (2), discoloration silica gel (3), needle valve (4) and quality
Flowmeter (5) forms, and the air source (1) is high-purity argon gas；
There are three purifying part tools, the mass flowmenter (5) of the first purifying part by pipeline connection ball valve (6) and
Mixed gas tank (10) is connected, and the mass flowmenter (5) of the second purifying part connects Ti carrying shields (7), third purifying part by pipeline
Mass flowmenter (5) Al carrying shields (8) are connected by pipeline, Ti carrying shields (7) and Al carrying shields (8) with mixed gas tank (10) phase
Even, the other end of mixed gas tank (10) is placed in the quartz glass tube settling chamber (12) in horizontal electric resistance furnace (13) by pipeline connection
The outlet end of input end, the quartz glass tube settling chamber (12) is connected with device for absorbing tail gas (14).
Temperature control table (9) is connected on the Ti carrying shields (7), Al carrying shields (8) and horizontal electric resistance furnace (13).
Road is taken between ball valve (6) and mixed gas tank (10), the connecting line between Ti carrying shields (7) and mixed gas tank (10),
Connecting line between Al carrying shields (8) and mixed gas tank (10), mix gas tank (10) and quartz glass tube settling chamber (12) input end it
Between connecting line be placed in heating tape (11), the connecting line passes through heating tape heating and thermal insulation.
There is heating and temperature control device on the outside of the Ti carrying shields (7) and Al carrying shields (8).
The Ti carrying shields (7) and Al carrying shields (8) inlet/outlet pipe road are respectively equipped with ball valve.
The pipeline that quartz glass tube settling chamber (12) outlet end is connect with device for absorbing tail gas (14) is equipped with ball valve.
The Ti carrying shields (7) and Al carrying shields (8) connection mix gas tank (10) and mixed gas tank (10) even quartz glass tube deposition
Pipeline between room (12) input end is 4 internal diameter stainless steel tubes of 316L types Φ.
It is a kind of that stainless steel surface TiO is carried out using foregoing device2-Al2O3The method that dense coating is co-deposited, should
Method includes the following steps：
Step 1：The pretreatment of stainless steel sample：
Stain removal cleaning agent cleans the dust of stainless steel sample and fine impurity, and the scavenging period is 15-30min；
It uses mass fraction to carry out pickling for 1~3% hydrochloric acid solution, removes the oxidation film and corrosion product of sample surfaces,
The pickling time is 15-30min；
Ultrasonic cleaning 15-30min is carried out using the high deionized water of degree of purity, removes surface residual debris；
Finally it is cleaned by ultrasonic using acetone and removes degreasing and other organic substances, scavenging period is 15~30min, later
It is put into baking oven and is dried for standby at 120 DEG C, drying time 1h；
Step 2：The assembly of coating exemplar：
The stainless steel deck (21) that a width is less than quartz glass tube settling chamber (12) internal diameter is made first, in deck
The conduit (22) that a width is 2mm is opened at one short side center, it would be desirable to the stainless steel print (20) of deposition blocks in the channel,
The two is packed into quartz glass tube jointly, ensures that deck is horizontal, stainless steel sample strip be located at quartzy tube hub and
Quartz ampoule settling chamber (12) input end is connected by horizontal electric resistance furnace (13) interior constant temperature zone with mixed gas tank (10) outlet conduit, stone
The outlet end of the settling chambers Ying Guan (12) is connected with device for absorbing tail gas (14)；
Step 3：Heat up depositing operation
First by the argon gas in air source (1) after over-molecular sieve (2) and discoloration silica gel (3) filter, with the speed of 1L/min
Purge whole device 10 minutes, the air in removing device；Pass through horizontal electric resistance furnace (13) heating heated quartz glass tube deposition
Room (12), is heated to 250-450 DEG C of intended deposition temperature, and it is anti-to be passed through filtered argon gas protection gas always during heating
Only sample is aoxidized；
It opens heating tape (11) and is heated to 150 DEG C, open temperature control table (9) on Ti carrying shields (7) and Al carrying shields (8), point
It is not heated to 70 DEG C and 120 DEG C, to provide saturated vapor pressure, the saturated vapor pressure that the Ti carrying shields (7) provide is TTIP
1.2KPa, the saturated vapor pressure that the Al carrying shields (8) provide are ATSB 1.0KPa；
After all temperature rise to 250-450 DEG C of temperature, protection gas argon flow amount is adjusted to 0.4L/min, waits for flow
After stabilization, Ti carrying shields (7) and Al carrying shields (8) are opened, for argon gas as carrier gas, adjusting needle valve (4) makes the carrier gas flux of Ti carrying shields
Carrier gas flux for 0.3L/min, Al carrying shields is 0.3L/min, and carrier gas argon gas is made to reach Ti carrying shields (7) and Al carrying shields in advance
(8) at inlet valve, Ti carrying shields (7) inlet valve and outlet valve are first opened simultaneously, then opens simultaneously Al carrying shields (8) inlet valve and outlet
Valve, record reaction time started；
When reaching the predetermined time of 30-60min in the reaction time, simultaneously close off Ti carrying shields (7) and Al carrying shields (8) into
Mouth valve and outlet valve stop being passed through the metal organic precursor provided by Ti carrying shields (7) and Al carrying shields (8) to mixed gas tank (10),
After the protection gas argon gas in air source (1) is adjusted simultaneously with 1L/min purging whole devices 30min, protection gas and heating tape are closed,
Allow device Temperature fall.
Step 4：Exemplar takes out：
Horizontal electric resistance furnace (13) uses Temperature fall, waits for that temperature is reduced to room temperature, and it is heavy to be taken out from quartz glass tube settling chamber
Product exemplar, obtains required depositing Ti O2-Al2O3The sample of coating, the coating layer thickness are about 2 μm.The coating and single TiO2
Coating is compared, and surface hole defect and crack disappear, and composition coated microgranules are also relatively fine, show that the coating is comparatively dense
Stainless steel substrates are 310S stainless steel substrates.
The high deionized water of degree of purity is conductivity in step 1<10us/cm ionized waters.
Multiple empty slots can be opened up in deck short side in step 2, realize the multiple stainless steel samples of primary coating.
The metal organic precursor that Ti carrying shields (7) and Al carrying shields (8) provide in step 3 is respectively isopropyl titanate (TTIP)
With aluminium secondary butylate (ATSB).
Embodiment：Elongated 310S stainless steel substrates (80mm*10mm*2mm), outer surface TiO2-Al2O3Composite coating deposits work
Skill, 350-450 DEG C of temperature, settling chamber and connection type are as shown in attached drawing 2-1 and 2-2.
1) pretreatment of exemplar：
Stain removal is cleaned, and the dust in process and fine impurity are removed；Pickling is carried out, the oxidation of sample surface is removed
Film and corrosion product；It is cleaned by ultrasonic using the high deionized water of degree of purity, removes surface residual debris；It is cleaned by ultrasonic using acetone and is removed
Greasy dirt and other organic substances, each scavenging period are 15-30min.Finally, stainless steel sample is put into baking oven at 120 DEG C
It is spare to dry 1h.
2) assembly of coating exemplar：
In the empty slot for the 2mm wide that the stainless steel print handled well is stuck in deck side, by both deck and stainless steel substrates
It is common to be packed into quartz glass tube, ensure that deck is horizontal, stainless steel sample strip is located at quartzy tube hub and heating furnace
Quartz ampoule one end is connected by flat-temperature zone with mixed gas tank outlet pipeline, and the other end is connected with device for absorbing tail gas.
3) heat up depositing operation
High-purity argon gas 1L/min is used before heating, purges whole system 10 minutes, the air in removing system；By setting
Fixed temperature program heating reaction tube furnace, is heated to intended deposition temperature, high-purity argon protection gas is passed through during heating
Prevent sample from being aoxidized；
It opens heating tape and is heated to 150 DEG C, open heating isopropyl titanate (TTIP) saturator, aluminium secondary butylate (ATSB) saturation
Device is separately heated to 70 DEG C and 120 DEG C, provides certain saturated vapor pressure；
After all temperature rise to the temperature of experiment setting, according to preset experimental technique, adjust protection air-flow amount to
0.4L/min after throughput to be protected is stablized, opens carrier gas steel cylinder main valve and pressure reducing valve, rotates carrier gas flux meter needle valve, make
Carrier gas is reached in advance at saturator inlet valve, first opens simultaneously titanium source saturator terminal valve, then open simultaneously silicon source saturator
Terminal valve makes titanium source and silicon source while supplying, and at the beginning of record experiment, ensures that the flow of two-way argon carrier is
0.3L/min；
During testing progress, the moment monitors reaction process, it is ensured that the progress of entire reaction safe and continuous.It waits testing
The scheduled time is reached, the inlet valve and outlet valve of saturator is simultaneously closed off, stops being passed through metal organic precursor to reaction tube,
Protection air-flow amount is adjusted simultaneously to the entire reaction system of 1 L/min purgings.
After reaction system 30min is swept in air-blowing to be protected, protection gas and heating tape is closed, allows system Temperature fall.
4) exemplar taking-up and quality testing.
Heating furnace uses Temperature fall, waits for that temperature is down to room temperature, and deposition exemplar is taken out from quartz glass deposition room, is obtained
Required coating sample.SEM and EDS is carried out for deposition exemplar and analyzes its surface topography and element composition, if Fig. 3 is 350 DEG C
When in stainless steel surface coat single TiO2Coating surface microscopic appearance, the TiO as can be seen from the figure prepared2Coating is due to interior
Stress and lead to coating cracking, the presence in crack, which reduces, inhibits coking effect.It is illustrated in figure 4 in present example in difference
At a temperature of prepares coating topography scan electron micrograph, wherein SEM lengths of the scale be 10um；It can be seen from Fig. 4 (a)
250 DEG C of coating growth rates are slower, and sedimentation time is 30min, therefore matrix surface does not have apparent TiO2-Al2O3Compound painting
Layer pattern.Depositing temperature rises, and coating growth rates are accelerated, and coating surface grows spherical particle, and particle size is at 1 μm
Left and right, coating surface have apparent crack (Fig. 4 (b)).Change in 350 DEG C of coating morphologies, coating surface is by small
Spherical particle composition, coating uniform densification (Fig. 4 (c)).Depositing temperature continues to rise, and coating surface particle is changed by spherical
Grain shape (Fig. 4 (d)).(Fig. 4 (e)) is formed by the cotton-shaped particle packing of bigger in 450 DEG C of coating surfaces.
Fig. 5 is 350 DEG C of different sedimentation time coating morphologies；Due to Al2O3Doping vario-property effect, coating surface is smoothed
Fine and close surface particles covering, as sedimentation time increases to 60min from 30min, coating layer thickness gradually increases, coating surface
There is no crackle to generate (Fig. 5 (a1)~(a4)).
Fig. 6 be in coating O, Al, Ti element with depositing temperature variation, by figure it may be seen that at 350 DEG C or less
Two kinds of coatings are doped relatively good.It is original to examine coating inhibition of coke formation situation, hexamethylene using atmospheric cracking coking experiment porch
Material carries out cracking coking experiment at 800 DEG C, and experimental period 1.5h, the cracking coking experimental result that the results are shown in Figure 7 can
To find out the TiO prepared at 350 DEG C2-Al2O3Coated foil relative to blank stainless steel substrates have good suppression coke effect, and with
Coating layer thickness increases, and coking effect is inhibited to improve.
It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.In addition, it should also be understood that,
After reading the content taught by the present invention, those skilled in the art can make various modifications or changes to the present invention, these
Equivalent form is also fallen within the scope of the appended claims of the present application.
Claims (10)
1. a kind of medium temperature composite coating chemical gaseous phase is co-deposited device, it is characterised in that the device includes with lower component, purification portion
Part mixes gas tank (10), heating tape (11), quartz glass tube settling chamber (12), horizontal electric resistance furnace (13) and device for absorbing tail gas
(14)；
The purifying part is by sequentially connected air source (1), molecular sieve (2), discoloration silica gel (3), needle valve (4) and mass flow
(5) composition is counted, the air source (1) is high-purity argon gas；
There are three the purifying part tools, and the mass flowmenter (5) of the first purifying part passes through pipeline connection ball valve (6) and mixed gas
Tank (10) is connected, and the mass flowmenter (5) of the second purifying part connects Ti carrying shields (7), the matter of third purifying part by pipeline
It measures flowmeter (5) and Al carrying shields (8) is connected by pipeline, Ti carrying shields (7) and Al carrying shields (8) are connected with mixed gas tank (10), mix gas
The other end of tank (10) is placed in quartz glass tube settling chamber (12) input end in horizontal electric resistance furnace (13) by pipeline connection, should
The outlet end of quartz glass tube settling chamber (12) is connected with device for absorbing tail gas (14)；
Temperature control table (9) is connected on the Ti carrying shields (7), Al carrying shields (8) and horizontal electric resistance furnace (13)；
Connecting line between ball valve (6) and mixed gas tank (10), the connecting line between Ti carrying shields (7) and mixed gas tank (10), Al
Connecting line between carrying shield (8) and mixed gas tank (10) mixes between gas tank (10) and quartz glass tube settling chamber (12) input end
Connecting line be placed in heating tape (11), the connecting line passes through heating tape heating and thermal insulation.
2. a kind of medium temperature composite coating chemical gaseous phase as described in claim 1 is co-deposited device, which is characterized in that the sources Ti
There is heating and temperature control device on the outside of tank (7) and Al carrying shields (8).
3. a kind of medium temperature composite coating chemical gaseous phase as described in claim 1 is co-deposited device, which is characterized in that the sources Ti
Tank (7) and Al carrying shields (8) inlet/outlet pipe road are respectively equipped with ball valve.
4. a kind of medium temperature composite coating chemical gaseous phase as described in claim 1 is co-deposited device, which is characterized in that the quartz
The pipeline that glass tube settling chamber (12) outlet end is connect with device for absorbing tail gas (14) is equipped with ball valve.
5. a kind of medium temperature composite coating chemical gaseous phase as described in claim 1 is co-deposited device, which is characterized in that the sources Ti
Tank (7) and the mixed gas tank (10) of Al carrying shields (8) connection and mixed gas tank (10) connect between quartz glass tube settling chamber (12) input end
Pipeline be 4 internal diameter stainless steel tubes of 316L types Φ.
6. a kind of device using as described in claim 1-5 carries out stainless steel surface TiO2-Al2O3What dense coating was co-deposited
Method, this approach includes the following steps：
Step 1：The pretreatment of stainless steel sample：
Stain removal cleaning agent cleans the dust of stainless steel sample and fine impurity, and the scavenging period is 15-30min；
It uses mass fraction to carry out pickling for 1~3% hydrochloric acid solution, removes the oxidation film and corrosion product of sample surfaces, it is described
Pickling time is 15-30min；
Ultrasonic cleaning 15-30min is carried out using the high deionized water of degree of purity, removes surface residual debris；
Finally it is cleaned by ultrasonic using acetone and removes degreasing and other organic substances, scavenging period is 15~30min, is put into baking later
It is dried for standby at 120 DEG C in case, drying time 1h；
Step 2：The assembly of coating exemplar：
The stainless steel deck (21) that a width is less than quartz glass tube settling chamber (12) internal diameter is made first, at one of deck
The conduit (22) that a width is 2mm is opened at short side center, it would be desirable to which the stainless steel print (20) of deposition blocks in the channel, by two
Person is packed into quartz glass tube jointly, ensures that deck is horizontal, and stainless steel sample strip is located at quartzy tube hub and horizontal
Quartz glass tube settling chamber (12) input end is connected by resistance furnace (13) interior constant temperature zone with mixed gas tank (10) outlet conduit, stone
The outlet end of English glass tube settling chamber (12) is connected with device for absorbing tail gas (14)；
Step 3：Heat up depositing operation
The argon gas in air source (1) is purged after over-molecular sieve (2) and discoloration silica gel (3) filter with the speed of 1L/min first
Whole device 10 minutes, the air in removing device；Pass through horizontal electric resistance furnace (13) heating heated quartz glass tube settling chamber
(12), it is heated to 350 DEG C of intended deposition temperature, being passed through filtered argon gas protection gas always during heating prevents sample
It is aoxidized；
It opens heating tape (11) and is heated to 150 DEG C, open temperature control table (9) on Ti carrying shields (7) and Al carrying shields (8), add respectively
Heat is to 70 DEG C and 120 DEG C, and to provide saturated vapor pressure, the saturated vapor pressure that the Ti carrying shields (7) provide is TTIP
1.2KPa, the saturated vapor pressure that the Al carrying shields (8) provide are ATSB 1.0KPa；
After all temperature rise to 350 DEG C of temperature, protection gas argon flow amount is adjusted to 0.4L/min, after stability of flow, is beaten
Ti carrying shields (7) and Al carrying shields (8) are opened, for argon gas as carrier gas, adjusting needle valve (4) makes the carrier gas flux of Ti carrying shields be 0.3L/
The carrier gas flux of min, Al carrying shield is 0.3L/min, and carrier gas argon gas is made to reach Ti carrying shields (7) and Al carrying shields (8) inlet valve in advance
Place, first opens simultaneously Ti carrying shields (7) inlet valve and outlet valve, then open simultaneously Al carrying shields (8) inlet valve and outlet valve, and record is anti-
Answer the time started；
When reaching the predetermined time of 30-60min in the reaction time, simultaneously close off Ti carrying shields (7) and Al carrying shields (8) inlet valve and
Outlet valve stops being passed through the metal organic precursor provided by Ti carrying shields (7) and Al carrying shields (8) to mixed gas tank (10), adjust simultaneously
After protection gas argon gas in solar term source (1) is with 1L/min purging whole devices 30min, protection gas and heating tape are closed, allows device
Temperature fall；
Step 4：Exemplar takes out：
Horizontal electric resistance furnace (13) uses Temperature fall, waits for that temperature is reduced to room temperature, and deposition sample is taken out from quartz glass tube settling chamber
Part obtains required depositing Ti O2-Al2O3The sample of coating, the coating layer thickness are about 2 μm.
7. method as claimed in claim 6, it is characterised in that stainless steel substrates are 310S stainless steel substrates.
8. method as claimed in claim 6, which is characterized in that the high deionized water of degree of purity is conductivity in step 1<10μ
S/cm ionized waters.
9. method as claimed in claim 6, which is characterized in that can open up multiple empty slots in deck short side in step 2, realize
The multiple stainless steel samples of primary coating.
10. method as claimed in claim 6, which is characterized in that the metal that Ti carrying shields (7) and Al carrying shields (8) provide in step 3
Organic precursor is respectively isopropyl titanate and aluminium secondary butylate.
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| CN109055915A (en) * | 2018-10-30 | 2018-12-21 | 四川大学 | TiN coating chemical vapor deposition unit and preparation method based on electric current heating |
| CN109468614B (en) * | 2018-12-07 | 2020-03-17 | 西安交通大学 | Surface anti-coking nano composite film and preparation method thereof |
| CN113025948B (en) * | 2021-03-08 | 2022-12-27 | 安徽寒锐新材料有限公司 | Preparation method of anti-sticking boat for reducing cobalt powder and recycling method of boat cleaning material |
| CN114150293A (en) * | 2021-11-25 | 2022-03-08 | 四川大学 | Deposition method and device for TiN and silicon dioxide double-layer coating |
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| CN1842901A (en) * | 2003-08-25 | 2006-10-04 | 株式会社爱发科 | Process for producing oxide thin film and production apparatus therefor |
| CN102418085A (en) * | 2011-12-14 | 2012-04-18 | 无锡迈纳德微纳技术有限公司 | Micronano-scale powder protective layer wrapping device and method |
| CN104264126A (en) * | 2014-09-17 | 2015-01-07 | 四川大学 | Long-range micro-channel inner wall TiO2 coating chemical vapor deposition device and coating method |
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