CN106367732A - Device for medium-temperature organometallic chemical vapor deposition of TiO2-Al2O3 composite coating and coating method - Google Patents
Device for medium-temperature organometallic chemical vapor deposition of TiO2-Al2O3 composite coating and coating method Download PDFInfo
- Publication number
- CN106367732A CN106367732A CN201610841130.7A CN201610841130A CN106367732A CN 106367732 A CN106367732 A CN 106367732A CN 201610841130 A CN201610841130 A CN 201610841130A CN 106367732 A CN106367732 A CN 106367732A
- Authority
- CN
- China
- Prior art keywords
- carrying shield
- temperature
- coating
- mixed gas
- settling chamber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention discloses a device for medium-temperature organometallic chemical vapor deposition of a TiO2-Al2O3 composite coating and a coating method. An organometallic chemical vapor deposition method and a horizontal furnace device are adopted, and raw materials are pre-mixed in a small deposition chamber, so that dense codeposition of the TiO2-Al2O3 composite coating on the surface of stainless steel within the temperature range of 250-450 DEG C is achieved, and the purpose of restraining coking and carbon deposition on the surface of the stainless steel is achieved.
Description
Technical field
The invention belongs to material surface is processed and coating technology field, it is related to middle temperature metal organic chemical vapor deposition
Tio2-al2o3 composite coating device and painting method
Background technology
, in high-speed flight, amount of heat is released in the indoor combustion reaction of burning so that the wall of combustor for future aircraft
Face temperature is up to 3000k, and beyond the resistance to extreme temperature of current material, therefore, rational thermal management scheme becomes restriction high-speed flight
The key point that device develops further.Become current using the method that Endothermic Hydrocarbon Fuel carries out active cooling and solve heat management
The potential effective scheme of problem.Hydrocarbon fuel, before spraying into combustor, moves in engine wall surface current, first by fuel itself
Physics rises gentle high temeperature chemistry cracking reaction and absorbs combustion chamber wall surface heat thus cooling down electromotor, has a clear superiority.
But, Endothermic Hydrocarbon Fuel while cracking reaction generates combustibility excellent small molecule product, due to
Fuel conduit typically can contain the metallic element such as fe, ni, and they are contacted with fuel high-temperature pyrolysis product and surface catalysis can be occurred to tie
Burnt reaction.These cokings be attached to fuel pipe surface not only can blocking pipeline, cause pressure-drop in pipeline raise, and can lead to pass
Heat deteriorates, and reduces the mechanical performance of fuel pipe material, causes the major accident of engine misses when serious.Therefore, killer tube
Road surfaces coking becomes urgent problem.
Suppression Metal catalytic coke can be realized by face coat modification technology, prepares one layer in metal base surface
Inert inorganic coating, blocks the catalytic action of metal surface, thus eliminating Metal catalytic coke.At present, conventional coating preparation
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 in the preparation of biomaterial, chemical vapor deposition exists such as physical vapour deposition (PVD)
The process of carbide tool, sol-gal process all obtains at aspects such as surface polishings in the production of catalyst, electrochemical coating
Good application.But the complexity in view of true cooling channel structure, only has chemical gaseous phase depositing process in above method
It is not only restricted to the labyrinth of sample.And traditional high temperature chemical vapor deposition is too high due to depositing temperature, matrix material can be caused
Expect the structural behaviour change of itself, and metal organic chemical vapor deposition technology can be effectively reduced depositing temperature, does not change base
The body material structural behaviour of itself, but existing problems be single coating internal stress larger, coating cracking easily occurs.Cause
This, by metal organic chemical vapor deposition scheme reasonable in design, realize on middle temperature composite coating deposition possible effective solution determines
State problem.
tio2-al2o3Composite coating even compact, has good heat conductivility, antioxygenic property, heat shock resistance, coking
The catalytically inactive of reaction, the advantages of close with matrix material thermal coefficient of expansion, overcomes single coating and leads because of internal stress
One of the problem of Cracking causing, thus become the preferred version of middle temperature depositing coating.Therefore, we are had by using for reference traditional metal
Chemical machine CVD method, for the specific demand of the codeposition coating of stainless steel surfaces even compact under mesophilic condition, leads to
Crossing and redesign middle temperature chemical vapor depsotition equipment, developing new coating process and method, thus finally realizing cooling duct table
The coating treatment technology in face.
Content of the invention
The purpose of patent of the present invention be to provide a kind of middle temperature composite coating chemical gaseous phase to co-deposit device it is characterised in that
This device is included with lower component, purifying part, mixed gas tank (10), heating tape (11), quartz glass tube settling chamber (12), Horizontal electric
Resistance stove (13) and device for absorbing tail gas (14)；
Described purifying part is by the source of the gas (1) being sequentially connected, molecular sieve (2), variable color silica gel (3), needle valve (4) and quality
Effusion meter (5) forms, and described source of the gas (1) is high-purity argon gas；
Described purifying part has three, the mass flowmenter (5) of the first purifying part pass 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 shield (7), the 3rd purifying part by pipeline
Mass flowmenter (5) al carrying shield (8) is connected by pipeline, ti carrying shield (7) is all connected with mixed gas tank (10) with al carrying shield (8),
The other end of mixed gas tank (10) connects, by pipeline, quartz glass tube settling chamber (12) import being placed in horizontal electric resistance furnace (13)
End, the port of export of this quartz glass tube settling chamber (12) is connected with device for absorbing tail gas (14).
Described ti carrying shield (7), al carrying shield (8) and horizontal electric resistance furnace (13) are upper to connect temperature control table (9).
Adapter road between ball valve (6) and mixed gas tank (10), the connecting line between ti carrying shield (7) and mixed gas tank (10),
Connecting line between al carrying shield (8) and mixed gas tank (10), mixed gas tank (10) and quartz glass tube settling chamber (12) entrance point it
Between connecting line be placed in heating tape (11), described connecting line passes through heating tape heating and thermal insulation.
There is outside described ti carrying shield (7) and al carrying shield (8) heating and attemperating unit.
It is respectively equipped with ball valve on described ti carrying shield (7) and al carrying shield (8) the import and export pipeline.
The pipeline that described quartz glass tube settling chamber (12) port of export is connected with device for absorbing tail gas (14) is provided with ball valve.
Described ti carrying shield (7) and al carrying shield (8) connect mixed gas tank (10) and mixed gas tank (10) even quartz glass tube deposition
Pipeline between room (12) entrance point is 316l type φ 4 internal diameter stainless steel tube.
One kind carries out stainless steel surfaces tio using foregoing device2-al2o3The method of dense coating codeposition, should
Method comprises the following steps:
Step one: the pretreatment of stainless steel sample:
Stain removal abluent cleans the dust of stainless steel sample and fine impurity, and described scavenging period is 15-30min；
Pickling is carried out for 1～3% hydrochloric acid solution using mass fraction, removes oxide-film and the corrosion product of sample surfaces,
Described pickling time is 15-30min；
Carry out being cleaned by ultrasonic 15-30min using the deionized water of high purity, remove surface residual debris；
Acetone is finally adopted to be cleaned by ultrasonic except degreasing and other organic substance, scavenging period is 15～30min, puts afterwards
Enter in 120 DEG C of dry for standby in baking oven, drying time is 1h；
Step 2: the assembling of coating exemplar:
Make the rustless steel deck (21) that a width is less than quartz glass tube settling chamber (12) internal diameter first, in deck
The conduit (22) that a width is 2mm is opened it would be desirable to the rustless steel print (20) of deposition blocks in the channel in one minor face center,
Both are loaded jointly it is ensured that deck is horizontal in quartz glass tube, rustless steel sample strip be located at quartzy tube hub and
The interior constant temperature zone of horizontal electric resistance furnace (13), quartz ampoule settling chamber (12) entrance point is connected with mixed gas tank (10) outlet conduit, stone
The port of export of Ying Guan settling chamber (12) is connected with device for absorbing tail gas (14)；
Step 3: intensification depositing operation
After filtering the argon in source of the gas (1) through over-molecular sieve (2) and variable color silica gel (3) first, with the speed of 1l/min
Purging whole device 10 minutes, the air in removing device；Deposited by horizontal electric resistance furnace (13) intensification heated quartz glass tubing
Room (12), is heated to 250-450 DEG C of intended deposition temperature, is passed through filtered argon shielding gas always and prevents during heating up
Only sample is oxidized；
Open heating tape (11) and be heated to 150 DEG C, open ti carrying shield (7) and the upper temperature control table (9) of al carrying shield (8), point
It is not heated to 70 DEG C and 120 DEG C, thus providing saturated vapor pressure, the saturated vapor pressure that described ti carrying shield (7) provides is ttip
1.2kpa, the saturated vapor pressure that described al carrying shield (8) provides is atsb 1.0kpa；
After the temperature that all temperature rise to 250-450 DEG C, adjust shielding gas argon flow amount to 0.4l/min, treat that flow is steady
After fixed, open ti carrying shield (7) and al carrying shield (8), as carrier gas, regulation needle valve (4) makes the carrier gas flux of ti carrying shield be to argon
The carrier gas flux of 0.3l/min, al carrying shield is 0.3l/min, makes that carrier gas argon reaches ti carrying shield (7) in advance and al carrying shield (8) enters
At mouth valve, first open ti carrying shield (7) inlet valve and outlet valve simultaneously, then open al carrying shield (8) inlet valve and outlet valve simultaneously, note
The record reaction time started；
When the question response time reaches the scheduled time of 30-60min, simultaneously close off ti carrying shield (7) and the import of al carrying shield (8)
Valve and outlet valve, stop being passed through, to mixed gas tank (10), the metal organic precursor being provided by ti carrying shield (7) and al carrying shield (8), with
When adjust shielding gas argon in source of the gas (1) with 1l/min purging whole device 30min after, close shielding gas and heating tape, allow
Device Temperature fall.
Step 4: exemplar takes out:
Horizontal electric resistance furnace (13) adopts Temperature fall, treats that temperature is reduced to room temperature, and it is heavy to take out from quartz glass tube settling chamber
Long-pending exemplar, obtains required deposition tio2-al2o3The sample of coating, described coating layer thickness is about 2 μm.This coating and single tio2
Coating is compared, and surface hole defect and crack disappear, and composition coated microgranules are also relatively fine, show that this coating is comparatively dense
Stainless steel substrates are 310s stainless steel substrates.
In step one, the deionized water of high purity is electrical conductivity < 10us/cm ionized water.
Multiple dead slots can be opened up in deck minor face in step 2, realize the multiple stainless steel sample of primary coating.
The metal organic precursor that in step 3, ti carrying shield (7) and al carrying shield (8) provide is respectively isopropyl titanate (ttip)
With aluminium secondary butylate (atsb).
Beneficial effect:
The invention has the beneficial effects as follows realizing stainless steel substrates surface, tio in 350-450 DEG C of temperature range2-al2o3Compound
The fine and close codeposition of coating, eliminates single coating cracking phenomena, reaches the purpose of good suppression surface coking carbon distribution.
Using traditional organic chemical vapor deposition thought, for elongated stainless steel substrates surface tio2-al2o3Composite coating
Chemical gaseous phase co-deposits particular/special requirement and the purpose of suppression coking, and we adopt atsb/ttip organometallic sources system to ensure al
Source and ti source are synchronously supplied, and at lower deposition temperatures, realize the fine and close codeposition of composite coating using mocvd method.Using
Horizontal chamber furnace (oven) and draw-in groove fix the method that print vertically stands on settling chamber, solve sample both sides distribution of air flow in deposition process uneven
Problem.Prepared composite coating surface even compact, substantially occur without crack (300 DEG C, 350 DEG C when be obtained coating, see Fig. 4
Middle c and d), with tio2Single coating and al2o3Single coating is compared, and the consistency on surface and bond strength are all more preferable.
Brief description
Fig. 1 is stainless steel surfaces tio of the present invention2-al2o3Composite coating chemical gaseous phase co-deposits coating unit schematic diagram；
Fig. 2-1 is the connected mode schematic diagram of the stainless steel sample of 1-310s of the present invention and deck；
Fig. 2-2 is the quartz glass tube settling chamber schematic diagram of the present invention；
Fig. 3 prepares tio at being 350 DEG C2Single coating surface topography；
Fig. 4 is the tio of present example same time different deposition temperatures preparation2-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)30min,(a2)40min,
(a3)50min,(a4)60min；
Fig. 6 changes with depositing temperature for o, al, ti element in the prepares coating of present example；
Fig. 7 is 350 DEG C of stainless steel substrates tio of present example2-al2o3The suppression coking effect of composite coating.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.
The present invention be directed to existing chemical vapour deposition technique not enough and provide a kind of new for stainless steel surfaces
tio2-al2o3Middle temperature composite coating chemical gaseous phase codeposition device and its depositing operation, are characterized in: for reaching suppression surface knot
The purpose of burnt carbon distribution, using chemical gaseous phase depositing process and horizontal furnace apparatus, in stainless steel surfaces, in 350-450 DEG C of temperature strip
Tio is realized under part2-al2o3The fine and close codeposition of composite coating.
The deposition principle of the present invention: the present invention rationale here is that, as follows using occurring under the conditions of middle temperature 350-450 DEG C
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 co-deposits.And in order to realize in 310s
The depositing operation on stainless steel substrates surface, wherein needs to solve the problems, such as the following aspects successively:
First, settling chamber's condition of chemical vapor deposition, because deposition workpiece is elongated 310s stainless steel substrates, therefore,
In order that 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 dead slot
Centre and diameter parallel region, it is ensured that the even flow field of sample strip two sidewind, make sample front and back end using higher gas flow rate
Coating layer thickness essentially identical.
Second, the control of reacting gas system.Chemical vapor deposition needs reacting gas to reach enough purity and aridity,
Therefore two-step purification system is adopted to initial reacting gas；Simultaneously in order to ensure the mix homogeneously of reacting gas, reacting gas
Before entering in the reaction chamber premixing is carried out using mixed gas system.
3rd, organic titanium, the temperature control of silicon source saturator.Because the decomposition temperature of isopropanol state and aluminium secondary butylate, full
All different with vapour pressure, in order to ensure inlet amount and the proportioning of both abundances, need to set different saturator temperature, both met
The required material quantity of reaction, is less than the decomposition temperature of metallorganics again.
4th, temperature control system.Whole reacting pipe, before entering settling chamber, using heating tape heating and thermal insulation, is controlled
Temperature processed is more than 150 DEG C；Whole furnace temperature system is controlled by temperature programming switch board it is ensured that final heating reaches temperature
In the target temperature setting.
5th, gas flow controls.For ensureing accuracy and the repeatability of technique, whole gas flow adopts quality stream
Gauge is controlled.
On the basis of above each several part condition is guaranteed, we are according to tio2-al2o3The chemical gaseous phase of composite coating
Codeposition reactions, are uniformly passed through reacting gas in elongated rustless steel exemplar, finally can achieve tio2-al2o3Compound painting
The surface vapor codeposition of layer.And the quality of coating can pass through thickness, the testing result such as elementary analysiss and surface topography is carried out
Analysis, and its suppression coking behavior can be verified by the coking of high temperature.
As illustrated, a kind of middle temperature composite coating chemical gaseous phase co-deposit device it is characterised in that this device include following
Part, purifying part, mixed gas tank (10), heating tape (11), quartz glass tube settling chamber (12), horizontal electric resistance furnace (13) and tail gas
Absorption plant (14)；
Described purifying part is by the source of the gas (1) being sequentially connected, molecular sieve (2), variable color silica gel (3), needle valve (4) and quality
Effusion meter (5) forms, and described source of the gas (1) is high-purity argon gas；
Described purifying part has three, the mass flowmenter (5) of the first purifying part pass 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 shield (7), the 3rd purifying part by pipeline
Mass flowmenter (5) al carrying shield (8) is connected by pipeline, ti carrying shield (7) is all connected with mixed gas tank (10) with al carrying shield (8),
The other end of mixed gas tank (10) connects, by pipeline, quartz glass tube settling chamber (12) import being placed in horizontal electric resistance furnace (13)
End, the port of export of this quartz glass tube settling chamber (12) is connected with device for absorbing tail gas (14).
Described ti carrying shield (7), al carrying shield (8) and horizontal electric resistance furnace (13) are upper to connect temperature control table (9).
Adapter road between ball valve (6) and mixed gas tank (10), the connecting line between ti carrying shield (7) and mixed gas tank (10),
Connecting line between al carrying shield (8) and mixed gas tank (10), mixed gas tank (10) and quartz glass tube settling chamber (12) entrance point it
Between connecting line be placed in heating tape (11), described connecting line passes through heating tape heating and thermal insulation.
There is outside described ti carrying shield (7) and al carrying shield (8) heating and attemperating unit.
It is respectively equipped with ball valve on described ti carrying shield (7) and al carrying shield (8) the import and export pipeline.
The pipeline that described quartz glass tube settling chamber (12) port of export is connected with device for absorbing tail gas (14) is provided with ball valve.
Described ti carrying shield (7) and al carrying shield (8) connect mixed gas tank (10) and mixed gas tank (10) even quartz glass tube deposition
Pipeline between room (12) entrance point is 316l type φ 4 internal diameter stainless steel tube.
One kind carries out stainless steel surfaces tio using foregoing device2-al2o3The method of dense coating codeposition, should
Method comprises the following steps:
Step one: the pretreatment of stainless steel sample:
Stain removal abluent cleans the dust of stainless steel sample and fine impurity, and described scavenging period is 15-30min；
Pickling is carried out for 1～3% hydrochloric acid solution using mass fraction, removes oxide-film and the corrosion product of sample surfaces,
Described pickling time is 15-30min；
Carry out being cleaned by ultrasonic 15-30min using the deionized water of high purity, remove surface residual debris；
Acetone is finally adopted to be cleaned by ultrasonic except degreasing and other organic substance, scavenging period is 15～30min, puts afterwards
Enter in 120 DEG C of dry for standby in baking oven, drying time is 1h；
Step 2: the assembling of coating exemplar:
Make the rustless steel deck (21) that a width is less than quartz glass tube settling chamber (12) internal diameter first, in deck
The conduit (22) that a width is 2mm is opened it would be desirable to the rustless steel print (20) of deposition blocks in the channel in one minor face center,
Both are loaded jointly it is ensured that deck is horizontal in quartz glass tube, rustless steel sample strip be located at quartzy tube hub and
The interior constant temperature zone of horizontal electric resistance furnace (13), quartz ampoule settling chamber (12) entrance point is connected with mixed gas tank (10) outlet conduit, stone
The port of export of Ying Guan settling chamber (12) is connected with device for absorbing tail gas (14)；
Step 3: intensification depositing operation
After filtering the argon in source of the gas (1) through over-molecular sieve (2) and variable color silica gel (3) first, with the speed of 1l/min
Purging whole device 10 minutes, the air in removing device；Deposited by horizontal electric resistance furnace (13) intensification heated quartz glass tubing
Room (12), is heated to 250-450 DEG C of intended deposition temperature, is passed through filtered argon shielding gas always and prevents during heating up
Only sample is oxidized；
Open heating tape (11) and be heated to 150 DEG C, open ti carrying shield (7) and the upper temperature control table (9) of al carrying shield (8), point
It is not heated to 70 DEG C and 120 DEG C, thus providing saturated vapor pressure, the saturated vapor pressure that described ti carrying shield (7) provides is ttip
1.2kpa, the saturated vapor pressure that described al carrying shield (8) provides is atsb 1.0kpa；
After the temperature that all temperature rise to 250-450 DEG C, adjust shielding gas argon flow amount to 0.4l/min, treat that flow is steady
After fixed, open ti carrying shield (7) and al carrying shield (8), as carrier gas, regulation needle valve (4) makes the carrier gas flux of ti carrying shield be to argon
The carrier gas flux of 0.3l/min, al carrying shield is 0.3l/min, makes that carrier gas argon reaches ti carrying shield (7) in advance and al carrying shield (8) enters
At mouth valve, first open ti carrying shield (7) inlet valve and outlet valve simultaneously, then open al carrying shield (8) inlet valve and outlet valve simultaneously, note
The record reaction time started；
When the question response time reaches the scheduled time of 30-60min, simultaneously close off ti carrying shield (7) and the import of al carrying shield (8)
Valve and outlet valve, stop being passed through, to mixed gas tank (10), the metal organic precursor being provided by ti carrying shield (7) and al carrying shield (8), with
When adjust shielding gas argon in source of the gas (1) with 1l/min purging whole device 30min after, close shielding gas and heating tape, allow
Device Temperature fall.
Step 4: exemplar takes out:
Horizontal electric resistance furnace (13) adopts Temperature fall, treats that temperature is reduced to room temperature, and it is heavy to take out from quartz glass tube settling chamber
Long-pending exemplar, obtains required deposition tio2-al2o3The sample of coating, described coating layer thickness is about 2 μm.This coating and single tio2
Coating is compared, and surface hole defect and crack disappear, and composition coated microgranules are also relatively fine, show that this coating is comparatively dense
Stainless steel substrates are 310s stainless steel substrates.
In step one, the deionized water of high purity is electrical conductivity < 10us/cm ionized water.
Multiple dead slots can be opened up in deck minor face in step 2, realize the multiple stainless steel sample of primary coating.
The metal organic precursor that in step 3, ti carrying shield (7) and al carrying shield (8) provide 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, temperature 350-450 DEG C, settling chamber and connected mode are as shown in accompanying drawing 2-1 and 2-2.
1) pretreatment of exemplar:
Stain removal is cleaned, and removes the dust in the course of processing and fine impurity；Carry out pickling, remove the oxidation of sample surface
Film and corrosion product；Deionized water using high purity is cleaned by ultrasonic, and removes surface residual debris；It is cleaned by ultrasonic using acetone and remove
Greasy dirt and other organic substance, each scavenging period is 15-30min.Finally, stainless steel sample is put in baking oven at 120 DEG C
Dry 1h standby.
2) assembling of coating exemplar:
The rustless steel handled well print is stuck in the wide dead slot of 2mm of deck side, by deck and stainless steel substrates
It is ensured that deck is horizontal in common loading quartz glass tube, rustless steel sample strip is located at quartzy tube hub and heating furnace
Flat-temperature zone, quartz ampoule one end is connected with mixed gas tank outlet pipeline, the other end is connected with device for absorbing tail gas.
3) intensification depositing operation
Using high-purity argon gas 1l/min before intensification, purging whole system 10 minutes, the air in removing system；By setting
Fixed heating schedule reacting by heating tube furnace, is heated to intended deposition temperature, is passed through high-purity argon shielding gas during heating up
Prevent sample oxidized；
Open heating tape and be 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；
Rise to after the temperature that experiment sets after all temperature, according to default experimental technique, adjust shielding gas flow to
0.4l/min, after throughput to be protected is stable, opens carrier gas steel cylinder main valve and air relief valve, rotates carrier gas flux meter needle valve, make
Carrier gas reaches at saturator inlet valve in advance, first opens titanium source saturator terminal valve simultaneously, then opens silicon source saturator simultaneously
Terminal valve, makes titanium source and silicon source supply simultaneously, and the time started of record experiment is it is ensured that the flow of two-way argon carrier is
0.3l/min；
During experiment is carried out, the moment monitors course of reaction it is ensured that entirely reacting the carrying out of safe and continuous.Wait to test
Reach the predetermined time, simultaneously close off inlet valve and the outlet valve of saturator, stop being passed through metal organic precursor to reaction tube,
Adjust shielding gas flow simultaneously and purge whole response system to 1l/min.
After response system 30min is swept in air-blowing to be protected, close shielding gas and heating tape, allow system Temperature fall.
4) exemplar takes out and quality testing.
Heating furnace adopts Temperature fall, treats that temperature is down to room temperature, takes out deposition exemplar, obtain from quartz glass deposition room
Required coating sample.Sem and eds is carried out for deposition exemplar and analyzes its surface topography and elementary composition, such as Fig. 3 is 350 DEG C
When stainless steel surfaces coat single tio2Coating surface microscopic appearance, the tio as can be seen from the figure preparing2Coating is due to interior
Stress and lead to coating cracking, the presence in crack reduces suppression 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 length of the scale be 10um；Be can be seen that by Fig. 4 (a)
250 DEG C of coating growth rates are slower, and sedimentation time is 30min, and therefore matrix surface does not have obvious 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 has obvious crack (Fig. 4 (b)).Change in 350 DEG C of coating morphology, coating surface is by small
Spherical particle composition, coating uniform densification (Fig. 4 (c)).Depositing temperature continues to rise, and coating surface granule is changed into by spherical
Grain shape (Fig. 4 (d)).In 450 DEG C of coating surfaces, (Fig. 4 (e)) is formed by bigger cotton-shaped particle packing.
Fig. 5 is 350 DEG C of different sedimentation time coating morphology；Due to al2o3Doping vario-property effect, coating surface is smoothed
Fine and close surface particles cover, and increase to 60min with sedimentation time from 30min, coating layer thickness is gradually increased, and coating surface does not have
Crackle is had to produce (Fig. 5 (a1)～(a4)).
Fig. 6 be in coating o, al, ti element with the change of depositing temperature, by figure it may be seen that when below 350 DEG C
Two kinds of coatings are doped relatively good.Coating inhibition of coke formation situation is checked using atmospheric cracking coking experiment porch, hexamethylene is former
Material, carries out cracking coking experiment at 800 DEG C, experimental period is 1.5h, result cracking coking experimental result as shown in Figure 7 can
To find out the tio preparing when 350 DEG C2-al2o3Coated foil has good suppression Jiao's effect with respect to blank stainless steel substrates, and with
Coating layer thickness increases, and suppression coking effect improves.
It should be understood that these embodiments are only illustrative of the invention and is not intended to limit the scope of the invention.In addition, it is to be understood that
After having read the content of present invention instruction, those skilled in the art can make various changes or modifications to the present invention, these
The equivalent form of value equally falls within the application appended claims limited range.
Claims (10)
1. a kind of middle temperature composite coating chemical gaseous phase codeposition device is it is characterised in that this device is included with lower component, purification portion
Part, mixed gas tank (10), heating tape (11), quartz glass tube settling chamber (12), horizontal electric resistance furnace (13) and device for absorbing tail gas
(14)；
Described purifying part is by the source of the gas (1) being sequentially connected, molecular sieve (2), variable color silica gel (3), needle valve (4) and mass flow
Meter (5) composition, described source of the gas (1) is high-purity argon gas；
Described purifying part has three, 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 shield (7), the matter of the 3rd purifying part by pipeline
Amount effusion meter (5) connects al carrying shield (8) by pipeline, and ti carrying shield (7) is all connected with mixed gas tank (10) with al carrying shield (8), mixed gas
The other end of tank (10) connects, by pipeline, quartz glass tube settling chamber (12) entrance point being placed in horizontal electric resistance furnace (13), should
The port of export of quartz glass tube settling chamber (12) is connected with device for absorbing tail gas (14)；
Described ti carrying shield (7), al carrying shield (8) and horizontal electric resistance furnace (13) are upper to connect temperature control table (9)；
Adapter road between ball valve (6) and mixed gas tank (10), the connecting line between ti carrying shield (7) and mixed gas tank (10), al source
Connecting line between tank (8) and mixed gas tank (10), between mixed gas tank (10) and quartz glass tube settling chamber (12) entrance point
Connecting line is placed in heating tape (11), and described connecting line passes through heating tape heating and thermal insulation.
2. one kind as claimed in claim 1 middle temperature composite coating chemical gaseous phase codeposition device is it is characterised in that described ti source
There is outside tank (7) and al carrying shield (8) heating and attemperating unit.
3. one kind as claimed in claim 1 middle temperature composite coating chemical gaseous phase codeposition device is it is characterised in that described ti source
It is respectively equipped with ball valve on tank (7) and al carrying shield (8) the import and export pipeline.
4. one kind as claimed in claim 1 middle temperature composite coating chemical gaseous phase codeposition device is it is characterised in that described quartz
The pipeline that glass tubing settling chamber (12) port of export is connected with device for absorbing tail gas (14) is provided with ball valve.
5. one kind as claimed in claim 1 middle temperature composite coating chemical gaseous phase codeposition device is it is characterised in that described ti source
Tank (7) and the mixed gas tank (10) of al carrying shield (8) connection and mixed gas tank (10) are even between quartz glass tube settling chamber (12) entrance point
Pipeline be 316l type φ 4 internal diameter stainless steel tube.
6. a kind of stainless steel surfaces tio is carried out using the device as described in claim 1-52-al2o3Dense coating codeposition
Method, the method comprises the following steps:
Step one: the pretreatment of stainless steel sample:
Stain removal abluent cleans the dust of stainless steel sample and fine impurity, and described scavenging period is 15-30min；
Pickling is carried out for 1～3% hydrochloric acid solution using mass fraction, removes oxide-film and the corrosion product of sample surfaces, described
Pickling time is 15-30min；
Carry out being cleaned by ultrasonic 15-30min using the deionized water of high purity, remove surface residual debris；
Acetone is finally adopted to be cleaned by ultrasonic except degreasing and other organic substance, scavenging period is 15～30min, puts into baking afterwards
In 120 DEG C of dry for standby in case, drying time is 1h；
Step 2: the assembling of coating exemplar:
Make the rustless steel deck (21) that a width is less than quartz glass tube settling chamber (12) internal diameter first, the one of deck
Individual minor face center opens the conduit (22) that a width is 2mm it would be desirable to the rustless steel print (20) of deposition blocks in the channel, will
It is ensured that deck is horizontal in both common loading quartz glass tubes, rustless steel sample strip is located at quartzy tube hub and crouches
The interior constant temperature zone of formula resistance furnace (13), quartz ampoule settling chamber (12) entrance point is connected with mixed gas tank (10) outlet conduit, quartz
The port of export of pipe settling chamber (12) is connected with device for absorbing tail gas (14)；
Step 3: intensification depositing operation
After filtering the argon in source of the gas (1) through over-molecular sieve (2) and variable color silica gel (3) first, with the speed purging of 1l/min
Whole device 10 minutes, the air in removing device；By horizontal electric resistance furnace (13) intensification heated quartz glass tubing settling chamber
(12), it is heated to 250-450 DEG C of intended deposition temperature, being passed through filtered argon shielding gas always during heating up prevents
Sample is oxidized；
Open heating tape (11) be heated to 150 DEG C, open ti carrying shield (7) and al carrying shield (8) go up temperature control table (9), respectively plus
To 70 DEG C and 120 DEG C, thus providing saturated vapor pressure, the saturated vapor pressure that described ti carrying shield (7) provides is ttip to heat
1.2kpa, the saturated vapor pressure that described al carrying shield (8) provides is atsb 1.0kpa；
After the temperature that all temperature rise to 250-450 DEG C, adjust shielding gas argon flow amount to 0.4l/min, treat stability of flow
Afterwards, ti carrying shield (7) and al carrying shield (8) are opened, as carrier gas, adjust needle valve (4) makes the carrier gas flux of ti carrying shield be to argon
The carrier gas flux of 0.3l/min, al carrying shield is 0.3l/min, makes that carrier gas argon reaches ti carrying shield (7) in advance and al carrying shield (8) enters
At mouth valve, first open ti carrying shield (7) inlet valve and outlet valve simultaneously, then open al carrying shield (8) inlet valve and outlet valve simultaneously, note
The record reaction time started；
When the question response time reaches the scheduled time of 30-60min, simultaneously close off ti carrying shield (7) and al carrying shield (8) inlet valve and
Outlet valve, stops being passed through, to mixed gas tank (10), the metal organic precursor being provided by ti carrying shield (7) and al carrying shield (8), adjusts simultaneously
After shielding gas argon in solar term source (1) is with 1l/min purging whole device 30min, close shielding gas and heating tape, allow device
Temperature fall.
Step 4: exemplar takes out:
Horizontal electric resistance furnace (13) adopts Temperature fall, treats that temperature is reduced to room temperature, takes out deposition sample from quartz glass tube settling chamber
Part, obtains required deposition tio2-al2o3The sample of coating, described coating layer thickness is about 2 μm.
7. method as claimed in claim 6 is it is characterised in that stainless steel substrates are 310s stainless steel substrates.
8. method as claimed in claim 6 it is characterised in that in step one high purity deionized water be electrical conductivity <
10us/cm ionized water.
9. method as claimed in claim 6 is it is characterised in that can open up multiple dead slots in deck minor face in step 2, real
The existing multiple stainless steel sample of primary coating.
10. method as claimed in claim 6 is it is characterised in that gold that in step 3, ti carrying shield (7) and al carrying shield (8) provide
Belong to organic precursor and be respectively isopropyl titanate (ttip) and aluminium secondary butylate (atsb).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610841130.7A CN106367732B (en) | 2016-09-22 | 2016-09-22 | A kind of medium temperature metal organic chemical vapor deposition TiO2-Al2O3Composite coating device and painting method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610841130.7A CN106367732B (en) | 2016-09-22 | 2016-09-22 | A kind of medium temperature metal organic chemical vapor deposition TiO2-Al2O3Composite coating device and painting method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106367732A true CN106367732A (en) | 2017-02-01 |
| CN106367732B CN106367732B (en) | 2018-11-06 |
Family
ID=57898055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610841130.7A Active CN106367732B (en) | 2016-09-22 | 2016-09-22 | A kind of medium temperature metal organic chemical vapor deposition TiO2-Al2O3Composite coating device and painting method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106367732B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108335972A (en) * | 2018-02-06 | 2018-07-27 | 沈阳拓荆科技有限公司 | A kind of circular arc type heating tape and heating tape method for coating |
| 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 |
| CN109468614A (en) * | 2018-12-07 | 2019-03-15 | 西安交通大学 | A kind of surface anti-coking nano compound film and preparation method thereof |
| CN113025948A (en) * | 2021-03-08 | 2021-06-25 | 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2011151298A (en) * | 2010-01-25 | 2011-08-04 | Taiyo Nippon Sanso Corp | Mocvd device |
| 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 |
| CN204325494U (en) * | 2014-12-05 | 2015-05-13 | 上海微世半导体有限公司 | A kind of LPCVD deposition boiler tube |
-
2016
- 2016-09-22 CN CN201610841130.7A patent/CN106367732B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2011151298A (en) * | 2010-01-25 | 2011-08-04 | Taiyo Nippon Sanso Corp | Mocvd device |
| 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 |
| CN204325494U (en) * | 2014-12-05 | 2015-05-13 | 上海微世半导体有限公司 | A kind of LPCVD deposition boiler tube |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108335972A (en) * | 2018-02-06 | 2018-07-27 | 沈阳拓荆科技有限公司 | A kind of circular arc type heating tape and heating tape method for coating |
| 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 |
| CN109468614A (en) * | 2018-12-07 | 2019-03-15 | 西安交通大学 | A kind of surface anti-coking nano compound film and preparation method thereof |
| CN113025948A (en) * | 2021-03-08 | 2021-06-25 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106367732B (en) | 2018-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106367732B (en) | A kind of medium temperature metal organic chemical vapor deposition TiO2-Al2O3Composite coating device and painting method | |
| CN107119264B (en) | Iridium-alumina high temperature coating apparatus and technique are deposited with chamber In-situ reaction | |
| CN101050515A (en) | Method for raising service life of coat layer of heat barrier by surface modification of metal binder course | |
| CN104498899A (en) | Method for inhibiting metal surface carbon deposition by using atomic layer deposition passivation layer | |
| EP2194162B1 (en) | Use of a coating | |
| CN104264126B (en) | Long-range microchannel interior walls TiO2coating chemical vapor deposition unit and painting method | |
| EP3102717B1 (en) | Protective layer for pecvd graphite boats | |
| DE102007025151A1 (en) | Coating method comprises producing plasma jet from process gas and introducing precursor material into it, coating being deposited from jet on to substrate or existing coating on it and substrate being heated | |
| CN110106463A (en) | A kind of preparation method with interlayer pore structure thermal barrier coating | |
| US10053780B2 (en) | Method for depositing an anti-corrosion coating | |
| Zhang et al. | Characterization of MOCVD TiO2 coating and its anti-coking application in cyclohexane pyrolysis | |
| CN114956825A (en) | Method for growing TaC coating on surface of graphite-based material | |
| CN102728414A (en) | Preparation method of catalyst for preparing single-walled carbon nanotube and application of catalyst | |
| CN105986247B (en) | The fluidized bed plant and method of a kind of diamond surface plated film and the product prepared using this method | |
| CN103172381A (en) | Preparation method and applications of cold-wall fluidized bed | |
| JP2002516750A (en) | Method for producing metal fiber board functionalized by catalyst | |
| CN111468092A (en) | Carbon-based titanium dioxide composite combustion catalyst for propellant and preparation method thereof | |
| CN109055915A (en) | TiN coating chemical vapor deposition unit and preparation method based on electric current heating | |
| US8591991B2 (en) | Fabrication method and fabrication apparatus for fabricating metal oxide thin film | |
| CN202297763U (en) | Metal-organic chemical vapor deposition (MOCVD) device | |
| Skandan et al. | Low‐pressure flame deposition of nanostructured oxide films | |
| CN113403607A (en) | Component inner wall ALD coating equipment and method | |
| CN116159554B (en) | Ethylene cracking furnace tube coating material and preparation method and application thereof | |
| CN116288207B (en) | Thermal barrier coating, preparation method thereof and application thereof in high-temperature alloy | |
| CN2750872Y (en) | Improvement of spray gun structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |