CN114059040A - Deposition method and device for TiN coating on inner surface of pipe network - Google Patents

Deposition method and device for TiN coating on inner surface of pipe network Download PDF

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Publication number
CN114059040A
CN114059040A CN202111405602.1A CN202111405602A CN114059040A CN 114059040 A CN114059040 A CN 114059040A CN 202111405602 A CN202111405602 A CN 202111405602A CN 114059040 A CN114059040 A CN 114059040A
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pipe network
heating furnace
coating
end valve
positive
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朱权
李象远
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Sichuan University
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Sichuan University
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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
    • C23C16/34—Nitrides
    • 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
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45557—Pulsed pressure or control pressure
    • 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

Abstract

A method for depositing TiN coating on the inner surface of a pipe network comprises the following steps: s1: carrying out pretreatment operation on the pipe network; s2: connecting the pretreated piping network to an interior surface coating deposition apparatus; s3: carrying out a positive and negative pressure alternate coating reaction on the pipe network by using inner surface coating deposition equipment; s4: and taking out the pipe network after the reaction is finished. A deposition device for TiN coatings on the inner surface of a pipe network comprises inner surface coating deposition equipment, wherein the inner surface coating deposition equipment comprises a raw material gas supply pipeline, a heating furnace, a vacuum system and a positive and negative pressure control system; the feed gas supply pipeline is connected to a gas inlet of the heating furnace, and a gas outlet of the heating furnace is connected with a vacuum system; the heating furnace is used for heating a pipe network, and the pipe network is connected to an air inlet and an air outlet of the heating furnace; the positive and negative pressure control system controls the air inlet and the air outlet of the heating furnace to form a periodic positive and negative pressure state on the pipe network. The complete coating of the inner surface of the complex pipe network is realized.

Description

Deposition method and device for TiN coating on inner surface of pipe network
Technical Field
The invention relates to the field of material surface treatment and coating, in particular to a deposition method and a deposition device for a TiN coating on the inner surface of a pipe network.
Background
When the aircraft flies at high speed, the high thermal load of the combustion chamber and the related components becomes a key factor influencing the flight safety of the aircraft. Although the material science develops rapidly, the improvement of the material performance can not meet the requirement of a combustion chamber on the temperature resistance of the material, the improvement of the material performance has a limit value, and the required research and development period is long. Therefore, active cooling technology is an excellent solution for thermal management of high-temperature hot components, i.e. onboard fuel flows through the hot-end components to absorb heat, thereby effectively cooling the overheated components. However, the fuel oil pyrolysis process after heat absorption is accompanied by serious coking problem, which is a great obstacle to the mature application of the technology. In the matrix material, Fe and Ni elements have catalytic action, and the speed of catalyzing and generating the filamentous coke is high, so that the Fe and Ni elements become a main reason for blocking a cooling channel. The inert passivation coating can effectively isolate the metal catalytic active sites in the matrix, and plays roles in inhibiting surface coking and improving running time. Currently, there is much research on passivation coatings, which can be largely divided into metal nitride and metal oxide coatings. The nitride coating is an excellent choice for a passivation coating because of small mismatching degree and strong binding force with a matrix. The coking inhibition performance of the TiN coating is widely verified and becomes one of the main selection types of the passivation coating.
Passivation coatings are produced in a variety of ways, although chemical vapor deposition is the most effective way for the channels within the pores. Research shows that chemical vapor deposition can coat long-range channel effectively to obtain homogeneous coating. However, in many types of active cooling technologies, the fuel cooling channels are often complex pipe network structures formed by cross-connecting different pipe diameters. Under static conditions, there are dead zones of flow when fluids flow in this cross pipe network. Therefore, the common chemical vapor deposition method adopts a reaction gas self-flowing deposition mode, and cannot meet the requirement of comprehensive deposition on the inner surface of a complex pipe network.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method and a device for depositing a TiN coating on the inner surface of a pipe network, aiming at the problem that a dead zone in a complex pipe network is difficult to coat, positive and negative pressure alternate deposition is carried out, and the inner surface of the complex pipe network is completely coated.
The purpose of the invention is realized by the following technical scheme:
a method for depositing TiN coating on the inner surface of a pipe network comprises the following steps:
s1: carrying out pretreatment operation on the pipe network;
s2: connecting the pretreated piping network to an interior surface coating deposition apparatus;
s3: carrying out a positive and negative pressure alternate coating reaction on the pipe network by using inner surface coating deposition equipment;
s4: and taking out the pipe network after the reaction is finished.
Further, the step S3 includes the following sub-steps:
s301: introducing protective gas into the pipe network by the inner surface coating deposition equipment;
s302: heating the pipe network by using inner surface coating deposition equipment and keeping protective gas flow;
s303: raw material gas is introduced into the pipe network by the inner surface coating deposition equipment, and a periodic positive and negative pressure state is formed in the pipe network by the inner surface coating deposition equipment.
Further, in the sub-step S303, the front end valve and the rear end valve of the inner surface coating deposition apparatus are controlled to form a periodic positive and negative pressure state, the rear end valve is opened and the front end valve is closed to form a negative pressure state, and the front end valve is opened and the rear end valve is closed to form a positive pressure state.
Further, in the substep S303, a pressure relief mode after switching at a fixed period is adopted to ensure the forward flow of the feed gas.
A deposition device for TiN coatings on the inner surface of a pipe network comprises inner surface coating deposition equipment, wherein the inner surface coating deposition equipment comprises a raw material gas supply pipeline, a heating furnace, a vacuum system and a positive and negative pressure control system;
the feed gas supply pipeline is connected to a gas inlet of the heating furnace, and a gas outlet of the heating furnace is connected with a vacuum system;
the heating furnace is used for heating a pipe network, and the pipe network is connected to an air inlet and an air outlet of the heating furnace;
the positive and negative pressure control system controls the air inlet and the air outlet of the heating furnace to form a periodic positive and negative pressure state on the pipe network.
Further, the positive and negative pressure control system comprises a front end valve, a rear end valve and an electromagnetic valve control system; the front end valve is arranged at the air inlet of the heating furnace, the rear end valve is arranged at the air outlet of the heating furnace, and the front end valve and the rear end valve are electrically connected to the electromagnetic valve control system.
Further, after the opening and closing cycles of the front end valve and the rear end valve are cycled for two cycles, an emptying time period for opening the electromagnetic valves simultaneously occurs to form constant-cycle switching and then relief pressure so as to ensure the forward flow of the raw material gas.
Further, the solenoid valve control system comprises a PLC controller; the front end valve and the rear end valve are electromagnetic valves.
Further, the feed gas supply line comprises TiCl4Steam supply line, H2Feed gas supply line, N2A raw gas supply pipeline and a gas mixing tank; the TiCl4Steam supply line, H2Feed gas supply line and N2The feed gas supply pipelines are all connected to a gas mixing tank, and the gas mixing tank is connected to the heating furnace.
Further, the TiCl4The vapor supply pipeline comprises a carrier gas supply pipeline and TiCl which are connected in sequence4An evaporator; the TiCl4The evaporator is connected to the gas mixing tank.
The invention has the beneficial effects that:
aiming at the problem that the dead zone in the complex pipe network is difficult to coat, the positive and negative pressure alternate deposition is carried out, and the whole coating of the inner surface of the complex pipe network is realized.
Drawings
FIG. 1 is a schematic structural view of a deposition apparatus for TiN coating on the inner surface of a pipe network;
FIG. 2 is a schematic structural diagram of a simple pipe network;
FIG. 3 is a diagram of a simplified pipeline network;
FIG. 4 is a schematic diagram of the solenoid valve switching cycle;
FIG. 5 is a thickness diagram of different positions in the simple pipe network;
FIG. 6 is a diagram of the distribution of coating elements in the simple pipe network;
FIG. 7 is an XRD pattern of a coating in a simple pipe network;
FIG. 8 is a diagram of the coating effect of a simple pipe network obtained by a conventional chemical vapor deposition method;
FIG. 9 is a diagram of the coating effect of the simple pipe network obtained by the method and the device of the present invention;
fig. 10 is a graph of the coating effect of a complex pipe network obtained by the method and the device of the invention.
In the figure, 1-feed gas supply line, 11-TiCl4Vapor supply line, 111-carrier gas supply line, 112-TiCl4Evaporator, 12-H2Feed gas supply line, 13-N2The system comprises a raw material gas supply pipeline, a 14-mixed gas tank, a 2-heating furnace, a 21-front-end valve, a 22-rear-end valve, a 3-vacuum pump, a 4-PLC controller, a 5-temperature control table, a 6-heating belt, a 7-buffer tank, an 81-molecular sieve drying pipe, an 82-needle valve, an 83-mass flow meter and a 9-furnace temperature control system.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict.
It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.
The first embodiment is as follows:
as shown in fig. 1 to 4, a deposition apparatus for TiN coating on the inner surface of a pipe network comprises an inner surface coating deposition device, wherein the inner surface coating deposition device comprises a raw material gas supply pipeline, a heating furnace 2, a vacuum system and a positive and negative pressure control system;
the raw material gas supply pipeline is connected to a gas inlet of the heating furnace 2, and a gas outlet of the heating furnace 2 is connected with a vacuum system;
the heating furnace 2 is used for heating a pipe network, and the pipe network is connected to the air inlet and the air outlet of the heating furnace 2;
the positive and negative pressure control system controls the air inlet and the air outlet of the heating furnace 2 to form a periodic positive and negative pressure state on the pipe network.
The positive and negative pressure control system comprises a front end valve 21, a rear end valve 22 and an electromagnetic valve control system; the front end valve 21 is arranged at an air inlet of the heating furnace 2, the rear end valve 22 is arranged at an air outlet of the heating furnace 2, and the front end valve 21 and the rear end valve 22 are electrically connected to an electromagnetic valve control system.
The vacuum system is a vacuum pump 3.
The electromagnetic valve control system comprises a PLC (programmable logic controller) 4; the front end valve 21 and the rear end valve 22 are electromagnetic valves.
The heating furnace 2 is a box furnace.
The feed gas supply line comprises TiCl4 Steam supply pipe 11, H2Raw gas supply pipeline 12, N2A raw gas supply pipeline 13 and a gas mixing tank 14; the TiCl4 Steam supply pipe 11, H2Raw material gas supply line 12 and N2The feed gas supply pipes 13 are each connected to a gas mixing tank 14, which is connected to the heating furnace 2.
The TiCl4Steam generating deviceThe supply pipe 11 supplies TiCl4Steam of said H2Feed gas supply line 12 supplies H2Feed gas of said N2A raw material gas supply pipe 13 for supplying N2A raw material gas.
The TiCl4The vapor supply pipe 11 includes a carrier gas supply pipe 111 and TiCl connected in sequence4An evaporator 112; the TiCl4The evaporator 112 is connected to the gas mixing tank.
The TiCl4A heating belt 6 is arranged on a connecting pipeline between the evaporator 112 and the gas mixing tank.
The carrier gas supply pipe 111 supplies a carrier gas; the carrier gas is H2And (4) a carrier gas.
Said H2Raw gas supply pipeline 12, N2The raw gas supply line 13 and the carrier gas supply line 111 are provided with a molecular sieve drying pipe 81 and a constant pressure gas supply system.
The constant pressure air supply system includes a needle valve 82 and a mass flow meter 83.
The TiCl4The evaporator 112 is connected to a temperature control table 5. Temperature control table 5 pairs of TiCl4The evaporator 112 is temperature controlled.
The heating furnace 2 is connected with a furnace temperature control system 9.
The constant pressure air supply system is at a constant flow (N)2The raw material gas is 1235 mL/min; h2Raw material gas is 821 mL/min; h2Carrier gas 896 mL/min). The raw material gas enters a pipe network through a molecular sieve drying pipe 81, a needle valve 82 and a mass flow meter 83 in sequence; wherein H2Passing a carrier gas through TiCl4Evaporator 112 feeding TiCl4Steam entrainment. The heating furnace 2 is a box-type furnace with a constant temperature zone as long as 1.6m, and the pipe network is placed in the heating furnace 2 and connected to the air inlet and the air outlet of the heating furnace 2.
After the opening and closing cycles of the front end valve 21 and the rear end valve 22 are cycled for two cycles, an emptying time period for opening the electromagnetic valves simultaneously occurs to form constant-cycle switching and then relief pressure so as to ensure the forward flow of the raw material gas.
The electromagnetic valve control system controls the opening and closing of the front end valve 21 and the rear end valve 22 through Siemens PLC, and the opening and closing period of the front end valve 21 and the rear end valve 22 is shown in figure 4. The opening and closing period can be changed according to the volume of the cavity in the heating furnace 2, and the final purpose is to ensure that the reaction gas does not flow backwards. The vacuum system keeps working all the time, the pumping speed of the vacuum pump 3 reaches 2L/s, which is far larger than the gas amount in the heating furnace 2; the constant-pressure air supply system can be filled with the pipe network in a short time. The open and close cycle of the front and rear valves 21 and 22 is cycled two cycles before a 1 second drain period occurs with the solenoid valve open simultaneously, as shown in fig. 4. The emptying time period is the key for smooth operation of the whole positive-negative pressure alternate coating, on one hand, the emptying process can release the pressure of the air accumulated at the front end, and the forward flow of the front end is ensured to be maintained; on the other hand, the rapid flow in the emptying period is helpful to take away the by-products of the reaction system, and the deposition quality of the coating is improved.
A buffer tank 7 with large volume is connected between the vacuum system and the heating furnace 2, and porous media are filled in the buffer tank 7 to filter the gas after reaction.
A method for depositing TiN coating on the inner surface of a pipe network comprises the following steps:
s1: carrying out pretreatment operation on the pipe network;
the pretreatment operation comprises stain removal and cleaning, acid washing, deionized water rinsing, acetone cleaning, direct injection type cleaning and leak point detection.
The pipe network is formed by connecting a plurality of pipe bodies.
The method comprises the following steps of removing stains, cleaning, pickling, rinsing with deionized water, cleaning with acetone and directly injecting to clean pipe bodies, connecting the pipe bodies into a pipe network, and detecting leakage points of the pipe network.
Cleaning stains, and removing dust and fine impurities in the processing process; acid washing is carried out, and an oxide film and a corrosion product on the inner wall of the pipe network are removed; rinsing with deionized water, namely rinsing with deionized water with higher purity to remove surface residues; and (3) acetone cleaning, namely cleaning with acetone to remove oil stains and other organic substances. The direct injection type cleaning method is characterized in that a cleaning process of direct injection type repeated cleaning is adopted for repeatedly cleaning the tube body for 3-4 times, cotton gloves are needed to be worn in the operation process, and the inner wall of the tube body is cleaned. Purging the stainless steel pipe network cleaned by acetone for 5min by an air pump to accelerate the volatilization of acetone remained on the inner wall, removing the acetone remained on the inner wall, and drying in an oven at 80 ℃ for later use.
The leak point detection is to connect the processed stainless steel pipe bodies (such as according to the communication mode in fig. 2) through the clamping sleeves to form a pipe network, block the outlet of the pipe after the pipe connection is finished, communicate 0.2MPa gas with the pipe network, place the pipe network in water, observe whether bubbles are emitted in the water to judge the location of the leak point, process the leak point and ensure that the pipe network is airtight.
S2: connecting the pretreated piping network to an interior surface coating deposition apparatus;
on the premise of ensuring that the pipe network is airtight, the whole pipe network is placed into a heating furnace 2 of the inner surface coating deposition equipment, an air inlet of the heating furnace 2 is connected with an inlet pipeline of the pipe network, an outlet pipeline of the pipe network is blocked, the airtightness of a joint of the pipe network is further judged according to the gas flow, and then the outlet pipeline of the pipe network is connected to an air outlet of the heating furnace 2.
S3: carrying out a positive and negative pressure alternate coating reaction on the pipe network by using inner surface coating deposition equipment;
s301: introducing protective gas into the pipe network by the inner surface coating deposition equipment;
introducing protective gas for emptying and using the protective gas as the protective gas for the temperature rise process in S302.
Before S301, a vacuum system and a solenoid valve control system of the inner surface coating deposition equipment are started, and N is introduced according to the flow during deposition2And (4) carrying out periodic switching test on the raw material gas by using an electromagnetic valve, and judging the switching period of the electromagnetic valve. And after the parameters are determined, the vacuum system and the electromagnetic valve control system are closed.
S302: heating the pipe network by using inner surface coating deposition equipment and keeping protective gas flow;
according to a temperature rise program of the set furnace temperature of the heating furnace 2, a switch of the heating furnace 2 is started to raise the temperature, and the flow of protective gas is kept in the whole temperature rise process;
s303: introducing raw material gas into the pipe network by the inner surface coating deposition equipment, and forming a periodic positive and negative pressure state in the pipe network by the inner surface coating deposition equipment;
the deposition principle consists in using the surface chemical reaction under high temperature conditions of the formula:
2TiCl4+N2+4H2＝2TiN+8HCl (1)
the feed gas comprises TiCl4Steam, H2Raw material gas, N2A raw material gas. The protective gas is N in the raw material gas2A raw material gas.
After the heating furnace 2 is heated to reach the target temperature of 850 ℃, a switch of the heating belt 6 is turned on until the target temperature is reached; then introducing H2Raw material gas and start TiCl4Evaporator 112 to be TiCl4After the target temperature is reached, H is introduced2Carrier gas, H2The carrier gas is TiCl4The steam is brought into a pipe network to be deposited for reaction; switching to a vacuum gas path, and starting a vacuum pump 3; and starting a solenoid valve control system with a preset period, observing the change of the gas flow, and stopping the reaction after 120 minutes.
In step S303, a pressure relief mode after switching at a fixed period is adopted to ensure the forward flow of the feed gas.
When the negative pressure is formed, the rear valve 22 of the inner surface coating deposition device needs to be opened, and the front valve 21 of the inner surface coating deposition device needs to be closed; similarly, the gas supply rate is much greater than the gas amount in the system, and the front valve 21 needs to be opened and the rear valve 22 needs to be closed when positive pressure is formed.
The average reaction gas flow rate of positive and negative pressure alternate coating depends on the volume V between the deposition inlet and outlet valves and the switching period T, and the volume flow rate is as follows:
Figure BDA0003372723460000061
in order to meet the requirements of the feed gas supply and the positive pressure of the inner surface coating deposition equipment during high-frequency switching, the feed gas supply pipeline needs to provide larger air input, so that the deviation exists between the feed gas supply pipeline and the inherent volume flow, and the feed gas backflow caused by the accumulation of the front-end pressure is easily caused. Therefore, as shown in fig. 4, the positive flow of the raw material gas is ensured by means of pressure relief after switching in fixed periods.
S4: and taking out the pipe network after the reaction is finished.
After the reaction is finished, the electromagnetic valve control system is closed to be in a normally open state, the vacuum system is closed after the rear end valve 22 is closed, the gas path is switched to the normal pressure flow path, and the rear end valve 22 is opened for cooling after the system pressure recovers to positive pressure. And opening the connecting clamp sleeves at two ends after the temperature is reduced to 200 ℃, and taking out the pipe network.
S5: and carrying out deposition detection on the pipe network.
Cutting coating pipes at different positions in a pipe network, placing one coating pipe in the middle of a test tube, pouring organic glass solution (1.5g of benzoyl peroxide and 48.5g of methacrylic acid solution) into an oven, keeping the temperature for 48 hours at 30 ℃ to initiate polymerization reaction, taking out, and placing at normal temperature for about one week to enable the organic glass to continue to polymerize until the organic glass is completely cured. And cutting, grinding and polishing the embedded coating pipe to expose the fracture of the section of the coating pipe, and finally measuring the thickness of the coating at the fracture of the inner wall of the coating pipe by adopting a metallographic microscope. Other coated tubes were used for SEM, EDS and XRD analysis.
Aiming at the problem that the dead zone in the complex pipe network is difficult to coat, the positive and negative pressure alternate deposition is carried out, and the whole coating of the inner surface of the complex pipe network is realized.
By utilizing chemical vapor deposition, aiming at the problem that the dead zone in a complex pipe network is difficult to coat, a solenoid valve control system and a vacuum system are adopted to realize positive and negative pressure alternate deposition. The change range of the existing deposition device is small, and various special-shaped components or sample pieces with dead angle areas can be coated on the premise of not damaging the original complex structure.
A deposition method and apparatus for TiN coating on the internal surface of pipe network features that a chemical vapor deposition technique for TiN coating on the internal surface of microchannel of complicated pipe network with longitudinal and transverse diameter variation is used to develop a new chemical vapor deposition technique for coating the internal surface of said pipe network. The method realizes the coating of TiN coating on the channel in the complex pipe network to form a stable coating process of the complex pipeline system, provides a coating deposition technology aiming at the inner surface of the channel of the complex pipe network system aiming at the defects of the existing normal pressure chemical vapor deposition technology, and is characterized in that: in order to uniformly coat the flowing dead zones in the channels of the complex pipe network system, a chemical vapor deposition method is adopted, the periodic transformation of positive and negative pressure in a deposition system is realized by using the peak staggering switching of a pipeline electromagnetic valve and a tail end high-pumping-speed vacuum pump 3, the flow of dead zone volume reaction gas is forced, and the uniform coating of the coating is realized.
Example two:
the pipe bodies are connected to the simple pipe network shown in fig. 2, the simple pipe network is 60cm long and 20cm wide, the middle transverse pipe is an arched bent pipe and is about 20cm long, and the obtained object diagram is shown in fig. 3.
The simple pipe network is deposited with the TiN coating according to the method for depositing the TiN coating on the inner surface of the pipe network of the first embodiment by adopting the device for depositing the TiN coating on the inner surface of the pipe network of the first embodiment.
The deposition detection result of the simple pipe network is as follows:
the coating thickness results are shown in FIG. 5, where it can be seen that the coating thickness varies a little from four different locations, indicating a more uniform coating deposition. The results of EDX elemental analysis are shown in fig. 6, which shows that coating elements Ti and N are main elements and the presence of TiN is determined. The XRD analysis result is shown in figure 7, and the diffraction peak of TiN crystal form is sharp and obvious and the crystallinity is high. In addition, the spectrum shows complete (111), (200), (220), (311) and (222) crystal diffraction peaks, and the phenomenon shows that the TiN coating deposited by positive and negative pressure alternation and the coating deposited by the conventional vapor deposition method have no obvious difference or defects.
Comparative example one:
the pipe bodies are connected to the simple pipe network shown in fig. 2, the simple pipe network is 60cm long and 20cm wide, the middle transverse pipe is an arched bent pipe and is about 20cm long, and the obtained object diagram is shown in fig. 3. And coating the simple pipe network by adopting a conventional chemical vapor deposition method.
In a complex piping network system, the most challenging site for coating is the theoretical gas flow dead zone, such as the flow cross tube shown by the central arrow in fig. 2, where the pressure is the same at both ends according to bernoulli's equation, and it is impossible to coat the flow cross tube effectively by conventional vapor deposition. The effective coating length from the source was evaluated as Thiele length, taking into account the thermal diffusion of the gas at atmospheric pressure, 850 ℃ deposition temperature conditions. Wherein, TiCl is contained in the reaction system4Minimum molecular diffusion coefficient (0.18 cm)3S) and thus its molecular diffusion process determines the distance that can be coated by diffusion. TiCl is obtained according to formula (2-4)4Ternary mutual diffusion coefficient D in systemTiCl4,mix＝1.39cm2/s
Figure BDA0003372723460000081
Figure BDA0003372723460000082
Figure BDA0003372723460000083
The Thiele length can be calculated according to the formula (5) after the diffusion coefficient is obtained.
Lth＝(H·D/Ks)1/2 (5)
According to the formula, the Thiele length in the transverse pipe with the inner diameter of 2mm is 1.67cm, namely, the TiN coating can be effectively coated at the position of only 1.67cm at two ends of the transverse pipe theoretically.
The results of comparing the coating effects of example two and comparative example one are shown in fig. 8 and 9. As can be seen from fig. 8, no golden TiN coating is present in the middle of the tubule, the tail and the middle of the transverse tube in the pipe network by the conventional chemical vapor deposition method, which indicates that the flow dead zone cannot be effectively coated by the conventional vapor deposition method; the simple pipe network adopting the positive-negative pressure alternate coating mode has the effect as shown in fig. 9, and the fact that the thin pipes and the transverse pipes are effectively coated with the golden yellow TiN coating can be observed, which is enough to prove the effectiveness of the positive-negative pressure alternate coating on the coating of the complex anisotropic member.
Example three:
connecting the pipe bodies to a complex pipe network shown in the figure 10, and depositing the TiN coating on the inner surface of the pipe network by using the TiN coating deposition device in the first embodiment according to the TiN coating deposition method in the first embodiment.
The coating effect of the complex pipe network is shown in fig. 10. As can be seen from the figure, after the complex pipe network is coated alternately by positive pressure and negative pressure, the crossroad channel and the branch channel both have obvious golden yellow TiN coatings, which shows that the positive pressure and negative pressure alternate coating method can effectively coat the complex pipe network and has wide application conditions.
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.

Claims (10)

1. A deposition method of TiN coating on the inner surface of a pipe network is characterized in that: the method comprises the following steps:
s1: carrying out pretreatment operation on the pipe network;
s2: connecting the pretreated piping network to an interior surface coating deposition apparatus;
s3: carrying out a positive and negative pressure alternate coating reaction on the pipe network by using inner surface coating deposition equipment;
s4: and taking out the pipe network after the reaction is finished.
2. A method for depositing TiN coating on the inner surface of pipe network as claimed in claim 1, wherein: the step S3 includes the following sub-steps:
s301: introducing protective gas into the pipe network by the inner surface coating deposition equipment;
s302: heating the pipe network by using inner surface coating deposition equipment and keeping protective gas flow;
s303: raw material gas is introduced into the pipe network by the inner surface coating deposition equipment, and a periodic positive and negative pressure state is formed in the pipe network by the inner surface coating deposition equipment.
3. A method for depositing TiN coating on the inner surface of pipe network as claimed in claim 2, wherein: in the substep S303, a front end valve and a rear end valve of the inner surface coating deposition apparatus are controlled to form a periodic positive and negative pressure state, the rear end valve is opened and the front end valve is closed to form a negative pressure state, and the front end valve is opened and the rear end valve is closed to form a positive pressure state.
4. A method for depositing TiN coating on the inner surface of pipe network as claimed in claim 2, wherein: in the substep S303, a pressure relief mode after switching at fixed period is adopted to ensure the positive flow of the feed gas.
5. A deposition device for TiN coating on the inner surface of a pipe network is characterized in that: the device comprises an inner surface coating deposition device, wherein the inner surface coating deposition device comprises a raw material gas supply pipeline, a heating furnace, a vacuum system and a positive and negative pressure control system;
the feed gas supply pipeline is connected to a gas inlet of the heating furnace, and a gas outlet of the heating furnace is connected with a vacuum system;
the heating furnace is used for heating a pipe network, and the pipe network is connected to an air inlet and an air outlet of the heating furnace;
the positive and negative pressure control system controls the air inlet and the air outlet of the heating furnace to form a periodic positive and negative pressure state on the pipe network.
6. A deposition apparatus for TiN coating on the inner surface of pipe network as claimed in claim 5, wherein: the positive and negative pressure control system comprises a front end valve, a rear end valve and an electromagnetic valve control system; the front end valve is arranged at the air inlet of the heating furnace, the rear end valve is arranged at the air outlet of the heating furnace, and the front end valve and the rear end valve are electrically connected to the electromagnetic valve control system.
7. A deposition apparatus for TiN coating on the inner surface of pipe network as claimed in claim 6, wherein: after the opening and closing cycles of the front end valve and the rear end valve are cycled for two cycles, an emptying time period for opening the electromagnetic valves simultaneously appears to form constant-cycle switching and then pressure relief so as to ensure the forward flow of the raw material gas.
8. A deposition apparatus for TiN coating on the inner surface of pipe network as claimed in claim 6, wherein: the electromagnetic valve control system comprises a PLC controller; the front end valve and the rear end valve are electromagnetic valves.
9. A deposition apparatus for TiN coating on the inner surface of pipe network as claimed in claim 5, wherein: the feed gas supply line comprises TiCl4Steam supply line, H2Feed gas supply line, N2A raw gas supply pipeline and a gas mixing tank; the TiCl4Steam supply line, H2Feed gas supply line and N2The feed gas supply pipelines are all connected to a gas mixing tank, and the gas mixing tank is connected to the heating furnace.
10. A device for depositing TiN coating on the inner surface of pipe network as claimed in claim 9, wherein: the TiCl4The vapor supply pipeline comprises a carrier gas supply pipeline and TiCl which are connected in sequence4An evaporator; the TiCl4The evaporator is connected to the gas mixing tank.
CN202111405602.1A 2021-11-24 2021-11-24 Deposition method and device for TiN coating on inner surface of pipe network Pending CN114059040A (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4089998A (en) * 1976-07-13 1978-05-16 Gibson Jack Edward Method of powder coating the interior of tubular goods
JPS58193778A (en) * 1982-04-30 1983-11-11 Hakko Co Ltd Repairing method of inside surface of installed pipe
US20100304567A1 (en) * 2009-05-28 2010-12-02 Hitachi Kokusai Electric Inc. Method of manufacturing a semiconductor device and substrate processing apparatus
US7867366B1 (en) * 2004-04-28 2011-01-11 Alameda Applied Sciences Corp. Coaxial plasma arc vapor deposition apparatus and method
JP2012164736A (en) * 2011-02-04 2012-08-30 Hitachi Kokusai Electric Inc Substrate processing apparatus and semiconductor device manufacturing method
CN103938185A (en) * 2013-01-21 2014-07-23 中国兵器工业第五九研究所 Preparation method for inner hole coating of tubular part
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
US20150322568A1 (en) * 2014-05-12 2015-11-12 Tokyo Electron Limited Method of depositing a film
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

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4089998A (en) * 1976-07-13 1978-05-16 Gibson Jack Edward Method of powder coating the interior of tubular goods
JPS58193778A (en) * 1982-04-30 1983-11-11 Hakko Co Ltd Repairing method of inside surface of installed pipe
US7867366B1 (en) * 2004-04-28 2011-01-11 Alameda Applied Sciences Corp. Coaxial plasma arc vapor deposition apparatus and method
US20100304567A1 (en) * 2009-05-28 2010-12-02 Hitachi Kokusai Electric Inc. Method of manufacturing a semiconductor device and substrate processing apparatus
JP2012164736A (en) * 2011-02-04 2012-08-30 Hitachi Kokusai Electric Inc Substrate processing apparatus and semiconductor device manufacturing method
CN103938185A (en) * 2013-01-21 2014-07-23 中国兵器工业第五九研究所 Preparation method for inner hole coating of tubular part
US20150322568A1 (en) * 2014-05-12 2015-11-12 Tokyo Electron Limited Method of depositing a film
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
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

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