Ultrathin seamless thin-walled tube and preparation method thereof

Abstract

The invention discloses an ultrathin seamless thin-walled tube and a preparation method thereof, and belongs to the technical field of ultrathin tube preparation. According to the preparation method disclosed by the invention, after the substrate is pretreated, the outer wall of the substrate is subjected to gluing treatment, and then soft baking treatment is performed; preparing a thin film on the outer wall of the substrate subjected to soft baking treatment by adopting a physical vapor deposition technology to obtain a substrate deposited with the thin film; sequentially carrying out ultraviolet exposure treatment and photoresist removal treatment on the substrate on which the thin film is deposited to obtain a separated thin film; and carrying out post-treatment on the separated thin film to obtain the ultrathin seamless thin-walled tube. According to the method, the problems that the diameter-thickness ratio of the pipe is limited by a traditional machining technology and a thin-wall plate cannot be adopted for curling connection due to the fact that the pipe wall is too thin are solved, the process is simple, energy consumption is low, precision is high, and large-batch production of various ultrathin seamless thin-wall pipes can be achieved. The obtained ultrathin seamless thin-walled tube has nanoscale wall thickness control precision and surface roughness, and has a wide application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of ultra-thin pipe preparation, and specifically relates to an ultra-thin seamless thin-wall pipe and a preparation method thereof. Background Art

[0002] Ultra-thin seamless wall tubes, as a special type of tube with a diameter-to-wall thickness ratio of more than 100, have become an indispensable key material in high-end equipment such as aerospace, biomedicine, and nuclear industry. They are also a technical bottleneck that needs to be solved in the current development of advanced equipment manufacturing automation and industrial chain. With the increasing demand for ultra-thin seamless wall tubes with extreme size specifications in various fields, especially ultra-thin seamless tubes with an outer diameter span of 3~1000 mm and a wall thickness of 0.015~0.030 mm, they have become key basic materials urgently needed in many cutting-edge scientific and technological fields.

[0003] The traditional preparation process includes complex multi-step processes such as high-energy consumption melting and casting billets, high-load hot forging and blanking, hot rolling perforation, multi-pass hot rolling thinning, high-energy consumption heat treatment, cold rolling sizing and correction, and the obtained ultra-thin seamless wall tubes generally have problems such as poor uniformity of organization, uneven wall thickness, large deformation force, easy cracking, etc., accompanied by high energy consumption, high cost, low yield rate and difficulty in producing high-quality ultra-thin seamless wall tubes. For example, the Chinese patent application with publication number CN112371752A, through the segmented swimming drawing process, has achieved micron-level ultra-thin wall copper tubes with a maximum wall thickness of 0.08-0.15 mm. Similarly, the Chinese patent application with publication number CN117086122A, through repeated cold deformation processing and annealing heat treatment of preformed tubular copper materials, has obtained ultra-thin copper tubes for micro-heat pipes, and the wall thickness of the tube reaches 0.055-0.060 mm. These preparation methods still inherit the complexity and high energy consumption characteristics of traditional processes, and it is difficult to achieve stable production of high-precision, high-quality ultra-thin seamless wall tubes.

[0004] Although the development of additive manufacturing technology has made it possible to simplify the process and reduce energy consumption, the Chinese patent application with publication number CN117718494A uses 3D printing technology to prepare small-sized thin-walled tube blanks and perform heat treatment, followed by rolling and drawing, to produce small-sized ultra-thin tubes with an outer diameter of 0.9~4.0 mm and a wall thickness of 0.04~0.08 mm. However, this method still relies on traditional mechanical processing, resulting in limited precision control, and the material range is limited to easily processed metals and alloys, which cannot meet the preparation requirements of ultra-thin seamless wall tubes such as semiconductors and ceramics.

[0005] It can be seen that developing a method with simple process, low energy consumption, high precision, and capable of realizing mass production of various types of ultra-thin seamless thin-walled tubes has important engineering practical value and economic benefits. Summary of the invention

[0006] The object of the present invention is to provide an ultra-thin seamless thin-walled tube and a preparation method thereof, so as to solve the technical problem that the existing preparation method is difficult to achieve mass production due to the complex process and high preparation requirements.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions: The invention discloses a method for preparing an ultra-thin seamless thin-walled tube, comprising the following steps: After the substrate is pre-treated, the outer wall of the substrate is coated with glue, and then soft-baked; A thin film is prepared on the outer wall of the substrate after soft baking by using physical vapor deposition technology to obtain a substrate on which the thin film has been deposited; The substrate on which the thin film has been deposited is subjected to UV exposure treatment and degumming treatment in sequence to obtain a detached thin film; After post-processing the detached film, an ultra-thin seamless thin-walled tube is obtained.

[0008] Furthermore, the pretreatment step is: ultrasonically cleaning the substrate in acetone and anhydrous ethanol solutions for 10 to 30 minutes in sequence, and drying; The substrate is a glass tube; the material of the glass tube is alumina, sapphire or quartz glass.

[0009] Furthermore, the coating treatment is to uniformly coat the outer wall of the substrate with a positive photoresist; the positive photoresist is any one of diazoquinone, polyimide, methacrylic acid, epoxy resin and acrylic acid; The glue coating method includes dipping glue coating, spraying glue coating, brushing glue coating, dripping glue coating, rolling glue coating, electrostatic glue coating or ultrasonic glue coating; the thickness of the glue coating is 0.001-0.01 mm.

[0010] Furthermore, the temperature of the soft baking treatment is 90-100°C, and the time is 10-60 s.

[0011] Furthermore, the physical vapor deposition technique is any one of vacuum evaporation plating, sputtering plating and ion plating; The material used to prepare the film is one of metal, alloy, semiconductor or ceramic; The material used to prepare the film is a multilayer or composite material formed by free combination of metals, alloys, semiconductors or ceramics.

[0012] Further, the UV exposure treatment of the substrate on which the thin film has been deposited is to perform UV exposure treatment on the inner wall of the glass tube on which the thin film has been deposited; the UV light source used in the UV exposure treatment is one of g-line, i-line, KrF line and ArF line; The UV exposure treatment time is 15 to 50 s.

[0013] Furthermore, the degumming treatment method is wet degumming; the time of the wet degumming is 5 to 30 minutes; the degumming reagent used in the wet degumming is one or more of acetone, ethanol, isopropanol, sodium hydroxide, potassium hydroxide, 1-methyl-2-pyrrolidone, nitrogen ethyl pyrrolidone, dimethyl sulfoxide and tetramethylammonium hydroxide.

[0014] Furthermore, the outer diameter of the substrate is 1-100 mm.

[0015] The invention also discloses an ultra-thin seamless thin-walled tube prepared by the preparation method.

[0016] Furthermore, the inner diameter of the ultra-thin seamless thin-walled tube is 1-100 mm, and the wall thickness is 0.001-0.05 mm.

[0017] Compared with the prior art, the present invention has the following beneficial effects: The present invention discloses a method for preparing an ultra-thin seamless thin-walled tube. A thin film is deposited on the surface of a substrate based on physical vapor deposition technology, which overcomes the limitation of the diameter-to-thickness ratio of the tube by traditional mechanical processing technology, and the problem that a thin-walled plate cannot be used for curling connection due to the tube wall being too thin. The method has a simple process, low energy consumption and high precision, and can realize mass production of various types of ultra-thin seamless thin-walled tubes, and has important engineering practical value and economic benefits.

[0018] Furthermore, the physical vapor deposition technology used includes vacuum evaporation plating, sputtering plating and ion plating. The constituent materials of the ultra-thin seamless thin-walled tube include various metals, alloys, semiconductors, ceramics and multi-layer or composite materials freely combined therefrom, which have strong universality, can realize high-precision, large-scale industrial production, and are easy to promote and apply.

[0019] The present invention also discloses an ultra-thin seamless thin-walled tube prepared by the preparation method. The wall thickness of the prepared ultra-thin seamless thin-walled tube is 0.001-0.05 mm, the wall tube structure and thickness are uniform, and the wall thickness control accuracy and surface roughness are at the nano level, and the ultra-thin seamless thin-walled tube has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The present invention is a process flow chart of the method for preparing the ultra-thin seamless thin-walled tube. DETAILED DESCRIPTION

[0021] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.

[0022] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0023] In this article, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible secondary ranges and individual values ​​within the range (including integers and fractions).

[0024] In this document, unless otherwise specified, “includes,” “including,” “contains,” “has,” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”

[0025] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0026] The present invention provides a method for preparing an ultra-thin seamless thin-walled tube, which is prepared based on a physical vapor deposition technology. The physical vapor deposition technology covers vacuum evaporation, sputtering and ion plating, including but not limited to resistance heating evaporation, electron beam evaporation, induction heating evaporation, magnetron sputtering, radio frequency sputtering, ion beam sputtering, magnetron sputtering ion plating, vacuum evaporation ion plating, multi-arc ion plating, etc. The ultra-thin seamless thin-walled tube is made of various metals, alloys, semiconductors, ceramics and multi-layer or composite materials freely combined therefrom; Figure 1 As shown, it mainly includes the following steps: S1, pretreatment: select a substrate with an outer diameter of 1-100 mm, ultrasonically clean it in acetone and anhydrous ethanol solution for 10-30 min, and dry it; S2, glue coating: using positive photoresist to evenly coat the outer wall of the pre-treated substrate; S3, soft baking: Place the substrate evenly coated with photoresist on a hot plate or oven for soft baking at a temperature of 90-100 °C for 10-60 s. S4, physical vapor deposition: the substrate after soft baking is placed in a deposition chamber, and a thin film with a thickness of 0.001-0.05 mm is prepared on its outer wall by physical vapor deposition technology; S5, UV exposure: UV exposure treatment is performed on the inner wall of the substrate on which the thin film has been deposited, and the exposure time is 15-50 s; S6, wet degumming: using a wet degumming process, the glass tube after UV exposure is immersed in a degumming agent for 5 to 30 minutes to remove the photoresist between the film and the glass tube and separate the film from the glass tube; then, the separated ultra-thin wall tube is cleaned with anhydrous ethanol and dried to obtain an ultra-thin seamless thin-walled tube with an inner diameter of 1 to 100 mm and a wall thickness of 0.001 to 0.05 mm.

[0027] Preferably, the substrate is a glass tube; the glass tube includes but is not limited to one or more of alumina, sapphire, quartz glass, and other glass components.

[0028] Preferably, the positive photoresist is any one of diazoquinone type, polyimide type, methacrylic type, epoxy resin type, acrylic type and the like.

[0029] Preferably, the gluing method includes but is not limited to dipping gluing, spraying gluing, brushing gluing, dripping gluing, rolling gluing, electrostatic gluing, ultrasonic gluing and the like.

[0030] Preferably, the thickness of the photoresist coated on the outer wall of the substrate is 0.001-0.01 mm.

[0031] Preferably, the physical vapor deposition technique is any one of vacuum evaporation plating, sputtering plating or ion plating.

[0032] Preferably, the film constituent material is one of various metals, alloys, semiconductors, ceramics, and multilayer or composite materials freely combined therefrom.

[0033] Preferably, the selected ultraviolet light source is one of g-line, i-line, KrF line, or ArF line.

[0034] Preferably, the degumming agent includes but is not limited to organic solvents such as acetone, ethanol, isopropanol, and alkaline inorganic solutions such as sodium hydroxide and potassium hydroxide, or one or more special degumming solutions such as 1-methyl-2-pyrrolidone, nitrogen ethyl pyrrolidone, dimethyl sulfoxide, and tetramethylammonium hydroxide.

[0035] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0036] The following examples use conventional instruments and equipment in the art. The experimental methods in the following examples where specific conditions are not specified are usually carried out under conventional conditions or under conditions recommended by the manufacturer. The various raw materials used in the following examples are conventional commercial products unless otherwise specified, and their specifications are conventional specifications in the art. In the specification of the present invention and the following examples, unless otherwise specified, "%" means weight percentage, "part" means weight part, and ratio means weight ratio.

[0037] Example 1 A method for preparing an ultra-thin seamless Al thin-walled tube comprises the following steps: Step 1: Select a quartz glass tube with an outer diameter of 5 mm as the substrate for pretreatment. Immerse the selected quartz glass tube in acetone and anhydrous ethanol for ultrasonic cleaning for 10 min in turn, rinse it with deionized water after taking it out, and blow it dry with high-purity nitrogen; Step 2: The outer wall of the pretreated quartz glass tube is evenly coated with glue, and BP-212 diazonaphthoquinone type UV positive photoresist is selected, and the ultrasonic coating process is used for uniform coating, the spraying frequency is 120 kHz, the spraying speed is 0.5 m / s, and the thickness of the coated positive photoresist is 0.005 mm; Step 3: Place the quartz glass tube evenly coated with positive photoresist on a constant temperature heating table for soft baking, with the temperature set to 90 °C and the time set to 50 s, to promote the volatilization of residual solvent in the photoresist, so that the photoresist is cured and hardened, and the adhesion to the substrate is enhanced; Step 4: Using magnetron sputtering ion plating technology, select an Al target with a purity of 99.99 wt.% as the sputtering source material, install the soft-baked quartz glass tube into the chamber, and use a mechanical pump and a molecular pump to evacuate the chamber to 3×10 -3 Pa, then inert gas Ar (purity of 99.99%) was introduced, the gas flow rate was 18 sccm, the substrate negative bias voltage was adjusted to 65 V, the Al target sputtering power was 420 W, the workpiece holder speed was 5 rpm, and the working pressure in the chamber was 1.12×10 -1 Pa, working time is 100 min, after deposition, wait for the chamber temperature to drop to room temperature and take it out; Step 5: The inner wall of the quartz glass tube on which the thin film has been deposited is subjected to ultraviolet exposure treatment, i-line ultraviolet light is selected as the exposure light source, and the exposure time is 30 s; Step 6: Immerse the quartz glass tube after UV exposure in N-methylpyrrolidone solution for 15 min to remove the photoresist between the film and the glass tube, and separate the film from the glass tube; then, take out the Al thin-walled tube that has been debonded, and then clean and dry it with anhydrous ethanol to obtain an ultra-thin seamless Al thin-walled tube with an inner diameter of 5 mm and a wall thickness of 0.001 mm.

[0038] Example 2 A method for preparing an ultra-thin seamless Cu thin-walled tube comprises the following steps: Step 1: Select a sapphire tube with an outer diameter of 5 mm as the substrate for pretreatment. Immerse the selected sapphire tube in acetone and anhydrous ethanol for ultrasonic cleaning for 30 min in turn, rinse it with deionized water, and blow it dry with high-purity nitrogen; Step 2: The outer wall of the pretreated sapphire tube is evenly coated with glue, and BP-212 diazonaphthoquinone type UV positive photoresist is selected. The ultrasonic coating process is used for uniform coating. The spraying frequency is 120 kHz, the spraying speed is 0.5 m / s, and the thickness of the coated photoresist is 0.005 mm; Step 3: Place the sapphire tube evenly coated with positive photoresist on a constant temperature heating table for soft baking. The temperature is set to 90 °C for 50 seconds to promote the volatilization of residual solvent in the photoresist, so that the photoresist is cured and hardened, and the adhesion to the substrate is enhanced; Step 4: Using magnetron sputtering ion plating technology, a Cu target with a purity of 99.99 wt.% was selected as the sputtering source material. The sapphire tube after soft baking was placed in the chamber, and the vacuum in the chamber was evacuated to 3×10 - 3 Pa, then inert gas Ar (purity of 99.99%) was introduced, the gas flow rate was 18 sccm, the substrate negative bias voltage was adjusted to 65 V, the Cu target sputtering power was 405 W, the workpiece holder speed was 5 rpm, and the working pressure in the chamber was 1.12×10 -1 Pa, working time is 370 min, after deposition, wait for the chamber temperature to drop to room temperature and take it out; Step 5: The inner wall of the sapphire tube on which the thin film has been deposited is subjected to ultraviolet exposure treatment, i-line ultraviolet light is selected as the exposure light source, and the exposure time is 30 s; Step 6: Immerse the sapphire tube after UV exposure in N-methylpyrrolidone solution for 10 minutes to remove the photoresist between the film and the sapphire tube, and separate the film from the sapphire tube; then, take out the debonded Cu thin-walled tube, and then clean and dry it with anhydrous ethanol to obtain an ultra-thin seamless Cu thin-walled tube with an inner diameter of 5 mm and a wall thickness of 0.03 mm.

[0039] Example 3 A method for preparing an ultra-thin seamless FeCrAl thin-walled tube comprises the following steps: Step 1: Select a sapphire tube with an outer diameter of 5 mm as the substrate for pretreatment. Immerse the selected sapphire tube in acetone and anhydrous ethanol for ultrasonic cleaning for 15 min in turn. After taking it out, rinse it with deionized water and blow it dry with high-purity nitrogen; Step 2: The outer wall of the pretreated sapphire tube is evenly coated with glue, and BP-212 diazonaphthoquinone type UV positive photoresist is selected. The ultrasonic coating process is used for uniform coating. The spraying frequency is 120 kHz, the spraying speed is 0.5 m / s, and the thickness of the coated photoresist is 0.005 mm; Step 3: Place the sapphire tube evenly coated with positive photoresist on a constant temperature heating table for soft baking. The temperature is set to 90 °C for 50 seconds to promote the volatilization of residual solvent in the photoresist, so that the photoresist is cured and hardened, and the adhesion to the substrate is enhanced; Step 4: Using magnetron sputtering ion plating technology, a FeCrAl alloy target with a mass percentage of 94:13:6 wt.% was selected as the sputtering source material. The sapphire tube after soft baking was placed in the chamber, and the vacuum in the chamber was evacuated to 3×10 -3 Pa, then inert gas Ar (purity of 99.99%) was introduced, the gas flow rate was 20 sccm, the substrate negative bias voltage was adjusted to 65 V, the sputtering power of the FeCrAl alloy target was 900 W, the workpiece holder speed was 5 rpm, and the working pressure in the chamber was 1.12×10 -1 Pa, working time is 220 min, after deposition, wait for the chamber temperature to drop to room temperature and take it out; Step 5: The inner wall of the sapphire tube on which the thin film has been deposited is subjected to ultraviolet exposure treatment, i-line ultraviolet light is selected as the exposure light source, and the exposure time is 30 s; Step 6: Immerse the sapphire tube after UV exposure in N-methylpyrrolidone solution for 15 minutes to remove the photoresist between the film and the sapphire tube, and separate the film from the sapphire tube; then, take out the FeCrAl thin-walled tube from which the photoresist has been removed, and then clean and dry it with anhydrous ethanol to obtain an ultra-thin seamless FeCrAl thin-walled tube with an inner diameter of 5 mm and a wall thickness of 0.05 mm.

[0040] Example 4 A method for preparing an ultra-thin seamless AlN thin-wall tube comprises the following steps: Step 1: Select a quartz glass tube with an outer diameter of 20 mm as the substrate for pretreatment. Immerse the selected quartz glass tube in acetone and anhydrous ethanol for ultrasonic cleaning for 15 min in turn, rinse it with deionized water after taking it out, and blow it dry with high-purity nitrogen; Step 2: The outer wall of the pretreated quartz glass tube is evenly coated with glue, and BP-212 diazonaphthoquinone type UV positive photoresist is selected, and the ultrasonic coating process is used for uniform coating, the spraying frequency is 120 kHz, the spraying speed is 0.5 m / s, and the thickness of the coated photoresist is 0.005 mm; Step 3: Place the quartz glass tube evenly coated with positive photoresist on a constant temperature heating table for soft baking, with the temperature set to 90 °C and the time set to 50 s, to promote the volatilization of residual solvent in the photoresist, so that the photoresist is cured and hardened, and the adhesion to the substrate is enhanced; Step 4: Using magnetron sputtering ion plating technology, select an Al target with a purity of 99.99 wt.% as the sputtering source material, install the soft-baked quartz glass tube into the chamber, and use a mechanical pump and a molecular pump to evacuate the chamber to 3×10 -3 Pa, then inert gas Ar (purity 99.99%) was introduced with a gas flow rate of 20 sccm and N2 with a gas flow rate of 30 sccm. The substrate negative bias voltage was adjusted to 65 V, the Al target sputtering power was 420 W, the workpiece holder rotation speed was 5 rpm, and the working pressure in the chamber was 1.12×10 -1 Pa, the working time is 450 min, after the deposition is completed, wait for the chamber temperature to drop to room temperature and take it out; Step 5: The inner wall of the quartz glass tube on which the thin film has been deposited is subjected to ultraviolet exposure treatment, i-line ultraviolet light is selected as the exposure light source, and the exposure time is 30 s; Step 6: Immerse the quartz glass tube after UV exposure in N-methylpyrrolidone solution for 15 min to remove the photoresist between the film and the glass tube, and separate the film from the glass tube; then, take out the AlN thin-walled tube from which the photoresist has been removed, and then clean and dry it with anhydrous ethanol to obtain an ultra-thin seamless AlN thin-walled tube with an inner diameter of 20 mm and a wall thickness of 0.03 mm.

[0041] Example 5 A method for preparing an ultra-thin seamless CrN thin-wall tube comprises the following steps: Step 1: Select a quartz glass tube with an outer diameter of 100 mm as the substrate for pretreatment. Immerse the selected quartz glass tube in acetone and anhydrous ethanol for ultrasonic cleaning for 15 min in turn, rinse it with deionized water after taking it out, and blow it dry with high-purity nitrogen; Step 2: The outer wall of the pretreated quartz glass tube is evenly coated with glue, and BP-212 diazonaphthoquinone type UV positive photoresist is selected, and the ultrasonic coating process is used for uniform coating, the spraying frequency is 120 kHz, the spraying speed is 0.5 m / s, and the thickness of the coated photoresist is 0.005 mm; Step 3: Place the quartz glass tube evenly coated with positive photoresist on a constant temperature heating table for soft baking, with the temperature set to 90 °C and the time set to 50 s, to promote the volatilization of residual solvent in the photoresist, so that the photoresist is cured and hardened, and the adhesion to the substrate is enhanced; Step 4: Using magnetron sputtering ion plating technology, a Cr target with a purity of 99.99 wt.% was selected as the sputtering source material. The soft-baked quartz glass tube was placed in the chamber, and the vacuum in the chamber was evacuated to 3×10 -3 Pa, then inert gas Ar (purity 99.99%) was introduced with a gas flow rate of 20 sccm and N2 with a gas flow rate of 30 sccm. The substrate negative bias voltage was adjusted to 65 V, the Cr target sputtering power was 900 W, the workpiece holder rotation speed was 5 rpm, and the working pressure in the chamber was 1.12×10 -1 Pa, the working time is 300 min, after the deposition is completed, wait for the chamber temperature to drop to room temperature and take it out; Step 5: The inner wall of the quartz glass tube on which the thin film has been deposited is subjected to ultraviolet exposure treatment, i-line ultraviolet light is selected as the exposure light source, and the exposure time is 30 s; Step 6: Immerse the quartz glass tube after UV exposure in N-methylpyrrolidone solution for 15 min to remove the photoresist between the film and the glass tube, and separate the film from the glass tube; then, take out the CrN thin-walled tube from which the photoresist has been removed, and then clean and dry it with anhydrous ethanol to obtain an ultra-thin seamless CrN thin-walled tube with an inner diameter of 100 mm and a wall thickness of 0.05 mm.

[0042] Example 6 A method for preparing an ultra-thin seamless TiO2 thin-wall tube comprises the following steps: Step 1: Select a quartz glass tube with an outer diameter of 100 mm as the substrate for pretreatment. Immerse the selected quartz glass tube in acetone and anhydrous ethanol for ultrasonic cleaning for 15 min in turn, rinse it with deionized water after taking it out, and blow it dry with high-purity nitrogen; Step 2: The outer wall of the pretreated quartz glass tube is evenly coated with glue, and BP-212 diazonaphthoquinone type UV positive photoresist is selected, and the ultrasonic coating process is used for uniform coating, the spraying frequency is 120 kHz, the spraying speed is 0.5 m / s, and the thickness of the coated photoresist is 0.005 mm; Step 3: Place the quartz glass tube evenly coated with positive photoresist on a constant temperature heating table for soft baking, with the temperature set to 90 °C and the time set to 50 s, to promote the volatilization of residual solvent in the photoresist, so that the photoresist is cured and hardened, and the adhesion to the substrate is enhanced; Step 4: Using electron beam evaporation technology, select TiO2 particles with a purity of 99.99 wt.% as the evaporation source material, place them in a graphite crucible, put the soft-baked quartz glass tube into the chamber, and use a mechanical pump and a molecular pump to evacuate the chamber to a vacuum of 6×10 -4 Pa, adjust the preset current to 0.4 A, the preheating current adjustment rate to 0.02 A / min, adjust the spot position to the center of the crucible, adjust the voltage to 8.2 kV, the current to 0.5 A, the beam current to 18 mA, the deposition time to 400 min, and after the deposition is completed, wait for the chamber temperature to drop to room temperature and take it out; Step 5: The inner wall of the quartz glass tube on which the thin film has been deposited is subjected to ultraviolet exposure treatment, i-line ultraviolet light is selected as the exposure light source, and the exposure time is 30 s; Step 6: Immerse the quartz glass tube after UV exposure in N-methylpyrrolidone solution for 15 min to remove the photoresist between the film and the glass tube, and separate the film from the glass tube; then, take out the TiO2 thin-walled tube from which the photoresist has been removed, and then clean and dry it with anhydrous ethanol to obtain an ultra-thin seamless TiO2 thin-walled tube with an inner diameter of 100 mm and a wall thickness of 0.03 mm.

[0043] The present invention discloses a method for preparing an ultra-thin seamless thin-walled tube by using physical vapor deposition technology, which overcomes the limitation of the diameter-to-thickness ratio of the tube by traditional mechanical processing technology, and the problem that the thin tube wall cannot be crimped and connected by thin-walled plates, and is applicable to various metals, alloys, semiconductors, ceramics, and multilayer or composite materials freely combined from them. The physical vapor deposition technology in the method of the present invention covers vacuum evaporation plating, sputtering plating and ion plating, and the obtained ultra-thin seamless thin-walled tube has a wall thickness of 0.001-0.05 mm, and its wall tube structure and thickness are uniform, with nanometer-level wall thickness control accuracy and surface roughness. The method adopted by the present invention is simple and has low energy consumption, can realize high-precision, large-scale industrial production, and is easy to promote and apply.

[0044] The above contents are only for explaining the technical idea of ​​the present invention and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution in accordance with the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing an ultra-thin seamless thin-walled tube, characterized in that: The following steps are involved: After the substrate is pre-treated, the outer wall of the substrate is coated with glue, and then soft-baked; A thin film is prepared on the outer wall of the substrate after soft baking by using physical vapor deposition technology to obtain a substrate on which the thin film has been deposited; The substrate on which the thin film has been deposited is subjected to UV exposure treatment and degumming treatment in sequence to obtain a detached thin film; After post-processing the detached film, an ultra-thin seamless thin-walled tube is obtained.

2. The method for preparing an ultra-thin seamless thin-walled tube according to claim 1, characterized in that: The pretreatment steps are: ultrasonically cleaning the substrate in acetone and anhydrous ethanol solutions for 10 to 30 minutes in sequence, and drying; The substrate is a glass tube; the material of the glass tube is alumina, sapphire or quartz glass.

3. The method for preparing an ultra-thin seamless thin-walled tube according to claim 1, characterized in that: The coating treatment is to use positive photoresist to evenly coat the outer wall of the substrate; the positive photoresist is any one of diazoquinone, polyimide, methacrylic acid, epoxy resin and acrylic acid; The glue coating method includes dipping glue coating, spraying glue coating, brushing glue coating, dripping glue coating, rolling glue coating, electrostatic glue coating or ultrasonic glue coating; the thickness of the glue coating is 0.001-0.01 mm.

4. The method for preparing an ultra-thin seamless thin-walled tube according to claim 1, characterized in that: The temperature of the soft baking treatment is 90~100 ℃ and the time is 10~60 s.

5. The method for preparing an ultra-thin seamless thin-walled tube according to claim 1, characterized in that: The physical vapor deposition technology is any one of vacuum evaporation plating, sputtering plating and ion plating; The material used to prepare the film is one of metal, alloy, semiconductor or ceramic; The material used to prepare the film is a multilayer or composite material formed by free combination of metals, alloys, semiconductors or ceramics.

6. The method for preparing an ultra-thin seamless thin-walled tube according to claim 1, characterized in that: The step of sequentially performing ultraviolet exposure treatment on the substrate on which the thin film has been deposited is to perform ultraviolet exposure treatment on the inner wall of the glass tube on which the thin film has been deposited; the ultraviolet light source used in the ultraviolet exposure treatment is one of g-line, i-line, KrF line and ArF line; The UV exposure treatment time is 15 to 50 s.

7. The method for preparing an ultra-thin seamless thin-walled tube according to claim 1, characterized in that: The degumming treatment method is wet degumming; the time of the wet degumming is 5 to 30 minutes; the degumming reagent used in the wet degumming is one or more of acetone, ethanol, isopropanol, sodium hydroxide, potassium hydroxide, 1-methyl-2-pyrrolidone, nitrogen ethyl pyrrolidone, dimethyl sulfoxide and tetramethylammonium hydroxide.

8. The method for preparing an ultra-thin seamless thin-walled tube according to claim 1, characterized in that: The outer diameter of the substrate is 1~100 mm.

9. An ultra-thin seamless thin-walled tube, characterized in that: The method is prepared by any one of claims 1 to 8.

10. The ultra-thin seamless thin-walled tube according to claim 9, characterized in that: The inner diameter of the ultra-thin seamless thin-walled tube is 1-100 mm, and the wall thickness is 0.001-0.05 mm.

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