A metallized polymer film and a method for producing the same

Abstract

The application provides a metallized polymer film and a preparation method thereof, which comprises the following steps: S10: providing a polymer base film; S20: spraying a metal powder to the surface of the polymer base film by an atmospheric plasma torch to form a metal coating on the surface of the polymer base film, so as to obtain the metallized polymer film. By using the atmospheric plasma torch and controlling the spraying conditions, the application realizes the control of the high-speed plasma jet energy, and then the momentum and heat input to the surface of the polymer base film, so that the metal coating is deposited on the surface of the polymer base film without damaging the polymer base film, thereby obtaining the metallized polymer film with the stable and firm combination of the metal coating and the polymer base film.

Description

Technical Field

[0001] This application relates to the field of surface metallization technology, specifically to a metallized polymer film and its preparation method. Background Technology

[0002] With the development of flexible electronics, wearable devices, flexible circuits, flexible displays, and electronic skin have emerged rapidly and are widely used in health monitoring, disease diagnosis, and smart wearables. Metallized polymer films possess excellent flexibility and processability, and are often used as flexible electrodes and circuits. However, due to the different mechanical properties and thermal stability of the metal coating and the polymer base film, the metallized polymer film is highly susceptible to metal coating detachment during mechanical and thermal deformation, thus affecting the normal operation of flexible devices and circuits. Therefore, providing a metallized polymer film with a stable and robust bond between the metal coating and the polymer base film is crucial. Summary of the Invention

[0003] This application provides a metallized polymer film and a method for preparing the same, aiming to obtain a metallized polymer film with a stable and firm bond between a metal coating and a polymer base film by using atmospheric plasma spraying technology.

[0004] In a first aspect, this application provides a method for preparing a metallized polymer film, comprising the following steps:

[0005] S10: Provides a polymer-based film;

[0006] S20: Metal powder is sprayed onto the surface of the polymer base film using an atmospheric plasma spray gun to form a metal coating on the surface of the polymer base film, thereby obtaining a metallized polymer film.

[0007] The atmospheric plasma spray gun includes:

[0008] The plasma ionization chamber includes: a plasma working gas channel for introducing plasma working gas into the plasma ionization chamber; a powder feeding channel for feeding metal powder into the plasma ionization chamber via a carrier gas; and a nozzle for ejecting the plasma gas formed in the plasma ionization chamber to form a high-speed plasma jet.

[0009] The electrode includes: a positive electrode disposed around the inner layer of the nozzle, and a negative electrode housed in the plasma ionization chamber, for generating an electric arc by applying a spraying current to ionize the plasma working gas in the plasma ionization chamber to form plasma gas;

[0010] In this process, plasma working gas is introduced into the plasma ionization chamber at a flow rate of 5–15 L / min, and metal powder is fed into the plasma ionization chamber at a feed rate of 3–10 mg / s using carrier gas at a flow rate of 3–10 L / min. The plasma working gas is ionized under the action of a spraying current of 50–350 A, and expands upon heating to form plasma gas that is ejected from the nozzle, forming a high-speed plasma jet. The metal powder melts in the plasma ionization chamber under the action of the plasma gas and is sprayed onto the surface of a polymer base film with a spraying distance of 30–100 mm along with the high-speed plasma jet. The atmospheric plasma spray gun moves relative to the polymer base film at a moving speed of 50–200 mm / s and a moving interval of 1–8 mm, causing the metal powder to deposit on the surface of the polymer base film to form a metal coating.

[0011] According to this application, by using the above-mentioned atmospheric plasma spray gun and simultaneously controlling the spraying conditions, the energy of the high-speed plasma jet is controlled, thereby inputting momentum and heat to the surface of the polymer base film. Without damaging the polymer base film, a metal coating is deposited on the surface of the polymer base film, thereby obtaining a metallized polymer film in which the metal coating and the polymer base film are stably and firmly bonded.

[0012] In some embodiments, the polymer-based film comprises one or more of polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, polyimide, polydimethylsiloxane, polyurethane, polycarbonate, polyamide, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, and polyvinylidene fluoride.

[0013] In some embodiments, the metal powder comprises elemental metals and / or alloys, wherein the elemental metals include one or more of zinc, nickel, titanium, copper, tin, aluminum, and silver; optionally, the average particle size of the metal powder is 1 to 100 μm, preferably 10 to 50 μm.

[0014] In some embodiments, the plasma working gas includes one or more of argon, nitrogen, and hydrogen; and / or the carrier gas includes one or more of argon, nitrogen, and hydrogen; preferably, the plasma working gas is a hydrogen-argon mixture with a hydrogen gas fraction of 1% to 10%.

[0015] In some embodiments, the atmospheric plasma spray gun further includes a protective gas device, which includes: a protective gas nozzle surrounding the nozzle, and a protective gas channel communicating with the protective gas nozzle, for blowing protective gas to prevent oxidation of metals in the high-speed plasma jet;

[0016] In step S20, during the spraying process, a protective gas is blown at a flow rate of 3 to 10 L / min to encapsulate the high-speed plasma jet. The protective gas includes one or more of argon, nitrogen, and hydrogen.

[0017] In some embodiments, the angle between the powder feeding pipe and the nozzle is 30° to 90°; preferably 30° to 60°.

[0018] In some embodiments, the nozzle has an orifice diameter of 1.5 to 2 mm; and / or the diameter of the negative electrode near the nozzle end is 0.3 to 2 mm.

[0019] In some embodiments, the number of spraying operations in step S20 is 1 to 15.

[0020] In a second aspect, this application provides a metallized polymer film prepared according to the method described in any embodiment of the first aspect.

[0021] According to this application, since the metallized polymer film is prepared according to the method of any embodiment of the first aspect, it has the beneficial effects of the first aspect and has great application prospects in flexible electrodes and circuits.

[0022] In some embodiments, the thickness of the metal coating is 1 to 150 μm, preferably 10 to 80 μm; optionally, the adhesion level of the metal coating on the polymer base film is at least level 2, preferably at least level 1.

[0023] According to this application, a metallized polymer film and its preparation method are provided. This method, through a unique spray gun structure design and controllable process parameters, achieves control over the energy of the high-speed plasma jet, thereby adjusting the heat and momentum input to the surface of the polymer base film. Without damaging the polymer base film, a metal coating with high bonding strength is deposited. This method is applicable to various polymer base films, yielding different metallized polymer films. Furthermore, this preparation method can effectively suppress high-temperature oxidation of metals, achieving high-purity metal coatings and expanding its application areas. This preparation method also has several other advantages, such as high preparation efficiency, fast speed, simple operation, a vacuum-free working environment, and good substrate versatility, thus showing great application potential in flexible electrodes and circuits. Attached Figure Description

[0024] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this application and, together with the description, serve to explain the principles of this application.

[0025] Figure 1 This is a schematic diagram of the atmospheric plasma spray gun structure used in the embodiments of this application.

[0026] Figure 2 The XRD patterns of the metal layers prepared in Examples 2, 4 and 5 of this application are shown.

[0027] Figure 3 a, Figure 3 b、 Figure 3 c. Figure 3 d are microscope images of the metal layer surfaces prepared in Examples 2, 4, 5 and Comparative Example 1 of this application, respectively.

[0028] Reference numerals in the attached diagram: 1. Plasma working gas channel; 2. Powder feeding channel; 3. Nozzle; 4. Positive electrode; 5. Negative electrode; 6. Protective gas nozzle; 7. Protective gas channel; 8. Cooling liquid device; 9. High-speed plasma jet; 10. Protective gas.

[0029] The accompanying drawings illustrate specific embodiments of this application, which will be described in more detail below. These drawings and descriptions are not intended to limit the scope of the concept in any way, but rather to illustrate the concept of this application to those skilled in the art through reference to particular embodiments. Detailed Implementation

[0030] The various embodiments or implementation schemes in this specification are described in a progressive manner, with each embodiment focusing on the differences from other embodiments.

[0031] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "illustrative embodiment," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with an embodiment or example is included in at least one embodiment or example of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0032] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this application, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0033] As described in the background section above, there is a need for a metallized polymer film in which a metal coating is stably and firmly bonded to a polymer base film.

[0034] To address this, various methods for metallizing polymer-based films have been developed, primarily including electroless plating, electroplating, and physical vapor deposition (PVD). Since most polymer-based films are insulating, direct electroless or electroplating on their surfaces is very difficult. It is necessary to first form an active conductive layer on the polymer-based film surface, and then deposit a catalytic metal layer on the surface through methods such as oxidation etching, laser direct writing, light irradiation, surfactant electrostatic adsorption, and covalent grafting to catalyze the subsequent electroless plating reaction. To increase adhesion, whether electroless or electroplating, the polymer-based film inevitably undergoes a complex roughening and activation process. Different polymer-based films with different physicochemical properties require different pretreatment processes, significantly increasing the preparation difficulty. Physical vapor deposition techniques, such as vacuum evaporation and magnetron sputtering, use physical methods to vaporize the metal source into atoms, molecules, or ions, which then adsorb, nucleate, grow, and form a film on the polymer-based film surface. This method is performed in a vacuum environment, resulting in a slow deposition rate, suitable for preparing thin coatings, but therefore costly, and the coating thickness cannot meet the required specifications.

[0035] Based on this, this application provides a method for preparing a metallized polymer film, mainly employing atmospheric plasma spraying technology to directly deposit a metal coating onto the surface of a polymer base film, thereby obtaining a metallized polymer film in which the metal coating is stably and firmly bonded to the polymer base film. The following provides a detailed description of the metallized polymer film and its preparation method provided in this application.

[0036] In a first aspect, this application provides a method for preparing a metallized polymer film, comprising the following steps:

[0037] S10: Provides a polymer-based film;

[0038] S20: Metal powder is sprayed onto the surface of a polymer base film using an atmospheric plasma spray gun to form a metal coating on the surface of the polymer base film, thereby obtaining a metallized polymer film.

[0039] Atmospheric plasma spray guns include:

[0040] The plasma ionization chamber includes: a plasma working gas channel for introducing plasma working gas into the plasma ionization chamber; a powder feeding channel for feeding metal powder into the plasma ionization chamber via a carrier gas; and a nozzle for ejecting the plasma gas formed in the plasma ionization chamber to form a high-speed plasma jet.

[0041] The electrode includes a positive electrode disposed around the inner layer of the nozzle and a negative electrode housed in the plasma ionization chamber, used to generate an electric arc by applying a spraying current to ionize the plasma working gas in the plasma ionization chamber to form plasma gas;

[0042] In this process, plasma working gas is introduced into the plasma ionization chamber at a flow rate of 5–15 L / min, and metal powder is fed into the plasma ionization chamber at a feed rate of 3–10 mg / s using carrier gas at a flow rate of 3–10 L / min. The plasma working gas is ionized under the action of a spraying current of 50–350 A, and expands upon heating to form plasma gas that is ejected from the nozzle, forming a high-speed plasma jet. The metal powder melts in the plasma ionization chamber under the action of the plasma gas and is sprayed onto the surface of a polymer base film with a spraying distance of 30–100 mm along with the high-speed plasma jet. The atmospheric plasma spray gun moves relative to the polymer base film at a moving speed of 50–200 mm / s and a moving interval of 1–8 mm, causing the metal powder to deposit on the surface of the polymer base film to form a metal coating.

[0043] According to this application, a metallized polymer film is prepared by atmospheric plasma spraying technology. The structure of the atmospheric plasma spray gun has been optimized by simultaneously setting the plasma working gas channel and the powder feeding channel in the plasma ionization chamber. This can effectively reduce the time of direct contact between the metal and the air. Under the protection of the carrier gas, the oxidation of the metal is effectively reduced, and the formation of high-melting-point metal oxides is reduced, thereby promoting the full melting of the metal powder. This allows the metal to be better deposited on the surface of the polymer base film, making the metal coating and the polymer base film more firmly bonded.

[0044] Furthermore, in this application, while using the atmospheric plasma spray gun, a large number of process parameters are controlled, such as the flow rate of the plasma working gas, the flow rate of the carrier gas, the powder feeding rate of the metal powder, the spraying current, the spraying spacing, the moving speed of the atmospheric plasma spray gun, and the moving interval. When the above process parameters are controlled within the above range, a high-speed plasma jet carrying molten or semi-molten metal with suitable heat and momentum can be obtained. At this time, the high-speed plasma jet can avoid the polymer base film from being damaged (melted or penetrated) while stably depositing the molten or semi-molten metal on the polymer base film to form a metal coating, thereby obtaining a metallized polymer film in which the metal coating and the polymer base film are stably and firmly bonded.

[0045] It should be noted that the structure and process parameters of the aforementioned atmospheric plasma spray gun are synergistic. Only when all the above requirements are met can a high-speed plasma jet carrying molten or semi-molten metal with appropriate heat and momentum be obtained. For example, the spraying current, combined with the appropriate structure of the atmospheric plasma spray gun, the flow rate of the appropriate plasma working gas and carrier, and the powder feeding rate, allows the metal powder to melt rapidly while simultaneously obtaining a high-speed plasma jet carrying molten or semi-molten metal with appropriate heat and momentum. The spraying distance, moving speed, and moving interval are also important controlling factors affecting the heat and momentum of the high-speed plasma jet when it reaches the polymer base film. In addition, the spraying distance also affects the oxidation of the metal. Therefore, the structure and process parameters of the aforementioned atmospheric plasma spray gun will individually or jointly affect the preparation of the metallized polymer. When all the above requirements are met simultaneously, a metallized polymer film with a stable and firm bond between the metal coating and the polymer base film can be obtained.

[0046] For example, the flow rate of the plasma working gas can be 5 L / min, 6 L / min, 7 L / min, 8 L / min, 9 L / min, 10 L / min, 11 L / min, 12 L / min, 13 L / min, 14 L / min, 15 L / min, or any of the values ​​described above. The flow rate of the carrier gas can be 3 L / min, 4 L / min, 5 L / min, 6 L / min, 7 L / min, 8 L / min, 9 L / min, 10 L / min, or any of the values ​​described above. The powder delivery rate can be 3 mg / s, 4 mg / s, 5 mg / s, 6 mg / s, 7 mg / s, 8 mg / s, 9 mg / s, 10 mg / s, or any of the values ​​described above. The spraying current can be 50A, 60A, 70A, 80A, 90A, 100A, 110A, 120A, 130A, 140A, 150A, 180A, 200A, 220A, 240A, 260A, 280A, 300A, 350A, or any value within the range described above. The spraying spacing can be 30mm, 40mm, 50mm, 60mm, 70mm, 80mm, 90mm, 100mm, or any value within the range described above. The moving speed can be 50mm / s, 60mm / s, 70mm / s, 80mm / s, 90mm / s, 100mm / s, 110mm / s, 120mm / s, 130mm / s, 140mm / s, 150mm / s, 160mm / s, 170mm / s, 180mm / s, 190mm / s, 200mm / s, or any of the values ​​described above. The moving interval can be 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, or any of the values ​​described above.

[0047] In addition, this preparation method has many other advantages, such as high preparation efficiency, fast speed, simple operation, no vacuum working environment, and good substrate versatility. Therefore, it has great application prospects in flexible electrodes and circuits.

[0048] In some embodiments, step S10 further includes cleaning the polymer base film to remove organic matter and impurities from the surface of the base film and fixing the polymer base film onto the carrier. Optionally, the carrier can be glass.

[0049] In some embodiments, the polymer base film includes one or more of polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, polyimide, polydimethylsiloxane, polyurethane, polycarbonate, polyamide, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, and polyvinylidene fluoride.

[0050] In the above embodiments, some commonly used polymer-based films in the art are specifically listed, and one or more of them can be selected according to actual needs. It is understood that polymer-based films include, but are not limited to, the above-mentioned types, and any known polymer-based film in the art can also be selected.

[0051] In some embodiments, the metal powder includes elemental metals and / or alloys, and the elemental metals include one or more of zinc, nickel, titanium, copper, tin, aluminum, and silver; optionally, the average particle size of the metal powder is 1 to 100 μm, preferably 10 to 50 μm.

[0052] In some of the above embodiments, the type of metal powder is not specifically required and may include elemental metals and / or alloys. Elemental metals can be selected from metals commonly used in the art for metal coatings. Furthermore, the particle size of the metal powder is preferred. It is understood that, under the same conditions, the smaller the average particle size, the larger the specific surface area, meaning it is easier to melt and better bond to the polymer base film surface. When the metal powder particle size is within the above range, the metal powder is less prone to oxidation, and the resulting metal coating bonds more firmly to the polymer base film. For example, the average particle size of the metal powder can be 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, or any of the above values. Preferably, it can be 10–50 μm.

[0053] In some embodiments, the plasma working gas includes one or more of argon, nitrogen, and hydrogen; and / or the carrier gas includes one or more of argon, nitrogen, and hydrogen; preferably, the plasma working gas is a hydrogen-argon mixture with a hydrogen gas fraction of 1% to 10%.

[0054] In some of the above embodiments, the plasma working gas may include one or more of argon, nitrogen, and hydrogen, and the carrier gas may include one or more of argon, nitrogen, and hydrogen. These gases do not react with the metal powder and can provide a protective atmosphere for the spraying process. Preferably, the plasma working gas can be a hydrogen-argon mixture with a hydrogen gas fraction of 1% to 10%. Argon has a high gas density, which is beneficial for accelerating the melting of metal; however, argon has a low thermal conductivity, which is not conducive to heating the metal powder. Adding a certain volume ratio of hydrogen with a high thermal conductivity is beneficial for heat exchange between the high-speed plasma jet and the metal powder, promoting the full melting of the metal powder and improving the adhesion of the metal coating to the polymer base film surface. For example, the hydrogen gas fraction in the hydrogen-argon mixture can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or any of the above values.

[0055] In some embodiments, the atmospheric plasma spray gun further includes a protective gas device, which includes: a protective gas nozzle surrounding the nozzle, and a protective gas channel communicating with the protective gas nozzle for blowing protective gas to prevent oxidation of metals in the high-speed plasma jet.

[0056] In step S20, during the spraying process, a protective gas is blown at a flow rate of 3 to 10 L / min to encapsulate the high-speed plasma jet. The protective gas includes one or more of argon, nitrogen, and hydrogen.

[0057] In some of the above embodiments, the atmospheric plasma spray gun also includes a protective gas device, which can blow protective gas to reduce the contact between the high-speed plasma jet and the air, thereby further preventing metal oxidation and making it more conducive to obtaining a pure metal coating. Simultaneously, the flow rate of the protective gas is further limited to 3–10 L / min, which effectively protects the metal in the high-speed plasma jet from oxidation. The protective gas can be one or more of argon, nitrogen, and hydrogen. For example, the flow rate of the protective gas can be 3 L / min, 4 L / min, 5 L / min, 6 L / min, 7 L / min, 8 L / min, 9 L / min, 10 L / min, or any of the values ​​described above within the range.

[0058] In some embodiments, the angle between the powder feeding pipe and the nozzle is 30° to 90°; preferably 30° to 60°.

[0059] In some of the above embodiments, the angle between the powder feeding pipe and the nozzle has been further optimized. It is understood that the angle between the powder feeding pipe and the nozzle will, to some extent, affect the melting of the metal powder. Within the aforementioned range, a smaller spraying current can be used to fully melt the metal powder, thereby improving the adhesion of the metal coating to the polymer base film surface. For example, the angle between the powder feeding pipe and the nozzle can be 30°, 35°, 40°, 45°, 50°, 55°, 60°, 65°, 70°, 75°, 80°, 85°, 90°, or any of the values ​​described above. Preferably, it can be 30° to 60°.

[0060] In some embodiments, the nozzle orifice diameter is 1.5 to 2 mm; and / or the diameter of the negative electrode near the nozzle end is 0.3 to 2 mm.

[0061] In some of the above embodiments, the nozzle orifice diameter and the diameter of the negative electrode near the nozzle side end have been further optimized. It is understood that the positive electrode is located in the inner layer of the nozzle, and the nozzle orifice diameter and the diameter of the negative electrode near the spray side end can affect the arc intensity, allowing the high-speed plasma jet to have more suitable heat and momentum, resulting in a stronger bond between the metal coating and the polymer base film. Simultaneously, the nozzle orifice diameter can also affect the shape of the plasma jet, which can be selected according to the base film. It should also be noted that the shape of the negative electrode near the nozzle side end can be one of a pointed, flat, or hemispherical shape, and the diameter of the end refers to the maximum diameter of the end shape. For example, the nozzle orifice diameter can be 1.5mm, 1.6mm, 1.7mm, 1.8mm, 1.9mm, 2mm, or any of the values ​​described above; the diameter of the negative electrode near the nozzle end can be 0.3mm, 0.4mm, 0.5mm, 0.8mm, 1.0mm, 1.2mm, 1.4mm, 1.6mm, 1.8mm, 2.0mm, or any of the values ​​described above.

[0062] In some implementations, the positive electrode is made of copper; the negative electrode is made of one or more of tungsten, tungsten-molybdenum alloy, and graphite.

[0063] In some embodiments, the number of spraying operations in step S20 is 1 to 15.

[0064] In some of the above embodiments, the number of spraying times is further limited. It is understood that by adjusting the number of spraying times, metal coatings of different thicknesses can be deposited, allowing for selection based on needs and expanding the application scope of the preparation method of this application. Simultaneously, the metal coating obtained through multiple sprayings has a more uniform surface and better adhesion between the metal coating and the polymer base film. Furthermore, it is understood that different metal powders can be used in different spraying processes to obtain multi-layered metal coatings, further expanding the application scenarios of this method.

[0065] In some embodiments, the atmospheric plasma spray gun includes a coolant device that may be disposed around the nozzle to reduce the heat carried by the high-speed plasma jet. The coolant may be circulating cooling water.

[0066] As an example, the atmospheric plasma spray gun used in some embodiments of this application is the atmospheric plasma spray gun integrated into the INOCON Micro-Nanoparticle-Coater-1700013 spraying equipment. A schematic diagram of the structure of this atmospheric plasma spray gun is shown below. Figure 1 As shown, it includes: a plasma ionization chamber, including: a plasma working gas channel 1 for introducing plasma working gas into the plasma ionization chamber; and a powder feeding channel 2 for feeding metal powder into the plasma ionization chamber through a carrier gas; and a nozzle 3 for ejecting the plasma gas formed in the plasma ionization chamber to form a high-speed plasma jet, the nozzle having a nozzle diameter of 2mm and the angle between the powder feeding channel and the nozzle being 45°;

[0067] The electrode includes a positive electrode 4 disposed around the inner layer of the nozzle and a negative electrode 5 housed in the plasma ionization chamber, used to generate an electric arc by applying a spraying current to ionize the plasma working gas in the plasma ionization chamber and form plasma gas.

[0068] The protective gas device includes: a protective gas nozzle 6 surrounding the nozzle, and a protective gas channel 7 communicating with the protective gas nozzle, for blowing protective gas 10 to prevent oxidation of metal in the high-speed plasma jet 9;

[0069] The coolant device 8 is arranged around the nozzle to reduce the heat carried by the high-speed plasma jet. The coolant is circulating cooling water.

[0070] It should be noted that the structure of the above-described spray gun is merely exemplary, and those skilled in the art can select other atmospheric plasma spray guns that meet the requirements of this application as needed.

[0071] Secondly, this application provides a metallized polymer film prepared according to any embodiment of the first aspect.

[0072] According to this application, since the metallized polymer film is prepared according to the method of any embodiment of the first aspect, it has the beneficial effects of the first aspect and has great application prospects in flexible electrodes and circuits.

[0073] In some embodiments, the thickness of the metal coating is 1 to 150 μm, preferably 10 to 80 μm; optionally, the adhesion level of the metal coating on the polymer base film is at least level 2, preferably at least level 1.

[0074] In some of the above embodiments, the thickness of the metal coating is specifically defined as 1–150 μm, which allows for a wide range of metal coating thicknesses. This means that metallized polymer films with different metal coating thicknesses can be selected according to actual needs. Furthermore, in some embodiments, the adhesion level of the metal coating to the polymer base film is at least level 2, indicating a strong bond between the metal coating and the polymer base film, which can be widely used in flexible electrodes and circuits. For example, the adhesion level can be level 2, level 1, or level 0, preferably at least level 1.

[0075] It should be noted that the thickness of the metal coating can be tested using any method and instrument known in the art, for example, using a step tester (Dektak-XT, Bruker); the adhesion level of the metal coating on the polymer base film is tested using the cross-cut test according to GB / 9286-1998.

[0076] The following describes embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.

[0077] Metallized release films were prepared using an INOCON Micro-Nanoparticle-Coater-1700013 spraying system. The thickness of the prepared metal coating was measured using a profilometer (Dektak-XT, Bruker). The phase composition of the metal coating was characterized using X-ray diffraction (XRD, D8, Bruker). The surface morphology of the metal coating was observed using a laser confocal microscope (OSL4000, OLYMPUS). The adhesion of the coating was tested using the cross-cut adhesion test according to GB / 9286-1998.

[0078] Example 1

[0079] Preparation of metallized polymer films:

[0080] Polyimide film was selected as the polymer base film, and a metallic nickel coating was deposited using atmospheric plasma spraying equipment. The plasma working gas was a hydrogen-argon mixture with a hydrogen content of 5 vol.%, the protective gas was argon, and the carrier gas was argon. The specific steps are as follows:

[0081] 1) Use ethanol to clean the organic matter and impurities on the surface of the polyimide film, then attach the cleaned film to the glass and fix it on the worktable.

[0082] 2) Powder feeding and atmospheric plasma spraying: Add metallic nickel powder (average particle size 30μm) to the atmospheric plasma spraying feeding system. Install the flat-headed tungsten electrode (1mm end diameter) and nozzle. Turn on the main switch, power switch, all air circuit switches, air compressor and vacuum cleaner switches in sequence, and run the cooling water program.

[0083] The plasma working gas flow rate was set to 12 L / min, the carrier gas flow rate to 10 L / min, and the powder feed rate to 4 mg / s. The spraying current was set to 190 A, the spraying distance to 5.5 cm, and the number of sprays to 3. The high-speed plasma jet purging movement interval was set to 3 mm, and the movement speed to 200 mm / s. The starting coordinates (X = 25 mm, Y = 25 mm) and ending coordinates (X = 45 mm, Y = 45 mm) of the high-speed plasma jet purging were set, and the spraying operation was carried out.

[0084] The resulting nickel-coated polyimide film has a uniform surface and a coating thickness of approximately 23 μm. Adhesion is rated at grade 1, indicating good bonding between the nickel layer and the polyimide.

[0085] Example 2

[0086] Preparation of metallized polymer films:

[0087] Polyethylene film was selected as the polymer base film, and a metallic copper coating was deposited using atmospheric plasma spraying equipment. The plasma working gas, the protective gas, and the carrier gas were all hydrogen-argon mixtures, with a hydrogen content of 5 vol.%. The specific steps are as follows:

[0088] 1) Use ethanol to clean the organic matter and impurities on the surface of the polyethylene film. After cleaning, attach the film to the glass and fix it on the worktable.

[0089] 2) Powder feeding and atmospheric plasma spraying: Add metallic copper powder (average particle size 30μm) to the atmospheric plasma spraying feeding system. Install the pointed tungsten electrode (end diameter 0.5mm) and nozzle. Turn on the main switch, power switch, each stage air circuit switch, air compressor and vacuum cleaner switches in sequence, and run the cooling water program.

[0090] The plasma working gas flow rate is set to 12 L / min, the carrier gas flow rate to 6 L / min, and the powder feed rate to 5 mg / s. The spraying current is set to 140 A, the spraying distance to 6 cm, and the number of sprays to 5. The high-speed plasma jet purging movement interval is set to 2 mm, and the movement speed is set to 50 mm / s. The starting coordinates (X = 20 mm, Y = 20 mm) and ending coordinates (X = 40 mm, Y = 40 mm) of the high-speed plasma jet purging are set, and the spraying operation is performed.

[0091] The resulting copper-coated polyethylene film has a uniform surface and a coating thickness of approximately 34 μm. Adhesion is rated at grade 0, indicating good bonding between the copper layer and the polyethylene film.

[0092] Example 3

[0093] Preparation of metallized polymer films:

[0094] Polyethylene terephthalate (PET) film was selected as the polymer base film, and a metallic silver coating was deposited using atmospheric plasma spraying equipment. The plasma working gas was a hydrogen-argon mixture with a hydrogen content of 5 vol.%, the protective gas was argon, and the carrier gas was argon. The specific steps are as follows:

[0095] 1) Use ethanol to clean the organic matter and impurities on the surface of the polyethylene terephthalate film. After cleaning, attach the film to the glass and fix it on the worktable.

[0096] 2) Powder feeding and atmospheric plasma spraying: Add metallic silver powder (average particle size 20μm) to the atmospheric plasma spraying feeding system. Install the pointed tungsten electrode (end diameter 0.5mm) and plasma nozzle. Turn on the main switch, power switch, all air circuit switches, air compressor and vacuum cleaner switches in sequence, and run the cooling water program.

[0097] The plasma working gas flow rate is set to 10 L / min, the carrier gas flow rate to 5 L / min, and the powder feed rate to 4 mg / s. The spraying current is set to 120 A, the spraying distance to 5.5 cm, and the number of sprays to 5. The high-speed plasma jet purging movement interval is set to 3 mm, and the movement speed is set to 100 mm / s. The starting coordinates (X = 35 mm, Y = 35 mm) and ending coordinates (X = 55 mm, Y = 55 mm) of the high-speed plasma jet purging are set, and the spraying operation is performed.

[0098] The resulting silver-coated polyethylene terephthalate (PET) film has a uniform surface and a coating thickness of approximately 25 μm. The adhesion is grade 2, indicating good bonding between the silver layer and the PET film.

[0099] Example 4

[0100] Polyethylene terephthalate (PET) film was selected as the polymer base film, and a metallic copper coating was deposited using atmospheric plasma spraying equipment. The plasma working gas, the protective gas, and the carrier gas were all argon.

[0101] The specific steps are as follows:

[0102] 1) Use ethanol to clean the organic matter and impurities on the surface of the polyethylene terephthalate film. After cleaning, attach the film to the glass and fix it on the worktable.

[0103] 2) Powder feeding and atmospheric plasma spraying: Add metallic copper powder (average particle size 20μm) to the atmospheric plasma spraying feeding system. Install the pointed tungsten electrode (end diameter 0.5mm) and plasma nozzle. Turn on the main switch, power switch, all air circuit switches, air compressor and vacuum cleaner switches in sequence, and run the cooling water program.

[0104] The plasma working gas flow rate is set to 10 L / min, the carrier gas flow rate to 5 L / min, and the powder feed rate to 5 mg / s. The spraying current is set to 130 A, the spraying distance to 5.5 cm, and the number of sprays to 5. The high-speed plasma jet purging movement interval is set to 1 mm, and the movement speed is set to 200 mm / s. The starting coordinates (X = 35 mm, Y = 35 mm) and ending coordinates (X = 55 mm, Y = 55 mm) of the high-speed plasma jet purging are set for the spraying operation.

[0105] The obtained copper-coated polyethylene terephthalate film has a uniform surface and a coating thickness of approximately 28 μm. The adhesion is grade 1, indicating good bonding between the copper layer and the polyethylene terephthalate film.

[0106] Example 5

[0107] Polydimethylsiloxane film was selected as the polymer base film, and a metallic copper coating was deposited using atmospheric plasma spraying equipment. The plasma working gas, the protective gas, and the carrier gas were all argon. The specific steps are as follows:

[0108] 1) Use ethanol to clean the organic matter and impurities on the surface of the polydimethylsiloxane film, attach the cleaned film to the glass, and then fix it on the worktable.

[0109] 2) Powder feeding and atmospheric plasma spraying: Add metallic copper powder (average particle size 20μm) to the atmospheric plasma spraying feeding system. Install the flat-head tungsten electrode (end diameter 1mm) and plasma nozzle. Turn on the main switch, power switch, all air circuit switches, air compressor and vacuum cleaner switches in sequence, and run the cooling water program.

[0110] The plasma working gas flow rate is set to 12 L / min, the carrier gas flow rate to 5 L / min, and the powder feed rate to 5 mg / s. The spraying current is set to 150 A, the spraying distance to 5.5 cm, and the number of sprays to 10. The high-speed plasma jet purging movement interval is set to 1 mm, and the movement speed is set to 200 mm / s. The starting coordinates (X = 35 mm, Y = 35 mm) and ending coordinates (X = 55 mm, Y = 55 mm) of the high-speed plasma jet purging are set, and the spraying operation is performed.

[0111] The obtained copper-coated polydimethylsiloxane film has a uniform surface and a coating thickness of approximately 56 μm. The adhesion is grade 0, indicating good bonding between the copper layer and the polydimethylsiloxane film.

[0112] Example 6

[0113] Polypropylene was selected as the polymer base film, and an aluminum coating was deposited using an atmospheric plasma spraying system. The plasma working gas, the protective gas, and the carrier gas were all argon. The specific steps are as follows:

[0114] 1) Use ethanol to clean the organic matter and impurities on the surface of the polypropylene film. After cleaning, attach the film to the glass and fix it on the worktable.

[0115] 2) Powder feeding and atmospheric plasma spraying: Add metallic aluminum powder (average particle size 30μm) to the atmospheric plasma spraying feeding system. Install the pointed tungsten electrode (end diameter 0.5mm) and plasma nozzle. Turn on the main switch, power switch, all air circuit switches, air compressor and vacuum cleaner switches in sequence, and run the cooling water program.

[0116] The plasma working gas flow rate is set to 10 L / min, the carrier gas flow rate to 5 L / min, and the powder feed rate to 4 mg / s. The spraying current is set to 110 A, the spraying distance to 5.5 cm, and the number of sprays to 5. The high-speed plasma jet purging movement interval is set to 2 mm, and the movement speed is set to 100 mm / s. The starting coordinates (X = 25 mm, Y = 25 mm) and ending coordinates (X = 45 mm, Y = 45 mm) of the high-speed plasma jet purging are set, and the spraying operation is performed.

[0117] The resulting aluminum-coated polypropylene film has a uniform surface and a coating thickness of approximately 37 μm. Adhesion is rated at grade 1, indicating good bonding between the aluminum layer and the polypropylene film.

[0118] Example 7

[0119] Polyethylene-tetrafluoroethylene copolymer was selected as the polymer base film, and a metallic tin coating was deposited using atmospheric plasma spraying equipment. The plasma working gas, the protective gas, and the carrier gas were all argon. The specific steps are as follows:

[0120] 1) Use ethanol to clean the organic matter and impurities on the surface of the polyethylene-tetrafluoroethylene copolymer, then attach the cleaned film to the glass and fix it on the worktable.

[0121] 2) Powder feeding and atmospheric plasma spraying: Add metallic tin powder (average particle size 30μm) to the atmospheric plasma spraying feeding system. Install the pointed tungsten electrode (end diameter 0.5mm) and plasma nozzle. Turn on the main switch, power switch, all air circuit switches, air compressor and vacuum cleaner switches in sequence, and run the cooling water program.

[0122] The plasma working gas flow rate is set to 10 L / min, the carrier gas flow rate to 5 L / min, and the powder feed rate to 4 mg / s. The spraying current is set to 80 A, the spraying distance to 5.5 cm, and the number of sprays to 5. The high-speed plasma jet purging movement interval is set to 3 mm, and the movement speed is set to 100 mm / s. The starting coordinates (X = 25 mm, Y = 25 mm) and ending coordinates (X = 45 mm, Y = 45 mm) of the high-speed plasma jet purging are set, and the spraying operation is performed.

[0123] The obtained tin-coated polyethylene-tetrafluoroethylene copolymer has a uniform surface and a coating thickness of approximately 32 μm. The adhesion is grade 1, indicating good bonding between the tin layer and the polyethylene-tetrafluoroethylene copolymer.

[0124] Example 8

[0125] Polyvinyl chloride (PVC) film was selected as the polymer base film, and a zinc coating was deposited using atmospheric plasma spraying equipment. The plasma working gas, the protective gas, and the carrier gas were all argon. The specific steps are as follows:

[0126] 1) Use ethanol to clean the organic matter and impurities on the surface of the polyvinyl chloride film. After cleaning, attach the film to the glass and fix it on the worktable.

[0127] 2) Powder feeding and atmospheric plasma spraying: Add zinc powder (average particle size 30μm) to the atmospheric plasma spraying feeding system. Install the pointed tungsten electrode (end diameter 0.5mm) and plasma nozzle. Turn on the main switch, power switch, all air circuit switches, air compressor and vacuum cleaner switches in sequence, and run the cooling water program.

[0128] The plasma working gas flow rate is set to 12 L / min, the carrier gas flow rate to 5 L / min, and the powder feeding rate to 5 mg / s. The spraying current is set to 100 A, the spraying distance to 6 cm, and the number of sprays to 3. The high-speed plasma jet purging movement interval is set to 3 mm, and the movement speed is set to 100 mm / s. The starting coordinates (X = 35 mm, Y = 35 mm) and ending coordinates (X = 55 mm, Y = 55 mm) of the high-speed plasma jet purging are set, and the spraying operation is performed.

[0129] The obtained zinc-coated PVC film has a uniform surface and a coating thickness of approximately 21 μm. The adhesion is grade 1, indicating good bonding between the zinc layer and the PVC film.

[0130] Comparative Example 1

[0131] Polydimethylsiloxane film was selected as the polymer base film, and a metallic copper coating was deposited using atmospheric plasma spraying equipment. The plasma working gas, the protective gas, and the carrier gas were all argon. The specific steps are as follows:

[0132] 1) Use ethanol to clean the organic matter and impurities on the surface of the polydimethylsiloxane film, attach the cleaned film to the glass, and then fix it on the worktable.

[0133] 2) Powder feeding and atmospheric plasma spraying: Add metallic copper powder (average particle size 20μm) to the atmospheric plasma spraying feeding system. Install the pointed tungsten electrode (end diameter 0.5mm) and plasma nozzle. Turn on the main switch, power switch, all air circuit switches, air compressor and vacuum cleaner switches in sequence, and run the cooling water program.

[0134] The plasma working gas flow rate was set to 12 L / min, the carrier gas flow rate to 11 L / min, and the powder feed rate to 2 mg / s. The spraying current was set to 130 A, the spraying distance to 6.5 cm, and the number of sprays to 5. The high-speed plasma jet purging movement interval was set to 9 mm, and the movement speed to 200 mm / s. The starting coordinates (X = 35 mm, Y = 30 mm) and ending coordinates (X = 55 mm, Y = 55 mm) of the high-speed plasma jet purging were set, and the spraying operation was carried out.

[0135] Only a small amount of metallic copper adheres to the surface of the polydimethylsiloxane film, and the bonding strength is very low, making it easy for the copper to detach from the surface.

[0136] Comparative Example 2

[0137] Polydimethylsiloxane film was selected as the polymer base film, and a metallic copper coating was deposited using atmospheric plasma spraying equipment. The plasma working gas, the protective gas, and the carrier gas were all argon. The specific steps are as follows:

[0138] 1) Use ethanol to clean the organic matter and impurities on the surface of the polydimethylsiloxane film, attach the cleaned film to the glass, and then fix it on the worktable.

[0139] 2) Powder feeding and atmospheric plasma spraying: Add metallic copper powder (average particle size 20μm) to the atmospheric plasma spraying feeding system. Install the pointed tungsten electrode (end diameter 0.5mm) and plasma nozzle. Turn on the main switch, power switch, all air circuit switches, air compressor and vacuum cleaner switches in sequence, and run the cooling water program.

[0140] The plasma working gas flow rate is set to 4 L / min, the carrier gas flow rate to 11 L / min, and the powder feeding rate to 2 mg / s. The spraying current is set to 40 A, the spraying distance to 11 cm, and the number of sprays to 10. The high-speed plasma jet purging movement interval is set to 2 mm, and the movement speed is set to 100 mm / s. The starting coordinates (X = 35 mm, Y = 30 mm) and ending coordinates (X = 55 mm, Y = 60 mm) of the high-speed plasma jet purging are set for the spraying operation.

[0141] No copper layer is attached to the surface of the polydimethylsiloxane film.

[0142] Comparative Example 3

[0143] Polydimethylsiloxane film was selected as the polymer base film, and a metallic copper coating was deposited using atmospheric plasma spraying equipment. The plasma working gas, the protective gas, and the carrier gas were all argon. The specific steps are as follows:

[0144] 1) Use ethanol to clean the organic matter and impurities on the surface of the polydimethylsiloxane film, attach the cleaned film to the glass, and then fix it on the worktable.

[0145] 2) Powder feeding and atmospheric plasma spraying: Add metallic copper powder (average particle size 10μm) to the atmospheric plasma spraying feeding system. Install the round-headed tungsten electrode (end diameter 2mm) and plasma nozzle. Turn on the main switch, power switch, each stage air circuit switch, air compressor and vacuum cleaner switches in sequence, and run the cooling water program.

[0146] The plasma working gas flow rate was set to 17 L / min, the carrier gas flow rate to 11 L / min, and the powder feed rate to 12 mg / s. The spraying current was set to 360 A, the spraying distance to 8 cm, and the number of sprays to 5. The high-speed plasma jet purging movement interval was set to 3 mm, and the movement speed to 250 mm / s. The starting coordinates (X = 35 mm, Y = 45 mm) and ending coordinates (X = 55 mm, Y = 50 mm) of the high-speed plasma jet purging were set, and the spraying operation was carried out.

[0147] Melting occurred on the surface of the polydimethylsiloxane film, and a metallized polymer film was not obtained.

[0148] Test section:

[0149] The above embodiments show that the adhesion level between the metal coating and the polymer base film in the metallized polymer film is at least level 2, and except for Example 3, the adhesion level is at least level 1, which is better than the adhesion of the metallized polymer film obtained in the comparative example.

[0150] Figure 2 The figure shows the XRD patterns of the metal coatings in the metallized polymer films prepared in Examples 2, 4 and 5 of this application. As can be seen from the figure, although the preparation is carried out in an atmospheric environment, the metal is not easily oxidized, and a high-purity metal coating can be obtained, thus expanding the application range of this method.

[0151] Figure 3 a, Figure 3 b、 Figure 3 c. Figure 3 Images d are microscopic images of the metal coating surfaces prepared in Examples 2, 4, 5, and Comparative Example 1 of this application. As can be seen from the images, the metal coatings obtained in the examples of this application are uniformly deposited with good deposition results, while only a small amount of copper adheres to the surface of the polymer base film in Comparative Example 1. Furthermore, no copper adheres to the surface of the polymer base film in Comparative Example 2, and the surface of the polymer base film in Comparative Example 3 melts, failing to effectively obtain a metallized polymer film. This indicates that process parameters have a significant impact on the preparation of the metallized polymer film.

[0152] In summary, the metal coating in the metallized polymer film prepared by this application exhibits excellent adhesion to the polymer base film surface, and the two are stably bonded together. Furthermore, the preparation method is simple, efficient, and does not require a vacuum environment, thus having broad application prospects in the field of flexible electrodes and circuits.

[0153] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A method of preparing a metallized polymer film, characterized by, Includes the following steps: S10: Provides a polymer-based film; S20: Metal powder is sprayed onto the surface of the polymer base film using an atmospheric plasma spray gun to form a metal coating on the surface of the polymer base film, thereby obtaining a metallized polymer film. The atmospheric plasma spray gun includes a plasma ionization chamber and electrodes; The plasma ionization chamber includes: a plasma working gas channel for introducing plasma working gas into the plasma ionization chamber; a powder feeding channel for feeding metal powder into the plasma ionization chamber via a carrier gas; and a nozzle for ejecting the plasma gas formed in the plasma ionization chamber to form a high-speed plasma jet, wherein the nozzle has a nozzle diameter of 1.5~2mm. The electrode includes: a positive electrode surrounding the inner layer of the nozzle, and a negative electrode housed in the plasma ionization chamber, for generating an electric arc by applying a spraying current to ionize the plasma working gas in the plasma ionization chamber to form plasma gas; In this process, plasma working gas is introduced into the plasma ionization chamber at a flow rate of 5-15 L / min, and metal powder is fed into the plasma ionization chamber at a feed rate of 3-10 mg / s with a carrier gas flow rate of 3-10 L / min. The plasma working gas is ionized under the action of a spraying current of 50-350 A, and expands upon heating to form plasma gas that is ejected from the nozzle, forming a high-speed plasma jet. The metal powder melts in the plasma ionization chamber under the action of the plasma gas and is sprayed onto the surface of the polymer base film with a spraying distance of 30-100 mm along with the high-speed plasma jet. The atmospheric plasma spray gun moves relative to the polymer base film at a moving speed of 50-200 mm / s and a moving interval of 1-8 mm, so that the metal powder is deposited on the surface of the polymer base film to form a metal coating.

2. The method of claim 1, wherein, The polymer base film includes one or more of polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, polyimide, polydimethylsiloxane, polyurethane, polycarbonate, polyamide, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, and polyvinylidene fluoride.

3. The method of claim 1, wherein, The metal powder comprises elemental metals and / or alloys, wherein the elemental metals include one or more of zinc, nickel, titanium, copper, tin, aluminum, and silver.

4. The method of claim 3, wherein, The average particle size of the metal powder is 1~100μm.

5. The method of claim 4, wherein, The average particle size of the metal powder is 10~50μm.

6. The method according to claim 1, characterized in that, The plasma working gas includes one or more of argon, nitrogen, and hydrogen. The carrier gas includes one or more of argon, nitrogen, and hydrogen.

7. The method according to claim 6, characterized in that, The plasma working gas is a hydrogen-argon mixture with a hydrogen gas integral of 1% to 10%.

8. The method according to claim 1, characterized in that, The atmospheric plasma spray gun also includes a protective gas device, which includes: a protective gas nozzle surrounding the nozzle, and a protective gas channel communicating with the protective gas nozzle, for blowing protective gas to prevent oxidation of metals in the high-speed plasma jet. In step S20, during the spraying process, a protective gas is blown at a flow rate of 3~10L / min to encapsulate the high-speed plasma jet. The protective gas includes one or more of argon, nitrogen, and hydrogen.

9. The method according to claim 1, characterized in that, The angle between the powder feeding channel and the nozzle is 30°~90°.

10. The method according to claim 9, characterized in that, The angle between the powder feeding channel and the nozzle is 30°~60°.

11. The method according to claim 1, characterized in that, The diameter of the negative electrode near the nozzle end is 0.3~2mm.

12. The method according to claim 1, characterized in that, In step S20, the number of spraying operations is 1 to 15.

13. A metallized polymer film, characterized in that, Prepared according to the method according to any one of claims 1 to 12.

14. The metallized polymer film according to claim 13, characterized in that, The thickness of the metal coating is 1~150μm.

15. The metallized polymer film according to claim 14, characterized in that, The thickness of the metal coating is 10~80μm.

16. The metallized polymer film according to claim 14, characterized in that, The adhesion level of the metal coating on the polymer base film is at least level 2.

17. The metallized polymer film according to claim 16, characterized in that, The adhesion level of the metal coating on the polymer base film is at least level 1.

Images