Method for coating conductive film on surface of bone-imitating fire extinguishing glass ball based on magnetron sputtering

Abstract

The invention discloses a magnetron sputtering-based method for coating a conductive film on the surface of a bone-imitating fire-extinguishing glass ball. The method comprises the following steps: S1, cleaning the glass ball; s2, activating the surfaces of the glass balls; s3, forming an anti-coating film barrier by utilizing a laser heat effect, then coating a film, and forming an observation window; and S4, plasma-assisted annealing. According to the method for coating the conductive film on the surface of the bone-imitating fire extinguishing glass ball based on magnetron sputtering, magnetron sputtering coating is conducted on the surface of the glass ball in a step-pulse composite power mode, and the problem of mutual exclusion of compactness, stress and binding force in traditional coating is solved through energy-time-space coordinated regulation and control; according to the invention, high-reliability, ultra-thin and defect-free nanoscale film coating can be obtained, the bonding strength between film layers is increased, the conductivity is effectively ensured, and the conductive triggering and zero resistance functions of the glass ball are realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of special functional material preparation and fire extinguishing technology, and particularly relates to a surface modification method for fire extinguishing glass balls, in particular to a coating process for depositing a conductive functional film on the surface of a bone-shaped structure glass ball through a magnetron sputtering technology. BACKGROUND

[0002] Lithium battery energy storage system is the key support for building a new type of power system, but the fire safety problem of lithium ion battery energy storage system has become a key bottleneck restricting the large-scale promotion of energy storage system. The energy storage system contains BMS, small air switch, distribution box and other electrical system equipment lines. These electrical equipment lines will generate a large amount of heat after a long time of operation. If the heat exceeds the limit, the electrical equipment short circuit and the line aging are easy to cause electrical fire. At present, the electrical fire protection ability of the energy storage system is weak, the means is single, the initial fire suppression ability is poor, and once a fire occurs, it is easy to cause the rapid spread and expansion of the fire. Therefore, for the electrical equipment lines of the electrochemical energy storage system, it is necessary to develop targeted and efficient fire prevention and extinguishing micro products in combination with the structural characteristics of the energy storage system electrical lines, and effectively improve the fire protection technology level of the electrical (communication) lines in the lithium ion battery energy storage power station.

[0003] In view of the technical problems that the internal space of the lithium ion battery energy storage power station module is small, the existing measures cannot effectively and quickly reach the thermal runaway point, and the fire extinguishing and explosion suppression prevention and control are difficult, the applicant has overcome the key technologies such as high dielectric, non-corrosive fire extinguishing agent mixing and compounding, and temperature-sensitive glass ball forming at multiple nominal operating temperatures, formed a bone-shaped temperature-sensitive explosion suppression fire extinguishing glass ball, and has applied for a patent CN119733191A - a micro fire extinguishing device for energy storage system electrical lines and a manufacturing method thereof. The above-mentioned fire extinguishing device is coated with a conductive film. In order to make the glass ball have the function of fuse, it is necessary to coat a conductive layer on the surface of the glass ball to realize the conductive glass ball which can be integrated into the circuit, and then develop a micro passive temperature-sensitive series fire extinguishing device with passive temperature-sensitive starting, over-temperature cutting, and targeted and precise fire extinguishing functions. SUMMARY

[0004] The present application aims to solve at least one of the problems in the prior art, and discloses a bone-shaped fire extinguishing glass ball surface conductive film coating method based on magnetron sputtering. The present application uses a "ladder-pulse composite power mode" magnetron sputtering coating on the surface of the glass ball. Through the synergistic control of energy-time-space, the mutual repulsion problem of density-stress-bonding force in traditional coating is solved, the coating of high reliability, ultra-thin defect-free nanometer film is obtained, the conductive triggering and zero resistance functions of the glass ball are realized, and the uniformity and adhesion of the coating of the complex structure are solved.

[0005] The present application is realized by the following technical solutions:

[0006] The application provides a bone-like fire extinguishing glass ball surface conductive film coating method based on magnetron sputtering, characterized by comprising the following steps.

[0007] S1, cleaning the glass ball;

[0008] S2, activating the glass ball surface;

[0009] S3, forming an anti-coating film barrier by using laser heat effect and then coating, and forming an observation window;

[0010] S4, plasma-assisted annealing.

[0011] As a further scheme, the specific method of S3 is:

[0012] S31, forming an anti-coating film barrier by using laser heat effect to locally recrystallize the glass ball;

[0013] S32, coating the glass surface, and the film layers from inside to outside are a first coating layer and a second coating layer;

[0014] S33, after the coating is completed, completely removing the film layer of the anti-coating film barrier residue to form an observation window.

[0015] As a further scheme, the specific method of S31 is: scanning along the length direction of the glass ball by using ultraviolet laser, the scanning path is a spiral progressive trajectory, and a continuous amorphous-crystal phase conversion band with a width of 1.5 mm is formed.

[0016] As a further scheme, the material of the first coating layer in S32 is metal chromium, and the thickness ranges from 10 to 15 nm; the material of the second coating layer is pure gold or pure silver, and the thickness ranges from 5 to 15 nm.

[0017] As a further scheme, S32 further comprises a third coating layer, the material of the third coating layer is PSS or AgNW / PI composite polymer, and the thickness ranges from 5 to 10 nm.

[0018] As a further scheme, the coating method in S32 is magnetron sputtering coating in a "ladder-pulse composite power mode", and the specific method is:

[0019] ①In the initial stage of 0-5 min: low-frequency pulse sputtering with a frequency of 1-10 Hz and a duty cycle of 30%-50%, a base value power of 0.3 kW + a peak value power of 2.0 kW, the glass surface is activated by periodic high-energy particle bombardment to form an atomic-level clean interface; and heat stress is released during the intermittent period, so that the generation of microcracks is inhibited.

[0020] ② In the 5-30min coating stage, the power is increased in steps: 0.5kW every 5min, the kinetic energy of the deposited particles is gradually increased, the upper limit of the power is less than or equal to 2.5kW, the plasma focusing magnetic field is turned on at the same time, the magnetic field strength is increased from 50Gauss to 150Gauss, the magnetic field enhances the plasma, the particles are vertically incident on the substrate, and the shadow effect is eliminated.

[0021] As a further solution, the sputtering chromium rate of the first coating layer is 0.1-0.3 nm / s.

[0022] As a further solution, the coating method in S32 is vapor coating, the glass ball is placed in a vacuum evaporation chamber, a vacuum pump is started, the pressure in the vacuum chamber is reduced to 10⁻³~10⁻ 5 Pa, metal chromium is used as the evaporation source and the evaporation source is heated, the evaporation rate is controlled to be 0.1~1 nm / s, when the thickness of the first coating layer reaches 10-15nm, the heating is stopped, and the first coating layer is cooled; then pure gold or pure silver is used as the evaporation source and the evaporation source is heated, the evaporation rate is controlled to be 0.1~1 nm / s, when the thickness of the second coating layer reaches 5-15nm, the heating is stopped, and the second coating layer is cooled.

[0023] As a further solution, the specific method of S33 is: after the coating is completed, the film layer of the anti-coating barrier is completely removed to form an observation window by selectively etching with hydrofluoric acid vapor with a concentration of 5%-10% for 60s.

[0024] As a further solution, the specific method of S4 is: in a vacuum environment, argon atmosphere at 320℃ ~ 380℃, using plasma assisted annealing, the annealing time is not less than 30min.

[0025] The characteristics and benefits of the present application are:

[0026] (1) The present application uses a "ladder-pulse compound power mode" magnetron sputtering coating on the surface of the glass ball, through the synergistic control of energy-time-space, solves the mutual exclusion problem of density-stress-bonding force in traditional coating, can get high reliability, ultra-thin defect-free nanometer film coating, increases the bonding strength between the film layers, and effectively guarantees the conductivity, realizes the conductive triggering and zero resistance function of the glass ball, effectively guarantees the conductivity and service life of the fire extinguishing glass ball; solves the uniformity and adhesion problem of complex structure coating.

[0027] (2) The method for making the observation window of the present application can be operated by equipment, compared with the method of covering the mask entity in the prior art, it does not need manual participation, has high automation degree, small error, high product qualification rate, can be used in large quantities, and saves the production cost of mask materials and the like. BRIEF DESCRIPTION OF DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or prior art description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without any creative effort based on these drawings.

[0029] Figure 1 A flow chart of the conductive film plating method described in the embodiments of the present application. DETAILED DESCRIPTION

[0030] In order to facilitate the understanding of the present application, the present application will be described more fully below, and embodiments of the present application are given, but the scope of the present application is not limited by this.

[0031] In the description of the present application, it should be understood that the terms "center", "longitudinal", "transverse", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation of the present application. In addition, the terms "first", "second" and the like are only for the purpose of description and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined with "first", "second" and the like can explicitly or implicitly include one or more of the features. In the description of the present application, unless otherwise specified, the meaning of "a plurality of" is two or more.

[0032] In the description of the present application, it should be noted that unless otherwise specified and limited, the terms "mounting", "connecting", "connecting" should be understood broadly, for example, it can be fixedly connected, or it can be detachably connected, or integrally connected; it can be mechanically connected, or it can be electrically connected; it can be directly connected, or it can be indirectly connected through an intermediate medium; it can be the communication inside two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0033] A bone-like conductive film plating method based on magnetron sputtering for fire extinguishing glass ball surface, as shown in Figure 1 The method comprises the following steps:

[0034] S1, cleaning the glass ball;

[0035] In one embodiment, the glass spheres are sequentially cleaned with acetone and ethanol by ultrasonic cleaning, and the cleaning time is not less than 15 minutes. If the cleaning time is too short, the glass spheres cannot be completely cleaned.

[0036] Acetone has strong fat solubility and can quickly dissolve oil stains and organic residues (such as photoresist and fingerprint grease). Acetone has strong volatility and is easy to dry after cleaning, and almost no residues are left. Ethanol has both water solubility and fat solubility, and can remove water-soluble impurities (such as inorganic salts) and light organic stains. In addition, ethanol is mild and can neutralize some polar pollutants that acetone cannot dissolve. The high-frequency vibration generated by ultrasonic waves forms micro-bubbles (cavitation effect), which can penetrate into the micro-cracks (such as micro-channels and etched lines) on the surface of the glass, and can strip stubbornly adhered impurities. The cleaning blind area is much less than that of manual or spray cleaning. Acetone and ethanol are both chemically inert solvents and do not react with glass (silicon dioxide), so they will not corrode the surface of the glass or cause scratches. Compared with traditional brush cleaning, ultrasonic cleaning does not require physical contact, which can protect the light transmittance of optical glass (such as lenses and glass slides), the microstructure of coated layers or precision glass devices, and avoid mechanical damage. Therefore, by sequentially cleaning with acetone and ethanol and ultrasonic cleaning, the ultrasonic vibration uniformly acts on the surface of the glass, which can effectively remove various pollutants on the surface of the glass spheres, and the glass is not damaged.

[0037] S2, activating the surface of the glass sphere;

[0038] The surface of the glass sphere is etched by argon plasma for not less than 10 minutes, with a power of 200 W and a gas pressure of 1.0 Pa.

[0039] In one embodiment, steps 1 and 2 can be combined. Specifically, in a vacuum environment, high-energy particles of argon or nitrogen or oxygen plasma are used to "bombard" the surface of the glass, for not less than 30 minutes, with a power of 200 W and a gas pressure of 1.0 Pa. This can decompose and remove organic residues, and activate the surface, preparing for subsequent coating. This method can make the surface of the glass sphere free of chemical solvent residues, with high cleaning precision, and can achieve nanometer level without damaging the microstructure of the glass surface. Preferably, argon is used as the plasma.

[0040] S3, coating the surface of the glass sphere;

[0041] In order to solve the problem of uneven coating caused by the shadow effect of the bone-shaped structure, the glass sphere is placed on a support, which effectively solves the problem of uneven coating of the glass sphere. The support is a commonly used planetary workpiece disc for coating, and a simple planetary workpiece disc suitable for magnetron sputtering with application number CN220116655U and name can be used.

[0042] The specific method for coating the surface of the glass sphere is as follows:

[0043] S31, generating a strip mask on the surface of the glass ball, so that the glass ball is pre-formed with an observation window on the surface for observing the bubble size after the liquid inside the glass ball is filled.

[0044] A 1.5 mm wide strip mask is generated on the surface of the glass ball along the length direction by using ultraviolet laser 320-355 nm, and the local recrystallization of silicon dioxide (the material of the glass ball) is formed by using the thermal effect of the laser to form an anti-plating film barrier. Preferably, the strip mask is rectangular, the width is not less than 1.5 mm, and the length is determined according to the model and length of the fire extinguishing glass ball. When the width is too small, it is not conducive to observe the internal situation of the fire extinguishing device.

[0045] The specific method is: scanning along the length direction of the glass ball by using ultraviolet laser (wavelength 320-355 nm, pulse width 10 ns, energy density 0.8-1.5 J / cm²), the scanning path is a spiral progressive trajectory (line width 0.1 mm, pitch 0.05 mm), forming a continuous amorphous-crystalline phase conversion zone (SiO2→cristobalite phase) with a width of 1.5 mm, that is, using the thermal effect of ultraviolet laser to locally recrystallize silicon dioxide to form an anti-plating film barrier. When plating in the subsequent step, the film layer at this place is not easy to adhere to the surface of the glass ball, which lays the foundation for removing the film layer at this place in the subsequent step.

[0046] S32, plating a film on the glass surface, the film layer from inside to outside is first plating layer, second plating layer,

[0047] Since the first plating layer is a transition layer and the second plating layer is a conductive layer, it provides high conductivity, but there are small gaps between nanowires, which are easy to oxidize; therefore, in order to protect the second plating layer of the glass ball, a third plating layer can also be provided as a protective layer, the third plating layer is a transparent polymer, which takes into account the conductivity and flexibility, and is used to fill the gap between the nanowires of the second plating layer to form a “continuous conductive path”, as a protective layer, to isolate oxygen / water vapor, prevent Ag nanowire oxidation, while maintaining overall transparency. Improve the stability of the conductive; based on the above effects, the third plating layer needs a visible light transmittance ≥85%, to avoid blocking the characteristics of the second plating layer, the volume resistivity ≤10⁻²Ω・cm, which can assist the second plating layer conductive layer to form a “conductive network”, or independently bear the low current conduction demand; the bending radius ≤5 mm and no cracks. Preferably, the material of the third plating layer is PSS or AgNW / PI composite polymer.

[0048] In one embodiment, a “ladder-pulse composite power mode” magnetron sputtering is used to coat a film on the surface of the glass ball. The advantage of the “ladder-pulse composite power mode” is that through the synergistic control of energy-time-space, it solves the mutual exclusion problem of density-stress-bonding force in traditional plating, and can obtain a high-reliability, ultra-thin defect-free nanoscale film coating.

[0049] In order to increase the conductivity and stability of the coating, the material of the first coating layer is metal chromium, and the material of the second coating layer is pure gold or pure silver, and the purity of the pure gold or pure silver is not less than 99.99%. The material of the third coating layer is PSS or AgNW / PI composite polymer.

[0050] The vacuum degree required for the coating is ≤5.0×10⁻³Pa, the working gas pressure range is 0.8-1.2Pa of argon, the sputtering power is DC 1.5-2.5kW, the substrate temperature range is 80-120℃, and the coating time is 20-40min.

[0051] The specific method is:

[0052] ①In the initial stage of 0-5min: low-frequency pulse sputtering with frequency 1-10Hz and duty cycle 30%-50%, base power 0.3kW + peak power 2.0kW, activate the glass surface by periodic high-energy particle bombardment to form an atomic-level clean interface; release thermal stress during the intermittent period to inhibit the generation of micro-cracks.

[0053] ②In the coating stage of 5-30min, the power increases in steps: increase by 0.5kW every 5min, gradually increase the kinetic energy of the deposited particles (chromium, gold, silver) to promote surface diffusion; the upper limit of the power is ≤2.5kW to avoid grain coarsening caused by high temperature; simultaneously turn on the plasma focusing magnetic field, and the magnetic field strength increases from 50Gauss to 150Gauss, the magnetic field enhances the plasma, increases the ionization rate, and the particles vertically incident on the substrate, eliminating the shadow effect. The main purpose of this step is to inhibit the growth of columnar crystals and optimize the film layer density. The generation of the plasma focusing magnetic field needs to rely on an external controllable electromagnetic system, and the core equipment is an electromagnetic coil array or a programmable permanent magnet array, which realizes precise control of the magnetic field strength and direction by integrating with the coating machine.

[0054] The sputtering chromium rate of the first coating layer is 0.1-0.3nm / s. The thickness of the first coating layer is 10-15nm, and the first coating layer is a chromium coating layer, which can effectively increase the adhesion of the glass sphere and the second coating layer.

[0055] The thickness of the second coating layer is 5-15nm, and the thickness of the third coating layer is 5-10nm.

[0056] In another embodiment, a vapor coating is used, and the treated glass spheres are installed on a support and placed in a vacuum evaporation chamber. Start the vacuum pump and evacuate the vacuum chamber to a high vacuum state (usually 10⁻³~10⁻ 5 Pa) to avoid the influence of film purity caused by the collision of vapor molecules with air.

[0057] First plating layer evaporation: take metal chromium as evaporation source and heat the evaporation source, control the evaporation rate of 0.1-1 nm / s (real-time monitoring by film thickness monitor), when the thickness of the first plating layer reaches 10-15 nm, stop heating, cool the first plating layer. Second plating layer evaporation: take pure gold or pure silver as evaporation source and heat the evaporation source, control the evaporation rate of 0.1-1 nm / s (real-time monitoring by film thickness monitor), when the thickness of the second plating layer reaches 5-15 nm, stop heating, cool the second plating layer, ensure that the two plating layer film interfaces are tightly combined. Similarly, for the third plating layer evaporation, when the thickness of the third plating layer reaches 5-10 nm, the evaporation is completed, the vacuum chamber pressure is slowly reduced, and the substrate is taken out after cooling. The evaporation rate must be kept within 0.1-1 nm / s, too fast can easily lead to loose film layer, too slow leads to low efficiency.

[0058] S33, after the plating is completed, the residual film layer of the observation window is completely removed by selectively etching with hydrofluoric acid vapor with a concentration of 5%-10% for 60s, and the remaining crystal phase mask becomes a permanent blank strip, that is, the observation window.

[0059] The prior art observation window manufacturing method is: according to the size and shape of the observation window, a mask film is made to be attached to the glass. The mask film material is a metal sheet or a rubber strip, and the mask film is accurately attached to the preset observation window position and is pressed flat by a pressing roller; after the plating is completed, the metal sheet or rubber strip is removed, and the method of physical covering is used, which greatly increases the workload, and the placement and removal of the mask film material need to be manually performed, which reduces the production efficiency, has a large error, and has a high defect rate; and the method for manufacturing the observation window of the present application can be operated by the equipment without manual participation, has a high degree of automation, has a small error, has a high qualified product rate, can be used in large quantities, and saves production costs such as mask film materials.

[0060] Preferably, when the concentration of hydrofluoric acid is less than 5%, the etching is insufficient, and when the concentration of hydrofluoric acid is greater than 10%, the etching is excessive.

[0061] S4, plasma-assisted annealing to improve the conductivity and bonding strength of the film layer.

[0062] In a vacuum environment, high-energy particles of argon or nitrogen or oxygen plasma are used without overall high-temperature heating, the film layer atoms obtain diffusion energy through the "energy bombardment" of the plasma, and stress release and structure optimization can be realized at a relatively low temperature of 200-400°C; preferably, in a vacuum environment, argon atmosphere at 320°C-380°C, plasma-assisted annealing is used, and the annealing time is not less than 30 min, which can simultaneously improve the film layer density (such as reducing the film layer porosity), improve the corrosion resistance and adhesion, and further improve the conductivity and bonding strength of the film layer.

[0063] Comparative example

[0064] R1, clean the surface of the glass sphere;

[0065] R2, etch the surface of the glass sphere;

[0066] R3, coat the surface of the glass sphere;

[0067] R31, according to the size and shape of the observation window, make a mask that is attached to the glass. The mask material is a metal sheet. Then, the mask is accurately attached to the predetermined observation window position, and a press roller is used to compact it;

[0068] R32, use high-energy ions (such as Ar+) to bombard the ITO target (a mixed ceramic target of In2O3 and SnO2, with a Sn doping amount of usually 5%~10%), so that the atoms / ions on the surface of the target are "sputtered" out, and then deposited on the surface of the substrate at a high speed under normal or low temperature, forming an ITO film with good crystallinity.

[0069] R33, after the coating is completed, carefully peel off the mask at room temperature, and the observation window area exposes a clean glass surface, surrounded by an intact conductive film.

[0070] R4, anneal in an inert atmosphere (such as N2) at 150~300℃ for 10~30 minutes.

[0071] Test the conductivity of the conductive film, and use the grid method to judge the grade of the bonding degree. The specific values are shown in Table 1.

[0072] Example 1

[0073] X1, clean the glass sphere with acetone and ethanol in sequence by ultrasonic cleaning, with a cleaning time of 15 minutes;

[0074] X2, etch the surface of the glass sphere by argon plasma, with a time of 11 minutes, a power of 200W, and a gas pressure of 1.0Pa;

[0075] X3, coat the surface of the glass sphere;

[0076] X31, use ultraviolet laser 320~355nm to scan the surface of the glass sphere along the length direction to generate a strip-shaped mask, and use the laser heat effect to make the silicon dioxide locally recrystallize to form an anti-coating barrier. The anti-coating barrier is rectangular, with a width of 1.6mm and a length of 2mm.

[0077] X32, the glass ball surface is coated by using "ladder-pulse composite power mode" magnetron sputtering, the vacuum degree required for coating is ≤5.0×10-3 Pa, the working gas pressure range is: 0.8-1.2 Pa of argon); the sputtering power is: DC 1.5-2.5 kW; the substrate temperature range is: 80-120℃, the coating time is 20-40 min. The material of the first coating layer is metal chromium, and the thickness is 12 nm. The material of the second coating layer is metal silver, and the thickness is 10 nm.

[0078] X33, after the coating is completed, the residual film layer of the observation window is completely removed by using 6% hydrofluoric acid vapor selective etching for 60 s to form a permanent observation window.

[0079] X4, in a vacuum environment, argon atmosphere at 350℃, using plasma assisted annealing, annealing time 30 min, can improve the film layer density (such as reducing the film layer porosity), improve the corrosion resistance and adhesion, and further improve the conductivity and bonding strength of the film layer.

[0080] The conductivity of the conductive film is tested, and the grade of the bonding degree is judged by using the grid method. The specific values are shown in Table 1.

[0081] Example 2

[0082] Y1, the glass ball is sequentially cleaned by ultrasonic cleaning with acetone and ethanol, and the cleaning time is 15 min;

[0083] Y2, the surface of the glass ball is etched by argon plasma, the time is 11 min, the power is 200 W, and the gas pressure is 1.0 Pa;

[0084] Y3, the surface of the glass ball is coated;

[0085] Y31, a strip-shaped mask is generated on the surface of the glass ball by scanning along the length direction using ultraviolet laser 320-355 nm, and the laser thermal effect is used to make the local recrystallization of silicon dioxide to form an anti-coating barrier. The anti-coating barrier is rectangular, the width is 1.6 mm, and the length is 2 mm.

[0086] Y32, the glass ball surface is coated by using "ladder-pulse composite power mode" magnetron sputtering, the vacuum degree required for coating is ≤5.0×10-3 Pa, the working gas pressure range is: 0.8-1.2 Pa of argon); the sputtering power is: DC 1.5-2.5 kW; the substrate temperature range is: 80-120℃, the coating time is 20-40 min. The material of the first coating layer is metal chromium, and the thickness is 12 nm. The material of the second coating layer is metal silver, and the thickness is 10 nm. The material of the third coating layer is PSS, and the thickness is 8 nm.

[0087] Y33, after the film is completed, a 6% hydrofluoric acid vapor is used for selective etching for 60s, and the residual film layer of the observation window is completely removed to form a permanent observation window.

[0088] Y4, in a vacuum environment, argon atmosphere at 350°C, using plasma assisted annealing, annealing time 30min, can improve the film density (such as reducing the film porosity), improve the corrosion resistance and adhesion, and further improve the conductivity and bonding strength of the film.

[0089] The conductivity of the conductive film is tested, and the grade of the bonding degree is judged by using the grid method. The specific values are shown in Table 1.

[0090] Example 3

[0091] Z1, the glass balls are sequentially cleaned by ultrasonic cleaning with acetone and ethanol, and the cleaning time is 15min;

[0092] Z2, the surface of the glass ball is etched by argon plasma, the time is 11min, the power is 200W, and the gas pressure is 1.0Pa;

[0093] Z3, the surface of the glass ball is coated;

[0094] Z31, a strip-shaped mask is generated on the surface of the glass ball along the length direction by using ultraviolet laser 320~355nm, and the laser thermal effect is used to make the silicon dioxide locally recrystallize to form an anti-coating barrier. The anti-coating barrier is rectangular, the width is 1.6mm, and the length is 2mm.

[0095] Z32, the surface of the glass ball is coated by using vapor coating, and the vacuum degree required for the coating is 10⁻ 4 Pa, the first coating layer is evaporated by using metal chromium as the evaporation source and heating the evaporation source, the evaporation rate is controlled to be 0.1~1 nm / s, the heating is stopped when the thickness of the first coating layer reaches 12nm, and the first coating layer is cooled. The second coating layer is evaporated by using pure silver as the evaporation source and heating the evaporation source, the evaporation rate is controlled to be 0.1~1 nm / s, the heating is stopped when the thickness of the second coating layer reaches 10nm, and the second coating layer is cooled to ensure that the two coating layer film interfaces are tightly combined.

[0096] Z33, after the film is completed, a 6% hydrofluoric acid vapor is used for selective etching for 60s, and the residual film layer of the observation window is completely removed to form a permanent observation window.

[0097] Z4, in a vacuum environment, argon atmosphere at 350°C, using plasma assisted annealing, annealing time 30min, can improve the film density (such as reducing the film porosity), improve the corrosion resistance and adhesion, and further improve the conductivity and bonding strength of the film.

[0098] The conductivity of the conductive film is tested, and the bonding degree is judged by the crosshatch method. The specific values are shown in Table 1. The bonding degree is judged as follows: 0 level (no any falling) is the best, and 5 level (more than 65% area falling) is unqualified.

[0099] Table 1

[0100] Comparative Example Example 1 Example 2 Example 3 Conductivity (S / m) 1 x 10 4 ]] 35.0 x 10 6 ]]> 35.0 x 10 6 ]] 35.0 x 10 6 ]]> Bonding (Rank) 3rd 1st 0th 2nd

[0101] As shown in Table 1, the bonding degree of the comparative example is the lowest, that is, the bonding strength is the smallest. The examples 1 to 3 show that the material of the application can increase the conductivity and the bonding strength of the conductive film when used as the coating layer. Especially, the protective layer can increase the bonding strength of the conductive film without affecting the conductivity.

[0102] In summary, the method can increase the bonding strength between the film layers and effectively ensure the conductivity. The glass ball conductive trigger and zero resistance function are realized. The conductivity and service life of the fire extinguishing glass ball are effectively ensured.

[0103] It should be noted that the above only describes the preferred embodiments of the application and is not intended to limit the application. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the application shall be included in the protection scope of the application.

Claims

1. A method for coating a bone-like fire extinguishing glass sphere surface conductive film based on magnetron sputtering, characterized in that: It comprises the following steps: S1, cleaning the glass sphere; S2, activating the surface of the glass sphere; S3, forming an anti-plating film barrier by using the laser heat effect first, then plating, and forming an observation window; S4, plasma-assisted annealing.

2. The method for coating a bone-like fire extinguishing glass ball surface conductive film based on magnetron sputtering according to claim 1, characterized in that: The specific method of S3 is: S31, using the laser heat effect to make the glass sphere locally recrystallize to form an anti-plating film barrier; S32, plating on the glass surface, and the film layer from inside to outside is first plating layer, second plating layer; S33, after plating is completed, the film layer of the anti-plating film barrier is completely removed to form an observation window.

3. The method for coating a bone-imitating fire extinguishing glass sphere surface conductive film based on magnetron sputtering according to claim 2, characterized in that: The specific method of S31 is: scanning along the length direction of the glass sphere with ultraviolet laser, the scanning path is a spiral progressive trajectory, forming a continuous amorphous-crystal phase conversion zone with a width of 1.5mm.

4. The method for coating a bone-imitating fire extinguishing glass sphere surface conductive film based on magnetron sputtering according to claim 2, characterized in that: The material of the first plating layer in S32 is metal chromium, and the thickness range is 10-15nm; the material of the second plating layer is pure gold or pure silver, and the thickness range is 5-15nm.

5. The method for coating a bone-imitating fire extinguishing glass sphere surface conductive film based on magnetron sputtering according to claim 4, characterized in that: S32 also includes a third plating layer, and the material of the third plating layer is PSS or AgNW / PI composite polymer, and the thickness range is 5-10nm.

6. The method for coating a conductive film on the surface of a bone-shaped fire extinguishing glass sphere based on magnetron sputtering according to claim 5, characterized in that: The plating method in S32 is to use "ladder-pulse composite power mode" magnetron sputtering plating, and the specific method is: ①In the initial stage of 0-5min: low-frequency pulse sputtering with frequency 1-10Hz and duty cycle 30%-50%, base power 0.3kW + peak power 2.0kW, activate the glass surface by periodic high-energy particle bombardment to form an atomic-level clean interface; release thermal stress during the intermittent period to inhibit the generation of microcracks; ②In the plating stage of 5-30min, the power increases in steps: increase by 0.5kW every 5min, gradually increase the kinetic energy of the deposited particles, and the upper limit of the power is ≤2.5kW; at the same time, the plasma focusing magnetic field is turned on, and the magnetic field strength is increased from 50Gauss to 150Gauss, and the magnetic field enhances the plasma, and the particles vertically enter the substrate, eliminating the shadow effect.

7. The method according to claim 5, wherein the method is a method for coating a surface conductive film on a bone-imitating fire extinguishing glass sphere based on magnetron sputtering. The sputtering chromium rate of the first plating layer is 0.1-0.3nm / s.

8. The method for coating a bone-imitating fire extinguishing glass sphere surface conductive film based on magnetron sputtering according to claim 5, characterized in that: The coating method in S32 is vapor coating. The glass balls are placed in a vacuum evaporation chamber, a vacuum pump is started, and the pressure in the vacuum chamber is pumped to 10-3~10-4Pa. Metal chromium is used as the evaporation source and the evaporation source is heated. The evaporation rate is controlled to be 0.1~1 nm / s. When the thickness of the first coating layer reaches 10-15nm, the heating is stopped and the first coating layer is cooled. Then, pure gold or pure silver is used as the evaporation source and the evaporation source is heated. The evaporation rate is controlled to be 0.1~1 nm / s. When the thickness of the second coating layer reaches 5-15nm, the heating is stopped and the second coating layer is cooled. 5 The coating method in S32 is vapor coating. The glass balls are placed in a vacuum evaporation chamber, a vacuum pump is started, and the pressure in the vacuum chamber is pumped to 10-3~10-4Pa. Metal chromium is used as the evaporation source and the evaporation source is heated. The evaporation rate is controlled to be 0.1~1 nm / s. When the thickness of the first coating layer reaches 10-15nm, the heating is stopped and the first coating layer is cooled. Then, pure gold or pure silver is used as the evaporation source and the evaporation source is heated. The evaporation rate is controlled to be 0.1~1 nm / s. When the thickness of the second coating layer reaches 5-15nm, the heating is stopped and the second 9. The method for coating a bone-imitating fire extinguishing glass sphere surface conductive film based on magnetron sputtering according to claim 2, characterized in that: The specific method of S33 is: after plating is completed, use hydrogen fluoride acid vapor with a concentration of 5%-10% to selectively etch for 60s, and then completely remove the film layer of the anti-plating film barrier to form an observation window.

10. The method for coating a bone-imitating fire extinguishing glass sphere surface conductive film based on magnetron sputtering according to claim 1, characterized in that: The specific method of S4 is: in a vacuum environment, use argon atmosphere at 320℃-380℃ for plasma-assisted annealing, and the annealing time is not less than 30min.

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