Acid-resistant magnetic cobalt particles, method for preparing same, use thereof, and electronic device

Abstract

This application provides an acid-resistant magnetic cobalt particle, comprising cobalt particles and a shell covering the surface of the cobalt particles. The shell is made of a substance represented by formula (I), wherein R is selected from N, P, or a six-membered ring. The cobalt particles in this acid-resistant magnetic cobalt particle are magnetic, and the surface of the cobalt particles has the substance represented by formula (I), thereby giving the acid-resistant magnetic cobalt particle excellent acid resistance, which is beneficial for its use in acid etching compositions. This application also provides a method for preparing the acid-resistant magnetic cobalt particle, its applications, and electronic devices.

Description

Technical Field

[0001] This application belongs to the field of electronic product technology, specifically relating to acid-resistant magnetic cobalt particles, their preparation methods, applications, and electronic devices. Background Technology

[0002] As electronic devices continue to develop, users have increasingly higher demands for their appearance. Therefore, to meet these rising aesthetic expectations, the design of electronic devices needs continuous improvement and refinement to provide users with a better experience. Summary of the Invention

[0003] In view of this, this application provides an acid-resistant magnetic cobalt particle, its preparation method, application, and electronic device.

[0004] In a first aspect, this application provides an acid-resistant magnetic cobalt particle, comprising cobalt particles and a shell covering the surface of the cobalt particles, wherein the shell is made of a substance represented by formula (I), wherein R is selected from N, P, or a six-membered ring.

[0005]

[0006] Secondly, this application provides a method for preparing acid-resistant magnetic cobalt particles, comprising:

[0007] Cobalt salt, triphenylphosphine and fatty acid are dissolved in a nonpolar solvent to obtain a mixture, and the mixture is heated to a first temperature, wherein the fatty acid has 10 or more carbon atoms, and the first temperature is 170°C-260°C.

[0008] After cooling the mixture from the first temperature to 60℃-90℃, a reducing agent is added to the mixture, and then the temperature is raised to a second temperature for reaction. The second temperature is 170℃-260℃. The boiling point of the non-polar solvent is greater than that of the first temperature and the second temperature.

[0009] After cooling the mixture from the second temperature to 25℃-35℃, the substance shown in formula (I) is added, wherein R is selected from N, P, or a six-membered ring, to obtain acid-resistant magnetic cobalt particles. The acid-resistant magnetic cobalt particles include cobalt particles and a shell covering the surface of the cobalt particles. The material of the shell includes the substance shown in formula (I).

[0010]

[0011] Thirdly, this application provides an acidic etching composition comprising an acidic etching component and acid-resistant magnetic particles. The acidic etching component comprises at least one of a frosting solution and a frosting powder. The acid-resistant magnetic particles comprise at least one of acid-resistant magnetic cobalt particles and acid-resistant magnetic iron oxide particles. The acid-resistant magnetic cobalt particles comprise cobalt particles and a shell covering the surface of the cobalt particles. The shell is made of a substance represented by formula (I), wherein R is selected from N, P, or a six-membered ring.

[0012]

[0013] The mass ratio of the acidic etching component to the acid-resistant magnetic cobalt particles is less than 80, and the mass ratio of the acidic etching component to the acid-resistant magnetic iron oxide particles is less than 40.

[0014] Fourthly, this application provides a method for preparing a glass shell, comprising:

[0015] A glass substrate is placed in a solution containing an acidic etching composition. The glass substrate has a first surface. The acidic etching composition includes an acidic etching component and acid-resistant magnetic particles. The acidic etching component includes at least one of a frosting solution and a frosting powder. The acid-resistant magnetic particles include at least one of acid-resistant magnetic cobalt particles and acid-resistant magnetic iron oxide particles. The acid-resistant magnetic cobalt particles include cobalt particles and a shell covering the surface of the cobalt particles. The shell is made of a substance represented by formula (I), where R is selected from N, P, or a six-membered ring. The mass ratio of the acidic etching component to the acid-resistant magnetic cobalt particles is less than 80, and the mass ratio of the acidic etching component to the acid-resistant magnetic iron oxide particles is less than 40.

[0016]

[0017] A magnetic field is applied to the glass substrate so that the acid-resistant magnetic particles are arranged in a predetermined pattern on the first surface;

[0018] The acid etching composition etches the first surface to form a texture on the first surface corresponding to the preset pattern;

[0019] The etched glass substrate is cleaned to obtain a glass shell.

[0020] Fifthly, this application provides an electronic device, comprising:

[0021] The housing includes a glass housing prepared by the preparation method described in the fourth aspect, the housing defining an accommodating space;

[0022] The motherboard is located inside the accommodating space.

[0023] This application provides an acid-resistant magnetic cobalt particle. The cobalt particles are magnetic, and their surface contains a substance as shown in formula (I), thus giving the acid-resistant magnetic cobalt particle excellent acid resistance, which is beneficial for its use in acidic etching compositions. The preparation method of this acid-resistant magnetic cobalt particle is simple and convenient, enabling industrial production and facilitating its application. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the embodiments of this application will be described below.

[0025] Figure 1 This is a schematic diagram of the structure of acid-resistant magnetic cobalt particles provided in one embodiment of this application.

[0026] Figure 2 A flowchart illustrating the preparation method of acid-resistant magnetic cobalt particles provided in one embodiment of this application.

[0027] Figure 3 A flowchart illustrating the preparation method of the glass shell provided in one embodiment of this application.

[0028] Figure 4 This is a schematic diagram of the structure of an electronic device provided in one embodiment of this application.

[0029] Figure 5 This is a schematic diagram of the structural composition of an electronic device provided in one embodiment of this application.

[0030] Figure 6 This is an electron microscope image of the acid-resistant magnetic cobalt particles prepared in Example 1.

[0031] Figure 7 The image shows the energy spectrum of the acid-resistant magnetic cobalt particles prepared in Example 1.

[0032] Figure 8 This is an electron microscope image of the acid-resistant magnetic cobalt particles prepared in Example 1 after being soaked in hydrofluoric acid for 10 hours.

[0033] Figure 9 This is a schematic diagram of the surface of a glass shell obtained according to an embodiment of this application.

[0034] Figure 10 This is a schematic diagram of the surface of a glass housing obtained according to another embodiment of this application. Detailed Implementation

[0035] The following are preferred embodiments of this application. It should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principles of this application, and these improvements and modifications are also considered to be within the scope of protection of this application.

[0036] The following disclosure provides many different embodiments or examples for implementing different structures of this application. To simplify the disclosure, specific examples of components and arrangements are described below. Of course, these are merely examples and are not intended to limit the scope of this application. Furthermore, reference numerals and / or letters may be repeated in different examples; such repetition is for simplification and clarity and does not in itself indicate a relationship between the various embodiments and / or arrangements discussed. In addition, examples of various specific processes and materials are provided in this application, but those skilled in the art will recognize the application of other processes and / or the use of other materials.

[0037] Please see Figure 1 This is a schematic diagram of the structure of an acid-resistant magnetic cobalt particle provided in one embodiment of this application. The acid-resistant magnetic cobalt particle 10 includes a cobalt particle 11 and a shell 12 covering the surface of the cobalt particle 11. The material of the shell 12 includes the substance shown in formula (I), wherein R is selected from N, P or a six-membered ring.

[0038]

[0039] In this application, the cobalt particles 11 in the acid-resistant magnetic cobalt particles 10 are magnetic, thereby endowing the acid-resistant magnetic cobalt particles 10 with magnetism. Simultaneously, the exterior of the acid-resistant magnetic cobalt particles 10 has a substance as shown in formula (I), thereby improving the acid resistance of the acid-resistant magnetic cobalt particles 10. In related technologies, when the cobalt particles 11 are used alone or when their surface is covered with a shell 12, the overall structure is not acid-resistant and cannot exist stably in acidic solutions for extended periods, thus hindering their use in acidic environments and limiting their application scenarios. This application, by providing a shell 12 containing the substance shown in formula (I) on the surface of the cobalt particles 11, gives them excellent acid resistance, enabling their use in various acidic environments.

[0040] In this application embodiment, the acid-resistant magnetic cobalt particles 10 are stable in a 1 mol / L acid solution for more than 10 hours, where the acid solution includes at least one of hydrofluoric acid, sulfuric acid, and phosphoric acid. The acid-resistant magnetic cobalt particles 10 provided in this application exhibit excellent acid resistance, remaining stable in various acid solutions for more than 10 hours. That is, even after 10 hours in an acid solution, the acid-resistant magnetic cobalt particles 10 retain their complete structure and their performance remains unchanged. This excellent acid resistance allows them to be used in various acidic environments, thus expanding their application range. It is understood that the acid-resistant magnetic cobalt particles 10 provided in this application can be stable in solutions with a pH less than 7. In one embodiment of this application, the acid-resistant magnetic cobalt particles 10 provided in this application are stable in acidic solutions with a pH greater than 0 for more than 10 hours. Specifically, the acid-resistant magnetic cobalt particles 10 can be stable in a 1 mol / L acid solution for 10 hours, 11 hours, 12 hours, 13 hours, etc.

[0041] In this embodiment, the substance represented by formula (I) is connected to the cobalt particles 11 via coordinate bonds and hydrogen bonds. The presence of coordinate bonds and hydrogen bonds between the substance represented by formula (I) and the cobalt particles 11 ensures the overall structural stability and acid resistance of the acid-resistant magnetic cobalt particles 10. Specifically, phosphorus atoms form coordinate bonds with oxygen atoms connected to cobalt particles 11 via double bonds, and hydrogen bonds are also formed between the substance represented by formula (I) and the cobalt particles 11. Furthermore, the substance represented by formula (I) has two acidic carboxyl groups, which provide pH buffering capacity, preventing a significant increase in the ζ-potential of the acid-resistant magnetic cobalt particles 10 in an acidic environment, thus ensuring structural stability and uniform dispersion in an acidic environment.

[0042] In this application, R is selected from N, P, or a six-membered ring. In one embodiment of this application, R is N; that is, the material of the outer shell 12 includes N-(phosphonomethyl)iminodiacetic acid. Further, the outer shell 12 of the acid-resistant magnetic cobalt particles 10 is an N-(phosphonomethyl)iminodiacetic acid layer. That is, the acid-resistant magnetic cobalt particles 10 include cobalt particles 11 and an N-(phosphonomethyl)iminodiacetic acid layer coating the surface of the cobalt particles 11, thereby further improving the stability of the acid-resistant magnetic cobalt particles 10 in an acidic environment. In another embodiment of this application, R is P. In yet another embodiment of this application, R is a six-membered ring. Further, the six-membered ring is a saturated six-membered ring or an unsaturated six-membered ring. Specifically, the six-membered ring may be, but is not limited to, cyclohexane, cyclohexene, cyclohexadiene, benzene ring, tetrahydropyran, piperidine, pyran, or pyridine, and the six-membered ring may be, but is not limited to, a meta-substituted six-membered ring.

[0043] In this embodiment, the particle size of the acid-resistant magnetic cobalt particles 10 is greater than or equal to 20 nm. Further, the particle size of the acid-resistant magnetic cobalt particles 10 is 20 nm to 15 μm. Further, the particle size of the acid-resistant magnetic cobalt particles 10 is 20 nm to 10 μm. Specifically, the particle size of the acid-resistant magnetic cobalt particles 10 can be, but is not limited to, 50 nm, 100 nm, 200 nm, 300 nm, 500 nm, 1 μm, 3 μm, 6 μm, 7 μm, or 9 μm. In one embodiment of this application, the particle size of the acid-resistant magnetic cobalt particles 10 is 20 nm to 300 nm. In another embodiment of this application, the particle size of the acid-resistant magnetic cobalt particles 10 is greater than 300 nm and less than or equal to 15 μm. Further, the particle size of the acid-resistant magnetic cobalt particles 10 is greater than 300 nm and less than or equal to 10 μm. In this application, the acid-resistant magnetic cobalt particles 10 have a wide range of particle sizes and are highly selectable, which is beneficial for their use in acidic environments under different application requirements; and the acid-resistant magnetic cobalt particles 10 with the above-mentioned particle size range have better stability and a wider range of applications.

[0044] In this embodiment, the thickness of the outer shell 12 is less than or equal to 3 nm. The outer shell 12 of the acid-resistant magnetic cobalt particles 10 provided in this application is thin, and its presence does not excessively increase the particle size of the acid-resistant magnetic cobalt particles 10. Its main function is to improve the acid resistance of the cobalt particles 11 without affecting the magnetism of the acid-resistant magnetic cobalt particles 10. In one embodiment of this application, the thickness of the outer shell 12 is 1 nm-3 nm. Specifically, the thickness of the outer shell 12 can be, but is not limited to, 1 nm, 1.5 nm, 2 nm, 2.5 nm, or 3 nm. In one embodiment of this application, the particle size of the acid-resistant magnetic cobalt particles 10 is greater than or equal to 20 nm, and the thickness of the outer shell 12 is less than or equal to 3 nm. Further, the particle size of the acid-resistant magnetic cobalt particles 10 is 20 nm-15 μm, and the thickness of the outer shell 12 is less than or equal to 3 nm. Even further, the particle size of the acid-resistant magnetic cobalt particles 10 is 20 nm-10 μm, and the thickness of the outer shell 12 is less than or equal to 3 nm. In another embodiment of this application, the particle size of the acid-resistant magnetic cobalt particles 10 is greater than or equal to 300 nm, and the thickness of the outer shell 12 is less than or equal to 3 nm. Further, the particle size of the acid-resistant magnetic cobalt particles 10 is 300 nm to 15 μm, and the thickness of the outer shell 12 is less than or equal to 3 nm. Even further, the particle size of the acid-resistant magnetic cobalt particles 10 is 300 nm to 10 μm, and the thickness of the outer shell 12 is less than or equal to 3 nm.

[0045] In this embodiment, the acid-resistant magnetic cobalt particles 10 have a particle size of 20nm-300nm and exhibit superparamagnetism. In this application, the acid-resistant magnetic cobalt particles 10 with a particle size of 20nm-300nm exhibit superparamagnetism and have application value in catalysis, detection, separation, and other fields. Further, the particle size of the acid-resistant magnetic cobalt particles 10 is 20nm-60nm, 50nm-100nm, 100nm-180nm, 200nm-270nm, or 250nm-300nm.

[0046] In this embodiment, the acid-resistant magnetic cobalt particles 10 have a particle size greater than 300 nm and are ferromagnetic. In this application, the acid-resistant magnetic cobalt particles 10 with a particle size greater than 300 nm are ferromagnetic, thus allowing them to be used with a magnetic field. Further, the particle size of the acid-resistant magnetic cobalt particles 10 is 300 nm to 15 μm. Specifically, the particle size of the acid-resistant magnetic cobalt particles 10 can be, but is not limited to, 300 nm to 600 nm, 500 nm to 1 μm, 1 μm to 2 μm, 2.5 μm to 3 μm, 4 μm to 6 μm, 5.5 μm to 7 μm, 300 nm to 10 μm, or 8 μm to 10 μm, etc.

[0047] Please see Figure 2 The flowchart below shows a method for preparing acid-resistant magnetic cobalt particles according to an embodiment of this application, including:

[0048] S101: Dissolve cobalt salt, triphenylphosphine and fatty acid in a nonpolar solvent to obtain a mixture, and heat the mixture to a first temperature, wherein the number of carbon atoms in the fatty acid is greater than or equal to 10, and the first temperature is 170℃-260℃.

[0049] S102: After cooling the mixture from the first temperature to 60℃-90℃, a reducing agent is added to the mixture, and then the temperature is raised to the second temperature for reaction. The second temperature is 170℃-260℃. The boiling point of the non-polar solvent is higher than that of the first and second temperatures.

[0050] S103: After cooling the mixture from the second temperature to 25℃-35℃, add the substance shown in formula (I), where R is selected from N, P or a six-membered ring, to obtain acid-resistant magnetic cobalt particles. The acid-resistant magnetic cobalt particles include cobalt particles and a shell covering the surface of the cobalt particles. The material of the shell includes the substance shown in formula (I).

[0051] The method for preparing acid-resistant magnetic cobalt particles 10 provided in this application is simple and easy to operate. The inventors have found that related methods for preparing magnetic cobalt particles are complex and cumbersome, and the resulting magnetic cobalt particles are not acid-resistant, limiting their application in acidic environments. Furthermore, when cobalt particles are directly provided and their surfaces are modified, the modification rate is low, or even impossible to adhere and modify, thus failing to obtain acid-resistant magnetic particles. Therefore, by employing a one-pot reduction-modification method, acid-resistant magnetic cobalt particles 10 with acid resistance can be directly obtained, and the process conditions are simple and suitable for industrial production.

[0052] In step S101, a homogeneous mixture is obtained by heating a mixture of cobalt salt, triphenylphosphine, and fatty acid. In this embodiment, the mixture is maintained at a first temperature for 1-3 hours, which facilitates uniform mixing and subsequent reactions. Specifically, the mixture may be maintained at the first temperature for, but is not limited to, 1 hour, 1.5 hours, 2 hours, 2.5 hours, or 3 hours. In this application, the first temperature may be, but is not limited to, 170°C, 180°C, 200°C, 230°C, 240°C, or 250°C. In this embodiment, before heating to the first temperature, an inert gas is introduced into the mixture to remove oxygen and ensure the subsequent reactions proceed. In one embodiment, the mixture may be purged with nitrogen to remove oxygen. In this embodiment, the cobalt salt includes at least one of cobalt acetate, cobalt nitrate, cobalt sulfate, and cobalt chloride, which can dissolve in a nonpolar solvent and generate cobalt particles under the action of a reducing agent. In this application, the fatty acid has 10 or more carbon atoms. Furthermore, the fatty acid has 10-20 carbon atoms, which is beneficial for its coordination with triphenylphosphine, thereby obtaining cobalt particles of the desired particle size. Specifically, the fatty acid may have, but is not limited to, 10, 12, 13, 15, 18, or 20 carbon atoms. In this application, the fatty acid may be, but is not limited to, at least one of saturated and unsaturated fatty acids. In one embodiment of this application, the fatty acid includes oleic acid. By using oleic acid to coordinate with triphenylphosphine, the particle size of the cobalt particles can be better controlled, cobalt particles with the desired properties can be obtained, and the modification of the substance shown in formula (I) is also beneficial.

[0053] In S102, a reducing agent is added to the mixture at low temperature to generate magnetic cobalt particles. At the same time, triphenylphosphine and fatty acids are adsorbed on the surface of the cobalt particles as surfactants. The fatty acids form strong bonds with the surface of the cobalt particles, which slows down the growth rate of the cobalt particles, while the triphenylphosphine forms weak bonds with the surface of the cobalt particles, which increases the growth rate of the cobalt particles. The interaction between the two results in cobalt particles of the desired size.

[0054] In this application, by adding a reducing agent in a low-temperature environment, cobalt particles can be generated more gently, and the particle size of the cobalt particles is more controllable. Simultaneously, after the low-temperature reaction, the temperature is raised to a second temperature, and the particle size of the cobalt particles is further controlled through the interaction of surfactants. In this embodiment, the mixture is maintained at the second temperature for 20-40 minutes. Specifically, the mixture can be maintained at the second temperature for, but is not limited to, 20, 25, 30, 35, or 40 minutes. In this application, the first temperature can be, but is not limited to, 170°C, 180°C, 200°C, 230°C, 240°C, or 250°C. In this embodiment, the reducing agent includes dithiothreitol (DTT). DTT has a relatively mild reducing effect, making the cobalt particle preparation process more controllable and the process window wider. In this application, a non-polar solvent is selected to ensure uniform dispersion of the substances in the mixture, and the boiling point of the non-polar solvent is higher than that of the first and second temperatures, thereby ensuring the progress of the entire reaction process. In the embodiments of this application, the nonpolar solvent includes at least one of diphenyl ether and octyl ether.

[0055] In S103, the substance shown in formula (I) is added to the mixture containing cobalt particles at room temperature. The substance shown in formula (I) forms coordination bonds and hydrogen bonds with the cobalt particles, thereby modifying the surface of the cobalt particles with the substance shown in formula (I), thus obtaining acid-resistant magnetic cobalt particles 10. In this embodiment, a solution containing the substance shown in formula (I) is added to the mixture. In a specific embodiment, an ethanol solution containing N-(phosphonomethyl)iminodiacetic acid is added to the mixture.

[0056] In this embodiment, the time for the mixture to cool from the second temperature to 25°C-35°C is less than 6 hours, the addition rate of the substance shown in formula (I) is 0.5 L / h-2 L / h, and the acid-resistant magnetic cobalt particles 10 exhibit superparamagnetism. By controlling the cooling rate of the mixture and the addition rate of the substance shown in formula (I), the particle size of the acid-resistant magnetic cobalt particles 10 is controlled, thereby obtaining acid-resistant magnetic cobalt particles 10 with superparamagnetism. In one embodiment of this application, the time for the mixture to cool from the second temperature to 25°C-35°C is less than 6 hours, the addition rate of the substance shown in formula (I) is 0.5 L / h-2 L / h, and the particle size of the obtained acid-resistant magnetic cobalt particles 10 is 20 nm-300 nm. Further, the time for the mixture to cool from the second temperature to 25°C-35°C is 2 hours-4 hours, the addition rate of the substance shown in formula (I) is 0.5 L / h-2 L / h, and the acid-resistant magnetic cobalt particles 10 exhibit superparamagnetism. Specifically, the time for the mixture to cool from the second temperature to 25℃-35℃ can be, but is not limited to, 2h, 2.5h, 3h, 3.5h or 4h, and the addition rate of the substance shown in formula (I) can be, but is not limited to, 0.5L / h, 1L / h, 1.5L / h or 2L / h, to obtain superparamagnetic acid-resistant magnetic cobalt particles 10.

[0057] In this embodiment, the time for the mixture to cool from the second temperature to 25°C-35°C is greater than or equal to 6 hours, and the acid-resistant magnetic cobalt particles 10 exhibit ferromagnetism. By slowing down the cooling rate, acid-resistant magnetic cobalt particles 10 with ferromagnetism are obtained. In one embodiment of this application, the time for the mixture to cool from the second temperature to 25°C-35°C is greater than or equal to 6 hours, and the particle size of the obtained acid-resistant magnetic cobalt particles 10 is greater than 300 nm. Further, the time for the mixture to cool from the second temperature to 25°C-35°C is 6 hours to 48 hours. Even further, the time for the mixture to cool from the second temperature to 25°C-35°C is 6 hours to 48 hours, and the addition rate of the substance shown in formula (I) is 0.2 L / h to 0.4 L / h, thereby obtaining acid-resistant magnetic cobalt particles 10 with superior acid resistance in acidic environments. Specifically, the time for the mixture to cool from the second temperature to 25℃-35℃ can be, but is not limited to, 6h, 8h, 10h, 15h, 20h, 28h, 35h, or 40h, and the addition rate of the substance shown in formula (I) can be, but is not limited to, 0.2L / h, 0.25L / h, 0.3L / h, 0.35L / h, or 0.4L / h, to obtain ferromagnetic, acid-resistant magnetic cobalt particles 10. In one embodiment of this application, the time for the mixture to cool from the second temperature to 25℃-35℃ is 6h-48h, the addition rate of the substance shown in formula (I) is 0.2L / h-0.4L / h, and the particle size of the obtained acid-resistant magnetic cobalt particles 10 is greater than 500nm. Further, the particle size of the acid-resistant magnetic cobalt particles 10 is greater than 500nm and less than or equal to 12μm.

[0058] In this embodiment, the mass ratio of cobalt salt, triphenylphosphine, and fatty acid is 1:(0.7-0.95):(0.89-1.78). Further, the mass ratio is 1:(0.8-0.9):(1-1.5). Even further, the mass ratio is 1:(0.8-0.9):(1-1.2). Specifically, the mass ratio of cobalt salt, triphenylphosphine, and fatty acid can be, but is not limited to, 1:0.8:1.33, 1:0.7:0.89, 1:0.8:1.5, 1:0.9:1.6, or 1:0.75:1.78, etc. Using the above mass ratio range, the particle size of cobalt particles 11 is controllable, which is beneficial for the preparation of cobalt particles 11.

[0059] In this embodiment, the mass ratio of cobalt salt to reducing agent is 1:(0.6-0.8). Further, the mass ratio of cobalt salt to reducing agent is 1:(0.65-0.75). Specifically, the mass ratio of cobalt salt to reducing agent can be, but is not limited to, 1:0.6, 1:0.65, 1:0.7, 1:0.75, or 1:0.8. Using the above-mentioned mass ratio range is beneficial for the formation of cobalt particles 11.

[0060] In this embodiment, the mass ratio of the cobalt salt to the substance shown in formula (I) is 1:(0.25-0.35). Further, the mass ratio of the cobalt salt to the substance shown in formula (I) is 1:(0.27-0.32). Specifically, the mass ratio of the cobalt salt to the substance shown in formula (I) can be, but is not limited to, 1:0.25, 1:0.26, 1:0.28, 1:0.3, 1:0.32, or 1:0.35, etc. Using the above-mentioned mass ratio range is beneficial for the modification and coating of the substance shown in formula (I) on the surface of the cobalt particles 11, thereby obtaining acid-resistant magnetic cobalt particles 10.

[0061] This application also provides an acidic etching composition comprising an acidic etching component and acid-resistant magnetic particles. The acidic etching component comprises at least one of frosting liquid and frosting powder. The acid-resistant magnetic particles comprise at least one of acid-resistant magnetic cobalt particles 10 and acid-resistant magnetic iron oxide particles. The acid-resistant magnetic cobalt particles 10 comprise cobalt particles 11 and a shell 12 covering the surface of the cobalt particles 11. The material of the shell 12 comprises the substance shown in formula (I). The mass ratio of the acidic etching component to the acid-resistant magnetic cobalt particles 10 is less than 80, and the mass ratio of the acidic etching component to the acid-resistant magnetic iron oxide particles is less than 40.

[0062] The acid etching composition provided in this application contains acid-resistant magnetic particles. These particles possess both acid resistance and magnetism, and can serve as functional additives in the acid etching composition. They are stably present in the composition and their arrangement can be controlled under a magnetic field, which is beneficial for the application of the acid etching composition. Specifically, under the influence of a magnetic field, the acid-resistant magnetic particles can be arranged regularly or irregularly on the surface to be etched, thereby preventing the acid etching component from contacting the surface. The acid etching component cannot etch the surface containing the acid-resistant magnetic particles, allowing for partial etching of the surface and partial non-etching, producing a patterned texture effect, also known as a magnetic field texture. In this application, the mass ratio of the acid etching component to the acid-resistant magnetic cobalt particles 10 is less than 80, and the mass ratio of the acid etching component to the acid-resistant magnetic iron oxide particles is less than 40. This ensures that the acid-resistant magnetic particles effectively block the etching by the acid etching component, which is beneficial for the generation of the magnetic field texture.

[0063] In this embodiment, the acid-resistant magnetic cobalt particles 10 in the acid etching composition have a particle size greater than 300 nm, thereby making the acid-resistant magnetic cobalt particles 10 ferromagnetic and able to better arrange themselves under the influence of a magnetic field, which is beneficial to the generation of magnetic field texture. Further, the particle size of the acid-resistant magnetic cobalt particles 10 in the acid etching composition is greater than 300 nm and less than or equal to 15 μm. Even further, the particle size of the acid-resistant magnetic cobalt particles 10 in the acid etching composition is greater than 300 nm and less than or equal to 10 μm. In one embodiment, the particle size of the acid-resistant magnetic cobalt particles 10 in the acid etching composition is 1 μm-5 μm, thereby effectively blocking the surface to be etched under the influence of a magnetic field, while also exhibiting stronger acid resistance and allowing for long-term preservation in the acid etching composition.

[0064] In this embodiment, the mass ratio of the acidic etching component to the acid-resistant magnetic cobalt particles 10 is 20-60. Further, the mass ratio of the acidic etching component to the acid-resistant magnetic cobalt particles 10 is 20-40, 30-50, or 40-60. Specifically, the mass ratio of the acidic etching component to the acid-resistant magnetic cobalt particles 10 can be, but is not limited to, 20, 25, 33, 40, 45, 50, 55, or 60. Using the above-mentioned mass ratios ensures the content of the acid-resistant magnetic cobalt particles 10 in the acidic etching composition, which is beneficial for the acid-resistant magnetic cobalt particles 10 to generate effective blocking under the action of a magnetic field, and does not affect the content of the acidic etching component, thus ensuring the generation of magnetic field texture.

[0065] In this embodiment, the acid-resistant magnetic iron oxide particles in the acid etching composition have a particle size of 40nm-60nm, which allows for better arrangement under the influence of a magnetic field, thus facilitating the generation of magnetic field textures. Further, the particle size of the acid-resistant magnetic iron oxide particles in the acid etching composition is 45nm-55nm. Specifically, the particle size of the acid-resistant magnetic iron oxide particles can be, but is not limited to, 40nm, 42nm, 45nm, 48nm, 50nm, 54nm, 55nm, 59nm, or 60nm. The acid-resistant magnetic iron oxide particles can be, but are not limited to, Merck's iron oxide (II,III) magnetic nanopowder.

[0066] In this embodiment, the mass ratio of the acidic etching component to the acid-resistant magnetic iron oxide particles is 5-20. Further, the mass ratio is 8-15. Specifically, the mass ratio can be, but is not limited to, 6, 9, 10, 12, 14, 15, 18, or 20. Using the above-mentioned mass ratios ensures the content of acid-resistant magnetic iron oxide particles in the acidic etching composition, which is beneficial for the acid-resistant magnetic iron oxide particles to effectively block the magnetic field and does not affect the content of the acidic etching component, thus ensuring the generation of magnetic field texture.

[0067] In one embodiment of this application, the acid etching composition includes an acid etching component and acid-resistant magnetic cobalt particles 10. Further, the acid etching composition also includes acid-resistant magnetic iron oxide particles. In another embodiment of this application, the acid etching composition includes an acid etching component and acid-resistant magnetic iron oxide particles. Further, the acid etching composition also includes acid-resistant magnetic cobalt particles 10.

[0068] In one embodiment of this application, the frosting solution comprises, by weight, 60-100 parts of ammonium fluoride, 2.5-10 parts of fluorosilicic acid, 35-50 parts of inorganic acid, and 30-50 parts of water. In the frosting solution, the ammonium fluoride reacts with the inorganic acid to form hydrofluoric acid. The hydrofluoric acid reacts with silicon dioxide in the glass to form fluorosilicic acid (4HF + SiO2 → SiF4 + 2H2O). The fluorosilicic acid reacts with ammonium ions in the ammonium fluoride to form ammonium fluorosilicate (H2SiF6 + 2NH4). + →(NH4)2SiF6+2H +In the aforementioned frosting solution, inorganic acids provide hydrogen ions, and ammonium fluoride salts provide fluoride and ammonium ions to facilitate the generation of hydrofluoric acid and ammonium fluorosilicate, thereby creating a frosting and shimmering effect on the glass shell surface. Fluorosilicic acid is used to generate fluorosilicates and also saturates the initially formed fluorosilicates, causing them to crystallize and adhere to the glass surface. In one embodiment, the ammonium fluoride salt includes at least one of NH4HF2 and NH4F, both of which can provide fluoride and ammonium ions. Further, the molar ratio of NH4HF2 to NH4F is 1:(0.8-1.2). In another embodiment, the inorganic acid can be, but is not limited to, nitric acid, hydrochloric acid, sulfuric acid, oxalic acid, etc. In one embodiment of this application, the frosting solution comprises, by weight, 30-50 parts of NH4HF2, 30-50 parts of NH4F, 2.5-10 parts of fluorosilicic acid, 35-50 parts of inorganic acid, and 30-50 parts of water. Furthermore, by weight, the frosting solution comprises 30-40 parts NH4HF2, 40-50 parts NH4F, 3-7 parts fluorosilicic acid, 40-50 parts inorganic acid, and 38-45 parts water. When glass shells are prepared using this frosting solution, the surface of the glass shell has multiple micron-sized pointed protrusions, giving the glass shell a frosted effect and a shimmering effect.

[0069] In another embodiment of this application, the frosting solution comprises, by weight, 10-30 parts sodium fluoride, 30-50 parts sodium hydrogen fluoride, 5-10 parts ammonium fluoride, 2.5-10 parts fluorosilicic acid, 35-50 parts inorganic acid, and 30-50 parts water. In the frosting solution, ammonium fluoride reacts with the inorganic acid to generate hydrofluoric acid. The hydrofluoric acid reacts with silicon dioxide in the glass to generate fluorosilicic acid. The fluorosilicic acid further reacts with hydrofluoric acid and fluorides to generate fluorosilicates. Most of the fluorosilicates obtained are polygonal sodium fluorosilicates, which can form a raised structure and achieve a shimmering effect. Furthermore, the frosting solution may also include 5-10 parts barium sulfate. This allows the frosting solution to be in a suspension state, increasing its viscosity and allowing for a more complete reaction on the glass surface.

[0070] In another embodiment of this application, the frosting solution comprises, by weight, 30-40 parts of ammonium fluoride, 0.1-1 parts of potassium and / or magnesium salts, 0.1-0.5 parts of surfactant, 30-45 parts of inorganic acid, and 20-30 parts of water. In the frosting solution, the ammonium fluoride reacts with the inorganic acid to form hydrofluoric acid. The hydrofluoric acid reacts with silica in the glass to form fluorosilicic acid. The fluorosilicic acid reacts with potassium and / or magnesium salts to form potassium fluorosilicate and / or magnesium fluorosilicate. The crystal nuclei of these ultrafine particles adhere to the glass surface, serving as primary crystal nuclei. Furthermore, the fluorosilicic acid reacts with ammonium ions in the ammonium fluoride to form ammonium fluorosilicate, and reacts with salts in the glass to form other fluorosilicates. These fluorosilicates are adsorbed onto the primary crystal nuclei via adsorption nucleation, thus promoting crystal growth and expansion. In the aforementioned frosting solution, inorganic acids provide hydrogen ions, and ammonium fluoride salts provide fluoride and ammonium ions to facilitate the generation of hydrofluoric acid and ammonium fluorosilicate, thereby giving the glass shell a frosted and sparkling effect. Potassium and / or magnesium salts react with fluorosilicic acid to generate fluorosilicates as primary crystal nuclei. Surfactants regulate the distribution and growth of fluorosilicate crystals to ensure uniformity. In this application, the fluorosilicate may be, but is not limited to, at least one of ammonium hydrogen fluoride and ammonium fluoride; the potassium salt may be, but is not limited to, at least one of potassium nitrate, potassium sulfate, and potassium chloride; the magnesium salt may be, but is not limited to, at least one of magnesium nitrate, magnesium sulfate, and magnesium chloride; and the surfactant may be, but is not limited to, phosphate surfactants, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, hydroxymethyl cellulose, etc. In one embodiment, the frosting solution comprises, by mass percentage, 30%-40% ammonium bifluoride, 0.1%-0.5% potassium nitrate, 0.1%-0.5% magnesium nitrate, 0.1%-0.5% phosphate surfactant, 30%-40% nitric acid, 0%-5% hydrochloric acid, and 20%-30% water.

[0071] In another embodiment of this application, the frosting solution comprises, by weight, 1-8 parts hydrofluoric acid, 3-15 parts inorganic acid, 20-75 parts crystal growth agent, and 10-30 parts water. In this application, the inorganic acid includes at least one of sulfuric acid, hydrochloric acid, oxalic acid, and nitric acid; the crystal growth agent includes at least one of hydrofluoric acid salts, sulfates, chlorides, and nitrates. Specifically, the crystal growth agent includes at least one of ammonium hydrofluoric acid, potassium hydrofluoric acid, sodium chloride, potassium chloride, ammonium chloride, sodium nitrate, potassium nitrate, ammonium nitrate, sodium sulfate, potassium sulfate, ammonium sulfate, sodium fluoride, potassium fluoride, and ammonium fluoride. Further, by weight, the frosting solution comprises 3-8 parts hydrofluoric acid, 3-10 parts inorganic acid, 65-75 parts crystal growth agent, and 15-25 parts water. In one specific embodiment, the frosting solution comprises, by weight, 4.6 parts hydrofluoric acid, 63.3 parts ammonium fluoride, 7.3 parts potassium sulfate, 1.8 parts ammonium sulfate, 4.8 parts sulfuric acid, and 18.2 parts water.

[0072] In another embodiment of this application, the frosting solution comprises, by weight, 5-20 parts ammonium bifluoride, 3-15 parts ammonium sulfate, 10-20 parts inorganic acid, 25-40 parts glycerol, and 20-50 parts water. Further, by weight, the frosting solution comprises 5-12 parts ammonium bifluoride, 4-10 parts ammonium sulfate, 10-15 parts inorganic acid, 25-33 parts glycerol, and 40-50 parts water. In this application, the inorganic acid includes at least one of sulfuric acid, hydrochloric acid, oxalic acid, and nitric acid. In a specific embodiment, by weight, the frosting solution comprises 8 parts ammonium bifluoride, 4 parts ammonium sulfate, 12 parts oxalic acid, 30 parts glycerol, and 50 parts water.

[0073] In this application, the frosting solution and frosting powder can also be commercially available frosting solution or frosting powder. The acid-resistant magnetic particles provided in this application can be mixed with it and remain stable, ensuring the use of the acid etching composition.

[0074] This application also provides a method for preparing glass housings using the acid etching composition described in any of the above embodiments. Please refer to [link to relevant documentation]. Figure 3 The flowchart illustrates a method for preparing a glass shell according to an embodiment of this application, including:

[0075] S201: A glass substrate is placed in a solution containing an acidic etching composition. The glass substrate has a first surface. The acidic etching composition includes an acidic etching component and acid-resistant magnetic particles. The acidic etching component includes at least one of frosting liquid and frosting powder. The acid-resistant magnetic particles include at least one of acid-resistant magnetic cobalt particles and acid-resistant magnetic iron oxide particles. The acid-resistant magnetic cobalt particles include cobalt particles and a shell covering the surface of the cobalt particles. The material of the shell includes the substance shown in formula (I), wherein R is selected from N, P or a six-membered ring. The mass ratio of the acidic etching component to the acid-resistant magnetic cobalt particles is less than 80, and the mass ratio of the acidic etching component to the acid-resistant magnetic iron oxide particles is less than 40.

[0076] S202: Apply a magnetic field to the glass substrate to arrange acid-resistant magnetic particles in a preset pattern on the first surface.

[0077] S203: An acidic etching composition is used to etch a first surface to form a texture on the first surface corresponding to a preset pattern.

[0078] S204: Clean the etched glass substrate to obtain a glass shell.

[0079] In this application, a glass substrate is placed in an acidic etching composition containing acid-resistant magnetic particles. Under the action of a magnetic field, the acid-resistant magnetic particles are arranged on the surface of the glass substrate, which protects the surface of the glass substrate and prevents it from contacting the acidic etching components, thereby avoiding etching. As a result, the surface of the glass substrate is partially etched and partially unetched, thus producing patterned magnetic field textures and obtaining a glass shell with rich appearance effects.

[0080] In step S201, the glass substrate is placed in an acidic etching composition solution to facilitate the subsequent etching process. In this embodiment, the glass substrate and the solution containing the acidic etching composition are placed in an etching tank. An electromagnet array is provided on the inner wall of the etching tank to generate a magnetic field. It is understood that when the acidic etching composition includes a frosting solution, the glass substrate can be placed directly in it; when the acidic etching component of the acidic etching composition is frosting powder, inorganic acid needs to be added before placing the glass substrate in it. Specifically, the etching tank is made of tetrafluoroethylene (PTFE). In this application, the magnetic field effect generated by the electromagnet array is controlled by programming, thereby affecting the arrangement of the acid-resistant magnetic cobalt particles 10 on the first surface.

[0081] In step S202, by applying a magnetic field to the glass substrate, acid-resistant magnetic particles are arranged in a preset pattern on the first surface according to the magnetic field, thus shielding a portion of the first surface and preventing it from contacting the acidic etching components, thereby avoiding etching. Specifically, the arrangement of the acid-resistant magnetic particles on the first surface can be programmed and controlled by the electromagnet array as needed.

[0082] In S203, the acidic etching composition etches the surface of the first surface that is not covered by acid-resistant magnetic particles, producing a frosted effect. At the same time, the surface not covered by acid-resistant magnetic particles has a frosted effect, while the surface not covered by acid-resistant magnetic particles does not have a frosted effect, thereby creating a texture on the first surface, which can also be called a magnetic field texture, and this texture corresponds to a preset pattern.

[0083] In this embodiment, the etching temperature is 5℃-40℃, and the time is 10s-10min. Choosing these etching conditions facilitates etching while avoiding increased manufacturing costs. Further, the etching temperature is 15℃-35℃, and the time is 20s-5min. Even further, the etching temperature is 20℃-32℃, and the time is 30s-2min. Specifically, the etching temperature can be, but is not limited to, 5℃, 10℃, 15℃, 20℃, 27℃, 30℃, 34℃, 40℃, etc., and the etching time can be, but is not limited to, 10s, 40s, 50s, 60s, 1min, 2min, 3min, or 4min, etc.

[0084] In S204, the glass shell is obtained by washing away the residual acid etching composition on the surface with water.

[0085] In this embodiment, prior to S201, a barrier layer may be formed on the surface of the glass substrate other than the first surface. By providing the barrier layer, contact between the surface of the glass substrate other than the first surface and the etching solution can be prevented. Furthermore, the material of the barrier layer can be ink, which not only effectively prevents other parts of the glass substrate from being etched, but also has good stability and does not participate in the reaction.

[0086] In this embodiment, the glass housing can also be subjected to computer-controlled precision machining (CNC machining). The glass housing with the final required assembly dimensions is obtained through CNC machining. In this embodiment, the glass housing can also be strengthened. In one embodiment, the glass housing is strengthened using a chemical strengthening method. Specifically, this can be, but is not limited to, subjecting the glass housing to a salt bath, the salt bath including at least one of sodium and potassium salts, at a temperature of 400°C-500°C for 2-10 hours. In this embodiment, a protective material can also be sprayed or vapor-deposited onto the second surface of the glass housing to form a protective layer. In one embodiment, an anti-fingerprint layer is formed by vapor-depositing an anti-fingerprint material onto the second surface of the glass housing, thereby improving the anti-fingerprint effect of the glass housing. It is understood that the second surface of the glass housing is the same surface as the first surface of the glass substrate, and the second surface is the first surface after etching.

[0087] This application also provides an electronic device 200, including a housing 100, which comprises a glass housing manufactured according to any of the above embodiments. It is understood that the electronic device 200 may be, but is not limited to, a mobile phone, tablet computer, laptop computer, watch, MP3 player, MP4 player, GPS navigator, digital camera, etc. Please refer to... Figure 4 This is a schematic diagram of the structure of an electronic device provided according to an embodiment of this application. The electronic device 200 includes a housing 100 and a motherboard. The housing 100 includes a glass housing manufactured according to any of the above embodiments. The housing 100 defines an accommodating space, and the motherboard is located inside the accommodating space. This housing 100 can improve the appearance and product competitiveness of the electronic device 200. Please refer to... Figure 5This is a schematic diagram of the structural composition of an electronic device provided in one embodiment of this application. The electronic device 200 may include an RF circuit 210, a memory 220, an input unit 230, a display unit 240, a sensor 250, an audio circuit 260, a WiFi module 270, a processor 280, and a power supply 290. The RF circuit 210, memory 220, input unit 230, display unit 240, sensor 250, audio circuit 260, and WiFi module 270 are all connected to the processor 280; the power supply 290 provides power to the entire electronic device 200. Specifically, the RF circuit 210 is used to receive and transmit signals; the memory 220 is used to store data instruction information; the input unit 230 is used to input information, and may include a touch panel and other input devices such as operation buttons; the display unit 240 may include a display screen; the sensor 250 includes an infrared sensor, a laser sensor, etc., for detecting user proximity signals, distance signals, etc.; the speaker 261 and the microphone 262 are connected to the processor 280 through the audio circuit 260 for receiving and transmitting sound signals; the WiFi module 270 is used to receive and transmit WiFi signals; and the processor 280 is used to process the data information of the electronic device 200.

[0088] The preparation and application of the acid-resistant magnetic cobalt particles in this application will be further explained below through specific embodiments and comparative examples.

[0089] Examples 1-13

[0090] In a 5L reactor, 100g of cobalt acetate, 80g of triphenylphosphine, and 150mL of oleic acid were dissolved in 1L of diphenyl ether solution to obtain a mixture. After nitrogen purging, the mixture was heated to 170°C and maintained for 1 hour. Then, it was cooled to 80°C, and 250mL of diphenyl ether solution containing 70g of dithiothreitol (DTT) was added dropwise over 1 hour. The temperature was then raised to 170°C and the reaction continued for 30 minutes, followed by cooling to 25°C (cooling time). Then, 1L of ethanol solution containing 30g of PMIDA was added dropwise (dropping time), yielding acid-resistant magnetic cobalt particles. The particle size range of the acid-resistant magnetic cobalt particles was obtained by scanning electron microscopy (SEM), and the results are shown in Table 1. SEM and energy dispersive spectroscopy (EDS) analyses were performed on the acid-resistant magnetic cobalt particles prepared in Example 1, and the SEM images are shown in Table 1. Figure 6 As shown, the energy spectrum is as follows Figure 7 As shown, the acid-resistant magnetic cobalt particles can be clearly observed through electron microscopy. They are spherical in shape with a particle size of about 70 nm. Furthermore, the energy dispersive spectroscopy (EDS) spectrum shows that the acid-resistant magnetic cobalt particles are rich in cobalt and are cobalt-based substances.

[0091] Comparative Example 1

[0092] Magnetic cobalt particles with a diameter of approximately 300 nm were obtained using the method described in Reference 1. Reference 1 is "Synthesis and Characterization of Cobalt Nanoparticles Using Hydrazine and Citric Acid[J]. Journal of Nanotechnology, 2014, 2014: 525193, DOI: 10.1155 / 2014 / 525193". Hydrazine hydrate and cobalt sulfate heptahydrate (CoSO4·7H2O) were used as raw materials. A 0.4 M sodium citrate dihydrate solution was added to 20 mL of a 0.2 M cobalt sulfate aqueous solution. The pH of the solution was adjusted to between 11 and 12 using 1 M sodium hydroxide and dilute sulfuric acid, and the solution was degassed by bubbling argon gas through it for 30 min. The solution was maintained at 80 °C and allowed to react for 60-120 min. After centrifugation, the suspension was removed, washed three times with distilled water to obtain magnetic cobalt particles, which were then dispersed in a 1% sodium oleate aqueous solution for later use.

[0093] Comparative Example 2

[0094] Polypyrrole-modified magnetic cobalt nanoparticles with a particle size of approximately 10 nm were obtained using the method described in Reference 2. Reference 2 is Synthesis and surface modification of cobalt nanoparticles and electromagnetic property of Co / PPy nanocomposites[J]. Rare Metals (English Edition), 2015, 34(4):223-228.DOI:10.1007 / s12598-014-0438-5. 1 mM cobalt acetate, 1 mM oleic acid, and 20 mL benzyl ether were mixed under argon and heated to 100 °C. Then, 3 mM triphenylphosphine was added, and the mixture was heated to 200 °C. During magnetic stirring, a benzyl ether superhydride solution (2 mL, 2 mM superhydride) was injected, and the solution color changed from dark blue to black. The black solution was stirred at 200 °C for 30 min and then cooled to room temperature. Ethanol was added to the dispersion, and after centrifugation, the precipitate was redispersed in 15 mL of hexane containing 200 μL of oleic acid. 0.5 mL of mercaptoacetic acid was added to the above solution to obtain a mercaptoacetic acid-modified cobalt nanoparticle dispersion. 0.2 g of sodium dodecylbenzenesulfonate and 2 mL of pyrrole monomer were mixed in deionized water, and then the mercaptoacetic acid-modified cobalt nanoparticle dispersion was added. After ultrasonic mixing, ammonium persulfate aqueous solution cooled to 278 K was added, and in-situ polymerization was maintained for 6-8 hours to obtain polypyrrole-modified magnetic cobalt nanoparticles.

[0095] Performance testing

[0096] The particles obtained in Example 1 and Comparative Examples 1-2 were immersed in 1 mol / L hydrofluoric acid, sulfuric acid, and phosphoric acid solutions for 10 h, respectively. The presence of particle residue in the acid solutions was then confirmed under an electron microscope to evaluate the acid resistance of the particles. The results are shown in Table 2. Electron micrographs of the acid-resistant magnetic cobalt provided in Example 1 after immersion in 1 mol / L hydrofluoric acid for 10 h were also taken. Figure 8 As shown.

[0097] Table 1. Particle size of acid-resistant magnetic cobalt particles

[0098]

[0099]

[0100] Table 2 Acid Resistance

[0101]

[0102] As shown in Table 1, the method of this application can obtain acid-resistant magnetic cobalt particles of different sizes, and the particle size range of the acid-resistant magnetic cobalt particles is controllable. Furthermore, by controlling the cooling time and dropping time, paramagnetic or ferromagnetic acid-resistant magnetic cobalt particles can be obtained. The particles obtained in Example 1 and Comparative Examples 1-2 were immersed in 1 mol / L hydrofluoric acid, sulfuric acid, and phosphoric acid solutions for 10 hours, respectively. If there was residue, it indicates that the particles would not be completely dissolved by the acid solution even after long-term storage, and the particles have excellent acid resistance. If there was no residue, it indicates that the particles would be corroded by the acid solution until completely dissolved, and the particles have poor acid resistance. As shown in Table 2, the particles provided by Comparative Examples 1 and 2 could not remain stable in hydrofluoric acid for 10 hours, and the particles obtained in Comparative Example 2 could not remain stable in sulfuric acid and phosphoric acid for 10 hours either. The particles provided by Comparative Examples 1 and 2 are not suitable for use in acidic environments and have poor acid resistance. Figure 8 As can be seen, compared with Comparative Example 1 and Comparative Example 2, the surface of the cobalt particles in the acid-resistant magnetic cobalt particles provided in Example 1 of this application is modified with PMIDA, which improves the pH buffering capacity of the acid-resistant magnetic cobalt particles. This allows the acid-resistant magnetic cobalt particles to maintain structural stability even after being soaked in hydrofluoric acid, sulfuric acid and phosphoric acid for more than 10 hours. They have excellent acid resistance and can be used in acidic environments, showing broad application prospects.

[0103] The preparation and application of the acid etching composition in this application will be further illustrated below through specific examples and comparative examples.

[0104] Example 14

[0105] The frosting solution A consists of 4.6 parts by weight of hydrofluoric acid, 63.3 parts by weight of ammonium fluoride, 7.3 parts by weight of potassium sulfate, 1.8 parts by weight of ammonium sulfate, 4.8 parts by weight of sulfuric acid, and 18.2 parts by weight of water. The acid etching composition is obtained by mixing frosting solution A with acid-resistant magnetic cobalt particles (particle size 2μm-5μm) at a mass ratio of 40:1.

[0106] Examples 15-19

[0107] It is largely the same as Example 14, except that the particle size of the acid-resistant magnetic cobalt particles is different.

[0108] Examples 20-21

[0109] It is largely the same as Example 18, except that the mass ratio of frosting liquid A to acid-resistant magnetic cobalt particles is different.

[0110] Example 22

[0111] The frosting solution B consists of 8 parts by weight of ammonium bifluoride, 4 parts by weight of ammonium sulfate, 12 parts by weight of oxalic acid, 30 parts by weight of glycerol, and 50 parts by weight of water. An acidic etching composition is obtained by mixing frosting solution B with iron oxide (II,III) magnetic nanoparticles (50 nm particle size, purchased from Merck) at a mass ratio of 20:1.

[0112] Example 23

[0113] It is largely the same as Example 20, except that the mass ratio of frosting solution B to iron oxide (II,III) magnetic nanopowder is 5:1.

[0114] Comparative Example 3

[0115] It is largely the same as Example 14, except that iron oxide is used instead of acid-resistant magnetic cobalt particles.

[0116] Comparative Example 4

[0117] Similar to Example 23, except that iron(II,III) oxide magnetic nanoparticles are used instead of iron(III) oxide.

[0118] Comparative Examples 5-6

[0119] It is largely the same as Example 20, except that the particle size of the iron oxide (II,III) magnetic nanopowder is different.

[0120] Comparative Example 7

[0121] It is largely the same as Example 18, except that the mass ratio of frosting liquid A to acid-resistant magnetic cobalt particles is 80:1.

[0122] Comparative Example 8

[0123] Similar to Example 20, except that the mass ratio of frosting solution B to iron oxide (II,III) magnetic nanopowder is 40:1.

[0124] Performance testing

[0125] The acidic etching composition prepared in Example 14 was poured into an etching tank with temperature control and a programmable electromagnet array embedded in its inner wall (made of tetrafluoroethylene). A glass substrate (0.6 mm thick) was placed at the bottom of the etching tank, and a set static magnetic field was activated. Under the influence of the magnetic field, acid-resistant magnetic cobalt particles were arranged on the surface of the glass substrate on the side away from the bottom of the etching tank. After immersion for 60 seconds, a glass shell was obtained. The texture of the surface of the glass shell was observed under a 200x optical microscope as shown in the image. Figure 9 As shown, it can be seen that by controlling the arrangement of acid-resistant magnetic cobalt particles on the glass with a magnetic field, the acid-resistant magnetic cobalt particles can block the surface of the glass substrate, thus producing a corresponding texture pattern.

[0126] The acidic etching composition prepared in Example 22 was poured into an etching tank with temperature control and a programmable electromagnet array embedded in its inner wall (made of tetrafluoroethylene). A glass substrate (0.6 mm thick) was placed at the bottom of the etching tank, and a set static magnetic field was turned on. Under the action of the magnetic field, acid-resistant magnetic cobalt particles were arranged on the surface of the glass substrate on the side away from the bottom of the etching tank. After immersion for 4 minutes, a glass shell was obtained. The texture of the surface of the glass shell was observed under a 200x optical microscope as shown in the image. Figure 10 As shown, it can be seen that by controlling the arrangement of iron oxide (II,III) magnetic nanopowder on the glass with a magnetic field, the iron oxide (II,III) magnetic nanopowder can block the surface of the glass substrate, thereby producing a corresponding texture pattern.

[0127] The acid etching compositions obtained in Examples 15-19, Example 23, and Comparative Examples 3-6 were used to etch glass substrates to obtain glass shells according to the same operation described above. Item 1 involved immersing the glass substrate for 4 minutes and observing whether textures were formed on the surface of the resulting glass shell. Item 2 involved immersing the glass substrate for 1 minute and observing whether textures were formed on the surface of the resulting glass shell. Item 3 involved placing the prepared acid etching composition for 10 hours, then etching the glass substrate, immersing the glass substrate for 4 minutes, and observing whether textures were formed on the surface of the resulting glass shell. Item 4 involved placing the prepared acid etching composition for 12 hours, then etching the glass substrate, immersing the glass substrate for 4 minutes, and observing whether textures were formed on the surface of the resulting glass shell. The results are shown in Table 3.

[0128] The acid etching compositions obtained in Examples 20-23 and Comparative Examples 7-8 were used to etch glass substrates to obtain glass shells using the same operation as described above. The tests for items one to three were also performed, and the results are shown in Table 4.

[0129] Table 3. Performance Test Results of Acidic Etching Compositions

[0130]

[0131] Table 4. Performance Test Results of Acidic Etching Compositions (Part 2)

[0132]

[0133] As shown in Table 3, the acid-resistant magnetic cobalt particles provided in this application, when their particle size is greater than 300 nm, are ferromagnetic, thus they can shield the surface of the glass substrate under the action of a magnetic field, avoiding etching by the frosting solution. Surfaces without acid-resistant magnetic cobalt particles will be etched under the action of the frosting solution, thus producing magnetic field textures. Furthermore, even after being stored in the acidic environment of the frosting solution for 10 hours, glass shells with magnetic field textures can still be produced. Similarly, iron oxide (II,III) magnetic nanopowder particles with a particle size greater than 50 nm are acid-resistant iron oxide particles, which can also produce glass shells with magnetic field textures. In Comparative Example 3, the larger iron oxide particles can exist in the frosting solution for a short time to produce glass shells with magnetic field textures, but after long-term placement in the frosting solution, they will be corroded, thus failing to produce magnetic field textures. In Comparative Example 4, the smaller iron oxide particles are rapidly corroded in the frosting solution, thus failing to produce magnetic field textures. The iron oxide (II,III) magnetic nanopowders provided in Comparative Examples 5 and 6 have small particle sizes and lack acid resistance, making them unable to exist stably in frosting solution and thus unable to generate magnetic field textures.

[0134] As shown in Table 4, when the mass ratio of frosting solution to acid-resistant magnetic cobalt particles is less than 80 and the mass ratio of frosting solution to acid-resistant magnetic iron oxide particles is less than 40, glass shells with magnetic field textures can be produced. Furthermore, even after being stored in an acidic environment of the frosting solution for 10 hours, acid-resistant magnetic cobalt particles can still produce glass shells with magnetic field textures. However, when the mass ratio of frosting solution to acid-resistant magnetic cobalt particles is 80 and the mass ratio of frosting solution to acid-resistant magnetic iron oxide particles is 40, there is too much frosting solution and too few acid-resistant magnetic particles. As a result, a covering layer with a shielding effect cannot be formed on the surface of the glass substrate, which cannot effectively block the etching of the frosting solution and thus cannot produce magnetic field textures.

[0135] The foregoing has provided a detailed description of the embodiments of this application, and has elucidated and explained the principles and implementation methods of this application. However, the above description is only for the purpose of helping to understand the method and core ideas of this application; at the same time, for those skilled in the art, there will be changes in specific implementation methods and application scope based on the ideas of this application. In summary, the content of this specification should not be construed as a limitation of this application.

Claims

1. An acidic etching composition characterized in that, The acid etching component includes at least one of a resist solution and a resist powder, and the acid-resistant magnetic particles include at least one of acid-resistant magnetic cobalt particles and acid-resistant magnetic iron oxide particles, the acid-resistant magnetic cobalt particles include cobalt particles and a shell coated on the surface of the cobalt particles, and the shell is made of a substance represented by formula (I), wherein R is selected from N, （I）， The mass ratio of the acid etching component and the acid-resistant magnetic cobalt particles is less than 80, the mass ratio of the acid etching component and the acid-resistant magnetic iron oxide particles is less than 40, and the acid-resistant magnetic iron oxide particles include iron (II, III) oxide magnetic nano-powder.

2. The acidic etching composition of claim 1, wherein The substance represented by formula (I) is connected to the cobalt particles by coordination bonds and hydrogen bonds.

3. The acidic etching composition of claim 1, wherein The acid-resistant magnetic cobalt particles can stably exist in an acid solution of 1 mol / L for more than 10 hours, and the acid solution includes at least one of hydrofluoric acid, sulfuric acid and phosphoric acid.

4. The acidic etching composition of claim 1, wherein The particle size of the acid-resistant magnetic cobalt particles is 20 nm-15 μm.

5. The acidic etching composition of claim 4, wherein The thickness of the shell is less than or equal to 3 nm.

6. The acidic etching composition of claim 1, wherein The particle size of the acid-resistant magnetic cobalt particles is 20 nm-300 nm, and the acid-resistant magnetic cobalt particles have superparamagnetism.

7. The acidic etching composition of claim 1, wherein The particle size of the acid-resistant magnetic cobalt particles is greater than 300 nm, and the acid-resistant magnetic cobalt particles have ferromagnetism.

8. The acidic etching composition of claim 1, wherein, The preparation method of the acid-resistant magnetic cobalt particles includes: dissolving cobalt salt, triphenylphosphine and fatty acid in a non-polar solvent to obtain a mixed solution, heating the mixed solution to a first temperature, wherein the number of carbon atoms of the fatty acid is greater than or equal to 10, and the first temperature is 170-260°C; after cooling the mixed solution from the first temperature to 60-90°C, adding a reducing agent to the mixed solution, and then heating to a second temperature for reaction, the second temperature is 170-260°C, and the boiling point of the non-polar solvent is greater than the first temperature and the second temperature; after cooling the mixed solution from the second temperature to 25-35°C, adding the substance represented by formula (I) to obtain the acid-resistant magnetic cobalt particles.

9. The acidic etching composition of claim 8, wherein The time for cooling the mixed solution from the second temperature to 25-35°C is less than 6 hours, the addition rate of the substance represented by formula (I) is 0.5-2 L / h, and the acid-resistant magnetic cobalt particles have superparamagnetism.

10. The acidic etching composition of claim 8, wherein The time for cooling the mixed solution from the second temperature to 25-35°C is greater than or equal to 6 hours, and the acid-resistant magnetic cobalt particles have ferromagnetism.

11. The acidic etching composition of claim 10, wherein The time for cooling the mixed solution from the second temperature to 25-35°C is 6-48 hours, and the addition rate of the substance represented by formula (I) is 0.2-0.4 L / h.

12. The acidic etching composition of claim 8, wherein The mass ratio of the cobalt salt, triphenylphosphine and fatty acid in the mixed solution is 1:(0.7-0.95):(0.89-1.78), the mass ratio of the cobalt salt and the reducing agent is 1:(0.6-0.8), and the mass ratio of the cobalt salt and the substance represented by formula (I) is 1:(0.25-0.35).

13. The acidic etching composition of claim 8, wherein The cobalt salt comprises at least one of cobalt acetate, cobalt nitrate, cobalt sulfate and cobalt chloride, the fatty acid comprises oleic acid, the reducing agent comprises dithiothreitol, and the non-polar solvent comprises at least one of diphenyl ether and octyl ether.

14. The acidic etching composition of claim 1, wherein The mass ratio of the acid-etching component to the acid-resistant magnetic cobalt particles is 20-60, and the mass ratio of the acid-etching component to the acid-resistant magnetic iron oxide particles is 5-20.

15. The acidic etching composition of claim 1, wherein The particle size of the acid-resistant magnetic cobalt particles is greater than 300 nm, and the particle size of the acid-resistant magnetic iron oxide particles is 40-60 nm.

16. The acidic etching composition of claim 1, wherein The frosting solution comprises 60-100 parts by weight of a fluorinated ammonium salt, 2.5-10 parts by weight of a fluorosilicic acid, 35-50 parts by weight of an inorganic acid, and 30-50 parts by weight of water; or The frosting solution comprises 10-30 parts by weight of sodium fluoride, 30-50 parts by weight of sodium hydrogen fluoride, 5-10 parts by weight of ammonium fluoride, 2.5-10 parts by weight of a fluorosilicic acid, 35-50 parts by weight of an inorganic acid, and 30-50 parts by weight of water; or The frosting solution comprises 30-40 parts by weight of a fluorinated ammonium salt, 0.1-1 parts by weight of a potassium salt and / or a magnesium salt, 0.1-0.5 parts by weight of a surfactant, 30-45 parts by weight of an inorganic acid, and 20-30 parts by weight of water; or The frosting solution comprises 1-8 parts by weight of hydrofluoric acid, 3-15 parts by weight of an inorganic acid, 20-75 parts by weight of a crystal-growing agent, and 10-30 parts by weight of water; or The frosting solution comprises 5-20 parts by weight of ammonium hydrogen fluoride, 3-15 parts by weight of ammonium sulfate, 10-20 parts by weight of an inorganic acid, 25-40 parts by weight of glycerol, and 20-50 parts by weight of water. The inorganic acid comprises at least one of sulfuric acid, hydrochloric acid, oxalic acid and nitric acid, and the crystal-growing agent comprises at least one of a fluorohydrogenated salt, a sulfate, a chloride and a nitrate.

17. A method of making a glass shell, characterized by, Comprising: placing a glass substrate in a solution containing the acid-etching composition according to any one of claims 1-16, the glass substrate having a first surface; applying a magnetic field to the glass substrate to arrange the acid-resistant magnetic particles in a preset pattern on the first surface; etching the first surface by the acid-etching composition to form a texture corresponding to the preset pattern on the first surface; cleaning the etched glass substrate to obtain a glass shell.

18. The production method according to claim 17, wherein The placing of the glass substrate in the solution containing the acid-etching composition comprises: placing the glass substrate and the solution containing the acid-etching composition in an etching tank, the inner wall of the etching tank being provided with an electromagnet array, the electromagnet array being used to generate the magnetic field.

Images