CN116574995A - Method for carrying out surface modification on metal matrix by utilizing metal wires - Google Patents
Method for carrying out surface modification on metal matrix by utilizing metal wires Download PDFInfo
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- CN116574995A CN116574995A CN202310547735.5A CN202310547735A CN116574995A CN 116574995 A CN116574995 A CN 116574995A CN 202310547735 A CN202310547735 A CN 202310547735A CN 116574995 A CN116574995 A CN 116574995A
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- Prior art keywords
- metal
- wire
- matrix
- surface modification
- substrate
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 205
- 239000002184 metal Substances 0.000 title claims abstract description 198
- 239000011159 matrix material Substances 0.000 title claims abstract description 85
- 230000004048 modification Effects 0.000 title claims abstract description 25
- 238000012986 modification Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000009792 diffusion process Methods 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 32
- 239000000956 alloy Substances 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 22
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000004804 winding Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 abstract description 21
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 238000004880 explosion Methods 0.000 abstract description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 12
- 229910000861 Mg alloy Inorganic materials 0.000 description 7
- 235000019270 ammonium chloride Nutrition 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005269 aluminizing Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010288 cold spraying Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/60—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for carrying out surface modification on a metal matrix by utilizing metal wires, wherein the metal wires and the metal matrix to be modified are placed in the same or connected containers, the metal wires are the sources of diffusion metal elements, the metal matrix is the matrix to be permeated, and then a permeation promoter is placed in the metal matrix, and the permeation promoter is prevented from being in direct contact with the metal matrix; then placing the metal matrix and the metal wire together with the catalyst into a heat treatment space for heating treatment, and cooling to finish the surface modification of the metal matrix. The invention does not adopt metal powder as an active metal element source of the thermal diffusion agent, avoids the risk of explosion of the metal powder when dispersing in the air and meets open fire, and improves the safety of the thermal diffusion method.
Description
Technical Field
The invention relates to a metal surface modification method, in particular to a method for carrying out surface modification on a metal matrix by utilizing metal wires.
Background
The surface strengthening effect can be achieved by preparing a metal coating on the metal surface. In order to obtain a metal coating on a metal surface, cold spraying, thermal spraying, hot dip plating, molten salt diffusion, powder diffusion, electroplating, electroless plating, and the like may be generally performed.
The above-described manner of preparing a metal coating on a metal surface is characterized by various operating environments, instrumentation, surface treatment processes, and chemical reagents that are required. The preparation method of the metal coating is selected according to specific conditions. Developing more metal coating preparation methods can provide more choices for the preparation of metal coatings on metal surfaces.
The powder diffusion process is one typical metal surface modifying process, and the process adopts metal powder as diffusion agent, oxide powder as stuffing and halogen powder as permeation promoter at certain temperature. However, the metal powder is a flammable and explosive product, and when the content of the metal powder in the air reaches a certain limit and meets open fire, the explosion accident is extremely easy to be caused. Therefore, there is a need to develop a safer and more reliable means of metal thermal diffusion to enhance the safety of production.
Disclosure of Invention
The invention provides a metal surface thermal diffusion method which takes metal wires and halogen-containing elements as raw materials, wherein the metal wires are in a winding state, so that the metal elements in the metal wires are transferred to the surface of a metal matrix, and the surface modification of the metal matrix is realized. The invention does not adopt metal powder as the active metal element of the thermal diffusion agent, avoids the risk of explosion of the metal powder when dispersing in the air and meets open fire, and improves the safety of the thermal diffusion method.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a method for carrying on the surface modification to the metal matrix with the metal wire, place metal wire and metal matrix to be modified in the identity or link container at first, the metal wire is the diffusion metal element source, the metal matrix is the matrix to be permeated, put into the catalyst, said catalyst avoids contacting with said metal matrix directly; then placing the metal matrix and the metal wire together with the catalyst into a heat treatment space for heating treatment, and cooling to finish the surface modification of the metal matrix.
The metal wire is wound, the metal wire can be wound and wrapped on the metal matrix, and the metal wire can be in the same or connected container with the metal matrix in a self-winding mode.
Wherein, the metal wire can be wrapped on the metal matrix.
The metal wire is wound on the metal matrix, and the metal wire can be directly wound on the surface of the metal matrix and is in direct contact with the metal matrix; the metal wire can also be not in direct contact with the metal matrix, i.e. the metal matrix is suspended around the outside of the metal matrix.
Wherein the metal wire comprises a metal wire or an alloy wire, and the metal matrix comprises a metal matrix or an alloy matrix.
Wherein the permeation promoter is a halogen element simple substance or compound.
Wherein the wire diameter should not be greater than 1/10 of the characteristic dimension of the substrate; the substrate feature dimensions include, but are not limited to, diameter, length, side length, etc. of the metal substrate.
Wherein the diameter of the metal wire can be 1 nm-10 cm.
Wherein the container for placing the metal wire and the metal matrix is a covered crucible.
Wherein the mass ratio of the metal wire to the catalyst is within 1:1-100:1. Preferably, the mass ratio of the metal wire to the catalyst is 3:1-30:1. If too much of the catalyst is used, it may affect the surface quality of the coating produced. Too little of the catalyst is not suitable, and too little of the catalyst may not have an effective catalytic effect.
The atmosphere in the heat treatment space can be an atmospheric atmosphere, or can be a controlled vacuum atmosphere or an inert atmosphere.
Wherein, the metal matrix and the metal wire are placed in a heat treatment space together with the catalyst for heating treatment, and the heating temperature and time are specifically set according to the type of the metal wire, the metal matrix and the type of the catalyst in actual operation.
The invention adopts metal wire or alloy wire as the diffusion agent of metal element, and adopts halogen element simple substance or compound as the permeation agent, so that the halogen element compound generates gaseous substances at high temperature and reacts with the metal wire or alloy wire to generate gaseous substances with active metal element, and then the active metal element is transferred to the surface of the metal matrix or alloy matrix to be diffused in gaseous form, thereby realizing the surface modification of the matrix.
The invention can adopt metal wires with different diameters as diffusion metal element sources, and when the metal wires with small diameters are used as diffusion sources, the contact area of the metal elements and halogen elements in the air is larger, and the reaction is more sufficient and rapid; when the large-diameter metal wire is used as an diffusion source, only surface metal atoms of the metal wire participate in the reaction, but after the diffusion is finished, the surface reaction product layer of the metal wire is ground, and the metal wire can be reused for a plurality of times.
The metal or alloy matrix and the metal wire are combined in the mode of the invention, the metal wire can be directly wound and wrapped on the surface of the metal matrix, the metal wire is directly contacted with the metal matrix, and the metal wire and the metal matrix can be kept relatively independent, namely, the metal wire is suspended and surrounds the outside of the metal matrix, and metal elements in adjacent metal wires reach the surface of the matrix through gaseous transmission.
The diameter of the metal wire or alloy wire can be 1 nm-10 cm. And the matching between the metal wire or alloy wire and the size of the matrix is considered. Generally, the wire or alloy wire diameter should not be greater than 1/10 of the characteristic dimension of the substrate. The characteristic dimensions of the matrix refer to the diameter, length, side length and the like of the matrix.
The metal thermal diffusion surface modification protection method has the following advantages:
1. the invention does not adopt metal powder as an active metal element source of the thermal diffusion agent, avoids the risk of explosion of the metal powder when dispersing in the air and meets open fire, and improves the safety of the thermal diffusion method.
2. The invention does not adopt metal powder as an diffusion source and metal oxide powder as a filler, avoids dust pollution generated in the original thermal diffusion process diffusion source and filler adding and moving processes, protects the environment and is beneficial to the health of operators.
In addition, the invention does not need to carry out pretreatment operations such as degreasing, decontamination, oxide removal and the like on the metal or alloy matrix and the metal wire or alloy wire, simplifies the steps, reduces the personnel operation and saves the cost.
Drawings
FIG. 1 is a surface modification of a wire directly wrapped around a metal substrate in accordance with the present invention.
Fig. 2 shows a surface modification of the invention in which the wires are separated from the metal matrix.
Fig. 3 shows a surface modification of a wire and metal matrix suspension in accordance with the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications of the invention may be made by those skilled in the art after reading the disclosure of the invention, and such equivalents are intended to fall within the scope of the invention as defined by the claims.
Unless otherwise indicated, the reagents used in the following examples were all commercially available from regular sources.
Firstly, wrapping a metal or alloy matrix to be surface-reinforced by using a metal or alloy wire; or placing the wire or alloy wire in the same space as the metal or alloy substrate (e.g., in a covered crucible), but not in direct contact with the metal or alloy substrate.
Then, a halogen element simple substance or compound is adopted as a permeation promoter, namely an active agent. Such as ammonium chloride, and the like, containing a halogen element such as F, cl, br, I.
Then, the metal wire or the alloy wire, the metal matrix or the alloy matrix and the catalyst are heated in heat treatment, so that the metal wire and the alloy wire react with the catalyst to generate metal halides, such as metal chlorides; the atmosphere in the heat treatment furnace can be an atmospheric atmosphere, a controlled vacuum atmosphere or an inert atmosphere.
Finally, after heat preservation for a certain time, removing the matrix coated with the metal wire or alloy wire, removing the surface metal wire and loose covering, cleaning and blow-drying the expanded metal matrix, and obtaining the surface modified metal matrix.
Example 1
Taking aluminum wire winding on the surface of the magnesium alloy matrix for aluminizing as an example.
The thermal diffusion surface modification method comprises the following steps:
1. adopting AZ91D magnesium alloy as a matrix to be infiltrated;
2. aluminum wires and ammonium chloride powder with the mass ratio of 10:1 are used as a penetrating agent, the aluminum wires are used as a source of penetrating metal elements, and the ammonium chloride is used as a penetrating agent for later use.
3. As shown in fig. 1, aluminum wires are wound on the surface of a magnesium alloy matrix, and ammonium chloride powder is placed in an diffusion system to avoid the direct contact between the ammonium chloride and the magnesium alloy matrix; the diffusion system is arranged in a crucible with a cover;
4. putting the diffusion system in the second step into a common heat treatment furnace, heating and preserving heat in the atmosphere, wherein the heating and preserving heat temperature is 420 ℃, the heating and preserving heat time is 2 hours, and taking out and cooling to room temperature;
5. and (5) placing the base material subjected to diffusion into absolute ethyl alcohol for ultrasonic cleaning, and drying by a blower to obtain the composite material.
Example 2
The preparation method of this example is the same as that of example 1, except that: in the first step, the matrix to be infiltrated is pure magnesium.
Example 3
The preparation method of this example is the same as that of example 1, except that: in the second step, the weight ratio of the aluminum wire to the iodine powder is 9:1.
Example 4
The preparation method of this example is the same as that of example 1, except that: and in the second step, zinc wires are used as active metal element sources.
Example 5
The preparation method of this example is the same as that of example 1, except that: in the second step, iodine powder is used as a permeation promoter.
Example 6
The preparation method of this example is the same as that of example 1, except that: in the third step, the aluminum wire is not wound on the magnesium alloy matrix, but is placed in a crucible together with the magnesium alloy matrix and the ammonium chloride catalyst, and meanwhile, the magnesium alloy matrix is prevented from being in direct contact with the ammonium chloride catalyst, as shown in fig. 2.
Example 7
The preparation method of this example is the same as that of example 1, except that: and step four, adopting a vacuum atmosphere as a protective atmosphere, and heating and preserving the temperature of the system in the vacuum atmosphere.
Example 8
The preparation method of this example is the same as that of example 1, except that: the thermal diffusion temperature adopted in the fourth step is 430 ℃. Meanwhile, the position winding mode between the metal wire and the metal matrix is a suspension type as shown in fig. 3, and the metal wire is not in direct contact with the metal matrix.
Example 9
The preparation method of this example is the same as that of example 1, except that: and step four, the thermal diffusion time adopted in the step 1.5h.
Example 10
The preparation method of this example is the same as that of example 1, except that: and step four, taking out the sample, and immediately placing the sample into water for quenching.
The heating temperature and time during modification are specifically set according to the type of the metal wire, the metal matrix and the type of the catalyst during actual operation. There are different suitable temperatures for different metals. The time is related to the selection of the catalyst, the type of the metal wire and the metal matrix.
The invention winds the metal or alloy matrix to be surface treated with the metal or alloy wires of other components, and simultaneously places the metal or alloy matrix in the atmosphere with halide, when the temperature of the metal or alloy matrix and the metal or alloy wires wound outside the metal or alloy matrix is raised together, part of metal elements in the metal or alloy wires can migrate and cover the surface of the metal or alloy matrix, and a metal coating layer is formed on the surface of the metal or alloy matrix, wherein the metal coating layer is also a matrix surface modification layer.
The invention adopts metal wires or alloy wires as the heat diffusion metal element permeation agent, adopts halogen element simple substance or compound as the permeation accelerator, does not adopt metal powder as the active metal element of the heat diffusion agent, avoids the risk of dispersing metal powder in air and exploding when encountering open fire, improves the safety of a heat diffusion method, simultaneously avoids dust pollution generated in the original heat diffusion flow diffusion source and filling agent adding and moving processes, protects the environment, and is beneficial to the health of operators.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A method for carrying out surface modification on a metal matrix by utilizing metal wires is characterized in that firstly, the metal wires and the metal matrix to be modified are placed in the same or connected container, the metal wires are sources of diffusion metal elements, the metal matrix is a matrix to be permeated, and then, a permeation promoter is put in the metal matrix, so that the permeation promoter is prevented from being in direct contact with the metal matrix; then placing the metal matrix and the metal wire together with the catalyst into a heat treatment space for heating treatment, and cooling to finish the surface modification of the metal matrix.
2. The method for surface modification of a metal substrate with a wire according to claim 1, wherein the wire is in a wound form, and the wire is wound around the metal substrate, or the wire is in a container which is the same as or connected to the metal substrate in a self-winding manner.
3. The method for surface modification of a metal substrate by using a metal wire according to claim 2, wherein the wrapping of the metal wire around the metal substrate is that the metal wire can be directly wrapped around the surface of the metal substrate, and the metal wire is in direct contact with the metal substrate; the metal wire can also be not in direct contact with the metal matrix, i.e. the metal wire is suspended around the outside of the metal matrix.
4. The method of surface modifying a metal substrate with a metal wire of claim 1, wherein the metal wire comprises a metal wire or an alloy wire and the metal substrate comprises a metal substrate or an alloy substrate.
5. The method for surface modification of metal substrates by metal wires according to claim 1, wherein the permeation accelerator is a simple substance or compound of halogen elements.
6. The method for surface modification of a metal substrate with a wire according to claim 1, wherein the diameter of the wire is 1nm to 10cm.
7. The method of surface modification of a metal substrate with a wire of claim 1, wherein the mass ratio of the wire to the promoter is within the range of 1:1 to 100:1.
8. The method of surface modification of a metal substrate using a metal wire according to claim 1, wherein the atmosphere in the heat treatment space is an atmosphere, vacuum atmosphere or inert atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310547735.5A CN116574995A (en) | 2023-05-16 | 2023-05-16 | Method for carrying out surface modification on metal matrix by utilizing metal wires |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310547735.5A CN116574995A (en) | 2023-05-16 | 2023-05-16 | Method for carrying out surface modification on metal matrix by utilizing metal wires |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116574995A true CN116574995A (en) | 2023-08-11 |
Family
ID=87542739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310547735.5A Pending CN116574995A (en) | 2023-05-16 | 2023-05-16 | Method for carrying out surface modification on metal matrix by utilizing metal wires |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116574995A (en) |
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2023
- 2023-05-16 CN CN202310547735.5A patent/CN116574995A/en active Pending
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