A water electroplating process for substrates

Abstract

The present invention discloses a water electroplating process for a substrate, belonging to the technical field of substrate surface processing, comprising the steps of 1) degreasing and rust removal, wherein a flexible metal substrate is sequentially subjected to a degreasing solution and a rust removal solution for degreasing and rust removal; 2) acid etching, wherein the flexible metal substrate is placed in an acid etching solution for acid etching; 3) spray plating, wherein the flexible metal substrate is placed in an automatic spray plating machine, and the side to be plated is bent outward for spray plating to form a first metal coating; 4) water electroplating, wherein the spray-plated flexible metal substrate is subjected to water electroplating, wherein the side to be plated is bent outward for water electroplating, and a second metal coating is formed outside the first metal coating; and 5) vacuum plating, wherein the water electroplated flexible metal substrate is subjected to vacuum plating, wherein the side to be plated is bent outward for vacuum plating, and a third metal coating is formed outside the second metal coating. The present application reduces conductive resistance while improving the bonding strength of the coating.

Description

Technical Field

[0001] The present invention relates to the technical field of substrate surface treatment, in particular to a water electroplating process for a substrate. Background Art

[0002] Flexible metal substrates combine the bendability of flexible materials with the excellent properties of metal coatings, bringing new possibilities to a variety of fields, including electronics and the automotive industry. In particular, flexible metal substrates play a vital role in the field of flexible electronics, enabling the manufacture of flexible electronic products such as flexible displays, flexible batteries, and flexible circuit boards. These products offer advantages such as lightness, flexibility, and portability, bringing greater convenience to people's lives.

[0003] However, most existing flexible metal substrates suffer from insufficient electrical conductivity when used directly. Therefore, conventional electroplating can be used to improve the conductivity of flexible metal substrates. However, as the number of plating layers increases, the bonding strength between the plating layers decreases, making them susceptible to peeling. In particular, bending the flexible metal material often results in cracks in the plating or even peeling.

[0004] Therefore, the present application provides a water electroplating process for a substrate. How to improve the bonding strength of the coating while reducing the conductive resistance by improving the traditional processing technology is a technical problem that needs to be solved urgently by those skilled in the art. Summary of the Invention

[0005] To this end, the present invention provides a water electroplating process for a substrate to solve the related technical problems existing in the prior art.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] According to a first aspect of the present application, a water electroplating process for a substrate is provided, comprising the following steps:

[0008] Step 1) degreasing and rust removal: the flexible metal substrate is sequentially passed through a degreasing liquid and a rust removing liquid for degreasing and rust removal;

[0009] Step 2), acid etching, placing the flexible metal substrate into an acid etching solution for acid etching;

[0010] Step 3), spraying: placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating;

[0011] Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward and water electroplating, forming a second metal plating layer outside the first metal plating layer;

[0012] Step 5) vacuum plating: vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer.

[0013] Furthermore, an ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5).

[0014] Furthermore, in step 2), acid etching, the flexible metal substrate is placed in an acid etching solution for acid etching, specifically comprising:

[0015] The acid etching solution includes: concentrated sulfuric acid 75-100mL / L, sodium chloride 200-500g / L, KC corrosion inhibitor 3-5g / L, glycine 3-5g / L and sodium dodecyl sulfate 10-50g / L;

[0016] Place the flexible metal substrate to be acid-etched into the acid etching solution at a temperature of 30-62°C and an etching time of 1.5-3.0 minutes.

[0017] Furthermore, before step 3), a grid layer processing step is also included:

[0018] Step 203 ), spraying the prepared grid layer liquid onto the surface of the flexible metal substrate, drying at a temperature of 230-350° C. for 1.5-2.0 hours;

[0019] In step 213 , the flexible metal substrate is placed in a ball mill for 0.5-1.5 minutes.

[0020] Furthermore, the grid layer liquid preparation method is:

[0021] Add 0.1-0.5 parts by weight of carboxylated carbon nanotubes, 5-30 parts by weight of copper chloride, and 2-25 parts by weight of nickel chloride to deionized water, mix and stir, adjust the pH to neutral with sodium hydroxide solution, and microwave-heat at 50-80° C. for 1-2 hours.

[0022] The precipitate was obtained by centrifugal filtration, washed twice with deionized water, and prepared into a grid layer liquid with a mass fraction of 5%.

[0023] Furthermore, in step 3), spraying, the flexible metal substrate is placed in an automatic spraying machine, and the side to be plated is bent outward for spraying to form a first metal coating, including:

[0024] The bending curvature of the flexible metal substrate is:

[0025] The bending curvature of the flexible metal substrate is:

[0026] ;

[0027] in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0028] Furthermore, in step 4), water electroplating is performed on the flexible metal substrate after spraying, and the side to be plated is bent outward for water electroplating to form a second metal plating layer outside the first metal plating layer, including:

[0029] The bending curvature of the flexible metal substrate is:

[0030] ;

[0031] in, The curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0032] Furthermore, in step 5), vacuum plating is performed on the flexible metal substrate after water electroplating, and the side to be plated is bent outward for vacuum plating to form a third metal plating layer outside the second metal plating layer, including:

[0033] The bending curvature of the flexible metal substrate is:

[0034] ;

[0035] in, The curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0036] Furthermore, the flexible metal substrate is a stainless steel sheet, a copper alloy sheet or a nickel alloy sheet.

[0037] According to a second aspect of the present application, a low-resistance conductive material is provided, comprising a flexible metal substrate prepared by the above-mentioned water electroplating process for substrates.

[0038] The present invention has the following advantages:

[0039] The present application improves the flexible metal substrate electroplating process in the prior art. On the one hand, after acid etching, a grid layer liquid is sprayed on the surface of the flexible metal substrate so that the grid layer liquid can penetrate into the rough surface of the flexible metal substrate. At the same time, the grid layer liquid can form a grid layer structure on the surface of the flexible metal substrate, which is beneficial to the adhesion and bonding of subsequent coatings. On the other hand, in the three steps of spraying, water electroplating and vacuum plating, the flexible metal substrate is bent to expose the grid layer, thereby improving the bonding of subsequent coatings while ensuring low resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] To more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for the embodiments or the description of the prior art. Obviously, the drawings described below are merely exemplary, and those skilled in the art can derive other implementation drawings based on the provided drawings without inventive effort.

[0041] The structures, proportions, sizes, etc. illustrated in this specification are intended only to complement the contents disclosed herein and to facilitate understanding and reading by persons familiar with the art. They are not intended to limit the conditions under which the present invention may be implemented and therefore have no substantive technical significance. Any structural modifications, changes in proportions, or adjustments in sizes, without affecting the efficacy and objectives of the present invention, shall still fall within the scope of the technical contents disclosed herein.

[0042] Figure 1 The present invention provides a flow chart of the steps of the water electroplating process for a substrate. DETAILED DESCRIPTION

[0043] The following describes the implementation of the present invention using specific embodiments. Those skilled in the art will readily understand the other advantages and benefits of the present invention from the disclosure herein. Obviously, the embodiments described are only a portion of the present invention, not all of it. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are intended to fall within the scope of protection of the present invention.

[0044] In order to solve the relevant technical problems existing in the prior art, this application improves the traditional flexible metal substrate plating process, in order to achieve the purpose of reducing the resistance of the flexible metal and improving the bonding strength of the coating, thereby improving the scope of use and performance of the flexible metal substrate.

[0045] According to the first aspect of this application, Figure 1 As shown, a water electroplating process for a substrate is provided, comprising the following steps:

[0046] Step 1) degreasing and rust removal: the flexible metal substrate is sequentially passed through a degreasing liquid and a rust removing liquid for degreasing and rust removal;

[0047] Step 2), acid etching, placing the flexible metal substrate into an acid etching solution for acid etching;

[0048] Step 3), spraying: placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating;

[0049] Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward and water electroplating, forming a second metal plating layer outside the first metal plating layer;

[0050] Step 5) vacuum plating: vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer.

[0051] Furthermore, an ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5).

[0052] Furthermore, in step 2), acid etching, the flexible metal substrate is placed in an acid etching solution for acid etching, specifically comprising:

[0053] The acid etching solution includes: concentrated sulfuric acid 75-100mL / L, sodium chloride 200-500g / L, KC corrosion inhibitor 3-5g / L, glycine 3-5g / L and sodium dodecyl sulfate 10-50g / L;

[0054] Place the flexible metal substrate to be acid-etched into the acid etching solution at a temperature of 30-62°C and an etching time of 1.5-3.0 minutes.

[0055] Furthermore, before step 3), a grid layer processing step is also included:

[0056] Step 203 ), spraying the prepared grid layer liquid onto the surface of the flexible metal substrate, drying at a temperature of 230-350° C. for 1.5-2.0 hours;

[0057] In step 213 , the flexible metal substrate is placed in a ball mill for 0.5-1.5 minutes.

[0058] Furthermore, the grid layer liquid preparation method is:

[0059] Add 0.1-0.5 parts by weight of carboxylated carbon nanotubes, 5-30 parts by weight of copper chloride, and 2-25 parts by weight of nickel chloride to deionized water, mix and stir, adjust the pH to neutral with sodium hydroxide solution, and microwave-heat at 50-80° C. for 1-2 hours.

[0060] The precipitate was obtained by centrifugal filtration, washed twice with deionized water, and prepared into a grid layer liquid with a mass fraction of 5%.

[0061] Furthermore, in step 3), spraying, the flexible metal substrate is placed in an automatic spraying machine, and the side to be plated is bent outward for spraying to form a first metal coating, including:

[0062] The bending curvature of the flexible metal substrate is:

[0063] ;

[0064] in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0065] Furthermore, in step 4), water electroplating is performed on the flexible metal substrate after spraying, and the side to be plated is bent outward for water electroplating to form a second metal plating layer outside the first metal plating layer, including:

[0066] The bending curvature of the flexible metal substrate is:

[0067] ;

[0068] in, The curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0069] Furthermore, in step 5), vacuum plating is performed on the flexible metal substrate after water electroplating, and the side to be plated is bent outward for vacuum plating to form a third metal plating layer outside the second metal plating layer, including:

[0070] The bending curvature of the flexible metal substrate is:

[0071] ;

[0072] in, The curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0073] Furthermore, the flexible metal substrate is a stainless steel sheet, a copper alloy sheet or a nickel alloy sheet.

[0074] According to a second aspect of the present application, a low-resistance conductive material is provided, comprising a flexible metal substrate prepared by the above-mentioned water electroplating process for substrates.

[0075] To better illustrate the technical effects of the processing technology provided by this application, the present application provides the following examples and comparative examples. The flexible metal substrate selected is a stainless steel sheet with a thickness of 200 μm, the first metal coating is a copper coating with a thickness of 300 nm, the second metal coating is a copper coating with a thickness of 500 nm, and the third metal coating is a copper coating with a thickness of 400 nm. During the processing, when the flexible metal substrate is bent, the adjustment coefficient is between 0.0001 and 0.0001, which can be selected according to the selected materials and needs. The specific examples are as follows:

[0076] Example 1

[0077] Example 1 provides a water electroplating process for a substrate, comprising the following steps:

[0078] Step 1) Degreasing and rust removal: the flexible metal substrate is sequentially passed through a degreasing liquid and a rust removing liquid for degreasing and rust removal.

[0079] In this embodiment, the degreasing liquid formula used is as follows:

[0080] Sodium hydroxide 15g / L, sodium bicarbonate 10g / L, sodium phosphate 35g / L, alkylphenol polyoxyethylene ether 0.8g / L. Degreasing treatment temperature 28-32℃, treatment time 2-3min.

[0081] In this embodiment, the rust removal liquid formula used is as follows:

[0082] Sulfuric acid 160g / L, hexamethylenetetramine 3g / L, triethanolamine 2g / L, sodium lauryl sulfonate 10g / L, sodium chloride 150g / L. Rust removal temperature 15-25°C, treatment time 2-3 minutes.

[0083] Ultrasonic water washing is used between the above treatment processes to ensure that no residual liquid is generated during the treatment process, thereby ensuring the stability of subsequent treatments.

[0084] Step 2) acid etching: placing the flexible metal substrate into an acid etching solution for acid etching; wherein the formula and treatment scheme of the acid etching solution are as follows:

[0085] The etching solution includes: 75 mL / L concentrated sulfuric acid, 450 g / L sodium chloride, 4 g / L KC corrosion inhibitor, 4 g / L glycine and 35 g / L sodium dodecyl sulfate; the flexible metal substrate to be etched is placed in the etching solution, the temperature is 35° C., and the etching time is 2.5 minutes.

[0086] Also includes the mesh layer processing steps:

[0087] In step 203, 0.1 parts by weight of carboxylated carbon nanotubes, 28 parts by weight of copper chloride, and 22 parts by weight of nickel chloride are added to deionized water, mixed, and stirred. The pH is adjusted to neutral with sodium hydroxide solution, and microwave-heated to 55°C for 1.5 hours. The precipitate is centrifuged and filtered, washed twice with deionized water, and prepared into a 5% by weight grid layer solution. The prepared grid layer solution is sprayed onto the surface of the flexible metal substrate and dried at 350°C for 2.0 hours.

[0088] In step 213 , the flexible metal substrate is placed in a ball mill for 0.5 min.

[0089] Step 3) spraying: placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating;

[0090] The bending curvature of the flexible metal substrate is:

[0091] ;

[0092] in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0093] Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward and water electroplating, forming a second metal plating layer outside the first metal plating layer;

[0094] The bending curvature of the flexible metal substrate is:

[0095] ;

[0096] in, The curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0097] Step 5) vacuum plating: vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer.

[0098] The bending curvature of the flexible metal substrate is:

[0099] ;

[0100] in, The curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0101] Among them, in the above steps, an ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5). The purpose is to prevent the impact on subsequent steps by sufficient flushing and cleaning between the previous and next steps.

[0102] The resistance and bonding strength of the plated flexible metal substrate were tested, as shown in Table 1.

[0103] Example 2

[0104] Example 2 provides a water electroplating process for a substrate, comprising the following steps:

[0105] Step 1) Degreasing and rust removal: the flexible metal substrate is sequentially passed through a degreasing liquid and a rust removing liquid for degreasing and rust removal.

[0106] In this embodiment, the degreasing liquid formula used is as follows:

[0107] Sodium hydroxide 15g / L, sodium bicarbonate 10g / L, sodium phosphate 35g / L, alkylphenol polyoxyethylene ether 0.8g / L. Degreasing treatment temperature 28-32℃, treatment time 2-3min.

[0108] In this embodiment, the rust removal liquid formula used is as follows:

[0109] Sulfuric acid 160g / L, hexamethylenetetramine 3g / L, triethanolamine 2g / L, sodium lauryl sulfonate 10g / L, sodium chloride 150g / L. Rust removal temperature 15-25°C, treatment time 2-3 minutes.

[0110] Ultrasonic water washing is used between the above treatment processes to ensure that no residual liquid is generated during the treatment process, thereby ensuring the stability of subsequent treatments.

[0111] Step 2) acid etching: placing the flexible metal substrate into an acid etching solution for acid etching; wherein the formula and treatment scheme of the acid etching solution are as follows:

[0112] The etching solution includes: 92 mL / L concentrated sulfuric acid, 350 g / L sodium chloride, 3 g / L KC corrosion inhibitor, 5 g / L glycine and 44 g / L sodium dodecyl sulfate; the flexible metal substrate to be etched is placed in the etching solution at a temperature of 42° C. and the etching time is 2.0 min.

[0113] Also includes the mesh layer processing steps:

[0114] In step 203, 0.3 parts by weight of carboxylated carbon nanotubes, 25 parts by weight of copper chloride, and 23 parts by weight of nickel chloride are added to deionized water, mixed, and stirred. The pH is adjusted to neutral with sodium hydroxide solution, and microwave-heated to 60°C for 1.3 hours. The precipitate is centrifuged and filtered, washed twice with deionized water, and prepared into a 5% by weight grid layer solution. The prepared grid layer solution is sprayed onto the surface of the flexible metal substrate and dried at 250°C for 1.5 hours.

[0115] In step 213 , the flexible metal substrate is placed in a ball mill and milled for 1 minute.

[0116] Step 3), spraying: placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating;

[0117] The bending curvature of the flexible metal substrate is:

[0118] ;

[0119] in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0120] Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward and water electroplating, forming a second metal plating layer outside the first metal plating layer;

[0121] The bending curvature of the flexible metal substrate is:

[0122] ;

[0123] in, The curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0124] Step 5) vacuum plating: vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer.

[0125] The bending curvature of the flexible metal substrate is:

[0126] ;

[0127] in, The curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0128] Among them, in the above steps, an ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5). The purpose is to prevent the impact on subsequent steps by sufficient flushing and cleaning between the previous and next steps.

[0129] The resistance and bonding strength of the plated flexible metal substrate were tested, as shown in Table 1.

[0130] Example 3

[0131] Example 3 provides a water electroplating process for a substrate, comprising the following steps:

[0132] Step 1) Degreasing and rust removal: the flexible metal substrate is sequentially passed through a degreasing liquid and a rust removing liquid for degreasing and rust removal.

[0133] In this embodiment, the degreasing liquid formula used is as follows:

[0134] Sodium hydroxide 15g / L, sodium bicarbonate 10g / L, sodium phosphate 35g / L, alkylphenol polyoxyethylene ether 0.8g / L. Degreasing treatment temperature 28-32℃, treatment time 2-3min.

[0135] In this embodiment, the rust removal liquid formula used is as follows:

[0136] Sulfuric acid 160g / L, hexamethylenetetramine 3g / L, triethanolamine 2g / L, sodium lauryl sulfonate 10g / L, sodium chloride 150g / L. Rust removal temperature 15-25°C, treatment time 2-3 minutes.

[0137] Ultrasonic water washing is used between the above treatment processes to ensure that no residual liquid is generated during the treatment process, thereby ensuring the stability of subsequent treatments.

[0138] Step 2) acid etching: placing the flexible metal substrate into an acid etching solution for acid etching; wherein the formula and treatment scheme of the acid etching solution are as follows:

[0139] The etching solution includes: 100 mL / L concentrated sulfuric acid, 250 g / L sodium chloride, 5 g / L KC corrosion inhibitor, 4 g / L glycine and 50 g / L sodium dodecyl sulfate; the flexible metal substrate to be etched is placed in the etching solution, the temperature is 30° C., and the etching time is 3 minutes.

[0140] Also includes the mesh layer processing steps:

[0141] In step 203, 0.4 parts by weight of carboxylated carbon nanotubes, 21 parts by weight of copper chloride, and 18 parts by weight of nickel chloride were added to deionized water, mixed, and stirred. The pH was adjusted to neutral with sodium hydroxide solution, and microwave-heated to 75°C for 1.1 hours. The precipitate was centrifuged and filtered, washed twice with deionized water, and prepared into a 5% by weight grid layer solution. The prepared grid layer solution was sprayed onto the surface of the flexible metal substrate and dried at 280°C for 1.8 hours.

[0142] In step 213 , the flexible metal substrate is placed in a ball mill for 1.2 minutes.

[0143] Step 3), spraying: placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating;

[0144] The bending curvature of the flexible metal substrate is:

[0145] ;

[0146] in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0147] Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward and water electroplating, forming a second metal plating layer outside the first metal plating layer;

[0148] The bending curvature of the flexible metal substrate is:

[0149] ;

[0150] in, The curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0151] Step 5) vacuum plating: vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer.

[0152] The bending curvature of the flexible metal substrate is:

[0153] ;

[0154] in, The curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0155] Among them, in the above steps, an ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5). The purpose is to prevent the impact on subsequent steps by sufficient flushing and cleaning between the previous and next steps.

[0156] The resistance and bonding strength of the plated flexible metal substrate were tested, as shown in Table 1.

[0157] Example 4

[0158] Example 4 provides a water electroplating process for a substrate, comprising the following steps:

[0159] Step 1) Degreasing and rust removal: the flexible metal substrate is sequentially passed through a degreasing liquid and a rust removing liquid for degreasing and rust removal.

[0160] In this embodiment, the degreasing liquid formula used is as follows:

[0161] Sodium hydroxide 15g / L, sodium bicarbonate 10g / L, sodium phosphate 35g / L, alkylphenol polyoxyethylene ether 0.8g / L. Degreasing treatment temperature 28-32℃, treatment time 2-3min.

[0162] In this embodiment, the rust removal liquid formula used is as follows:

[0163] Sulfuric acid 160g / L, hexamethylenetetramine 3g / L, triethanolamine 2g / L, sodium lauryl sulfonate 10g / L, sodium chloride 150g / L. Rust removal temperature 15-25°C, treatment time 2-3 minutes.

[0164] Ultrasonic water washing is used between the above treatment processes to ensure that no residual liquid is generated during the treatment process, thereby ensuring the stability of subsequent treatments.

[0165] Step 2) acid etching: placing the flexible metal substrate into an acid etching solution for acid etching; wherein the formula and treatment scheme of the acid etching solution are as follows:

[0166] The etching solution includes: 81 mL / L concentrated sulfuric acid, 400 g / L sodium chloride, 5 g / L KC corrosion inhibitor, 3 g / L glycine and 30 g / L sodium dodecyl sulfate; the flexible metal substrate to be etched is placed in the etching solution at a temperature of 55° C. and the etching time is 1.8 minutes.

[0167] Also includes the mesh layer processing steps:

[0168] In step 203, 0.2 parts by weight of carboxylated carbon nanotubes, 15 parts by weight of copper chloride, and 20 parts by weight of nickel chloride are added to deionized water, mixed, and stirred. The pH is adjusted to neutral with sodium hydroxide solution, and microwave-heated to 80°C for 2 hours. The precipitate is centrifuged and filtered, washed twice with deionized water, and prepared into a 5% by weight grid layer solution. The prepared grid layer solution is sprayed onto the surface of the flexible metal substrate and dried at 320°C for 2 hours.

[0169] In step 213 , the flexible metal substrate is placed in a ball mill and milled for 1.5 minutes.

[0170] Step 3) spraying: placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating;

[0171] The bending curvature of the flexible metal substrate is:

[0172] ;

[0173] in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0174] Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward and water electroplating, forming a second metal plating layer outside the first metal plating layer;

[0175] The bending curvature of the flexible metal substrate is:

[0176] ;

[0177] in, The curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0178] Step 5) vacuum plating: vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer.

[0179] The bending curvature of the flexible metal substrate is:

[0180] ;

[0181] in, The curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0182] Among them, in the above steps, an ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5). The purpose is to prevent the impact on subsequent steps by sufficient flushing and cleaning between the previous and next steps.

[0183] The resistance and bonding strength of the plated flexible metal substrate were tested, as shown in Table 1.

[0184] Example 5

[0185] Example 5 provides a water electroplating process for a substrate, comprising the following steps:

[0186] Step 1) Degreasing and rust removal: the flexible metal substrate is sequentially passed through a degreasing liquid and a rust removing liquid for degreasing and rust removal.

[0187] In this embodiment, the degreasing liquid formula used is as follows:

[0188] Sodium hydroxide 15g / L, sodium bicarbonate 10g / L, sodium phosphate 35g / L, alkylphenol polyoxyethylene ether 0.8g / L. Degreasing treatment temperature 28-32℃, treatment time 2-3min.

[0189] In this embodiment, the rust removal liquid formula used is as follows:

[0190] Sulfuric acid 160g / L, hexamethylenetetramine 3g / L, triethanolamine 2g / L, sodium lauryl sulfonate 10g / L, sodium chloride 150g / L. Rust removal temperature 15-25°C, treatment time 2-3 minutes.

[0191] Ultrasonic water washing is used between the above treatment processes to ensure that no residual liquid is generated during the treatment process, thereby ensuring the stability of subsequent treatments.

[0192] Step 2) acid etching: placing the flexible metal substrate into an acid etching solution for acid etching; wherein the formula and treatment scheme of the acid etching solution are as follows:

[0193] The etching solution includes: 85 mL / L concentrated sulfuric acid, 300 g / L sodium chloride, 4 g / L KC corrosion inhibitor, 3 g / L glycine and 25 g / L sodium dodecyl sulfate; the flexible metal substrate to be etched is placed in the etching solution at a temperature of 60° C. and the etching time is 1.5 minutes.

[0194] Also includes the mesh layer processing steps:

[0195] In step 203, 0.5 parts by weight of carboxylated carbon nanotubes, 30 parts by weight of copper chloride, and 15 parts by weight of nickel chloride are added to deionized water, mixed, and stirred. The pH is adjusted to neutral with sodium hydroxide solution, and microwave-heated to 68°C for 1.8 hours. The precipitate is centrifuged and filtered, washed twice with deionized water, and prepared into a 5% by weight grid layer solution. The prepared grid layer solution is sprayed onto the surface of the flexible metal substrate and dried at 300°C for 1.5 hours.

[0196] In step 213 , the flexible metal substrate is placed in a ball mill for 0.8 min.

[0197] Step 3), spraying: placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating;

[0198] The bending curvature of the flexible metal substrate is:

[0199] ;

[0200] in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0201] Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward and water electroplating, forming a second metal plating layer outside the first metal plating layer;

[0202] The bending curvature of the flexible metal substrate is:

[0203] ;

[0204] in, The curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0205] Step 5) vacuum plating: vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer.

[0206] The bending curvature of the flexible metal substrate is:

[0207] ;

[0208] in, The curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

[0209] Among them, in the above steps, an ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5). The purpose is to prevent the impact on subsequent steps by sufficient flushing and cleaning between the previous and next steps.

[0210] The resistance and bonding strength of the plated flexible metal substrate were tested, as shown in Table 1.

[0211] Comparative Example 1

[0212] The solution of Comparative Example 1 follows that of Example 1, but the mesh layer processing step is omitted.

[0213] The resistance and bonding strength of the plated flexible metal substrate were tested, as shown in Table 1.

[0214] Comparative Example 2

[0215] The solution of Comparative Example 2 follows that of Example 1, but the bending process of the flexible metal substrate in the plating step is omitted.

[0216] The resistance and bonding strength of the plated flexible metal substrate were tested, as shown in Table 1.

[0217] Table 1: Resistance and bonding strength test results of flexible metal substrates

[0218] Square resistance (mΩ) Bonding force (N / cm) Example 1 25.7 11.2 Example 2 23.4 12.5 Example 3 22.1 13.8 Example 4 24.2 13.1 Example 5 25.1 11.6 Comparative Example 1 46.8 7.5 Comparative Example 2 55.3 8.2

[0219] From the above experimental results, it can be seen that in Examples 1-5, the technical solution of the present application can significantly reduce the square resistance. At the same time, the square resistance of Example 3 reaches the lowest level, which is significantly different from the comparative example. In terms of bonding strength, compared with Comparative Examples 1 and 2, Examples 1-5 significantly improve the bonding strength of the coating on the flexible metal substrate through the combination of the above-mentioned spraying grid layer liquid processing steps and plating processing parameters.

[0220] The present application improves the flexible metal substrate electroplating process in the prior art. On the one hand, after acid etching, a grid layer liquid is sprayed on the surface of the flexible metal substrate so that the grid layer liquid can penetrate into the rough surface of the flexible metal substrate. At the same time, the grid layer liquid can form a grid layer structure on the surface of the flexible metal substrate, which is beneficial to the adhesion and bonding of subsequent coatings. On the other hand, in the three steps of spraying, water electroplating and vacuum plating, the flexible metal substrate is bent to expose the grid layer, thereby improving the bonding of subsequent coatings while ensuring low resistance.

[0221] Although the present invention has been described in detail above using general descriptions and specific embodiments, it will be apparent to those skilled in the art that modifications and improvements may be made thereto. Therefore, such modifications and improvements, without departing from the spirit of the present invention, are intended to be within the scope of protection claimed herein.

Claims

1. A water electroplating process for a substrate, characterized in that: The steps include: Step 1) degreasing and rust removal: the flexible metal substrate is sequentially passed through a degreasing liquid and a rust removing liquid for degreasing and rust removal; Step 2), acid etching, placing the flexible metal substrate into an acid etching solution for acid etching; Step 3) spraying: placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating; Among them, step 3) spraying, placing the flexible metal substrate into an automatic spraying machine, bending the side to be plated outward for spraying, and forming a first metal coating layer, includes: The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during spraying. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating; Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward and water electroplating, forming a second metal plating layer outside the first metal plating layer; Step 5), vacuum plating, vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer; Before step 3), the following grid layer processing steps are also included: Step 203 ), spraying the prepared grid layer liquid onto the surface of the flexible metal substrate, drying at a temperature of 230-350° C. for 1.5-2.0 hours; Step 213 ), placing the flexible metal substrate into a ball mill for 0.5-1.5 min; Wherein, the grid layer liquid preparation method is: Add 0.1-0.5 parts by weight of carboxylated carbon nanotubes, 5-30 parts by weight of copper chloride, and 2-25 parts by weight of nickel chloride to deionized water, mix and stir, adjust the pH to neutral with sodium hydroxide solution, and microwave-heat at 50-80° C. for 1-2 hours. The precipitate was obtained by centrifugal filtration, washed twice with deionized water, and prepared into a grid layer liquid with a mass fraction of 5%.

2. The water electroplating process for a substrate according to claim 1, wherein: An ultrasonic cleaning step is included between step 1) and step 2), between step 2) and step 3), between step 3) and step 4), and between step 4) and step 5).

3. The water electroplating process for a substrate according to claim 1, wherein: in, Step 2), acid etching, placing the flexible metal substrate into an acid etching solution for acid etching, specifically comprising: The acid etching solution includes: concentrated sulfuric acid 75-100mL / L, sodium chloride 200-500g / L, KC corrosion inhibitor 3-5g / L, glycine 3-5g / L and sodium dodecyl sulfate 10-50g / L; Place the flexible metal substrate to be acid-etched into the acid etching solution at a temperature of 30-62°C and an etching time of 1.5-3.0 minutes.

4. The water electroplating process for a substrate according to claim 1, wherein: in, Step 4), water electroplating, water electroplating the flexible metal substrate after spraying, bending the side to be plated outward for water electroplating, and forming a second metal plating layer outside the first metal plating layer, including: The bending curvature of the flexible metal substrate is: ; in, The curvature of the flexible metal substrate during water electroplating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

5. The water electroplating process for a substrate according to claim 4, wherein: in, Step 5), vacuum plating, vacuum plating the flexible metal substrate after water electroplating, bending the side to be plated outward for vacuum plating, and forming a third metal plating layer outside the second metal plating layer, including: The bending curvature of the flexible metal substrate is: ; in, It is the curvature of the flexible metal substrate during vacuum plating. is the thickness of the flexible metal substrate, is the expected thickness of the first metal coating, is the expected thickness of the second metal coating, is the expected thickness of the third metal coating, is the adjustment coefficient for the thickness of the flexible metal substrate, is the adjustment factor for the expected thickness of the metal coating.

6. The water electroplating process for a substrate according to claim 1, wherein: The flexible metal substrate is a stainless steel sheet, a copper alloy sheet or a nickel alloy sheet.

7. A low-resistance conductive material, characterized in that: The invention comprises a flexible metal substrate prepared by applying the water electroplating process for a substrate as claimed in claim 1.

Images