COPPER PLATED AUSTENITIC STAINLESS STEEL COIL

Abstract

According to the present disclosure, a copper-plated austenitic stainless steel coil can be provided, the coil comprising: an austenitic stainless steel coil base material; and a copper plating layer provided on an outer surface of the base material, wherein an average thickness of the copper plating layer is from 1µm to 100µm, and a ratio of the average thickness of the copper plating layer to an average thickness of the base material is 0.2 or less.

Description

13134.37 1 TARIFF COPPER-COATED AUSTENITIC STAINLESS STEEL COIL [Technical Area] 5 The present invention relates to a copper-clad austenitic stainless steel coil. [Previous Technique] Copper plating on a stainless steel surface results in a lower defect compared to stainless steel itself. Soldering and joining applications are possible using the melting point. However, coating on the surface of stainless steel coils Finding examples is difficult. Meanwhile, from a coating perspective, nickel is used to increase surface conductivity. Examples of aluminum coatings to improve coating and saltwater corrosion resistance. It is available. However, it is difficult to find copper plating on a stainless steel coil. In addition, copper cladding is used to increase the conductivity of the stainless steel surface. 20 Although the method exists, stainless steel can be made from copper using a coating method. Examples of its application to coil surfaces are also difficult to find. Stainless steel typically forms a passive film that provides corrosion resistance. The passive film in question mainly contains chromium and oxygen compounds and is 25 It is evenly and densely distributed on the surface. This makes it suitable for copper plating. This results in poor adhesion when used. Furthermore, it prevents successful copper plating. Even after processing, the copper plating layer remains on copper-clad stainless steel. The products are prone to peeling during the shaping process. The present invention, Copper coating resulting from the passive film of the stainless steel coil 30 It aims to solve their problems. 13134.37 2 [Explanation] [Technical Problem] A method for producing a copper-clad stainless steel coil. is provided. [Technical Solution] In an application that is the subject of the present invention, a copper-clad austenitic stainless steel The steel coil includes: an austenitic stainless steel coil base. a copper provided on an outer surface of the material and base material coating layer, where the copper coating layer has an average thickness of 1 µm. It is between 100 µm and here the average thickness of the copper plating layer is 15 The ratio of the base material to its average thickness is 0.2 or less. Here the base material is 1, 2 or more as defined by Formula (1) below. It meets a small film index: (Si+2Al) / Mn. The coil is a copper-clad austenitic stainless steel coil as in Claim 1, where 20 Austenitic stainless steel coil base material, 1.2 or less film. It meets the index and the film index (Si+2Al) / Mn (where Si, Al and Mn are the relevant (represents the contents of the elements) The subject of the present invention is an application involving an austenitic stainless steel coil base 25 The material has a composition that includes the following by weight percentage: It is possible to have: C: 0.005% to 0.080%, Si: 0.1% to 1.0%, Mn: 0.1% to 1.5%, Cu: 0.05% to 0.5%, Ni: 8% to 13%, Cr: 16% to 20%, Mo: 0.05% to 2.5%, and Al: 0.001% to 0.2%. 13134.37 3 The subject of the present invention is an application on a surface area of ​​100 × 100 mm², The copper plating layer can have a surface area ratio of 95% or more. In an application of the present invention, the copper plating layer shall constitute 75% or more by weight. It may contain more copper. 5 The subject of the present invention is a copper-clad stainless steel, in comparison to another application. A method for producing steel coils includes: an austenitic Provision of stainless steel coil base material and base material, 10 g / L to 500 g / L CuSO4·5H2O, 10 g / L to 500 g / L H2SO4 and the remaining amount of water 10 by immersing in a solution containing 1 to 50 A / dm² for 1 to 150 seconds. Copper electroplating is performed by applying a current density between certain parameters. The subject of the present invention is an application of a copper-clad austenitic stainless steel. In the method for producing coils, the austenitic stainless steel coil base is 15. The material can meet a film index of 1.2 or less. (Si+2Al) / Mn (where Si, Al and Mn represent the content of the respective elements) It is represented by (is). The subject of the present invention is an application of a copper-clad austenitic stainless steel 20 In the method for producing coils, an austenitic stainless steel coil base is used. The material has a composition that includes the following by weight percentage: It is possible to have: C: 0.005% to 0.080%, Si: 0.1% to 1.0%, Mn: 0.1% to 1.5%, Cu: 0.05% to 0.5%, Ni: 8% to 13%, Cr: 16% to 20%, Mo: 0.05% to 2.5%, and Al: 0.001% to 0.2%. 25 The subject of the present invention is an application of a copper-clad austenitic stainless steel. In the method for producing coils, the method also involves electroplating copper. First, the base material must be immersed in the following for 1 to 120 seconds. It may contain: (a) sulfuric acid at a concentration of 5 g / L to 200 g / L 30 13134.37 4 solution or (b) 5 g / L to 200 g / L nitric acid and 1 g / L to 20 g / L hydrofluoric acid a mixed acid solution containing. [Advantageous Effects] As presented in the current invention, copper-clad austenitic stainless steel, excellent soldering properties and copper plating after shaping. It exhibits excellent resistance to peeling of its outer layer. [Explanation of Figures] 10 FIGURE 1 shows an austenitic stainless steel coil base material and a copper a copper-clad austenitic stainless steel containing a coating layer This is a cross-sectional view of the coil. Figure 2 is a photograph showing the appearance characteristics of Sample 1. 15 FIGURE 3 shows the appearance characteristics of comparison sample 1. It is a photograph. [Modes of Discovery] The preferred applications of the present invention are described below. However, the applications of the present invention are subject to various other modifications. is also suitable and the technical content of the present invention is explained hereafter. It is not limited to applications. In addition, the applications covered by the present invention are existing. 25 more comprehensive presentation of the invention to individuals with moderate technical expertise It is provided for this purpose. The terms used in the present invention are intended only to describe specific instances. It is used in this way. Therefore, for example, when the context does not explicitly indicate a singular meaning. In this process, singular expressions contain plural expressions. In addition, the existing 30 Terms such as “include” or “cover” used in the invention refer to the terms specified in the specification. 13134.37 features, steps, functions, components, or combinations thereof It is used to explicitly state its existence and other features, steps, the existence of functions, components or combinations thereof in advance It should be noted that it is not used for exclusionary purposes. Unless otherwise defined, the understanding of all terms used herein is provided. generally by persons with a moderate level of expertise in the art to which the invention relates It must be consistent with the understood meanings. Accordingly, the interpretation of a particular term here unless clear definitions are available, it is either overly idealized or in a formal sense. It shouldn't be. 10 Furthermore, in the present invention, terms such as "approximately," "significantly," and similar terms are used as specified. It is used in the sense of being close to or approximately equal to a numerical value, in the indicated sense. The manufacturing and material tolerances found have been taken into consideration. The use of terms, The content of the invention, which specifies precise or absolute numerical values, could be maliciously infringed upon by a malicious infringer. 15 This further prevents its unauthorized use; such prevention is... It helps in understanding the existing invention. In the present invention, unless specifically stated otherwise, the percentage content of each element... Representative weights are given as a percentage. 20 Firstly, according to the present invention, for copper-clad austenitic stainless steel coils An explanation is provided. According to a sample of the present invention, a copper-clad austenitic stainless steel coil 25 This includes: an austenitic stainless steel coil base material and base. a layer of copper plating arranged on an outer surface of the material, Here, the average thickness of the copper plating layer is between 1 µm and 100 µm. and here the average thickness of the copper plating layer is one of the base material Its ratio to average thickness is 0.2 or less. 30 13134.37 6 FIGURE 1 shows an austenitic stainless steel coil according to a sample of the present invention. a copper-plated base material containing a copper plating layer This is a cross-sectional view of an austenitic stainless steel coil. The subject of the present invention is an austenitic stainless steel coil base material, 1, 2 or 5 It meets a lower film index, and the film index, Si, Al and Mn, are related. It is represented by (Si+2Al) / Mn, where the elemental content is represented; this is a It retains the austenitic stainless steel microstructure and has a specific It is not limited by compositional range. For example, austenitic stainless steel coil base The material's composition includes the following as a percentage by weight: C: 10 0.005% to 0.080%, Si: 0.1% to 1.0%, Mn: 0.1% to 1.5%, Cu: 0.05% to 0.5%, Ni: Composition: 8% to 13%, Cr: 16% to 20%, Mo: 0.05% to 2.5%, and Al: 0.001% to 0.2%. These are not the only ones. A film index greater than 1.2 indicates that the passive film contains 15 Si oxides or Al oxides. This leads to a strengthening of the passive film's properties; which in turn further enhances them. This reveals its effect. This, conversely, leads to a decrease in adhesion. Mn, on the other hand, prevents passive film formation; thus Si or it has the opposite effect of AI. Film index 1.2 or less, preferably 1. or less, and preferably controlled to be 0.7 or less. 20 Additionally, one method to increase the surface conductivity of stainless steel is to use copper. It contains a coating. The thickness of the copper coating layer is between 1 µm and 100 Controlling the measurement to be between µm, using copper cladding. It is significantly easier than gluing. A thin copper 25 by cladding. A process for creating layers involves significant costs. Cladding Copper layers produced in this way are generally 100 µm or thicker. It is manufactured in a way that facilitates post-shaping delamination. Accordingly, the average thickness of the copper plating layer, which is the subject of the present invention, is 1 µm 30 The average thickness of the copper plating layer can be between 100 µm and 100 µm. 13134.37 7 a ratio of 0.2 or less to the average thickness of the base material It is possible that the base material is defined by Formula (1) below, 1,2 or meets a film index less than: (Si+2Al) / Mn. Copper plating, on one or both surfaces of the austenitic stainless steel coil base material This can be achieved. During shaping after coating, 5% of the copper... To prevent delamination, the average thickness of the copper plating layer is 1 µm. between 100 µm, preferably 75 µm or less, even more preferably 60 µm or It may be less. During shaping, the copper plating layer where it is located on the inner or outer surface of a bent part, stainless steel The difference in formability (i.e., elongation) between the copper plating layer and the copper plating layer is 10 Due to its large size, delamination occurs. Accordingly, copper Thickness control of the coating layer and the base material coil is required and The ratio of the copper plating layer thickness to the stainless steel thickness is 0.2 It needs to be controlled to be at least 0.1%. Preferably, the ratio should be 0.1%. or less, and preferably 0.05 or less. 15 Furthermore, in one example of the present invention, the area ratio of the copper plating layer is copper 95% of the surface area of ​​the coated austenitic stainless steel coil is 100x100 mm². or more. A copper plating area ratio of less than 95% means that copper does not perform its function in the unplated parts. This leads to it not performing adequately. This type of situation occurs with soldering. inadequate coating on uncoated parts in contact with the bonding material during the process This leads to a bonding problem. The area ratio of the copper plating layer is preferably... It is 99% or more. 25 Furthermore, copper-clad austenitic stainless steel according to a sample of the present invention. coil, copper cladding layer containing 75% or more copper by weight It includes. 13134.37 8 Copper content is a central component in one thickness direction of the copper plating layer. This refers to the average copper content measured by 5-point spot analysis in the stratum. It comes with less than 75% copper content, indicating inadequate copper plating; this This situation can lead to partial measurement of the components of the substrate material. One such situation is the separation of the copper plating layer during shaping. 5 This reveals the problem. The copper content of the copper plating layer is preferably... 85% or more, preferably 95% or more. The copper plating, which is below the mentioned area ratio or content, is visible on the surface. It is unable to offer a uniform copper color, which detracts from the aesthetic appearance and 10 The user determined during visual inspection that the copper plating was not properly applied. This leads to giving. Next, a project aimed at producing copper-clad austenitic stainless steel coils. The method will be explained. 15 The subject matter of the present invention is, according to an example, a copper-clad stainless steel coil. One method for producing it includes: an austenitic stainless steel. Provision of coil base material and austenitic stainless steel coil base The material consists of 10 g / L to 500 g / L CuSO4·5H2O, 10 g / L to 500 g / L H2SO4, and the remaining 20 by immersing in a solution containing a remaining amount of water and for 1 to 150 seconds. Copper electrodes are heated by applying a current density between 1 A / dm² and 50 A / dm². Coating application. Copper plating can be done using various methods, but electro 25 Coating is preferred. This is because of the acid treatment or coating mentioned above. It is advantageous for production in coil units together with the nickel layer. Electro coating, stainless steel as cathode and an insoluble electrode as anode by using and applying a current density between 1 A / dm² and 50 A / dm², g / L to 500 g / L CuSO4·5H2O, 10 g / L to 500 g / L H2SO4 and the remaining amount 30 This can be carried out in a solution containing water. This method allows for the processing of copper. 13134.37 9 It provides optimal conditions for adhesion to stainless steel without peeling. and it is also a factor that determines the thickness of the copper plating layer. Furthermore On the other hand, low solution concentration or low current density can cause copper to be improperly distributed. This prevents the adhesive from sticking properly, leading to the formation of insufficient space. This leads to a decrease in the area ratio of the coating layer or coating 5 a factor causing the copper content within the layer to be measured as low. This is due to excessively high solution concentration or high current density. the copper layer coated on stainless steel easily separates This leads to a problem. Therefore, the control is within the specified range. is being carried out. 10 A copper-clad austenitic stainless steel coil, an example of the present invention. One method for producing copper is also done before the electroplating process is carried out. Austenitic stainless steel coil base material 5 g / L to 200 g / L sulfuric acid at a concentration of 1 g / L to 20 g / L or nitric acid at a concentration of 15 This involves immersion in a hydrofluoric acid mixture for 1 to 120 seconds. During the shaping process in copper electroplating. Passive coating on the surface of stainless steel base material to prevent peeling. The layer needs to be removed. On the surface of the stainless steel base material. The passive film increases corrosion resistance while preventing copper adhesion. Copper 20 Before electroplating, the stainless steel substrate material is immersed in sulfuric acid or immersed in a mixed acid of nitric acid and hydrofluoric acid for 1 to 120 seconds. Immersion provides healing under these conditions. Between the passive film and the acid To maximize the reaction, the sulfuric acid concentration should be between 5 g / L and 200 g / L. It is among them. For a mixed acid consisting of nitric acid and hydrofluoric acid, nitric acid is 25. The concentrations are 5 g / L to 200 g / L respectively, while the hydrofluoric acid concentration is... The concentration ranges from 1 g / L to 20 g / L. In coil units, production and holding time depend on the length of the coil. It defines the duration of immersion of a 1 m coil in acid along its direction as 1 Durations between 120 seconds and 120 seconds are preferred. From here on, the present invention will be explained in more detail through examples. 13134.37 (example) In the present invention, 0.02% is given as an example of a representative component in terms of weight percentage. 5 based on C, 0.7% Si, 1.0% Mn, 0.3% Cu, 10% Ni, 16.1% Cr, 2.1% Mo and 0.01% Al. Specifically, samples with the compositions and film indices in Table 1 below, and comparison samples of austenitic stainless steel coil base materials, These coils are manufactured in the thickness ranges shown in Table 2 below. a bath containing 50 g / L sulfuric acid for 30 seconds on a continuous line It was immersed and, after washing with water, immediately treated with 100 g / L copper sulfate pentahydrate and 10 It was immersed in a copper plating bath containing 100 g / L sulfuric acid. 15 A / dm² By applying current density, a copper sheet with the thicknesses shown in Table 2 below can be produced. a coating layer was formed and the average of the said copper coating layer the ratio of its thickness to the austenitic stainless steel coil base material in question shown. 15 The stainless steel compositions in Table 1 below are commonly used in industry and academia. equipment used such as inductively coupled plasma scanners or spectroscopes Measured using. The composition of the coating layer, stainless steel base Due to its relatively thin thickness compared to the material, scanning electron 20 energy dispersive spectroscopy associated with a microscope or transmission electron microscope This can be measured using energy dispersive spectroscopy. During the measurement, carbon and oxygen were present due to contamination of the sample. This can affect the component content and is therefore excluded from the final result; The elements coated for sample analysis are also deduced from the result. Copper and 25 Nickel plating layers, five randomly selected layers from the central layer in the direction of thickness. It was calculated by taking the average of the points. Determining post-shaping peeling, stretching, Erichsen shaping, and It uses various methods such as precipitation. In the present invention, for example, 15-30% Uniaxial stress was used. Following this, a stainless steel base material was applied. 13134.37 11 Peeling was observed between the copper plating layer and the surface. The peeling is general. It is a concept known as visual inspection and can be detected by examining the eye; however, convenience In terms of this, a copper plating layer with an area of ​​10x10 mm² separated from the stainless steel base material by a distance of 1 mm or more It is accepted. 5 Appearance Assessment Method: It is difficult to quantitatively measure aesthetic appearance. However, in the present invention, it is within a range that is normally acceptable. The determined level is considered “successful” as shown in Table 1 below. It has been defined. 10 On the surface, the area of ​​the copper plating layer is measured in a 100x100 mm² area. Surface refers to the surface of a material as observed from a direction perpendicular to the material's surface. The surface position is such that the material is centered along its width. It takes. In the longitudinal direction, the measurement for a coil is 1 m 15 from one end of the coil. This can be done at a distance; however, there are numerous scratches. In this case, a distance of 1 to 10 m can be disregarded. Area ratio, It allows image analysis after a photograph is taken with a traditional digital camera. It is recognizable. The copper plating layer, when photographed on the surface with a digital camera, It displays an orange color and the base material is predominantly white and gray 20 It displays a colorless shade between the two colors; therefore, the group between the two colors This separation allows for the calculation of the area ratio of the coating layer. Two If it is difficult to distinguish between the groups, as explained above... It is possible to separate the two groups by color separation, such as in a 100x100 mm² area. It is divided equally into 100 areas and the divided areas are photographed, then 25 Optical microscopes use objectives with 5x or 10x magnification. STS is a thickness measurement method for copper plating and nickel plating layers. mirror surface polishing of a cross-section and then optical measurement of the cross-section 30 involves observation with a microscope or scanning electron microscope 13134.37 12 It is measured using an optical microscope or a scanning electron microscope. The measurement method can follow traditional practices. [Table 1] Classification Si Content (by weight) % Get Contents (by weight) % Mn Content (by weight) % Film Index Subject of the Invention Example 1 0.60 0.112 1.10 0.75 Subject of the Invention Example 2 0.70 0.012 1.05 0.69 Subject of the Invention Example 3 0.88 0.003 1.15 0.77 Subject of the Invention Example 4 0.35 0.005 1.25 0.29 Subject of the Invention Example 5 0.66 0.140 0.81 1.16 Subject of the Invention Example 6 0.12 0.006 1.45 0.09 To compare Example 1 1.22 0.005 0.89 1.38 To compare Example 2 1.32 0.010 0.92 1.46 To compare Example 3 0.65 0.160 0.76 1.28 To compare Example 4 0.77 0.110 0.58 1.71 To compare Example 5 0.75 0.009 0.61 1.26 [Table 2] Classification Copper Area Rate (%) Copper Content (by weight) % Appearance STS Thickness (mm) Copper Covering Thickness (mm) Thickness Rate Forming Post Peeling Subject of the Invention Example 1 100 95 Successful 0.61 0.015 0.02 Good 13134.37 13 Subject of the Invention Example 2 100 76 Successful 0.75 0.005 0.01 Good Subject of the Invention Example 3 100 98 Successful 0.38 0.074 0.19 Good Subject of the Invention Example 4 100 98 Successful 0.65 0.089 0.14 Good Subject of the Invention Example 5 100 77 Successful 0.99 0.095 0.10 Good Subject of the Invention Example 6 100 99 Successful 1.21 0.050 0.04 Good Subject of the Invention Example 7 95 95 Successful 0.62 0.055 0.09 Good Subject of the Invention Example 8 91 88 Successful 0.65 0.060 0.09 Good To compare Example 1 85 95 Failed 0.55 0.088 0.16 Good To compare Example 2 88 99 Failed 0.77 0.066 0.09 Good To compare Example 3 94 55 Failed 0.65 0.022 0.03 Good To compare Example 4 93 44 Failed 0.71 0.015 0.02 Good To compare Example 5 60 80 Failed 0.62 0.180 0.29 Peeling To compare Example 6 100 95 Successful 0.61 0.150 0.25 Peeling To compare Example 7 100 94 Successful 0.41 0.088 0.21 Peeling To compare Example 8 100 99 Successful 0.74 0.211 0.29 Peeling To compare Example 9 100 91 Successful 0.95 0.250 0.26 Peeling To compare Example 10 100 99 Successful 0.55 0.122 0.22 Peeling Examples 1 to 8 of the subject matter of the invention in Table 1, as presented in the present invention, contain Si. A film index of 1.2 or less based on Al content and Mn content. It satisfies the value of (Si+2Al) / Mn. Subject of the invention: Examples 1 to 8, Table 2. as shown, the copper plating layer area ratio is 95% or more. 13134.37 14 and the copper content in the copper plating layer is 75% or more This shows that and the appearance assessment results are in FIGURE 1. It is indicated as 'successful' as shown. Meanwhile, Comparison Example 1 to 5 has shown a film index exceeding 1.2 and, as shown in FIGURE 2, copper The surface area ratio did not reach 95%, and the copper content of the coating layer was 75% to 5%. It was not reached and the appearance assessment results were indicated as 'failed'. Meanwhile, the subject matter of the invention, Samples 1 to 8, involves stainless steel with copper plating. a thickness ratio to the layer within the range covered by the present invention, i.e., 0.2 It has provided or less of this and has also shown good peel resistance. In contrast, the Comparison Sample met a film index of 6 to 10 but had a thickness of 10. It did not meet the required ratio; this led to delamination. Although example applications of the present invention have been described above, the present The invention is not limited to these and a person skilled in the art may, as defined below: Various changes without deviating from the content and scope of the requests and 15 He will understand that he can make modifications.

Claims

13134.37 REQUESTS 1. A copper-clad austenitic stainless steel coil, which includes the following: It includes: an austenitic stainless steel coil base material and a copper coating provided on an outer surface of the base material layer, Here, the average thickness of the copper plating layer is between 1 µm and 100 µm. between and 10 Here, the average thickness of the copper plating layer is the base. The ratio of the material's thickness to its average thickness is 0.2 or less.

2. A copper-clad austenitic stainless steel coil as in Claim 1, Here, the austenitic stainless steel coil base material is given in Formula (1). It meets a film index of 1, 2 or less as defined. Formula (1): (Si+2Al) / Mn (Here, Si, Al, and Mn represent the percentage by weight of each element) (It represents.) 20 3. Copper-clad austenitic stainless steel coil as in Claim 1, where A composition of austenitic stainless steel coil base material, by weight It includes the following in percentage terms: C: 0.005% to 0.080%, Si: 0.1% to 1.0%, Mn: 0.1% to 1.5%, Cu: 0.05% to 0.5%, Ni: 8% to 13%, Cr: 16 to 25% 20%, Mo: 0.05% to 2.5%, and Al: 0.001% to 0.2%.

4. The coil is a copper-clad austenitic stainless steel coil, as in Claim 1. Here, in a 100 × 100 mm² area of ​​a surface, 30 copper plating The area ratio of this layer is 95% or more. 13134.37 16 5. The coil is a copper-clad austenitic stainless steel coil, as in Claim 1. Here, the copper plating layer contains 75% or more copper by weight. It includes 5.

6. The coil is a copper-clad austenitic stainless steel coil, as in Claim 1. also copper plating with austenitic stainless steel coil base material. It contains a nickel plating layer between the layers. 10 7. A method for producing a copper-clad austenitic stainless steel coil. This method includes the following: Providing an austenitic stainless steel coil base material and 15 Base material 10 g / L to 500 g / L CuSO4·5H2O, 10 g / L to 500 g / L by immersing in a solution containing H2SO4 and the remaining amount of water, and 1 to A current density of between 1 A / dm2 and 50 A / dm2 for 150 seconds. Copper electroplating is performed by applying this method.

8. The method is the same as in claim 7, Here, the austenitic stainless steel coil base material is 1, 2 or less. It meets a film index and is represented by the film index (Si+2Al) / Mn. is being done, 25 (Here, Si, Al, and Mn represent the percentage by weight of each element) (It represents.) 9. The method is the same as in claim 7, 13134.37 17 Here is a composition of austenitic stainless steel coil base material. It includes the following as a percentage by weight: C: 0.005% to 0.080%, Si: 0.1% to 1.0%, Mn: 0.1% to 1.5%, Cu: 0.05% to 0.5%, Ni: 8% to 13%, Cr: 16% to 20%, Mo: 0.05% to 2.5%, and Al: 0.001% to 0.2%.

10. The method is the same as in claim 7, Furthermore, before electroplating the copper, the base material must be between 1 and 120 This involves immersion for a period of seconds in: (a) 5 g / L to 200 (b) a sulfuric acid solution at a concentration of 5 g / L or (b) 5 g / L to 200 10 a mixed acid containing 1 g / L nitric acid and 1 g / L to 20 g / L hydrofluoric acid solution.

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