Patent Application
20240026558
The present invention relates to an Ag-plated material, a method for producing an Ag-plated material, and an electrical component.
Conventionally, silver (Ag)-plated materials, which are conductor materials coated with silver, have been used as materials for sliding contact parts such as switches, connectors, and terminals used in automobiles and the like, to prevent oxidation of the conductor materials such as copper and copper alloys due to heating during a sliding process.
Patent document 1 discloses a plated product in which a multi-layered plated film is formed on a substrate that comprises a conductive metal, having a porous plated layer containing Ni or Cu as a main component and a surface plated layer containing Au or Ag as a main component in this order on the substrate, with a large number of pores formed on the surface of the multi-layered plated film (claim 1).
In addition, Patent document 1 discloses the following content as a reason for forming the large number of pores on the surface of the multi-layered plated film ([0020]).
That is, by forming the surface-plated layer on the porous plated layer, the surface-plated layer is formed along unevenness of the porous plated layer, and pores are also formed on the surface-plated layer. The surface-plated layer is easily formed on the projections on the surface of the porous plated layer, and is hardly formed on the bottoms and side surfaces of the pores on the surface of the porous plated layer. As a result, there will be a portion where the surface-plated layer is not formed and a portion where the surface-plated layer is thin. Due to the unevenness of the surface-plated layer containing Au or Ag as a main component, the concentration of a corrosion current that causes a galvanic corrosion can be prevented, and rather a corrosion resistance improves.
Patent document 2 discloses that the surface of the plated film described in Patent document 1 has a large number of pores, and the pores are filled with lubricating particles by blasting to provide slidability (abstract).
Patent document 3 discloses an electrical contact material for connectors with excellent wear resistance, having a substrate that comprises a metal material, a porous metal layer having a large number of pores provided on the substrate, and filling portions filled in the pores on the porous metal layer, the filling portions comprising a metal material having a hardness lower than that of the metal material comprised in the porous metal layer, to thereby maintain good electrical connectivity for a long period of time even when the connector is repeatedly inserted and removed (abstract, claim 1).
Patent documents 4 and 5 disclose a silver-plated material whose silver surface layer is formed on the surface of a nickel underlayer formed on the substrate, with excellent wear resistance, in which in order to improve the productivity of the silver-plated material, the surface of the substrate is roughened, and after forming the nickel underlayer on the roughened surface of the substrate, or after forming the nickel underlayer on the substrate and roughening the surface of the underlayer, a surface layer comprising silver is formed on the surface of this underlayer (abstract, claim 1).
In recent years, demand for electric vehicles such as EVs and PHVs is increasing due to problems under environmental regulations. A silver-plated wrought copper material is often used for electrified vehicles, from a viewpoint of electrical conductivity and contact reliability.
Properties required for such a high-voltage terminal include insertion/removal resistance and wear resistance (collectively referred to as wear resistance in this specification), and preferably include a performance (vibration resistance) to withstand fretting wear.
An object of the present invention is to provide an Ag-plated material with excellent wear resistance.
A first aspect of the present invention provides an Ag-plated material, including:
A second aspect of the present invention provides the Ag-plated material according to the first aspect, further including:
A third aspect of the present invention provides the Ag-plated material according to the second aspect, wherein the underlying Ni-plated layer has a thickness of 0.05 to 2 μm.
A fourth aspect of the present invention provides the Ag-plated material according to any one of the first to third aspects, wherein the Ag-plated material has a large number of pores on its surface.
A fifth aspect of the present invention provides the Ag-plated material according to the fourth aspect, wherein a number density of the pores is 5000 to 100,000/mm2.
A sixth aspect of the present invention provides the Ag-plated material according to the fourth or fifth aspect, wherein the pores have an average diameter of 1 to 10 μm.
A seventh aspect of the present invention provides the Ag-plated material according to any one of the first to sixth aspects, wherein the porous Ni-plated layer has a thickness of 0.1 to 3 μm.
An eighth aspect of the present invention provides the Ag-plated material according to any one of the first to seventh aspects, wherein the Ag-plated layer has a thickness of 0.1 to 3 μm.
A ninth aspect of the present invention provides a method for producing an Ag-plated material, which is a method for producing an Ag-plated material including an Ag-plated layer on a substrate that comprises a conductive metal, the method including:
A tenth aspect of the present invention provides the method for producing an Ag-plated material according to the ninth aspect, including:
An eleventh aspect of the present invention provides the method for producing an Ag-plated material according to the tenth aspect, wherein the underlying Ni-plated layer has a thickness of 0.05 to 2 μm.
A twelfth aspect of the present invention provides the method for producing an Ag-plated material according to any one of the ninth to eleventh aspect, wherein the porous Ni-plated layer has a thickness of 0.1 to 3 μm.
A thirteenth aspect of the present invention provides the method for producing an Ag-plated material according to any one of the ninth to twelfth aspect, wherein the Ag-plated layer has a thickness of 0.1 to 3 μm.
A fourteenth aspect of the present invention provides an electrical component that is a contact or terminal component using the Ag-plated material according to any one of the first to eighth aspects as a material.
According to the present invention, an Ag-plated material with excellent wear resistance can be provided.
The present embodiment will be described below. In this specification, “−” refers to a predetermined numerical value or more and a predetermined numerical value or less.
An Ag-plated material according to the present embodiment is an Ag-plated material, including: an Ag-plated layer on a substrate that comprises a conductive metal; and a plurality of two-layer plating structures on the substrate, the two-layer plating structures having a porous Ni (nickel) plated layer and an Ag (silver) plated layer in this order from a substrate side (lower side).
The substrate is not limited as long as it comprises a conductive metal, and may be copper or a copper alloy.
The porous Ni-plated layer is, as the name suggests, a porous plated layer.
The porous Ni-plated layer is a porous Ni-plated film having a three-dimensional structure that can be produced, for example, by a known porous Ni plating solution and electrolytic plating method, and when observed from the surface, each pores having a diameter of about 1 μm to several tens of μm, and has a high specific surface area.
The porous Ni-plated layer is a plated layer containing Ni as a main component, and may contain other elements such as P, B, Co, Fe, Cr, Cu, Zn, etc. within a range in which the effects of the present invention are exhibited. Hereinafter, the Ni-plated layer and Ag-plated layer mean that Ni and Ag are main components, respectively.
Specifically, the content of Ni in the porous Ni-plated layer is, for example, 90% by mass or more, preferably 95% by mass or more, and more preferably 99% by mass or more.
It is preferable that the porous Ni-plated layer has a thickness of 0.1 to 3 μm. With this thickness, the Ni-plated layer can be made porous after appropriately setting the number density of the pores and the average diameter of the pores. The thickness of the porous Ni-plated layer is more preferably 0.3 to 2 μm, still more preferably 0.8 μm or more.
The Ag-plated layer may be an Ag-plated film obtained by applying Ag plating (main plating) after applying Ag strike plating. Then, it is a plated layer containing Ag as a main component. Other elements such as C, N, S, Se, Sb, Co, Cu, Au, In, P, Zn, Sn, Pd, Bi, etc., may be contained in the Ag-plated layer within a range in which the effects of the present invention are exhibited. For convenience, in this specification, in order to distinguish between the Ag strike plated layer and the Ag-plated layer formed thereon, the Ag-plated layer on the Ag strike plated layer may be referred to as a main Ag-plated layer.
Specifically, the content of Ag in the Ag-plated layer is, for example, 90% by mass or more, preferably 95% by mass or more, and may be 99% by mass or more from a viewpoint of conductivity.
A large number of pores are preferably formed on the surface of the Ag-plated material. That is, a large number of pores are preferably observed on an outermost surface side (exposed surface) of the plurality of Ag-plated layers. Further, a large number of pores may be observed on any upper surface of the Ag-plated layer that constitutes the Ag-plated material. It can be considered that the pores of the Ag-plated layer are observed so that the surface of the porous Ni-plated layer, which is formed under the Ag-plated layer and covered with the Ag-plated layer, is not covered with Ag plating until the pore portions of the porous Ni-plated layer is completely filled.
A two-layer plating structure having the porous Ni-plated layer and the Ag-plated layer in this order (alternately overlapping) is formed from the substrate side, and the presence of the plurality of two-layer plating structures can be confirmed by observing the cross section using an electron microscope. For example,
Further, a number density of pores on the surface of the Ag-plated material and a diameter of the pores were evaluated. A shape measurement was performed with an objective lens ×100 using a laser microscope VK-X150 manufactured by Keyence Corporation, and volume and area measurements were performed in an analysis range of 100 μm×100 μm, using a multi-file analysis application. With a height of a largest detected area as a reference (height 0) (calculated by the analysis application), a portion where an object (plated surface) was not detected at a distance (position) of 0.5 μm in a depth direction of the Ag-plated layer from the reference height is regarded as a pore (porous portion), to measure the number and area of the pores. Then the number density of the pores per unit area and the average diameter of the pores were calculated. Pores having a diameter of less than 1 μm were excluded from the measurement targets.
Further, a large number of pores (unevennesses) are formed on the upper surface of the Ag-plated layer other than the outermost layer constituting the Ag-plated material (surface side of the Ag-plated material), and the porous Ni-plated layer is formed on the upper surface of the Ag-plated layer.
It is preferable that the number density of the pores on the surface of the Ag-plated material is 5,000 to 100,000/mm2.
The average diameter of the pores is preferably 1 to 30 μm, more preferably 2 to 20 μm.
The Ag-plated layer preferably has a thickness of 0.1 to 3 μm, more preferably 0.2 to 2 μm. With this thickness, a large number of pores can be formed on the Ag-plated layer after appropriately setting the number density of the pores and the average diameter of the pores. When the thickness is more than 3 μm, the pores on the surface of the porous Ni-plated layer may be filled with the Ag-plated layer, resulting in insufficient formation of a large number of pores on the surface. However, the above numerical range is only an example, and after all, the thickness of the Ag-plated layer may be any thickness that allows a large number of pores to be formed on the upper surface of the Ag-plated layer. It is more preferable that any Ag-plated layer constituting the Ag-plated material has a thickness that allows a large number of pores to be formed on the upper surface of the Ag-plated layer, and specifically, the thickness is more preferably 0.2 to 2 μm, and still more preferably 0.5 μm or more.
In the present embodiment, a plurality of two-layer plating structures each having a pair of the porous Ni-plated layer and the Ag-plated layer formed directly thereon are provided. With this configuration, the Ag-plated material of the present embodiment has excellent wear resistance and preferably has excellent vibration resistance.
It is preferable that the underlying Ni-plated layer is further formed between the two-layer plating structures closest to the substrate, and the substrate. Particularly, it is preferable to form the underlying Ni-plated layer directly on the substrate and form the porous Ni-plated layer directly on the underlying Ni-plated layer.
By forming the underlying Ni-plated layer, for example, when the Ag-plated material is heated, elements such as Cu and Fe, which are components of the substrate, can be prevented from diffusing into the Ag-plated layer, and deterioration of properties such as deterioration of adhesion between the substrate and the porous Ni-plated layer can be suppressed.
When good adhesion can be ensured between the substrate (or a layer when some layer is formed on the substrate) and the porous Ni-plated layer, there is no limitation on the underlying Ni-plated layer. The thickness of the underlying Ni-plated layer is preferably 0.05 to 2 μm, from a viewpoint of good adhesion and bending workability.
There is provided a method for producing an Ag-plated material of the present embodiment, which is a method for producing an Ag-plated material including an Ag-plated layer on a substrate that comprises a conductive metal, the method including:
Contents not described below are the same as those described in the <Ag-plated material> item.
As a pretreatment, electrolytic degreasing and pickling are preferably performed to the substrate. For example, with the substrate as a cathode and a separately prepared SUS plate as an anode, electrolytic degreasing is preferably performed, to remove organic substances on the substrate. Thereafter, the substrate is preferably pickled with an aqueous solution containing an acid such as a sulfuric acid.
Next, it is preferable to form an underlying Ni-plated layer. There are no restrictions on the configuration (composition) of the plating bath and plating conditions when forming the underlying Ni-plated layer, and a plating bath (sulfamic acid bath; comprising nickel sulfamate and boric acid, nickel chloride, etc.) and plating conditions listed in the examples below can be used. Other plating baths include a Watts bath (comprising nickel sulfate and nickel chloride, boric acid, etc.) and an all-chloride bath (comprising nickel chloride and boric acid, etc.).
The Ni concentration in the underlying Ni plating solution is preferably 5 to 200 g/L, more preferably 10 to 180 g/L, most preferably 20 to 150 g/L, and electroplating is preferably performed using such a plating solution.
The temperature of the plating solution for forming the underlying Ni-plated layer is preferably 10 to 70° C., more preferably 25 to 55° C. A current density is preferably 15 A/dm2 or less, more preferably 10 A/dm2 or less, still more preferably 0.5 to 7 A/dm2.
It is preferable to form a porous Ni-plated layer directly on the underlying Ni-plated layer. There are no restrictions on the configuration (composition) of the plating bath (liquid) and plating conditions when forming the porous Ni-plated layer, and it is sufficient that plating is performed in a plating bath containing Ni ions to form the porous plated layer containing Ni as a main component.
Specifically, examples of methods include a method of electroplating in a plating bath to which a water-soluble quaternary ammonium salt containing Ni ions and having a hydrophobic group is added. The quaternary ammonium salt can be added to a known Ni electroplating bath.
Examples of known electroplating baths include Watts bath, Ni sulfamate bath, and Ni organic acid bath.
The Ni concentration in this porous Ni plating solution is preferably to 200 g/L, more preferably 10 to 180 g/L, most preferably 20 to 150 g/L.
The temperature of the plating solution for forming the porous Ni-plated layer is preferably 10 to 70° C., more preferably 25 to 55° C. The current density is preferably 15 A/dm2 or less, more preferably 10 A/dm2 or less, still more preferably 0.5 to 7 A/dm2.
It is preferable to form an Ag strike plated layer directly on the porous Ni-plated layer. The composition of the plating bath and the plating conditions for forming the Ag strike plated layer are not limited, and known plating baths and plating conditions can be applied. Further, the plating baths and plating conditions listed in the examples below can be used.
Ag concentration in this Ag strike plating solution is preferably 0.01 to 15 g/L, more preferably 0.1 to 10 g/L, most preferably 0.2 to 5 g/L. Further, Ag strike plating is preferably performed by electroplating.
The temperature of the plating solution for forming the Ag strike plated layer is preferably 10 to 60° C., more preferably 15 to 55° C. The current density is preferably 8 A/dm2 or less, more preferably 5 A/dm2 or less, still more preferably 0.2 to 3 A/dm2.
It is preferable to form a main Ag-plated layer directly on the Ag strike plated layer. The composition of the plating bath and the plating conditions for forming the main Ag-plated layer are not limited, and the plating baths and plating conditions described in the examples below can be used. The thickness of the main Ag-plated layer may be set to a thickness at which a large number of pores are formed in the main Ag-plated layer, and formation by electroplating is preferable.
The Ag concentration in this main Ag-plated solution is preferably 5 to 200 g/L, more preferably 20 to 180 g/L, and most preferably 50 to 150 g/L.
The temperature of the plating solution for forming the main Ag-plated layer is preferably 10 to 60° C., more preferably 15 to 55° C. The current density is preferably 15 A/dm2 or less, more preferably 10 A/dm2 or less, still more preferably 0.5 to 7 A/dm2.
In the Ag strike plated layer and the main Ag-plated layer formed on the Ag strike plated layer, for example, even when the cross section of the Ag plating material is observed using a microscope, the thickness of the Ag strike plated layer is very thin, and the composition is also Ag and it is difficult to distinguish. Therefore, these Ag strike plated layer and the main Ag-plated layer are regarded as a single Ag-plated layer.
Next, the set of (step 3) to (step 5) is repeated. Then, a desired number (plurality) of two-layer plating structures are formed, and then, washing with water was appropriately performed, to obtain an Ag-plated material.
When producing electrical components such as switches, connectors, contacts or terminal parts using the Ag-plated material of the present embodiment as a material, the electronic components with excellent wear resistance and vibration resistance can be obtained.
The technical scope of the present invention is not limited to the above-described embodiments, and includes various modifications and improvements within a range where specific effects obtained by the constituent elements of the invention and their combinations can be derived.
Next, the present invention will be specifically described by showing examples. The present invention is not limited to the following examples. Contents not described below are the same as those described in the present embodiment.
First, a pure copper metal plate (C 1020) of 67 mm×50 mm×0.3 mm was prepared as a substrate, and this substrate and a separately prepared SUS plate were placed in an alkaline degreasing solution, and this substrate and the separately prepared SUS plate were placed in an alkaline degreasing solution, and electrolytically degreased at a voltage of 5 V for 30 seconds with the substrate as a cathode and the SUS plate as an anode. Thereafter, the substrate was pickled in a 3% sulfuric acid aqueous solution for 15 seconds. Washing with water was performed for 15 seconds between each operation.
Next, a plating solution (bath) that comprises an aqueous solution containing 540 g/L of nickel sulfamate tetrahydrate, 25 g/L of nickel chloride and 35 g/L of boric acid was prepared. Then, in the plating solution, with the substrate as a cathode and the separately prepared SK (sulfur-containing) nickel electrode plate as an anode, electroplating was performed at a current density of 7 A/dm2 and a liquid temperature of 50° C. while stirring at 500 rpm with a magnetic stirrer, to form an underlying Ni-plated layer having a thickness of 0.2 μm directly on the substrate.
Next, a plating solution that comprises 540 g/L of nickel sulfamate tetrahydrate, 25 g/L of nickel chloride, 35 g/L of boric acid, and 10 mL/L of top porous nickel RSN (manufactured by Okuno Chemical Industry Co., Ltd.) as an additive for nickel plating to obtain a nickel plating film having a porous structure, was prepared. A total amount of the plating solution was 1 L.
Then in the plating, with the substrate on which the underlying Ni-plated layer was formed (hereinafter, the intermediate is referred to as the “plated material”) as the cathode, and the SK nickel electrode plate as the anode, electroplating was performed for 500 seconds at a current density of 1 A/dm2 and a liquid temperature of 50° C., while stirring at 500 rpm with a magnetic stirrer, to form Ni having a volume corresponding to a non-porous Ni-plated layer having a thickness of 1 μm (set value), and form a porous Ni-plated layer directly on the underlying Ni-plated layer. The thickness of the porous Ni-plated layer (set value above) at that time is shown in Table 1 below.
For material after formation of the porous Ni-plated layer, the thickness of the Ni-plated layer at a central part of the sample was measured under conditions of a collimator diameter of 0.2 mm and a measurement time of 10 sec, using a fluorescent X-ray film thickness gauge (FT-110A manufactured by Hitachi High-Tech Science Co., Ltd.). As a result, it was confirmed that the film thickness was 1.2 μm, which was a set value. From a measurement principle of the fluorescent X-ray film thickness gauge, it is considered that the sum of the thicknesses of the underlying Ni-plated layer and the porous Ni-plated layer is measured as the thickness of the Ni-plated layer.
Next, a plating solution that comprises an aqueous solution containing 3 g/L of potassium silver cyanide and 90 g/L of potassium cyanide was prepared. Then in the plating solution, with a material to be plated as a cathode, and a platinum-coated titanium electrode plate as an anode, electroplating was performed for 10 seconds at a liquid temperature of 25° C. and a current density shown in the table, while stirring at 500 rpm with a magnetic stirrer, and then washing with water was performed for 15 seconds.
Next, a silver plating bath that comprises an aqueous solution containing 175 g/L of potassium silver cyanide, 95 g/L of potassium cyanide and 6 mg/L of selenium was prepared. In the plating bath, with the material to be plated as a cathode and a silver electrode plate with a purity of 99.99% or more as an anode, and in order to form the Ag-plated layer having a thickness of 1 μm (set value), electroplating was performed for 240 seconds at a current density of 0.5 A/dm2 and a liquid temperature of 18° C., while stirring at 500 rpm with a magnetic stirrer, to form a main Ag-plated layer directly on the Ag strike plated layer. The thickness of the Ag-plated layer in Table 1 is a total thickness (above set value) of the Ag strike plated layer and the main Ag-plated layer. After forming the main Ag-plated layer, washing with water was performed for 15 seconds.
For the material after the formation of the Ag-plated layer, the thickness of the Ag-plated layer at the center of the sample was measured under conditions of a collimator diameter of φ0.2 mm and a measurement time of 10 seconds, using a fluorescent X-ray film thickness gauge (FT-110A manufactured by Hitachi High-Tech Science Co., Ltd.). As a result, it was confirmed that the film thickness was 1 μm, which was a set value.
Next, (the set of) (step 3) to (step 5) are repeated twice to produce an Ag-plated material comprising a total of seven plated layers including the underlying Ni-plating layer (the Ag strike plated layer is counted as one layer together with the main Ag-plated layer).
The film thickness of each layer of the produced Ag-plated material was measured for Ag and Ni while etching the surface of the Ag-plated material in a depth direction by Ar sputtering (acceleration voltage 3 kV, emission current 25 mA), under conditions of an acceleration voltage of 10 kV, an irradiation current of 1×10−7 A, and a beam diameter of 100 μmφ, using an Auger electron spectrometer (Auger microprobe JAMP-7800 manufactured by JEOL Ltd.), to calculate the plating thickness from a depth profile of Ag and Ni. A measurement data step interval was 0.5 minutes between 0 and 300 seconds, 1 minute between 300 and 600 seconds, and 2 minutes above 600 seconds.
A measurement example is shown in
Local maximum and minimum values on each moving average line are plotted (not shown) (Ag moving average line has 2 local maximum values and 2 local minimum values, Ni moving average line has 3 local maximum values and 2 local minimum values, except for an outermost surface), and (further, a value obtained by dividing the sum of the adjacent (concentration) local maximum and minimum values of the moving average lines of each of Ag and Ni by 2 is defined as a median value, and the median value was plotted on a line segment between the local maximum and minimum values and set as a midpoint (indicated by a white circle in the figure).
In the moving average line of the profile of Ag in the depth direction, the midpoint on the side (outermost surface side) where the sputtering time is smaller than the local minimum value closest to the surface is the midpoint plotted on the moving average line (between the local minimum value and the outermost surface) where the concentration is the same as the midpoint plotted adjacent to the local minimum value and on the side of larger sputtering time.
Further, in the moving average line of the profile in the depth direction of Ag, the midpoint on the side (substrate side) where the sputtering time is larger than the local maximum value closest to the substrate is the midpoint plotted on the moving average line (between the local maximum value and the substrate) where the concentration is the same as the midpoint plotted adjacent to the local maximum value and on the side of smaller sputtering time.
In the moving average line of the profile of Ni in the depth direction, the midpoint on the side where the sputtering time is smaller than the local maximum value closest to the surface (outermost surface side) is the midpoint plotted on the moving average line (between the local maximum value and the outermost surface) where the concentration is the same as the midpoint plotted adjacent to the local maximum value and on the side of larger sputtering time.
In the moving average line of the profile of Ni in the depth direction, the midpoint on the side (substrate side) where the sputtering time is larger than the local maximum value closest to the substrate is the midpoint plotted on the moving average line (between the local maximum value and the substrate) where the concentration is the same as the midpoint plotted adjacent to the local maximum value and on the side of smaller sputtering time.
Then, in each moving average line of Ag and Ni, these adjacent midpoints are connected with a line, a length in a horizontal axis direction (sputtering time) of a section where the local maximum value is above this line was measured, and this length was converted into a thickness from an etching rate of SiO2 (etching rate of 20 nm/min), to obtain a plated film thickness of each of the Ag-plated layer and the Ni-plated layer.
For the Ag-plated layer on the outermost surface (indicated by 7 layers in the figure), the length (time) on the horizontal axis from the outermost surface (sputtering time is zero) to the midpoint closest to the outermost surface was converted to the above etching rate to obtain the thickness of the Ag-plated layer. The plating thickness defined in the claims of the present invention is calculated by such a method.
The result is that the thickness of the Ag-plated layer (7 layers) was μm, the thickness of the porous Ni-plated layer (6 layers) was 1.148 μm, the thickness of the Ag-plated layer (5 layers) was 0.739 μm, the thickness of the porous Ni-plated layer (4 layers) was 1.453 μm, the thickness of the Ag-plated layer (3 layers) was 0.69 μm, and the thickness of the porous Ni-plated layer (2 layers) was 1.099 nm, in an order from the surface side of the Ag-plated material.
In order to evaluate the wear resistance of the produced silver-plated material, and using a precision sliding tester CRS-G2050-DWA type, one of the silver-plated material is processed into an embossed shape (hemispherical shape) having an inner diameter R=1.5 mm, and after contacting the plate surface of the other (same plate-shaped) silver-plated material with a load of 5 N, it slides back and forth at a sliding speed of 1.67 mm/sec and a sliding distance of 5 mm, and the number of times until the copper substrate was exposed was measured. However, when the contact resistance exceeded 1 mΩ, it was determined as NG at that point. The result is that in the Ag-plated material of example 1, the copper substrate was not exposed even after sliding 1,000 times, and the contact resistance was less than 1 mΩ, indicating excellent wear resistance.
In order to evaluate the wear resistance of the produced silver-plated material, and using a precision sliding tester CRS-G2050-DWA manufactured by Yamazaki Seiki Laboratory Co., Ltd., one side of the silver-plated material was processed into an embossed shape (hemispherical shape) having an inner diameter R=1.5 mm, and after contacting the plate surface of the other (same plate-shaped) silver-plated material with a load of 5 N, it was reciprocated at a sliding speed of 0.2 mm/sec and a sliding distance of 0.1 mm, and the number of times until the contact resistance became 1 mΩ or more was measured.
The result is that the Ag-plated material of example 1 had a contact resistance of less than 1 mΩ even after sliding 50,000 times, indicating excellent vibration resistance.
The number density of pores and average diameter of the pores observed on the surface of the Ag-plated material were evaluated.
Using a laser microscope VK-X150 manufactured by Keyence Corporation, shape measurement was performed using an objective lens 100×, and a volume and an area were measured using a multi-file analysis application, with an analysis range of 100 μm×100 μm.
In the analysis range, with a height of a largest area detected as a surface (calculated by the analysis application), a portion where an object (plated surface) was not detected at a distance (position) of 0.5 μm in a depth direction from the surface is regarded as a pore (porous portion), the number and area of the pores were calculated. Then, an average area of the pores was calculated from the measured number of pores and the area of the pores, and a diameter of a circle having the same area as the average area of the pores was calculated as an average diameter of the pores. Further, a number density of the pores per unit area was calculated from the measurement result.
The result is that the number density of the pores was 9,300/mm2, and the average diameter of the pores was 16.3 μm.
The composition, evaluation results, etc. of the Ag-plated material in each example are shown in Table 1 below.
Ni 1 μm
Ni 1 μm
Ni 1 μm
Ni 1 μm
Ni 1 μm
Ni 1 μm
Ni 1 μm
Ni 1 μm
Ni 0.5 μm
Ni 0.5 μm
Ni 0.5 μm
Ni 0.5 μm
Ni 0.5 μm
Ni 0.5 μm
Ni 1 μm
Ni 1 μm
Ni 1 μm
Ni 1 μm
Ni 1 μm
Ni 3 μm
1 μm
1 μm
)
/dm2
/dm2
/dm2
/dm2
/dm2
/dm2
3000 times
/dm2
/dm2
/dm2
/dm2
,400
/dm2
/dm2
/dm2
/dm2
/dm2
/dm2
/dm2
/dm2
/dm2
/dm2
/dm2
/dm2
/dm2
/dm2
/dm2
/dm2
/dm2
/dm2
A value of a plate structure indicates a set-value of a thickness of each film
PNi indicates a Ni-plated layer
Com. Ex. = Comparative Example
indicates data missing or illegible when filed
In example 2, an Ag-plated material was produced in the same manner as in example 1, except that a plating solution that comprises an aqueous solution containing 540 g/L of nickel sulfamate tetrahydrate, 25 g/L of nickel chloride, 35 g/L of boric acid, and 8 mL/L of top porous nickel RSN (manufactured by Okuno Pharmaceutical Co., Ltd.) which is an additive for nickel plating to obtain a nickel-plated film having a porous structure, was used as a composition of the Ni plating solution for porous Ni plating, and a plating solution that comprises an aqueous solution containing 175 g/L of potassium silver cyanide, 95 g/L of potassium cyanide, and 55 mg/L of selenium, was prepared as a composition of the Ag plating solution for main Ag plating in the step of forming the main Ag-plated layer, with the material to be plated as a cathode and a silver electrode plate with a purity of 99.99% by mass or more as an anode, and in order to form the Ag-plated layer having a thickness of 1 μm, electroplating was performed for 24 seconds at a current density of 5 A/dm2 and a liquid temperature of 18° C., while stirring at 500 rpm with a stirrer, to form a main Ag-plated layer.
As a result of measuring and calculating the thickness of each plating of this Ag-plated material in the same manner as in the example, the thickness of the Ag-plated layer (7 layers) was 0.613 μm, the thickness of the porous Ni-plated layer (6 layers) was 0.998 μm, the thickness of the Ag-plated layer (5 layers) was 0.825 μm, the thickness of the porous Ni-plated layer (4 layers) was 1.384 μm, the thickness of the Ag-plated layer (3 layers) was 0.637 μm, and the thickness of the porous Ni-plated layer (2 layers) was 1.415 μm, in an order from the surface side of the Ag-plated material.
As a result of evaluating the wear resistance of this Ag-plated material in the same manner as in example 1, the copper substrate was not exposed even after sliding 1000 times, and the contact resistance was less than 1 mΩ, indicating excellent wear resistance.
Further, as a result of evaluating the vibration resistance of the Ag-plated material in the same manner as in example 1, the contact resistance was less than 1 mΩ even after sliding 50,000 times, indicating excellent vibration resistance.
Further, as a result of evaluating the number density of pores on the surface of the Ag-plated material and the average diameter of the pores in the same manner as in example 1, they were 10,800/mm2 and 16.2 μm, respectively.
An Ag-plated material was produced in the same manner as in example 2, except that (the set of) (steps 3) to (steps 5) was repeated once to make a total of 5 layers.
As a result of evaluating the wear resistance of this Ag-plated material in the same manner as in example 1, the copper substrate was not exposed even after sliding 1000 times, and the contact resistance was less than 1 mΩ, indicating excellent wear resistance.
Further, as a result of evaluating the vibration resistance of the Ag-plated material in the same manner as in example 1, the contact resistance was less than 1 mΩ even after sliding 13,000 times, indicating excellent vibration resistance. (The contact resistance after sliding 20,000 times exceeded 1 mΩ.)
Further, as a result of evaluating the number density of pores on the surface of the Ag-plated material and the average diameter of the pores in the same manner as in example 1, they were 25,500/mm2 and 7.1 nm, respectively.
An Ag-plated material was produced in the same manner as in example 2, except that (the set of) (step 3) to (step 5) were repeated three times to make a total of nine layers.
As a result of evaluating the wear resistance of this Ag-plated material in the same manner as in example 1, the copper substrate was not exposed even after sliding 1000 times, and the contact resistance was less than 1 mΩ, indicating excellent wear resistance.
Further, as a result of evaluating the vibration resistance in the same manner as in example 1, the contact resistance was less than 1 mΩ even after sliding 50,000 times, indicating excellent vibration resistance.
Further, as a result of evaluating the number density of pores on the surface of the Ag-plated material and the average diameter of the pores in the same manner as in example 1, they were 23,100/mm2 and 7.7 nm, respectively.
An Ag-plated product was produced in the same manner as in example 2, except that the electroplating time of the porous Ni plating was 250 seconds and the electroplating time of the main Ag plating was 12 seconds.
As a result of measuring and calculating the thickness of each plating of this Ag-plated material in the same manner as in the example, the thickness of the Ag-plated layer (7 layers) was 0.439 μm, the thickness of the porous Ni-plated layer (6 layers) was 0.425 μm, the thickness of the Ag-plated layer (5 layers) was 0.463 μm, the thickness of the porous Ni-plated layer (4 layers) was 0.561 μm, the thickness of the Ag-plated layer (3 layers) was 0.386 μm, and the thickness of the porous Ni-plated layer (two layers) was 0.439 μm, in an order from the surface side of the Ag-plated material.
As a result of evaluating the wear resistance of this Ag-plated material in the same manner as in example 1, there was no exposure of the copper substrate even after 400 times of sliding, and the contact resistance was less than 1 mΩ, indicating excellent wear resistance.
Further, as a result of evaluating the vibration resistance of the Ag-plated material in the same manner as in example 1, the contact resistance was less than 1 mΩ even after sliding 20,000 times, indicating excellent vibration resistance (the contact resistance after sliding 30,000 times exceeded 1 mΩ).
Further, as a result of evaluating the number density of pores on the surface of the Ag-plated material and the average diameter of the pores in the same manner as in example 1, they were 43,400/mm2 and 4.9 μm, respectively.
An Ag-plated material was produced in the same manner as in example 4, except that the electroplating time of the porous Ni plating was 250 seconds and the electroplating time of the main Ag plating was 12 seconds.
As a result of evaluating the wear resistance of this Ag-plated material in the same manner as in example 1, there was no exposure of the copper substrate even after 800 times of sliding, and the contact resistance was less than 1 mΩ, indicating excellent wear resistance.
Further, as a result of evaluating the vibration resistance of the Ag-plated material in the same manner as in example 1, the contact resistance was less than 1 mΩ even after sliding 50,000 times, indicating excellent vibration resistance.
Further, as a result of evaluating the number density of pores on the surface of the Ag-plated material and the average diameter of the pores in the same manner as in example 1, they were 38,800/mm2 and 4.5 μm, respectively.
An Ag-plated material was produced in the same manner as in example 3, except that the electroplating time of the porous Ni plating was 250 seconds and the electroplating time of the main Ag plating was 12 seconds.
As a result of evaluating the wear resistance of this Ag-plated material in the same manner as in example 1, the copper substrate was not exposed even after sliding 150 times, and the contact resistance was less than 1 mΩ, indicating excellent wear resistance.
Further, as a result of evaluating the vibration resistance of the Ag-plated material in the same manner as in example 1, the contact resistance was less than 1 mΩ even after sliding 10,000 times, indicating excellent vibration resistance. (The contact resistance after sliding 15,000 times exceeded 1 mΩ.)
Further, when the number density of pores on the surface of the Ag-plated material and the average diameter of the pores were evaluated in the same manner as in example 1, they were 36,600/mm2 and 6.0 μm, respectively.
In comparative example 1, an Ag-plated material was produced in the same manner as in example 2 except that only one two-layer plating structure was formed (3 layers in total without repeating (Step 3) to (Step 5)).
As a result of evaluating the wear resistance of this Ag-plated material in the same manner as in example 1, the copper substrate was exposed after siding 100 times, indicating insufficient wear resistance.
Further, as a result of evaluating the vibration resistance of the Ag-plated material in the same manner as in example 1, the contact resistance exceeded 1 mΩ after sliding 5,000 times, indicating insufficient vibration resistance.
Further, as a result of evaluating the number density of pores on the surface of the Ag-plated material and the average diameter of the pores in the same manner as in example 1, they were 18,800/mm2 and 9.0 μm, respectively.
An Ag-plated material was produced in the same manner as in example 1, except that only one two-layer plating structure was formed (3 layers in total without repeating (Step 3) to (Step 5)), and the electroplating time for the main Ag plating was 720 seconds.
As a result of evaluating the wear resistance of this Ag-plated material in the same manner as in example 1, the copper substrate was exposed after sliding 100 times, indicting insufficient wear resistance.
Further, as a result of evaluating the vibration resistance of the Ag-plated material in the same manner as in example 1, the contact resistance exceeded 1 mΩ after sliding 2,000 times, indicating insufficient vibration resistance.
Further, as a result of evaluating the number density of pores on the surface of the Ag-plated material and the average diameter of the pores in the same manner as in example 1, they were 12,400/mm2 and 9.4 μm, respectively.
An Ag-plated material was produced in the same manner as in example 1, except that only one two-layer plating structure was formed (3 layers in total without repeating (step 3) to (step 5)), and the electroplating time for the main Ag plating was 1,200 seconds.
As a result of evaluating the wear resistance of this Ag-plated material in the same manner as in example 1, the copper substrate was exposed after sliding 100 times, indicating insufficient wear resistance.
Further, as a result of evaluating the vibration resistance of the Ag-plated material in the same manner as in example 1, the contact resistance exceeded 1 mΩ after sliding 5,000 times, indicating insufficient vibration resistance.
Further, as a result of evaluating the number density of pores on the surface of the Ag-plated material in the same manner as in example 1, no pores were found (0/mm2).
An Ag-plated material was produced in the same manner as in example 1, except that the current density at the time of porous Ni plating was 3 A/dm2, the electroplating time was 165 seconds, the current density at the time of Ag strike plating was 2 A/dm2, only one two-layer plating structure was formed ((Step 3) to (Step 5) was not repeated, forming 3 layers in total), and the electroplating time for the main Ag plating was 1200 seconds.
As a result of evaluating the wear resistance of this Ag-plated material in the same manner as in example 1, the copper substrate was exposed after sliding 100 times, indicating insufficient wear resistance.
Further, as a result of evaluating the number density of pores on the surface of the Ag-plated material in the same manner as in example 1, no pores were found (0/mm2).
An Ag-plated material was produced in the same manner as in comparative example 4, except that the current density at the time of porous Ni plating was 5 A/dm2 and the electroplating time was 100 seconds.
As a result of evaluating the wear resistance of this Ag-plated material in the same manner as in example 1, the copper substrate was exposed after sliding 100 times, indicating insufficient wear resistance.
Further, as a result of evaluating the number density of pores on the surface of the Ag-plated material in the same manner as in example 1, no pores were found (0/mm2).
An Ag-plated material was produced in the same manner as in example 1, except that only one two-layer plating structure was formed ((Step 3) to (Step 5) were not repeated, forming 3 layers in total, and the electroplating time for this porous Ni plating was 1,500 seconds, and the electroplating time for the main Ag plating was 720 seconds.
As a result of evaluating the wear resistance of this Ag-plated material in the same manner as in example 1, the contact resistance exceeded 1 mΩ after sliding 100 times, indicating insufficient wear resistance.
Further, as a result of evaluating the vibration resistance of this Ag-plated material in the same manner as in example 1, the contact resistance exceeded 1 mΩ after sliding 3,000 times, indicating insufficient vibration resistance.
Further, as a result of evaluating the number density of pores on the surface of the Ag-plated material and the average diameter of the pores in the same manner as in example 1, they were 4,600/mm2 and 31.2 μm, respectively.
In comparative example 7, an Ag-plated material was produced in the same manner as in example 1, except that a Ni-plated layer having a thickness of 1 μm was formed without providing the underlying Ni plating, and without adding an additive (top porous nickel RSN) to the Ni plating solution in step 3 of example 1 (that is, without providing porous Ni-plated layer), and the current density of Ag strike plating was 2 A/dm2.
As a result of evaluating the wear resistance of this Ag-plated material in the same manner as in example 1, the copper substrate was exposed after sliding 100 times, indicating insufficient wear resistance.
Further, as a result of evaluating the vibration resistance of this Ag-plated material in the same manner as in example 1, the contact resistance exceeded 1 mΩ after sliding 5,000 times, indicating insufficient vibration resistance.
Further, as a result of evaluating the number density of pores on the surface of the Ag-plated material in the same manner as in example 1, no pores were found (0/mm2).
In comparative example 8, an Ag-plated material was produced in the same manner as in example 2, except that a Ni-plated layer having a thickness of 1 μm was formed without providing the underlying Ni-plated layer and without adding the additive (top porous nickel RSN) to the Ni plating solution in step 3 of example 1 (that is, without providing the porous Ni-plated layer), and on top of this, only one Ag-plated layer having a thickness of 5 μm was formed, with a current density of the Ag strike plating set as 2 A/dm2, and the time for the main Ag plating set as 120 seconds.
As a result of evaluating the wear resistance of this Ag-plated material in the same manner as in example 1, the copper substrate was exposed after sliding 100 times, indicating insufficient wear resistance.
Further, as a result of evaluating the vibration resistance in the same manner as in example 1, the contact resistance exceeded 1 mΩ after sliding times, indicating insufficient vibration resistance.
Further, as a result of evaluating the number density of pores on the surface of the Ag-plated material in the same manner as in example 1, no pores were found (0/mm2).
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As shown in Table 1, each example shows good wear resistance and vibration resistance, but each comparative example does not show the same level of wear resistance and vibration resistance as each example.
The purity of Ni in the Ni-plated layer and the porous Ni-plated layer of examples and comparative examples is 99% by mass or more, and the purity of Ag in both the Ag strike plating layer and the main Ag-plated layer is 99% by mass or more.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-214110 | Dec 2020 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/026414 | 7/14/2021 | WO |
