JP2017197825A - Electroformed structure and structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electroformed structure having an electroformed material excellent in tensile strength by controlling a ratio of nickel and cobalt and conducting a heat treatment if needed, and a structure using the electroformed material.SOLUTION: An electroformed structure has an electroformed material with Co content of over 40 mass% and 55 mass% or less, the balance Ni with inevitable impurities, and tensile strength of at least 1200 N/mm, the structure is constituted by arranging the electroformed material on a substrate surface or a part of substrate or forming with only the electroformed material. The electroformed structure also may have an electroformed material with Co content of over 30 mass% and 60 mass% or less, the balance Ni with inevitable impurities and heat treated at 200 to 300°C.SELECTED DRAWING: None

Description

The present invention relates to an electroformed structure (electroformed material itself and electroformed material) having an electroformed material (electroformed alloy) containing nickel (Ni) and cobalt (Co) used in general structures, machines and parts thereof. ) And a structure.

In the nickel-cobalt plating layer, the higher the cobalt content, the better the wear resistance. It has been proposed to contain Co-based plating.

Further, Patent Document 2 proposes a cobalt-nickel alloy material in which layers with a high amount of nickel and layers with a low amount of nickel are alternately stacked. This alloy not only has excellent heat resistance, corrosion resistance, and wear resistance, but also exhibits elongation. Has been disclosed to be a significantly improved article and can be optimally applied to steel continuous casting molds.

JP 2000-263190 A Japanese Patent Laying-Open No. 2015-166383

However, Patent Document 1 relates to a casting mold for continuous casting, and contains 70 wt% or more of Co. Therefore, although it is strong against wear resistance and corrosion resistance, there is a problem that tensile strength is as small as 400 to 600 MPa. It was.
In addition, the article described in Patent Document 2 has a small nickel ratio layer and a large layer thickness of 1 to 500 μm, respectively, and the difference in ratio between the small nickel ratio layer and the large layer is 1 to 20 wt%. There was a problem that the tensile strength was as small as 600 to 700 MPa, the use was limited, and the construction was complicated and costly.

The present invention has been made in view of such circumstances, and an electroformed structure having an electroformed material excellent in tensile strength by controlling the ratio of nickel and cobalt and performing heat treatment if necessary, and the electroformed An object is to provide a structure using a material.

The electroformed structure according to the first invention that meets the above object has a Co content of more than 40% by mass and 55% by mass or less, the balance being made of Ni and inevitable impurities, and a tensile strength of at least 1200 N / mm ² ( The electroformed material is 1200 MPa.
When describing the composition of the electroformed material, the Co content is specified, and the composition of the balance (Ni and inevitable impurities) is described as the Ni content.

In addition, the electroformed structure according to the second invention that meets the above object has a Co content of more than 30% by mass and 60% by mass or less, and the balance is made of Ni and inevitable impurities, and is heat-treated at 200 to 400 ° C. Have electroformed material.
Here, the heat treatment time is preferably at least 0.5 hour, for example, 0.5 to 48 hours.

Furthermore, in the structure according to the third invention, the electroformed material according to the first invention is provided on the surface of the substrate or a part of the substrate, for example, by plating or the like, or the electroformed material Is formed only from.
The thickness of the electroformed material is set according to the application.

In the electroformed structure according to the first invention, the tensile strength of the electroformed material can be at least 1200 N / mm ² by controlling the ratio of nickel and cobalt contained in the electroformed material. The material can be applied to various uses.

In the electroformed structure according to the second aspect of the present invention, the mechanical properties of the electroformed material are maintained by controlling the ratio of nickel and cobalt and heat-treating at 200 to 400 ° C. The range of application of the electroformed material can be further expanded.

In the structure according to the third aspect of the invention that meets the above-mentioned purpose, the electroformed material of the first aspect is provided on the surface of the base material or a part of the base material. A large-sized structure can be easily produced by combining a plurality of base materials each having an electroformed material on the surface with a structure having a simple shape. Further, by removing the base material after the electroformed material is formed, a structure formed only from the electroformed material can be easily produced.

It is explanatory drawing of the plating apparatus which manufactures the electroformed material in the electroformed structure which concerns on one embodiment of this invention. It is a graph which shows the quantitative relationship between the cobalt concentration in a nickel-cobalt alloy plating solution, and the cobalt content in a nickel-cobalt alloy plating film. It is a graph which shows the relationship between the heat processing temperature and the mechanical property of the electroforming material of the pure nickel formed on the titanium plate using the nickel plating liquid. It is a graph which shows the relationship between the heat processing temperature and mechanical property of the electrocast material of Co10 mass%-Ni90 mass% formed on the titanium plate using the nickel-cobalt alloy plating solution. It is a graph which shows the relationship between the heat processing temperature and mechanical property of the electroforming material of Co20 mass% -Ni80 mass% formed on the titanium plate using the nickel-cobalt alloy plating solution. It is a graph which shows the relationship between the heat processing temperature and mechanical property of the electroforming material of Co30 mass% -Ni70 mass% formed on the titanium plate using the nickel-cobalt alloy plating solution. It is a graph which shows the relationship between the heat processing temperature of the electroformed material of Co40 mass% -Ni60 mass% formed on the titanium plate using the nickel-cobalt alloy plating solution, and mechanical properties. It is a graph which shows the relationship between the heat processing temperature and mechanical property of the electrocast material of Co50 mass%-Ni50 mass% formed on the titanium plate using the nickel-cobalt alloy plating solution. It is a graph which shows the relationship between the heat processing temperature and mechanical property of the electrocast material of Co60 mass%-Ni40 mass% formed on the titanium plate using the nickel-cobalt alloy plating solution. It is a graph which shows the relationship between the heat processing temperature and mechanical property of electrocast material of Co70 mass% -Ni30 mass% formed on the titanium plate using the nickel-cobalt alloy plating solution. It is a graph which shows the relationship between the heat processing temperature and mechanical property of the electrocast material of Co80 mass%-Ni20 mass% formed on the titanium plate using the nickel-cobalt alloy plating solution. It is a graph which shows the relationship between the heat processing temperature of the electroforming material of Co90 mass% -Ni10 mass% formed on the titanium plate using the nickel-cobalt alloy plating solution, and mechanical properties. It is a graph which shows the relationship between the heat processing temperature and mechanical property of the electrocast material of pure cobalt formed on the titanium plate using the cobalt plating solution. It is explanatory drawing which shows the range of cobalt content when the tensile strength in an electrocast material is 1200 N / mm < ² > or more, 0.2% yield strength is 800 N / mm < ² > or more, and Vickers hardness becomes 400 or more. It is a graph which shows the relationship between the cobalt content in an electroformed material, and the tensile strength after heat-processing an electroformed material in the temperature range of 200-450 degreeC.

Next, embodiments of the present invention will be described with reference to the accompanying drawings for understanding of the present invention.
First, a method for producing an electroformed material in the electroformed structure according to the first embodiment of the present invention will be described. The electroformed structure has a Co content of more than 40% by mass and 55% by mass or less, preferably a Co content of more than 40% by mass and 45% by mass, with the balance being Ni and inevitable impurities. The electroformed material 10 has a strength of at least 1200 N / mm ² (1200 MPa).
As shown in FIG. 1, in the production of the electroformed material 10, a nickel plating solution in which nickel and various additives are dissolved is placed in a plating tank 11, a titanium plate 12 is disposed as a cathode, a cobalt plate 13 is disposed as an anode, Nickel plates 14 are respectively disposed. A first power supply 15 is connected between the titanium plate 12 and the cobalt plate 13, and a second power supply 16 is connected between the titanium plate 12 and the nickel plate 14.

Since cobalt is not contained in the nickel plating solution, for example, a cobalt elution electrode (not shown) made of stainless steel (SUS) is arranged around the cobalt plate 13, and the titanium plate of the first power supply 15. The connection terminal on the 12 side is connected to the cobalt elution electrode, and a current is passed between the cobalt elution electrode and the cobalt plate 13 by the first power supply 15, and cobalt is eluted from the cobalt plate 13 into the nickel plating solution. Thus, a nickel-cobalt alloy plating solution 17 is produced. At this time, the amount of cobalt dissolved from the cobalt plate 13 into the nickel plating solution is a quantitative relationship between the cobalt concentration in the nickel-cobalt alloy plating solution and the cobalt content in the nickel-cobalt alloy plating film (see FIG. 2), the ratio is determined from the ratio of nickel and cobalt of the electroformed material 10 to be manufactured. Here, the above quantitative relationship is that a nickel-cobalt alloy plating film is prepared using a nickel-cobalt alloy plating solution in which nickel and cobalt are dissolved at various concentrations, and the produced nickel-cobalt alloy plating film It is created by chemical analysis.
The nickel-cobalt alloy plating solution 17 can also be produced by dissolving various additives in a plating solution in which the concentrations of nickel and cobalt are adjusted based on the above quantitative relationship.

When the preparation of the nickel-cobalt alloy plating solution 17 is completed, the first and second power sources 15 and 16 are operated to place the titanium plate 12 and the cobalt plate 13 between the titanium plate 12 and the nickel plate 14. Current flows through each. Note that the ratio of the current flowing between the titanium plate 12 and the cobalt plate 13 and the current flowing between the titanium plate 12 and the nickel plate 14 is set according to the ratio of nickel and cobalt constituting the electroformed material 10. To do. Thus, a nickel-cobalt alloy plating layer (or simply called an alloy plating layer) in which nickel and cobalt are mixed at a constant ratio is formed on the surface of the titanium plate 12. And the electrocast material 10 is produced by forming an alloy plating layer until it becomes a predetermined shape.
In the nickel-cobalt alloy plating solution 17, cobalt and nickel corresponding to the weight of cobalt and nickel deposited on the titanium plate 12 are dissolved from the cobalt plate 13 and the nickel plate 14, respectively. The contents of cobalt and nickel in the liquid 17 are maintained at the contents at the start of plating.

When the production of the electroformed material 10 on the titanium plate 12 is completed, the first and second power sources 15 and 16 are operated to connect the titanium plate 12 and the cobalt plate 13 between the titanium plate 12 and the nickel plate 14. The current flowing between them is stopped. Then, the electroformed material 10 is pulled up from the nickel-cobalt alloy plating solution 17 together with the titanium plate 12. Then, after the electroformed material 10 and the titanium plate 12 are washed, the electroformed material 10 is separated from the titanium plate 12. An electroformed structure is formed from the separated electroformed material 10 or by combining a plurality of electroformed materials 10 processed as required.

Next, a method for producing an electroformed material in the electroformed structure according to the second embodiment of the present invention will be described. The electroformed structure has a Co content of more than 30% by mass and 60% by mass or less, preferably a Co content of 50% by mass or more and 60% by mass or less, with the balance being Ni and inevitable impurities, It has an electroformed material heat-treated at 400 ° C. Here, the method for producing the electroformed material has a process for producing the electroformed material and a heat treatment step for the electroformed material at 200 to 400 ° C., and the method for producing the electroformed material is the first embodiment. Since it can carry out similarly to the preparation methods of the electroformed material 10 in the electroformed structure of this, detailed description is abbreviate | omitted.

In the heat treatment step of the electroformed material, the electroformed material separated from the titanium plate 12 is set in a heat treatment furnace and heated to 200 to 400 ° C. in a vacuum or in an inert gas atmosphere (for example, in an argon gas atmosphere), Hold for 0.5 to 48 hours and then slowly cool. And an electroformed structure is comprised from the electroformed material annealed or combining the several electroformed material which processed as needed.
By heat-treating the electroformed material at 200 to 400 ° C., the strain accompanying the internal stress of the electroformed material (the electrodeposition stress introduced when the alloy plating layer is formed) without changing the structure of the electroformed material. The mechanical properties of the electroformed material are improved. Thereby, it becomes possible to further expand the application range of the electroformed material.

In the method for manufacturing a structure according to the third embodiment of the present invention, a base material is attached to the titanium plate 12, the first and second power sources 15 and 16 are operated, and the titanium plate 12 is interposed via the base material. A current is passed between the cobalt plate 13 and the nickel plate 14.
The method for producing the electroformed material is the same as the method for producing the electroformed material 10 in the electroformed structure according to the first embodiment, and thus detailed description thereof is omitted. Thereby, an alloy plating layer can be formed on the base material surface, and an electroformed material (thickness is set according to the application) can be provided integrally with the base material surface.

Here, the material of the base material is selected from conductive materials such as steel, stainless steel, copper, or copper alloy material according to the purpose of the structure, and the shape of the base material is the structure of the structure. It is processed into a predetermined shape according to the shape. By processing the base material in advance, a structure having a complicated shape can be easily produced. Moreover, a large-sized structure can be easily produced by combining a plurality of base materials provided with an electroformed material on the surface.
In addition, it is preferable to form an uneven surface on the surface of the base material (surface on which the electroformed material is provided) by, for example, blasting. Thereby, the joint strength between a base material and an electroformed material can be improved.
Further, an electrodeposition layer having a predetermined material and a predetermined shape can be formed on the titanium plate 12 and used as a base material.
For example, when aluminum (including an aluminum alloy) is used as the base material, after forming an electroformed material on the base material, the base material is pulled up from the nickel-cobalt alloy plating solution and washed, and then the melting point of aluminum The base material can be melted and removed from the electroformed material by heating to 1, or the base material can be dissolved and removed from the electroformed material by immersing in an acid solution or an alkaline solution. A structure formed of only the material can be easily manufactured.
Further, instead of the titanium plate, a base material can be used as a cathode, and an electric current can be passed between the base material and the cobalt plate, or between the base material and the nickel plate to form an electroformed material on the base material.
It is also possible to produce a structure in which an electroformed material is provided on a part of the base material.

Next, examples performed to confirm the operation and effect of the present invention will be described.
Heat treatment temperature and mechanical properties of pure nickel electroformed material formed on a titanium plate using a nickel plating solution (tensile strength (N / mm2), 0.2% proof stress (N / mm2), Vickers hardness (hereinafter, The relationship between the hardness (referred to as Hv) and the elongation (%)) is shown in FIG.
Further, Co 10 mass% -Ni 90 mass% to Co 90 mass% formed on a titanium plate using each nickel-cobalt alloy plating liquid whose cobalt content was adjusted to 90 mass% at a pitch of 10 mass% based on the nickel plating liquid. The relationship between the heat treatment temperature and the mechanical properties in each of the electroformed materials of Ni of 10 mass% is shown in FIGS.
Further, FIG. 13 shows the relationship between the heat treatment temperature and mechanical properties of a pure cobalt electroformed material formed on a titanium plate using a cobalt plating solution.

3 to 13, the tensile strength, 0.2% proof stress, and hardness (Hv) of the electroformed material that is not heat-treated are read, and the tensile strength is 1200 N / mm ^{2 with} respect to the cobalt content of the electroformed material. or 0.2% proof stress 800 N / mm ² or more, when the respective ○ mark hardness (Hv) is 400 or more, a tensile strength of less than 1200 N / mm ^2, less than 0.2% yield strength 800 N / mm ^2, The case where the hardness (Hv) is less than 400 is indicated as x, as shown in FIG.

From FIG. 14, the lower limit value of the cobalt content when the tensile strength of the electroformed material is 1200 N / mm ² or more exists in the range of 10 to 20% by mass, and the upper limit value exists in the range of 50 to 60% by mass. I understand that. Further, it can be seen that the lower limit value of the cobalt content when the 0.2% proof stress is 800 N / mm ² or more exists in the range of 20 to 30% by mass, and the upper limit value exists in the range of 50 to 60% by mass. . Furthermore, it can be seen that when the hardness (Hv) is 400 or more, the lower limit of the cobalt content is in the range of 30 to 40% by mass, and the upper limit is in the range of 60 to 70% by mass.
In particular, when the cobalt content of the electroformed material exceeds 40% by mass and is equal to or less than 45% by mass, both the tensile strength, 0.2% proof stress, and hardness (Hv) of the electroformed material can be increased.

From FIG. 3 to FIG. 13, the tensile strength of the electroformed material heat treated at 200 ° C., 240 ° C., 300 ° C., 350 ° C., and 450 ° C. is read, and the relationship between the cobalt content and the tensile strength is shown in FIG. It becomes like this.
From FIG. 15, with respect to the nickel electroformed material (cobalt content is 0%) and the cobalt electroformed material (cobalt content is 100%), the cobalt content is in the range of more than 30% by mass and 60% by mass or less. By performing heat treatment at 200 to 400 ° C., an improvement in tensile strength is observed. And in the electroformed material whose Co content is 40% by mass or more and 60% by mass or less, it is possible to improve the tensile strength of the electroformed material to a level exceeding 1200 MPa, particularly by performing a heat treatment at 200 to 300 ° C. I understand that there is.

The present invention is not limited to the above-described embodiment, and the configuration thereof can be changed without changing the gist of the present invention.
Moreover, although this invention was demonstrated using the specific number, numerical limitation can be removed in the range which does not change a summary.
For example, an electroformed structure is made of an electroformed structure in which the Co content is more than 40% by mass and 55% by mass or less, tungsten and molybdenum are each 0.1% by mass to 5% by mass, and the balance is Ni and inevitable impurities. It can be set as the structure which has material. Further, the electroformed structure has a Co content of more than 30% by mass and 60% by mass or less, tungsten and molybdenum of 0.1% by mass or more and 5% by mass or less, with the balance being Ni and inevitable impurities, It can be set as the structure which has the electroformed material heat-processed at -400 degreeC. By adding tungsten and molybdenum, respectively, the hardness and corrosion resistance of the electroformed structure can be increased.

10: Electroformed material, 11: Plating tank, 12: Titanium plate, 13: Cobalt plate, 14: Nickel plate, 15: First power source, 16: Second power source, 17: Nickel-cobalt alloy plating solution

Claims (4)

An electroformed structure comprising an electroformed material having a Co content of more than 40% by mass and 55% by mass or less, the balance being Ni and inevitable impurities, and a tensile strength of at least 1200 N / mm ² . An electroformed structure comprising an electroformed material having a Co content of more than 30% by mass and not more than 60% by mass, the balance being made of Ni and inevitable impurities and heat-treated at 200 to 400 ° C. 3. The electroformed structure according to claim 2, wherein the heat treatment time is at least 0.5 hour. 2. The structure according to claim 1, wherein the electroformed material according to claim 1 is provided on a surface of a base material or a part of the base material, or is formed only from the electroformed material.

Images