JP6825470B2 - Test power wearing cathode plate and its manufacturing method - Google Patents

Description

The present invention relates to a test electrode wearing cathode plate for confirming the electrodeposition status of a target metal before the present operation in an electrowinning method for non-ferrous metals, and a method for manufacturing the same.

In the electrowinning method for non-ferrous metals, there is known a cathode plate in which dozens of circular electrodeposited portions are provided on both sides of a titanium plate and the other parts are masked (masked) with an insulating paint. As the anode for this, an insoluble anode plate substantially similar to the above-mentioned basic outer shape of the cathode is used. An electrolytic solution containing a target metal ion is supplied to the electrolytic cell, and the anode plate and the cathode plate are immersed in the electrolytic cell to perform electrodeposition (electrolysis).

In this electrowinning method, in the cathode used in a general operation, circular electrodeposited portions occupying an area approximately equal to that of the masking portion are uniformly arranged in a staggered pattern on each surface of the metal plate. The staggered arrangement is an arrangement in which a plurality of objects are arranged continuously in the horizontal direction at predetermined intervals, whereas in the next line, the objects are arranged alternately by being horizontally shifted by half of the predetermined intervals. To say.

For example, Patent Document 1 knows a method for producing a specially shaped electric nickel for plating containing a trace amount of sulfur. In purification by electrolysis of metals such as nickel, a base plate made of a material that can be used repeatedly, such as titanium, which is different from the metal collected by electrowinning, is used as the cathode, and after electrolysis for a predetermined time, the electrodeposit is used as the base plate. A method of more peeling and manufacturing is generally performed. At this time, by masking the cathode with an insulating material, an electrodeposited object having an arbitrary special shape can be obtained.

Nickel electronickel used as an anode for plating is often preferred to have a rounded, small-lump shape with no sharp corners from the viewpoint of filling property and handling in the anode box during use. Therefore, when such specially shaped nickel nickel is produced by electrolysis, it is produced by energizing using a cathode masked so as to have a large number of circular electrodeposition portions on the surface and peeling off the electrodeposited material. doing.

Further, in Patent Document 2, regarding the cathode used for electrowinning specially shaped nickel for plating, the electrodeposited portion formed by masking with an insulator is prevented from shrinking or deforming, and the special shape of the electrodeposited portion is described. The methods that can be maintained are disclosed.

As disclosed in Patent Documents 1 and 2, dozens of circular electrodeposition portions are arranged in a staggered pattern on both sides of the titanium plate, and the other parts are masked with an insulating paint so as to expose the circular electrodeposition surface. A cathode plate (hereinafter, also referred to as a "staggered cathode plate") is known. As a result of electrodeposition by the staggered cathode plate, a disk-shaped electrodeposited product is obtained in which the disk surface is flat and the peripheral portion includes a bulge about the thickness of the disk rather than the flat surface.

However, the disadvantage of the staggered cathode plate is that there is a loss in the number of metal plates taken with respect to the surface shape. Even if the first row is arranged efficiently with respect to the plate width, there is a range in which electrodeposition cannot be obtained in the vicinity of both ends in the width direction of the second and fourth rows due to the staggered arrangement. Therefore, there is a disadvantage that the production efficiency of the electrodeposited product is wasted.

JP-A-2002-302787 Japanese Unexamined Patent Publication No. 2008-106292

As described above, in the electrowinning method for non-ferrous metals, a test electrode wearing cathode plate for confirming the electrodeposition status of the target metal is required before the main operation, and a more convenient one has been desired. .. As this test electrode wearing cathode plate, a titanium plate or the like provided with a plurality of electrodeposited portions on at least one surface and masked with an insulating paint is used for a simulated experiment conducted prior to the main operation. In particular, there has been a demand for a test piece that can simplify the preliminary experiment for pursuing the optimum shape of the cathode electrodeposited surface in order to respond to changes in the electrolytic solution and other environments that change with each operation.

The method for producing specially shaped nickel for plating disclosed in Patent Document 1 is an electrolysis method in which the surface is masked with an insulating material and a plurality of circular exposed surfaces other than the masked portion are used as electrodeposition portions of the cathode. .. However, regarding the shape of the electrodeposited surface, the range where the electrodeposited material cannot be obtained is minimized to increase the number of electrodeposited products to enable efficient production, and the four corners (corners) of the electrodeposited surface. In addition to the abnormal growth state corresponding to the radius of curvature R value of the chamfered corners, the minimum required radius of curvature R value, etc. is not specialized for test pieces that can be easily known with only one test electrodeposition. Absent. In other words, there is no disclosure of the test electrode wearing cathode plate for preliminary experiments that is carried out prior to this operation.

Further, the method for manufacturing a cathode for electrowinning of specially shaped electronickel disclosed in Patent Document 2 prevents the electrodeposited portion formed by masking with an insulator from shrinking or deforming, and is special in the electrodeposited portion. It is a method of maintaining the shape. Again, this is not disclosed for the test electrode wearing cathode plate for preliminary experiments conducted prior to this operation.

The present invention has been made in view of the above problems, and the present invention is made in addition to minimizing the range in which an electrodeposited product cannot be obtained and further increasing the number of electrodeposited products to enable efficient production. A test piece that allows you to know the electrodeposition status of the target metal before operation, that is, a rounded corner with the four corners (corners) of the electrodeposition surface chamfered in order to obtain high quality and stable without abnormal growth of the target metal. It is an object of the present invention to provide a test electrode wearing cathode plate which can easily know the correlation between the radius of curvature R value and the abnormal growth.

One aspect of the present invention is test electrodeposition in which a non-ferrous metal is immersed in the electrolytic solution (90) for test electrodeposition in order to confirm the electrodeposition morphology according to the conditions of the electrolytic solution (90) in the electrowinning operation. Cathode plate (100)
A plurality of protrusions (21 to 22) were formed as electrodeposited surfaces (21 to 32) on at least one surface (18) in a grid pattern of J rows and K columns (both J and K are natural numbers of 1 or more). Metal plate (17) and
A non-conductive film (50) in which a mask (13) having a predetermined shape is applied to a surface (19) other than the protrusions (21 to 32) of the metal plate (17).
Have,
The shape of the protrusions (21 to 32) visually recognized in a plane is
Based on a square with a predetermined length (E) on one side,
The four corners (41 to 44) of the square are chamfered with rounded corners at a specified radius of curvature R value.
The radius of curvature R value that forms the rounded corners is
It is a configuration defined to change based on the difference in the position of the grid-like arrangement.

Further, in the test electrode wearing cathode plate (100) according to one aspect of the present invention, the radius of curvature R value is
The first line counting from one end of the grid arrangement is the smallest,
The last J-th line counted to the other end of the grid-like arrangement is the maximum.
It is preferable to set the same on the same line.

Further, in the test electrode wearing cathode plate (100) according to one aspect of the present invention, the order in which the radius of curvature R value increases is determined.
Count the number of rows J from one end of the grid-like arrangement,
First, advance one line at the position where you advanced two lines,
If there is a place to return from the position where the two lines are advanced, the order is advanced by one line, but if there is no place to return, the order is repeated to advance the order by one at the position where the position is further advanced by two lines.
The number of lines J is 1,3,2,4,6,5,7,9,8,10, ..., J, in that order.
It is preferable to change the radius of curvature R value so as to gradually increase it.

Further, in the test electrode wearing cathode plate (100) according to one aspect of the present invention, the basic outer shape of the metal plate (17) visually recognized in a plane is a vertically long rectangle.
The number of rows J of the grid-like arrangement is in descending order or ascending order in the vertical direction of the rectangle.
The number of columns K in the grid arrangement is ascended in the horizontal direction of the rectangle.
The number of lines J is 2 or more and 10 or less.
The number of columns K is 2 or more and 10 or less.
The height (H) of the protrusions (21 to 32) is 50 μm or more and 1000 μm or less.
The minimum film thickness (T) of the non-conductive film (50) is
It is preferable that the height (H) of the protrusions (21 to 32) is the same as the height (H) at the position (M) passing between the centers of the adjacent protrusions (21 to 32).

Further, in the test electrode wearing cathode plate (100) according to one aspect of the present invention,
The minimum film thickness (T) of the non-conductive film (50) at a position passing between the centers (M) of the adjacent protrusions (21 to 32), and
The height (H) of the protrusions (21 to 32) and
The difference (G) is preferably 200 μm or less.

Further, in the test electrode wearing cathode plate (100) according to one aspect of the present invention, the metal plate (17) is preferably made of titanium or stainless steel.

Further, the test electrode wearing cathode plate (100) according to one aspect of the present invention is preferably used for producing nickel for plating.

Further, one aspect of the present invention is a test electrodeposition in which the electrolytic solution (90) is immersed in the electrolytic solution (90) for test electrodeposition in order to confirm the electrodeposition morphology according to the conditions of the electrolytic solution (90) in a non-metal electrowinning operation. A method for manufacturing a worn cathode plate (100).
On at least one surface (18) of the metal plate (17), a plurality of protrusions (21 to 32) are arranged on the electrodeposited surface (21) in a grid pattern of J rows and K columns (both J and K are natural numbers of 1 or more). The first step (S10) formed as ~ 32) and
A mask (13) having a predetermined shape by a non-conductive film (50) on a surface (40) other than the metal plate (17) in which a plurality of protrusions (21 to 22) are formed as electrodeposited surfaces (21 to 32). ) In the second step (S20),
In the first step (S10),
The shape of the protrusions (21 to 32) visually recognized in a plane is
Based on a square with a predetermined length (E) on one side,
The four corners (41 to 44) of the square are chamfered with rounded corners at a specified radius of curvature R value.
The radius of curvature R value that forms the rounded corners is
It is defined to change based on the difference in the position of the grid arrangement.
This is a method for manufacturing a cathode plate (100) for wearing a test electric wire.

Further, in the method for manufacturing the test electrode wearing cathode plate (100) according to one aspect of the present invention, the radius of curvature R value is
The first line counting from one end of the grid arrangement is the smallest,
The last J-th line counted to the other end of the grid-like arrangement is the maximum.
It is preferable that they are set to be the same in the same line.

Further, in the method for manufacturing the test electrode wearing cathode plate (100) according to one aspect of the present invention, the order in which the radius of curvature R value increases is determined.
Count the number of rows J from one end of the grid-like arrangement,
First, advance one line at the position where you advanced two lines,
If there is a place to return from the position where the two lines are advanced, the order is advanced by one line, but if there is no place to return, the order is repeated to advance the order by one at the position where the position is further advanced by two lines.
The number of lines J is 1,3,2,4,6,5,7,9,8,10, ..., J, in that order.
It is preferable to change the radius of curvature R value so as to gradually increase it.

As described above, according to the present invention, the range in which electrodeposition products cannot be obtained is minimized, and the number of electrodeposition products to be taken is increased to enable efficient production. A test piece that can know the electrodeposition status of a metal, that is, the radius of curvature R value of a rounded corner with chamfered four corners (corners) of the electrodeposited surface in order to obtain high quality and stable without abnormal growth of the target metal. And, it is possible to provide a test electrode wearing cathode plate which can easily know the correlation between the abnormal growth and the abnormal growth.

It is a perspective view which shows the use state of the test electrode wearing cathode plate (hereinafter, also referred to as "this cathode plate") which concerns on one Embodiment of this invention. It is a perspective view which showed the outline of this cathode plate. The radius of curvature R value (hereinafter, simply referred to as "R value") of the rounded corners of the four corners (corners) of the electrodeposited surface changes based on the difference in the positions where a plurality of protrusions are arranged in a grid pattern. (Hereinafter, also referred to as “change of R value according to arrangement”), FIG. 3 (A) is a plan view, and FIG. 3 (B) is a sectional view taken along line YY. 3 (C) is a sectional view taken along line XX, FIG. 3 (D) is an enlarged view of the broken line circled portion of FIG. 3 (C), and FIG. 3 (E) is a broken line circled portion of FIG. 3 (D). The enlarged view of is shown respectively. It is a flowchart for demonstrating the procedure of the manufacturing method (hereinafter, also referred to as "the present method") of the test electrode wearing cathode plate which concerns on one Embodiment of this invention. It is a partial plan enlarged view for demonstrating the result of test electrodeposition on this cathode plate in the use state of FIG. It is a perspective view for demonstrating the relationship between the R value and abnormal growth, FIG. 6A is a product generated in a distorted shape because the R value is small, and FIG. 6B is a large R value. , Products produced in a shape close to the ideal, respectively.

Hereinafter, preferred embodiments of the present invention will be described in detail. It should be noted that the present embodiment described below does not unreasonably limit the content of the present invention described in the claims, and all the configurations described in the present embodiment are essential as a means for solving the present invention. Is not always the case.

FIG. 1 is a perspective view showing a usage state of the cathode plate. As shown in FIG. 1, in electrowinning of a metal, an anode (hereinafter, also referred to as “anode (Ni) plate”) 80 and a cathode (main cathode) are added to an aqueous solution (hereinafter, referred to as an electrolytic solution 90) containing ions of the metal to be collected. The plate) 100 is immersed and energized to deposit the metal on the main cathode plate 100. Bubbles are supplied from below the cathode plate 100 from an air blow nozzle (not shown). On the other hand, the electrolyte supply mechanism will be omitted here together with the illustrated explanation. Further, as a typical example of electrowinning, copper, zinc, nickel, cobalt, lead and platinum group metals are applied. Here, electrowinning used in the production of nickel for plating is illustrated.

The cathode plate 100 is a metal plate 17 that can be repeatedly used for test electrodeposition to confirm the electrodeposition status of the target metal before the main operation in the electrowinning method for non-ferrous metals such as nickel. In the electrowinning method for nickel, the electrolytic cell is filled with an aqueous solution of NiCl ₂ (nickel (II) chloride, nickel (II) chloride) as the electrolytic solution 90, and the electrolytic cell 90 is filled with an anode 80 made of a solid Ni plate. For example, the main cathode plate 100 made of titanium is immersed. A predetermined direct current is passed from the DC power supply device to each of the anode (Ni) plate 80 and the main cathode plate 100.

Due to this direct current, Ni ions in the electrolytic solution 90 move to the main cathode plate 100 side. The Ni ions are electrodeposited on the main cathode plate 100 to which a negative voltage is applied to become metallic Ni. The metal Ni electrodeposited to a desired thickness in this way is peeled off from the cathode plate 100 by a machine tool or the like to obtain a product. The shape of the metallic Ni product produced here is influenced by the "shape of the electrodeposited surface" formed on the cathode plate 100, which will be described later.

FIG. 2 is a perspective view showing an outline of the cathode plate. As shown in FIG. 2, the metal plate 17 forming the base material of the cathode plate 100 is a rectangular solid plate made of titanium or stainless steel, and the electrodeposition surface 21 to a predetermined position on the surface thereof in the electrowinning method is used. It is used as 32. The metal plate 17 is preferably made of titanium having high hardness and excellent durability.

FIG. 3 shows that the radius of curvature R value of the rounded corners chamfered at the four corners (corners) of the electrodeposited surface changes based on the difference in the positions where a plurality of protrusions are arranged in a grid pattern (depending on the arrangement). It is a figure for demonstrating (change of R value). FIG. 3A is a plan view. FIG. 3B is a sectional view taken along line YY. FIG. 3C is a cross-sectional view taken along line XX. FIG. 3 (D) is an enlarged view of the broken line circled portion in FIG. 3 (C). FIG. 3 (E) is an enlarged view of the broken line circled portion in FIG. 3 (D). Further, the plan view referred to in FIG. 3A means a view viewed from the front in a posture in which the cathode plate 100 is erected as shown in FIG.

The curvature is the reciprocal (1 / R) of the radius of curvature R value. In the case of showing a chamfered rounded corner shape for each of the four corners 41 to 44 on the electrodeposited surfaces 21 to 22 of a square (hereinafter, a square as an example), the radius of curvature R value and its reciprocal (1 / R) However, in the present application, the radius of curvature R value is unified. Even if the electrodeposited surfaces 21 to 22 have different R values, the four corners 41 to 44 are described with common reference numerals such as 41 for the upper left, 42 for the upper right, 43 for the lower right, and 44 for the lower left. ing. Further, although the same R value is illustrated for the four corners 41 to 44 with respect to one electrodeposition surface, the R value may not be limited to that.

As shown in FIG. 3, in the metal plate 17, a plurality of protrusions 21 to 22 forming a table shape having a minute height H are formed on at least one surface 18 in rows J and columns K (both J and K are 1). It is arranged in a grid pattern on the above natural numbers), and its surface is formed as electrodeposited surfaces 21 to 32. As will be described later, the plane visual recognition shape with respect to the protrusions 21 to 22 at each position is configured to be deformed according to the positioning.

As illustrated in FIG. 3A, the basic outer shape of the metal plate 17 viewed in a plane is a vertically long rectangle, and as an example, length x width x thickness = 200 mm x 100 mm x 4 mm. Further, regarding the grid-like arrangement of the protrusions (electroplated surfaces) 21 to 22, the number of rows J value is in descending order or ascending order in the vertical direction of the rectangle. Similarly, the K value of the number of columns arranged in a grid pattern shall be in descending or ascending order in the horizontal direction of the rectangle. The number of rows J value is preferably 2 or more and 10 or less, and the number of columns K value is preferably 2 or more and 10 or less. As an example, the number of rows J and the number of columns K are 3 rows × 3 columns.

In this way, the reason why 2 ≦ J ≦ 10, 2 ≦ K10 is that the external dimensions of the cathode plate (hereinafter, also referred to as “cathode plate for main operation”) used in the main operation by the electrowinning method of Ni is 1 m. It is about × 1m. On the other hand, the test electrode wearing cathode plate 100 is much smaller than the cathode plate for main operation, and is easy to achieve the test purpose with the minimum necessary size.

The shape of the cathode plate 100 will be more specifically illustrated below. The shape of the protrusions 21 to 22 of the cathode plate 100 viewed in a plane is basically a square having a predetermined length E on one side. E = 15 mm, the mutual distance between the protrusions 21 to 32 is 12 mm, and the grid arrangement of the protrusions (electroplated surfaces) 21 to 32 has a number of rows J and a number of columns K of 3 rows × 3 columns. Even if the protrusions (electroplated surfaces) 21 to 22 are expanded to 10 rows x 10 columns in a grid pattern without changing their individual sizes, the external dimensions are within 0.3 m x 0.3 m. Therefore, it is a range that feels easy.

The height H of the protrusions 21 to 32 is 50 μm or more and 1000 μm or less, and the minimum film thickness (hereinafter, also referred to as “resin film”, “coating film” or “mask”) of the non-conductive film (hereinafter, also referred to as “resin film”, “coating film” or “mask”) 50. "Resin film thickness", "coating film thickness", or simply "film thickness") T refers to the protrusions 21 to 22 at the position M (FIG. 3) passing between the centers of the adjacent protrusions 21 to 32. It is the same as the height H. For example, it is preferable that H = 300 μm.

It is preferable that the height H of the protrusions 21 to 32 and the film thickness T are the same, the film thickness T is uniform, and both are flush with each other. However, as shown in FIG. 3 (E), if the difference (hereinafter, also referred to as “error”) G between the height H of the protrusions 21 and 22 and the film thickness T is within the specified range, it is practical. There are few problems. Regarding this point, more specifically, the difference G between the minimum film thickness T of the non-conductive film 50 and the height H of the protrusions 21 to 22 at the position passing between the centers M of the adjacent protrusions 21 to 32. Is preferably 200 μm or less. Although only T <H is shown in FIG. 3 (E), the same applies to the case of H <T.

On the other hand, the heights H of the protrusions 21 to 22 are all uniform in that they have an extremely low table shape. Further, here, it is more important to clearly specify where the plurality of protrusions 21 to 22 are located on the surface 18 of the metal plate 17. Therefore, the protrusions 21 to 22 at each position and the electrodeposited surfaces 21 to 32 are illustrated and described with the same reference numerals.

As shown in FIGS. 3 (D) and 3 (E), on the surface 18 of the metal plate 17, for example, a resin mask 50 is coated on the surface 19 other than the electrodeposited surfaces 21 to 32. The mask 50 has a window frame shape that exposes a plurality of protrusions 21 to 22 arranged on the surface 18 of the metal plate 17, and the protrusions 21 to 32 are tightly fitted into the respective window holes.

Further, the mask 50 has a thickness corresponding to a minute height H of the table-shaped protrusions 21 to 32. Therefore, it is preferable that the electrodeposited surfaces 21 to 32 forming the surface of each table and the mask 50 are flush with each other. However, being flush does not have to be overly strict, and there may be an error G with respect to flush as long as it is within the allowable range (200 μm or less) described above.

Further, as shown in FIG. 1, not all the surfaces 19 other than the electrodeposited surfaces 21 to 22 are covered with the resin mask 50, and the upper surface and the edge portion of the surface 18 of the metal plate 17 are not always covered with the resin mask 50. , The mask 50 is not covered, and the part where the solid metal plate 17 is exposed is left.

As a result, the mask 50 has a rectangular outer shape slightly downward on the surface 18 of the metal plate 17, leaving a frame-shaped exposed portion. In the mask 50, substantially square electrodeposited surfaces 21 to 32 are arranged in a grid pattern of three horizontal rows and three vertical rows. Hereinafter, the electrodeposited surfaces 21 to 32 (same reference numerals) formed on the surfaces of the protrusions 21 to 32 arranged in a grid pattern in rows J and K will be described in more detail.

The shape of the protrusions 21 to 22 viewed in a plane is basically a square having a predetermined length E on one side. The four corners (hereinafter, also referred to as "corners") 41 to 44 of these squares are chamfered with rounded corners at a specified R value. The R-values that form these rounded corners are defined to change based on the difference in the position of the grid arrangement. This R value is set to be the same in the same row, with the first line counting from one end of the grid arrangement being the minimum and the last J line counting to the other end of the grid arrangement being the maximum. .. Hereinafter, "change in R value according to arrangement" will be described in more detail.

The magnitude relationship of the R value is R1 <R2 <R3 <R4. However, the order in which the R value increases is not simply proportional to the number of rows J value. As shown in FIG. 3, regarding the R value, the protrusions 21 to 23 in the first row are R1, the protrusions 24 to 26 in the second row are R3, and the protrusions 27 to 29 in the third row are R2 and the fourth row. The protrusions 30 to 32 of the above are R4.

Regarding the number of rows J value, first, one end of the grid arrangement, here, J = 1st row from the top. That is, the protrusions 21 to 23 in the first row are R1. At the position of J = 3rd line, which is advanced two lines downward from there, the R value advances one order and increases by one step from R1 to R2. That is, the protrusions 27 to 29 on the third row are R2.

In this way, if there is a place to return from the position of the third line advanced by two lines, the R value advances one line in order at the position of J = the second line returned by one line and increases by one step from R2 to R3. That is, the protrusions 24 to 26 in the second row are R3. At the position of J = 4th line, which is advanced two lines downward from there, the R value advances one order and increases by one step from R3 to R4. That is, the protrusions 30 to 32 on the fourth row are R4.

Only up to the number of lines J = 4 is illustrated, but when 5 ≦ J, there is no place to return even if you want to return one line from J = 4 to J = 3, that is, the third line that has returned one line is already It is being counted. If there is no place to return in this way, the order of the R values is advanced by one from R4 to R5 on the sixth line, which is advanced two lines further down. The magnitude relationship of the R value is changed according to the order in which the line skipping is repeated in this way. That is, with respect to "change in R value according to arrangement", the radius of curvature of the number of rows J value is 1,3,2,4,6,5,7,9,8,10, ..., J in that order. The R value is changed significantly in sequence.

Regarding the above-mentioned "change in R value according to arrangement", the magnitude relationship of R value is changed according to the order in which line skipping is repeated. This has the effect of avoiding the problem that the electrolytic solution 90 has an extreme component change depending on the position. Here, the operation will be described. Regarding the electrodeposition speed, in the vicinity of the electrodeposition surface 22 having a small R value, the electrolytic solution 90 undergoes an extreme change in component as the electrodeposited material rapidly grows abnormally with respect to the corners 41 to 44 having a high current density. To do.

In that respect, it is relatively slow in the vicinity of the electrodeposited surface 31 having a large R value. Therefore, by changing the magnitude relation of the R value according to the order in which the jumping of the rows is repeated, there is an effect of alleviating the "extreme change of the R value according to the arrangement". Therefore, in combination with the air blow from below the main cathode plate 100, there is an effect of avoiding an extreme component change due to the position of the electrolytic solution 90.

FIG. 4 is a flowchart for explaining a procedure of a method for manufacturing a test electrode wearing cathode plate (hereinafter, also referred to as “the present method”) according to an embodiment of the present invention. This method is a method for manufacturing a test electrode-wearing cathode plate 100 which is immersed in an electrolytic solution 90 and subjected to test electrodeposition in order to confirm the electrodeposition morphology according to the conditions of the electrolytic solution 90 in a non-metal electrowinning operation. As shown in FIG. 4, this method has a first step (S10) and a second step (S20).

In the first step (S10), a plurality of protrusions 21 to 22 are electrodeposited on at least one surface 18 of the metal plate 17 in a grid pattern of J rows and K columns (both J and K are natural numbers of 1 or more). It is formed as 21 to 32. In this first step (S10), the shape of the protrusions 21 to 22 that are visually recognized in a plane is based on a square having a predetermined length E on one side, and the four corners 41 to 44 of the square are rounded with a predetermined radius of curvature R value. Chamfer. At this time, the radius of curvature R value forming the rounded corners is defined to change based on the difference in the position of the grid arrangement.

In the next second step (S20), a mask 50 having a predetermined shape is applied to the surface 19 other than the metal plate 17 in which the plurality of protrusions 21 to 32 are formed as the electrodeposited surfaces 21 to 32 by the non-conductive film 50. .. The mask 50 may leave a frame-shaped exposed portion on the surface 18 of the metal plate 17. Alternatively, the entire surface 19 other than those formed as the electrodeposited surfaces 21 to 22 and the entire back surface and end surface may be completely covered.

In that case, as described above with reference to FIG. 3 (E), the difference G between the (minimum) film thickness T of the non-conductive film 50 and the height H of the protrusions 21 to 32, that is, the error G with respect to the plane. As long as is within the permissible range (200 μm or less), the thickness of the film thickness T may be slightly uneven on the entire back surface and end surface of the metal plate 17. As a result, in the second step (S20), it is possible to adopt a simpler method of insulating coating with an insulating paint, a resin coating, or the like.

The electrodeposited surfaces 21 to 22 are chamfered so that the four corners 41 to 44 of the square have different radius of curvature R values for each column K. This is to correct defects due to abnormal growth of the electrodeposited material at the four corners 41 to 44 of the electrodeposited surfaces 21 to 22 where current concentration is likely to occur in the electrolytic solution 90, and to efficiently produce the electrodeposited material. This is for confirming and selecting the chamfered shape of the electrodeposited surfaces 21 to 22 with respect to the four corners 41 to 44.

Therefore, the cathode plate 100 has a different chamfered shape of the electrodeposited surfaces 21 to 32 for each column K, so that the electrodeposited material is electrodeposited based on the difference in the shape of the electrodeposited surfaces 21 to 32 during the test electrolysis before the main operation. Differences in state can be tested, which can contribute to the determination of the chamfered shape of the electrodeposited surface in the cathode plate for this operation.

The cathode plate 100 is masked so that the electrodeposited surfaces 21 to 32 are lined up in a grid pattern and the electrodeposited surfaces 21 to 32 are square, and the four corners 41 to 44 of the square are respectively. It has a different radius of curvature R value and (curvature).

Since the cathode plate 100 having such a shape feature can minimize the range in which the above-mentioned electrodeposited product cannot be obtained, the electrodeposited product can be efficiently produced. Furthermore, the relationship between the radius of curvature R value and the product defect can be investigated.

FIG. 5 is a partially enlarged plan view for explaining the result of test electrodeposition on the cathode plate in the state of use of FIG. As shown in FIG. 5, in the electrowinning method, as a result of test electrodeposition using the cathode plate 100 in order to confirm the electrodeposition status of the target metal before the main operation, the electrodeposition surfaces 21 to 22 were respectively. Electrowinning is performed in a tendency shape based on the R value of. Further, not only the plane visual recognition shape but also the three-dimensional visual recognition shape will be described later using the perspective view of FIG. Here, metal Ni is exemplified as the electrodeposited material.

The electrodeposited surfaces 21 to 23 have a small R value of R1 at their corners 41 to 44, and the current density is concentrated higher than those where they are not, so that the electrodeposited surfaces project greatly accordingly and the metal has a distorted shape. Ni is electrodeposited. The electrodeposition surfaces 21 to 23 are electrodeposited thinly with an average thickness P1 although they are different in the vertical and horizontal directions.

As described above, when the electrodeposition thickness P1 is thin, a range (hereinafter, also referred to as “non-electroplated portion”) Q in which an electrodeposited object cannot be obtained is generated between adjacent surfaces 21 to 23. At the same time, the large protruding corners 41 to 44 form a bridge V and are connected to each other adjacent to each other. Therefore, the R value for obtaining the ideal shape of the electrodeposited object (the second evaluation standard described later) is searched for while minimizing the non-electroplated portion Q to secure the electrodeposition amount (the first evaluation standard described later). This is the main purpose of the cathode plate 100.

On the other hand, contrary to the electrodeposition surfaces 21 to 23, on the electrodeposition surfaces 30 to 32, the R values at the corners 41 to 44 are as gentle as R4, so that they do not protrude significantly and are generally in the vertical and horizontal directions. Metal Ni is electrodeposited on a more rounded planar visual shape with a uniform and relatively large thickness P4. Further, at the intermediate positions between the electrodeposited surfaces 21 to 23, 30 to 32 in the first and fourth rows described above, that is, the electrodeposited surfaces 24 to 26, 27 to 29 in the second and third rows, those Although it varies in the vertical and horizontal directions, it is electrodeposited with medium thicknesses P3 and P2, respectively.

The cathode plate 100 is a test piece for test electrodeposition, and the electrodeposition status of the target metal can be easily confirmed by one electrowinning before the main operation. Here, in order to confirm the electrodeposition status, the result of the test electrodeposition shown in FIG. 5 is evaluated. Among the evaluation criteria covering multiple items, the evaluation is limited to the following two points.

As the first evaluation criterion, the amount of electrodeposition at any one of the electrodeposited surfaces 21 to 22 existing in a large number on one plate is compared and considered. That is, the first evaluation criterion refers to the amount of electrodeposition obtained from one electrodeposition surface. Of course, the more this is, the better. As the second evaluation standard, the product shapes obtained for each R value of the electrodeposited surfaces 21 to 22 in which many types of R values are mixed in one plate are compared and considered. This is better as it is closer to a thin rectangular parallelepiped or a thick disk shape, and naturally it is better to have a uniform finish. That is, the second evaluation standard refers to the good shape of the electrodeposited product.

According to the first evaluation standard, which refers to the amount of electrodeposition described above, the electrodeposited surfaces 21 to 23 are disadvantageous as much as the non-electroplated portion Q is generated except for the corner portions 41 to 44. The landing surface 30 to 32 is more advantageous. Further, according to the second evaluation standard for the product shape and its uniformity described above, not only the corners 41 to 44 of the electrodeposited surfaces 21 to 23 project greatly in a distorted manner, but also a plurality of units of the bridge V. In the state of being connected, it is disadvantageous because the commercial value cannot be obtained, and the electrodeposited surfaces 30 to 32 are more advantageous in the same shape.

Here, the electrodeposition surface 31 having an R value of R4 is a good evaluation, and the electrodeposition surface 22 having an R value of R1 is a poor evaluation, but this is only an example. That is, each time the electrolytic solution 90 and other environments change, the optimum chamfer shape for the four corners 41 to 44 also changes, so it is natural that the result may differ from the result shown in FIG.

FIG. 6 is a perspective view for explaining the relationship between the R value of the rounded corners chamfered at the four corners (corners) of the electrodeposited surface shown in FIG. 3 and the abnormal growth. First, FIG. 6A shows a product in which electrodeposited Ni is generated in a distorted shape because the R value is as small as R1 at the corners 41 to 44 of the electrodeposited surface 22 in FIGS. 2 and 3. .. On the contrary, FIG. 6B shows a product in which electrodeposited Ni is generated in a shape close to an ideal because the R value is as large as R4 at the corners 41 to 44 of the electrodeposited surface 31 in FIGS. 2 and 3. ing.

In the preliminary test of electrodeposition using the cathode plate 100, the electrodeposition state of the central column rather than the columns at both ends in the same row is adopted as a highly reliable test result. For example, in FIGS. 3 (A) and 5, the electrodeposition results of the first and third rows located at both ends are only viewed as a reference, and the electrodeposition results of the second row located at the center are adopted as test results. To do.

As described above, since the cathode plate 100 is a cathode plate in which the electrodeposited surfaces 21 to 22 having a square shape are arranged in a grid pattern, it is compared with the conventional cathode plate in which the electrodeposited surfaces having only a circular shape are arranged in a staggered manner. , It is possible to minimize the range in which electrodeposition products cannot be obtained and increase the number of electrodeposition products to be taken, enabling efficient production.

Not only that, it is possible to avoid the problem that the product shape is distorted due to the abnormal growth of the target metal at the four corners 41 to 44 of the square and the mask 50 is damaged. That is, the rounded corners of the R value for which the optimum value should be obtained are formed by trial and error so that the current concentration that causes the abnormal growth can be alleviated. Further, rounded corners having a plurality of different R values are formed on the surface of one test piece.

As a result, a test piece can be obtained that allows the electrodeposition status of the target metal to be easily known in one preliminary experiment before the main operation. That is, in order to obtain high quality and stable target metal without abnormal growth, the relationship of abnormal growth with respect to the radius of curvature R value of the rounded corners chamfered at the four corners (corners) of the electrodeposited surface is set once. It is possible to provide a test electrode wearing cathode plate 100 which can be easily known in a preliminary experiment.

The cathode plate 100 sets different R values for the corners 41 to 44 of each of the electrodeposited surfaces 21 to 32. Therefore, the relationship between the radius of curvature R value and the product defect can be investigated by one test electrodeposition. Further, when each of the electrodeposited surfaces having only a circle is arranged in a staggered manner, there is a range in which the above-mentioned electrodeposited material cannot be obtained. Regarding this point, the cathode plate 100 can minimize the range in which the above-mentioned electrodeposited material cannot be obtained by making each electrodeposited surface from a circular shape to a square shape, so that the electrodeposited product can be efficiently produced. It will be possible. Hereinafter, this point will be described in more detail.

As disclosed in Patent Documents 1 and 2, as a result of electrodeposition by the staggered cathode plate, the disk surface is flat, and the peripheral portion is generally a disk containing a bulge about the thickness of the disk rather than the flat surface. The shape of the electrodeposited product is obtained. For the cathode plate for this operation, it is preferable to adopt a cathode plate having a shape that makes the best use of the advantages of the staggered cathode plate.

However, the disadvantage of the staggered cathode plate is that there is a loss in the number of metal plates taken with respect to the surface shape. That is, even if the first row is efficiently arranged with respect to the plate width, there is a wasteful range in which electrodeposits cannot be obtained due to the staggered arrangement near both ends in the width direction of the second and fourth rows. To do. Therefore, there is a disadvantage that waste is generated in terms of production efficiency in which the number of electrodeposited products that can be produced in one electrowinning operation is pursued to the maximum.

Therefore, instead of the staggered arrangement of the circular electrodeposition portions, the electrodeposition portions (hereinafter, also referred to as "square electrodeposition portions" or simply "electrodeposition portions") having a square table shape as a basic shape are arranged in a grid pattern. By arranging it in, it was possible to eliminate waste in the production efficiency of electrodeposited products. That is, if the cathode plates (hereinafter, also referred to as “cathode plates of a square lattice row”) 100 in which the square electrodeposited portions 21 to 22 are arranged in a grid pattern, one row is efficiently arranged at equal intervals with respect to the plate width. The eyes are arranged so that the row spacing F is aligned with the column spacing F, and the second and subsequent rows are arranged in an orderly and even manner.

Further, the vertical and horizontal dimensions of the cathode plate 100 are the length E of one side of the square electrodeposited portions 21 to 32, the interval F of each row, the interval F of each column, and half or less to the number of these intervals F. Consideration is given to setting a double margin portion on the peripheral edge portion of the cathode plate 100.

As described above, the main cathode plate 100 of the square grid array has advantages that the staggered cathode plate does not have, but also has the following disadvantages. That is, unlike the circular electrodeposition portion, the square electrodeposition portions 21 to 22 have a higher current density at the edge portions, particularly at the four corners 41 to 44, so that more electrodeposition is generated than at other locations. The disadvantage is that the shape of the target product is uneven.

In order to solve this problem, there is an attempt to chamfer the four corners 41 to 44 of the square electrodeposited portions 21 to 22 to form a gentle curved surface. On the other hand, the electrolyte 90 and other environments change with each operation. Along with such changes in the environment, the chamfered shape of the optimum four corners 41 to 44 also changes. Therefore, in order to confirm the electrodeposition form according to the electrolytic solution 90 and other environmental conditions in the electrowinning operation of the non-ferrous metal, it is necessary to immerse in the electrolytic solution 90 and perform test electrodeposition. For this purpose, a test piece formed small by simulating the cathode plate for this operation, that is, a cathode plate worn with a test electrode is used.

In this way, the optimum chamfer shape for the four corners 41 to 44 also changes each time the electrolyte 90 and other environments change, and the optimum radius of curvature of the chamfer shape for the four corners 41 to 44 is performed by simple test electrodeposition. It was requested to find the R value. Further, it is desirable that the relationship between the radius of curvature R value and the product defect can be investigated by one test electrodeposition.

The purpose of the investigation is to suppress the abnormal growth of the target metal at the four corners 41 to 44 of the substantially square electrodeposited portions 21 to 22 without losing the amount of electrodeposition of one electrodeposited product and the number of electrowinnings taken at one time. It is to be. Due to this abnormal growth, the shape of the product becomes distorted and the mask 50 is damaged. In order to suppress this abnormal growth, by chamfering the four corners 41 to 44 with rounded corners, the current concentration that causes the abnormal growth is alleviated as the R value is increased to make a gentle curved surface.

However, if the R value is made too large, the square becomes circular and returns to the staggered cathode plate, which is lost due to the number of takes. It is necessary to find a compromise between such conflicting interests and disadvantages. Therefore, the present inventors have invented a test piece in which various types of electrodeposited surfaces 21 to 22 having different R values are arranged on the surface of a single plate. According to this test piece, that is, this cathode plate 100, not only does it not lose in the number of takens, but also the correlation between the R value and abnormal growth, as well as the investigation of the minimum necessary R value, etc. It is devised so that you can know it by wearing it.

According to the present invention, in the electrowinning method for non-ferrous metals such as electrolytic nickel, the range in which electrodeposition products cannot be obtained is minimized, and the number of electrodeposition products taken is increased to enable efficient production. Then, a test piece that can know the electrodeposition status of the target metal before the main operation, that is, the four corners (corners) of the electrodeposition surface in order to obtain high quality and stable without abnormal growth of the target metal. It is possible to provide a test electrode wearing cathode plate capable of easily knowing the correlation between the radius of curvature R value of the chamfered rounded corners and the abnormal growth.

INDUSTRIAL APPLICABILITY The present invention may be used as a means for obtaining a control index for the electrodeposition status of a target metal before the main operation in the electrowinning method for non-ferrous metals. In particular, as a test piece that can simplify the preliminary experiment for pursuing the optimum shape of the cathode electrodeposited surface to respond to changes in the electrolyte and other environments that change with each operation, that is, a cathode plate that wears a test electrode, and a manufacturing method thereof. It may be preferably used.

Although each embodiment and each embodiment of the present invention have been described in detail as described above, those skilled in the art can understand that many modifications that do not substantially deviate from the novel matters and effects of the present invention are possible. , Will be easy to understand. Therefore, all such modifications are included in the scope of the present invention.

For example, a term described at least once in a specification or drawing with a different term in a broader or synonymous manner may be replaced by that different term anywhere in the specification or drawing. Further, the material and structure of the cathode plate worn by the test electrode and the non-conductive material and the structure for coating the mask on the cathode plate are not limited to those described in the respective embodiments and the respective examples of the present invention, and various modifications can be carried out. is there.

13 Mask, 17 Metal plate, 18 One surface (of this cathode plate), 19 Surface (other than protrusions 21 to 32), 21 to 32 (Metal plate 10) Projection / electrodeposition surface, 41 to 44 square Four corners (corners), 50 non-conductive (resin film, coating), 80 anode 80 (Ni) plate, 90 electrolyte, 100 test electrode wearing cathode plate (main cathode plate), E (one side of square) length , F row / column spacing, G (relative to flush) difference (error), H (protrusions 21 to 22) height, J rows, K columns (natural numbers of 1 or more for both J and K), M Position (passing between the centers of each of the protrusions 21 to 32), P1, P2, P3 (electrodeposition) thickness, Q non-electrodeposition part, R (forming rounded corners) radius of curvature R value, T (non-conductive) Minimum film thickness (of film 50), S10 1st step, S20 2nd step, V-bridge

Claims (10)

A test electrode-wearing cathode plate that is immersed in the electrolytic solution and subjected to test electrodeposition in order to confirm the electrodeposition morphology according to the conditions of the electrolytic solution in the electrowinning operation of a non-ferrous metal.
A metal plate in which a plurality of protrusions are formed as electrodeposited surfaces in a grid pattern of J rows and K columns (both J and K are natural numbers of 1 or more) on at least one surface.
A non-conductive film that applies a mask of a predetermined shape to the surface other than the protrusions of the metal plate, and
Have,
The shape of the protrusions viewed in a plane is
The basic shape is a square with one side of a predetermined length.
The four corners of the square are chamfered with rounded corners with a specified radius of curvature R value.
The radius of curvature R value that forms the rounded corners is
A test electrode wearing cathode plate defined to change based on the difference in the position of the grid arrangement. The radius of curvature R value is
The first line counting from one end of the grid arrangement is the smallest,
The last J-th line counted to the other end of the grid-like arrangement is the maximum.
Set the same on the same line,
The cathode plate for wearing a test electric according to claim 1. The order in which the radius of curvature R value increases is
Count the number of rows from one end of the grid layout and
First, advance one line at the position where you advanced two lines,
If there is a place to return from the position where the two lines are advanced, the order is advanced by one line, but if there is no place to return, the order is repeated to advance the order by one at the position where the position is further advanced by two lines.
The number of lines J is 1,3,2,4,6,5,7,9,8,10, ..., J, in that order.
The radius of curvature R value was changed so as to increase sequentially.
The cathode plate for wearing a test electric according to claim 2. The basic outer shape of the metal plate viewed in a plane is a vertically long rectangle.
The number of rows J of the grid-like arrangement is in descending order or ascending order in the vertical direction of the rectangle.
The number of columns K in the grid arrangement is ascended in the horizontal direction of the rectangle.
The number of lines J is 2 or more and 10 or less.
The number of columns K is 2 or more and 10 or less.
The height of the protrusion is 50 μm or more and 1000 μm or less.
The minimum film thickness of the non-conductive film is
It is the same as the height of the protrusion at a position passing between the centers of the adjacent protrusions.
The cathode plate for wearing a test electrode according to any one of claims 1 to 3. The minimum film thickness of the non-conductive film at a position passing between the centers of the adjacent protrusions, and
The difference from the height of the protrusion is 200 μm or less.
The cathode plate for testing electricity according to any one of claims 1 to 4. The metal plate is made of titanium or stainless steel.
The cathode plate for wearing a test electrode according to any one of claims 1 to 5. Used in the manufacture of nickel for plating,
The cathode plate for wearing a test electrode according to any one of claims 1 to 6. This is a method for manufacturing a test electrode-wearing cathode plate which is immersed in the electrolytic solution and subjected to test electrodeposition in order to confirm the electrodeposition morphology according to the conditions of the electrolytic solution in a non-metal electrowinning operation.
The first step (S10) of forming a plurality of protrusions as electrodeposited surfaces on at least one surface of a metal plate in a grid pattern of J rows and K columns (both J and K are natural numbers of 1 or more).
It has a second step (S20) of applying a mask having a predetermined shape by a non-conductive film on a surface other than a plurality of protrusions formed as electrodeposited surfaces on the metal plate.
In the first step (S10),
The shape of the protrusions viewed in a plane
The basic shape is a square with one side of a predetermined length.
The four corners of the square are chamfered with rounded corners with a specified radius of curvature R value.
The radius of curvature R value that forms the rounded corners is
It is defined to change based on the difference in the position of the grid arrangement.
A method for manufacturing a cathode plate for testing electricity. The radius of curvature R value is
The first line counting from one end of the grid arrangement is the smallest,
The last J-th line counted to the other end of the grid-like arrangement is the maximum.
Set the same on the same line,
The method for manufacturing a test electrode wearing cathode plate according to claim 8. The order in which the radius of curvature R value increases is
Count the number of rows J from one end of the grid-like arrangement,
First, advance one line at the position where you advanced two lines,
If there is a place to return from the position where the two lines are advanced, the order is advanced by one line, but if there is no place to return, the order is repeated to advance the order by one at the position where the position is further advanced by two lines.
The number of lines J is 1,3,2,4,6,5,7,9,8,10, ..., J, in that order.
The radius of curvature R value was changed so as to increase sequentially.
The method for manufacturing a test electrode wearing cathode plate according to claim 9.