JPH0653959B2 - Cell for contact between liquid and wire - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a liquid contact cell used for electrolytic treatment, pickling treatment, degreasing treatment, etc. of a wire, and for cooling a plated wire or a general wire. In particular, regarding the contact cell between the liquid and the wire, which has been developed for the purpose of improving the traveling speed of the wire, that is, the processing speed by increasing the contact efficiency between the wire and the liquid. is there.

[Prior Art] In the following description regarding this type of treatment, electrolytic treatment of a wire rod,
In particular, the description will focus on the case of using it for electroplating.
Conventionally, an electrolytic cell as shown in FIG. 6 has been used for electroplating a wire. That is, an electrolytic plating solution (hereinafter referred to as an electrolytic solution) L extracted from the tank 1 by a pump P is injected into the electrolytic cell 2 from above, and the electrolytic cell 2
In addition to filling the inside of the tank, a large amount of it is more positively injected to cause overflow, and the overflow is returned to the tank 1.
Then, the anode 3 is immersed in the electrolytic solution La in the electrolysis cell 2, and the wire W is passed through the electrolysis cell 2 while being in contact with the roller (cathode) 4, so that the wire W is electroplated. .

By the way, if an electroplating operation is to be carried out efficiently and economically using such an electrolysis cell for electroplating wire, the electrolysis conditions are high current density (improvement of electrolysis rate) and low electrolysis voltage (reduction of power cost). And need to.

However, if the current density during electrolysis is increased to above a certain value (this value is called the limiting current density), the plated surface of the wire will become a blackish state with no metallic luster (this is called burn phenomenon). Therefore, it is impossible to increase the electrolytic current density unnecessarily, and therefore the improvement of the plating operation efficiency is currently at the ceiling. It is considered that the cause of the above-described burning phenomenon is a deficiency of plating metal ions in the vicinity of the wire-plated surface.

On the other hand, regarding the decrease of the electrolysis voltage, it is necessary to consider the configuration of the electrolysis voltage. That is, the electrolytic voltage is (1) anodic decomposition voltage V ₁ , (2) cathodic decomposition voltage V ₂ , (3) voltage V ₃ due to the specific resistance of the wire, (4) voltage V ₄ due to the resistance of the plating solution, (5). Since it corresponds to the sum of the voltage V ₅ due to the circuit resistance and (6) the cut-off resistance voltage V ₆ due to the gas generated at the anode, if a part or all of each component is reduced in voltage, the sum of them is obtained. It is thought that a certain electrolytic voltage can be reduced. However, among the above, the anodic decomposition voltage V ₁ and the cathodic decomposition voltage V ₂ are voltages for performing the electrolytic reaction represented by the following formula (1) and are theoretically constant.

M-SO ₄ + H ₂ O → M + 1/20 ₂ + H ₂ SO ₄ ......
(1) M: Plating metal element Further, the voltage V ₃ due to the specific resistance of the wire is determined by the material, thickness and length of the wire, and must be considered to be constant in operation. Further, V ₅ is a value that can be ignored in a practical machine. Therefore, the voltage V ₄ due to the resistance of the plating solution and the interruption resistance voltage V ₆ due to the gas must be reduced. Of these, the breaking resistance voltage V due to gas
₆ is O ₂ generated according to the reaction represented by the above formula (1).
Is a voltage generated by adhesion and accumulation on the anode surface, and its value occupies a considerable proportion, and it seems that there is a lot of room for improvement. Therefore, in order to reduce the electrolysis voltage, it is considered promising to reduce the cutoff resistance voltage due to gas by some means. Since the voltage V ₄ due to the resistance of the plating solution is substantially determined by the scale of the electrolytic cell, it is not possible to expect a reduction effect as much as the interruption resistance voltage V ₆ due to the gas.

[Problems to be Solved by the Invention] The present invention has been made in view of these circumstances.
For example, by solving the deficiency of plating metal ions in the vicinity of the plated surface of the wire rod, the electrolysis current density is increased to improve the electroplating efficiency. An object of the present invention is to provide a contact cell capable of achieving cost reduction, that is, a contact cell capable of contacting an electrolytic solution and a wire with high efficiency.

Although the problems in the electroplating process have been described above, the ultimate problem is the same in the case of pickling process, degreasing process, and cooling of general wire rods such as plated wire rods. For example, in the case of cooling plated wire rods, the cooling process is provided after the immersion plating process, so if the plating operation speed is to be increased, highly efficient cooling is required. It is necessary to contact the coolant at a high flow rate.

However, all of the conventional cooling cells, like those in Fig. 6, supply and pass the plated wire into the natural falling flow utilizing the height difference, and the cooling speed of the cooling agent is increased to increase the cooling capacity. In order to raise it, the retained liquid level must be raised. However, as a matter of course, there is a limit to this measure, so that there is also a limit to improvement of cooling efficiency. Further, in improving the cooling efficiency, there is also a disadvantage that the coolant leaked from the cooling cell is scattered to the surroundings. Particularly, when the splashed liquid is mixed in the plating bath, the plating liquid is scattered to cause a serious safety problem. Therefore, leakage of the coolant from the cooling cell must be avoided. That is, it is desired to provide a contact cell which does not leak the coolant as the cooling cell and which can efficiently bring the plated wire material and the coolant into contact with each other.

[Means for Solving the Problems] The contact cell of the present invention, which has achieved the above object, has a through hole for allowing the wire rod to travel freely, and the through hole is used as a flow path for the introduction liquid. It is composed of a tubular cell and a liquid introducing member and a liquid discharging member which are coaxially connected to the tubular cell at one end portion and the other end portion thereof, respectively, and the liquid introducing member is a substantially tubular body portion. A body is provided with a liquid introducing portion that is introduced into the body from a substantially diametrical direction, and the flow of the introduced liquid introduced from the liquid introducing portion is directed to one end side of the tubular cell after or while being swirled. A circulation forming part,
A solid liquid flow forming portion for restricting the flow of the introduced liquid whose direction is changed by the circulation forming portion to form a solid liquid flow and then sending the solid liquid flow into the cylindrical cell is provided in the barrel portion, and the liquid discharging member is substantially a cylinder. A gas introduction part for feeding gas from a direction opposite to the flow of the introduction liquid in the tubular cell is formed in the body part having a shape, and the gas introduction part is fed to the other end side of the tubular cell with respect to the gas introduction part in the body part. The gist is that it is provided with a liquid discharge part that discharges the generated gas and the introduced liquid sent from the other end in a substantially diametrical direction of the body part.

[Operation] An electroplating process will be described below as an example. The present inventors embarked on the research, considering that it is better to increase the passage speed of the electrolytic solution in the region where the wire to be treated is immersed in order to carry out the high current density operation and the low electrolytic voltage operation. However, if an attempt is made to increase the electrolytic solution passage speed by using an open type cell like the conventional one, it is necessary to raise the electrolytic cell tank height above the overflow section considerably to increase the liquid pressure in the overflow section. Has a practical problem because it requires a large-scale cell tank. Moreover, the velocity can be increased only by the flow velocity in the vicinity of the overflow part, and the flow distribution in the horizontal direction occurs in the central part of the cell tank. Therefore, when the whole region is averaged, the effect of increasing the flow velocity is slight.

Therefore, in the present invention, the cell is formed into a tubular shape, and the basic configuration in which the wire rod passing through hole of the tubular cell is used for the electrolytic solution flowing portion is adopted, and the electrolytic solution is introduced into one end of the tubular cell. In addition to the member, an electrolytic solution discharge member is provided at the other end of the tubular cell so that the electrolytic solution is forced to flow from one end of the wire rod through hole to the other end.
That is, by allowing forced flow of the electrolytic solution, the passing rate of the electrolytic solution can be dramatically increased over the entire area of the through hole. This configuration can be a common and mutually complementary solution to the above two problems. That is, by increasing the flow rate of the electrolytic solution, the electrolytic solution in the vicinity of the wire-plated surface (electrolytic solution whose metal ion concentration has decreased due to electrolytic plating) is flown away, and a new electrolytic solution with a high metal ion concentration is supplied to efficiently perform the plating reaction. It was able to proceed well and prevent the burning phenomenon from occurring even at high current densities. In addition, by increasing the flow rate of the electrolytic solution, the O ₂ gas staying on the surface of the anode is flown away, and by sufficiently contacting the electrolytic solution with the surface of the anode, the gas cutoff resistance voltage is reduced, and the electrolytic plating reaction is sufficiently performed even at a low electrolytic voltage. I am trying to make it progress. Moreover, it became possible to make the electrolytic cell itself compact.

Further, in the above-mentioned electrolytic cell, it is necessary to prevent the electrolytic solution from leaking out from the electrolytic solution discharging member, and since the flow rate of the electrolytic solution is increased, it is necessary to be fully equipped to prevent leakage. In the present invention, with respect to the electrolyte flow flowing from one end to the other end of the tubular cell, a gas is fed from the side opposite to this to collide with it, thereby preventing leakage of the electrolyte flow, The electrolytic solution discharge member is provided with a gas introduction portion for introducing gas from the direction opposite to the electrolytic solution flow.

Next, the electrolytic solution introducing member applied to the present invention will be described. The electrolytic solution introducing member is indispensable for forcibly flowing the electrolytic solution into the through-hole for running the wire rod of the tubular cell without causing leakage. It is connected to the through hole on the discharge side). That is, the tubular cell of the present invention can be applied to the case where the running direction of the wire and the flowing direction of the electrolytic solution are the same (forward flow) and the case where they are the opposite direction (counterflow), respectively. The introducing member is connected to the wire rod introducing port of the tubular cell, and in the case of the counterflow, it is connected to the wire rod discharging port of the tubular cell.

The electrolytic solution introducing member has a wire rod running through space in the axial direction, and has a wire rod inlet on one end side thereof and a wire rod outlet on the other end side thereof, and either the wire rod inlet or the wire rod outlet is provided. One will also serve as the electrolyte delivery port.

An electrolytic solution introducing port is provided in the body of the electrolytic solution introducing member, a circulation forming part is provided in a through space extending from the electrolytic solution introducing port to the electrolytic solution outlet, and the electrolytic solution passes through the circulating forming part. In the process, turning force is applied and it becomes a circulation. As a result of the formation of the circular flow, the electrolytic solution flow is pressed against the inner surface of the inner wall of the body portion by the centrifugal force to become a hollow liquid flow. Then, the hollow liquid flow is moved by being pushed by the subsequent electrolytic solution flow and being pushed to the electrolytic solution outlet side, but between the above-mentioned circulation forming portion and the electrolytic solution outlet on the downstream side thereof. Is provided with a throttling portion (solid liquid flow forming portion) in which the through space is narrowed to reduce the liquid flow passage cross-sectional area. When the electrolytic solution passes through the throttling portion, the hollow liquid flow is It is squeezed to become a solid liquid flow and reaches the electrolyte solution outlet.

With the liquid introducing member having the above-mentioned configuration, the introduced electrolytic solution exhibits a hollow liquid flow state on the liquid introduction side and a solid liquid flow state on the liquid delivery side connected to the through hole of the tubular cell. Therefore, it is possible to forcibly introduce the electrolytic solution into the through hole of the cylindrical cell while preventing the electrolytic solution from leaking on the liquid introducing side. Further, since the air in the central portion is pushed back at the stage of transition from the hollow liquid flow to the solid liquid flow, intimate contact between the wire and the electrolyte is ensured without the air being entrained in the electrolyte flow. .

There are no particular restrictions on the cross-sectional shape of the cylindrical cell and the through hole for passing the wire, and it may be circular or polygonal. Also, the structure and shape of the electrolytic solution introducing member and the electrolytic solution discharging member are not particularly limited as long as they satisfy the requirements described above and later.For the electrolytic solution discharging member, the same direction or reverse direction with respect to the wire passing direction is used. Any structure may be used as long as it can change the direction of the flowing electrolyte solution to a direction intersecting with the wire passing direction and discharge.

[Embodiment] FIG. 1 is a cross-sectional view showing a structure of a contact cell according to the present invention. A contact cell 2a is a cylindrical anode body 3a having a through hole 5 for passing a wire rod (hereinafter referred to as a tubular cell). The electrolyte solution introduction guide 6 (liquid introduction member) having the structure shown in FIG. 2 is provided at one end (right end in the drawing) and the electrolyte solution discharge portion (liquid discharge member) at the other end (left end in the drawing). ) 8 is provided. A supply line (liquid introducing section) 9 is connected to the electrolytic solution introducing guide 6, and an electrolytic solution discharging line (liquid discharging section) 10 is connected to the electrolytic solution discharging section 8. Then, the wire W is sandwiched between the guide rollers 4 and introduced into the contact cell 2a from the electrolyte discharge side, and the cylindrical cell 3
The liquid is introduced from the liquid introduction side through the through hole 5 of a. A porous insulating plate 7 is attached to the inner peripheral wall of the cylindrical cell 3a for the purpose of preventing a short circuit with the wire W.

When electrolytically treating the wire W using such a contact cell 2a, the electrolytic solution extracted from the tank 1 by the pump P is forced into the cylindrical cell 3a from the electrolytic solution introduction guide 6 through the supply line 9. And is returned to the tank 1 from the electrolytic solution discharge portion 8 via the electrolytic solution discharge line 10. On the other hand, the air blown from the gas supply line (gas introduction part) 13 reaches the electrolytic solution discharge part 8 via the gas introduction guide 12 and the gas flow pipe 11, and is electrolyzed in a form facing the electrolytic solution flow. While being prevented from entering the air flow path pipe 11 side, the liquid is caught in the electrolyte flow and discharged from the electrolyte discharge line 10.

In such a contact cell, an electrolytic voltage is applied between the cylindrical cell 3a serving as the anode and the guide roller 4 serving as the cathode, and the wire W is passed from the left to the right in the figure. Since the flow speed is increased, the efficiency of supplying the electrolytic solution to the surface of the wire W, in particular, the efficiency of supplying the plating metal ions is increased, and a situation in which the plating metal ions are deficient is avoided. As a result, electrolytic plating with high current density is possible, and electrolytic plating can be completed in a short time. Further, the O ₂ retained on the inner surface of the through hole 5 of the tubular cell 3a is washed away by the high-speed electrolytic solution flow, and the tubular cell 3
The inner surface of a is exposed without being covered with O ₂ , and as a result, the breaking resistance voltage due to O ₂ gas is small,
Electroplating can be performed at a low electrolysis voltage.

In addition, the introduction of air from the gas supply line 13 avoids electrolyte leakage at the electrolyte discharge part 8. It should be noted that since the electrolyte solution is only suppressed from flowing into the gas introduction part and smoothly flows into the electrolyte solution discharge line 10, pressure loss at the time of introducing the electrolyte solution is small, and the electrolyte solution is efficiently produced. Circulation can be performed.

FIG. 2 is an exploded perspective view showing the structure of the above-mentioned electrolytic solution introducing guide 6. The electrolytic solution introducing guide 6 has an introducing member 130, an adapter 14 and a cover plate 24.
No. 0 has a through hole in the axial center part, and has a small diameter portion 130a.
And a large diameter portion 130b form a cylindrical body that forms a step, and a plurality of spiral guide blades 12 are provided on the tip end surface of the small diameter portion 130a. The adapter 14 also has a cylindrical body having a small diameter portion 14a and a large diameter portion 14b. The large diameter portion 14b has a storage hole portion 15a for storing the introduction member 130 and the storage hole portion. 15a
A supply line 9 is connected to communicate with. As shown in FIG. 3 (a view taken along the line III-III in FIG. 2), the small-diameter portion 14a has a tubular portion 21 for passing a wire rod in the axial center portion thereof, and the tubular portion 21 and the tubular portion 21. The diameter portion 14a is connected to the rectifying plate 16 arranged radially. The rectifying plate 16 is not always necessary. Also, the lid plate 2 made of a dish-shaped disc
A wire rod passage hole 22 is formed in the central portion of 4.

In attaching the electrolytic solution introducing guide 6 having such a structure to one end of the tubular cell 3a, first, the tubular cell 3 is to be mounted.
After inserting the small diameter portion 14a of the adapter 14 into the end enlarged diameter hole 5a of a, the introducing member 130 is accommodated in the accommodating hole portion 15a of the adapter 14 in the illustrated direction, and then the lid plate 24 is attached to the large diameter portion of the adapter 14. It fits on the peripheral surface of the end of the diameter portion 14b. When the electrolytic solution L is introduced from the supply line 9 into the electrolytic solution introducing guide 6 assembled in this way, the electrolytic solution L is generated between the outer wall of the small diameter portion 130a of the introducing member 130 and the inner wall of the accommodation hole 15a of the adapter 14. Flow into the cylindrical cell 3a, the flow is turned to the side of the tubular cell 3a, and is guided by the spiral guide plate 12 to flow into the center side. At this time, swirl is imparted to the electrolytic solution flow, and the electrolytic solution L is in a state of being pressed toward the outer peripheral side by the centrifugal force. Next, the electrolytic solution L enters into the through hole 15 of the small diameter portion 14a of the adapter, is rectified by the rectifying plate 15 while maintaining the state of being pressed to the outer peripheral side by the penetrating force, and becomes a hollow straight liquid flow. Adapter 14
Is discharged from the cylindrical cell 3a to the cylindrical cell 3a, is narrowed by the tapered diameter-reduced portion 3b functioning as a narrowed portion, becomes a solid liquid flow, and is introduced into the through hole 5 of the cylindrical cell 3a. The introduction member 130 and the adapter 14 can be regarded as a circulation flow forming portion, and the tapered diameter-reduced portion 3b can be regarded as a solid liquid flow forming portion.

In the electrolytic solution introducing guide 6, the introduced electrolytic solution L flows in the cylindrical cell 3a direction while being pressed to the outer peripheral side, so that the electrolytic solution L is prevented from flowing into the central portion through which the wire W passes, The leakage of the electrolytic solution L on the W extraction side is prevented. Moreover, since the air in the central part of the hollow liquid flow is throttled and pushed back to the side opposite to the direction in which the liquid flows in the throttled portion, the air is not trapped in the introduced electrolytic solution L, and as a result, gas is entrained by the air. There is no fear that the breaking resistance will increase.

FIG. 4 shows another embodiment of the electrolytic solution introducing guide. In this configuration, the introduction member 130c is the disk-shaped member 1
The adapter 17 is provided with a helix 17 spirally attached to the distal end side body portion of a tubular body having 30d and projecting from the axis thereof.
It is inserted in the small diameter portion 140a of 40. By using the electrolytic solution introducing guide having such a configuration, the same effect as described above can be obtained. Furthermore, the introduction member 130c
Instead of, the liquid flow guide cylinder 18 is projected from the axis of the disk-shaped member 130e as shown in FIG.
It is also possible to use an introducing member 130f that extends 8 to reach the tip of the small diameter portion 140a of the adapter 140. However, in this case, some leakage is expected. Other introduction guides having various shapes can be applied.

In the above-mentioned embodiments, various specific examples of the electrolyte introduction guide are shown, but all of them can be used as the gas introduction guide by changing the fluid to be handled from the electrolyte to gas.

Further, the contact cell of the present invention has been described in the above embodiment by taking the counterflow type in which the traveling direction of the wire and the flow direction of the electrolytic solution are opposed to each other as shown in FIG. 1, but the present invention is not limited to this. Instead, it can also be applied to the forward flow type.

EFFECTS OF THE INVENTION The present invention is configured as described above, and since the maximum electrolytic current density can be increased in the contact cell, the electrolytic plating of the wire can be efficiently performed in a short time.
By the way, the limiting current density which was 50 (A / dm ² ) in the conventional example shown in FIG. 6 increased to nearly 1000 (A / dm ² ) in the present invention. Moreover, since the electroplating can be performed at a low electrolysis voltage, power consumption can be reduced.

Further, in the contact cell for pickling or degreasing, the contact efficiency between the wire and the pickling solution or the degreasing solution is increased, so that the treatment can be completed in a short time.

In addition, in a cell for cooling a plated wire rod or the like, the coolant and the wire rod can be efficiently brought into contact with each other, so that the cooling can be performed promptly and the productivity of the immersion plating step or the like can be improved.

Further, when the liquid is introduced into or discharged from the contact cell, liquid leakage can be sufficiently prevented, and since the flow path resistance due to the liquid leakage prevention structure is small, the liquid can be efficiently circulated.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view showing the structure of a contact cell according to the present invention, FIG. 2 is an exploded perspective view showing the structure of an electrolyte introduction guide, and FIG. 3 is a sectional view taken along the line III-III in FIG. FIGS. 4 and 5 are exploded perspective views showing another embodiment of the electrolytic solution introducing guide, and FIG. 6 is an explanatory view showing a conventional electrolytic cell. 1 ... Tank, 2a ... Contacting cell 3a ... Cylindrical cell, 4 ... Guide roller 5 ... Wire material through hole, 6 ... Electrolyte introduction guide 8 ... Electrolyte discharge part, 9 ... Supply line 10 ... Discharge line, W ... Wire rod L ... Electrolyte

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Seiji Sekiya 3-2 Kamotanidai, Sakai City, Osaka Prefecture (56) References JP 48-42655 (JP, A) JP 57-39194 (JP, A) JP-A-61-136698 (JP, A) JP-A-62-280398 (JP, A) Actually developed JP-A-62-194764 (JP, U)

Claims (1)

[Claims] 1. A cylindrical cell having a through hole for allowing a wire rod to travel freely and using the through hole as a flow path for an introduction liquid, and one end portion and the other end thereof coaxial with the cylindrical cell. It is composed of a liquid introducing member and a liquid discharging member that are respectively connected to the end portions, and the liquid introducing member introduces the introduced liquid into the body portion from a substantially diametrical direction of the body portion having a substantially cylindrical shape. A swirl formation part that is provided with a liquid introduction part, and is directed by the swirl formation part after turning the flow of the introduction liquid introduced from the liquid introduction part, or while swirling, toward one end side of the tubular cell. The flow of the introduced liquid is changed, the solid liquid flow forming part for sending into the cylindrical cell after making a solid liquid flow is provided in the body part, and the liquid discharge member has a substantially cylindrical shape. A flow of the introduced liquid in the tubular cell is formed in the body of the eggplant. A gas introduction part for feeding gas from a direction opposite to is formed, the tubular cell on the other end side of the gas introduction part in the body part thereof, and the gas fed in and the other end sent out from the other end part. A cell for contacting a liquid and a wire, comprising a liquid discharge part for discharging the introduced liquid in a substantially diametrical direction of the body part.