Zinc-nickel composite plating bath, zinc-nickel composite plating film, mold and plating method

Abstract

This zinc-nickel composite plating bath contains a zinc source, a nickel source, silicon dioxide particles and an ammonium-based dispersant in such ranges that enable the achievement of a zinc-nickel composite plating film wherein the codeposition amount of nickel is 10-16 wt % and the codeposition amount of the silicon dioxide particles is 7 vol % or more. Meanwhile, the pH of this zinc-nickel composite plating bath is 5.6 to 6.8.

Claims

1. A zinc-nickel composite plating bath comprising a zinc source, a nickel source, a silicon dioxide particle, and an ammonium-based dispersant for forming a zinc-nickel composite plating coating having a co-deposited nickel content of 10 to 16 Wt % and a co-deposited silicon dioxide particle content of 7 Vol % or more, wherein the zinc-nickel composite plating bath has a pH of 5.6 to 6.8, wherein the silicon dioxide particle has a scale-like shape or a dendritic shape.

2. The zinc-nickel composite plating bath of claim 1, wherein the zinc-nickel composite plating bath has a pH of 6.1 to 6.8.

3. The zinc-nickel composite plating bath of claim 1, wherein the zin-nickel composite plating bath comprises 50 g/L of zinc chloride as the zinc source, 30 g/L of a nickel chloride as the nickel source, 200 g/L of the silicon dioxide particles and 200 g/L of the ammonium-based dispersant.

4. A plating method for forming a zinc-nickel composite plating coating on a surface of a steel material to be plated, the plating method comprising: a degreasing step of removing an oil component from the surface to be plated; an etching treatment step of removing an oxide layer from the surface to be plated after oil component removal; a desmutting step of removing a water-insoluble metal component from the surface to be plated after oxide layer removal; and a plating step of subjecting the surface to be plated to an electroplating treatment using a zinc-nickel composite plating bath after metal component removal to form the zinc-nickel composite plating coating, wherein the zinc-nickel composite plating bath contains a zinc source, a nickel source, a silicon dioxide particle, and an ammonium-based dispersant, the zinc-nickel composite plating bath has a pH of 5.6 to 6.8, wherein the silicon dioxide particle has a scale-like shape or a dendritic shape, and the zinc-nickel composite plating coating has a co-deposited nickel content of 10 to 16 Wt % and a co-deposited silicon dioxide particle content of 7 Vol % or more.

5. The plating method according to claim 4, wherein the steel material is a mold, and the surface to be plated is an inner surface of a coolant passage formed in the mold.

6. The plating method of claim 4, wherein the zinc-nickel composite plating bath has a pH of 6.1 to 6.8.

7. The plating method of claim 4, wherein the zin-nickel composite plating bath comprises 50 g/L of zinc chloride as the zinc source, 30 g/L of a nickel chloride as the nickel source, 200 g/L of the silicon dioxide particles and 200 g/L of the ammonium-based dispersant.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic cross-sectional view of a zinc-nickel composite plating coating formed on an inner surface of a coolant passage in a mold according to an embodiment of the present invention; and

(2) FIG. 2 is a schematic explanatory view for illustrating a plating method according to the embodiment of the present invention.

DESCRIPTION OF EMBODIMENTS

(3) A preferred embodiment of the zinc-nickel composite plating bath, the zinc-nickel composite plating coating, the mold, and the plating method of the present invention will be described in detail below with reference to the accompanying drawings.

(4) As shown in FIG. 1, a mold 12 has a bottomed hole of a coolant passage 14, and a zinc-nickel composite plating coating 10 according to this embodiment (hereinafter referred to simply as the plating coating 10) is formed on an inner surface of the coolant passage 14.

(5) Specifically, the mold 12 is intended to be used for casting, injection molding, or the like. For example, the coolant passage 14 is formed in a wall in the vicinity of a cavity (not shown), and a coolant water is circulated through the coolant passage 14. The mold 12 contains a steel material such as SKD61.

(6) The plating coating 10 is a composite plating layer containing a matrix 20 and silicon dioxide particles 22. The matrix 20 contains a zinc-nickel alloy, and the silicon dioxide particles 22 are co-deposited with the zinc-nickel alloy. The content of the co-deposited silicon dioxide particles 22 is 7 Vol % or more. The plating coating 10 has a thickness of 50 to 300 μm. The inner surface of the coolant passage 14 in the mold 12 is covered approximately uniformly with the plating coating 10 to prevent the contact between the inner surface and the coolant water.

(7) The content of the co-deposited nickel in the matrix 20 is 10 to 16 Wt %. Therefore, the nickel in the matrix 20 has a y single phase structure. The silicon dioxide particle 22 has a hydrophilic property, and has a scale-like shape or a dendritic shape with an increased specific surface area.

(8) The plating coating 10 can be formed by a plating method using a zinc-nickel composite plating bath (solution) according to this embodiment (hereinafter referred to simply as the plating bath). The plating method will be described below with reference to FIG. 2.

(9) The plating bath contains a zinc source, a nickel source, the silicon dioxide particles 22, and an ammonium-based dispersant in such a manner that the resultant plating coating 10 has a co-deposited nickel content of 10 to 16 Wt % and a co-deposited silicon dioxide particle content of 7 Vol % or more as described above.

(10) For example, the zinc source is preferably zinc chloride, and the nickel source is preferably nickel chloride. In this case, for example, it is preferred that the plating bath contains 50 g/L of the zinc chloride, 30 g/L of the nickel chloride, 200 g/L of the ammonium-based dispersant, and 200 g/L of the silicon dioxide particles 22.

(11) The pH of the plating bath is controlled to a value of 5.6 to 6.8 by the ammonium-based dispersant. It is more preferred that the plating bath has a pH of 6.2 to 6.6. In this case, the co-deposited silicon dioxide particle 22 content can be easily controlled within the above range while effectively preventing recrystallization or the like of the zinc source or the nickel source in the plating bath.

(12) As shown in FIG. 2, an electroplating treatment using an electrolytic treatment apparatus 30 may be used in the plating method. The electrolytic treatment apparatus 30 has an electrode 32 and a supply/discharge portion 34, and further has a treatment liquid feeding means, a treatment liquid tank, and an external power source (not shown).

(13) For example, the electrode 32 is a tubular body containing a platinum-coated titanium material or the like. The supply/discharge portion 34 is detachably attached to the opening of the coolant passage 14, and is used for supplying/discharging the plating solution to/from the electrode 32 and the coolant passage 14.

(14) The treatment liquid feeding means is used for supplying the plating solution through the supply/discharge portion 34 into the coolant passage 14. The treatment liquid tank is used for storing the plating solution discharged from the coolant passage 14 through the supply/discharge portion 34. The external power source is used for supplying an electric current to the electrode 32, thereby generating an electric potential difference between the electrode 32 and the inner surface of the coolant passage 14.

(15) Thus, in the electrolytic treatment apparatus 30, an end of the electrode 32 protruding from the supply/discharge portion 34 is inserted into the coolant passage 14, and then the plating bath is provided from the treatment liquid feeding means to the supply/discharge portion 34. The plating solution flows between the outer periphery of the electrode 32 and the inner surface of the coolant passage 14, and reaches the end of the electrode 32 (the bottom of the coolant passage 14). The plating solution further flows from an opening formed on the end of the electrode 32 through the inside of the electrode 32 to the supply/discharge portion 34, and is collected in the treatment liquid tank. The collected plating solution is supplied again from the treatment liquid feeding means to the supply/discharge portion 34. That is, the plating bath is circulated in the electrolytic treatment apparatus 30 and the coolant passage 14.

(16) In the electrolytic treatment apparatus 30, a liquid such as a degreasing washing liquid, an etching liquid, a desmutting liquid, or water may be supplied to the supply/discharge portion 34 instead of the plating bath. The liquid may be circulated in the coolant passage 14. Thus, the treatment liquid feeding means may be used for supplying the liquid instead of the plating bath to the supply/discharge portion 34. The treatment liquid tank may be used for storing the liquid discharged from the supply/discharge portion 34.

(17) In the plating method using the electrolytic treatment apparatus 30, first, the electrode 32 is inserted into the coolant passage 14, and the supply/discharge portion 34 is attached to the opening of the coolant passage 14. Then, the degreasing washing liquid (such as a water-soluble alkaline detergent) is supplied from the supply/discharge portion 34 to the coolant passage 14, to carry out a degreasing step for removing an oil component from the inner surface of the coolant passage 14 (the surface to be plated).

(18) Next, the etching liquid (such as a 10-Wt % aqueous hydrochloric acid solution or a 10-Wt % aqueous sulfuric acid solution) is supplied through the supply/discharge portion 34 to the coolant passage 14, to carry out an etching treatment step for removing an oxide layer from the inner surface of the coolant passage 14. In the etching treatment step, an electrolytic etching treatment (an anodic electrolysis treatment) may be performed while applying an electric current from the external power source to the electrode 32.

(19) Next, the desmutting liquid (such as a solution of a mixture of sodium hydroxide and sodium citrate) is supplied through the supply/discharge portion 34 to the coolant passage 14, to carry out a desmutting step. In the above etching treatment step, the oxide layer is removed, whereby a water-insoluble metal component (a smut component) is exposed on the inner surface of the coolant passage 14. In the desmutting step, the smut component is removed from the coolant passage 14.

(20) Also in the desmutting step, an electrolytic treatment (a cathodic or anodic electrolysis treatment) may be performed while applying an electric current from the external power source to the electrode 32. In this case, the desmutting liquid is electrolyzed in the coolant passage 14 to generate oxygen, whereby the smut component can be removed more effectively.

(21) Next, the plating bath is supplied through the supply/discharge portion 34 to the coolant passage 14, and an electric current is applied from the external power source to the electrode 32, to carry out an electroplating treatment in a plating step. In the plating step, for example, the plating solution having a temperature of 35° C. is supplied to the coolant passage 14 at a flow rate of 1 m/second. For example, the electric current applied to the electrode 32 is controlled in such a manner that the current density is 10 A/dm.sup.2 on the inner surface of the coolant passage 14. The plating coating 10 can be formed on the inner surface of the coolant passage 14 in this manner.

(22) The obtained plating coating 10 can have both of a hydrophilic property and an anticorrosion property. A sediment derived from calcium, bacterium, or the like in the coolant water can be easily washed out with water due to the hydrophilic property, and generation of a corrosion product can be prevented due to the anticorrosion property.

(23) Thus, when the pH value is controlled within the above range by using the ammonium-based dispersant, 7 Vol % or more of the hydrophilic silicon dioxide particles 22 can be effectively co-deposited while preventing the recrystallization or the like of the zinc source or the nickel source. In this case, for example, the plating coating 10 can have a water contact angle of less than 40°, resulting in the excellent hydrophilic property. Furthermore, when the silicon dioxide particles 22 have a scale-like shape or a dendritic shape, the silicon dioxide particles 22 can have a specific surface area larger than that of grain-shaped particles, whereby the plating coating 10 can have an improved hydrophilic property.

(24) Thus, even when the sediment is attached to the plating coating 10, water can easily penetrate between the sediment and the plating coating 10, so that the sediment can be easily removed from the inner surface of the coolant passage 14. Consequently, the sediment can be easily removed from the coolant passage before the amount of the attached sediment is increased.

(25) For example, a melt having a temperature of 500° C. or higher may be injected into the cavity formed in the mold 12. When the deposited nickel content is controlled within the above range, the plating coating 10 is excellent in heat resistance and is not decomposed even at such a high temperature. Furthermore, even when the silicon dioxide particles 22 are deposited as described above, the plating coating 10 can have a satisfactory thermal conductivity, so that thermal exchange between the coolant water and the inner surface of the coolant passage 14 is not inhibited by the plating coating 10.

(26) The matrix 20 of the plating coating 10 contains a zinc-nickel alloy. The zinc-nickel alloy has an ionization tendency higher than that of the steel material such as SKD61 in the base material of the mold 12. In addition, the electric potential difference between the steel material and the zinc-nickel alloy is smaller than that between the steel material and another metal material having an ionization tendency higher than that of the steel material.

(27) When the inner surface of the coolant passage 14 is covered with the plating coating 10 containing the matrix 20, the contact of water with the inner surface (the base material) can be prevented. Even if a part of the inner surface of the coolant passage 14 (the base material) is exposed on the plating coating 10, a sufficient sacrificial anticorrosion effect can be achieved. In addition, because the electric potential difference between the plating coating 10 and the inner surface of the coolant passage 14 (the base material) is small as described above, generation of a corrosion current can be prevented. Consequently, the inner surface of the coolant passage 14 can exhibit an effectively improved corrosion resistance.

(28) Because the co-deposited nickel content is controlled within the above range and the nickel can have the y single phase structure in the plating coating 10, the corrosion resistance of the plating coating 10 can be further improved. Consequently, the attachment of the corrosion product to the inner surface of the coolant passage 14 can be prevented by forming the plating coating 10.

(29) The plating coating 10 has a thickness of 50 to 300 μm as described above. Therefore, even when the plating coating 10 is exposed to a water pressure of the coolant water running through the coolant passage 14, the plating coating 10 can be prevented from being broken or peeled off from the inner surface of the coolant passage 14. Furthermore, in a case where the degreasing step, the etching treatment step, and the desmutting step are carried out prior to the plating step, the plating coating 10 can be formed more effectively on the inner surface of the coolant passage 14. The durability of the plating coating 10 can be improved in this manner.

(30) Even when the mold 12 is continuously used, the plating coating 10 formed on the inner surface of the coolant passage 14 can be maintained in a good state, so that the increase in the amount of the sediment attached and the attachment of the corrosion product can be effectively prevented. Therefore, the thermal exchange via the coolant passage 14 between the coolant water and the mold 12 can be prevented from being inhibited by the corrosion product having a low thermal conductivity. Furthermore, the coolant water can be efficiently circulated through the coolant passage 14. Consequently, the control of the temperature of the mold 12 can be stably performed, so that the mold 12 can be maintained at an optimum temperature in a molding process, and the mold 12 can be efficiently cooled after a molding process. Furthermore, the maintenance cycle of the mold 12 can be prolonged.

(31) The present invention is not particularly limited to the above embodiment, and various changes and modifications may be made therein without departing from the scope of the invention.

(32) For example, although the plating coating 10 is formed on the inner surface of the bottomed hole (the coolant passage 14) in the mold 12 in the above embodiment, the subject to be covered with the plating coating 10 is not particularly limited to the bottomed hole. The plating coating 10 may be formed on an inner surface of a line-shaped coolant passage instead of the bottomed hole. A subject other than the coolant passage of the mold may be covered with the plating coating 10.

DESCRIPTION OF REFERENCE NUMERALS AND SIGNS

(33) 10 . . . Plating coating 12 . . . Mold 14 . . . Coolant passage 20 . . . Matrix 22 . . . Silicon dioxide particle 30 . . . Electrolytic treatment apparatus 32 . . . Electrode 34 . . . Supply/discharge portion