KR20110083147A - Black metal plating method using the same for copper plate with low emissivity and high absorption of solar energy - Google Patents

Abstract

PURPOSE: A continuous and automatic electrode position method of environment-friendly black potassium chromium sulfate plating having low emissivity and high absorption rate is provided to improve the performance of the endothermic plate through an automatic series coating process. CONSTITUTION: A continuous and automatic electrode position method of environment-friendly black potassium chromium sulfate plating having low emissivity and high absorption rate is as follows. A copper metal plate is washed in 50~60°C for 1~3 minutes(10). After a rinse step(20), the copper metal plate is plated in a specific solution for 1~3 minutes using anode Ti basket +S round Ni(Nickel) in 50~55°C as an electric current density of 35(30). The solution is manufactured by mixing surfactant of 1~2cc, boric acid of 41g, nickel chloride of 68g, and nickel sulfate of 300g, in water of 1 liter. The copper metal plate is activated in sulfuric acid of 10% in room temperature for 1~3 minutes(50) after a rinse step(40). The copper metal plate is plated in the plating liquid in 20~35°C as the current density of 40 at a plating rate of 0.002~0.008mm/min(70) after rinse step(60). The copper metal plate is dried with hot air of 70~80°C(90) after a rinse step(80).

Description

Black metal plating method using the same for copper plate with low emissivity and high absorption of solar energy}

The present invention relates to a continuous automatic electrodeposition method of environmentally friendly chromium black potassium sulfate plating of low emissivity and high absorption rate on a copper metal plate to plate a selective absorption thin film capable of absorbing solar energy most effectively on the copper metal plate.

In order to increase the efficiency of the solar heat collecting plate, it is important to apply a selective thin film to the heat collecting plate to increase the heat of absorption of the sunlight irradiated to the heat collecting plate and to reduce heat loss due to radiation.

That is, the most important factor for determining the overall efficiency in the solar collector for utilizing solar heat as energy may be high absorption rate and low emissivity of the thin film of the heat collecting plate regardless of the type of the collector.

Conventionally, due to the limitation of the main metal, reducing agent and stabilizer, the selective absorption thin film plated on the copper foil had a solar heat absorption rate of 93 to 98%, but the emissivity was very high to 15 to 30% to radiate the absorbed solar heat into the atmosphere. This resulted in a decrease in utilization efficiency.

In order to prevent this, the product of the titanium vacuum deposition method is used abroad, but there is a disadvantage that the coating film is easily damaged by a specific material and the price of equipment and products is expensive.

There are various methods of manufacturing the selective thin film which solves this problem and has the optical properties required by the heat collecting plate. The most economical and relatively simple method of operation and operation is electroplating (direct current electrolysis, pulse electrolysis). Although it has been widely used, it is rarely used in recent years due to the electrolyte composition of hexavalent chromium (Cr + 6) and high emissivity.

In addition, as shown in Invention Patent No. 625258, the copper metal surface to be plated first is washed with volatile trichloroethylene to remove impurities, followed by 65 g of sulfuric acid (H ₂ SO ₄ ), 20 g of nitric acid (HNO ₃ ), and oxidation. The copper plate was degreased and activated with a solution of 10 g of chromium (CrO ₃ ), 1 g of hydrochloric acid, and 120 g of water, washed twice with water, and then immersed in a preheating bath preheated to 80 ° C. to heat the copper surface, and then transferred to the electroless plating bath. In an electroless plating bath, 72 g of arsenic oxide (AsO ₄ ), 35 g of potassium bromide (KBr), 65% of potassium hydroxide (KOH), vanadium pentoxide (V ₂ O ₅ ) and sodium phosphate were added to 1 liter of distilled water. (NaPO ₂ ) It is composed of stabilizer and reducing agent 3.1g each mixed in 50% each, the plating temperature is 75 ~ 90 ℃, 0.001 ~ 0.0015mm thickness plating proceeds for 30 to 150 seconds, plating in the plating bath When it is finished, I wash twice and about 60 degrees Celsius After the hot water is washed with hot water and dried by hot air at 60 to 80 ° C, the plating solution for the electroless plating solar heat collecting plate having the excellent adhesion of the copper plate (KS D0254) and the solar absorption rate of 94 to 98% and the emissivity of 7 to 15%. Although presented for the method, the plating solution described above was expensive and the plating process took a long time.

Republic of Korea Patent Registration 10-0625258 (Park, Youngjin, Hanbat National University Industry-Academic Cooperation Foundation), 2006.05.12

In the present invention, the thickness of the selective thin film to be coated on the surface of the conventional solar heat collecting plate is coated with a thickness of 0.001 to 0.0015 mm, which is disadvantageous in forming the ultra thin film, and also due to the electroless plating, the adhesion of the thin film is inferior. On the other hand, it is to solve the disadvantage that the plating rate is slow with the problem of high emissivity.

The present invention is subjected to a degreasing process that allows the black chromium sulphate to be electrodeposited well by electroplating on a copper metal plate, followed by a washing process and a nickel scribing process, followed by a washing process and a nickel strike process. After rinsing again, the surface of the copper plate is activated to allow the chromium black chromium to be plated satisfactorily, followed by rinsing. The conductive salt (Hy Cr) 400-450cc / l and chromium sulphate (CrK ( SO ₄ ) ₂ · 12H ₂ O) After completely dissolving 400 g / l, 32 g / l of complexing agent (Nu salt) and 25 cc / l of electrolyte salt (NC-2) and wetting agent (NF-ll) were added and dissolved. After immersing in the plating solution, the plating process proceeds with plating speed of 002 ~ 0.008mm / min, followed by water washing and hot air drying process to provide solar heat collecting plate with 94 ~ 98% of solar heat absorption rate, 3 ~ 8% emissivity and heat resistance of 980 ℃. Done.

The present invention is to provide a low-cost and environmentally friendly, low-emissivity and high-efficiency solar heat collector plate of chromium black potassium sulfate is electroplated on the surface of the copper plate with a thickness of 0.0001 ~ 0.0015mm while solar absorption rate 94-98%, emissivity 3-8% The continuous plating of the copper metal plate enables mass production in a short time.

In addition, the present invention provides potassium chromium sulfate, which is excellent in heat resistance, corrosion resistance and adhesion, does not generate pinholes, and reduces the plating time to 100% of the cathode current efficiency.

In addition, since the present invention is electrodeposition by electric current, the thickness of the coating layer can be arbitrarily adjusted to obtain an optimal value of solar absorption and emissivity, and the automatic continuous coating is possible to improve the performance of the heat absorbing plate and to uniform the quality of the electrode of the copper rod. Applicable to the electrode in the opposite direction can be applied to remove a portion of the electrodeposition material, the coating layer is uniform and roughness is uniform when the copper rod electrode is repeated once.

1 is a view schematically showing a plating mechanism of the present invention,
2 is a view schematically showing a process suitable for applying the plating method according to the present invention.

The present invention is to remove the impurities on the surface of the copper metal plate, the washing process, nickel strike process, activation process, washing process, plating process, washing process, drying process, the solar light on the surface of the copper metal plate used as solar heat collecting plate A high efficiency continuous plating method for plating a selective absorption thin film.

에서 양극은 합금봉을 사용하고, 음극은 구리봉을 사용하여 도금속도 002~0.008mm/min으로 구리 금속판을 연속적으로 이동시켜 도금이 이루어지게 한다.In the present invention, the plating solution to be plated is filled with clean water 1/3 to the plating tank, diluted with dilute conductive salt (Hy Cr) 400 ~ 450cc / l, potassium chromium sulfate (CrK (SO ₄ ) ₂ · 12H ₂ O) 400 g / l was added to continuously dissolve completely, followed by dissolving 32 g / l of complexing agent (Nu salt), dissolving electrolyte salt (NC-2), and adding 25 cc / l of wetting agent (NF-ll) In the plating tank filled with the above-described plating solution, the plating solution temperature is 20-35 ° C. and the current density is 15-60.

At the anode, the alloy rod is used, and the cathode is made of copper rod, and the plating is performed by continuously moving a copper metal plate at a plating speed of 002 to 0.008 mm / min.

Plating of the present invention is arranged to enable continuous production to produce a heat collecting plate of uniform quality, but a thin thickness of the plating is made while providing a high-quality heat collecting plate with high absorption and low emissivity, the embodiment of the present invention Look at the drawing.

In the present invention, a copper metal sheet wound on a coiling coil is degreased (10), washed with water (20), nickel strike (30), washed with water (40), activated (50), washed with water (60), and chromium black sulphate. Through the potassium plating process (70), water washing process (80), drying process (90) to produce a solar heat collecting plate using a copper metal plate plated with a low-emission rate and high efficiency solar selective absorption thin film in a short time, As the copper metal plate moves continuously, electroplating is performed to the surface of the copper metal plate to have a chromium potassium sulfate of 0.0001 to 0.0015 mm in thickness.

The present invention is an electroplating method of 94 to 98% of solar heat absorption rate and 3 to 8% emissivity by electroplating potassium chromium sulfate with a thickness of 0.0001 to 0.0015 mm on the surface of a copper metal plate used as a heat collecting plate of a solar collector by the above-described process. Solar panels will be manufactured.

In the present invention, the plating solution to be plated with black chromium sulfate on the surface of the copper metal plate is filled with 1/3 of the plating tank in clean water and diluted 400 ~ 450cc / l of the conductive salt (Hy Cr), potassium chromium sulfate (CrK (SO ₄ ) ₂ · 12H ₂ O) 400 g / l was added to continuously dissolve completely, followed by dissolving 32 g / l of complexing agent (Nu salt), dissolving electrolyte salt (NC-2), and wetting agent (NF- ll) 25 cc / l was added and dissolved.

에서 도금속도 0.002~0.008mm/min의 속도로 도금함으로써 이루어지게 된다.And in the present invention, the plating solution temperature of the plating bath 20 ~ 35 ℃, current density 15 ~ 60 in the present invention

In the plating speed is made by plating at a rate of 0.002 ~ 0.008mm / min.

Hereinafter, specific examples of the present invention will be described for each process.

First, the degreasing step 10 will be described.

Degreasing step (10) of the present invention is to remove impurities on the surface of the copper metal plate in order to ensure good electrodeposition of chromium black sulphate on the copper metal plate surface by electroplating, 40 ~ 50g of S-2000 in 1 liter of clean water By mixing and maintaining 50 ~ 60 ℃ copper metal plate to be impregnated for 1-3 minutes to be washed.

The water washing process 20 of the present invention is to supply a clean water to maintain the water wash water so that clean water is made.

인 상태로 양극 Ti 바스켓트+S라운드 Ni를 사용하며, 1-3분간 도금이 이루어지도록 한다.In the nickel strike process 30 of the present invention, a copper metal plate having been washed with water 20 is 300 g of nickel sulfate (NiSO ₄ · 6H ₂ O), 68 g of nickel chloride (NiCl ₂ · 6H ₂ O), and boric acid (1 L of water). H ₃ BO ₃ ) 41g, 1-2cc of surfactant is mixed to form a liquid, the current density at a temperature of 50 ~ 55 ℃ 35

Use the anode Ti basket + S round Ni in the in state, and allow plating for 1-3 minutes.

Nickel striking operation is fixed by using SCR rectifier to fix the specified current density, depositing metal nickel as the bottom surface of copper metal plate passes over anode, and installing storage tank separately to maintain plating solution concentration and storage tank using filter pump. Transfer the plating solution from the plating tank to the storage tank and return to the storage tank. The plating solution is heated in the storage tank. The copper metal plate and the roll of the cathode electrical contact are made of copper alloy using NC electrolyte.

The washing step 40 of the present invention is the same as the washing step 20 described above.

Activation process 50 of the present invention is to remove the thin oxide film formed on the copper metal plate to obtain a high adhesion black chromium potassium sulfate coating film, sulfuric acid (H ₂ SO ₄ ) 10% to 1-3 minutes at room temperature The copper metal plate surface is made active by being held for a while.

The washing step 60 of the present invention is the same as the washing step 20, 40 described above.

에서 도금속도 0.002~0.008mm/min의 속도로 도금이 진행되게 함으로써 도금액에 포함된 블랙황산크롬칼륨이 구리 금속판 표면에 0.0001∼0.0015mm 두께로 전기 도금이 이루어진다.The potassium chromium sulfate plating process 70 of the present invention is a process in which the surface of the copper metal plate is plated, so that a plating solution, that is, clean water, is maintained at a temperature of 20 to 35 ° C. contained in the black chromium potassium plating bath. After filling, dilute 400 ~ 450cc / l of conductive salt (Hy Cr), and add 400g / l of potassium chromium sulfate (CrK (SO ₄ ) ₂ · 12H ₂ O) to continuously dissolve it completely, followed by complexing agent (Nu salt) 32 g / l was dissolved, electrolyte salt (NC-2) was dissolved, 25 cc / l of humectant (NF-ll) was added and dissolved, and a plating solution was used.The anode was made of alloy rods and the cathode was made of copper rods. Current density 40

At the plating rate of 0.002 ~ 0.008mm / min at the plating is carried out by the electroplating is carried out to the surface of the copper metal plate of potassium chromium black sulphate contained in the plating solution to the thickness of 0.0001 ~ 0.0015mm.

This chromium black chromium sulfate plating method is fixed by using a SCR rectifier to the specified current density, and the lower surface of the copper metal plate passes through the anode to electrodeposit the black metal and to install a separate storage tank in the lower part to maintain a constant plating solution concentration The chemical pump is used to transfer the plating liquid from the storage tank to the plating tank and return to the storage tank again. The copper metal plate and the roll of the cathode electrical contact are made of alloy steel and are energized using NC electrolyte.

The washing process 80 of the present invention is the same as the washing process 20, 40, 60 described above.

In the drying process 90 of the present invention, after the plating is performed, the washed copper metal plate is dried by hot air at 70-80 ° C. using a ring blower, and the solar heat absorption rate is applied to the surface by using the copper metal plate that has undergone such a process. It will produce electroplating solar panels with 94-98% and emissivity of 3-8%.

When the electrode of the copper rod used as the cathode in the present invention is applied opposite to the electrodeposition, a portion of the electrodeposition material plated on the surface of the copper metal plate can be desorbed, so that when the copper rod electrode is repeated once, the plating layer is uniform and the illuminance is constant. have.

10: degreasing step 20,40,60,80,100: washing step
30 nickel strike process 50 activation process
70: black chromium sulfate plating process
90: drying process

Claims (1)

Degreasing step (10) is a degreasing step (10) of washing a copper metal plate by mixing 40-50 g of S-2000 in 1 liter of clean water, soaking for 1-3 minutes in a solution maintained at 50 ~ 60 ℃,
The copper metal plate after the degreasing step (10) was washed in the washing step (20), and then 300 g of nickel sulfate (NiSO ₄ · 6H ₂ O), 68 g of nickel chloride (NiCl ₂ · 6H ₂ O), and boric acid (H) in 1 liter of water. ₃ BO ₃ ) 41g, surfactant 1-2cc mixed, the current density at the temperature 50 ~ 55 ℃ 35

Nickel strike process 30 is plated for 1-3 minutes using the anode Ti basket + S round Ni in the state of, and
After the nickel strike process 30, the copper metal plate undergoes a washing process 40, and then activates 50 to activate by maintaining the sulfuric acid (H ₂ SO ₄ ) for 10 minutes at room temperature for 1-3 minutes,
After the activation process, the copper metal plate is washed with water (60) and filled with 1/3 of the plating tank with clean water to dilute 400 ~ 450cc / l of conductive salt (Hy Cr), and chromium potassium sulfate (CrK (SO ₄ )). ₂ · 12H ₂ O), and dissolved by the addition of 400g / l complexing agent (Nu salt) 32g / l, the electrolyte salt (NC-2), by using the wetting agent (NF-ll) plating solution obtained by dissolving a 25cc / l 20 Current Density 40 at ~ 35 ℃

Black chromium sulphate plating process (70) to allow the plating to proceed at a plating rate of 0.002 ~ 0.008 mm / min at
The copper metal plate, which has undergone the plating process (70), undergoes a drying process (90) for drying with hot air at 70 to 80 ° C. after the water washing process (80), and has low emissivity and high absorption rate. Continuous chromium sulfate plating method.

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