KR100403461B1 - Electro zinc plating method of steel sheet - Google Patents
Electro zinc plating method of steel sheet Download PDFInfo
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- KR100403461B1 KR100403461B1 KR10-1998-0044404A KR19980044404A KR100403461B1 KR 100403461 B1 KR100403461 B1 KR 100403461B1 KR 19980044404 A KR19980044404 A KR 19980044404A KR 100403461 B1 KR100403461 B1 KR 100403461B1
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- 238000007747 plating Methods 0.000 title claims abstract description 72
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 12
- 239000010959 steel Substances 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title description 4
- 239000011701 zinc Substances 0.000 title description 4
- 229910052725 zinc Inorganic materials 0.000 title description 4
- 239000000654 additive Substances 0.000 claims abstract description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 11
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 11
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005246 galvanizing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 5
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004327 boric acid Substances 0.000 claims abstract description 4
- -1 chlorine ions Chemical class 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 9
- 229910001335 Galvanized steel Inorganic materials 0.000 abstract description 3
- 239000008397 galvanized steel Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 25
- 239000010410 layer Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 7
- 238000009713 electroplating Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- PMMYEEVYMWASQN-DMTCNVIQSA-N Hydroxyproline Chemical compound O[C@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-DMTCNVIQSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- PMMYEEVYMWASQN-UHFFFAOYSA-N dl-hydroxyproline Natural products OC1C[NH2+]C(C([O-])=O)C1 PMMYEEVYMWASQN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229960002591 hydroxyproline Drugs 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- FGMPLJWBKKVCDB-UHFFFAOYSA-N trans-L-hydroxy-proline Natural products ON1CCCC1C(O)=O FGMPLJWBKKVCDB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/02—Heating or cooling
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
본 발명은 도금층의 광택도, 백색도, 조도, 전류효율을 양호하게 하여, 품질을 향상시키고, 우수한 전기아연도금강판을 제조할 수 있는 강관의 전기아연도금방법을 제공하는 데 그 목적이 있다.SUMMARY OF THE INVENTION An object of the present invention is to provide an electrozinc plating method of a steel pipe which can improve the glossiness, whiteness, roughness, and current efficiency of a plating layer, improve quality, and produce an excellent galvanized steel sheet.
본 발명의 강판의 전기아연도금방법은, 10 ~ 15 중량%의 폴리에틸렌글리콜과, 0.1 ~ 1.0 중량%의 안식향산 및, 상호간에 1:1 ~ 1:3 의 중량비를 갖되 중량 합계가 폴리에틸렌글리콜의 중량 대비 2 ~ 5 중량% 인 포름알데히드와 붕산의 혼합물을 함유하는 도금용액 첨가제를 도금용액 전체에 대하여 0.08 ~ 2.0 mL/L 로 첨가하고, 상기 도금용액의 아연이온의 몰농도를 0.7 ~ 2.0 몰/리터로 하고, 염소이온의 몰농도를 4.0 ~ 9.0 몰/리터로 하며, 온도를 40 ~ 75℃ 로 하고, pH를 1.5 ~ 6.0 으로 하며, 전류밀도를 30 ~ 200 A/dm2으로 하여 강판을 전기아연도금하는 것을 특징으로 한다.The electrogalvanizing method of the steel sheet of the present invention has a weight ratio of 10 to 15% by weight of polyethylene glycol, 0.1 to 1.0% by weight of benzoic acid and mutually 1: 1 to 1: 3, the total weight of the polyethylene glycol A plating solution additive containing a mixture of formaldehyde and boric acid in an amount of 2 to 5% by weight is added at 0.08 to 2.0 mL / L based on the entire plating solution, and the molar concentration of zinc ions in the plating solution is 0.7 to 2.0 mol / L. Liter, the molarity of chlorine ion is 4.0 ~ 9.0 mol / liter, the temperature is 40 ~ 75 ℃, pH is 1.5 ~ 6.0, the current density is 30 ~ 200 A / dm 2 It is characterized by electro-galvanizing.
Description
본 발명은 전기아연도금방법에 관한 것이며, 특히, 도금층의 표면외관(백색도, 광택도), 조도 및 전류 효율을 향상시키는 강판의 전기아연도금방법에 관한 것이다.The present invention relates to an electrozinc plating method, and more particularly, to an electrozinc plating method of a steel sheet which improves the surface appearance (whiteness, glossiness), roughness and current efficiency of the plating layer.
표면 처리 제품 중에서 전기아연도금강판은 도금의 용이성, 비용 및 내식성 등의 측면에서 유리한 점이 많아 가전제품, 건설, 자동차 등등의 소재로 널리 사용되고 있다. 특히, 전기아연도금강판의 경우 생산성 향상을 위한 고전류밀도 도금이 필수적이며, 도장용으로 사용되는 경우가 많아 도금층의 표면외관이 우수하여야 한다. 전기아연도금용액으로는 염화물계 용액, 황화물계 용액, 시안계 용액 등이 사용되고 있으며, 그 중 염화물계 용액은 전기 전도도가 우수하여 고전류밀도 도금에 적합한 것으로 알려져 있으나, 전류밀도가 증가하면 도금층의 표면외관이 저하되고, 표면이 거칠게 되어 후처리 공정(인산염 처리, 크롬 처리, 도장 처리 등)이 곤란하며, 도장을 하였을 때 표면이 어둡고 표면반사에 의하여 선명성이 불량한 문제점이 발생한다. 상기 문제점을 해결하기 위하여, 기존 업계에 널리 알려져 있는 첨가제를 소량 첨가하는 경우에도 전류효율이 감소한다는 문제점이 발생하는 것으로 알려져 있다.Among the surface-treated products, electro-galvanized steel sheet has many advantages in terms of ease of plating, cost and corrosion resistance, and is widely used as a material for home appliances, construction, automobiles, and the like. In particular, in the case of electro-galvanized steel sheet, high current density plating is essential for improving productivity, and in many cases, the surface appearance of the plating layer should be excellent. Chloride-based solution, sulfide-based solution, and cyanide-based solution are used as electro zinc plating solution. Among them, chloride-based solution is known to be suitable for high current density plating because of its excellent electrical conductivity. The appearance is degraded, the surface is rough, and post-treatment processes (phosphate treatment, chromium treatment, coating treatment, etc.) are difficult, and when the coating is performed, the surface is dark and poor surface sharpness occurs due to surface reflection. In order to solve the problem, it is known that the current efficiency decreases even when a small amount of an additive known in the art is added.
상기와 같은 문제점을 해결하기 위하여 종래에 알려져 있는 기술을 살펴보면 다음과 같다.Looking at the prior art known to solve the above problems are as follows.
'미국특허 제4,210,500호'의 내용은 도금 표면의 광택도를 개선하기 위한 기술에 관한 것이고, '미국특허 제4,146,441호'의 내용은 황화물계 용액에서 도금층의 광택도 개선과 도금 전류밀도의 범위 확대를 위하여 포름알데히드의 혼합물을 첨가한다는 내용이며, '미국특허 제4,149,510호'는 염화물계 용액에서 아민계 폴리머를 첨가하여 광택도를 개선한다는 내용이고, '미국특허 제3,855,085호'는 염화물계 용액에서 비이온성 폴리옥시에틸렌(polyoxyethylene)의 첨가에 의하여 표면광택을 개선한다는 내용이다.The contents of US Patent No. 4,210,500 are related to the technology for improving the glossiness of the plating surface, and the contents of US Patent No. 4,146,441 are for improving the glossiness of the plating layer in the sulfide-based solution and expanding the range of plating current density. For the purpose of adding a mixture of formaldehyde, 'US Patent No. 4,149,510' improves the glossiness by adding an amine polymer in a chloride solution, and 'US Patent No. 3,855,085' refers to a chloride solution. The surface gloss is improved by the addition of nonionic polyoxyethylene.
한편, '일본국 특개소58-48639호'는 염화암모늄, 염화칼륨, 염화나트륨, 염화알루미늄, 염화바륨, 염화칼슘, 염화마그네슘 등을 선택적으로 사용하고, 도금 조건을 변경하여 도금 표면의 광택도를 개선시킨다는 내용이며, 마찬가지로 '일본국 특개소61-204389호'는 아미노산, 글리신, 히드록신프로린 등의 첨가제를 첨가하여 도금 표면의 광택도를 개선시킨다는 내용이다.On the other hand, Japanese Patent Application Laid-Open No. 58-48639 uses ammonium chloride, potassium chloride, sodium chloride, aluminum chloride, barium chloride, calcium chloride, magnesium chloride, etc. selectively and improves the glossiness of the plating surface by changing the plating conditions. Similarly, Japanese Patent Application Laid-Open No. 61-204389 describes the addition of additives such as amino acids, glycine, and hydroxyproline to improve the glossiness of the plating surface.
그러나, 상기 기술들은 대부분 아연도금층의 표면외관인 광택도 개선에 주로 한정된 것으로 표면외관, 조도 및 전류효율 등의 복합적인 품질 향상을 가져오기에는 부적합하다는 문제점이 있었다.However, the above techniques are mainly limited to improving the glossiness, which is the surface appearance of the zinc plated layer, and thus, there is a problem in that it is unsuitable for bringing complex quality improvements such as surface appearance, roughness and current efficiency.
본 발명은 앞서 설명한 바와 같은 종래 기술의 문제점을 해결하기 위하여 안출된 것으로서, 도금층의 표면외관(광택도, 백색도), 조도 및 전류효율 등을 개선시키는 강판의 전기아연도금방법을 제공하는 데 그 목적이 있다.The present invention has been made in order to solve the problems of the prior art as described above, the object of the present invention to provide an electro-galvanizing method of the steel sheet to improve the surface appearance (glossiness, whiteness), roughness and current efficiency of the plating layer, etc. There is this.
앞서 설명한 바와 같은 목적을 달성하기 위한 본 발명의 강판의 전기아연도금방법은, 10 ~ 15 중량%의 폴리에틸렌글리콜과, 0.1 ~ 1.0 중량%의 안식향산 및, 상호간에 1:1 ~ 1:3 의 중량비를 갖되 중량 합계가 폴리에틸렌글리콜의 중량 대비 2 ~ 5 중량%인 포름알데히드와 붕산의 혼합물을 함유하는 도금용액 첨가제를 도금용액 전체에 대하여 0.08 ~ 2.0 mL/L 로 첨가하고, 상기 도금용액의 아연이온의 몰농도를 0.7 ~ 2.0 몰/리터로 하고, 염소이온의 몰농도를 4.0 ~ 9.0 몰/리터로 하며, 온도를 40 ~ 75℃ 로 하고, pH를 1.5 ~ 6.0 으로 하며, 전류밀도를 30 ~ 200 A/dm2으로 하여 강판을 전기아연도금하는 것을 특징으로 한다.Electro-galvanizing method of the steel sheet of the present invention for achieving the object as described above, the weight ratio of 10 to 15% by weight polyethylene glycol, 0.1 to 1.0% by weight benzoic acid and mutually 1: 1 to 1: 3 A plating solution additive containing a mixture of formaldehyde and boric acid having a total weight of 2 to 5% by weight based on the weight of polyethylene glycol was added at 0.08 to 2.0 mL / L to the entire plating solution, and zinc ions of the plating solution were added. The molar concentration of is 0.7 to 2.0 mol / liter, the molar concentration of chlorine ion is 4.0 to 9.0 mol / liter, the temperature is 40 to 75 ℃, the pH is 1.5 to 6.0, and the current density is 30 to The steel sheet is characterized by electroplating with 200 A / dm 2 .
아래에서, 본 발명에 따른 양호한 일 실시예를 상세히 설명하겠다.In the following, a preferred embodiment according to the present invention will be described in detail.
상기 도금용액의 아연이온은 몰농도를 0.7 ~ 2.0 몰/리터로 하는데, 0.7 몰/리터 이하에서는 피복된 이온의 농도 부족에 의하여 도금이 검게 되는 버닝(Burning)과 줄무늬가 발생하며, 2.0 몰/리터 이상에서는 도금층의 표면이 거칠어지고 아연이온의 고농도로 인하여 비용이 많이 드는 문제점이 발생한다.The zinc ion of the plating solution has a molar concentration of 0.7 to 2.0 moles / liter, and below 0.7 moles / liter, burning and streaking occurs in which plating becomes black due to insufficient concentration of coated ions, and 2.0 moles / liter. Above the liters, the surface of the plating layer becomes rough and expensive problems occur due to the high concentration of zinc ions.
또한, 상기 도금용액의 염소이온은 몰농도를 5.0 ~ 9.0 몰/리터로 하는데, 4.0 몰/리터 이하에서는 전기 전도도의 감소로 인하여 버닝이 다량 발생하고, 9.0 몰/리터 이상에서는 과포화로 인하여 도금층의 표면 박리 현상이 발생한다.In addition, the chlorine ion of the plating solution has a molar concentration of 5.0 to 9.0 mol / liter, but in 4.0 mol / liter or less, a large amount of burning occurs due to a decrease in electrical conductivity. Surface peeling phenomenon occurs.
본 실시예에 따른 도금 조건을 상세히 살펴보면 다음과 같다.Looking at the plating conditions according to the embodiment in detail as follows.
상기 도금용액의 온도는 40 ~ 75 ℃ 로 하는데, 40 ℃ 이하에서는 전기 전도도의 감소로 인하여 도금층의 표면이 분말화되는 현상과 함께 줄무늬가 발생하고, 75 ℃ 이상에서는 도금용액의 증발로 인하여 농도 조절이 곤란하다는 문제점이 발생한다.The temperature of the plating solution is 40 ~ 75 ℃, below 40 ℃, due to the reduction of the electrical conductivity, the surface of the plating layer is powdered with the phenomenon that the streaks occur, above 75 ℃ concentration control due to the evaporation of the plating solution This problem arises.
또한, 상기 도금용액의 pH는 1.5 ~ 6.0 으로 하는데, 1.5 이하에서는 도금 설비의 부식으로 인하여 불순물의 증가와 함께 도금 표면층이 어두워지며, 6.0 이상에서는 노란색의 변색이 발생하는 문제점이 발생한다.In addition, the pH of the plating solution is 1.5 to 6.0, but below 1.5, the plating surface layer darkens with the increase of impurities due to corrosion of the plating equipment, and above 6.0, yellow discoloration occurs.
또한, 상기 도금용액의 전류밀도는 30 ~ 200 A/dm2로 하는데, 30 A/dm2이하에서는 전류효율이 감소되어 생산성이 떨어져 비용이 상승되고, 200 A/dm2이상에서는 금속이온의 확산 속도의 제한으로 인하여 버닝 발생 등 정상적인 도금 품질을 얻기가 어려운 문제점이 발생한다.In addition, the current density of the plating solution is 30 ~ 200 A / dm 2 , but less than 30 A / dm 2 current efficiency is reduced, the productivity is lowered, the cost is increased, above 200 A / dm 2 diffusion of metal ions Due to the limitation of speed, it is difficult to obtain normal plating quality such as burning.
또한, 상기 도금용액과 음극의 상대유속은 0.5 ~ 2.5 m/sec 로 하는데, 0.5 m/sec 이하에서는 금속 이온의 확산 속도가 제한되므로 고 전류밀도 도금을 어렵게 하며, 2.5 m/sec 이상의 유속을 얻는다는 것은 연속 도금 설비상 어렵다.In addition, the relative flow rate of the plating solution and the cathode is 0.5 ~ 2.5 m / sec, the diffusion rate of the metal ion is limited to less than 0.5 m / sec, making high current density plating difficult, and obtain a flow rate of 2.5 m / sec or more It is difficult on the continuous plating equipment.
본 실시예에서 제안하는 아연 - 철 합금전기도금에 사용되는 첨가제에 관하여 상세히 살펴보면 다음과 같다.Looking at the additive used in the zinc-iron alloy electroplating proposed in this embodiment in detail as follows.
상기 도금용액의 첨가제의 한 성분으로서 폴리에틸렌글리콜이 사용되며, 중합도 n의 수가 10 ~ 20 범위인 폴리에틸렌글리콜과 20 ~ 30 범위인 폴리에틸렌글리콜이 각각 1종 이상 혼합되며, 그 혼합비는 중량비로 1:2 ~ 1:5 이고, 상기 혼합 폴리에틸렌글리콜의 농도는 10 ~ 15 중량% 이다. 중합도 n의 수가 10 이하에서는 도금 결정립의 미세화 효과가 미약하고 표면의 평탄도가 떨어지며, 30 이상이면 도금층의 백색도 및 광택도 향상 효과가 저하된다. 중합도 n의 수가 10 ~ 20 사이의 성분과 20 ~ 30 사이의 성분의 비율을 1:2 ~ 1:5 로 제한한 것은 마찬가지로 도금층의 표면외관 향상 효과를 위한 것이며, n 수가 많은 성분은 표면외관 향상 기능이 있다. 이들의 수용액 중 농도가 10 중량% 이하에서는 도금결정의 미세화 효과가 적어서 도금 표면이 거칠어지고, 15 중량% 이상에서는 도금층의 백색도 및 광택도의 향상 효과가 저하되는 문제점이 발생한다.Polyethylene glycol is used as one component of the additive of the plating solution, at least one of polyethylene glycol having a degree of polymerization n of 10 to 20 and polyethylene glycol of 20 to 30 is mixed, and the mixing ratio is 1: 2 by weight. ˜1: 5, and the concentration of the mixed polyethylene glycol is 10-15 wt%. If the number of the polymerization degree n is 10 or less, the effect of miniaturization of the plating crystal grains is poor and the surface flatness is inferior. If it is 30 or more, the effect of improving the whiteness and glossiness of the plating layer is reduced. Limiting the ratio of the number of the polymerization degree n to the component between 10 and 20 and the component between 20 and 30 to 1: 2 to 1: 5 is for the effect of improving the surface appearance of the plated layer. There is a function. If the concentration in these aqueous solutions is 10% by weight or less, the plating crystals have a small effect of miniaturization, resulting in roughening of the plating surface, and in the case of 15% by weight or more, problems of improving the whiteness and glossiness of the plating layer occur.
또한, 상기 도금용액의 첨가제의 한 성분으로서 방향족산인 안식향산의 농도는 0.1 ~ 1.0 중량% 이다. 안식향산의 농도가 0.1 중량% 이하이면 도금 표면층의 평탄도가 저하되며, 1.0 중량% 이상에서는 도금층에 노란 줄무늬가 발생하며 도금 밀착성도 불량해지는 문제점이 발생한다.In addition, the concentration of benzoic acid which is an aromatic acid as one component of the additive of the plating solution is 0.1 to 1.0% by weight. If the concentration of benzoic acid is 0.1 wt% or less, the flatness of the plating surface layer is lowered. At 1.0 wt% or more, yellow stripes occur in the plating layer and plating adhesion is poor.
또한, 상기 도금용액의 첨가제의 성분으로서 포름알데히드와 붕산이 중량비로 1:1 ~ 1:3 의 비율로 혼합되고, 이들 합계 중량은 폴리에틸렌글리콜에 대하여 2 ~ 5 중량% 로 도금용액에 첨가된다. 상기의 범위를 벗어나면 표면이 어두워지고 광택이 감소되는 문제점이 발생한다.In addition, formaldehyde and boric acid are mixed at a weight ratio of 1: 1 to 1: 3 as a component of the plating solution additives, and these total weights are added to the plating solution at 2 to 5% by weight based on polyethylene glycol. Outside the above ranges, the surface becomes dark and gloss decreases.
상기와 같이 제조된 첨가제는 도금용액 전체에 대하여 0.08 ~ 2.0 mL/L 의 농도로 첨가된다. 첨가제의 농도가 0.08 mL/L 이하에서는 도금층의 광택도, 백색도 및 조도의 향상 효과를 얻을 수 없으며, 2.0 mL/L 이상 첨가되면 오히려 광택도, 백색도 및 조도가 저하되고 도금전류의 효율이 낮아지는 문제점이 발생한다.The additive prepared as described above is added at a concentration of 0.08 to 2.0 mL / L based on the entire plating solution. When the concentration of the additive is 0.08 mL / L or less, the effect of improving the glossiness, whiteness and roughness of the plating layer cannot be obtained. When the concentration of the additive is added more than 2.0 mL / L, the glossiness, whiteness and roughness are lowered, and the efficiency of the plating current is lowered. A problem occurs.
한편, 본 발명의 첨가제는 피도금체의 금속 종류, 형상에 관계없이 산성 염화물을 이용하는 전기아연도금에 적용될 수 있으며, 특히 고 전류밀도 도금이 필요한 강판의 연속 전기아연도금시 우수한 도금 품질을 용이하게 얻을 수 있다.On the other hand, the additive of the present invention can be applied to electro-galvanizing using acid chloride regardless of the metal type and shape of the plated body, in particular, excellent plating quality in the case of continuous electro-galvanization of steel sheet requiring high current density plating easily You can get it.
상기 실시예에 따른 본 발명의 효과를 알아보기 위하여 도금 용액의 조성을 바꾸어가면서 표 1과 같은 실험을 해 보았다. 상기 실험에서는 냉연 강판을 피도금 금속으로 하였으며, 아연 이온의 농도는 90g/L, 염소 이온의 농도는 270g/L, 도금부착량은 40 g/dm2이 되게 도금하였을 때 도금층 표면의 광택도, 백색도, 조도, 전류효율을 알아보았다. 도금조건은 pH = 4.5, 온도 = 60℃, 전류밀도 = 100 A/dm2으로 설정하였다.In order to determine the effect of the present invention according to the embodiment, the experiments of Table 1 were made while changing the composition of the plating solution. In the above experiment, the cold-rolled steel sheet was a plated metal, and the glossiness and the whiteness of the surface of the plating layer when the zinc ion concentration was 90 g / L, the chlorine ion concentration was 270 g / L, and the plating amount was 40 g / dm 2 were applied. , Illumination and current efficiency were examined. Plating conditions were set to pH = 4.5, temperature = 60 ℃, current density = 100 A / dm 2 .
표 1. 첨가제의 성분 구성에 따른 도금층 표면의 특성Table 1. Characteristics of plating layer surface according to the composition of additives
* 광택도의 상태 : 광택도계로 측정된 수치가 19 이상이면 ○, 그 이외에는 ×* State of glossiness: ○ If the value measured with glossmeter is 19 or more, other than ×
* 백색도의 상태 : 색차계로 측정된 수치가 82 이상이면 ○, 그 이외에는 ×* State of whiteness: ○ if the value measured by color difference meter is 82 or more, otherwise ×
* 조도의 상태 : 3차원 조도계로 측정하였고, 도금표면층의 조도와 피도금금속 원판의 최대(Rmax) 조도차이가 1 μm 이하이면 ○, 그 이외에는 ×* Condition of roughness: Measured by 3D illuminometer, ○ if the difference between roughness of plating surface layer and maximum (Rmax) roughness difference of original metal plated is 1 μm or less, otherwise ×
* 전류효율의 상태 : 패러데이 법칙에 의한 이론 도금 전류효율 대비 실제* Current Efficiency: Theoretical Plating Current Efficiency by Faraday's Law
도금에 대한 전류효율과의 비가 97 % 이상이면 ○, 그 이외에는 ×○ If ratio to current efficiency for plating is more than 97%, otherwise ×
상기 표 1에 나타낸 바와 같이 본 발명에 부합되는 조건에서는 광택도, 백색도, 조도, 전류효율 등이 양호하지만, 본 발명의 범위를 벗어난 도금조건하에서는 그러하지 아니함을 알 수 있다.As shown in Table 1, the glossiness, whiteness, roughness, current efficiency, and the like are good under the conditions consistent with the present invention, but it is understood that this is not the case under plating conditions outside the scope of the present invention.
앞서 상세히 설명한 바와 같이 본 발명은 아연의 전기도금에 있어서, 염화물계의 도금용액에 첨가제를 사용함으로써, 광택도, 백색도, 조도, 전류효율을 양호하게 하여 품질을 향상시키고, 우수한 전기아연도금강판을 만들 수 있는 효과가 있다. 특히 고전류밀도 도금이 필요한 강판의 연속 전기도금시 우수한 도금 품질을 용이하게 얻을 수 있다.As described in detail above, the present invention improves the quality by improving the glossiness, whiteness, roughness, and current efficiency by using an additive in the plating solution of chloride system in the electroplating of zinc. There is an effect that can be made. In particular, excellent plating quality can be easily obtained during continuous electroplating of a steel sheet requiring high current density plating.
이상에서 본 발명에 대한 기술사상을 서술하였지만 이는 본 발명의 가장 양호한 실시예를 예시적으로 설명한 것이지 본 발명을 한정하는 것은 아니다. 또한, 이 기술분야의 통상의 지식을 가진 자이면 누구나 본 발명의 기술사상의 범주를 이탈하지 않는 범위내에서 다양한 변형 및 모방이 가능함은 명백한 사실이다.Although the technical spirit of the present invention has been described above, the present invention is described by way of example and not limitation of the present invention. In addition, it is obvious that any person skilled in the art can make various modifications and imitations without departing from the scope of the technical idea of the present invention.
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| KR960017925A (en) * | 1994-11-22 | 1996-06-17 | 김만제 | Additives of chloride-based zinc-iron alloy electroplating solutions and plating solutions containing them |
| JPH08283982A (en) * | 1995-04-17 | 1996-10-29 | Yuken Kogyo Kk | Chloride bath electrogalvanizing method |
| KR19980050699A (en) * | 1996-12-21 | 1998-09-15 | 김종진 | Manufacturing method of electro-galvanized steel sheet with good adhesion, surface appearance and roughness |
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| KR960017925A (en) * | 1994-11-22 | 1996-06-17 | 김만제 | Additives of chloride-based zinc-iron alloy electroplating solutions and plating solutions containing them |
| JPH08283982A (en) * | 1995-04-17 | 1996-10-29 | Yuken Kogyo Kk | Chloride bath electrogalvanizing method |
| KR19980050699A (en) * | 1996-12-21 | 1998-09-15 | 김종진 | Manufacturing method of electro-galvanized steel sheet with good adhesion, surface appearance and roughness |
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