KR100425594B1 - Solution spray for minimized spangle - Google Patents
Solution spray for minimized spangle Download PDFInfo
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- KR100425594B1 KR100425594B1 KR10-1999-0057668A KR19990057668A KR100425594B1 KR 100425594 B1 KR100425594 B1 KR 100425594B1 KR 19990057668 A KR19990057668 A KR 19990057668A KR 100425594 B1 KR100425594 B1 KR 100425594B1
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- South Korea
- Prior art keywords
- steel sheet
- sequins
- solution
- dip galvanized
- hot
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- 239000007921 spray Substances 0.000 title description 10
- 239000000243 solution Substances 0.000 claims abstract description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 23
- 239000008397 galvanized steel Substances 0.000 claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 23
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 15
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 13
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims abstract description 12
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 12
- -1 sodium lauryl sulfate compound Chemical class 0.000 claims abstract description 12
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims abstract description 12
- 239000010959 steel Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 238000007670 refining Methods 0.000 claims description 9
- 230000007547 defect Effects 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 abstract description 7
- 239000007924 injection Substances 0.000 abstract description 7
- 239000010960 cold rolled steel Substances 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000005246 galvanizing Methods 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 238000007747 plating Methods 0.000 description 22
- 238000005507 spraying Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000004254 Ammonium phosphate Substances 0.000 description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 6
- 235000019289 ammonium phosphates Nutrition 0.000 description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 241000519995 Stachys sylvatica Species 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
- C23C2/265—After-treatment by applying solid particles to the molten coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating With Molten Metal (AREA)
Abstract
본 발명은 냉연강판에 아연도금을 하는 공정에 있어서, 냉연강판에 도금된 아연의 결정립이 미세하며, 환경 친화적인 조업을 수행할 수 있도록 하는 용융아연 도금강판의 스팽글 미세화용 수용액을 제공하는 데 그 목적이 있다.The present invention provides a solution for minimizing the sequins of hot-dip galvanized steel sheet in the process of galvanizing the cold-rolled steel sheet, the crystal grains of zinc plated on the cold-rolled steel sheet is fine, environmentally friendly operation. There is a purpose.
본 발명에 따르면, 안티몬이 단독 혹은 다른 성분과 함께 첨가된 아연용액이 강판에 도포되고, 응고하면서 발생하는 스팽글을 미세화 하는 분사용액에 있어서, 소디움라우릴설페이트 화합물(CH3(CH2)11OSO3Na) 및 소르비탄(Sorbitan)계 비이온 계면활성제 중에서 선택된 1종 또는 2종의 화합물을 첨가재로 하여 용융아연 도금강판에 분사되는 용융아연 도금강판의 스팽글을 미세화 하는 분사용액이 제공된다.According to the present invention, a zinc solution in which antimony is added alone or in combination with other components is applied to a steel sheet, and the sodium lauryl sulfate compound (CH 3 (CH 2 ) 11 OSO is used in the injection solution to refine the sequins generated during solidification. Provided is an injection solution for miniaturizing the sequins of a hot dip galvanized steel sheet sprayed onto a hot dip galvanized steel sheet using one or two compounds selected from 3 Na) and a sorbitan-based nonionic surfactant as an additive.
Description
본 발명은 용융아연 도금강판에 발생하는 스팽글을 미세화 할 수 있도록 도금강판에 분사하는 수용액에 관한 것이며, 특히, 안티몬이 함유된 도금층의 표면에 형성된 스팽글을 미세화 할 수 있고, 피팅의 발생을 줄일 수 있는 환경 친화적인 스팽글 미세화용 수용액에 관한 것이다.The present invention relates to an aqueous solution sprayed on a plated steel sheet so that the sequins generated in the hot-dip galvanized steel sheet can be refined, and in particular, it is possible to refine the sequins formed on the surface of the antimony-containing plated layer and to reduce the occurrence of fittings. The present invention relates to an environmentally friendly aqueous solution for sequin micronization.
일반적으로 아연도금강판을 제조하기 위해서 용융된 아연을 수용하는 도금욕의 내부로 냉연강판을 통과시키고 냉연강판에 도포된 용융아연이 응고되면서 도금강판이 제조된다. 이 때, 안티몬(Sb) 또는 납(Pb)을 함유하고 있는 용융아연의 응고속도에 따라 수지상 모양의 스팽글(Spangle)이 형성되는데, 이런 스팽글의 결정립의 크기에 따라 제로 스팽글(Zero Spangle), 미니 스팽글(Mini Spangle), 레귤러 스팽글(Regular Spangle) 등으로 구분한다.Generally, in order to manufacture a galvanized steel sheet, a cold rolled steel sheet is passed into an inside of a plating bath containing molten zinc, and a molten zinc coated on the cold rolled steel sheet is solidified to produce a galvanized steel sheet. At this time, a dendritic spangle is formed according to the solidification rate of molten zinc containing antimony (Sb) or lead (Pb). According to the size of the crystal grains of the sequins, zero spangle and mini It is divided into Mini Spangle, Regular Spangle and the like.
한편, 이런 스팽글이 존재하는 도금층 표면은 도료의 밀착성이 불량하고 도장 후에도 스팽글에 의한 표면요철이 제거되지 않고, 도료를 투과해 스팽글이 보여지므로 외관이 불량해지는 단점을 갖고 있다.On the other hand, the surface of the plating layer having such sequins has a disadvantage in that the adhesion of the paint is poor and the surface irregularities caused by the sequins are not removed even after coating, and the appearance is poor because the sequins are seen through the paint.
도 1은 일반적인 용융아연 도금 공정의 도금욕을 나타낸 단면도이다.1 is a cross-sectional view showing a plating bath of a general hot dip zinc plating process.
도 1에 도시된 바와 같이, 현재의 연속식 용융아연 도금공정(CGL; Continuous Galvanizing Line)에서는 스팽글이 현저하게 나타나는 제품 즉 레귤러 스팽글과 같은 제품과, 스팽글이 거의 보이지 않는 제로 스팽글 또는 미니 스팽글을 병행 생산하기 위해 통상적으로 납이 0.05∼0.2wt%첨가된 도금욕(1)을 사용하고, 제로 스팽글 또는 미니 스팽글을 제조하기 위해서는 이런 도금욕(1)을 통과한 도금강판(3)에 인산암모늄계 또는 인산나트륨계 수용액(4)을 분사하여 스팽글의 결정립 성장을 억제하여 스팽글 미세화 제품을 생산한다.As shown in FIG. 1, in the current continuous galvanizing line (CGL), a product in which sequins are remarkably displayed, that is, a product such as regular sequins, and a zero sequin or a mini sequin in which sequins are almost invisible In order to produce a plating bath (1) containing 0.05 to 0.2 wt% of lead, and to produce zero sequins or mini sequins, an ammonium phosphate type is applied to the plated steel sheet (3) passed through the plating bath (1). Or by spraying the sodium phosphate-based aqueous solution (4) to suppress the grain growth of the sequins to produce a sequins refined product.
그러나, 도금욕 내에 납이 함유된 용융 아연을 사용하였을 때, 수요가의 장기간 보관한 후에 가공할 때에는 도금층 내의 납이 도금밀착성을 열화시키는 문제점이 발생하고, 또한, 최근 환경오염 규제강화로 인한 도금욕(1) 내의 납 성분 사용을 억제하고 있다는 문제점이 있다.However, when molten zinc containing lead in the plating bath is used, when processing after long-term storage of demand, the lead in the plating layer deteriorates the plating adhesion, and in addition, plating due to the recent tightening of environmental pollution regulation There is a problem that the use of lead in the bath 1 is suppressed.
따라서, 이러한 문제점을 보완하기 위해, 도금욕(1)에 납 대신 안티몬을 첨가하는 용융아연 도금강판의 제조공정으로 급속히 전환되는 추세에 있다. 그러나, 안티몬은 납과 비교하여 스팽글의 형성속도가 2∼3배 빠르므로, 안티몬을 함유한용융아연 도금욕(1)에서 스팽글을 극 미세화 시켜서 표면외관을 향상시키기 위해서는 기존의 인산암모늄계 또는 인산 나트륨계 분사용액으로는 스팽글 극 미세화의 효과를 볼 수 없게 된다.Therefore, in order to compensate for such a problem, there is a tendency to rapidly switch to the manufacturing process of hot-dip galvanized steel sheet in which antimony is added to the plating bath 1 instead of lead. However, since antimony has a two to three times faster formation rate of sequins than lead, in order to improve the surface appearance by making the sequins extremely fine in the molten zinc plating bath (1) containing antimony, conventional ammonium phosphate or phosphoric acid is used. Sodium spray solution is not able to see the effect of the refining of the sequins.
이런 종래부터 스팽글 미세화 용융아연 도금강판을 제조하기 위해, 강판의 표면에 부착된 용융아연(2)이 응고하기 직전에 흡열성을 나타내는 스팽글 미세화 용액을 분사하는 수용액 분사방법으로는 "일본국 특공소 45-26961호"에서 소개하는 황산동, 초산나트륨, 인산나트륨 및 인산암모늄 등의 수용액과 같은 단일 성분의 수용성 무기염 용액을 용융된 아연(2)이 도포된 강판에 분사하는 방법과, "일본 특공소 51-20168호"에서 소개하는 인산암모늄에 폴리인산나트륨을 첨가한 수용액을 분사하는 방법 및, "일본 특개소 50-92831호"에 기재되어 있는 인산암모늄에 계면활성제를 첨가한 수용액을 분사하는 방법이 있다.In order to manufacture such a spangle-miniaturized hot-dip galvanized steel sheet, an aqueous solution spraying method for spraying a sequin-fine solution showing endotherm immediately before the molten zinc (2) adhered to the surface of the steel sheet is solidified, A method of spraying a single component water-soluble inorganic salt solution, such as an aqueous solution of copper sulfate, sodium acetate, sodium phosphate and ammonium phosphate, introduced in No. 45-26961 to a steel plate coated with molten zinc (2), A method of spraying an aqueous solution in which sodium polyphosphate is added to the ammonium phosphate introduced in SO 51-20168, and an aqueous solution in which a surfactant is added to ammonium phosphate described in "Japanese Patent Application No. 50-92831" There is a way.
그러나, 환경문제의 해결책으로 안티몬이 단독 혹은 다른 성분들과 함께 첨가된 용융아연은 납이 단독 혹은 다른 성분과 함께 첨가된 용융아연보다 표면장력이 감소되어 스팽글 형성속도가 증가하게 되어 종래의 수용액(4)을 사용한 통상의 분사조건에서는 스팽글이 도금표면에 잔존하게 되는 문제점이 발생한다.However, as a solution to environmental problems, molten zinc added with antimony alone or with other components has a lower surface tension than molten zinc with lead added alone or with other components, thus increasing the sequin formation rate. Under ordinary spraying conditions using 4), sequins remain on the plating surface.
또한, 2류체 분사노즐의 공기압력을 낮추거나, 용액압력을 증가시켜 용액분사량을 증가시키면, 스팽글은 미세화 되지만, 피팅(Pitting)이라 불리는 백색 반점형태의 표면결함이 나타나서 표면외관 및 광택성을 현저히 떨어뜨리는 문제점이 발생한다. 피팅은 용융상태의 아연에 입경이 큰 분무 입자가 고속으로 충돌할 때 상대적으로 불균일하고 불완전한 아연 결정립들이 분화구 형태의 백색 반점에 존재하는 물리적 혹은 화학적인 결함을 의미하며, 이러한 피팅결함을 줄이기 위해서는 분무입경을 작게 하고 용액분사량을 최소화하는 것이 효과적이다.In addition, when the air pressure of the two-fluid injection nozzle is decreased or the solution pressure is increased by increasing the solution pressure, the sequins become fine, but surface defects in the form of white spots called fittings appear, resulting in remarkable surface appearance and glossiness. Dropping problem occurs. A fitting is a physical or chemical defect in which the relatively uneven and incomplete zinc grains are present in the crater-shaped white spots when spray particles with a large particle size collide with molten zinc at high speed. It is effective to reduce the particle diameter and minimize the solution injection amount.
그러나, 공지된 인산암모늄계 또는 인산나트륨계 베이스의 수용액(4)은 흡열성은 우수하나, 아연도금 표면에 흡착성이 약하기 때문에 용융아연의 표면장력을 거의 변화시키지 못하여 스팽글 잔존 혹은 피팅결함을 유발하는 문제점이 발생한다.However, the known aqueous solution (4) of ammonium phosphate or sodium phosphate-based base has excellent endotherm, but since it has poor adsorption on the surface of zinc plating, it hardly changes the surface tension of molten zinc, causing sequins remaining or fitting defects. This happens.
본 발명은 앞서 설명한 바와 같은 종래 기술의 문제점을 해결하기 위하여 제공된 것으로서, 안티몬이 함유된 아연도금층에 발생하는 스팽글을 미세화할 수 있는 용융아연도금강판의 스팽글 미세화용 수용액을 제공하는데 그 목적이 있다.The present invention has been made to solve the problems of the prior art as described above, and an object thereof is to provide an aqueous solution for refining the sequins of the hot-dip galvanized steel sheet capable of miniaturizing the sequins generated in the antimony-containing galvanized layer.
도 1은 일반적인 용융아연 도금 공정의 도금욕을 나타낸 단면도이다.1 is a cross-sectional view showing a plating bath of a general hot dip zinc plating process.
♠ 도면의 주요부분에 대한 부호의 설명 ♠♠ Explanation of symbols on the main parts of the drawing ♠
1 : 도금욕 2 : 용융아연1: plating bath 2: molten zinc
3 : 도금강판 4 : 수용액3: plated steel sheet 4: aqueous solution
앞서 설명한 바와 같은 목적을 달성하기 위한 본 발명에 따르면, 안티몬이 단독 혹은 다른 성분과 함께 첨가된 아연용액이 강판에 도포되고, 응고하면서 발생하는 스팽글을 미세화 하는 분사용액에 있어서, 소디움라우릴설페이트 화합물(CH3(CH2)11OSO3Na) 및 소르비탄(Sorbitan)계 비이온 계면활성제 중에서 선택된 1종 또는 2종의 화합물을 첨가제로 하여 용융아연 도금강판에 분사되는 용융아연 도금강판의 스팽글을 미세화 하는 분사용액이 제공된다.According to the present invention for achieving the object as described above, in the injection solution in which the zinc solution to which antimony is added alone or in combination with other components is applied to the steel sheet and refines the sequins generated while solidifying, the sodium lauryl sulfate compound Sequins of the hot-dip galvanized steel sheet sprayed on the hot-dip galvanized steel sheet with one or two compounds selected from (CH 3 (CH 2 ) 11 OSO 3 Na) and sorbitan-based nonionic surfactants as additives A spray solution to be refined is provided.
또한, 본 발명에 따르면, 상기 첨가제에는 인산계 무기염 수용액 혹은 인산계 스팽글 미세화 용액 중에서 선택된 1종 또는 2종의 화합물이 첨가되는 용융아연 도금강판의 스팽글을 미세화 하는 분사용액이 제공된다.In addition, according to the present invention, the additive is provided with a spray solution for miniaturizing the sequins of the hot-dip galvanized steel sheet to which one or two compounds selected from an aqueous phosphate-based inorganic salt solution or a phosphate-based sequin refinement solution is added.
또한, 본 발명에 따르면, 상기 첨가제가 1종만으로 선택될 때에는 상기 소디움라우릴설페이트 화합물 및 소르비탄계 비이온 계면활성제는 각각 0.1~20g/ℓ범위 내이고, 2종으로 선택될 때에는 첨가제의 총량은 0.1~20g/ℓ범위 내인 용융아연 도금강판의 스팽글을 미세화 하는 분사용액이 제공된다.According to the present invention, the sodium lauryl sulfate compound and the sorbitan nonionic surfactant are each in the range of 0.1 to 20 g / l when the additive is selected from only one kind, and the total amount of the additive is selected from two kinds. Silver is provided with a spray solution for miniaturizing the sequins of the hot-dip galvanized steel sheet in the range of 0.1 ~ 20g / ℓ.
아래에서, 본 발명에 따른 용융아연도금강판의 스팽글 미세화용 수용액의 양호한 실시예를 상세히 설명하겠다.In the following, a preferred embodiment of the aqueous solution for refining the sequins of the hot-dip galvanized steel sheet according to the present invention will be described in detail.
본 발명은 안티몬이 단독 혹은 다른 성분과 함께 첨가되어 용융아연 도금강판의 스팽글을 미세화 하는 분사용액으로, 소디움라우릴설페이트 화합물(CH3(CH2)11OSO3Na) 및 소르비탄(Sorbitan)계 비이온 계면활성제 화합물을 인산계 무기염 수용액 혹은 인산계 스팽글 미세화 용액에 첨가한 수용액이다.The present invention is a spray solution that antimony is added alone or with other components to refine the sequins of a hot-dip galvanized steel sheet, and is a sodium lauryl sulfate compound (CH 3 (CH 2 ) 11 OSO 3 Na) and a sorbitan system. It is an aqueous solution which added the nonionic surfactant compound to the aqueous solution of phosphate inorganic salts, or the phosphoric acid sequin refinement solution.
이런 스팽글 미세화용 첨가제인 소디움라우릴설페이트 화합물 및 소르비탄계 비이온 계면활성제의 각각 또는 총 배합량이 0.1-20g/ℓ이며, 특히, 0.5-20g/ℓ일 때에, 가장 양호하다. 이들 스팽글 미세화용 첨가제인 소디움라우릴설페이트 화합물 및 소르비탄계 비이온 계면활성제는 1종 단독 혹은 2종을 혼합해서 인산계 무기염 수용액 혹은 기존 인산계 스팽글 미세화 용액에 첨가하여 사용한다.The amount or the total amount of each of the sodium lauryl sulfate compound and the sorbitan-based nonionic surfactant, which are additives for refining the sequins, is 0.1-20 g / l, and is particularly preferable when it is 0.5-20 g / l. Sodium lauryl sulfate compound and sorbitan nonionic surfactant which are additives for refine | separating sequins are used individually or in mixture of 2 types of phosphate inorganic salts, or an existing phosphate sequin refinement solution.
소디움라우릴설페이트 화합물 및 소르비탄계 비이온 계면활성제의 총 배합량을 0.1-20g/ℓ의 농도로 한정한 이유는, 그 총 배합량이 0.1g/ℓ이하의 농도에서는 스팽글 미세화에 미치는 첨가제의 효과가 없고, 20g/ℓ이상일 경우에는 효과가 포화하여 상한치 이상의 첨가는 용액의 경제성 및 안정성을 저하시키기 때문에 상기 스팽글 미세화용 첨가제는 그 함량을 0.1-20g/ℓ로 한다.The reason for limiting the total compounding amount of the sodium lauryl sulfate compound and the sorbitan nonionic surfactant to the concentration of 0.1-20 g / L is that the effect of the additive on the sequin refinement is less than 0.1 g / L. If the content is 20 g / l or more, the effect is saturated, and the addition of the upper limit or more lowers the economical efficiency and stability of the solution. Therefore, the additive for minimizing the sequins is 0.1-20 g / l.
이와 같이 구성된 용융아연도금강판의 스팽글 미세화용 수용액을 이용하여 실험한 데이터를 표 1에 도시되어 있다.Table 1 shows the experimental data using the aqueous solution for refining the sequins of the hot-dip galvanized steel sheet thus constructed.
도금욕(1)에 수용된 도금액의 조성은 0.2wt% Al, 0.1wt% Sb, 나머지는 불가피한 불순물 및, 잔량의 아연(Zn)으로 이루어지고, 그 도금욕(1)의 온도는 약 460℃이며, 두께가 3mm인 냉연강판을 도금욕(1)에 침지시킨 후에, 수용액 1ℓ중에서 기존 인산계 스팽글 미세화 용액 20g과 소디움라우릴설페이트 화합물 및 소르비탄계 비이온 계면활성제 10g을 첨가한 분사용액을 2류체 분사노즐을 사용하여 용액압력 1.9kg/cm2, 공기압력 3.2kg/cm2로 분사하고, 용액 분사시에 용융아연 도금강판의 온도를 약 430℃로 한 다음, 상기 강판 표면에 분무량이 단면기준 약 60g/m2가 되도록 분사하여 스팽글 미세화 용융아연 도금강판을 얻었다.The plating liquid contained in the plating bath 1 is composed of 0.2wt% Al, 0.1wt% Sb, the remainder is made of inevitable impurities and the remaining amount of zinc (Zn), and the temperature of the plating bath 1 is about 460 ° C. After immersing the cold rolled steel sheet having a thickness of 3 mm in the plating bath (1), 2 g of a spray solution containing 20 g of a conventional phosphate-type sequin micronizing solution, 10 g of sodium lauryl sulfate compound, and 10 g of sorbitan nonionic surfactant was added in 1 L of an aqueous solution. A spray nozzle is used to spray at a solution pressure of 1.9 kg / cm 2 and an air pressure of 3.2 kg / cm 2 , and during spraying the solution, the temperature of the hot-dip galvanized steel sheet is about 430 ° C. It was sprayed so that the reference might be about 60 g / m 2 to obtain a sequin refined hot dip galvanized steel sheet.
상기와 같은 조건에서 제조된 스팽글 미세화 용융아연 도금강판에 대하여 스팽글 크기와 피팅 발생정도를 측정하고, 그 결과를 하기 표 1에 나타내었다.Sequin size and fitting generation degree were measured for the sequin fine-galvanized hot-dip galvanized steel sheet prepared under the above conditions, and the results are shown in Table 1 below.
여기에서, 표면의 스팽글 크기는 육안으로 검사하여 평가한 것으로 3은 스팽글의 크기가 양호(200㎛ 이하)한 상태를 나타내고, 2는 보통(500㎛한)으로 스팽글이 육안으로 관찰되며, 1은 불량(통상 크기 3∼10mm)으로 스팽글이 혼재한 상태를 나타낸다.Herein, the sequin size of the surface was visually evaluated and 3 indicates that the sequins have a good size (200 μm or less), 2 is normal (500 μm), and sequins are visually observed. It shows the state which the sequins mixed in defect (normally 3-10 mm in size).
또한, 피팅 정도는 용액분사후 도금층 표면 100mm2에 발생한 백색반점 형태의 피팅 수를 육안으로 검사한 것으로, 3은 피팅 수가 5개 이하로 발생한 상태를 나타내고, 2는 피팅 수가 6∼30개 발생하였을 때를 나타내며, 1은 피팅 30이상 발생하였을 때를 나타낸다.In addition, the degree of fitting was visually inspected the number of fittings in the form of white spots on the surface of the coating layer 100mm 2 after the solution injection, 3 indicates the state where the number of fittings is less than 5, 2 represents 6 to 30 fittings 1 indicates when more than 30 fittings have occurred.
그리고, 비교예 1은 수용액 1ℓ중에 소디움라우릴설페이트 화합물 및 소르비탄계 비이온 계면활성제의 첨가제 없이 인산계 스팽글 미세화 용액 20g만으로 분사하였을 때의 결과를 나타낸 것으로, 실험예 1~7과 동일한 도금 및 분사조건으로 제조한 강판에 대해 검사한 결과이다.And, Comparative Example 1 shows the result of spraying with only 20g of phosphate-based sequin micronizing solution without additives of sodium lauryl sulfate compound and sorbitan nonionic surfactant in 1L of the aqueous solution, the same plating and It is the result of inspection about the steel plate manufactured by the injection condition.
그리고, 표 2에서는 소디움라우릴설페이트 화합물 및 소르비탄계 비이온 계면활성제의 첨가량을 변화시키면서 스팽글의 크기와 피팅의 수를 평가하였다.In Table 2, the size of the sequins and the number of fittings were evaluated while changing the amount of the sodium lauryl sulfate compound and the sorbitan-based nonionic surfactant.
실험조건은 수용액 1ℓ중에서 인산계 스팽글 미세화 용액 20g과 소디움라우릴설페이트 화합물 및 소르비탄계 비이온 계면활성제를 각각 0.05-30g의 범위로 첨가하였고, 기타 외 실험조건은 표 1과 동일하고, 평가방법 또한 동일한다.The experimental conditions were 20 g of a phosphate-type sequin refined solution, sodium lauryl sulfate compound and sorbitan nonionic surfactant in the range of 0.05-30 g, respectively, in 1 L of the aqueous solution. It is also the same.
표 1의 실험예 1~7과 비교예 1로부터 알 수 있듯이 인산계 스팽글 미세화 용액 20g/ℓ과 본 발명의 스팽글 미세화용 첨가제 10g/ℓ은 도금강판 표면상의 스팽글을 미세화 시키는 한편 내 피팅성을 향상시키는 데에 효과를 나타내었다.As can be seen from Experimental Examples 1 to 7 and Comparative Example 1 of Table 1, 20 g / l of a phosphate-based sequin refinement solution and 10 g / l of an additive for refining sequins of the present invention refine the sequins on the surface of the plated steel sheet and improve the fitting resistance. The effect was to make.
또한, 표 2의 실험예 8~10에 나타난 바와 같이, 본 발명의 스팽글 미세화용 첨가제의 적정 첨가량은 0.1~20g/ℓ이고, 특히, 0.5~20g/ℓ가 양호하며, 30g/ℓ 이상을 첨가할 경우에는 효과가 포화하여 경제성이 없고, 용액이 불안정한 상태를 보였다.In addition, as shown in Experimental Examples 8 to 10 of Table 2, the appropriate addition amount of the sequins refinement additive of the present invention is 0.1 to 20 g / L, in particular, 0.5 to 20 g / L is good, 30 g / L or more is added In this case, the effect was saturated, so there was no economic effect, and the solution was unstable.
본 발명의 조성 중에 실험예 4~7과 같이, 백색도 향상용 첨가제를 2종 혼합한 경우에는 단독으로 첨가한 실험예 1~3의 경우보다 스팽글 미세화 및 내 피팅성에 우수한 효과를 보인다.In the composition of the present invention, as in Experimental Examples 4-7, when two kinds of additives for improving whiteness are mixed, the effect of improving sequin fineness and fitting resistance is better than that of Experimental Examples 1 to 3 added alone.
앞서 상세히 설명한 바와 같이, 본 발명의 용융아연도금강판의 스팽글 미세화용 수용액은 안티몬을 함유한 용융된 아연이 응고하면서 결정립 성장하는 것을 억제하여 스팽글의 크기를 축소시키며, 피팅의 결함을 예방할 수 있는 장점이 있다.As described in detail above, the sequins fine aqueous solution of the hot-dip galvanized steel sheet of the present invention to suppress the growth of the crystal grains while the molten zinc containing antimony solidified to reduce the size of the sequins, and to prevent fitting defects There is this.
이상에서 본 발명의 용융아연도금강판의 스팽글 미세화용 수용액에 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 범위 내에서 다양한 변형 및 모방이 가능함은 명백한 사실이다.The technical idea of the aqueous solution for refining the sequins of the hot-dip galvanized steel sheet of the present invention has been described above, but the exemplary embodiments of the present invention have been described by way of example and are not intended to limit 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.
Claims (3)
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| KR10-1999-0057668A KR100425594B1 (en) | 1999-12-14 | 1999-12-14 | Solution spray for minimized spangle |
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| KR10-1999-0057668A KR100425594B1 (en) | 1999-12-14 | 1999-12-14 | Solution spray for minimized spangle |
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| KR20010056279A KR20010056279A (en) | 2001-07-04 |
| KR100425594B1 true KR100425594B1 (en) | 2004-04-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101138136B1 (en) | 2009-12-01 | 2012-04-23 | 동부제철 주식회사 | Control Apparatus and Method of Spangle Size at Continuous Hot-Dip Galvanizing Line That Easy Spray Position Control |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5092831A (en) * | 1973-12-20 | 1975-07-24 | ||
| JPS5528346A (en) * | 1978-08-21 | 1980-02-28 | Nisshin Steel Co Ltd | Manufacture of aqueous phosphate solution for making minimum spangle hot zinc dipped steel sheet |
| KR960014383A (en) * | 1994-10-21 | 1996-05-22 | 김만제 | Manufacturing method of high gloss zero-spangle hot-dip galvanized steel sheet |
-
1999
- 1999-12-14 KR KR10-1999-0057668A patent/KR100425594B1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5092831A (en) * | 1973-12-20 | 1975-07-24 | ||
| JPS5528346A (en) * | 1978-08-21 | 1980-02-28 | Nisshin Steel Co Ltd | Manufacture of aqueous phosphate solution for making minimum spangle hot zinc dipped steel sheet |
| KR960014383A (en) * | 1994-10-21 | 1996-05-22 | 김만제 | Manufacturing method of high gloss zero-spangle hot-dip galvanized steel sheet |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101138136B1 (en) | 2009-12-01 | 2012-04-23 | 동부제철 주식회사 | Control Apparatus and Method of Spangle Size at Continuous Hot-Dip Galvanizing Line That Easy Spray Position Control |
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