KR20200109918A - Molten salt flux for molten aluminium plating and flux bath comprising the same - Google Patents

Molten salt flux for molten aluminium plating and flux bath comprising the same Download PDF

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KR20200109918A
KR20200109918A KR1020190029743A KR20190029743A KR20200109918A KR 20200109918 A KR20200109918 A KR 20200109918A KR 1020190029743 A KR1020190029743 A KR 1020190029743A KR 20190029743 A KR20190029743 A KR 20190029743A KR 20200109918 A KR20200109918 A KR 20200109918A
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plating
flux
molten
aluminum
weight
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Korean (ko)
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김창민
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덕산산업주식회사
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Priority to KR1020190029743A priority Critical patent/KR20200109918A/en
Publication of KR20200109918A publication Critical patent/KR20200109918A/en
Priority to KR1020210128052A priority patent/KR102365280B1/en

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    • 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
    • C23C2/30—Fluxes or coverings on molten baths
    • 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
    • C23C2/12—Aluminium or alloys based thereon

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  • 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

The present invention relates to a molten salt flux for plating molten aluminum and a flux bath including the same, wherein the molten salt flux for plating molten aluminum forms a uniform plating layer on a plating portion and prevents defects from being generated thereon when the molten aluminum is plated. Also, the molten salt flux for plating molten aluminum contains cryolite, aluminum fluoride, potassium chloride, sodium chloride, lithium chloride and lead chloride, individually, thereby nearly zeroing a non-plating rate and a pinhole generating rate of a surface of a final product manufactured by molten aluminum plating.

Description

용융 알루미늄도금용 용융염 플럭스 및 이를 포함하는 플럭스욕{Molten salt flux for molten aluminium plating and flux bath comprising the same}Molten salt flux for molten aluminum plating and flux bath comprising the same

본 발명은 용융 알루미늄 도금시, 도금 부위에 균일한 도금층 형성함과 아울러 결함 생성을 방지하기 위한 용융 알루미늄도금용 용융염 플럭스 및 이를 포함하는 플럭스욕에 관한 것이다. The present invention relates to a molten salt flux for hot-dip aluminum plating and a flux bath including the same for forming a uniform plating layer on a plating portion and preventing defects from being generated during hot-dip aluminum plating.

대부분의 금속은 대기중에서 산소의 영향으로 산화막을 형성한다. 이러한 산화막은 용융 알루미늄 도금과정에 악영향을 미친다. 특히 순수한 용융 알루미늄 도금욕을 사용할 경우에는, 산화로 인해 모재 표면에 산화막이 형성되고 이러한 산화막은 최종제품의 품질에 악영향을 미친다. Most metals form an oxide film under the influence of oxygen in the atmosphere. This oxide film adversely affects the hot-dip aluminum plating process. In particular, in the case of using a pure hot-dip aluminum plating bath, an oxide film is formed on the surface of the base material due to oxidation, and this oxide film adversely affects the quality of the final product.

종래의 방법은 건식 플럭스법으로 플럭스막을 모재의 표면에 퇴적시키는 것으로서, 모재 표면에 건식 플럭스를 뿌림으로씨 산화막을 줄이는 한편 건식 플럭스에 의해 산화막을 분해시켜 모재 표면에 있는 산화막을 환원시키게 된다. The conventional method is to deposit a flux film on the surface of the base material by a dry flux method, and reduce the oxide film by spraying dry flux on the base material surface, while decomposing the oxide film by the dry flux to reduce the oxide film on the base material surface.

그러나, 상기와 같은 건식 플럭스를 이용한 알루미늄 용융도금방법은 약 700℃ 이상의 도금온도에 의하여 고온욕중에서 알루미늄의 산화가 빈번하게 발생하게 되고, 이로 인하여 피도금물이 되는 모재의 표면을 철저하게 전처리시킨다 하더라도 모재의 표면 일부가 도금이 되지 않거나, 도금층에 핀홀(Pin-hole)이 발생하여 모재와 도금층의 밀착성이 저하되는 것과 같이 도금제품의 품질에 좋지 못한 영향을 미치는 요인이 발생하였다. However, the aluminum hot-dip plating method using dry flux as described above frequently causes oxidation of aluminum in a high-temperature bath due to a plating temperature of about 700°C or higher, and thus, even if the surface of the base material to be plated is thoroughly pretreated. Factors that adversely affect the quality of the plated product have occurred, such as that a part of the surface of the base material is not plated, or pin-holes are generated in the plating layer, thereby deteriorating the adhesion between the base material and the plating layer.

이러한 문제를 해결하기 위해, 한국등록특허 제10-1045389호에는 피도금물이 되는 모재의 표면을 전처리하는 전처리공정(S10), 도금공정(S20), 부가공정(S30), 후처리공정(S40)을 포함하는 용융알루미늄 도금방법을 개시하고 있으며, 용융염 플럭스를 알루미늄과 함께 도금조의 내부로 투입시키므로서 도금액의 상층에 피막을 형성시켜 용융알루미늄의 산화와 외부로의 열손실을 방지할 수 있도록 하였다.In order to solve this problem, Korean Patent Registration No. 10-1045389 describes a pretreatment process (S10), a plating process (S20), an additional process (S30), and a post-treatment process (S40) for pre-treating the surface of the base material to be plated. ), and to prevent oxidation of molten aluminum and heat loss to the outside by injecting molten salt flux into the inside of the plating bath together with aluminum to form a film on the upper layer of the plating solution. I did.

그러나, 상기한 알루미늄 용융도금방법은 아연도금에 비하여 내식성 등 도금 특성이 우수한 것으로 알 수 있으나, 도금 후 부분적으로 관찰되는 표면결함(모재의 표면 일부가 도금이 되지 않거나, 도금층에 미세한 핀홀(Pin-hole)이 발생하는 문제점)에 의하여 사용수명에 악영향을 미치고 있어서 개선이 시급한 실정이다. However, it can be seen that the above-described aluminum hot dip plating method has superior plating properties such as corrosion resistance compared to zinc plating, but surface defects partially observed after plating (part of the surface of the base material is not plated, or fine pinholes in the plating layer) hole) has adversely affected the service life, so improvement is urgent.

한국등록특허 제10-1045389호Korean Patent Registration No. 10-1045389

본 발명은 상기와 같은 문제점을 해결하기 위해 안출한 것으로, 용융 알루미늄 도금시, 도금 부위에 균일한 도금층 형성함과 아울러 결함 생성을 방지하기 위한 용융 알루미늄도금용 용융염 플럭스를 제공함에 있다. The present invention has been conceived to solve the above problems, and is to provide a molten salt flux for hot-dip aluminum plating to prevent the generation of defects while forming a uniform plating layer on the plating area during hot-dip aluminum plating.

또한 본 발명은 상술한 용융 알루미늄도금용 용융염 플럭스를 포함하는 플럭스욕를 제공함에 있다. In addition, the present invention is to provide a flux bath comprising the molten salt flux for molten aluminum plating described above.

본 발명의 다른 목적 및 장점들은 하기의 설명에 의해서 이해될 수 있으며, 본 발명의 일 실시 예에 의해 보다 분명하게 알게 될 것이다. 또한, 본 발명의 목적 및 장점들은 특허청구범위에 나타낸 수단 및 그 조합에 의해 실현될 수 있음을 쉽게 알 수 있을 것이다.Other objects and advantages of the present invention can be understood by the following description, and will be more clearly understood by an embodiment of the present invention. In addition, it will be easily understood that the objects and advantages of the present invention can be realized by the means shown in the claims and combinations thereof.

이와 같은 목적을 달성하기 위하여, 본 발명의 일 실시예에 따른 용융 알루미늄도금용 용융염 플럭스는, 빙정석(Cryolite) 10~30 중량%, 불화알루미늄(AlF3) 10~40 중량%, 염화칼륨(KCl) 35~65 중량% 및 염화나트륨(NaCl) 10~25 중량%를 포함한다. In order to achieve this object, the molten salt flux for molten aluminum plating according to an embodiment of the present invention is 10 to 30% by weight of cryolite, 10 to 40% by weight of aluminum fluoride (AlF 3 ), and potassium chloride (KCl ) 35 to 65% by weight and sodium chloride (NaCl) 10 to 25% by weight.

본 발명의 일 실시예에 따른 용융 알루미늄도금용 용융염 플럭스는, 빙정석(Cryolite), 불화알루미늄(AlF3) 및 염화칼륨(KCl)을 합한 전체 중량에 대하여 염화리튬(LiCl) 1~5 중량%, 염화납(PbCl2) 1~5 중량% 및 염화니켈(NiCl2) 1~5 중량%를 더 포함할 수 있다. The molten salt flux for molten aluminum plating according to an embodiment of the present invention includes 1 to 5% by weight of lithium chloride (LiCl) based on the total weight of the total weight of cryolite, aluminum fluoride (AlF 3 ) and potassium chloride (KCl), Lead chloride (PbCl 2 ) 1-5 wt% and nickel chloride (NiCl 2 ) 1-5 wt% may be further included.

또한 본 발명은 용융 알루미늄에 용해되며, 상술한 용융 알루미늄도금용 플럭스를 포함하는 플럭스욕을 포함한다.In addition, the present invention is soluble in molten aluminum and includes a flux bath including the above-described molten aluminum plating flux.

본 발명에 따른 용융 알루미늄도금용 용융염 플럭스를 포함함으로써, 모재 표면의 부도금율과 핀홀(Pin hole) 발생율을 거의 제로(Zero)화시시키고, 이로 인하여 최종 도금제품의 내식성을 극대화시킬 수 있다. By including the molten salt flux for hot-dip aluminum plating according to the present invention, the non-plating rate and the occurrence rate of pin holes on the surface of the base material are almost zero, thereby maximizing the corrosion resistance of the final plated product.

본 발명에서 얻을 수 있는 효과는 이상에서 언급한 효과로 제한되지 않으며, 언급하지 않은 또 다른 효과들은 아래의 기재로부터 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 명확하게 이해될 수 있을 것이다.The effects obtainable in the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those of ordinary skill in the technical field to which the present invention belongs from the following description. .

이하 본 발명에 관하여 상세히 설명한다. 다음에 소개되는 실시예 및 도면들은 당업자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 예로서 제공되는 것이다. 또한, 본 발명의 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명 및 첨부 도면에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다.Hereinafter, the present invention will be described in detail. The following embodiments and drawings are provided as examples in order to sufficiently convey the spirit of the present invention to those skilled in the art. In addition, unless there are other definitions in the technical and scientific terms used in the present invention, the present invention has the meanings commonly understood by those of ordinary skill in the art to which this invention belongs, and the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may unnecessarily obscure the gist of are omitted.

본 발명자들은 용융 알루미늄 도금 공정을 완료한 제품에서 표면 일부가 도금이 되지 않거나, 도금층에 미세한 핀홀(Pin-hole)이 발생하는 문제점을 해결하기 위하여 오랜 기간 연구를 거듭하였다. 본 발명의 일 실시예에 따르면, 전처리한 모재를 수용성 플럭스 처리한 후에, 용융 알루미늄 도금 공정 시 특정 조성의 용융염 플럭스를 사용하는 경우 상기한 문제점을 해결할 수 있었다. The present inventors have been researching for a long period of time in order to solve the problem that a part of the surface is not plated or a fine pin-hole occurs in the plated layer in a product having completed the hot-dip aluminum plating process. According to an embodiment of the present invention, after the pretreated base material is treated with a water-soluble flux, the above problem can be solved when a molten salt flux having a specific composition is used in the hot-dip aluminum plating process.

이와 같은 문제점을 해결하기 위한 본 발명은 빙정석(Cryolite) 10~30 중량%, 불화알루미늄(AlF3) 10~40 중량%, 염화칼륨(KCl) 35~65 중량% 및 염화나트륨(NaCl) 10~25 중량%가 포함된 용융 알루미늄도금용 용융염 플럭스를 포함한다. The present invention to solve such a problem is cryolite (Cryolite) 10 to 30% by weight, aluminum fluoride (AlF 3 ) 10 to 40% by weight, potassium chloride (KCl) 35 to 65% by weight, and sodium chloride (NaCl) 10 to 25% by weight Contains molten salt flux for molten aluminum plating containing %.

용융 알루미늄 도금시 온도는 약 600 ~ 750℃이어서, 알루미늄의 산화가 쉽게 발생한다. 따라서, 피도금 소재의 산화를 최대한 억제하고 모재의 표면에 알루미늄 합금층(Fe-Al alloy)을 형성시키고 그 위에 알루미늄 도금층이 형성되도록 하기 위하여 상기 용융 알루미늄도금용 용융염 플럭스의 주성분으로는 빙정석(Cryolite), 불화알루미늄(AlF3), 염화칼륨(KCl) 및 염화나트륨(NaCl)을 포함하는 것이 바람직하다. During hot-dip aluminum plating, the temperature is about 600 to 750°C, so that oxidation of aluminum easily occurs. Therefore, in order to suppress oxidation of the material to be plated as much as possible, to form an aluminum alloy layer (Fe-Al alloy) on the surface of the base material, and to form an aluminum plating layer thereon, the main component of the molten salt flux for hot-dip aluminum plating is cryolite ( Cryolite), aluminum fluoride (AlF 3 ), potassium chloride (KCl) and sodium chloride (NaCl).

용융 알루미늄 도금 공정을 통해 본 발명의 목적 달성을 위한 일 실시예를 설명하면, 우선, 탈지, 산세, 수세 등을 포함하는 전처리 공정을 거친 모재를 염화칼륨(KCl) 30~60 중량%, 불화칼륨(KF) 20~40 중량% 및 불화암모늄(NH4F) 15~40 중량%가 포함된 수용성 플럭스를 물 100 중량%를 기준으로 하여 10~30 중량%로 첨가 및 용해시킨 플럭스 용제에 침지함으로써, 모재 표면에 약품피막층을 형성시키게 된다. When explaining an embodiment for achieving the object of the present invention through the hot-dip aluminum plating process, first, the base material that has undergone a pretreatment process including degreasing, pickling, water washing, etc. is prepared by using 30 to 60% by weight of potassium chloride (KCl) and KF) by immersing in a flux solvent added and dissolved in an amount of 10 to 30% by weight based on 100% by weight of water, a water-soluble flux containing 20 to 40% by weight and 15 to 40% by weight of ammonium fluoride (NH 4 F), A chemical film is formed on the surface of the base material.

이후 수용성 플럭스 처리된 모재를 후술할 플럭스욕에 침적하면, 모재 표면에 형성된 약품피막층은 알루미늄 용융 도금시에 도금조 상부로 부상하는 각종 불순물, 알루미나(Al2O3) 등으로부터 모재 표면이 오염되는 것을 방지할 수 있다. After that, when the water-soluble flux-treated base material is immersed in a flux bath to be described later, the chemical film layer formed on the surface of the base material is contaminated from various impurities and alumina (Al 2 O 3 ) floating on the top of the plating bath during aluminum hot dip plating. Can be prevented.

특히, 본 발명의 일 실시예에 따른 용융 알루미늄도금용 용융염 플럭스는 빙정석(Cryolite) 10~30 중량%, 불화알루미늄(AlF3) 10~40 중량%, 염화칼륨(KCl) 35~65 중량% 및 염화나트륨(NaCl) 10~25 중량%를 포함하되, 염화칼륨(KCl)/ 불화알루미늄(AlF3) 중량비가 3.5 내지 4.5로 제어되는 경우, 최종 도금 제품의 부도금율과 핀홀(Pin hole) 발생율을 거의 제로(Zero)화시킬 수 있고, 또한 표면외관 및 내식성을 크게 향상시킬 수 있다. In particular, the molten salt flux for molten aluminum plating according to an embodiment of the present invention includes 10 to 30% by weight of cryolite, 10 to 40% by weight of aluminum fluoride (AlF 3 ), 35 to 65% by weight of potassium chloride (KCl), and Including sodium chloride (NaCl) 10 to 25% by weight, but when the weight ratio of potassium chloride (KCl) / aluminum fluoride (AlF 3 ) is controlled to 3.5 to 4.5, the non-plating rate and the occurrence rate of pin holes of the final plated product are almost zero. (Zero) can be achieved, and the surface appearance and corrosion resistance can be greatly improved.

또한, 본 발명의 일 실시예에 따른 용융 알루미늄도금용 용융염 플럭스는 염화리튬(LiCl), 염화납(PbCl2) 및 염화니켈(NiCl2)을 더 포함함으로써, 최종 제품의 내식성을 극대화시킬 수 있는 장점이 있다. 이때, 상기 용융 알루미늄도금용 용융염 플럭스는 빙정석(Cryolite), 불화알루미늄(AlF3) 및 염화칼륨(KCl)을 합한 전체 중량에 대하여 염화리튬(LiCl) 1~5 중량%, 염화납(PbCl2) 1~5 중량% 및 염화니켈(NiCl2) 1~5 중량%를 더 포함할 수 있다. In addition, the molten salt flux for molten aluminum plating according to an embodiment of the present invention further includes lithium chloride (LiCl), lead chloride (PbCl 2 ), and nickel chloride (NiCl 2 ), thereby maximizing the corrosion resistance of the final product. There is an advantage. At this time, the molten salt flux for molten aluminum plating is lithium chloride (LiCl) 1-5% by weight, lead chloride (PbCl 2 ) with respect to the total weight of cryolite, aluminum fluoride (AlF 3 ) and potassium chloride (KCl). 1 to 5% by weight and nickel chloride (NiCl 2 ) may further contain 1 to 5% by weight.

한편, 본 발명은 상술한 용융 알루미늄도금용 용융염 플럭스를 포함하고, 용융 알루미늄에 용해되는 플럭스욕을 포함한다. On the other hand, the present invention includes the molten salt flux for molten aluminum plating described above, and includes a flux bath that is dissolved in molten aluminum.

본 발명의 일 실시예에 따른 플럭스욕은, 도금조 속에 상기 용융 알루미늄도금용 용융염 플럭스 5 내지 15 중량% 및 용융 알루미늄 85 내지 95 중량%를 포함할 수 있다. 이에 따라, 본 발명에 따른 플럭스욕은 상기 농도 범주에서 부도금율을 거의 제로(Zero)화 시킬 수 있다. The flux bath according to an embodiment of the present invention may include 5 to 15% by weight of molten salt flux for molten aluminum plating and 85 to 95% by weight of molten aluminum in a plating bath. Accordingly, the flux bath according to the present invention can make the non-plating rate almost zero in the above concentration range.

이하 본 발명을 실시예를 참조하여 상세히 설명한다. 그러나 이들은 본 발명을 보다 상세하게 설명하기 위한 것으로, 본 발명의 권리범위가 하기의 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples. However, these are for describing the present invention in more detail, and the scope of the present invention is not limited by the following examples.

[실시예 1~7, 비교예 1~3][Examples 1 to 7, Comparative Examples 1 to 3]

직경 50cm, 두께 20mm 규격의 탄소강관을 탈지조와 산세조 및 수세조에 순차로 침지시켜 그 표면을 전처리시켰다. 이후, 탄소강관을 염화칼륨(KCl) 40 중량%, 불화칼륨(KF) 25 중량%, 플루오르화 암모늄(NH4F) 35 중량%의 성분비율로 이루어지는 수용성 플럭스가 15 중량%의 농도로 용해된 플럭스 용제에 상기 탄소강관을 80℃의 온도조건하에서 약 2분간 침지 후 건조하였다. 수용성 플럭스 처리 후에 상기 탄소강관을 하기 표 1의 조성을 갖는 용융 알루미늄도금용 용융염 플럭스를 알루미늄에 용해시킨 플럭스욕에 침지하였다. 이때, 상기 알루미늄도금용 용융염 플럭스가 용융알루미늄 100 중량%를 기준으로 하여 8 중량%로 첨가되었고, 온도조건은 약 700 ℃이고, 약 10분간 유지하여 도금을 완료하였다. A carbon steel pipe having a diameter of 50 cm and a thickness of 20 mm was sequentially immersed in a degreasing tank, a pickling tank, and a water washing tank to pretreat the surface. Thereafter, the carbon steel pipe is a flux in which a water-soluble flux consisting of 40% by weight of potassium chloride (KCl), 25% by weight of potassium fluoride (KF), and 35% by weight of ammonium fluoride (NH 4 F) is dissolved in a concentration of 15% by weight. The carbon steel pipe was immersed in a solvent for about 2 minutes under a temperature condition of 80° C. and dried. After the water-soluble flux treatment, the carbon steel pipe was immersed in a flux bath in which a molten salt flux for molten aluminum plating having the composition shown in Table 1 was dissolved in aluminum. At this time, the molten salt flux for aluminum plating was added at 8% by weight based on 100% by weight of molten aluminum, and the temperature condition was about 700°C, and the plating was completed by holding for about 10 minutes.

다음으로, 도금처리된 상기 탄소강관을 질산(HNO3)의 10% 수용액 속에 약 5분간 침지시켰다가 꺼내어 수세 및 건조를 행하므로서 알루미늄이 도금된 탄소강관 제품을 제조하였다.Next, the plated carbon steel pipe was immersed in a 10% aqueous solution of nitric acid (HNO 3 ) for about 5 minutes, and then taken out and washed with water and dried to prepare a carbon steel pipe product with aluminum plating.

빙정석cryolite AlF3 AlF 3 KClKCl NaClNaCl LiClLiCl PbCl2 PbCl 2 NiCl2 NiCl 2 KCl/AlF3 KCl/AlF 3 실시예 1Example 1 3030 1010 3535 2525 3.53.5 실시예 2Example 2 3030 1010 4040 2020 4.04.0 실시예 3Example 3 2323 1212 5050 1515 4.24.2 실시예 4Example 4 1515 1515 6060 1010 4.04.0 실시예 5Example 5 1010 1515 6565 1010 4.34.3 실시예 6Example 6 2525 1010 4040 2525 0.50.5 0.50.5 0.50.5 4.04.0 실시예 7Example 7 2020 1010 4040 3030 33 33 33 4.04.0 비교예 1Comparative Example 1 3030 1010 3030 3030 3.03.0 비교예 2Comparative Example 2 1010 1515 7070 55 4.74.7 비교예 3Comparative Example 3 2020 1010 4545 2525 66 66 66 5.05.0

(표 1에서, 빙정석 + AlF3 + KCl + NaCl = 100 중량%이다. LiCl, PbCl2 및 NiCl2는 상호 독립적으로 AlF3, KCl 및 NaCl를 합한 전체 100 중량%에 대하여 추가로 투입한 양으로서 중량%를 의미한다)(In Table 1, cryolite + AlF 3 + KCl + NaCl = 100% by weight. LiCl, PbCl 2 and NiCl 2 are mutually independently added to the total 100% by weight of the combined AlF 3 , KCl and NaCl, Means weight percent)

[평가예][Evaluation example]

상기 실시예 및 비교예에서 제조된 알루미늄이 도금된 탄소강관 제품을 두께 0.8mm, 폭 100mm 및 길이 100mm인 시험편으로 절단한 후에, 상기 시험편의 핀홀 발생 유무, 표면외관, 내식성 등의 물성을 평가하고, 그 결과를 하기 표 2에 수록하였다. After cutting the aluminum-plated carbon steel pipe products manufactured in Examples and Comparative Examples into test pieces having a thickness of 0.8 mm, a width of 100 mm and a length of 100 mm, physical properties such as pinhole occurrence, surface appearance, and corrosion resistance of the test piece were evaluated. , The results are listed in Table 2 below.

이때, 물성평가는 다음의 기준으로 평가하였다. At this time, the property evaluation was evaluated based on the following criteria.

1. 핀홀 발생 유무: SEM을 이용하여 상기 시험편의 절단면을 관찰하였다. 1. Presence or absence of pinhole occurrence: The cut surface of the test piece was observed using an SEM.

○: 핀홀 미발생, ×: 핀홀 발생○: no pinhole, ×: pinhole

2. 표면외관: 3차원 표면조도 측정 및 드로스 또는 도금 결함을 육안으로 관찰하였다. 2. Surface appearance: Three-dimensional surface roughness measurement and dross or plating defects were observed with the naked eye.

○: 표면조도 1μm 미만, 드로스 또는 도금결함의 발생 없는 경우.○: When the surface roughness is less than 1 μm and no dross or plating defects occur.

△: 표면조도 1~3μm, 미량의 드로스 또는 도금 결함 발생한 경우.△: When the surface roughness 1 ~ 3μm, a small amount of dross or plating defects occurred.

×: 표면조도 3μm 초과, 도금층이 불균일하고, 도금 결함이 다량 발생한 경우.×: When the surface roughness exceeds 3 μm, the plating layer is uneven, and a large amount of plating defects occurs.

3. 내식성: 염수분무시험(KS-C-0223에 준하는 염수분무 규격시험)으로 부식촉진시험을 수행한 후 도금층 표면에 적청 발생면적이 5%가 될 때까지 경과된 시간을 측정하였다. 3. Corrosion resistance: After performing the corrosion promotion test with the salt spray test (salt spray standard test in accordance with KS-C-0223), the elapsed time was measured until the area of red rust generated on the surface of the plating layer became 5%.

○: 500 시간 초과한 경우.○: When it exceeds 500 hours.

△: 200~500 시간인 경우.△: In the case of 200 to 500 hours.

×: 200 시간 미만인 경우.X: When it is less than 200 hours.

핀홀 발생Pinhole occurrence 표면 외관Surface appearance 내식성 테스트Corrosion resistance test 실시예 1Example 1 ○○ ○○ △△ 실시예 2Example 2 ○○ ○○ △△ 실시예 3Example 3 ○○ ○○ △△ 실시예 4Example 4 ○○ ○○ △△ 실시예 5Example 5 ○○ ○○ △△ 실시예 6Example 6 ○○ ○○ △△ 실시예 7Example 7 ○○ ○○ ○○ 비교예 1Comparative Example 1 ×× ×× ×× 비교예 2Comparative Example 2 ×× ×× ×× 비교예 3Comparative Example 3 ×× ×× ××

상기한 각각의 실시예를 포함하여 본 발명에 따른 용융 알루미늄도금용 용융염 플럭스를 사용하여 제조된 알루미늄 도금제품은 모재(철재인 경우)의 표층으로부터 모재층(Fe), 합금층(FeAl3 ~ Fe2Al5), 알루미늄층(Al)이 순차적으로 형성되고, 알루미늄층의 상면에는 자연적인 산화에 의하여 얇은 산화알루미늄(Al2O3)층이 강력한 산화피막을 형성하므로서 외관상으로는 광택이 매우 우수한 은백색을 띠게 되며, 모재의 재질에 따라 다소 차이는 있으나 대부분 알루미늄층이 약 30 ~ 100 μm, 합금층이 30 ~ 50 μm 정도로 도금층이 모재의 표면과 매우 강력하게 밀착된 상태가 된다. 따라서, 본 발명은 빙정석(Cryolite) 10~30 중량%, 불화알루미늄(AlF3) 10~40 중량%, 염화칼륨(KCl) 35~65 중량% 및 염화나트륨(NaCl) 10~25 중량%를 포함하되, KCl/KF 중량비가 3.5~4.3인 경우, 도금표면 전체에 걸쳐 부도금된 부분이나 핀홀(Pin-hole)이 발생된 부분이 없는 매우 우수한 도금제품으로 제조된 것을 알 수 있다. The aluminum-plated products manufactured using the molten salt flux for hot-dip aluminum plating according to the present invention, including each of the above examples, are from the surface layer of the base material (in the case of iron) to the base material layer (Fe), the alloy layer (FeAl 3 ~ Fe 2 Al 5 ) and aluminum layers (Al) are sequentially formed, and a thin aluminum oxide (Al 2 O 3 ) layer forms a strong oxide film by natural oxidation on the upper surface of the aluminum layer. It has an excellent silver-white color, and there is some difference depending on the material of the base material, but most of the aluminum layer is about 30 ~ 100 μm and the alloy layer is 30 ~ 50 μm, so that the plating layer is in a very strong contact with the surface of the base material. Accordingly, the present invention includes 10 to 30% by weight of cryolite, 10 to 40% by weight of aluminum fluoride (AlF 3 ), 35 to 65% by weight of potassium chloride (KCl) and 10 to 25% by weight of sodium chloride (NaCl), When the KCl/KF weight ratio is 3.5 to 4.3, it can be seen that it is manufactured as a very excellent plating product without any non-plated parts or pin-holes over the entire plating surface.

상기와 같이 최종 제조된 알루미늄 도금제품은 본 발명에 따른 용융 알루미늄도금용 용융염 플럭스를 포함한 도금공정을 수행하여 제조됨에 따라, 모재의 표면에 대한 부도금율을 거의 제로화시킬 수 있으며, 모재의 표면전체에 걸쳐 30 ~ 100 μm 범위내의 일정한 두께를 가지는 알루미늄층과, 30 ~ 50 μm 범위내의 일정한 두께를 가지는 합금층(모재+알루미늄)을 형성시키므로서 도금제품의 내식성과 내후성 및 내열성을 크게 향상시킬 수 있게 된다. As the aluminum plating product finally manufactured as described above is manufactured by performing a plating process including the molten salt flux for hot-dip aluminum plating according to the present invention, the subplating rate on the surface of the base material can be reduced to almost zero, and the entire surface of the base material By forming an aluminum layer having a constant thickness within the range of 30 to 100 μm and an alloy layer (base material + aluminum) with a constant thickness within the range of 30 to 50 μm, the corrosion resistance, weather resistance, and heat resistance of the plated product can be greatly improved. There will be.

이상에서 본 발명의 바람직한 실시예를 설명하였으나, 본 발명은 다양한 변화와 변경 및 균등물을 사용할 수 있으며, 상기 실시예를 적절히 변형하여 동일하게 응용할 수 있음이 명확하다. 따라서 상기 기재 내용은 하기 특허청구범위의 한계에 의해 정해지는 본 발명의 범위를 정하는 것이 아니다.Although a preferred embodiment of the present invention has been described above, it is clear that the present invention can use various changes, modifications, and equivalents, and that the above embodiment can be appropriately modified and applied in the same manner. Therefore, the above description does not define the scope of the present invention, which is determined by the limits of the following claims.

Claims (3)

빙정석(Cryolite) 10~30 중량%, 불화알루미늄(AlF3) 10~40 중량%, 염화칼륨(KCl) 35~65 중량% 및 염화나트륨(NaCl) 10~25 중량%를 포함하는 용융 알루미늄도금용 용융 플럭스.
Melt flux for molten aluminum plating containing 10 to 30% by weight of cryolite, 10 to 40% by weight of aluminum fluoride (AlF 3 ), 35 to 65% by weight of potassium chloride (KCl) and 10 to 25% by weight of sodium chloride (NaCl) .
 제 1항에 있어서,
상기 용융 알루미늄도금용 용융 플럭스는
빙정석(Cryolite), 불화알루미늄(AlF3) 및 염화칼륨(KCl)을 합한 전체 중량에 대하여 염화리튬(LiCl) 1~5 중량%, 염화납(PbCl2) 1~5 중량% 및 염화니켈(NiCl2) 1~5 중량%를 더 포함하는 용융 알루미늄도금용 용융 플럭스.
The method of claim 1,
The molten flux for molten aluminum plating is
With respect to the total weight of cryolite, aluminum fluoride (AlF 3 ) and potassium chloride (KCl), lithium chloride (LiCl) 1-5 wt%, lead chloride (PbCl 2 ) 1-5 wt%, and nickel chloride (NiCl 2 ) Melt flux for molten aluminum plating further comprising 1 to 5% by weight.
 용융 알루미늄에 용해되며, 제1항 또는 제2항의 용융 알루미늄도금용 플럭스를 포함하는 것을 특징으로 하는 플럭스욕.
A flux bath, which is dissolved in molten aluminum and comprises the flux for molten aluminum plating of claim 1 or 2.
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