KR930008343B1 - Plating steel stock having heat resistance and corrosion resistance - Google Patents

Plating steel stock having heat resistance and corrosion resistance Download PDF

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KR930008343B1
KR930008343B1 KR1019890015483A KR890015483A KR930008343B1 KR 930008343 B1 KR930008343 B1 KR 930008343B1 KR 1019890015483 A KR1019890015483 A KR 1019890015483A KR 890015483 A KR890015483 A KR 890015483A KR 930008343 B1 KR930008343 B1 KR 930008343B1
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steel product
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마사요시 우수이
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우수이 고쿠사이 산교 가부시기가이샤
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

내용 없음.No content.

Description

내열성 및 내식성 도금층을 갖는 강제품Steel products with heat and corrosion resistant plating layers

본 발명은 내열성 및 내식성 도금층을 갖는 강제품에 관한 것으로, 특히, 시이트, 파이프, 커프링, 클램프, 볼트, 너트 등과 같이 자동차 및 기타 기계, 설비에 사용하는 것으로서 표면에 내열성 및 내식성 도금층을 갖는 강제품에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to steel products having heat-resistant and corrosion-resistant plating layers, and in particular, for use in automobiles and other machinery and equipment such as sheets, pipes, cuffings, clamps, bolts, nuts, etc. It is about a product.

자동차 및 기타 기계, 설비에 사용되는 시이트, 파이프, 커플링, 클램프, 볼트, 너트 등에 아연도금층을 형성시킨 후 크롬산염 막을 형성시키는 것은 이미 공지된 것이다. 종래의 도금 강제품은 통상온도하의 부식성 환경에 대해 개선된 내식성을 나타내지만, 자동차 엔진실과 같은 고온 환경에서는 그러한 특성을 나타내지 못한다.It is already known to form a chromate film after forming a galvanized layer on sheets, pipes, couplings, clamps, bolts, nuts, etc. used in automobiles and other machinery and equipment. Conventional plated steel products exhibit improved corrosion resistance to corrosive environments under normal temperatures, but do not exhibit such properties in high temperature environments such as automotive engine compartments.

본 발명의 목적은 이상의 문제점을 해결하기 위해 이루어진 것으로서, 본 발명의 목적은 높은 내식성 뿐만 아니라 우수한 내열성을 나타내는 도금층을 가지는 강제품을 제공하는 것이다.The object of the present invention is to solve the above problems, and an object of the present invention is to provide a steel product having a plating layer exhibiting not only high corrosion resistance but also excellent heat resistance.

본 발명자들은 일련의 실험을 거쳐 도금층을 특정두께의 니켈도금층(하층)과, 아연도금층(중간층)과, 크롬산염막(상층)으로 구성시키는 경우 본 발명의 목적을 달성시킬 수 있다는 것을 알게 되었다. 본 발명은 이러한 발견을 근거로 하여 완성된 것으로서, 본 발명의 요지는 하층으로서 형성된 0.2 내지 10μm 두께의 니켈 도금층과, 그 니켈도금층에 형성된 아연도금층과, 그 아연도금층에 형성된 크롬산염막으로 구성되는 내열성 및 내식성의 도금층을 가지는 강제품(또는 구리도금 강제품)에 있다.The inventors have learned through a series of experiments that the object of the present invention can be achieved when the plating layer is composed of a nickel plated layer (lower layer), a zinc plated layer (middle layer), and a chromate film (upper layer) having a specific thickness. The present invention has been completed based on these findings, and the gist of the present invention is a heat resistance composed of a 0.2 to 10 μm-thick nickel plated layer formed as a lower layer, a zinc plated layer formed on the nickel plated layer, and a chromate film formed on the zinc plated layer. And steel products (or copper plated steel products) having a corrosion-resistant plating layer.

본 발명의 강제품은 시이트, 파이프, 커플링, 클램프, 볼트, 너트 등을 포함하며, 또한 용접을 위한 구리도금층을 갖고 비교적 얇게 겹침 용접된 강관(10mm 이하의 외경을 가짐)을 포함한다(이러한 강관은 자동차의 유압 및 연료 배관에 사용된다). 상기의 강관은 3개의 도금층을 갖는데, 하층은 0.2 내지 10μm 두께의 니켈도금층으로서, 두께가 0.2μm 미만으로 되면, 니켈도금층이 강관의 표면에 완전히 덮히지 않게 되고 내열성 및 내식성에도 별다른 개선점이 없게 되며, 두께가 10μm를 초과하게 되면, 니켈도금층이 굽힘가공중에 벗겨지거나 균열이 생기기 쉽고, 이에 따라 두께 증가분 만큼 내식성에 개선점이 없게 된다. 이 니켈도 금층은 와트(Watts)욕을 사용하는 전기도금에 의해 형성될 수 있는데, 상기 전기도금에 의하면 응력이 적은 도금층이 제공되게 된다. 중간층은 아연도금층으로서, 이 도금층은 염화아연욕 또는 황산아연욕을 사용하는 전기도금에 의해 형성시킬 수 있다. 상기 아연도금층은 니켈도금층과의 계면에서 아연-니켈 확산층을 형성하여, 고온환경에서 내식성의 개선을 얻을 수 있게 한다. 상층은 크롬산염 막으로서, 이것은 크롬산염용액 또는 중크롬산염-황산용액 또는 시판되는 크롬산염 처리 용액(일례로, 디프졸 케미칼 컴퍼니 리미티드에서 제조한 Z-493 ; 성분으로 무수크롬산 30% 및 초산 11%를 함유하며, 비중은 25℃에서 1.40이다. 이 용액은 초저농도이므로 배수처리가 용이하고 내식성이 강하며, 미려한 황색피막을 형성한다.)으로부터 형성시킬 수 있다.Steel products of the present invention include sheets, pipes, couplings, clamps, bolts, nuts, and the like, and also include steel pipes (having an outer diameter of 10 mm or less) that are relatively thinly laminated and have a copper-plated layer for welding. Steel pipes are used for hydraulic and fuel piping in cars). The steel pipe has three plating layers, and the lower layer is a nickel plated layer having a thickness of 0.2 to 10 μm. When the thickness is less than 0.2 μm, the nickel plated layer is not completely covered on the surface of the steel pipe and there is no significant improvement in heat resistance and corrosion resistance. When the thickness exceeds 10 μm, the nickel plated layer is likely to peel off or crack during bending, and thus there is no improvement in corrosion resistance by increasing the thickness. The nickel-plated gold layer may be formed by electroplating using a Watts bath. The electroplating provides a plating layer having a low stress. The intermediate layer is a zinc plated layer, which can be formed by electroplating using a zinc chloride bath or a zinc sulfate bath. The zinc plated layer forms a zinc-nickel diffusion layer at an interface with the nickel plated layer, thereby improving corrosion resistance in a high temperature environment. The upper layer is a chromate membrane, which is a chromate solution or dichromate-sulfuric acid solution or a commercial chromate treatment solution (eg, Z-493 manufactured by Dipsol Chemical Company Limited; components 30% chromic anhydride and 11% acetic acid). It has a specific gravity of 1.40 at 25 ° C. The solution is extremely low in concentration, so that it can be easily drained, has high corrosion resistance, and forms a beautiful yellow film.

이와 같이 하여 얻어진 도금층을 갖는 강제품은 이하의 실시예에서 알수 있는 바와 같이 고온 환경에서도 그의 굽힘부에서 우수한 내식성을 나타낸다.The steel product having the plating layer thus obtained shows excellent corrosion resistance at its bends even in a high temperature environment as can be seen in the following examples.

이하 본 발명의 다음의 실시예와 관련하여 상세히 설명된다.It will now be described in detail with reference to the following examples of the invention.

[실시예 1]Example 1

직경이 8㎜, 두께가 0.7㎜, 길이가 380㎜인 겹침용접된 강관을 JIS G-3141에 따른 SPCC로서 지칭되는 냉각 압연 탄소 강판을 사용하여 준비하고, 그 표면에 용접을 위한 약 3㎛ 두께의 구리도금층을 피복시켰다. 그후, 이 강관을 와트욕에서 52 내지 57℃의 욕온도 및 3A/dm2의 전류밀도로 니켈도금을 하여, 도금두께를 0.5 내지 10㎛로 형성하였다. 그뒤에, 이와같이 도금된 강관을 28g/L의 ZnO, 50g/L의 NaCl, 80g/L의 NaOH을 함유하는 욕용액에서 25℃의 욕온도 및 3A/dm2의 전류밀도로 15분간 아연도금을 하여, 니켈도금층위에 8㎛ 두께의 아연도금층을 형성시켰다. 그뒤에, 상기 강관을 10mL/L의 Z-493(디프졸 케미칼 컴퍼니 리미티드의 제품)을 함유하는 용액에 20초간 그리고 욕온도를 25℃로 하여 침지시켜 상기 아연도금층에 크롬산염막을 피복시켰으며, 이와같이하여 상기와 같은 도금층을 갖는 강관을 얻게 되었다.An overlap welded steel pipe having a diameter of 8 mm, a thickness of 0.7 mm and a length of 380 mm was prepared using a cold-rolled carbon steel plate referred to as SPCC according to JIS G-3141, and about 3 mu m thick for welding on the surface thereof. The copper plating layer of was coat | covered. Thereafter, the steel pipe was nickel plated at a bath temperature of 52 to 57 DEG C and a current density of 3 A / dm 2 in a watt bath to form a plating thickness of 0.5 to 10 mu m. Subsequently, the plated steel pipe was galvanized for 15 minutes at a bath temperature of 25 ° C. and a current density of 3 A / dm 2 in a bath solution containing 28 g / L ZnO, 50 g / L NaCl, 80 g / L NaOH. Thus, a zinc plated layer having a thickness of 8 µm was formed on the nickel plated layer. Thereafter, the steel pipe was immersed in a solution containing 10 mL / L Z-493 (product of Deepsol Chemical Company Limited) for 20 seconds at a bath temperature of 25 ° C. to coat the chromate film on the zinc plated layer. In this way, a steel pipe having the plating layer as described above was obtained.

이 도금강관의 일단을 반경 25㎜의 맨드릴을 사용하여 180℃로 굽히고, 이것은 JIS Z-2371에 따른 염분무 시험에 의해 내식성 실험을 하였다. 붉은 녹이 발생되는데 요하는 시간(일)을 측정하였다. 또한, 도금강관을 24시간 동안 200℃로 가열한 후 JIS Z-2371에 따른 염분무 시험을 하여 내열성 및 내식성 실험을 하였다. 이때에도 붉은녹이 발생되는데 요하는 시간(일)을 측정하였다. 상기의 두 실험은 두개의 시료를 각각 사용하여 시행하였고, 그 결과는 표 1에 나타내었다(시료 제 1 호 내지 제 5 호).One end of this plated steel pipe was bent at 180 ° C using a mandrel having a radius of 25 mm, which was subjected to a corrosion resistance test by a salt spray test according to JIS Z-2371. The time required to develop red rust was measured. In addition, the plated steel pipe was heated to 200 ° C. for 24 hours, and then subjected to a salt spray test according to JIS Z-2371 to conduct heat and corrosion resistance tests. At this time, the time required for red rust was measured. The two experiments were carried out using two samples, respectively, and the results are shown in Table 1 (Samples No. 1 to 5).

[실시예 2]Example 2

JIS G-3454에 따른 STPG-38로서 지칭되는 탄소강을 사용하여 실시예 1과 동일한 칫수를 갖는 전기용접된 강관을 준비하여 이 강관을 실시예 1과 동일한 방식으로 도금한 후 시험하였다. 그 결과는 표 1에 나타내었다(시료 제 6 호 내지 제 10 호).An electrowelded steel pipe having the same dimensions as Example 1 was prepared using carbon steel, referred to as STPG-38 according to JIS G-3454, and the steel pipe was plated and tested in the same manner as in Example 1. The results are shown in Table 1 (Samples No. 6 to 10).

[비교예 1]Comparative Example 1

니켈도금층의 두께를 0.1㎛ 또는 15㎛로 하는 것외에는 실시예 1 및 실시예 2와 동일한 방식으로 도금층을 갖는 겹침 용접된 강관 및 전기용접된 강관을 준비하여, 실시예 1과 동일한 방식으로 시험하고, 그 결과를 표 1에 나타내었다(시료 제 11 호 내지 제 14 호).Except for setting the thickness of the nickel plated layer to 0.1 μm or 15 μm, an overlap welded steel pipe and an electro welded steel pipe having a plating layer were prepared in the same manner as in Example 1 and Example 2, and tested in the same manner as in Example 1. The results are shown in Table 1 (Samples 11-14).

[비교예 2]Comparative Example 2

실시예 1과 동일한 겹침용접된 강관과 실시예 2와 동일한 전기용접된 강관을 준비하여, 실시예 1과 동일한 방식으로 아연도금층과 크롬산염 막을 형성시키고, 니켈도금층은 형성시키지 않았다. 상기 강관들을 실시예 1과 동일한 방식으로 시험한 후, 결과를 표 1에 나타내었다(시료 제 15 호와 제 16 호).The same overlap welded steel pipe as in Example 1 and the same electro welded steel pipe as in Example 2 were prepared to form a galvanized layer and a chromate film in the same manner as in Example 1, but did not form a nickel plated layer. After the steel pipes were tested in the same manner as in Example 1, the results are shown in Table 1 (Samples 15 and 16).

[표 1]TABLE 1

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*A : 겹침용접된 강관 B : 전기용접된 강관* A: Overlap welded steel pipe B: Electro welded steel pipe

** 붉은 녹이 발생되는데 요하는 시간(일) 괄호로 표시한 것은 비교예의 번호임** Number of days required for red rust to occur in parentheses.

본 발명의 강제품은 특정두께의 니켈도금층으로된 하층과, 아연도금층으로된 중간층과, 크롬산염 막으로 된 상층으로 구성된 도금층들을 가지고 있다. 이 도금층들에 의해, 열처리후 또는 굽힘부에서 우수한 내식성이 나타나게 되며, 이에 따라 강제품을 자동차 엔진실과 같은 고온환경에 사용하는 것이 가능하다.The steel product of the present invention has a plating layer consisting of a lower layer of a nickel plated layer of a specific thickness, an intermediate layer of a zinc plated layer, and an upper layer of a chromate film. By these plating layers, excellent corrosion resistance is exhibited after heat treatment or at the bent portion, whereby it is possible to use the steel product in a high temperature environment such as an automobile engine room.

Claims (4)

아연도금층과, 그 아연도금층에 형성된 크롬산염막으로 구성된 도금층을 갖는 강제품에 있어서, 강제품의 표면에 하층으로 형성된 0.2 내지 10㎛ 두께의 니켈도금층을 포함하는 내열성 및 내식성 도금층을 갖는 것을 특징으로 하는 내열성 및 내식성 도금층을 갖는 강제품.A steel product having a galvanized layer and a plating layer composed of a chromate film formed on the galvanized layer, the steel product having a heat resistant and corrosion resistant plating layer comprising a nickel plated layer having a thickness of 0.2 to 10 μm formed as a lower layer on the surface of the steel product. Steel products with heat and corrosion resistant plating layers. 제 1 항에 있어서, 니켈도금층이 와트욕을 사용하는 전기도금에 의해 형성된 것을 특징으로 하는 내열성 및 내식성 도금층을 갖는 강제품.The steel product having a heat resistant and corrosion resistant plating layer according to claim 1, wherein the nickel plated layer is formed by electroplating using a watt bath. 아연도금층과, 그 아연도금층에 형성된 크롬산염막으로 구성된 도금층을 갖는 구리도금 강제품에 있어서, 강제품의 표면에 하층으로 형성된 0.2 내지 10㎛ 두께의 니켈도금층을 포함하는 내열성 및 내식성 도금층을 갖는 것을 특징으로 하는 내열성 및 내식성 도금층을 갖는 구리도금 강제품.A copper plated steel product having a galvanized layer and a plated layer composed of a chromate film formed on the galvanized layer, comprising: a heat-resistant and corrosion-resistant plated layer including a nickel plated layer having a thickness of 0.2 to 10 μm formed as a lower layer on the surface of the steel product. A copper plated steel product having a heat resistant and corrosion resistant plating layer. 제 3 항에 있어서, 니켈도금층이 와트욕을 사용하는 전기도금에 의해 형성된 것을 특징으로 하는 내열성 및 내식성 도금층을 갖는 구리 도금 강제품.The copper plated steel product having a heat resistant and corrosion resistant plating layer according to claim 3, wherein the nickel plated layer is formed by electroplating using a watt bath.
KR1019890015483A 1988-10-29 1989-10-27 Plating steel stock having heat resistance and corrosion resistance KR930008343B1 (en)

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JP63274220A JP2772804B2 (en) 1988-10-29 1988-10-29 Multi-layer plated steel with excellent plastic workability and heat and corrosion resistance

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