JP2991877B2 - Hot-dip Zn-Al plated steel sheet with excellent appearance, blackening resistance over time and corrosion resistance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hot-dip Zn-Al plated steel sheet mainly used for building materials and home appliances.

[0002]

2. Description of the Related Art Hot-dip Zn-Al-plated steel sheets are hot-dip
Compared with plated steel sheets, they are superior in bare corrosion resistance and corrosion resistance after painting, and their use in building materials and home appliances has recently been increasing. However, the hot-dip Zn-Al-plated steel sheet has a problem of poor appearance called a turtle pattern and a problem of blackening with time in which the surface turns black when exposed to a high temperature and high humidity environment. There is also a demand for further improvement in corrosion resistance. To solve these problems, for example, Japanese Patent Publication No.
one or two of i or Zr, one or two of Mn, Ni, Co or Fe, TiAl ₃ or ZrAl
A technique of a highly corrosion resistant Zn alloy to which one or two of the _three are added is disclosed.

[0003] Also, in Japanese Patent Application Laid-Open No. 2-274851,
A plated steel sheet having excellent corrosion resistance using an alloy obtained by adding one or two of Ti, B and Si, Mg, Mn or Cu to a Zn-Al alloy is disclosed. However, although these techniques can provide an effect of improving corrosion resistance, they do not improve performance in terms of appearance and blackening resistance with time. Also,
The method of adding various elements to the plating bath has caused a problem that it is difficult to control bath components in actual operation. For the improvement of blackening resistance over time, the surface of the steel sheet
A method of depositing a metal such as o, Ni or the like by electroplating or displacement plating has been applied. However, this method causes a reduction in corrosion resistance because a metal which is noble in potential with respect to Zn is deposited on the plating surface, and also requires a treatment after hot-dip plating, thereby increasing production costs. there were.

[0004]

As described above, it is possible to obtain a steel sheet having good corrosion resistance and blackening resistance over time by using the prior art described above. No good steel sheet was obtained. In particular, as shown in FIG. 2, if the spangle size of the plating surface is large, a problem of poor appearance called a turtle pattern occurs as shown in FIG.

[0005]

The present inventors have found the following means as a hot-dip Zn-Al plated steel sheet having excellent appearance, blackening resistance over time and corrosion resistance. The gist of the invention is that the composition of the plating film is Al: 3
-10% by weight, Ti: 0.01-1% by weight, Cr: 0.
A hot-dip Zn-Al-plated steel sheet comprising 0.01 to 1% by weight, with the balance being Zn and unavoidable impurities, having a spangle size of 0.5 mm or less on the plating surface and having excellent appearance, blackening resistance over time, and corrosion resistance. .

[0006]

[Function] Plating film composition: Al: 3 to 10% by weight, T:
i: 0.01 to 1% by weight, Cr: 0.01 to 1% by weight,
The balance consists of Zn and unavoidable impurities. Al forms a eutectic structure with Zn and exhibits excellent corrosion resistance. To obtain this effect, the content of Al is set to 3 to 10% by weight. If the Al content is less than 3% by weight, the effect of improving corrosion resistance due to the formation of a eutectic structure cannot be obtained. On the other hand, if the content is 10% by weight or more, the hardness of the plating layer increases, and problems such as peeling of the plating easily occur at a portion where the steel sheet is bent and used. Ti has an effect of improving corrosion resistance and time-dependent blackening by forming a Ti oxide film layer on the surface of the plating layer.

Further, since Ti forms an intermetallic compound with Al and finely precipitates in the plating layer, it has the effect of making the spangles of the plating layer fine, so that the crevices caused by the spangle coarsening are formed. And the effect of improving the plating surface appearance can be obtained. In order to obtain this effect, Ti is set to 0.01 to 1% by weight. Ti is 0.01
If the content is less than 1% by weight, the above effect cannot be obtained. If the content is 1% by weight or more, the viscosity of the plating bath increases, and there is a problem that it is difficult to control the amount of plating. Cr has the effect of forming stable rust on the plated surface when the plated steel sheet is exposed to a corrosive environment, and improves the corrosion resistance of the plated steel sheet. In order to obtain this effect, Cr is set to 0.01 to 1% by weight. If the Cr content is less than 0.01% by weight, the above effects cannot be obtained, and 1% by weight
In the above, there arises a problem that the viscosity of the plating bath increases and it becomes difficult to control the amount of plating.

The spangle size of the plating surface is 0.5 m
m or less. When the thickness exceeds 0.5 mm as shown in FIG. 2, individual spangles become conspicuous visually and the grain boundary depth between the spangles becomes deep, which causes a problem of poor appearance called a turtle pattern. Conversely, as shown in FIG.
In the case of not more than mm, individual spangles cannot be visually discriminated, and the grain boundary depth between the spangles is shallow, so that the problem of poor appearance called a turtle pattern does not occur.

[0009]

Next, an embodiment will be described. In a continuous hot-dip galvanizing line, a 0.4 mm thick Al-killed steel plate was immersed in a hot-dip galvanizing bath having a predetermined composition to produce a coated steel plate. The coating weight of the coated steel sheet is 100-1 on one side
It was adjusted to be 20 g / m ² . The temperature of the hot-dip plating bath was 440 ° C. When cooling the steel sheet after immersion plating in the hot-dip plating bath, the cooling rate is adjusted in the range of about 15 to 100 ° C./sec during the transition from the sheet temperature of 400 ° C. to 380 ° C., so that the spangle size of the plating surface becomes zero. .5m
m or less. Cooling of the plated steel sheet was performed by a mist spray method. However, among the materials manufactured as comparative examples, there was a steel sheet whose spangle size did not become 0.5 mm or less even though the cooling rate was adjusted. The appearance, blackening resistance over time, and corrosion resistance of the obtained plated steel sheet are evaluated by the following methods, and the results are shown in Table 1.

Examples 1 to 4 of the present invention are affected by the Al composition of the plating film, Examples 5 and 6 of the present invention are affected by the Ti composition,
No. 8 was obtained by examining the influence of the Cr composition.
Good resistance to blackening over time and corrosion resistance. On the other hand, in Comparative Example 1, where Ti was not added, the spangle size was large and the surface appearance, blackening resistance with time and corrosion resistance were slightly inferior. Comparative Example 2 is a case where the Al composition is low, and the corrosion resistance is significantly reduced. Comparative Examples 3 and 4 are currently commercially available Zn-A
In the evaluation of the l-type hot-dip coated steel sheet, Comparative Example 4 is remarkably inferior in blackening resistance with time, and Comparative Example 5 is inferior in surface appearance and corrosion resistance.

[0011]

[Table 1]

Evaluation method of surface appearance Evaluation was made by visual observation according to the following criteria. ：: No turtle pattern. Δ: Slightly turtle pattern is recognized. X: The turtle pattern is conspicuous.

Evaluation method for blackening resistance over time After subjecting the sample surface to chromate treatment,
1 Packing stack test in a constant temperature and humidity chamber at 95 ° C and RH 95%
After 4 days, the change in the lightness of the steel sheet surface before and after the test (Δ
L value) was measured and evaluated according to the following criteria. [Measuring equipment used: Color computer manufactured by Suga Test Instruments Co., Ltd.-Model SM-4] ○: less than 3 △: 3 or more and less than 10 ×: 10 or more

[0014] subjected to salt spray tests based on corrosion resistance JIS · Z2371 3 days, the corrosion products were washed off with chromic acid was determined plating corrosion weight loss before and after the test (g / m ² · day) at a gravimetric method And the following criteria. 5: 5 g / m less than ² · day 4: 5 g / m ² · day or more 10 g / m less than ² · day 3: 10 g / m ² · day or more 20 g / m ² · day less than 2: 20 g / m ² · day or more Less than 40 g / m ² · day 1: More than 40 g / m ² · day

[0015]

As described above, by using the present invention, a molten Z having excellent appearance, blackening resistance over time and corrosion resistance is obtained.
An n-Al-plated steel sheet is obtained, and the use of the hot-dip Zn-Al-plated steel sheet mainly for building materials and home appliances is expanded, and the industrially significant effect is exhibited.

[Brief description of the drawings]

FIG. 1 is a micrograph showing the surface of a plated steel sheet according to the present invention.

FIG. 2 is a micrograph showing the surface of a conventional plated steel sheet.

Claims (1)

(57) [Claims] 1. The composition of a plating film is as follows: Al: 3 to 10% by weight, Ti: 0.01 to 1% by weight, Cr: 0.01 to 1%.
% By weight, the balance being Zn and unavoidable impurities, and having a spangle size of 0.5 mm or less on the plating surface, characterized by excellent appearance, blackening resistance over time and corrosion resistance.
n-Al plated steel sheet.