JPS58221247A - Zn-al-ti alloy for hot dipping - Google Patents

Abstract

PURPOSE:To enhance the corrosion resistance and adhesive strength of the resulting titled alloy and to improve the work efficiency by adding a very small amount of Mg to a Zn-Al-Ti alloy having a specified composition. CONSTITUTION:A very small amount of Mg is added to a Zn-Al-Ti alloy. The relation between Al and Ti (wt%) in the Zn-Al-Ti alloy satisfies equation I (where Al<=8.0, 0.1<=Ti<=0.6, and X=1-10). The resulting Zn-Al-Ti alloy for hot dipping shows superior corrosion resistance and adhesive strength, and the work efficiency is improved.

Description

【発明の詳細な説明】 系溶融メッキ用合金に関する。[Detailed description of the invention] This invention relates to alloys for hot-dip plating.

近年、鉄鋼材料の亜鉛メッキ製品の用途は増々がより改
善されたメッキ用合金が要望されている。In recent years, the use of galvanized steel products is increasing, and there is a demand for improved plating alloys.

亜鉛メッキ製品の耐蝕性を向上させる方法として亜鉛メ
ッキ付着量を増加させる方法および、耐蝕性改善に有効
といわれるＴ１、Ｚｒ、　Ｏｒ、　Ｓｉ等の元素を添加
する方法が一般に採用されている。しかしながら、合金
メッキの場合、メッキ浴中の合金組成の安定性が悪く、
耐蝕性および密着性にバラツキを生ず欠陥を有している
。Ｚｎ−Ａｔ−Ｔｉ系溶融メッキ用合金が特公昭５３−
４７０５５号、特公昭詞−３３２２１Ｉ号、特公昭５５
−９０５５号、特開昭５１−１３６５３０号、特開昭５
４−２１９２４号等に開示されているが、これらの合金
においては密着性が改善されない欠陥を有している。As a method for improving the corrosion resistance of galvanized products, generally employed are a method of increasing the amount of zinc plating deposited, and a method of adding elements such as T1, Zr, Or, Si, etc., which are said to be effective in improving corrosion resistance. However, in the case of alloy plating, the stability of the alloy composition in the plating bath is poor,
Corrosion resistance and adhesion are inconsistent and have defects. Zn-At-Ti alloy for hot-dip plating was published in 1973.
No. 47055, Special Publication No. 33221I, Special Publication No. 55
-9055, JP-A-51-136530, JP-A-5
No. 4-21924, etc., but these alloys have defects that prevent their adhesion from being improved.

本発明は耐蝕性および密着性に優れ、かつ、作業性も良
好なＺｎ−Ａ４−Ｔｉ系溶融メッキ用合金を提供するこ
とを目的とする。An object of the present invention is to provide a Zn-A4-Ti alloy for hot-dip plating that has excellent corrosion resistance and adhesion and also has good workability.

本発明者等は、前記目的を達成すべく鋭意研究の結果、
Ｚｎ−Ａｔ−Ｔｉ系合金にお藝てＡｔとＴ１との組成が
ある関係式で示される範囲にある時硬れた耐蝕性を示す
ことを見出し本発明を完成した。As a result of intensive research to achieve the above objective, the present inventors have found that
The present invention was completed by discovering that Zn--At--Ti alloy exhibits high corrosion resistance when the composition of At and T1 is within the range shown by a certain relational expression.

本発明は、Ｚｎ−Ａｔ−Ｔｉ系合金においてＡｔとＴ１
との重量％で表す組成が Ａｔ＝（３，５〜５．０）＋’ｌ’ｉ・Ｘ　　　　・・
・・・・・・・（１）（式中Ｘは１〜１０の任意の数を
表す。）Ａｔ≦　８．０ ０．１　　≦　Ｔ１　≦　０．６ の関係を有し、かつ、微蓋のＭｌを含有することを特徴
とするＺｎ−Ａｔ−Ｔｉ系溶融メッキ用合金である。The present invention focuses on At and T1 in Zn-At-Ti alloys.
The composition expressed in weight percent is At=(3,5~5.0)+'l'i・X...
......(1) (In the formula, X represents any number from 1 to 10.) Having the relationship of At≦8.0 0.1≦T1≦0.6, and having a microlid This is a Zn-At-Ti alloy for hot-dip plating, which is characterized by containing Ml.

本発明において、前記関係式（１）中のＸが１〜１０の
範囲にあるＡｔとＴ１の組成関係を有するｚｎ−ｋｌ−
Ｔｉ系合金は、第１図に示すごとく塩水噴霧試験におい
て優れた耐蝕性を示す。Ｘの値が１未満において耐蝕性
が漸減する傾向を示し、１０を越えると酸化速度が極め
て大きくなるので好ましくない。In the present invention, the zn-kl-
As shown in FIG. 1, Ti-based alloys exhibit excellent corrosion resistance in salt spray tests. When the value of X is less than 1, the corrosion resistance tends to gradually decrease, and when it exceeds 10, the oxidation rate becomes extremely high, which is not preferable.

Ａｔが８．０％越えるとメッキ浴の粘性が増大し、かつ
、凝固温度範囲が大きくなるため長時間の保持により熱
分離を生じ易“くなり好ましくない。またＴ１が０．６
　％を越えるとメッキ浴温度が高くなり作業性が悪くな
るので好ましくない。さらにＭｆはＺｎ−Ａｔ系合金に
おいて粒間腐蝕防止のために通常添加される量が添加さ
れる。If At exceeds 8.0%, the viscosity of the plating bath will increase, and the solidification temperature range will increase, making it easy to cause thermal separation due to long-term holding, which is undesirable. Also, if T1 is 0.6
%, it is not preferable because the plating bath temperature increases and workability deteriorates. Furthermore, Mf is added in an amount normally added to Zn--At alloys to prevent intergranular corrosion.

本発明は、Ｚｎ−Ａｔ−Ｔｉ系合金においてＡｔとＴ１
との組成の関係を限定することにより、耐蝕性および蟹
着性さらには作業性をも改善された溶融メッキ用合金を
提供するものでありその産業的意義は極めて大きい。The present invention focuses on At and T1 in Zn-At-Ti alloys.
By limiting the compositional relationship between the two, it is possible to provide an alloy for hot-dip plating that has improved corrosion resistance, anti-cracking properties, and even workability, and is of extremely great industrial significance.

以下本発明を実施例によりさらに詳細に説明する。ただ
し本発明は下記実施例に限定されるものではない。The present invention will be explained in more detail below using examples. However, the present invention is not limited to the following examples.

実施例 板厚０．３　ｍの冷延鋼板を６チ苛性ソーダ水溶液で脱
脂し、６俤塩酸で酸洗し、さらに水洗した後ｌＯ％ＮＨ
４０ｔ−Ｚｎ０４　（ただしＮＨ＜Ｏｔ／ＺｎＯ７，＝
　３／ｌ　）水溶液に浸漬した。該鋼板を電気炉内で乾
燥後第丁２ １表中に示すＡｔおよび併組成のＺｎ　−Ａｔ−Ｔｉ系
メッキ浴にさらにＭｆ　０．０４　％を添加した中に１
０秒間浸漬し引き上げてメッキ鋼板を得た。該メッキ鋼
板の塩水噴霧試験による腐蝕速度（ｒ／ｍ”ｈ　）およ
び繰返し曲げ試験によるメッキ被膜はく離までの回数を
比較例と共に第１表中に示す、。Example A cold-rolled steel plate with a thickness of 0.3 m was degreased with 6 ml of caustic soda aqueous solution, pickled with 6 ml of hydrochloric acid, further washed with water, and then treated with 10% NH.
40t-Zn04 (However, NH<Ot/ZnO7,=
3/l) immersed in an aqueous solution. After drying the steel sheet in an electric furnace, 0.04% Mf was further added to a Zn-At-Ti plating bath having the At and co-composition shown in Table 2-1.
It was immersed for 0 seconds and pulled up to obtain a plated steel plate. The corrosion rate (r/m''h) of the plated steel plate in the salt spray test and the number of times until the plating film peeled off in the repeated bending test are shown in Table 1 together with comparative examples.

なお、塩水噴霧試験は、Ｔ工Ｓ　Ｚ−２３７１に準拠し
、７２時間の塩水噴霧後５０℃の５チ酢酸アンモニウム
水溶液に加秒間浸漬して錆を除去した後、重量を測定し
腐蝕速度を算出した。また、繰返し曲げ試験の曲げ角度
は９０度とした。The salt spray test was conducted in accordance with T Engineering S Z-2371, and after 72 hours of salt water spraying, the rust was removed by immersion in an aqueous solution of ammonium 5-thiacetate at 50°C, and the weight was measured to determine the corrosion rate. Calculated. Further, the bending angle in the repeated bending test was 90 degrees.

比較例 実施例と同様に処理した鋼板を第１表中に示す組成のメ
ッキ浴に実施例と同様に浸漬しメッキ鋼板を得た。得ら
れたメッキ鋼板を実施例と同様に塩水噴霧試験、および
繰返し曲げ試験を行った。Comparative Example A steel plate treated in the same manner as in the Example was immersed in a plating bath having the composition shown in Table 1 in the same manner as in the Example to obtain a plated steel plate. The obtained plated steel sheet was subjected to a salt spray test and a repeated bending test in the same manner as in the examples.

結果を実施例と共に第１表中に示す。The results are shown in Table 1 along with Examples.

　５−5-

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は、Ａｔ＝３．５＋Ｔｉ・Ｘの関係式でＡｔとＴ
１との組成関係を表わした時のＸと腐蝕速度（？／−・
ｈｒ）の関係を表す曲線 図中（１）はＴｉ　＝　０．２　ｗｔチ（２）はＴｉ　
＝　９．４　ｗｔチ （３）はＴｉ　＝　９．５　ｉｔチの場合を示す。 特許出願人　　日　留金属株式会社 代理人　伊　藤　晴　之 同　　　　　　横　　　山　　　吉　　　美　７− ２７５Figure 1 shows the relational expression At=3.5+Ti・X, and At and T
X when expressing the compositional relationship with 1 and corrosion rate (?/-・
(1) is Ti = 0.2 wt, (2) is Ti
= 9.4wtchi (3) shows the case where Ti = 9.5itchi. Patent Applicant Hidome Metal Co., Ltd. Agent Haruno Ito Yoshimi Yokoyama 7-275

Claims (1)

【特許請求の範囲】 １、　　Ｚｎ−Ａ、／、−Ｔｉ系合金において、Ａｔと
Ｔ１との重量％で表す組成が Ａｔ＝　（３，５〜５．０　）＋Ｔｉ・Ｘ（式中Ｘは１
〜１０の任意の数を表す。）Ａｔ≦８．０ 丁ル ０．１　≦　芒デ　≦　０．６ の関係を有し、かつ、機筺のＭｌを含有することを特徴
とするＺｎ−Ａｔ−Ｔｉ系溶融メッキ用合金。[Claims] 1. In the Zn-A,/,-Ti alloy, the composition expressed in weight percent of At and T1 is At=(3.5~5.0)+Ti・X (wherein, X is 1
Represents any number between ~10. ) A Zn-At-Ti alloy for hot-dip plating, which has the following relationships: At≦8.0, At≦0.1≦Adon≦0.6, and contains a certain amount of Ml.