JPS6146538B2 - - Google Patents
Info
- Publication number
- JPS6146538B2 JPS6146538B2 JP15986683A JP15986683A JPS6146538B2 JP S6146538 B2 JPS6146538 B2 JP S6146538B2 JP 15986683 A JP15986683 A JP 15986683A JP 15986683 A JP15986683 A JP 15986683A JP S6146538 B2 JPS6146538 B2 JP S6146538B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- alloy
- corrosion resistance
- content
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 229910001297 Zn alloy Inorganic materials 0.000 claims description 24
- 238000005260 corrosion Methods 0.000 claims description 21
- 230000007797 corrosion Effects 0.000 claims description 21
- 239000012535 impurity Substances 0.000 claims description 3
- 238000007747 plating Methods 0.000 description 41
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 238000005452 bending Methods 0.000 description 9
- 238000005336 cracking Methods 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000012943 hotmelt Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910007564 Zn—Co Inorganic materials 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Landscapes
- Coating With Molten Metal (AREA)
Description
この発明は、特に鉄鋼材料の表面を溶融メツキ
することによつて、耐食性にすぐれ、かつ曲げ加
工を施してもメツキ層に剥離や割れ発生のない材
料を得るための溶融メツキ用高耐食性Zn合金に
関するものである。
一般に、鉄鋼材料の耐食性を向上させるための
安価にして簡便な方法として、その表面にZnま
たはZn合金を溶融メツキする方法が知られてお
り、かつ溶融メツキ用Zn合金として数多くのも
のが提案されている。確かに、これらの従来Zn
合金の溶融メツキによつて鉄鋼材料は比較的良好
な耐食性をもつようになつたが、これが苛酷な使
用環境におかれた場合、必ずしも十分満足する耐
食性を示すものではなく、さらに通常、素地とメ
ツキ層間には脆いFe―Zn系合金層が形成されて
いるので、これに曲げ加工を施すと、メツキ層に
剥離や割れが発生するのを避けることができない
ものであつた。
そこで、本発明者等は、上述のような観点か
ら、苛酷な使用条件下におかれてもすぐれた耐食
性を示し、かつ曲げ加工を施してもメツキ層に剥
離や割れの発生がない溶融メツキ製品を確実容易
に得べく、特に溶融メツキ用Zn合金について研
究を行なつた結果、ZnにNiおよびCoのうちの１
種または２種を含有させると、Znと結合してZn
―Ni合金，Zn―Co合金，およびZn―Ni―Co合金
を形成し、これらの合金はいずれもTiとの相溶
性が良いことから、Zn中のTi含有量域が拡大さ
れるようになり、さらにNiおよびCo成分にはTi
成分を均一に分布せしめる作用のほか、合金自体
の結晶粒を微細化する作用があり、しかもこのよ
うにNiおよびCoの含有によつてTi含有量が増大
し、かつ結晶の微細化したZn合金は、著しくす
ぐれた耐食性をもつようになり、また、一方Ａ
および必要に応じてさらにSiを含有させると、メ
ツキ層と素地間のFe―Zn系合金層の形成が著し
く抑制されるようになるので、曲げ加工時に前記
Fe―Zn系合金層が原因のメツキ層剥離やメツキ
層に割れが生ずる現象が皆無となるという知見を
得たのである。
したがつて、この発明は、上記知見にもとづい
てなされたものであつて、重量％で（以下％は重
量％を示す）、
Ti：0.1〜２％、
NiおよびCoのうちの１種または２種：0.1〜1.6
％、
Ａ：0.1〜1.6％、
を含有し、さらに必要に応じて、
Si：0.01〜0.3％、
を含有し、残りがZnと不可避不純物からなる組
成を有し、特に鉄鋼材料の表面を溶融メツキする
のに用いた場合に、前記鉄鋼材料の苛酷な腐食環
境下での長期に亘つての安定した使用と、メツキ
層剥離や割れの発生のない曲げ加工を可能とする
溶融メツキ用高耐食性Zn合金に特徴を有するも
のである。
つぎに、この発明のZn合金の成分組成範囲を
上記の通りに限定した理由を説明する。
(a) Ti
Ti成分には、苛酷な腐食環境下でも十分満
足するすぐれた耐食性を付与する作用がある
が、その含有量が0.1％未満では所望のすぐれ
た耐食性を確保することができず、一方２％を
越えて含有させると、メツキ作業性が損なわれ
るようになり、したがつてメツキ作業性を良好
な状態に保持するには溶融メツキ浴温度をかな
り高くしなければならず、この結果被メツキ材
がメツキ浴中に溶解して浴組成を著しく乱すよ
うになることから、その含有量を0.1〜２％と
定めた。
(b) NiおよびCo
これらの成分には、上記のようにZn素地中
へのTiの固溶度を高め、かつ結晶粒および一
部分散析出するTi化合物を微細化すると共
に、Ti化合物の均一分布をはかり、もつて耐
食性を向上させる作用があるが、その含有量が
0.1％未満では前記作用に所望の効果が得られ
ず、一方1.6％を越えて含有させると合金の靭
性が極端に劣化するようになつてメツキ層に亀
裂や剥離が生じ易くなることから、その含有量
を0.1〜1.6％と定めた。
(c) Ａ
Ａ成分には、上記のように溶融メツキ時に
素地の表面部とメツキ層との間に脆いFe―Zn
系合金層が形成されるのを抑制し、もつて曲げ
加工時に前記Fe―Zn系合金層が原因のメツキ
層の剥離および割れを防止し、かつNiおよび
Coの含有によるメツキ層の硬化を緩和する作
用があるが、その含有量が0.1％未満では前記
作用に所望の効果が得られず、一方1.6％を越
えて含有させると、耐食性が低下するようにな
ることから、その含有量を0.1〜1.6％と定め
た。
(d) Si
Si成分には、メツキ浴の流動性を向上させて
平滑な光沢のあるメツキ層を形成するほか、
Fe―Zn系合金層の形成を一段と抑制し、かつ
耐食性を飛躍的に向上させる作用があるので、
特にこれらの特性が要求される場合に必要に応
じて含有されるが、その含有量が0.01％未満で
は前記作用に所望の向上効果が得られず、一方
0.3％を越えて含有させるとメツキ性が損なわ
れるようになることから、その含有量を0.01〜
0.3％と定めた。
つぎに、この発明のZn合金を実施例により比
較例と対比しながら説明する。
実施例
それぞれ第１表に示される成分組成をもつた本
発明Zn合金１〜20およびZnの溶融メツキ浴を調
製し、ついでメツキ浴温を460〜480℃に保持した
前記溶融メツキ浴中に、それぞれZnC２―
NH4C系フラツクスで前処理した厚さ0.4mmを有
する鋼板を５秒間浸漬することによつて該鋼板表
面に片面平均厚さ：10μｍのメツキ層を形成し
た。
ついで、この結果得られた本発明Zn合金メツ
キ鋼板１〜20および従来Znメツキ鋼板につい
て、Fe―Zn系合金層の有無を観察すると共に、
JIS・Z2371にもとづく塩水噴霧試験、並びに
JIS・Z2248にもとづく曲げ試験を行ない、前記
塩水噴霧試験では鋼板メツキ面に赤錆が発生
This invention is a highly corrosion-resistant Zn alloy for hot-dip plating to obtain a material that has excellent corrosion resistance and does not peel or crack in the plating layer even when subjected to bending, by hot-plating the surface of a steel material. It is related to. In general, it is known that hot-melt plating Zn or Zn alloys on the surface is an inexpensive and simple method for improving the corrosion resistance of steel materials, and many Zn alloys for hot-dip plating have been proposed. ing. Indeed, these conventional Zn
Although steel materials have come to have relatively good corrosion resistance through hot-dip plating of alloys, they do not necessarily show sufficient corrosion resistance when exposed to harsh usage environments, and moreover, the corrosion resistance of steel materials usually deteriorates compared to the base material. Since a brittle Fe--Zn alloy layer is formed between the plating layers, when this is subjected to bending, peeling and cracking of the plating layer cannot be avoided. Therefore, from the above-mentioned viewpoints, the present inventors have developed a melt-plated plating material that exhibits excellent corrosion resistance even under severe usage conditions and that does not cause peeling or cracking in the plating layer even when subjected to bending. In order to reliably and easily obtain products, we conducted research on Zn alloys for hot-dip plating, and found that one of Ni and Co was added to Zn.
When one species or two species are contained, it combines with Zn and becomes Zn.
- Forms Ni alloy, Zn-Co alloy, and Zn-Ni-Co alloy, and since these alloys all have good compatibility with Ti, the range of Ti content in Zn has been expanded. In addition, Ni and Co components include Ti.
In addition to the effect of uniformly distributing the components, it also has the effect of refining the crystal grains of the alloy itself, and in this way, the inclusion of Ni and Co increases the Ti content and the Zn alloy has fine crystals. A has significantly superior corrosion resistance, while A
If Si is further included as needed, the formation of a Fe-Zn alloy layer between the plating layer and the base material will be significantly suppressed, so the
We have found that there is no phenomenon of plating layer peeling or cracking in the plating layer caused by the Fe-Zn alloy layer. Therefore, this invention was made based on the above knowledge, and in weight% (hereinafter % indicates weight%), Ti: 0.1 to 2%, one or two of Ni and Co. Species: 0.1-1.6
%, A: 0.1 to 1.6%, and further contains Si: 0.01 to 0.3%, if necessary, and the remainder is Zn and unavoidable impurities, and is especially effective at melting the surface of steel materials. High corrosion resistance for hot-dip plating, which enables long-term stable use of the above-mentioned steel materials in harsh corrosive environments and bending without peeling or cracking of the plating layer when used for plating. This is a characteristic of Zn alloys. Next, the reason why the composition range of the Zn alloy of the present invention is limited as described above will be explained. (a) Ti The Ti component has the effect of imparting excellent corrosion resistance that satisfies even in severe corrosive environments, but if its content is less than 0.1%, the desired excellent corrosion resistance cannot be secured. On the other hand, if the content exceeds 2%, the plating workability will be impaired, and therefore, in order to maintain the plating workability in a good condition, the temperature of the molten plating bath must be raised considerably. Since the material to be plated dissolves in the plating bath and significantly disturbs the bath composition, its content was determined to be 0.1 to 2%. (b) Ni and Co As mentioned above, these components increase the solid solubility of Ti in the Zn matrix, refine the crystal grains and partially dispersed precipitated Ti compounds, and also improve the uniform distribution of the Ti compounds. It has the effect of improving corrosion resistance, but its content is
If the content is less than 0.1%, the desired effect cannot be obtained, while if the content exceeds 1.6%, the toughness of the alloy will be extremely deteriorated and the plating layer will be more likely to crack or peel. The content was set at 0.1-1.6%. (c) A The A component contains Fe-Zn, which is brittle between the surface of the substrate and the plating layer during melt plating as described above.
This suppresses the formation of the Fe--Zn alloy layer and prevents the plating layer from peeling and cracking caused by the Fe--Zn alloy layer during bending.
The content of Co has the effect of mitigating the hardening of the plating layer, but if the Co content is less than 0.1%, the desired effect will not be obtained, while if the Co content exceeds 1.6%, the corrosion resistance will decrease. Therefore, the content was set at 0.1 to 1.6%. (d) Si The Si component not only improves the fluidity of the plating bath to form a smooth and glossy plating layer, but also
It has the effect of further suppressing the formation of Fe-Zn alloy layer and dramatically improving corrosion resistance.
It is included as necessary especially when these properties are required, but if the content is less than 0.01%, the desired effect of improving the above functions cannot be obtained;
If the content exceeds 0.3%, the plating properties will be impaired, so the content should be adjusted to 0.01~
It was set at 0.3%. Next, the Zn alloy of the present invention will be explained using examples and comparing with comparative examples. Example A hot-melt plating bath of Zn alloys 1 to 20 of the present invention and Zn having the compositions shown in Table 1, respectively, was prepared, and then, in the hot-melt plating bath whose plating bath temperature was maintained at 460 to 480°C, ZnC 2 -
A steel plate having a thickness of 0.4 mm pretreated with an NH 4 C-based flux was immersed for 5 seconds to form a plating layer having an average thickness of 10 μm on one side on the surface of the steel plate. Next, the presence or absence of the Fe-Zn alloy layer was observed for the Zn alloy plated steel sheets 1 to 20 of the present invention and the conventional Zn alloy plated steel sheets obtained as a result, and
Salt spray test based on JIS/Z2371, and
A bending test was conducted based on JIS Z2248, and red rust occurred on the plated surface of the steel plate in the salt spray test.
【表】
するまでの時間を測定し、また前記曲げ試験では
曲げ面におけるメツキ層の状態を観察し、メツキ
層に剥離も割れも全く発生していない場合を◎
印、メツキ層に剥離および割れがはつきりと認め
られる場合を×印でそれぞれ評価した。これらの
測定結果を第１表に合せて示した。
第１表に示される結果から、本発明Zn合金メ
ツキ鋼板１〜20は、いずれもすぐれた耐食性を示
すと共に、曲げ加工を施しても剥離や割れの全く
発生しない密着性のよいメツキ層を有しているの
に対して、従来Znメツキ鋼板においては、Fe―
Zn系合金層の形成があり、かつ耐食性およびメ
ツキ層密着性の著しく劣つたものになつている。
また本発明Zn合金メツキ鋼板１〜20に見られる
ように、所定量のNi，Co，およびＡ、さらに
Siの存在の下でTi含有量が多くなればなるほど耐
食性がすぐれたものになることが明らかである。
また、本発明Zn合金を溶融メツキした上に、
さらにクロメート処理を施すと、一段と耐食性が
向上するようになることが確認された。
上述のように、この発明の溶融メツキ用高耐食
性Zn合金によれば、特に鉄鋼材料の表面を溶融
メツキすることにより、苛酷な使用条件におかれ
てもすぐれた耐食性を確保することができ、かつ
鉄鋼材料表面への密着性がきわめて良く、脆い
Fe―Zn系合金層の形成がほとんどないので、曲
げ加工時にメツキ層に剥離や割れの発生が皆無と
なるなど工業上有用な効果がもたらされるのであ
る。[Table] In addition, in the above bending test, the state of the plating layer on the bent surface was observed, and if there was no peeling or cracking at all in the plating layer, ◎
The cases where peeling and cracking were clearly observed in the plating layer were evaluated as x marks. These measurement results are also shown in Table 1. From the results shown in Table 1, the Zn alloy plated steel sheets 1 to 20 of the present invention all exhibit excellent corrosion resistance and have a plated layer with good adhesion that does not cause any peeling or cracking even when subjected to bending. In contrast, in conventional Zn-plated steel sheets, Fe-
A Zn-based alloy layer was formed, and the corrosion resistance and plating layer adhesion were significantly inferior.
In addition, as seen in Zn alloy plated steel sheets 1 to 20 of the present invention, predetermined amounts of Ni, Co, and A, and
It is clear that the higher the Ti content in the presence of Si, the better the corrosion resistance. In addition, in addition to melt-plating the Zn alloy of the present invention,
It was confirmed that further chromate treatment further improves corrosion resistance. As mentioned above, according to the highly corrosion-resistant Zn alloy for hot-dip plating of the present invention, excellent corrosion resistance can be ensured even under severe usage conditions, especially by hot-plating the surface of steel materials. It also has extremely good adhesion to the surface of steel materials and is brittle.
Since almost no Fe-Zn alloy layer is formed, industrially useful effects such as no peeling or cracking of the plating layer during bending are achieved.
Claims (1)
％、 Ａ：0.1〜1.6、 を含有し、残りがZnと不可避不純物からなる組
成（以上重量％）を有することを特徴とする溶融
メツキ用高耐食性Zn合金。 ２ Ti：0.1〜２％、 NiおよびCoのうちの１種または２種：0.1〜1.6
％、 Ａ：0.1〜1.6％、 を含有し、さらに、 Si：0.01〜0.3％、 を含有し、残りがZnと不可避不純物からなる組
成（以上重量％）を有することを特徴とする溶融
メツキ用高耐食性Zn合金。[Claims] 1 Ti: 0.1 to 2%, one or two of Ni and Co: 0.1 to 1.6
%, A: 0.1 to 1.6, and the remainder is Zn and unavoidable impurities (weight %). 2 Ti: 0.1-2%, one or two of Ni and Co: 0.1-1.6
%, A: 0.1 to 1.6%, and further contains Si: 0.01 to 0.3%, with the remainder consisting of Zn and unavoidable impurities (weight %). High corrosion resistance Zn alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15986683A JPS6086238A (en) | 1983-08-31 | 1983-08-31 | High corrosion resistant zn-alloy for hot dipping |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15986683A JPS6086238A (en) | 1983-08-31 | 1983-08-31 | High corrosion resistant zn-alloy for hot dipping |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6086238A JPS6086238A (en) | 1985-05-15 |
| JPS6146538B2 true JPS6146538B2 (en) | 1986-10-15 |
Family
ID=15702923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15986683A Granted JPS6086238A (en) | 1983-08-31 | 1983-08-31 | High corrosion resistant zn-alloy for hot dipping |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6086238A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113073280B (en) * | 2021-03-25 | 2021-10-01 | 温州泰昌铁塔制造有限公司 | Alloy for hot-dip galvanizing and production process thereof |
-
1983
- 1983-08-31 JP JP15986683A patent/JPS6086238A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6086238A (en) | 1985-05-15 |
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