JP2009280880A - Hot dip galvanization treating method - Google Patents
Hot dip galvanization treating method Download PDFInfo
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- JP2009280880A JP2009280880A JP2008136113A JP2008136113A JP2009280880A JP 2009280880 A JP2009280880 A JP 2009280880A JP 2008136113 A JP2008136113 A JP 2008136113A JP 2008136113 A JP2008136113 A JP 2008136113A JP 2009280880 A JP2009280880 A JP 2009280880A
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- 238000000034 method Methods 0.000 title claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000007747 plating Methods 0.000 claims abstract description 31
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 239000000956 alloy Substances 0.000 claims abstract description 18
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 18
- 238000005246 galvanizing Methods 0.000 claims abstract description 17
- 239000000498 cooling water Substances 0.000 claims abstract description 8
- 238000012360 testing method Methods 0.000 abstract description 22
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 15
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 15
- 238000001816 cooling Methods 0.000 description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 238000007654 immersion Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- -1 δ 1 or ζ Chemical compound 0.000 description 1
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- Coating With Molten Metal (AREA)
Abstract
Description
本発明は、鉄物製品の溶融亜鉛めっき処理方法に関し、特に亜鉛使用量の低減に効果的である。 The present invention relates to a hot dip galvanizing method for iron products, and is particularly effective in reducing the amount of zinc used.
鉄物製品に溶融亜鉛めっきを施す目的は、光沢のある外観、耐食性等にあり、日本工業規格ＪＩＳＨ８６４１にめっきの種類及び記号が定められている。
これによると１種Ａ、１種Ｂは、硫酸銅試験回数により品質が定められている。
具体的に説明すると１種Ａは硫酸銅試験回数４回以上、１種Ｂは同５回以上と定められている。
そこで、本願発明者らは、硫酸銅試験によるめっき厚の減耗量と溶融亜鉛めっきの処理条件の関係を調査した結果、本発明に至った。
溶融亜鉛めっき皮膜は、鉄素地側に形成するＦｅＺｎ７（７〜１１％Ｆｅ）の六方晶δ１合金層と、その上に形成するＦｅＺｎ１３（約６％Ｆｅ）の単斜晶に属する柱状組織からなるζ（ｚｅｔａ）合金層と、その上に稠密六方晶のη亜鉛層とが形成されている。
η亜鉛層は、δ１やζのような鉄との合金層ではないので、硫酸銅試験にて減耗量が大きいことが推定される。
例えば、特許文献１には、η亜鉛層が残留しないように亜鉛めっき処理後に合金化処理を施す技術を開示する。
しかし、溶融亜鉛めっきラインの他に処理工程を追加することはコストアップの要因になり、生産性も低下する。
The purpose of hot dip galvanizing on iron products is to have a glossy appearance, corrosion resistance, etc., and the type and symbol of plating are defined in Japanese Industrial Standard JISH8641.
According to this, the quality of Type 1 A and Type 1 B is determined by the number of copper sulfate tests.
More specifically, Type 1 A is defined as four or more times of copper sulfate test, and Type 1 B is defined as five or more times.
Therefore, the inventors of the present application have found the present invention as a result of investigating the relationship between the amount of wear of the plating thickness by the copper sulfate test and the processing conditions of hot dip galvanizing.
The hot dip galvanized film has a hexagonal δ 1 alloy layer of FeZn 7 (7 to 11% Fe) formed on the iron substrate side and a columnar shape belonging to a monoclinic crystal of FeZn 13 (about 6% Fe) formed thereon. A ζ (zeta) alloy layer composed of a structure and a dense hexagonal η zinc layer are formed thereon.
Since the η zinc layer is not an alloy layer with iron such as δ 1 or ζ, it is estimated that the amount of wear is large in the copper sulfate test.
For example, Patent Document 1 discloses a technique of performing an alloying process after a galvanizing process so that a η zinc layer does not remain.
However, adding a treatment process in addition to the hot dip galvanizing line causes an increase in cost and decreases productivity.
本発明は、耐硫酸銅試験性に優れ、生産性の高い溶融亜鉛めっき処理方法の提供を目的とする。 An object of this invention is to provide the hot-dip galvanization processing method which is excellent in copper-sulfate-proof test property and has high productivity.
本発明は、鉄物製品の溶融亜鉛めっき方法であって、鉄物製品を溶融亜鉛めっき浴に浸漬し、次に当該溶融亜鉛めっき浴から当該鉄物製品を上昇させ、トータルめっき皮膜厚さ（Ｔ）に対するζ合金層厚さ（Ｔζ）の割合が５０％以上になるように、空中で所定時間空冷後に冷却水に浸漬することを特徴とする。 The present invention is a method for hot dip galvanizing of iron products, wherein the iron product is immersed in a hot dip galvanizing bath, and then the iron product is raised from the hot dip galvanizing bath to obtain a total plating film thickness ( It is characterized by being immersed in cooling water after air cooling for a predetermined time in the air so that the ratio of the ζ alloy layer thickness (T ζ ) to T) is 50% or more.
ここでトータルめっき皮膜厚さ（Ｔ）とは、鉄素地の上に形成されるδ１合金層＋ζ合金層＋η亜鉛層等を合計しためっきの厚さをいい、ζ合金層厚さ（Ｔζ）はトータルめっき皮膜中のζ合金層の平均膜厚をいう。 Here, the total plating film thickness (T) refers to the total plating thickness of δ 1 alloy layer + ζ alloy layer + η zinc layer formed on the iron base, and ζ alloy layer thickness (T ζ ) Means the average film thickness of the ζ alloy layer in the total plating film.
従来は、鉄物製品をめっき浴に所定時間浸漬後に空中に引き上げ、そのまま水冷しており、その場合にはトータルめっき皮膜厚さ（Ｔ）に対する（Ｔζ）の割合は３０〜４０％レベルであった。
これに対して、本発明においては、（Ｔζ）の割合が５０％以上になるようにζ合金層を空中にて成長させた後に冷却水に浸漬したものである。
（Ｔζ）の割合が大きい方が硫酸銅試験にて試験１回当たりの減耗量が少なくなるので、品質１種Ａ、１種Ｂをクリアーするためのトータルめっき皮膜厚さ（Ｔ）の厚みが薄くてもよくなる。
よって、（Ｔζ）の割合は、好ましくは７０％以上、理想的には９０％以上にするのがよい。
また、ζ合金層の成長速度はめっき浴の浴温の影響も受けることから、浴温に応じて適切な空中空冷時間を設定するのがよい。
Conventionally, an iron product is immersed in a plating bath for a predetermined time and then pulled up into the air and cooled as it is. In this case, the ratio of (T ζ ) to the total plating film thickness (T) is 30 to 40% level. there were.
On the other hand, in the present invention, the ζ alloy layer is grown in the air so that the ratio of (T ζ ) is 50% or more, and then immersed in cooling water.
When the ratio of (T ζ ) is larger, the amount of wear per test is reduced in the copper sulfate test, so the total plating film thickness (T) thickness for clearing the quality 1 type A and 1 type B Can be thin.
Therefore, the ratio of (T ζ ) is preferably 70% or more, and ideally 90% or more.
Further, since the growth rate of the ζ alloy layer is also affected by the bath temperature of the plating bath, it is preferable to set an appropriate hollow cooling time according to the bath temperature.
本発明に係る溶融亜鉛めっき処理方法にあっては、鉄物製品を溶融亜鉛めっき浴から引き上げた後の空中空冷時間を長く設定するだけでζ合金層のトータルめっき皮膜中に対する割合が制御でき、硫酸銅試験１回当たりの減耗量を抑えることでＪＩＳＨ８６４１に規定する品質を確保するためのトータルめっき皮膜厚さ（Ｔ）を薄くできるので、めっき処理における亜鉛使用量の低減が可能になる。 In the hot dip galvanizing treatment method according to the present invention, the ratio of the ζ alloy layer to the total plating film can be controlled simply by setting the air hollow cooling time after the iron product is pulled up from the hot dip galvanizing bath, Since the total plating film thickness (T) for ensuring the quality specified in JISH8641 can be reduced by suppressing the amount of wear per copper sulfate test, the amount of zinc used in the plating process can be reduced.
本発明において評価に用いた硫酸銅試験は、ＪＩＳＨ０４０１に規定する硫酸銅試験方法に基づいて実施した。
試験の要旨は、試験片を所定の硫酸銅溶液の中に１分間浸漬し、これを繰り返して試験表面の銅の析出の有無を目視で判定し、光輝のある密着性金属銅が析出するまでの試験回数を測定するものである。
The copper sulfate test used for evaluation in the present invention was carried out based on the copper sulfate test method specified in JISH0401.
The gist of the test is that the test piece is immersed in a predetermined copper sulfate solution for 1 minute, and this is repeated until the presence or absence of copper deposition on the test surface is visually determined until the brilliant adhesive metallic copper is deposited. The number of tests is measured.
鉄鋳物からなる配管用の継手を試験片とし、溶融亜鉛めっき浴４６０℃に浸漬後に空中に引き上げ、次工程の冷却水に浸漬するまでの空中空冷時間とζ合金層の関係を調査した結果を図２のグラフに示す。
従来の生産ラインでは、めっき浴浸漬時間約８０〜１００秒、空冷時間を約１５秒以下に設定してあった。
これに対してこの空冷時間を長くするとトータルめっき皮膜厚さ（Ｔ）は、ほとんど変化しないがζ合金層の厚みが空冷時間とともに厚く成長することが判明した。
従来の空冷時間約１５秒レベルではトータルめっき皮膜厚さ（Ｔ）の値が約８６μｍでζ合金層の厚さ（Ｔζ）は約３２μｍと（Ｔζ）の割合は約３７％であった。
これに対して空冷時間を長くすると（Ｔζ）の割合が高くなり空冷時間約３０秒では（Ｔ）＝８６μｍ、（Ｔζ）＝５０μｍ、（Ｔζ）の割合約５８％と目標５０％以上をクリアーしている。
また、空冷時間約４５秒では（Ｔ）＝８６μｍ、（Ｔζ）＝７０μｍ、（Ｔζ）の割合８１％であった。
従って、空冷時間を約１０秒長くすると（Ｔζ）は約１２〜１３μｍ厚くなることが分かる。
The result of investigating the relationship between the air hollow cooling time and the ζ alloy layer until it is immersed in the cooling water of the next process, after being immersed in a hot dip galvanizing bath at 460 ° C. This is shown in the graph of FIG.
In the conventional production line, the plating bath immersion time was set to about 80 to 100 seconds, and the air cooling time was set to about 15 seconds or less.
On the other hand, it was found that when the air cooling time is increased, the total plating film thickness (T) hardly changes, but the thickness of the ζ alloy layer grows thicker with the air cooling time.
In the conventional air cooling time level of about 15 seconds, the total plating film thickness (T) value was about 86 μm, and the thickness (T ζ ) of the ζ alloy layer was about 32 μm, and the ratio of (T ζ ) was about 37%. .
Increasing the cooling time for which a rate high becomes cooling time of about 30 seconds (T ζ) (T) = 86μm, (T ζ) = 50μm, the proportion of about 58% and the target 50% (T zeta) Clear the above.
Further, in the air-cooling time of about 45 seconds (T) = 86μm, (T ζ) = 70μm, was 81% ratio of (T zeta).
Therefore, it can be seen that (T ζ ) becomes about 12 to 13 μm thick when the air cooling time is increased by about 10 seconds.
めっき浴温を４５０℃，４７０℃，４９０℃にそれぞれ設定し、冷却水に浸漬するまで空冷時間を３０秒と一定にし、試験片をめっき浴中に浸漬した時間とめっき厚の関係を調査した結果のグラフを図３に示す。
浴温の高い方が短時間でめっき層が厚くなり、また、浸漬時間の長さにめっき皮膜の厚みが影響を受けることも分かる。
従って、硫酸銅試験による１回当たりの減耗量が低減できれば、めっき厚をその分だけ薄くでき、亜鉛の使用量の低減が可能であることの他に空冷時間の延長分をめっき浴への浸漬時間の短縮にて吸収できる。
The plating bath temperatures were set to 450 ° C., 470 ° C., and 490 ° C., respectively, and the air cooling time was kept constant at 30 seconds until immersed in cooling water, and the relationship between the time during which the test piece was immersed in the plating bath and the plating thickness was investigated. The resulting graph is shown in FIG.
It can also be seen that the higher the bath temperature, the thicker the plating layer becomes, and the thickness of the plating film is affected by the length of immersion time.
Therefore, if the amount of wear per test by the copper sulfate test can be reduced, the plating thickness can be reduced by that much, and the amount of zinc used can be reduced, and the extended air cooling time can be immersed in the plating bath. It can be absorbed by shortening the time.
比較として従来のめっき浴４６０℃にて８０秒間浸漬し、その後に引き上げ１５秒間空冷後に冷却水に浸漬した試験片（従来方法）と浴温４７０℃にて４５秒間浸漬し、その後に引き上げて約５０秒間空冷後に冷却水に浸漬した本発明の実施例試験片（本発明方法）を比較評価した結果を図１に示す。
本発明に係るめっき処理方法では、従来方法に比較してζ合金層の割合が高く、硫酸銅試験回数は１０回であった。
なお、従来方法では硫酸銅試験回数は６回であることから本発明方法において従来と同等レベルの硫酸銅試験回数を確保するには、７．８μｍ／回×６回＝約４７μｍと試算でき、トータルめっき皮膜厚さ（Ｔ）は約３４μｍ（８１μｍ−４７μｍ＝３４μｍ）も薄くできることになり、その分だけ亜鉛の使用量の低減が可能になる。
As a comparison, the specimen was immersed in a conventional plating bath at 460 ° C. for 80 seconds, then pulled up for 15 seconds and then cooled in water after cooling for 15 seconds and immersed in cooling water for 45 seconds at a bath temperature of 470 ° C. FIG. 1 shows the result of comparative evaluation of the example test piece of the present invention (the method of the present invention) immersed in cooling water after air cooling for 50 seconds.
In the plating method according to the present invention, the proportion of the ζ alloy layer was higher than that in the conventional method, and the number of copper sulfate tests was 10.
In addition, since the number of times of copper sulfate tests in the conventional method is 6, in order to ensure the same number of copper sulfate tests as in the method of the present invention, 7.8 μm / times × 6 times = about 47 μm can be estimated The total plating film thickness (T) can be reduced by about 34 μm (81 μm−47 μm = 34 μm), and the amount of zinc used can be reduced accordingly.
Claims (1)
鉄物製品を溶融亜鉛めっき浴に浸漬し、次に当該溶融亜鉛めっき浴から当該鉄物製品を上昇させ、トータルめっき皮膜厚さ（Ｔ）に対するζ合金層厚さ（Ｔζ）の割合が５０％以上になるように、空中で所定時間空冷後に冷却水に浸漬することを特徴とする溶融亜鉛めっき処理方法。 A hot dip galvanizing method for iron products,
The iron product is immersed in a hot dip galvanizing bath, and then the iron product is raised from the hot dip galvanizing bath, and the ratio of the ζ alloy layer thickness (T ζ ) to the total plating film thickness (T) is 50. % Hot dip galvanizing method, which is immersed in cooling water after being air-cooled for a predetermined time in the air so as to be at least%.
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| JP2008136113A JP4198747B1 (en) | 2008-05-24 | 2008-05-24 | Hot dip galvanizing method |
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| JP2008136113A JP4198747B1 (en) | 2008-05-24 | 2008-05-24 | Hot dip galvanizing method |
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| JP2009280880A true JP2009280880A (en) | 2009-12-03 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018178217A (en) * | 2017-04-18 | 2018-11-15 | 新日鐵住金株式会社 | Hot-dip galvanized steel pipe |
| WO2019087649A1 (en) * | 2017-10-30 | 2019-05-09 | パナソニックＩｐマネジメント株式会社 | Steel pipe |
| JP7649009B2 (en) | 2021-06-30 | 2025-03-19 | 株式会社明石合銅 | Composite sliding part and manufacturing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01263255A (en) * | 1988-04-14 | 1989-10-19 | Nippon Aen Kogyo Kk | Aluminum-zinc alloy hot dipping method with high coating weight |
| JPH07207421A (en) * | 1994-01-13 | 1995-08-08 | Mitsui Mining & Smelting Co Ltd | Galvanizing method |
| JP2005256042A (en) * | 2004-03-10 | 2005-09-22 | Jfe Steel Kk | Alloyed hot-dip galvanized steel sheet and method for producing the same |
-
2008
- 2008-05-24 JP JP2008136113A patent/JP4198747B1/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01263255A (en) * | 1988-04-14 | 1989-10-19 | Nippon Aen Kogyo Kk | Aluminum-zinc alloy hot dipping method with high coating weight |
| JPH07207421A (en) * | 1994-01-13 | 1995-08-08 | Mitsui Mining & Smelting Co Ltd | Galvanizing method |
| JP2005256042A (en) * | 2004-03-10 | 2005-09-22 | Jfe Steel Kk | Alloyed hot-dip galvanized steel sheet and method for producing the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018178217A (en) * | 2017-04-18 | 2018-11-15 | 新日鐵住金株式会社 | Hot-dip galvanized steel pipe |
| WO2019087649A1 (en) * | 2017-10-30 | 2019-05-09 | パナソニックＩｐマネジメント株式会社 | Steel pipe |
| JPWO2019087649A1 (en) * | 2017-10-30 | 2020-07-27 | パナソニックＩｐマネジメント株式会社 | Steel pipe |
| JP7054827B2 (en) | 2017-10-30 | 2022-04-15 | パナソニックＩｐマネジメント株式会社 | Steel pipe |
| JP7649009B2 (en) | 2021-06-30 | 2025-03-19 | 株式会社明石合銅 | Composite sliding part and manufacturing method thereof |
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