JPH08218160A - Production of high corrosion resistant zinc-aluminum alloy plated steel sheet by double layer spray plating - Google Patents
Production of high corrosion resistant zinc-aluminum alloy plated steel sheet by double layer spray platingInfo
- Publication number
- JPH08218160A JPH08218160A JP7020090A JP2009095A JPH08218160A JP H08218160 A JPH08218160 A JP H08218160A JP 7020090 A JP7020090 A JP 7020090A JP 2009095 A JP2009095 A JP 2009095A JP H08218160 A JPH08218160 A JP H08218160A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- alloy
- steel sheet
- molten
- spray
- 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.)
- Withdrawn
Links
- 238000007747 plating Methods 0.000 title claims abstract description 121
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 74
- 239000010959 steel Substances 0.000 title claims abstract description 74
- 239000000956 alloy Substances 0.000 title claims abstract description 54
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 53
- 238000005260 corrosion Methods 0.000 title claims abstract description 31
- 230000007797 corrosion Effects 0.000 title claims abstract description 31
- 239000007921 spray Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229910000611 Zinc aluminium Inorganic materials 0.000 title 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 title 1
- 238000005507 spraying Methods 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 229910000838 Al alloy Inorganic materials 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 5
- 239000010419 fine particle Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229910007570 Zn-Al Inorganic materials 0.000 abstract description 52
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 230000006698 induction Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000005238 degreasing Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 51
- 238000000034 method Methods 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000005275 alloying Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000655 Killed steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000012733 comparative method Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- 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
- C23C28/02—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 only coatings only including layers of metallic material
- C23C28/021—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 only coatings only including layers of metallic material including at least one metal alloy layer
-
- 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
- C23C28/02—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 only coatings only including layers of metallic material
- C23C28/023—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 only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—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 only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、帯状鋼板へのＺｎ−Ａ
ｌ合金のスプレーめっき方法、特に高品質な２層スプレ
ーめっきによる高耐食性Ｚｎ−Ａｌ合金めっき鋼板の製
造方法に関するものである。The present invention relates to Zn-A for strip steel plate.
The present invention relates to a method for spray-plating an 1-alloy, and particularly to a method for producing a high corrosion-resistant Zn-Al alloy-plated steel sheet by high-quality two-layer spray plating.
【０００２】[0002]
【従来の技術】高耐食性のＺｎ−Ａｌ合金めっきの一例
として、Ｚｎ−５５ｗｔ％Ａｌ合金めっき鋼板（商品
名：ガルバリウム鋼板）等が知られている。この鋼板
は、亜鉛鉄板に比べて、極めて優れた耐食性を示す（特
公昭４６−７１６１号公報）。ところが、このめっき鋼
板は、通常、めっき原板を合金浴に直接浸漬してめっき
する方法で製造されている。一方、溶融亜鉛の如き溶融
金属をスプレーにより微粒化し、これを連続的に送られ
てくる帯状鋼板の表面に付着させてめっきするスプレー
めっき方法は、従来から、特開昭５３−９９０４７号公
報、特開平１−２０１４５６号公報で知られている。し
かし、いずれも溶融亜鉛のめっき方法に関するものであ
り、スプレーめっき方法にて外観良好なＺｎ−５５ｗｔ
％Ａｌ合金めっき鋼板のような高耐食性Ｚｎ−Ａｌ合金
めっき鋼板を製造する方法は確立されていないのが現状
である。2. Description of the Related Art Zn-55 wt% Al alloy plated steel sheet (trade name: Galvalume steel sheet) and the like are known as an example of highly corrosion resistant Zn-Al alloy plating. This steel sheet exhibits extremely excellent corrosion resistance as compared with the zinc iron sheet (Japanese Patent Publication No. 46-7161). However, this plated steel sheet is usually manufactured by a method in which the original plating plate is directly immersed in an alloy bath for plating. On the other hand, a spray plating method of atomizing a molten metal such as molten zinc by spraying and adhering the atomized molten metal to the surface of a strip-shaped steel sheet that is continuously fed to plate is conventionally disclosed in JP-A-53-99047. It is known from Japanese Patent Laid-Open No. 1-201456. However, all of them relate to a method of plating hot-dip zinc, and a Zn-55 wt.
At present, there is no established method for producing a Zn-Al alloy plated steel sheet having high corrosion resistance such as a% Al alloy plated steel sheet.
【０００３】[0003]
【発明が解決しようとする課題】Ｚｎ−Ａｌ合金のよう
な合金金属の場合、一般的に、溶融Ｚｎ−Ａｌ合金中の
Ａｌ含有量が低ければ、溶融Ｚｎ−Ａｌ合金の流動性が
極めて良好なため、均一な外観のめっき鋼板を得ること
が出来ることが分かっている。しかし高耐食性Ｚｎ−Ａ
ｌ合金めっき鋼板のように溶融Ｚｎ−Ａｌ合金中のＡｌ
含有量が高くなると溶融Ｚｎ−Ａｌ合金の流動性が著し
く悪化する。そのため、鋼板の至る所で、溶融Ｚｎ−Ａ
ｌ合金が鋼板上で十分に広がり切る前に固化し、鋼板表
面に微視的な凹凸が残ることになる。更に、局所的に観
察すると、溶融Ｚｎ−Ａｌ合金中のＡｌはＺｎ中に均一
に分散しておらず、流動性も不均一である。このため、
Ａｌの分散状態に応じて、流動性が変化する上、反応性
の高いＡｌと鋼板が不均一に合金化する現象と相俟っ
て、所々、斑点模様として残留する。従って、従来の溶
融亜鉛スプレーめっき方法と同じ方法では、めっき面全
体が均一な外観を有する高耐食性Ｚｎ−Ａｌ合金めっき
鋼板を得ることは極めて困難である。In the case of alloy metal such as Zn-Al alloy, generally, if the Al content in the molten Zn-Al alloy is low, the fluidity of the molten Zn-Al alloy is very good. Therefore, it is known that a plated steel sheet having a uniform appearance can be obtained. However, high corrosion resistance Zn-A
Al in hot-dip Zn-Al alloy like alloy plated steel sheet
When the content is high, the fluidity of the molten Zn-Al alloy is significantly deteriorated. Therefore, molten Zn-A can be found throughout the steel sheet.
The l-alloy solidifies before it fully spreads on the steel sheet, and microscopic unevenness remains on the steel sheet surface. Furthermore, when locally observed, Al in the molten Zn-Al alloy is not uniformly dispersed in Zn, and the fluidity is also non-uniform. For this reason,
The fluidity changes depending on the dispersed state of Al, and in addition to the phenomenon that highly reactive Al and the steel sheet are nonuniformly alloyed, spots remain in some places. Therefore, it is extremely difficult to obtain a highly corrosion-resistant Zn-Al alloy plated steel sheet having a uniform appearance on the entire plated surface by the same method as the conventional hot-dip zinc spray plating method.
【０００４】このように、従来の溶融亜鉛スプレーめっ
き方法を利用して、このままの条件で、Ｚｎ−Ａｌ合金
スプレーめっきを行なっても、良好な外観を有する高耐
食性Ｚｎ−Ａｌ合金めっき鋼板を製造することはできな
い。本発明は、溶融Ｚｎ−Ａｌ合金スプレーめっき方法
により、良好な外観を有する高耐食性Ｚｎ−Ａｌ合金め
っき鋼板、また、更には、塗装後の塗膜密着性にも優れ
たＺｎ−Ａｌ合金めっき鋼板の製造方法を提供すること
を目的とする。As described above, a high corrosion-resistant Zn-Al alloy-plated steel sheet having a good appearance is produced even if the conventional hot-dip zinc spray plating method is used to perform the Zn-Al alloy spray plating under the same conditions. You cannot do it. The present invention provides a highly corrosion-resistant Zn-Al alloy-plated steel sheet having a good appearance by a hot-dip Zn-Al alloy spray plating method, and further, a Zn-Al alloy-plated steel sheet having excellent coating film adhesion after coating. It aims at providing the manufacturing method of.
【０００５】[0005]
【課題を解決するための手段】この目的を達成するため
の本発明の要旨とするところは、前処理されて連続的に
送給されてくる帯状鋼板の表面に、非酸化性雰囲気中
で、溶融Ｚｎ−Ａｌ合金の微粒子を吹き付けることによ
りスプレーめっきして鋼板を製造するに際し、第一めっ
き層は溶融Ｚｎ−Ａｌ合金中のＡｌ含有量が２５ｗｔ％
以上７０ｗｔ％以下で残部が亜鉛及び不可避的不純物か
らなり、めっきする時の帯状鋼板の温度を５５０〜６５
０℃の温度範囲でスプレーめっきし、第二めっき層はＡ
ｌ含有量が０．０８ｗｔ％以下で残部が亜鉛及び不可避
的不純物からなり、帯状鋼板の温度を４２０℃以上でス
プレーめっきすることを特徴とする２層スプレーめっき
による高耐食性Ｚｎ−Ａｌ合金めっき鋼板の製造方法に
ある。The gist of the present invention for attaining this object is that the surface of a strip-shaped steel sheet that has been pretreated and continuously fed is subjected to a non-oxidizing atmosphere, When manufacturing a steel sheet by spray plating by spraying fine particles of a molten Zn-Al alloy, the first plating layer has an Al content in the molten Zn-Al alloy of 25 wt%.
If the content is 70 wt% or more and the balance is zinc and inevitable impurities, the temperature of the strip steel plate at the time of plating is 550 to 65.
Spray plating in the temperature range of 0 ° C, the second plating layer is A
High corrosion resistance Zn-Al alloy plated steel sheet by two-layer spray plating, characterized in that the content of l is 0.08 wt% or less, the balance is zinc and unavoidable impurities, and the strip steel sheet is spray-plated at a temperature of 420 ° C or more. In the manufacturing method.
【０００６】[0006]
【作用】以下、本発明について詳細に説明する。本発明
者らは、まず、吹き付ける溶融亜鉛にＡｌを２５ｗｔ％
以上７０ｗｔ％以下含有させた溶融Ｚｎ−Ａｌ合金の微
粒子をスプレーめっきすることにより、極めてめっき密
着性の良いかつ耐食性に優れた溶融Ｚｎ−Ａｌ合金めっ
き鋼板が製造できることを確認した。ところが、めっき
密着性および耐食性は極めて良好であるが、このままで
は、溶融Ｚｎ−Ａｌ合金の流動性が悪く、溶融Ｚｎ−Ａ
ｌ合金が鋼板上で十分に広がり切る前に固化してしま
い、鋼板表面に微視的な凹凸が残る。また合金化反応が
不均一に進行するため、至る所に斑点模様が形成して、
めっき外観は極めて不良である。The present invention will be described in detail below. The inventors of the present invention firstly prepare 25 wt% Al for molten zinc to be sprayed.
It was confirmed that by spray-plating the fine particles of the molten Zn-Al alloy containing 70 wt% or less, a fused Zn-Al alloy-plated steel sheet having excellent plating adhesion and excellent corrosion resistance can be manufactured. However, although the plating adhesion and the corrosion resistance are extremely good, if they remain as they are, the flowability of the molten Zn-Al alloy is poor and the molten Zn-A is
The l-alloy solidifies before it fully spreads on the steel sheet, leaving microscopic irregularities on the steel sheet surface. In addition, since the alloying reaction proceeds nonuniformly, spotted patterns are formed everywhere,
The plating appearance is extremely poor.
【０００７】そこで、本発明者らは、このめっき層の上
に、更にＡｌ含有量を０．０８ｗｔ％以下とした溶融Ｚ
ｎをスプレーめっきすることで、極めてめっき外観の良
い耐食性に優れた溶融Ｚｎ−Ａｌ合金めっき鋼板が製造
できることを確認した。Ａｌ含有量が０．０８ｗｔ％以
下の溶融Ｚｎは、極めて流動性が良好であるため、溶融
Ｚｎ微粒子は帯状鋼板上で速やかに拡がり、粒子同志が
良好に重なりあって、均一な外観のめっき鋼板になるた
めである。また、第一めっき層（下層）は高Ａｌ含有量
のＺｎ−Ａｌ合金めっき層であるので、溶融亜鉛と鉄の
合金化反応は、適正に抑えられる。従って、第二めっき
層（上層）にＡｌ含有量が低い溶融Ｚｎを吹き付けて
も、めっき密着性に悪影響を及ぼす溶融亜鉛と鉄の過度
な合金化反応は、第一めっき層（下層）で抑えられ、第
一めっき層と鋼板との優れた密着性が損なわれることは
ない。Therefore, the inventors of the present invention further applied molten Z on the plated layer with an Al content of 0.08 wt% or less.
It was confirmed that by spray-plating n, it is possible to manufacture a hot-dip Zn-Al alloy-plated steel sheet having an excellent plating appearance and excellent corrosion resistance. Since molten Zn having an Al content of 0.08 wt% or less has extremely good fluidity, the molten Zn fine particles spread rapidly on the strip-shaped steel sheet, and the particles are well overlapped with each other, and the plated steel sheet has a uniform appearance. This is because Further, since the first plating layer (lower layer) is a Zn-Al alloy plating layer having a high Al content, the alloying reaction between molten zinc and iron can be appropriately suppressed. Therefore, even if molten Zn with a low Al content is sprayed onto the second plating layer (upper layer), the excessive alloying reaction of molten zinc and iron that adversely affects the plating adhesion is suppressed in the first plating layer (lower layer). Therefore, the excellent adhesion between the first plating layer and the steel sheet is not impaired.
【０００８】このように、下層（第一めっき層）にＡｌ
含有量が２５ｗｔ％以上７０ｗｔ％以下の溶融Ｚｎ−Ａ
ｌ合金をスプレーめっきすることで、優れためっき密着
性を確保し、その上層（第二めっき層）にＡｌ含有量が
０．０８ｗｔ％以下の溶融Ｚｎをスプレーめっきするこ
とで、優れためっき外観を確保することができるのであ
る。更に、他の含有成分の影響について検討した結果、
第二めっき層の溶融Ｚｎとして、Ａｌ含有量を０．０８
ｗｔ％以下に抑え、残部がＺｎよりなる溶融Ｚｎ−Ａｌ
合金であれば、上記特性が発揮されることを確認した。
第一めっき層及び第二めっき層にめっきする溶融Ｚｎ−
Ａｌ合金中の不可避的不純物は、０．０１ｗｔ％以下で
あれば問題ない。As described above, the lower layer (first plating layer) is made of Al.
Molten Zn-A having a content of 25 wt% or more and 70 wt% or less
By spray-plating the 1-alloy, excellent plating adhesion is secured, and by plating the upper layer (second plating layer) with molten Zn having an Al content of 0.08 wt% or less, an excellent plating appearance is obtained. Can be secured. Furthermore, as a result of examining the influence of other contained components,
As the molten Zn of the second plating layer, the Al content is 0.08
Molten Zn-Al with a balance of Zn and less than wt%
It has been confirmed that the above-mentioned characteristics are exhibited in the case of an alloy.
Molten Zn- for plating the first plating layer and the second plating layer
There is no problem if the unavoidable impurities in the Al alloy are 0.01 wt% or less.
【０００９】さらに、発明者らは、溶融Ｚｎ−Ａｌ合金
をスプレーめっきする時の鋼板温度の影響を調査した。
図２は第一めっき層を形成するＺｎ−Ａｌ合金層の耐食
性に及ぼすめっき時の鋼板温度の影響を示すもので、本
発明の最適鋼板温度範囲をハッチングで表した。図２中
の○プロットは本発明方法で製造した良好な外観を有す
る高耐食性Ｚｎ−Ａｌ合金めっき鋼板のサンプル値であ
る。この図より、第一めっき層をスプレーめっきする時
の鋼板温度が５５０〜６５０℃の温度範囲中の状態でス
プレーめっきして形成させた溶融Ｚｎ−Ａｌ合金層は、
極めてめっき密着性の良いかつ耐食性に優れためっき層
であることが分かる。鋼板温度が６５０℃以上では、鉄
との合金化が顕著となり、めっき耐食性が著しく損なわ
れる。この状態を図２中の比較条件１の△プロットで表
した。一方、５５０℃以下では、Ｚｎ−Ａｌ合金めっき
層に空孔が存在し、めっき密着性および耐食性が著しく
悪化する。この状態を図２中の比較条件２の×プロット
で表した。従って、第一めっき層をスプレーめっきする
時の帯状鋼板の温度を５５０〜６５０℃の温度範囲にす
ることにより極めてめっき密着性の良いかつ耐食性に優
れた溶融Ｚｎ−Ａｌ合金めっき鋼板が製造できる。Further, the inventors investigated the influence of the steel plate temperature when spray-plating a molten Zn-Al alloy.
FIG. 2 shows the influence of the steel plate temperature during plating on the corrosion resistance of the Zn-Al alloy layer forming the first plating layer, and the optimum steel plate temperature range of the present invention is shown by hatching. Plots in FIG. 2 are sample values of the highly corrosion-resistant Zn-Al alloy-plated steel sheet having a good appearance produced by the method of the present invention. From this figure, the molten Zn-Al alloy layer formed by spray plating in the state where the steel plate temperature at the time of spray plating the first plating layer is in the temperature range of 550 to 650 ° C,
It can be seen that the plating layer has extremely good plating adhesion and excellent corrosion resistance. When the steel sheet temperature is 650 ° C. or higher, alloying with iron becomes remarkable, and the corrosion resistance of plating is significantly impaired. This state is represented by the Δ plot of comparative condition 1 in FIG. On the other hand, at 550 ° C or lower, pores are present in the Zn-Al alloy plating layer, and the plating adhesion and corrosion resistance are significantly deteriorated. This state is represented by a cross plot of comparative condition 2 in FIG. Therefore, by setting the temperature of the strip-shaped steel sheet at the time of spray-plating the first plating layer to a temperature range of 550 to 650 ° C., it is possible to manufacture a hot-dip Zn-Al alloy-plated steel sheet having excellent plating adhesion and excellent corrosion resistance.
【００１０】さらに、発明者らは、第一めっき層を形成
する溶融Ｚｎ−Ａｌ合金中のＡｌの影響を調査した。図
３に第一めっき層に用いた溶融Ｚｎ−Ａｌ合金中のＡｌ
含有量がめっき密着性に与える影響を調査した結果を示
す。めっき密着性は、第一めっき層に用いた溶融亜鉛中
のＡｌ含有量が０．２ｗｔ％以上であれば良く、Ａｌ含
有量が高くなる程、良好になっていることが分かるが、
Ａｌ１．２ｗｔ％を超えて含有させても密着性の向上代
は大きくならない。また、図４には、溶融Ｚｎ−Ａｌ合
金中のＡｌ含有量がめっき耐食性に与える影響を調査し
た結果を示す。２４ケ月屋外暴露試験により、表層の片
面当たりの重量変化を調査した結果である。図中の◎
は、２０ｇ／ｍ2 以下の重量減、○は、２０ｇ／ｍ2 以
上３０ｇ／ｍ2 未満の重量減、△は３０ｇ／ｍ2 以上４
０ｇ／ｍ2 未満の重量減、×は、４０ｇ／ｍ2 以上の重
量減をそれぞれ示している。めっき耐食性は、溶融Ｚｎ
−Ａｌ合金のＡｌ含有量が３．５ｗｔ％以上であれば良
いが、Ａｌ含有量が高くなる程、良好になっていること
が分かる。Furthermore, the inventors investigated the effect of Al in the molten Zn-Al alloy forming the first plating layer. FIG. 3 shows Al in the molten Zn-Al alloy used for the first plating layer.
The results of investigating the influence of the content on the plating adhesion are shown below. It can be seen that the plating adhesion is good if the Al content in the molten zinc used in the first plating layer is 0.2 wt% or more, and the higher the Al content, the better.
Even if Al is contained in an amount of more than 1.2 wt%, the margin for improving the adhesiveness does not increase. Further, FIG. 4 shows the results of investigation on the influence of the Al content in the molten Zn-Al alloy on the plating corrosion resistance. It is the result of investigating the weight change per one side of the surface layer by the 24-month outdoor exposure test. ◎ in the figure
Is a weight loss of 20 g / m 2 or less, ◯ is a weight loss of 20 g / m 2 or more and less than 30 g / m 2 , and Δ is 30 g / m 2 or more 4
Weight loss of less than 0 g / m 2 and x indicate weight loss of 40 g / m 2 or more, respectively. Plating corrosion resistance is hot Zn
It is understood that the Al content of the -Al alloy is 3.5 wt% or more, but the higher the Al content, the better.
【００１１】またさらに、図５に第二めっき層に用いた
溶融Ｚｎ中のＡｌ含有量がめっき外観に与える影響を調
査した結果を示す。めっき外観は、第二めっき層に用い
た溶融Ｚｎ中のＡｌ含有量が０．０８ｗｔ％以下であれ
ば問題ないが、Ａｌ含有量が低くなる程、良好になって
いることが分かる。第二めっき層に用いる溶融Ｚｎ中の
Ａｌ含有量は、できるだけ低く抑え、０．０１ｗｔ％以
下にすることが望ましい。更には溶融Ｚｎ中のＡｌ含有
量を０．０ｗｔ％にする、すなわち純溶融亜鉛にするこ
とが最も好ましい。なお、溶融亜鉛をスプレーして第二
めっき層を形成する際の鋼板温度は、亜鉛の融点、通常
４２０℃以上であれば良い。第一めっき層と第二めっき
層とを連続して処理する場合、実施例でも示すように第
二めっき層形成時の鋼板温度は第一めっき層形成時とほ
ぼ同様となる。Further, FIG. 5 shows the results of investigation on the influence of the Al content in the molten Zn used for the second plating layer on the appearance of the plating. It can be seen that the appearance of the plating is satisfactory if the Al content in the molten Zn used for the second plating layer is 0.08 wt% or less, but the lower the Al content, the better. The Al content in the molten Zn used for the second plating layer is preferably kept as low as possible and 0.01 wt% or less. Further, it is most preferable to set the Al content in the molten Zn to 0.0 wt%, that is, to use pure molten zinc. The temperature of the steel sheet when the molten zinc is sprayed to form the second plating layer may be the melting point of zinc, usually 420 ° C. or higher. When the first plating layer and the second plating layer are continuously treated, the steel plate temperature during the formation of the second plating layer is almost the same as during the formation of the first plating layer, as shown in the examples.
【００１２】[0012]
【実施例】図１に本発明を実施する製造プロセスの例を
示す。本実施例においては、表１〜表４左欄に示した製
造条件に従って、高耐食性Ｚｎ−Ａｌ合金めっき鋼板を
製造した。表１〜表４中の製造条件による具体的な製造
方法を下記に示す。帯状鋼板は、厚さ０．７５ｍｍ×幅
５００ｍｍ、低炭素Ａｌキルド鋼の冷延鋼板を使用し
た。帯状鋼板１は、予め酸洗処理又は水素還元加熱処理
により十分な脱脂を行ない、表面の清浄化を図る。次
に、非酸化性雰囲気下で誘導加熱装置５により、めっき
時の帯状鋼板１の温度は、溶融Ｚｎ−Ａｌ合金の融点以
上の所定温度まで加熱され、非酸化性雰囲気を保持した
まま、デフレクターロール２を介して、めっき室３に送
られる。帯状鋼板の温度は、めっき室３に送られる前の
適当な位置に放射温度計７を設置して、帯状鋼板の温度
を測定し、出力制御装置８により、誘導加熱装置５の出
力を調整して制御する。FIG. 1 shows an example of a manufacturing process for carrying out the present invention. In this example, a highly corrosion resistant Zn-Al alloy plated steel sheet was manufactured according to the manufacturing conditions shown in the left columns of Tables 1 to 4. Specific manufacturing methods according to the manufacturing conditions in Tables 1 to 4 are shown below. As the strip-shaped steel sheet, a cold rolled steel sheet of low carbon Al killed steel having a thickness of 0.75 mm and a width of 500 mm was used. The strip-shaped steel sheet 1 is sufficiently degreased in advance by a pickling treatment or a hydrogen reduction heating treatment to clean the surface. Next, the temperature of the strip-shaped steel sheet 1 at the time of plating is heated to a predetermined temperature equal to or higher than the melting point of the molten Zn-Al alloy by the induction heating device 5 in a non-oxidizing atmosphere, and the deflector is maintained while maintaining the non-oxidizing atmosphere. It is sent to the plating chamber 3 via the roll 2. Regarding the temperature of the strip steel sheet, a radiation thermometer 7 is installed at an appropriate position before being sent to the plating chamber 3, the temperature of the strip steel sheet is measured, and the output of the induction heating device 5 is adjusted by the output control device 8. Control.
【００１３】次に、めっき室３において、溶融Ｚｎ−Ａ
ｌ合金の吹き付けノズル４で、帯状鋼板の両面に溶融Ｚ
ｎ−Ａｌ合金を吹き付けてスプレーめっきする。この
時、スプレーするＺｎ−Ａｌ合金材料として、第一めっ
き層には、所定のＡｌ含有量に調整した溶融Ｚｎ−Ａｌ
合金を用い、第二めっき層には、通常電気亜鉛めっきに
用いられるＡｌ含有量０．０ｗｔ％の亜鉛インゴットを
用いた。スプレーめっき時の鋼板温度は表１中にめっき
時の帯状鋼板の温度として示している。溶融Ｚｎ−Ａｌ
合金の吹き付けノズル４は、ガスアトマイズ方式、すな
わち溶融Ｚｎ−Ａｌ合金を窒素ガスで微粒化する方式で
あり、累積重量平均粒径５０μｍ以下に微粒化する。各
層のめっき目付量は、ノズルへの溶融Ｚｎ−Ａｌ合金の
供給圧力や帯状鋼板のライン速度、帯状鋼板長手方向に
並んだノズル本数で調整される。その後、２〜３秒程
度、保熱炉６で、帯状鋼板温度を保持した後、ガスジェ
ットクーラーで速やかに常温まで冷却する。Next, in the plating chamber 3, molten Zn-A is used.
l Alloy spray nozzle 4 melts both sides of the strip steel
Spray n-Al alloy and spray plating. At this time, as the Zn-Al alloy material to be sprayed, the first plating layer contains molten Zn-Al alloy adjusted to a predetermined Al content.
An alloy was used, and a zinc ingot having an Al content of 0.0 wt% which is commonly used for electrogalvanizing was used for the second plating layer. The steel plate temperature during spray plating is shown in Table 1 as the temperature of the strip steel plate during plating. Molten Zn-Al
The alloy spray nozzle 4 is a gas atomization system, that is, a system in which a molten Zn—Al alloy is atomized with nitrogen gas, and atomizes to a cumulative weight average particle size of 50 μm or less. The coating weight of each layer is adjusted by the supply pressure of the molten Zn-Al alloy to the nozzle, the line speed of the strip steel plate, and the number of nozzles arranged in the strip steel plate longitudinal direction. After that, the strip steel plate temperature is maintained in the heat-retaining furnace 6 for about 2 to 3 seconds, and then rapidly cooled to room temperature by the gas jet cooler.
【００１４】[0014]
【表１】 [Table 1]
【００１５】[0015]
【表２】 [Table 2]
【００１６】[0016]
【表３】 [Table 3]
【００１７】[0017]
【表４】 [Table 4]
【００１８】図１の製造プロセスに従って、本発明の溶
融Ｚｎ−Ａｌ合金めっき鋼板の製造法によって製造され
た製品と比較方法の溶融Ｚｎ−Ａｌ合金スプレーめっき
方法で製造された比較材のめっき品質（めっき耐食性、
めっき外観、めっき密着性）を調査した結果を表１〜表
４右欄に示す。この表１及び表２のＮｏ．１からＮｏ．
２７は、本発明例であって、いずれも、良好なめっき耐
食性、めっき外観及びめっき密着性を有している。ま
た、表２に示すＮｏ．２８からＮｏ．３７までは、第一
めっき層スプレー時の鋼板温度が５５０℃以下の場合の
ものを示しており、また、表２及び表３に示すＮｏ．３
８からＮｏ．５５までは、第一めっき層スプレー時の鋼
板温度が６５０℃以上の場合のものを示しており、いず
れも、めっき耐食性は不良である。同表３及び表４に示
すＮｏ．５６からＮｏ．７３までは第一めっき層のＡｌ
含有量が低く、めっき耐食性が不良ないしは充分でな
い。また、表４に示すＮｏ．７４からＮｏ．７８まで
は、第二めっき層の溶融Ｚｎ−Ａｌ合金中のＡｌ含有量
が０．０９〜５．０ｗｔ％の範囲のものを用いた場合を
示しており、めっき外観が不良となる。このように本発
明によれば、２層溶融Ｚｎ−Ａｌ合金スプレーめっき方
法により、良好な外観・密着性を有し、且つ、極めて良
好なめっき耐食性を有する溶融Ｚｎ−Ａｌ合金めっき鋼
板を得ることができる。According to the manufacturing process of FIG. 1, the plating quality of the product manufactured by the manufacturing method of the hot-dip Zn-Al alloy plated steel sheet of the present invention and the comparative material manufactured by the hot-dip Zn-Al alloy spray plating method of the comparative method ( Plating corrosion resistance,
The results of the investigation of plating appearance and plating adhesion) are shown in the right columns of Tables 1 to 4. No. 1 in Table 1 and Table 2 1 to No.
No. 27 is an example of the present invention, and all have good plating corrosion resistance, plating appearance and plating adhesion. In addition, No. 28 to No. Up to 37, the steel plate temperature at the time of spraying the first plating layer is 550 ° C. or lower, and No. 37 shown in Tables 2 and 3 are shown. Three
8 to No. Up to 55, the steel plate temperature at the time of spraying the first plating layer is 650 ° C. or higher, and in both cases, the plating corrosion resistance is poor. Nos. Shown in Tables 3 and 4 are the same. 56 to No. Al of the first plating layer up to 73
The content is low and the plating corrosion resistance is poor or insufficient. In addition, No. 74 to No. Up to 78, the case where the Al content in the molten Zn-Al alloy of the second plating layer is in the range of 0.09 to 5.0 wt% is used, and the plating appearance becomes poor. Thus, according to the present invention, a two-layer hot-dip Zn-Al alloy spray-plating method is used to obtain a hot-dip Zn-Al alloy-plated steel sheet having good appearance and adhesion, and extremely good plating corrosion resistance. You can
【００１９】[0019]
【発明の効果】本発明によれば、２層溶融Ｚｎ−Ａｌ合
金スプレーめっき方法により、良好な外観・密着性を有
し、且つ、極めて良好なめっき耐食性を有する溶融Ｚｎ
−Ａｌ合金めっき鋼板を得ることができる。According to the present invention, a two-layer hot-dip Zn-Al alloy spray-plating method provides a hot-dip Zn having good appearance and adhesion, and extremely good corrosion resistance to plating.
-Al alloy plated steel sheet can be obtained.
【図１】本発明を実施する製造プロセスの例を示す図、FIG. 1 is a diagram showing an example of a manufacturing process for carrying out the present invention,
【図２】本発明の第一層スプレーめっき時の最適鋼板温
度範囲およびＡｌ含有量を示す図、FIG. 2 is a diagram showing an optimum steel plate temperature range and Al content during first layer spray plating of the present invention,
【図３】第一めっき層の溶融Ｚｎ−Ａｌ合金中のＡｌ含
有量がめっき密着性に与える影響を示す図、FIG. 3 is a diagram showing the influence of the Al content in the molten Zn—Al alloy of the first plating layer on the plating adhesion,
【図４】第一めっき層の溶融Ｚｎ−Ａｌ合金中のＡｌ含
有量がめっき耐食性に与える影響を示す図、FIG. 4 is a diagram showing the influence of the Al content in the molten Zn—Al alloy of the first plating layer on the plating corrosion resistance;
【図５】第二めっき層の溶融Ｚｎ中のＡｌ含有量がめっ
き外観に与える影響を示す図である。FIG. 5 is a diagram showing the influence of the Al content in molten Zn of the second plating layer on the plating appearance.
１ 帯状鋼板 ２ デフレクターロール ３ めっき室 ４ 吹き付けノズル ５ 誘導加熱装置 ６ 保熱炉 ７ 放射温度計 ８ 出力制御装置 1 strip steel plate 2 deflector roll 3 plating chamber 4 spray nozzle 5 induction heating device 6 heat-retaining furnace 7 radiation thermometer 8 output control device
───────────────────────────────────────────────────── フロントページの続き (72)発明者 吉野 博之 東京都千代田区大手町二丁目６番３号 新 日本製鐵株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroyuki Yoshino 2-6-3 Otemachi, Chiyoda-ku, Tokyo Inside Nippon Steel Corporation
Claims (1)
状鋼板の表面に、非酸化性雰囲気中で、溶融Ｚｎ−Ａｌ
合金の微粒子を吹き付けることによりスプレーめっきし
て鋼板を製造するに際し、第一めっき層は溶融Ｚｎ−Ａ
ｌ合金中のＡｌ含有量が２５ｗｔ％以上７０ｗｔ％以下
で残部が亜鉛及び不可避的不純物からなり、めっきする
時の帯状鋼板の温度を５５０〜６５０℃の温度範囲でス
プレーめっきし、第二めっき層はＡｌ含有量が０．０８
ｗｔ％以下で残部が亜鉛及び不可避的不純物からなり、
帯状鋼板の温度を４２０℃以上でスプレーめっきするこ
とを特徴とする２層スプレーめっきによる高耐食性Ｚｎ
−Ａｌ合金めっき鋼板の製造方法。1. Molten Zn--Al is applied to the surface of a strip-shaped steel sheet that has been pretreated and continuously fed in a non-oxidizing atmosphere.
When a steel sheet is manufactured by spray-plating by spraying fine particles of an alloy, the first plating layer is a molten Zn-A.
Al alloy content in the alloy 1 is 25 wt% or more and 70 wt% or less, and the balance is zinc and inevitable impurities, and the strip steel plate is plated by spraying in a temperature range of 550 to 650 ° C. to form a second plating layer. Has an Al content of 0.08
If the content is less than wt%, the balance consists of zinc and inevitable impurities,
High corrosion resistance Zn by two-layer spray plating, characterized in that the strip steel plate is spray-plated at a temperature of 420 ° C. or higher.
-The manufacturing method of an Al alloy plating steel plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7020090A JPH08218160A (en) | 1995-02-08 | 1995-02-08 | Production of high corrosion resistant zinc-aluminum alloy plated steel sheet by double layer spray plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7020090A JPH08218160A (en) | 1995-02-08 | 1995-02-08 | Production of high corrosion resistant zinc-aluminum alloy plated steel sheet by double layer spray plating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08218160A true JPH08218160A (en) | 1996-08-27 |
Family
ID=12017417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7020090A Withdrawn JPH08218160A (en) | 1995-02-08 | 1995-02-08 | Production of high corrosion resistant zinc-aluminum alloy plated steel sheet by double layer spray plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08218160A (en) |
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| EP2955238A1 (en) * | 2014-06-13 | 2015-12-16 | ThyssenKrupp Rasselstein GmbH | Method for producing an aluminized packaging steel |
| WO2018155245A1 (en) * | 2017-02-24 | 2018-08-30 | Ｊｆｅスチール株式会社 | Continuous molten metal plating apparatus and molten metal plating method using said apparatus |
| CN111826600A (en) * | 2020-07-02 | 2020-10-27 | 宁波大智机械科技股份有限公司 | Intelligent hot zinc spraying device |
| CN113755797A (en) * | 2020-06-02 | 2021-12-07 | 宝山钢铁股份有限公司 | System and method for moving heating and coating Zn layer on surface of strip steel |
-
1995
- 1995-02-08 JP JP7020090A patent/JPH08218160A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2955238A1 (en) * | 2014-06-13 | 2015-12-16 | ThyssenKrupp Rasselstein GmbH | Method for producing an aluminized packaging steel |
| CN105316595A (en) * | 2014-06-13 | 2016-02-10 | 蒂森克虏拉塞斯坦有限公司 | Method for production of aluminized packaging steel and related application of aluminized steel sheet |
| RU2621941C2 (en) * | 2014-06-13 | 2017-06-08 | ТиссенКрупп Рассельштайн ГмбХ | Method of manufacture of packaging aluminium steel and application of aluminium steel sheet |
| WO2018155245A1 (en) * | 2017-02-24 | 2018-08-30 | Ｊｆｅスチール株式会社 | Continuous molten metal plating apparatus and molten metal plating method using said apparatus |
| CN110325659A (en) * | 2017-02-24 | 2019-10-11 | 杰富意钢铁株式会社 | Continuous hot-dipping metal handling apparatus and the hot-dip plating metal processing method for using the device |
| US11162166B2 (en) | 2017-02-24 | 2021-11-02 | Jfe Steel Corporation | Apparatus for continuous molten metal coating treatment and method for molten metal coating treatment using same |
| CN113755797A (en) * | 2020-06-02 | 2021-12-07 | 宝山钢铁股份有限公司 | System and method for moving heating and coating Zn layer on surface of strip steel |
| CN111826600A (en) * | 2020-07-02 | 2020-10-27 | 宁波大智机械科技股份有限公司 | Intelligent hot zinc spraying device |
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