JPS648704B2 - - Google Patents
Info
- Publication number
- JPS648704B2 JPS648704B2 JP6282882A JP6282882A JPS648704B2 JP S648704 B2 JPS648704 B2 JP S648704B2 JP 6282882 A JP6282882 A JP 6282882A JP 6282882 A JP6282882 A JP 6282882A JP S648704 B2 JPS648704 B2 JP S648704B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- bath
- corrosion resistance
- corrosion
- amount
- 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
Links
- 238000007747 plating Methods 0.000 claims description 35
- 229910000831 Steel Inorganic materials 0.000 claims description 19
- 239000010959 steel Substances 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 10
- 239000008397 galvanized steel Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910018137 Al-Zn Inorganic materials 0.000 claims description 3
- 229910018573 Al—Zn Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims 4
- 238000005260 corrosion Methods 0.000 description 49
- 230000007797 corrosion Effects 0.000 description 48
- 238000012360 testing method Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002828 fuel tank Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 229910019064 Mg-Si Inorganic materials 0.000 description 1
- 229910019406 Mg—Si Inorganic materials 0.000 description 1
- 229910001327 Rimmed steel Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 230000037303 wrinkles Effects 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/12—Aluminium or alloys based thereon
Description
本発明は鋼板に前処理を施した後めつき浴に浸
漬して溶融めつきし、その後付着量の制御を行う
溶融めつき鋼板の製造方法において、アルミニウ
ムベースの合金浴を用いて耐食性、耐湿食性およ
び化成処理に優れた製品を得る方法に関する。
従来より使用されている溶融アルミニウムめつ
き鋼板の大部分はAl浴に合金層抑制用のSiを添
加して浴温650℃以上でめつきしたものである。
この溶融アルミニウムめつき鋼板は溶融亜鉛めつ
き鋼板やZn−Al合金溶融めつき鋼板に比べて耐
食性、耐熱性がとくに優れているため、これらの
特性をとくに必要とする屋根や壁などの建材、家
電製品の部材あるいは自動車部材などに広く使用
されている。
しかし溶融アルミニウムめつき鋼板の場合、Si
添加による合金層抑制は不十分であるためめつき
層と鋼素地との界面には硬くて脆いFe−Al系合
金が生成しており、絞り加工などの厳しい加工に
耐えられるだけの加工性は有していない。また耐
食性に関してもカソード防食作用がないため、加
工によりめつき層にクラツクが生じたり、めつき
の際ピンホールが発生すると容易に赤錆が発生す
るという欠点がある。
一方このような欠点のない製品を得る方法とし
て、Al浴にZn5〜25％、Si3〜12％添加したAlベ
ース合金浴でめつきする方法が知られている（特
公昭46−4045号）。この方法は前記溶融アルミニ
ウムめつき鋼板の製造法に比べ作業性はよく、ま
た得られる製品も改善され、めつき層の曲げ加工
性および曲げ加工部の耐食性などは向上してい
る。しかしClイオン雰囲気中ではめつき層の孔食
進行が激しく、塩害を受ける自動車下廻り部材な
どに使用するには問題があつた。
本発明は上述のような欠点がなく、しかもAl
ベース溶融めつき鋼板の多様化の一環として近年
要求の強い自動車マフラー用耐湿食性素材、アル
コール系燃料タンク用適正素材、あるいは高耐食
性表面処理鋼板用素材にも適合できる溶融めつき
鋼板の製造方法を提供するものである。
自動車マフラーは温度差の大きい湿乾サイクル
がくり返され、またアルコール系燃料は水分を含
んでいるため素材としては耐食性、耐熱性のほか
に耐湿食性に優れたものが要求されている。
また表面処理鋼板の場合化成処理性に優れ、し
かも高耐食性で、かつ片面30ｇ/m2以下の薄目付
にしてもピンホールのないものが要求されてい
る。
本発明者らは上述の欠点の解消およびこれらの
要求に対処するため、種々検討を重ねた結果、
Al75％超、Znを１％超17.5％未満、Siを１％超
12％以下含有するAlベースのAl−Zn合金浴に
Mg、Mn、Crおよびミツシユメタルのうちの１
種または２種以上をMg0.01〜1.0％、Mn0.01〜
0.5％、Cr0.01〜0.5％、ミツシユメタル0.01〜2.0
％添加した浴、またはこの浴にSbを0.01〜0.5％
添加した浴を用いればよいことを知見した。
以下本発明のめつき浴組成限定理由を述べる。
(1) Zn
ZnはSiとの共存によつてめつき温度を低下
させてFe−Al合金層の発達を抑制するととも
に、カソード防食作用により加工部の耐食性を
向上させ、さらに薄目付でもピンホールが発生
しないようにするもので、その効果を得るため
には１％より多くの添加を必要とする。しかし
17.5％以上になるとめつき層の結晶は初晶α−
Al相の領域が少くなつてβ−Zn相との共析組
織と３割合が多くなり、Alめつきの特性が損
なわれる。このためZnは１％超17.5％未満とし
た。
(2) Si
めつき層のFe−Al合金層の発達を抑制する
ために添加するものであるが、その効果は１％
以下の場合認められない。しかし、合金層の抑
制は6.5％添加すれば十分抑制できる。このた
めSiは１％超6.5％以下とした。
(3) Mg
Mgはめつき層凝固の際β−Zn相近傍に晶出
してα−Al相とβ−Zn相との接触腐食を抑制
し、孔食の進行を遅帯させるとともに、めつき
層表面に安定したMg酸化皮膜を形成してめつ
き層を保護し、耐食性を向上させる。しかし
Mgによりこのような効果が得られるのはMg
を0.01％以上添加した場合であつて、0.01％未
満では不十分である。
一方添加量が1.0％を超えると浴表面で容易
に酸化されて多量にドロス化し、Mg歩留低減
によるコスト上昇を招くとともに、浴組成の変
動が大きくなつて浴組成管理が困難となる。ま
た外観的にもめつき層表面にシワが形成された
り、黒色化したMg酸化物が生成される。さら
にめつき層中にはMg−Si金属間化合物が形成
され耐食性、加工性が低下する。このためMg
は0.01〜1.0％とした。
(4) MnおよびCr
Mn、CrはAl合金の耐食性を向上させるが、
Zn共存下ではその効果が低減する。このため
Zn1％超17.5％未満の共存下で耐食性を向上さ
せようとする場合にはMn、Crとも各0.01％以
上必要であつた。一方Mn、Crとも各0.5％を超
えて添加すると製品外観が悪くなり、かつめつ
き上浴温も上昇させねばならないので作業性の
低下を招き、合金層の発達をも促進することに
なる。このためMn、Crとも各0.01〜0.5％とし
た。
(5) ミツシユメタル
ミツシユメタルはα−Al結晶粒内に均一に
分散し、しかも結晶粒を微細化するため耐食
性、曲げ加工性を向上させる。また薄目付製品
のピンホール発生を抑制したり、Mgとの複合
添加により耐食性を大幅に向上させる効果もあ
る。この有効添加量は0.01％以上であるが、
2.0％を超えて添加してもめつき浴表面でドロ
ス化し、有効歩留が低下してコスト上昇を招く
とともに浴組成の管理が困難となる。このため
上限は2.0％とした。
(6) Sb
Sbは化成処理性（クロメート処理性、塗装
前処理性など）を向上させ、塗装した場合の塗
膜フクレを防止する。しかしSbは単独添加で
は孔食を促進し、耐食性を低下させるので、本
発明においてはMgやMnなどの耐食性向上元
素と複合添加により化成処理性を向上させよう
とするものである。
Sbによる化成処理性向上は0.01％以上の場合
に認められ、添加量の増加により向上するが、
逆に耐食性が劣化し、0.5％を超えるとMgや
Mnなどを複合添加しても耐食性の向上は期待
できない。またこれとともにめつき浴表面で
Sbはドロス化し、歩留低下による浴組成の変
動も激しくなつて浴管理が困難となる。従つて
Sbは0.01〜0.5％とした。
本発明は上述のような浴を用いて公知のめつき
工程によりめつきする。すなわち鋼板を前処理し
て鋼板表面を溶融めつきに適する表面状態にし、
その後浴に浸漬してめつきする。
本発明の場合、浴成分との関係において、特に
限定されない。
めつきの際の浴温はZnが多いとき低く、少い
時高くし約620℃〜670℃の範囲にする。
めつき後は付着量の調整を行う。この付着量の
調整は通常気体絞り法によるのが品質上好まし
く、本発明の場合現行の気体絞り法に30ｇ/m2
（片面）以下の薄目付に調整できる。
付着量調整後の外観調整はエアー冷却によりレ
ギユラースパングルにしてもよく、水滴噴霧によ
り急冷してミニマイズドスパングルにしてもよ
い。
以下実施例により本発明を説明する。
実施例 １
１ 供試材
0.6mm厚×150mm巾の未焼鈍リムド鋼帯
２ めつき条件
めつき前焼鈍
The present invention is a method for producing hot-dipped steel sheets in which a steel sheet is pretreated and then immersed in a plating bath for melt-plating, and then the coating amount is controlled. This article relates to a method for obtaining products with excellent edibility and chemical treatment. Most of the conventionally used hot-dip aluminum plated steel sheets are plated at a bath temperature of 650°C or higher in which Si is added to suppress the alloy layer in an Al bath.
This hot-dip aluminum-coated steel sheet has particularly superior corrosion resistance and heat resistance compared to hot-dip galvanized steel sheets and Zn-Al alloy hot-dip galvanized steel sheets, so it can be used for building materials such as roofs and walls that particularly require these properties. It is widely used in parts for home appliances and automobiles. However, in the case of hot-dip aluminum plated steel sheets, Si
Because the suppression of the alloy layer by addition is insufficient, a hard and brittle Fe-Al alloy is formed at the interface between the plating layer and the steel base, and the workability is insufficient to withstand severe processing such as drawing. I don't have it. In terms of corrosion resistance, since there is no cathodic anticorrosion effect, there is a drawback that cracks occur in the plated layer due to processing, and red rust easily occurs if pinholes occur during plating. On the other hand, as a method of obtaining a product without such defects, there is known a method of plating with an Al-based alloy bath in which 5-25% Zn and 3-12% Si are added (Japanese Patent Publication No. 46-4045). This method has better workability than the above-mentioned method for producing molten aluminum plated steel sheets, and the resulting product is also improved, with improved bending workability of the plated layer and corrosion resistance of the bent portion. However, in a Cl ion atmosphere, pitting corrosion of the plated layer progressed rapidly, making it difficult to use it in automobile underbody parts that are subject to salt damage. The present invention does not have the above-mentioned drawbacks, and moreover,
As part of the diversification of base hot-dip galvanized steel sheets, we have developed a manufacturing method for hot-dip galvanized steel sheets that can be used as moisture-corrosion-resistant materials for automobile mufflers, suitable materials for alcohol-based fuel tanks, and materials for highly corrosion-resistant surface-treated steel sheets, which have been in strong demand in recent years. This is what we provide. Automobile mufflers undergo repeated wet-dry cycles with large temperature differences, and alcohol-based fuels contain water, so materials that have excellent corrosion resistance, heat resistance, and moisture corrosion resistance are required. In addition, surface-treated steel sheets are required to have excellent chemical conversion treatment properties, high corrosion resistance, and no pinholes even with a thin basis weight of 30 g/m 2 or less on one side. In order to eliminate the above-mentioned drawbacks and meet these demands, the inventors of the present invention have conducted various studies and have found that
More than 75% Al, more than 1% less than 17.5% Zn, more than 1% Si
For Al-based Al-Zn alloy bath containing 12% or less
One of Mg, Mn, Cr and Mitsushi metal
Species or two or more species Mg0.01~1.0%, Mn0.01~
0.5%, Cr0.01~0.5%, Mitsushi Metal 0.01~2.0
% added bath, or 0.01-0.5% Sb in this bath
It has been found that it is sufficient to use a bath in which the additives are added. The reasons for limiting the plating bath composition of the present invention will be described below. (1) Zn When Zn coexists with Si, it lowers the plating temperature and suppresses the development of the Fe-Al alloy layer. It also improves the corrosion resistance of the machined part by its cathodic corrosion protection, and even with a thin coating weight, it can cause pinholes. This is to prevent the occurrence of carbon dioxide, and in order to obtain this effect, it is necessary to add more than 1%. but
At 17.5% or more, the crystals in the plating layer become primary α-
As the area of the Al phase decreases, the proportion of the eutectoid structure with the β-Zn phase increases, and the characteristics of Al plating are impaired. For this reason, Zn was set to more than 1% and less than 17.5%. (2) Si Added to suppress the development of the Fe-Al alloy layer in the plating layer, but its effect is 1%.
The following cases are not permitted. However, the alloy layer can be sufficiently suppressed by adding 6.5%. For this reason, the Si content was set to be more than 1% and less than 6.5%. (3) Mg Mg crystallizes near the β-Zn phase during solidification of the plating layer, suppresses contact corrosion between the α-Al phase and β-Zn phase, slows down the progress of pitting corrosion, and Forms a stable Mg oxide film on the surface to protect the plating layer and improve corrosion resistance. but
Mg provides this effect.
If 0.01% or more is added, less than 0.01% is insufficient. On the other hand, if the amount added exceeds 1.0%, it will be easily oxidized on the bath surface and turn into a large amount of dross, leading to an increase in costs due to a reduction in Mg yield, as well as increasing fluctuations in the bath composition, making it difficult to control the bath composition. Also, in terms of appearance, wrinkles are formed on the surface of the plating layer, and blackened Mg oxide is produced. Furthermore, Mg-Si intermetallic compounds are formed in the plating layer, resulting in decreased corrosion resistance and workability. For this reason, Mg
was set at 0.01 to 1.0%. (4) Mn and Cr Mn and Cr improve the corrosion resistance of Al alloys, but
This effect is reduced in the coexistence of Zn. For this reason
In order to improve corrosion resistance in the coexistence of Zn of more than 1% and less than 17.5%, Mn and Cr each need to be at least 0.01%. On the other hand, if both Mn and Cr are added in excess of 0.5% each, the appearance of the product deteriorates, and the temperature of the plating bath must also be raised, resulting in a decrease in workability and promoting the development of the alloy layer. For this reason, both Mn and Cr were set at 0.01 to 0.5% each. (5) Mitsushi Metal Mitsushi Metal is uniformly dispersed within α-Al crystal grains and refines the crystal grains, improving corrosion resistance and bending workability. It also has the effect of suppressing the occurrence of pinholes in products with a thin coating, and greatly improving corrosion resistance when combined with Mg. This effective addition amount is 0.01% or more, but
If more than 2.0% is added, it will turn into dross on the surface of the plating bath, lowering the effective yield and increasing costs, and making it difficult to control the bath composition. For this reason, the upper limit was set at 2.0%. (6) Sb Sb improves chemical conversion treatment properties (chromate treatment properties, pre-painting properties, etc.) and prevents blistering of the paint film when painted. However, when Sb is added alone, it promotes pitting corrosion and reduces corrosion resistance, so the present invention attempts to improve chemical conversion treatability by adding it in combination with corrosion resistance-improving elements such as Mg and Mn. Improvement in chemical conversion treatability due to Sb is observed when the amount is 0.01% or more, and the improvement increases with increasing amount of Sb added.
On the other hand, corrosion resistance deteriorates, and if it exceeds 0.5%, Mg and
Even if Mn or the like is added in combination, corrosion resistance cannot be expected to improve. Also, along with this, on the surface of the plating bath.
Sb turns into dross, and the bath composition fluctuates rapidly due to a decrease in yield, making bath management difficult. Accordingly
Sb was set at 0.01 to 0.5%. In the present invention, plating is carried out by a known plating process using the bath as described above. In other words, the steel plate is pretreated to make the steel plate surface suitable for hot melt welding.
After that, it is immersed in a bath and plated. In the case of the present invention, there are no particular limitations regarding the relationship with the bath components. The bath temperature during plating should be low when the Zn content is high, and high when the Zn content is low, to a range of approximately 620°C to 670°C. After plating, adjust the amount of adhesion. In terms of quality, it is usually preferable to adjust the amount of adhesion by the gas squeezing method, and in the case of the present invention, the amount of adhesion is adjusted to 30 g/m 2 compared to the current gas squeezing method.
(One side) Can be adjusted to the following thinness. After adjusting the adhesion amount, the appearance may be adjusted by air cooling to obtain regular spangles, or by rapid cooling by water droplet spray to obtain minimized spangles. The present invention will be explained below with reference to Examples. Example 1 1 Test material Unannealed rimmed steel strip 2 of 0.6 mm thickness x 150 mm width Plating conditions Annealing before plating
【表】 雰囲気ガス AXガス（H275％ N225％） めつき温度[Table] Atmospheric gas AX gas (H 2 75% N 2 25%) Plating temperature
【表】
ラインスピード 40〜60m/min
付着量の調整
燃焼排ガスを用いた気体絞り法
めつき後の冷却 放冷
３ 後処理
クロメート処理、オイリング処理…無
調質圧延…無
４ 試験方法
4.1 加工性
密着性…密着曲げおよび衝撃テスト（20
ポンドインチ）後のセロテープ剥離法。
曲げ加工性…密着曲げ部のクラツクの発
生状況をルーペ（X50〜100）にて観察。
判定基準
小…微小なクラツクあり。
中…粗大なクラツクあり。
大…粗大なクラツクとめつき層の浮上り
あり。
4.2 耐食性
塩水噴霧試験（JIS・Ｚ−2371に準ず
る。）
(i)赤錆発生開始時間と2000時間後の外観変
化
(ii) 10日後の腐食減量
カソード防食（犠性防食）性
Fe（素地鋼）とめつき層とのカツプリン
グにより、濃淡電池を形成して、電位を測
定する。
(i) 腐食液…(a)水道水
…(b)１／6000M NaCl（PH＝
5.8）
(ii) 浸漬時間…48時間
マフラー湿食性
(i) 腐食液
NH4Cl＋NH4SO4＋NH3＋水
(ii) 方法
50℃の腐食液中に30秒間浸漬し、その
後80℃の雰囲気中で20分間乾燥する操作
40回を１サイクルとし、このサイクルを
くり返す。
(iii) 供試材の加工
平坦部、2t折り曲げ加工部
(iv) 評価
赤錆の発生率
4.3 耐熱性
400℃雰囲気中で1000時間加熱後の表面外
観の変化とめつき層中の合金層の生成状態を
断面組織にて観察[Table] Line speed 40 to 60 m/min Adjustment of deposition amount Gas squeezing method using combustion exhaust gas Cooling after plating Cooling 3 Post-treatment Chromate treatment, oiling treatment...no Temper rolling...no 4 Test method 4.1 Workability Adhesion…Adhesion bending and impact test (20
lb inch) cellotape removal method. Bending workability: Observe the occurrence of cracks in closely bent parts with a magnifying glass (X50-100). Judgment criteria: Small...Minor cracks present. Medium: There is a rough crack. Large...There are rough cracks and a surface of the stuck layer. 4.2 Corrosion resistance Salt spray test (according to JIS Z-2371) (i) Start time of red rust occurrence and appearance change after 2000 hours (ii) Corrosion loss after 10 days Cathode corrosion protection (sacrificial corrosion protection) Fe (base steel) By coupling with a tacking layer, a concentration cell is formed and the potential is measured. (i) Corrosive liquid…(a) Tap water…(b) 1/6000M NaCl (PH=
5.8) (ii) Immersion time...48 hours Muffler wet corrosion (i) Corrosion liquid NH 4 Cl + NH 4 SO 4 + NH 3 + water (ii) Method Immerse in corrosive liquid at 50℃ for 30 seconds, then in an atmosphere at 80℃ Dry for 20 minutes with
One cycle is 40 times, and this cycle is repeated. (iii) Processing of specimen material Flat part, 2t bent part (iv) Evaluation Incidence of red rust 4.3 Heat resistance Change in surface appearance after heating in 400℃ atmosphere for 1000 hours and state of formation of alloy layer in plating layer observed in cross-sectional structure
【表】
表１に本発明により製造した製品（本発明製品
という）と従来製品の品質特性を浴組成とともに
示す。[Table] Table 1 shows the quality characteristics of the product manufactured according to the present invention (referred to as the product of the present invention) and the conventional product, together with the bath composition.
【表】
表１に示した各特性を検討すると次のようにな
る。
(1) 加工性
本発明製品の加工性はAl−Zn−Si合金の溶
融めつき鋼板とほぼ同等で、溶融アルミニウム
めつき鋼板よりは合金層が薄く加工性がよい。
また本発明の範囲内でのMg添加では加工性に
影響を与えない。
(2) 耐食性
塩水噴霧試験
Mgを添加した本発明製品の赤錆発生時間
および発生速度は遅く、Mgを0.3％以上添加
したもの（No.５）はMg無添加で同量のZnを
含有するもの（No.12）の２〜３倍となつてい
る。この傾向は腐食減量においても同様で、
すぐれた耐食性を有していることがわかる。
これはMg添加によりAlベース合金めつき鋼
板の致命的欠陥である孔食が抑制されるため
と考えられる。
表２はMg以外のMn、Cr、ミツシユメタ
ルおよびSbを添加した場合の耐食性を示し
たものである。[Table] When considering each characteristic shown in Table 1, the following results are obtained. (1) Workability The workability of the product of the present invention is almost the same as that of a hot-dip galvanized Al-Zn-Si alloy steel sheet, and the alloy layer is thinner and the workability is better than that of a hot-dip aluminum-plated steel sheet.
Further, addition of Mg within the scope of the present invention does not affect workability. (2) Corrosion resistance Salt spray test The red rust generation time and generation rate of the products of the present invention containing Mg are slow, and the product containing 0.3% or more of Mg (No. 5) is the same as the product containing the same amount of Zn without the addition of Mg. (No. 12) is two to three times as large. This trend is also the same for corrosion weight loss.
It can be seen that it has excellent corrosion resistance.
This is thought to be because the addition of Mg suppresses pitting corrosion, which is a fatal defect in Al-based alloy coated steel sheets. Table 2 shows the corrosion resistance when Mn, Cr, Mitsushi Metal and Sb other than Mg are added.
【表】
Mg添加の場合と同様、Al−Zn−Si浴に
Mn、Crおよびミツシユメタルを単独添加す
ると耐食性は向上する。しかしミツシユメタ
ルは他の元素に比べて若干劣る。このことよ
りミツシユメタルの場合Mgと複合添加する
のが好ましい。
Sbは比較に示すように添加するとかえつ
て耐食性を劣化させる。従つてSbはMg、
Mn、Crおよびミツシユメタルと複合添加す
ることを要する。
カソード防食性（犠性防食性）
Mg添加によりZnのカソード防食性は損な
われず、NaCl性溶液中でもカソード防食性
を有している。
湿食性
自動車マフラーの結露水による腐食を想定
した湿食試験では加工部の赤錆発生率が従来
製品に比べると著しく少く、優れた耐湿食性
を有している。
耐熱性
本発明製品はZnを多く含有しているのに
もかかわらず溶融アルミニウム鋼板並みの耐
熱性を有している。このように耐熱性が向上
するのはMgを添加しない場合（No.11、No.
12）に比べ耐熱性が向上している点、および
Mg添加量が少いと耐熱性の向上は小さい
（No.１）が増大させると向上する（No.２）点
よりしてMgがFe−Znの相互拡散を抑制する
ものと考えられる。
実施例 ２
実施例１同様の前処理、めつき条件で本発明の
浴を用い、片面付着量が30ｇ/m2以下になるよう
気体絞り条件を設定して薄目付製品の製造を行つ
た。付着量調整後の処理は次の条件で行つた。
めつき後の冷却
エアー冷却（エアー圧力3.0Kg/cm2）
エアーミツクス方式の水冷
（エアー圧力3.0Kg/cm2、水圧力3.0Kg/cm2）
調質圧延
ダル肌のスキンパス 伸び率1.0±0.2％
クロム酸処理
(i) 処理液…アロジン #1000
(ii) 処理条件…65℃、２秒浸漬
試験方法
(i) 耐食性…塩水噴霧試験による赤錆発生と時
間との対応
(ii) ピンホールテスト…湿潤試験（70℃、98％
RH）1000時間後の点状赤錆の有無
表３はこの試験結果を示すもので、化成処理性
はMg添加によつても向上するが、Sbを添加する
とさらに向上している。
またピンホールはZnが低い場合、またはMnの
単独添加の場合に発生しやすい。しかし後者の場
合はミツシユメタルとの複合添加によりピンホー
ルの発生は抑制できる。[Table] As in the case of Mg addition, in the Al-Zn-Si bath
Corrosion resistance improves when Mn, Cr and Mitsushi metal are added alone. However, Mitsushi Metal is slightly inferior to other elements. For this reason, in the case of Mitsushi Metal, it is preferable to add it in combination with Mg. As shown in the comparison, when Sb is added, it actually deteriorates the corrosion resistance. Therefore, Sb is Mg,
It is necessary to add Mn, Cr and Mitsushi metal in combination. Cathode corrosion protection (sacrificial corrosion protection) The addition of Mg does not impair the cathode protection of Zn, and it has cathode protection even in NaCl solutions. Moist corrosion resistance In a wet corrosion test simulating corrosion caused by condensed water on an automobile muffler, the rate of occurrence of red rust on processed parts was significantly lower than that of conventional products, demonstrating excellent moisture corrosion resistance. Heat Resistance Although the product of the present invention contains a large amount of Zn, it has heat resistance comparable to that of molten aluminum steel sheets. Heat resistance improves in this way when Mg is not added (No. 11, No.
12) has improved heat resistance compared to
When the amount of Mg added is small, the improvement in heat resistance is small (No. 1), but when it is increased, it is improved (No. 2), so it is thought that Mg suppresses the interdiffusion of Fe-Zn. Example 2 Using the bath of the present invention under the same pretreatment and plating conditions as in Example 1, a light weight product was produced by setting gas restriction conditions so that the amount of coating on one side was 30 g/m 2 or less. The treatment after adjusting the adhesion amount was carried out under the following conditions. Cooling after plating Air cooling (Air pressure 3.0Kg/cm 2 ) Air mix method water cooling (Air pressure 3.0Kg/cm 2 , Water pressure 3.0Kg/cm 2 ) Temper rolling Skin pass for dull skin Elongation rate 1.0±0.2% Chromic acid treatment (i) Treatment liquid…Alodine #1000 (ii) Treatment conditions…65℃, 2-second immersion Test method (i) Corrosion resistance…Correspondence between occurrence of red rust and time by salt spray test (ii) Pinhole test…wet Test (70℃, 98%
RH) Presence or absence of dotted red rust after 1000 hours Table 3 shows the results of this test. Chemical conversion treatment properties are improved by the addition of Mg, but are further improved by the addition of Sb. Furthermore, pinholes tend to occur when Zn is low or when Mn is added alone. However, in the latter case, the generation of pinholes can be suppressed by adding a compound with Mitsushi Metal.
【表】
以上の如く、本発明により製造した製品は塩水
雰囲気に対して優れた耐孔食性を有しているの
で、耐塩害用の自動車下廻り部材に使用できる。
また加工性にも優れ、かつ加工部の耐食性、耐
湿食にも優れ、耐熱性も有していることから自動
車マフラー、アルコール系燃料タンクに使用でき
る。
さらにSbを添加したものは化成処理性が向上
し、しかも薄目付にしてもピンホールの発生がな
いことからめつき層の耐食性と相俟つて高耐食性
表面処理鋼板用素材にも使用できる。[Table] As described above, the products manufactured according to the present invention have excellent pitting corrosion resistance in a salt water atmosphere, and therefore can be used in automobile underbody members for salt damage resistance. It also has excellent processability, excellent corrosion resistance and moisture corrosion resistance in processed parts, and heat resistance, so it can be used for automobile mufflers and alcohol fuel tanks. Furthermore, the addition of Sb improves the chemical conversion treatment properties and does not cause pinholes even when the coating weight is reduced, so it can be used as a material for highly corrosion-resistant surface-treated steel sheets due to the corrosion resistance of the plating layer.
Claims (1)
つきし、その後、付着量の制御を行う溶融めつき
鋼板の製造方法において、前記めつき浴として、
Alを75％超、Znを１％超17.5％未満、Siを１％
超6.5％以下含有するAlベースのAl−Zn合金浴に
Mg、Mn、Crおよびミツシユメタルのうちの１
種または２種以上をMg0.01〜1.0％、Mn0.01〜
0.5％、Cr0.01〜0.5％、ミツシユメタル0.01〜2.0
％添加した浴を用いることを特徴とするアルミニ
ウムベース複合溶融めつき鋼板の製造方法。 ２ 付着量を30ｇ/m2（片面）以下に制御するこ
とを特徴とする特許請求の範囲第１項に記載のア
ルミニウムベース複合溶融めつき鋼板の製造方
法。 ３ 鋼板を前処理した後、めつき浴に浸漬してめ
つきし、その後、付着量の制御を行う溶融めつき
鋼板の製造方法において、前記めつき浴として、
Alを75％超、Znを１％超17.5％未満、Siを１％
超6.5％以下含有するAlベースのAl−Zn合金浴に
Mg、Mn、Crおよびミツシユメタルのうちの１
種または２種以上をMg0.01〜1.0％、Mn0.01〜
0.5％、Cr0.01〜0.5％、ミツシユメタル0.01〜2.0
％添加するとともにさらにSbを0.01〜0.5％添加
した浴を用いることを特徴とするアルミニウムベ
ース複合溶融めつき鋼板の製造方法。 ４ 付着量を30ｇ/m2（片面）以下に制御するこ
とを特徴とする特許請求の範囲第３項に記載のア
ルミニウムベース複合溶融めつき鋼板の製造方
法。[Scope of Claims] 1. A method for producing a hot-dip galvanized steel plate in which a steel plate is pretreated, then immersed in a plating bath for plating, and then the amount of coating is controlled, wherein the plating bath comprises:
More than 75% Al, more than 1% less than 17.5% Zn, 1% Si
For Al-based Al-Zn alloy bath containing less than 6.5%
One of Mg, Mn, Cr and Mitsushi metal
Species or two or more species Mg0.01~1.0%, Mn0.01~
0.5%, Cr0.01~0.5%, Mitsushi Metal 0.01~2.0
1. A method for producing an aluminum-based composite hot-dip galvanized steel sheet, the method comprising using a bath containing an aluminum-based composite hot-dip galvanized steel sheet. 2. The method for producing an aluminum-based composite hot-dip galvanized steel sheet according to claim 1, characterized in that the amount of adhesion is controlled to 30 g/m 2 (one side) or less. 3. In a method for producing a hot-dip galvanized steel plate in which a steel plate is pretreated, immersed in a plating bath for plating, and then the amount of coating is controlled, the plating bath comprises:
More than 75% Al, more than 1% less than 17.5% Zn, 1% Si
For Al-based Al-Zn alloy bath containing less than 6.5%
One of Mg, Mn, Cr and Mitsushi metal
Species or two or more species Mg0.01~1.0%, Mn0.01~
0.5%, Cr0.01~0.5%, Mitsushi Metal 0.01~2.0
% and further contains 0.01 to 0.5% of Sb. 4. The method for producing an aluminum-based composite hot-dip galvanized steel sheet according to claim 3, characterized in that the amount of adhesion is controlled to 30 g/m 2 (one side) or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6282882A JPS58181855A (en) | 1982-04-15 | 1982-04-15 | Production of steel plate hot-dipped in aluminum base composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6282882A JPS58181855A (en) | 1982-04-15 | 1982-04-15 | Production of steel plate hot-dipped in aluminum base composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58181855A JPS58181855A (en) | 1983-10-24 |
| JPS648704B2 true JPS648704B2 (en) | 1989-02-15 |
Family
ID=13211568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6282882A Granted JPS58181855A (en) | 1982-04-15 | 1982-04-15 | Production of steel plate hot-dipped in aluminum base composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58181855A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0467301U (en) * | 1990-10-22 | 1992-06-15 |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6227558A (en) * | 1985-07-26 | 1987-02-05 | Nippon Steel Corp | Manufacture of steel sheet plated with molten zinc-aluminum alloy excellent in resistance to peeling-off of plating by lapse of time |
| CA2367506C (en) * | 1999-03-19 | 2005-08-23 | Nippon Steel Corporation | Tin-plating or aluminum-plating surface treated steel material with excellent corrosion resistance |
| JP4616433B2 (en) * | 1999-08-06 | 2011-01-19 | 新日本製鐵株式会社 | Hot-dip aluminized steel sheet with excellent corrosion resistance |
| JP2004043882A (en) * | 2002-07-11 | 2004-02-12 | Union Steel Manufacturing Co Ltd | Plating method of aluminum alloy plated steel sheet |
| JP4356423B2 (en) * | 2003-10-30 | 2009-11-04 | Ｊｆｅスチール株式会社 | Fused Al-Zn-Mg plated steel sheet and method for producing the same |
| JP2005264188A (en) * | 2004-03-16 | 2005-09-29 | Nippon Steel Corp | HOT DIP Zn-Al ALLOY PLATED STEEL HAVING EXCELLENT BENDABILITY, AND ITS MANUFACTURING METHOD |
| JP2005290418A (en) * | 2004-03-31 | 2005-10-20 | Jfe Steel Kk | HOT-DIP Al-Zn ALLOY PLATED STEEL SHEET SUPERIOR IN PRESS FORMABILITY, AND MANUFACTURING METHOD THEREFOR |
| WO2010082678A1 (en) | 2009-01-16 | 2010-07-22 | 新日本製鐵株式会社 | HOT-DIP Zn-Al-Mg-Si-Cr ALLOY COATED STEEL MATERIAL WITH EXCELLENT CORROSION RESISTANCE |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6056420B2 (en) * | 1981-07-02 | 1985-12-10 | 大同鋼板株式会社 | Zinc-aluminum alloy coated steel products |
| JPS58177450A (en) * | 1982-04-13 | 1983-10-18 | Nisshin Steel Co Ltd | Manufacture of composite hot dipped steel plate |
-
1982
- 1982-04-15 JP JP6282882A patent/JPS58181855A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0467301U (en) * | 1990-10-22 | 1992-06-15 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58181855A (en) | 1983-10-24 |
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