JPS6160896A - Steel plate for vessel for alcohol or alcohol-containing fuel - Google Patents
Steel plate for vessel for alcohol or alcohol-containing fuelInfo
- Publication number
- JPS6160896A JPS6160896A JP17995984A JP17995984A JPS6160896A JP S6160896 A JPS6160896 A JP S6160896A JP 17995984 A JP17995984 A JP 17995984A JP 17995984 A JP17995984 A JP 17995984A JP S6160896 A JPS6160896 A JP S6160896A
- Authority
- JP
- Japan
- Prior art keywords
- alcohol
- steel plate
- coating layer
- steel
- alloy
- 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.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はアルコール燃料及びアルコールを含有するガソ
リン燃料を収容する容器として最適な耐食性、加工性、
及び溶接性にすぐれた性能を発揮する燃料容器用鋼板に
関するものである。Detailed Description of the Invention (Industrial Field of Application) The present invention provides a container that has corrosion resistance, processability, and
The present invention also relates to a steel plate for fuel containers that exhibits excellent weldability.
（従来技術及び発明が解決しようとする問題点〕最近の
石油憂情の悪化（石油コストの上昇および生産量の減少
）に伴って、自動車用燃料としてガソリンに代って、メ
チルアルコールやエチルアルコールの如きアルコール燃
料或いはガソリンに対シテメチルアルコール、エチルア
ルコール、メチルターシャリ−ブチルアルコール（ＭＴ
ＢＡ）等の如きアルコールを混入した燃料（所謂、ガソ
ホール）を代替燃料として使用することが提案され実施
されつつある。(Problems to be solved by the prior art and the invention) With the recent deterioration of the oil crisis (rise in oil costs and decrease in production), methyl alcohol and ethyl alcohol are being used instead of gasoline as automobile fuels. Methyl alcohol, ethyl alcohol, methyl tert-butyl alcohol (MT
The use of alcohol-mixed fuel (so-called gasohol) such as BA) as an alternative fuel has been proposed and is being put into practice.
これらのアルコール慾料或いはアルコール添加ガソリン
（ガソホール）の自動車燃料容器材料には特開昭５０−
２３３４５号公報、特開昭５１−１１５２４０号公報な
ど多くの特許公報で発表されているＦＬＹ−８ｎ合金被
覆鋼板が使用されているが、その鋼板の耐食性を著しく
劣化せしめる問題がちった。すなわち、その原因はＰｂ
−３ｎ合金鋼板はｐｂ （ｉ−主体とするｐｂとＳｎの
共晶合金でその被覆石が構成されているために、例えば
（ａ） Ｐｂ金属はメチルアルコールに著しく腐食さ
れるため、被覆層のｐｂ金属層の部分が腐食され易い。Japanese Patent Application Laid-Open No. 1983-1999 is used for automobile fuel container materials for these alcoholic beverages or alcohol-added gasoline (gasohol).
FLY-8n alloy coated steel sheets, which have been published in many patent publications such as No. 23345 and JP-A No. 51-115240, have been used, but the steel sheets tend to have a problem of significantly deteriorating their corrosion resistance. In other words, the cause is Pb
Since the -3n alloy steel sheet is composed of a eutectic alloy of Pb and Sn, for example (a) Pb metal is severely corroded by methyl alcohol, the coating layer is The pb metal layer is easily corroded.
（ｂ） アルコール燃料又はアルコール添加ガソリン
が酸化されて生成されるアセトアルデヒド。(b) Acetaldehyde produced by oxidation of alcohol fuel or alcohol-added gasoline.
酢醒（エチルアルコールの酸化生成物）或イはフォルム
アルデヒド、ギ酸（メチルアルコールの酸化生成物）に
よって、ｐｂ金金属著しく腐食され、被覆層中のｐｂ金
属層の部分が腐食され易い。PB gold metal is severely corroded by acetic acid (oxidation product of ethyl alcohol), formaldehyde, and formic acid (oxidation product of methyl alcohol), and the portion of the PB metal layer in the coating layer is likely to be corroded.
（ｃ） アルコールに含有される水分或いはアルコー
ルの酸化生成物によって、被覆層で形成されたピンホー
ル部から腐食を増大せしめる。(c) Moisture contained in alcohol or oxidation products of alcohol increase corrosion from pinholes formed in the coating layer.
等の原因によって、Ｐｂ５ｎ ｒ合金メッキ鋼板はその
耐食性が著しく劣化せしめられる。Due to these reasons, the corrosion resistance of Pb5nr alloy plated steel sheets is significantly deteriorated.
このため、このような燃料を収容する容器鋼板として、
被覆層のピンホールが少なく、またアルコールやアルコ
ールの酸化生成物に対して耐食性のすぐれた、高耐食性
の素材が要求されることになる。For this reason, as a container steel plate for storing such fuel,
A highly corrosion-resistant material is required that has fewer pinholes in the coating layer and has excellent corrosion resistance against alcohol and alcohol oxidation products.
さらに燃料容器の加工形状或いは高速成形方式等によっ
ては、上記被覆層のピンホールの拡大、表面の″グレス
カノリ“現象による被覆層の疵付きによる地鉄に達する
欠陥の生成、又取扱い時の地鉄に達する疵発生等によシ
、これら欠陥部からの赤錆発生等の問題点が生じる現象
がみられた。Furthermore, depending on the processing shape of the fuel container or the high-speed molding method, etc., the pinholes in the coating layer may enlarge, the coating layer may be scratched due to the "grescano" phenomenon on the surface, causing defects that reach the base metal, or the base metal may be damaged during handling. Problems such as the occurrence of red rust from these defective parts were observed due to the occurrence of defects that reached 100%.
特に、ガソリン或いは外部から混入されるＣｔ−イオン
、水分等が多い場合や、アルコールとがソリンの混合燃
料から分離した水分によって腐食が進行し穿孔腐食によ
る孔わきの危険性もみられた。In particular, corrosion progressed when there was a large amount of Ct- ions, water, etc. mixed in from gasoline or from the outside, or water separated from a mixed fuel of alcohol and solin, and there was a danger of pitting due to perforation corrosion.
一方、タンク外面に対しても、融雪塩による腐食問題が
近年さらにシビアーにな）、前記同様に被覆層欠陥部或
いは道路散布塩の衝突（いわゆる、チッピング現象）に
よる地鉄に達する疵の発生によって、Ｃ２−イオンによ
る腐食、特に孔あきにつながる穿孔腐食の発生が懸念さ
れている。On the other hand, the problem of corrosion caused by snow melting salt on the outer surface of the tank has become more severe in recent years), and as mentioned above, due to defects in the coating layer or the occurrence of scratches that reach the base steel due to collisions with road sprayed salt (so-called chipping phenomenon). There is a concern about corrosion due to , C2- ions, particularly the occurrence of pitting corrosion that leads to pitting.
（問題を解決するための手段及び発明の作用、助船本発
明はこれらの状況に対してなされたものでＮｉ 、 Ｃ
ｏ 、 Ｓｎおよびこれらの合金及び該金属にＰ。(Means for solving the problem and the effect of the invention, the present invention was made in response to these situations.
o, Sn and their alloys, and P in the metals.
Ｍｏ 、 Ｃｒの１８１以上を含有せしめた合金のメ、
−？被′８ｉ、銅板のアルコール燃料、アルコール含有
燃料。An alloy containing 181 or more of Mo and Cr,
−? '8i, alcohol fuel on copper plate, alcohol-containing fuel.
ガソリン等に対する上記の耐食性に関する問題点及びタ
ンク外面に対する融雪塩からの腐食に関する問題点を解
決すると共に、成形加工性、溶接性などもすぐれた燃料
容器用鋼板を提供することを目的にしたものである。The purpose is to solve the above-mentioned problems regarding corrosion resistance to gasoline etc. and corrosion from snow-melting salt on the outer surface of the tank, and to provide a steel sheet for fuel containers that has excellent formability and weldability. be.
すなわち、本発明の要旨は、
劃すで
Ｃ；０．０２％以下
Ｃｒ；３〜２０ ％
酸可溶Ａｌ：０．００５〜０．１０チ
必要によってはＴｉ 、 Ｎｂ 、 Ｚｒ 、 Ｖの１
種または２種以上をそれぞれ０．０３〜０，５チ含有さ
せ、残部不可避不純物及び鉄よりなる鋼板の少なくとも
片面にＮｉ ｒ Ｓｎ Ｉ Ｃｏ １及びこれらの合金
、もしくは該金属にＰ ＋ Ｍｏ ＊ Ｃｒの１種以上
を含有せしめた合金のメッキ被覆層を施したアルコール
もしくはアルコール含有撚料容器用鋼板である。That is, the gist of the present invention is as follows: C: 0.02% or less Cr: 3 to 20% Acid-soluble Al: 0.005 to 0.10% Ti, Nb, Zr, V as necessary
Ni r Sn I Co 1 and alloys thereof, or P + Mo * Cr on at least one side of a steel plate containing 0.03 to 0.5 of each of two or more species, and the remainder being unavoidable impurities and iron. This is a steel sheet for use in alcohol or alcohol-containing twist containers, which is coated with a plating layer of an alloy containing one or more of the following.
以下に本発明について詳細に説明する。The present invention will be explained in detail below.
Ｃｒを３−以上、特に５チ以上含有する鋼板は、アルコ
ール、アルコールを含有する燃料、７！／ソリン、アル
コールの酸化生成物（アルデヒド類、キｉ、さくｍ等の
有機酸）、ガソリンに対してすぐれた耐食性を示す。A steel sheet containing 3 or more Cr, especially 5 or more Cr, can be used for alcohol, alcohol-containing fuel, and 7! Shows excellent corrosion resistance to /solin, alcohol oxidation products (aldehydes, organic acids such as chlorine, chlorine, etc.), and gasoline.
しかしながら、Ｃｒ含有量が２０チをこえると、加工性
と溶接性が劣化し、燃料容器製造時の成形加工、或いは
溶接性を困難にするので好ましくない。However, if the Cr content exceeds 20 inches, the workability and weldability deteriorate, making it difficult to form or weld the fuel container during manufacture, which is not preferable.
従って、上記の腐食生成物の赤錆に対する耐食性と加工
性、溶接性の両面からＣｒ含有金を３〜２０饅、好まし
くは５〜１５％の範囲に規定した。Therefore, the Cr-containing gold is defined to be in the range of 3 to 20%, preferably 5 to 15%, from the viewpoint of both corrosion resistance against red rust of the above-mentioned corrosion products, workability, and weldability.
以上、耐食性の点からは上記の如く、Ｃｒの効果が最も
大きいが、本発明では自動車その他貯蔵用の燃料タンク
素材を対象とする観点から、ｃ［’ｉ３２可溶Ａｌその
他の鋼成分についてもその含有ｆ：ｋを限定する。As mentioned above, from the point of view of corrosion resistance, Cr has the greatest effect, but in the present invention, from the viewpoint of targeting fuel tank materials for automobiles and other storage, c['i32 soluble Al and other steel components are also used. Its content f:k is limited.
Ｃは含有量の増加につれてクロムカーバイドを析出して
鋼の機椋的性質と耐食性を劣化する。As the C content increases, chromium carbide is precipitated and the mechanical properties and corrosion resistance of the steel deteriorate.
従って、Ｃ含有量は０．０２％以下、好ましくはｏ、ｏ
ｏｓ％以下が望ましい。Therefore, the C content is 0.02% or less, preferably o, o
os% or less is desirable.
Ａｌは、鋼中に残存する酸可溶Ａｌ（５ｏｔＡ１． ）
量がｏ、ｏｏｓ−未満の多官有量では、ｒｉ素性ガスに
よる気泡の発生を防止する事が困難であシ、鋼の表面欠
陥発生率を著しく高め鋼素材の耐食性劣化の起点となる
。また、０．１０チを越える過剰な酸可醇Ａ４は、Ａｌ
系敵化物を＠表面区点在せしめて耐食性劣化の起点或い
は本鋼板に対して施されるメッキ面においては不メッキ
、ピンホール等を発生してメッキ健全性を損じる。又、
本発明において第２の発明は、上記の鋼成分の他ＫＯ，
０３〜０．５０％のＴ＋ ＊ Ｎｂ ｒ Ｚｒ 、 Ｖ
を１種又は２種以上含有させて鍋中のＣと結合せしめて
含有されるＣｒの有効化を計り、更にすぐれた成形加工
性と、耐食性を向上せしめるものである。Al is acid-soluble Al (5otA1.) remaining in steel.
If the amount is less than o, oos-, it is difficult to prevent the generation of bubbles due to ri gas, and the occurrence rate of surface defects in steel is significantly increased, which becomes the starting point for deterioration of the corrosion resistance of the steel material. In addition, excess acid-soluble A4 exceeding 0.10% is
These chemical compounds are scattered on the surface, which is the starting point for deterioration of corrosion resistance, or causes non-plating, pinholes, etc. on the plated surface of the steel sheet, impairing the integrity of the plating. or,
A second aspect of the present invention is that in addition to the above steel components, KO,
03-0.50% T+*Nb r Zr , V
By containing one or more types of Cr, the Cr is combined with C in the pot to make the Cr contained in the pot more effective, thereby further improving moldability and corrosion resistance.
ＴＩなどの鋼成分の含有量が０．０３チ未満ではクロム
カーバイドの析出を防止して、成形加工性及び耐食性を
向上せしめる効果が少なく、またその含有量が０．５０
％を越えるとその効果が飽和に達し経済的でなくなる
と共に、これら成分の析出によって素材の硬質化を起し
、成形加工性を劣化する傾向にある。If the content of steel components such as TI is less than 0.03, the effect of preventing the precipitation of chromium carbide and improving formability and corrosion resistance is small, and the content is less than 0.50.
%, the effect reaches saturation and becomes uneconomical, and the precipitation of these components tends to harden the material and deteriorate moldability.
特に、好ましくはこれら元素の含有量が０．０７５〜０
．２０チの範囲である。Particularly preferably, the content of these elements is 0.075 to 0.
．． It is in the range of 20 inches.
本発明は、このような鋼板をその１ま燃料容器に使用し
たのでは、耐食性が不充分であり、これらの鋼板に対し
Ｎｉ 、 Ｃｏ 、 Ｓｎ 、これらの合金及び該金属
にＰ 、 Ｍｏ 、 Ｃｒの１種また２種以上を含有せ
しめた合金をメッキする。In the present invention, if such a steel plate is used for a fuel container, its corrosion resistance is insufficient, and these steel plates are treated with Ni, Co, Sn, alloys thereof, and the metal with P, Mo, Cr. An alloy containing one or more of these is plated.
すなわち、上記鋼板の＆までは、燃料容器内面に対して
は燃料中に含有される水分、Ｃ６−イオン等に対する耐
食性が不充分でラシ、また燃料容器の外面腐食に対して
は燃料容器外面以上に水分。In other words, the above-mentioned steel plate has insufficient corrosion resistance against the moisture contained in the fuel, C6- ions, etc. for the inner surface of the fuel container, and the corrosion resistance of the outer surface of the fuel container is insufficient for corrosion of the outer surface of the fuel container. Moisture.
Ｃｔ−イオンを多量に含有される腐食雰囲気のため赤錆
発生が著しく、板厚減少（腐食量）が著しく大きくなｐ
１充分な耐食性を有しない。従って、これらの問題点を
解決するためＫ、本発明においテハアルコール、アルコ
ール含有ｍ料、アルコールの酸化生成物６水分、ガソリ
ンＣｔ−イオン等に対して耐食性の良好な金属又は合金
の被覆層を設ける事によって耐食性を確保すると共に、
被覆層の欠陥部（ピンホール）、成形加工時の地鉄に対
する庇部等の鋼素地の耐食性を確保する事にある。Due to the corrosive atmosphere containing a large amount of Ct- ions, red rust occurs significantly, and the decrease in plate thickness (corrosion amount) is significantly large.
1. Does not have sufficient corrosion resistance. Therefore, in order to solve these problems, in the present invention, a coating layer of a metal or alloy having good corrosion resistance against Teha alcohol, alcohol-containing methanol, alcohol oxidation product 6 water, gasoline Ct- ions, etc. is used. By providing this, corrosion resistance is ensured, and
The purpose is to ensure the corrosion resistance of the steel base, such as defective parts (pinholes) in the coating layer and eaves against the base steel during forming.
畜らに加うるに、本発明のＣｒ ｆ含有する鋼成分と被
覆層を用いる事によって、第１図（０はＮｉ板１が陽極
、（＋）はＣｒ鋼２が陽極、３はｌ ％ ＮａＣ２溶液
）にその−例を示すように、鋼素地と被ｒｉ層のカップ
ル腐食電流を減少する効果によって、ピンホールや成形
加工時に生じる疵等の被覆層欠陥が存在しても、被覆層
が銅素地に比して電位的に卑な場合には被覆層の犠牲防
食による腐食量が小さく、また被覆層が鋼素地に比して
電位的に責な場合でも鋼素地の腐食量が小さく、穿孔腐
食の危険性が極めて少ない。その結果、本発明の被覆層
の被膜量（メッキ量）を少なくする（薄くする）事がで
きるので、被覆メッキ層の密着性、燃料容器に特に要求
される成形加工性の点で極めてすぐれた効果が得られる
。而して本発明では、アルコール、アルコール含有燃料
、アルコールの酸化生成物（アルデヒド、有機＠）ｆソ
リン、水分、Ｃ２−イオンに対して良好な耐食性を有す
るＮｉ ＋ Ｓｎ ＋ Ｃｏ ｔこれらの合金、もしく
は該金属ＫＰ 、 Ｍｏ 、 Ｃ１の１種または２種以
上を含有せしめた合金被覆層が施される。In addition, by using the Crf-containing steel component and coating layer of the present invention, it is possible to obtain the Cr steel as shown in Fig. 1 (0 indicates Ni plate 1 is the anode, (+) indicates Cr steel 2 is the anode, 3 indicates l% As shown in the example of NaC2 solution), the effect of reducing the coupled corrosion current between the steel substrate and the ri layer allows the coating layer to remain intact even if there are defects in the coating layer such as pinholes or flaws that occur during forming. If the potential is more base than the copper base, the amount of corrosion due to sacrificial corrosion of the coating layer is small, and even if the coating layer is more base in potential than the steel base, the amount of corrosion of the steel base is small. Extremely low risk of drilling corrosion. As a result, the coating amount (plating amount) of the coating layer of the present invention can be reduced (thinned), resulting in extremely excellent adhesion of the coating layer and moldability, which is particularly required for fuel containers. Effects can be obtained. Therefore, in the present invention, Ni + Sn + Cot alloys having good corrosion resistance against alcohol, alcohol-containing fuels, alcohol oxidation products (aldehydes, organic @) thorin, moisture, and C2- ions, Alternatively, an alloy coating layer containing one or more of the metals KP, Mo, and C1 is applied.
その被覆処理方法、被覆処理条件等は特に規定されるも
のでないが、脱脂、酸洗等のＣｒ含有鋼板に対する表面
清浄化、活性化処理を行なった後に、以下のような条件
で被覆処理が行なわれる。The coating treatment method, coating treatment conditions, etc. are not particularly stipulated, but after surface cleaning and activation treatment of the Cr-containing steel plate such as degreasing and pickling, the coating treatment is performed under the following conditions. It will be done.
（１） Ｎｉメッキ
メツキ浴組成；硫酸ニッケル ２５０９／ｉ：塩化ニッ
ケル ７０Ｆ／／ｌ
ホウ酸 ３０Ｖｌ
電流密度 ５〜１５０Ａ／ｄＴｒＬ２（２） Ｓ
ｎメッキ
メ ツキ浴組成： フェノールスルフォンｄ ２０Ｖｌ
硫酸第１錫 ６０ ＶＩ
ＥＮＳＡ（添加剤） １０Ｖｌ
（３） Ｎｉ−Ｓｎ合金メッキ
塩化ニッケル ｚ ５０ｇ／ｌ
塩化第１錫 ５０９／１
酸性弗化アンモニウム ５０ ｇ／１
（４） Ｎ１−Ｆ’合金メッキ
硫酸ニッケル ８０νｌ
塩化ニッケル ３０１１／１
亜リン酸 ２０ ｇ／ｌ
リ ン酸 １０ｇ／１（５） Ｎｔ
−Ｃｒ合金メッキ
硫酸ニッケル ２６０９／１
塩化クロム ５３，１７’／１
グリシン ２０Ｆｌ／１
塩化アンモン ２００９／１
（６）Ｃｏ−ＭＯ合金メッキ
硫酸コバルト ８５Ｖｌ
クエン酸ソーダ ８８１／１
モリブデン酸ソーダ ４０ ｇ／１
（７） Ｎ１−Ｃｏ−Ｐ合金メッキ
硫酸コバルト ３０ｇ／６
硫酸ニッケル ５０ Ｖｌ
塩化ニッケル ３０ｊｉ／１
亜リン酸 ２０ｇ／ｌ
リ ン酸 １０９／１このような被覆
メッキ層は、０．１〜１０μの厚さで施され、特に好ま
しくは０．５〜５μ厚さが望ましい。これは、０．１μ
厚さ未満では被覆層の均一被覆性が極めて不充分でちり
、ピンホールの生成量が多く、耐食性向上効果が得られ
ない場合がある。(1) Ni plating plating bath composition: Nickel sulfate 2509/i: Nickel chloride 70F//l Boric acid 30Vl Current density 5-150A/dTrL2 (2) S
N plating Plating bath composition: Phenol sulfone d 20Vl
Stannous sulfate 60 VI ENSA (additive) 10Vl (3) Ni-Sn alloy plating Nickel chloride z 50g/l Stannous chloride 509/1 Acidic ammonium fluoride 50 g/1 (4) N1-F' alloy plating Nickel sulfate 80νl Nickel chloride 3011/1 Phosphorous acid 20 g/l Phosphoric acid 10g/1(5) Nt
-Cr alloy plated nickel sulfate 2609/1 Chromium chloride 53,17'/1 Glycine 20Fl/1 Ammonium chloride 2009/1 (6) Co-MO alloy plated cobalt sulfate 85Vl Sodium citrate 881/1 Sodium molybdate 40 g/1 (7) N1-Co-P alloy plating Cobalt sulfate 30g/6 Nickel sulfate 50 Vl Nickel chloride 30ji/1 Phosphorous acid 20g/l Phosphoric acid 109/1 Such a coating plating layer has a thickness of 0.1 to 10μ. A thickness of 0.5 to 5 μm is particularly preferred. This is 0.1μ
If the thickness is less than that, the uniform coverage of the coating layer will be extremely insufficient, a large amount of dust and pinholes will be formed, and the effect of improving corrosion resistance may not be obtained.
さらに、被覆層の厚さが１０μをこえると、耐食性向上
効果が飽和するとともに１被覆層の密着性、成形加工性
が劣化する傾向にあり好ましいものでない。Furthermore, if the thickness of the coating layer exceeds 10 μm, the corrosion resistance improving effect tends to be saturated and the adhesion and moldability of one coating layer tend to deteriorate, which is not preferable.
また、被覆層の合金組成については、Ｎｌ ＋ Ｓｎ
。Moreover, regarding the alloy composition of the coating layer, Nl + Sn
.
Ｃｏを組み合わせた場合の合金組成は、合金ＩＪＸとも
ほぼ同様のすぐれた耐食性能を示し、全組成範囲の合金
組成が使用される。The alloy composition when combined with Co exhibits excellent corrosion resistance performance that is almost the same as that of alloy IJX, and alloy compositions in the entire composition range are used.
一方、これらの金弐合金に含有せしめられるＰ。On the other hand, P is contained in these gold alloys.
Ｍｏ 、 Ｃｒの１種以上の合金化の場合には、各々以
下の理由により合金化の好ましい量が選択される。In the case of alloying one or more of Mo and Cr, preferred amounts of alloying are selected for each of the following reasons.
すなわちＮｉ ｒ Ｓｎ 、 Ｃｏ及びこれらの合金に
対して、Ｐ 、 Ｍｏは４０％をこえて合金化される場
合、またＣｒは３０％金こえて合金化される場合、各々
被覆層を硬質化するとともに、被覆層の密着性及び成形
加工性を劣化し、風気メッキ作業における電解効率から
好１しくない。従って、Ｐ 、 Ｍｏ 、 Ｃｒの合金
化被覆層が設けられる場合にはＰ 、 Ｍｏは４０チ以
下、好筐しくは２０％以下、Ｃｒは３０％以下、好まし
くは１５％以下の含有量を使用するのがよい。さらにこ
れらが２種以上合金化される場合は、使用される合金化
元素の最大許容量の範囲内に組み合わ格れる合金化元素
の総オロがおさまるように選択されるのが好ましい。例
えばｐ−ｌ−Ｍｏ ： ４０％以下、Ｐ＋Ｃｒ：３０％
以下、Ｍｏ ＋ Ｃｒ ： ３０％以下、Ｐ ＋Ｍｏ
＋Ｃｒ ： ３０％以下の範囲内に抑制する事によって
被覆層の耐食性が一層向上し、耐食寿命が延長される。That is, when Ni r Sn, Co and their alloys are alloyed with more than 40% of P and Mo, and when Cr is alloyed with more than 30% of gold, the coating layer is hardened. At the same time, it deteriorates the adhesion and moldability of the coating layer, which is unfavorable from the viewpoint of electrolytic efficiency in air plating work. Therefore, when an alloyed coating layer of P, Mo, and Cr is provided, the content of P and Mo is 40% or less, preferably 20% or less, and the Cr content is 30% or less, preferably 15% or less. It is better to do so. Furthermore, when two or more of these are alloyed, it is preferable that the alloying elements be selected so that the total amount of the alloying elements that can be combined falls within the maximum allowable amount of the alloying elements used. For example, p-l-Mo: 40% or less, P+Cr: 30%
Below, Mo + Cr: 30% or less, P + Mo
+Cr: By suppressing it within the range of 30% or less, the corrosion resistance of the coating layer is further improved and the corrosion resistance life is extended.
また、これらの被覆層の耐食性向上或いは塗装性能の向
上、特に燃料容器外面の塗装による耐食寿命の延長を目
的にした塗装下地処理のためのクロメート系処理を本発
明の被覆／１１表面に施してもよい。In addition, a chromate-based treatment is applied to the surface of the coating/11 of the present invention to improve the corrosion resistance of these coating layers or to improve the coating performance, and in particular to extend the corrosion-resistant life of the coating on the outer surface of the fuel container. Good too.
クロメート系処理は、Ｃｒ Ｏｓ水溶液酸いはＣｒ ０
３に陰イオンを添加したＣｒｙ、−８ｏ４． ＣｒＯ３
−ＰＯ４゜Ｃｒ Ｏｓ −Ｆ″″″系浴いた浸漬処理、
電解処理等によシ行なわれる。この場合、本発明は、化
学反応性が安定した被覆層で構成されているので、Ｃｒ
Ｏ３に陰イオンが含有されたＣｒｙ５−Ｓｎ４．Ｃｒ０
３−Ｆ−系浴を用いた陰極電解処理により、Ｃｒ Ｈｉ
ｔとして１０〜１５０η／ｍ２（片面当υ）施したもの
がすぐれた効果（耐食性及び塗装性の向上）が得られ好
ましい。Chromate treatment is carried out using CrOs aqueous solution or CrO
3 with anion added, -8o4. CrO3
-PO4゜CrOs-F″″″ system bath immersion treatment,
This is done by electrolytic treatment, etc. In this case, since the present invention is composed of a coating layer with stable chemical reactivity, Cr
Cry5-Sn4. containing an anion in O3. Cr0
By cathodic electrolytic treatment using a 3-F-based bath, CrHi
It is preferable that the coating is applied with a t of 10 to 150 η/m 2 (on one side υ), since excellent effects (improved corrosion resistance and paintability) can be obtained.
さらに本発明の燃料容器外面に対してはＺｎ又はＺｎ系
合金メッキ被覆層を施して、その外面からの腐食に対す
る防食処理を行なってもよい・すなわち、道路散布塩等
からのｃｔ”−イ”ｙ ’Ｊ Ｋ 対し １ 比較的耐
食性がすぐれ、鋼素材に対して１義牲防食効果のあるＺ
ｎ又はＺｎ −（８〜２０％）Ｎｉ 、 Ｚｎ−（８〜
２０％）Ｃｏ、Ｚｎ−（８〜２０％） （Ｎｌ 十Ｃｏ
） 、 Ｚｎ −（８〜２０％）Ｆｅ系合金被覆層を
０．５〜１０μ施して、その外面からの腐食に対する耐
食寿命の延長を計ってもよい。Furthermore, the outer surface of the fuel container of the present invention may be coated with a Zn or Zn-based alloy plating layer to provide corrosion protection against corrosion from the outer surface. y 'J K vs. 1 Z has relatively excellent corrosion resistance and has a primary corrosion-preventing effect on steel materials.
n or Zn-(8~20%) Ni, Zn-(8~20%)
20%) Co, Zn- (8~20%) (Nl + Co
), a Zn-(8-20%) Fe-based alloy coating layer with a thickness of 0.5-10μ may be applied to extend the corrosion-resistant life against corrosion from the outer surface.
同様に、本発明の被覆処理を両面に施して、外面には前
記の如きクロメート系処理を施して防食と装飾を兼ねる
塗装処理を行なってもよい。まｆｃ外面腐食に対する間
食環境のマイルドな場合には、本発明の被覆層を燃料容
器内面のみに施し外面は銅素地のまま使用してもよい。Similarly, the coating treatment of the present invention may be applied to both surfaces, and the outer surface may be subjected to a chromate treatment as described above to provide a coating treatment that serves both as corrosion prevention and decoration. If the snacking environment is mild against corrosion of the fc outer surface, the coating layer of the present invention may be applied only to the inner surface of the fuel container, and the outer surface may be used as it is made of copper.
以上の如く、本発明によれば、自動車用等のアルコール
もしくはアルコール含有燃料タンク鋼板として、本発明
の鋼組成、被覆層の相剰効呆により、耐食性、成形加工
性に極めてすぐれ、また溶接性も確保しうる燃料容器用
鋼板を提供しうるものである。As described above, the present invention can be used as an alcohol or alcohol-containing fuel tank steel sheet for automobiles, etc. due to the steel composition of the present invention and the additive effect of the coating layer, and has extremely excellent corrosion resistance and formability, as well as weldability. Therefore, it is possible to provide a steel plate for a fuel container that can secure the same.
尚、本発明の鋼成分については、各々前述のように規定
したが、これら鋼中九転炉等からの不純物として、Ｎｌ
、 Ｍｏ等が各々１％以下、０３％以下含有されても
性能に及ぼす影響は小さい。In addition, although the steel components of the present invention are specified as described above, Nl is included as an impurity from the converter etc. in these steels.
, Mo, etc. contained in amounts of 1% or less and 0.3% or less, respectively, have little effect on performance.
又、同時に本発明はアルコールもしくはアルコールを含
有する燃料タンクについて説明したが、通常のガノリン
を対象とした燃料タンクに適用又は共用しても、その耐
食性は良好であシ何ら差支えない。Further, at the same time, although the present invention has been described with respect to alcohol or a fuel tank containing alcohol, there is no problem in applying or sharing the present invention to a fuel tank intended for ordinary ganoline as its corrosion resistance is good.
（実施例） 以下に本発明の実施例について述べる。(Example) Examples of the present invention will be described below.
表にＣｒ含有ｉを中心に変化させた鋼成分の鋼板を用い
、脱脂、酸洗工程を経て通常電気メツキ前処理を施して
から、鋼板の少なくとも片面に各々本発明の被覆層を所
定量節した本発明の鋼板について、タンク形状を想定し
た角筒絞シ材について、各々タンク外面及びタンク内面
を対象とした性能評価を行なった結果を示した。Using a steel plate whose steel composition is mainly changed with Cr content i on the front side, the steel plate is subjected to a degreasing and pickling process, and then subjected to normal electroplating pretreatment, and then a predetermined amount of the coating layer of the present invention is applied to at least one side of the steel plate. Regarding the steel plate of the present invention, performance evaluation was performed on the outer surface of the tank and the inner surface of the tank, respectively, and the results are shown for the rectangular tube drawn material assuming the shape of a tank.
この結果、本発明の製品は比較材に較べ、アルコールも
しくはアルコールを含有する燃料容器用鋼板として極め
てすぐれた特性を有する。As a result, the product of the present invention has extremely superior properties as a steel sheet for alcohol or alcohol-containing fuel containers, compared to comparative materials.
尚、評価試験については以下の方法で実施した。The evaluation test was conducted in the following manner.
１、 タンク内面の評価試験
（Ａ）ガソホール対象試験
（８４，５％ガソリン＋１５％メタノール＋０．２％ギ
酸＋１％ＮａＣ６水溶液を０．３％含有）系溶液（Ｂ）
ガソホール対象試験
（７９，８％ガソリン＋１９％エタノール＋０．２％さ
く酸＋１チ蒸溜水）系溶液
（Ｃ）ガソホール対象試験
（８２，４９％ガソリン＋７．５％メタノール＋０．０
１多ギ酸）系溶液
（Ｄ） １００％アルコール対象試験
（９５％メダノール＋０．２％ギ醒＋０．１％ホルムア
ルデヒド＋１％ＮａＣ２水溶液を４．７ｅｌＪ含有）系
水溶液
の各水溶液を用い、５００Ｘ５００＋ｉｉのブランクサ
イズから２００Ｘ２００ｗＸ８０ｆＪ＋高さの角筒絞シ
試験片を作成、該試験片の内部に上記腐食溶液を充填密
封して、約１年間振動と静置金繰り返し、その内部の腐
食状況を判定した。1. Tank inner surface evaluation test (A) Gasohol target test (contains 0.3% of 84.5% gasoline + 15% methanol + 0.2% formic acid + 1% NaC6 aqueous solution) system solution (B)
Gasohol target test (79.8% gasoline + 19% ethanol + 0.2% sulfuric acid + 1% distilled water) system solution (C) Gasohol target test (82,49% gasoline + 7.5% methanol + 0.0
1 polyformic acid) system solution (D) 100% alcohol target test (containing 4.7elJ of 95% medanol + 0.2% aqueous solution + 0.1% formaldehyde + 1% NaC2 aqueous solution) system aqueous solution, 500 x 500 + ii blank A rectangular cylindrical test piece of size 200 x 200 w x 80 fJ + height was prepared, the inside of the test piece was filled with the above corrosion solution and sealed, and vibration and standing were repeated for about 1 year to determine the corrosion state inside the test piece.
２、 タンク外面の評価試験
（ＩＯサイクルコローノヨン試験
■塩水噴霧（５％ＮａＣｊ ３５℃×４時間）→■乾燥
（７０℃湿度６０％ ２時間）→■湿潤（４９℃湿度９
８チ ２時間）→■冷却（−２０℃×２時間）→■塩水
噴霧
■〜■が１サイクル
上記サイクルを３５サイクル繰シ返し、腐食部の板厚減
少及び錆の発生状況を総合的に評価し、その耐食性能を
評価した。2. Tank outer surface evaluation test (IO cycle corona test ■ Salt water spray (5% NaCj 35℃ x 4 hours) → ■ Dry (70℃ humidity 60% 2 hours) → ■ Wet (49℃ humidity 9
8chi 2 hours)→■Cooling (-20℃ x 2 hours)→■Salt water spray■~■1 cycle Repeat the above cycle 35 times to comprehensively check the thickness reduction in corroded areas and the occurrence of rust. The corrosion resistance performance was evaluated.
尚、本発明の燃料容器外面に相当する面は、１００９／
ｌ Ｃｒ０５−０．６ Ｅｌ／ｍ２Ｓｏ４−２系浴を用
い、１０Ａ／ｄｍ２−１秒間の陰極電解処理により、ｌ
Ｂ、７ｍ９／ｒｎ２のクロメート処理を行なったもの
について、性能評価を行なった。Incidentally, the surface corresponding to the outer surface of the fuel container of the present invention is 1009/
Using lCr05-0.6 El/m2So4-2 bath, l0A/dm2-1 second cathodic electrolytic treatment
B. Performance evaluation was performed on those subjected to chromate treatment of 7 m9/rn2.
（０塗装後耐食性試験
前記の評価試験（Ｅ）のクロメート系処理全；ＫＵ Ｌ
：’ｊ評価材を用い、角筒絞シ後にエポキシ−フェノ
ール系塗料ｔｌ−２５μ塗装後、直径約７．５ ｍ径の
細石を圧力３．５μｇ／ｒｎ２で１０秒間、１ノ当シ２
Ｉが衝突するようにチッピングさせてから、前記（Ｅ’
）のサイクルテスト条件３０サイクルのテストを実施し
、チッピング部からの赤錆発生状況とその部分の板厚減
少の測定及びチッピング部以外の塗装面のブリスターの
発生状況よシ、その塗装後耐食性を評価した。(0 Corrosion resistance test after painting All chromate treatment of the above evaluation test (E); KU L
:'j Using the evaluation material, after drawing the square tube and painting it with epoxy-phenol paint TL-25μ, a fine stone with a diameter of about 7.5 m was crushed once for 10 seconds at a pressure of 3.5 μg/rn2.
After chipping so that I collides, the above (E'
) cycle test conditions 30 cycles of tests were conducted to measure the occurrence of red rust from the chipping area and the decrease in plate thickness in that area, as well as the occurrence of blisters on the painted surface other than the chipping area, and to evaluate the corrosion resistance after painting. did.
３、成形加工性評価試験
ブランクサイズ０．８Ｘ５００Ｘ５００■ １潤滑油塗
布後にしわ押え圧力３０Ｔの条件で１５０Ｘ１５０ｓｏ
＋＋角のポンチで角筒絞シを行ない、絞ｂｉさの限界と
角筒絞り材・外面のカジリ発生状況、被覆層の粉末状の
剥離状況（バクダリング現象）よシ、その成形加工性を
評価した。3. Molding processability evaluation test blank size 0.8 x 500 x 500 ■ 1 After applying lubricating oil, press 150 x 150 so under wrinkle pressure of 30 T
++ Draw a square tube with a square punch and evaluate the limit of drawing thickness, occurrence of galling on the square tube drawing material/outer surface, peeling of powdery coating layer (bacterial phenomenon), and formability. did.
第１図はクロム含有量の異る鋼板とニッケル板をカップ
ルさせて１％ＮａＣ２水溶液中に浸漬した場合に流れる
電流を測定しこれを鋼中Ｃｒ量との関係で表わした線図
である。
１：Ｎｌ板 ２：Ｃｒ鋼
３ ： １％ＮａＣ１溶液
第１図
Ｃｒｉ＆Ａ量九）FIG. 1 is a diagram showing the current flowing when a steel plate and a nickel plate having different chromium contents are coupled and immersed in a 1% NaC2 aqueous solution in relation to the Cr content in the steel. 1: Nl plate 2: Cr steel 3: 1% NaCl solution (Figure 1 Cri & A amount 9)
Claims (2)
に、Ｎｉ、Ｓｎ、Ｃｏ及びこれらの合金、もしくは該金
属にＰ、Ｍｏ、Ｃｒの１種または２種以上を含有せしめ
た合金のメッキ被覆層を施した事を特徴とするアルコー
ルもしくはアルコール含有撚料容器用鋼板。(1) C in weight%: 0.02% or less Cr: 3 to 20% Acid-soluble Al; 0.005 to 0.10% The balance is unavoidable impurities and at least one side of the steel plate made of iron is coated with Ni, Sn, Co. and a steel plate for an alcohol or alcohol-containing twist container, characterized in that a plating coating layer of an alloy thereof, or an alloy containing one or more of P, Mo, and Cr is applied to the metal.
．０３〜０．５％含有し残部不可避不純物及び鉄よりな
る鋼板の少なくとも片面にＮｉ、Ｓｎ、Ｃｏ、及びこれ
らの合金、もしくは該金属にＰ、Ｍｏ、Ｃｒの１種また
は２種以上を含有せしめた合金のメッキ被覆層を施した
事を特徴とするアルコールもしくはアルコール含有燃料
容器用鋼板。(2) C in weight%: 0.02% or less Cr: 3-20% Acid-soluble Al: 0.005-0.10% One or more of Ti, Nb, Zr, and V are each 0
．． Ni, Sn, Co, and alloys thereof, or the metal contains one or more of P, Mo, and Cr on at least one side of a steel plate containing 03 to 0.5% and the remainder being unavoidable impurities and iron. A steel sheet for use in alcohol or alcohol-containing fuel containers, characterized by being coated with a plating layer of an alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17995984A JPS6160896A (en) | 1984-08-29 | 1984-08-29 | Steel plate for vessel for alcohol or alcohol-containing fuel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17995984A JPS6160896A (en) | 1984-08-29 | 1984-08-29 | Steel plate for vessel for alcohol or alcohol-containing fuel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6160896A true JPS6160896A (en) | 1986-03-28 |
| JPS64475B2 JPS64475B2 (en) | 1989-01-06 |
Family
ID=16074955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17995984A Granted JPS6160896A (en) | 1984-08-29 | 1984-08-29 | Steel plate for vessel for alcohol or alcohol-containing fuel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6160896A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4979996A (en) * | 1988-04-25 | 1990-12-25 | Nippon Steel Corporation | Process for preparation of grain-oriented electrical steel sheet comprising a nitriding treatment |
| US4979997A (en) * | 1989-05-29 | 1990-12-25 | Nippon Steel Corporation | Process for producing grain-oriented electrical steel sheet having superior magnetic and surface film characteristics |
| US5190597A (en) * | 1990-11-07 | 1993-03-02 | Nippon Steel Corporation | Process for producing grain-oriented electrical steel sheet having improved magnetic and surface film properties |
| US5261972A (en) * | 1991-10-28 | 1993-11-16 | Nippon Steel Corporation | Process for producing grain-oriented electrical steel strip having high magnetic flux density |
| US5308411A (en) * | 1990-06-20 | 1994-05-03 | Nippon Steel Corporation | Ultrahigh silicon, grain-oriented electrical steel sheet and process for producing the same |
| JP2008076072A (en) * | 2006-09-19 | 2008-04-03 | Hitachi Engineering & Services Co Ltd | Method for inspecting surface rust of cylindrical member with its surface coated and device therefor |
| WO2011118848A1 (en) * | 2010-03-25 | 2011-09-29 | 新日本製鐵株式会社 | Steel sheet for vessel having excellent corrosion resistance |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5767186A (en) * | 1980-10-08 | 1982-04-23 | Nippon Steel Corp | Steel plate for fuel container |
| JPS5845397A (en) * | 1981-09-14 | 1983-03-16 | Nippon Steel Corp | Production of surface treated steel plate for fuel vessel |
| JPS5845396A (en) * | 1981-09-11 | 1983-03-16 | Nippon Steel Corp | Ni-zn alloy plated steel plate for fuel vessel |
-
1984
- 1984-08-29 JP JP17995984A patent/JPS6160896A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5767186A (en) * | 1980-10-08 | 1982-04-23 | Nippon Steel Corp | Steel plate for fuel container |
| JPS5845396A (en) * | 1981-09-11 | 1983-03-16 | Nippon Steel Corp | Ni-zn alloy plated steel plate for fuel vessel |
| JPS5845397A (en) * | 1981-09-14 | 1983-03-16 | Nippon Steel Corp | Production of surface treated steel plate for fuel vessel |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4979996A (en) * | 1988-04-25 | 1990-12-25 | Nippon Steel Corporation | Process for preparation of grain-oriented electrical steel sheet comprising a nitriding treatment |
| US4979997A (en) * | 1989-05-29 | 1990-12-25 | Nippon Steel Corporation | Process for producing grain-oriented electrical steel sheet having superior magnetic and surface film characteristics |
| US5308411A (en) * | 1990-06-20 | 1994-05-03 | Nippon Steel Corporation | Ultrahigh silicon, grain-oriented electrical steel sheet and process for producing the same |
| US5190597A (en) * | 1990-11-07 | 1993-03-02 | Nippon Steel Corporation | Process for producing grain-oriented electrical steel sheet having improved magnetic and surface film properties |
| US5261972A (en) * | 1991-10-28 | 1993-11-16 | Nippon Steel Corporation | Process for producing grain-oriented electrical steel strip having high magnetic flux density |
| JP2008076072A (en) * | 2006-09-19 | 2008-04-03 | Hitachi Engineering & Services Co Ltd | Method for inspecting surface rust of cylindrical member with its surface coated and device therefor |
| WO2011118848A1 (en) * | 2010-03-25 | 2011-09-29 | 新日本製鐵株式会社 | Steel sheet for vessel having excellent corrosion resistance |
| CN102822387A (en) * | 2010-03-25 | 2012-12-12 | 新日本制铁株式会社 | Steel sheet for vessel having excellent corrosion resistance |
| JP5158267B2 (en) * | 2010-03-25 | 2013-03-06 | 新日鐵住金株式会社 | Steel plate for containers with excellent corrosion resistance |
| KR101431941B1 (en) * | 2010-03-25 | 2014-08-19 | 신닛테츠스미킨 카부시키카이샤 | Steel sheet for vessel having excellent corrosion resistance |
| US8993118B2 (en) | 2010-03-25 | 2015-03-31 | Nippon Steel & Sumitomo Metal Corporation | Steel sheet for container excellent in corrosion resistance |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS64475B2 (en) | 1989-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1315846B1 (en) | Hexavalent chromium-free surface-treating agent for sn- or al-based coated steel sheet, and surface treated steel sheet | |
| US20090053551A1 (en) | Surface Treated Stainless Steel Sheet for Automobile Fuel Tank and for Automobile Fuel Pipe with Excellent Salt Corrosion Resistance and Weld Zone Reliability and Surface Treated Stainless Steel Welded Pipe for Automobile Fuel Inlet Pipe Excellent in Pipe Expandability | |
| JP3497413B2 (en) | Surface treated steel sheet for fuel containers with excellent corrosion resistance, workability and weldability | |
| EP0210302B1 (en) | Tinned steel sheet having a high degree of corrosion resistance and a method of producing the same | |
| US20030196715A1 (en) | Fuel tank or fuel pipe exhibiting excellent corrosion resistance and method for manufacturing the same | |
| JPS6160896A (en) | Steel plate for vessel for alcohol or alcohol-containing fuel | |
| JP3485457B2 (en) | Corrosion-resistant steel plates for fuel tanks with excellent corrosion resistance and weldability | |
| US6866944B2 (en) | Automobile fuel container material excellent in environment compatibility and automobile fuel container | |
| JPS6366916B2 (en) | ||
| JPH0525950B2 (en) | ||
| JPS61246058A (en) | High corrosion-resistant coated steel plate for fuel vessel | |
| JPS6168238A (en) | Coated steel plate for weldable high corrosion-resistant fuel vessel | |
| JPS61270389A (en) | Steel sheet for fuel vessel | |
| JPS64474B2 (en) | ||
| JPH0768634B2 (en) | Zinc-based plated steel sheet with excellent corrosion resistance, coating performance and workability | |
| JPS6187881A (en) | Steel sheet for alcohol or alcoholic fuel container | |
| JPH0689475B2 (en) | Steel plate for fuel container | |
| JPS61266596A (en) | Steel sheet for fuel container | |
| JPS642195B2 (en) | ||
| JPS61270388A (en) | Steel sheet for fuel vessel | |
| JPS61246346A (en) | Surface treated steel sheet for fuel vessel | |
| JPS61270390A (en) | Steel sheet for fuel vessel | |
| JPS61243192A (en) | Surface-treated steel sheet for fuel vessel | |
| JPS6164442A (en) | Steel plate for weldable high corrosion-resistant fuel vessel | |
| JPH05311464A (en) | Steel plate of vessel for alcohol or alcohol-containing fuel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |