JPS63125698A - Composite zinc electroplated steel sheet - Google Patents
Composite zinc electroplated steel sheetInfo
- Publication number
- JPS63125698A JPS63125698A JP26978486A JP26978486A JPS63125698A JP S63125698 A JPS63125698 A JP S63125698A JP 26978486 A JP26978486 A JP 26978486A JP 26978486 A JP26978486 A JP 26978486A JP S63125698 A JPS63125698 A JP S63125698A
- Authority
- JP
- Japan
- Prior art keywords
- corrosion resistance
- zinc
- steel sheet
- test
- electroplated steel
- 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.)
- Pending
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 51
- 239000010959 steel Substances 0.000 title claims abstract description 50
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 28
- 239000011701 zinc Substances 0.000 title claims description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 25
- 239000002131 composite material Substances 0.000 title abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 abstract description 49
- 238000005260 corrosion Methods 0.000 abstract description 49
- 238000009713 electroplating Methods 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract 2
- 238000007747 plating Methods 0.000 description 29
- 229910001297 Zn alloy Inorganic materials 0.000 description 21
- 150000003839 salts Chemical class 0.000 description 16
- 239000007921 spray Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 5
- 229910001335 Galvanized steel Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000008397 galvanized steel Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229910004647 CaMoO4 Inorganic materials 0.000 description 1
- 241000345998 Calamus manan Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GVGLGOZIDCSQPN-PVHGPHFFSA-N Heroin Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GVGLGOZIDCSQPN-PVHGPHFFSA-N 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
この発明は、自動車車体の塗装後の耐外面腐食性および
側内面腐食性に優れた亜鉛系複合電気めっき鋼板に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a zinc-based composite electroplated steel sheet that is excellent in corrosion resistance on the exterior surface and corrosion resistance on the inner side surface of an automobile body after painting.
近年、自動車車体に対する耐久性の要求が高まり、自動
車用鋼板として、防錆鋼板の使用量が増大している。In recent years, demands for durability of automobile bodies have increased, and the amount of rust-proof steel sheets used as automobile steel sheets has increased.
このような防錆鋼板として、電気亜鉛めっき鋼板、溶融
亜鉛めっき鋼板、熱処理合金めっき鋼板、鉄−亜鉛合金
電気めっき鋼板、ニッケルー亜鉛合金電気めっき鋼板等
、多品種に及ぶ鋼板が知られている。A wide variety of steel sheets are known as such rust-proof steel sheets, such as electrogalvanized steel sheets, hot-dip galvanized steel sheets, heat-treated alloy-plated steel sheets, iron-zinc alloy electroplated steel sheets, and nickel-zinc alloy electroplated steel sheets.
自動車車体の内板または外板内面のような部位では、比
較的湿った腐食環境となっているが、塗装としては電着
塗装までしか施されず、ここでの塗装後側食性が重要視
されている。上述の防錆鋼板は、この湿った環境での腐
食（以下内面腐食という）の発生個所に多く使用されて
おり、その使用形態は様々である。Areas such as the inner and outer surfaces of automobile bodies are relatively humid and corrosive environments, but the only coating that can be applied is electrodeposition, and the lateral corrosion after coating is important. ing. The above-mentioned anticorrosion steel plate is often used in locations where corrosion occurs in this humid environment (hereinafter referred to as internal corrosion), and there are various forms of use thereof.
上述した防錆鋼板の中でも、鉄−亜鉛合金電気めっき鋼
板は、耐内面腐食性に特に優れていることから、自動車
車体の内板用鋼板および内面がめつきされた外板用鋼板
として、古くから使用されている。鉄−亜鉛合金電気め
っき鋼板におけるめっき皮膜中の鉄含有割合は、加工性
等も考慮して、一般に１０〜２５ｗｔ、％である。Among the above-mentioned rust-proof steel sheets, iron-zinc alloy electroplated steel sheets have particularly excellent internal corrosion resistance, and have long been used as steel sheets for the inner panels of automobile bodies and steel plates for outer panels with plated inner surfaces. It is used. The iron content in the plating film of an iron-zinc alloy electroplated steel sheet is generally 10 to 25 wt.%, taking into consideration workability and the like.
また、ニッケルー亜鉛合金電気めっき鋼板も、耐内面腐
食性に優れていることから、鉄−亜鉛合金電気めっき鋼
板と同じように、自動車用鋼板として使用されている。Furthermore, nickel-zinc alloy electroplated steel sheets are also used as steel sheets for automobiles in the same way as iron-zinc alloy electroplated steel sheets because they have excellent internal corrosion resistance.
ニッケルー亜鉛合金電気めっき鋼板におけるめっき皮膜
中のニッケル含有割合は、一般に１０〜１３ｗｔ、係で
ある。The nickel content in the plating film of a nickel-zinc alloy electroplated steel sheet is generally 10 to 13 wt.
しかるに、最近では、各種の規制および高級化指向から
、自動車車体の外板用防錆鋼板は、その外面にも防御処
理を施すことが要求されている。However, in recent years, due to various regulations and the trend toward higher quality products, rust-proof steel plates for the exterior panels of automobile bodies are required to have a protective treatment applied to their exterior surfaces as well.
ところが、この自動車車体の外板外面での腐食環境は、
内板および外板内面のような湿った環境ではなく乾いた
環境であり、ここでは、一般にスキャグローソヨンと称
する内向腐食とは明らかに異なった腐食（以下外面腐食
という）を生じる。However, the corrosive environment on the outer surface of the car body is
It is a dry environment rather than a moist environment such as the inner surface of the inner and outer panels, and here corrosion (hereinafter referred to as outer surface corrosion) occurs which is clearly different from inward corrosion, which is generally referred to as skag growth corrosion.
耐外面腐食性の評価は、一般に大気暴露試験、および塩
水散布大気暴露試験によって行われている。亜鉛電気厚
めつき鋼板および溶融合金化亜鉛めっき鋼板の耐外向腐
食性は、比較的良好であるが、亜鉛電気薄めつき鋼板お
よび亜鉛合金電気めっき鋼板の耐外面腐食性は悪い。External corrosion resistance is generally evaluated by atmospheric exposure tests and salt water spray atmospheric exposure tests. The external corrosion resistance of zinc electroplated steel sheets and hot-fusion galvanized steel sheets is relatively good, but the external corrosion resistance of zinc electrolytic thinned steel sheets and zinc alloy electroplated steel sheets is poor.
例えは、耐内面腐食性は良好な、１０〜２５ｗｔ、％の
鉄を含有する鉄−亜鉛合金電気めっき鋼板でも、上述し
た耐外面腐食性の評価のための２試験結果は悪い。For example, even though the iron-zinc alloy electroplated steel sheet containing 10 to 25 wt.% iron has good internal corrosion resistance, the results of the above-mentioned two tests for evaluating external corrosion resistance are poor.
耐水性および耐クレータリング性向上を狙った防錆鋼板
として−１−下２層の鉄−亜鉛合金電気めっき層からな
り、上層のめつき層の鉄含有割合が下層よシも多い、鉄
−亜鉛合金電気めっき鋼板が知られている。しかしなが
ら、このような鉄−亜鉛合金電気めっき鋼板においても
、外面腐食は主として下層によって支配されること、お
よび鉄の含有割合が増加するほどかえって乾燥環境での
耐食性能が低下する傾向にあることなどの理由から、耐
外面腐食性は不十分である。As a rust-preventing steel sheet aimed at improving water resistance and cratering resistance - 1 - It consists of two lower iron-zinc alloy electroplated layers, and the iron content of the upper plating layer is higher than that of the lower layer. Zinc alloy electroplated steel sheets are known. However, even in such iron-zinc alloy electroplated steel sheets, the outer surface corrosion is mainly controlled by the lower layer, and as the iron content increases, the corrosion resistance performance in a dry environment tends to decrease. For these reasons, the external corrosion resistance is insufficient.
このようなことから、自動車用の防錆鋼板として、耐内
面腐食性および耐外向腐食性の両方が優れている亜鉛合
金電気めっき鋼板の開発が望まれているが、かかる特性
を具備した亜鉛合金電気めつ＠鋼板は、寸だ提案されて
いない。Therefore, it is desired to develop a zinc alloy electroplated steel sheet that has excellent both internal corrosion resistance and external corrosion resistance as a rust-proof steel sheet for automobiles. Electric eyeglasses @ steel plates have not been proposed at all.
従って、この発明の目的は、自動車用の防錆銅板として
好適な、耐内面腐食性および耐外向腐食性の両方が優れ
ている、亜鉛系複合電気めっき鋼板を提供することにあ
る。Therefore, an object of the present invention is to provide a zinc-based composite electroplated steel sheet that is suitable as a rust-proof copper sheet for automobiles and is excellent in both internal corrosion resistance and external corrosion resistance.
本発明者等は、上述の問題を解決するために鋭意研究を
重ねた。その結果、亜鉛合金電気めっき鋼板のめつき層
を、チタン、マンガン、アルミニウム、ストロンチウム
、クロム、モリブデン、マグネシウムおよびタングステ
ンの各々の酸化物のうちの少なくとも１つが、０．０１
〜１０ｗｔ、％の範囲内で含有する亜鉛複合電気めっき
層によって構成すれば、亜鉛複合電気めっき鋼板の耐外
面腐食性（耐スキャグコロージョン）の向上が図られ、
自動用防錆鋼板として好適な、優れた耐内面腐食性およ
び耐外向腐食性が得られることを知見した。The present inventors have conducted extensive research in order to solve the above-mentioned problems. As a result, at least one of the oxides of titanium, manganese, aluminum, strontium, chromium, molybdenum, magnesium, and tungsten was added to the plating layer of the zinc alloy electroplated steel sheet by 0.01%.
By forming a zinc composite electroplating layer containing within the range of ~10wt%, the outer surface corrosion resistance (scag corrosion resistance) of the zinc composite electroplated steel sheet can be improved,
It has been found that excellent internal corrosion resistance and external corrosion resistance suitable for use as a rust-preventing steel plate for automatic use can be obtained.
この発明は、上述の知見に基づいて外されたものであっ
て、鋼板の少なくとも１つの表面上に、チタン、マンガ
ン、アルミニウム、ストロンチウム、クロム、モリブデ
ン、マグネシウムおよびタングステンの各々の酸化物の
うちの少なくとも１つを、０．０１〜１０ｗｔ、％含有
し、残りが亜鉛、または亜鉛および鉄、才たけ亜鉛およ
びニッケルからなる亜鉛複合めっき層が形成されている
ことに特徴を有するものである。The present invention was developed based on the above-mentioned findings, and includes oxides of each of titanium, manganese, aluminum, strontium, chromium, molybdenum, magnesium, and tungsten on at least one surface of a steel sheet. It is characterized in that a zinc composite plating layer is formed, containing at least one of 0.01 to 10 wt%, and the rest being zinc, or zinc and iron, or zinc and nickel.
この発明において、亜鉛めっき層中に、チタン、マンガ
ン、アルミニウム、ストロンチウム、クロム、モリブデ
ン、マグネシウムおよびタングステンのうちの少なくと
も１つを酸化物の形態によって含有させることにより、
酬内向腐食性および耐外面腐食性が共に向上するメカニ
ズムの詳細は不明であるが、鋼板の腐食過程において、
これらの金属酸化物が鋼板の腐食を抑制するものと考え
られる。In this invention, by containing at least one of titanium, manganese, aluminum, strontium, chromium, molybdenum, magnesium, and tungsten in the form of an oxide in the galvanized layer,
The details of the mechanism by which both internal corrosion resistance and external corrosion resistance are improved are unknown, but in the corrosion process of steel plates,
It is thought that these metal oxides suppress corrosion of steel sheets.
チタン、マンガン、アルミニウム、ストロンチウム、ク
ロム、モリブデン、マグネシウムおよびタングステンの
各々の酸化物のうちの少なくとも１つの、めっき層中に
おける含有割合を０．０１〜１０ｗｔ、、％の範囲内に
限定した理由は、０．０１ｗｔ、％未満では上述した作
用に所望の効果が得られず、一方、１．Ｏｗｔ、％以上
は現状技術では含有させることができないからである。The reason why the content ratio of at least one of the oxides of titanium, manganese, aluminum, strontium, chromium, molybdenum, magnesium, and tungsten in the plating layer is limited to within the range of 0.01 to 10 wt% is , less than 0.01wt%, the desired effects described above cannot be obtained; This is because it is not possible to contain more than Owt% with the current technology.
この発明において、基本成分を鉄−亜鉛またはニッケル
ー亜鉛とすることにより、基本成分が亜鉛のみの場合よ
シも耐内面腐食性をよシ向上させることができる。In this invention, by using iron-zinc or nickel-zinc as the basic component, internal corrosion resistance can be improved even more than when the basic component is only zinc.
次にこの発明の亜鉛系複合電気めっき鋼板の性能を、実
施例により詳述する。Next, the performance of the zinc-based composite electroplated steel sheet of the present invention will be explained in detail using examples.
下記（１）のめつき浴組成および下記（２）のめつき条
件によって、鋼板に亜鉛合金電気めっき処理を施して、
第１表に示すこの発明の範囲内の亜鉛合金めっき層を有
する亜鉛合金電気めっき鋼板の供試体（以下本発明の供
試体という）Ａ１−３０と、第１表に併せて示すこの発
明の範囲外の供試体（以下比較用供試体という） Ａ
１〜１１とを調製した。A zinc alloy electroplating process is performed on a steel plate according to the plating bath composition shown in (1) below and the plating conditions shown below (2),
Specimen A1-30 of a zinc alloy electroplated steel sheet having a zinc alloy plating layer within the scope of the present invention shown in Table 1 (hereinafter referred to as the specimen of the present invention) and the scope of the present invention also shown in Table 1 Outside specimen (hereinafter referred to as comparative specimen) A
1 to 11 were prepared.
（１）めっき浴組成
（イ）金属イオン濃度
０）基本成分が亜鉛のみの場合
ｚｎ ： ６０〜１４０！／１
■基本成分が亜鉛および鉄の場合
Ｚｎ：３０〜６０ｙ／ｌ
Ｆｅ ： ５０〜７５ ｙ／ＩＪ
Ｃ６Ｈ８０７： １５ｆＪ／ｌ！
■基本成分が亜鉛およびニッケルの場合Ｚｏ：３０〜６
０り／ｌ
Ｎｉ ： ５０〜７５１！／１
（ロ）添加剤
電導補助剤およびＰｔ（緩衝剤
（２）めっき条件
（イ）めっき浴の温度：５０°Ｃ
（ロ）めっき電流密度：５０Ａ、’面′（ハ）めっき浴
のＰＨ： １〜３
に）めっき量： ］、 −６０！／ｍ”／ （片面）（
＝ｔ９ チタン、マンガン、アルミニウム、ストロンチ
ウム、クロム、モリブデン、マグネシウムおよびタング
ステンの各々の酸化物は、カチオン系外向活性剤を含ん
だ別のめつき液中に浸漬し、一定時間撹拌して前処理を
行う。(1) Plating bath composition (a) Metal ion concentration 0) When the basic component is only zinc zn: 60-140! /1 ■When the basic components are zinc and iron Zn: 30-60y/l Fe: 50-75y/IJ C6H807: 15fJ/l! ■When the basic components are zinc and nickel Zo: 30-6
0ri/l Ni: 50~751! /1 (b) Additive conductivity aid and Pt (buffer) (2) Plating conditions (a) Plating bath temperature: 50°C (b) Plating current density: 50A, 'surface' (c) PH of plating bath : 1 to 3) Plating amount: ], -60! /m”/ (one side) (
=t9 The oxides of titanium, manganese, aluminum, strontium, chromium, molybdenum, magnesium, and tungsten are pretreated by immersing them in a separate plating solution containing a cationic external activator and stirring for a certain period of time. conduct.
本発明の供試体茄８ 、１２ 、１．７ 、３０および
比較用供試体扁６および７に対しては、更に、上層とし
ての鉄−亜鉛合金電気めっき処理を、下記（３）のめつ
き浴組成および下記（４）のめつき条件によって施した
。For the test specimens No. 8, 12, 1.7, and 30 of the present invention and the comparative specimens No. 6 and No. 7, an iron-zinc alloy electroplating treatment as an upper layer was performed as described in (3) below. The plating was performed using the bath composition and the plating conditions shown in (4) below.
（３）めっき浴組成
（イ）金属イオン濃度
Ｚｎ：６ｙ／ｌ
Ｆ’ｅ ： ９５ ！／ｌ）
（ロ）添加剤
電導補助剤およびＰＨ緩衝剤
（２）めっき条件
（イ）めっき浴の温度：５０°Ｃ
（ロ）めっき電流密度： ５０Ａ／ｄｔｒ？０うめつき
浴のＰｌ−１： １〜３
に）めっき量：３ｙ／ぜ
次いで、上述の亜鉛合金電気めっきを施した本発明の供
試体篇１〜３０と、比較用供試体篇１〜１１とに対して
、各々、フルディップタイプのリン酸塩処理を施して、
次いでカチオンタイプの電着塗装（２０μｍ）を行なっ
た。(3) Plating bath composition (a) Metal ion concentration Zn: 6y/l F'e: 95! /l) (b) Additive conductivity aid and PH buffer (2) Plating conditions (a) Plating bath temperature: 50°C (b) Plating current density: 50A/dtr? Pl-1 of the 0 plating bath: 1 to 3) Plating amount: 3y/Z Next, the above-mentioned zinc alloy electroplating was performed on the specimens 1 to 30 of the present invention and the comparative specimens 1 to 11. and were subjected to full-dip phosphate treatment, respectively.
Next, cationic electrodeposition coating (20 μm) was performed.
■耐内面腐食性試験
このようにして塗膜の形成された供試体について、次に
述べる耐内面腐食性試験を施し、その結果を第１表に示
した。(2) Internal Corrosion Resistance Test The specimens on which the coating film was formed in this way were subjected to the following internal corrosion resistance test, and the results are shown in Table 1.
上述の塗装供試体にクロスカットを入れ、塩水噴霧試験
および複合サイクル試験（塩水噴震、塩水浸漬および乾
燥を複数回繰り返して行う試験）を一定期間行い、クロ
スカット部のふくれ程度、赤錆の発生程度について総合
的に評価した。A cross-cut was made in the above-mentioned painted specimen, and a salt spray test and a combined cycle test (a test in which salt water spray, salt water immersion, and drying are repeated multiple times) were conducted for a certain period of time, and the extent of blistering at the cross-cut part and the occurrence of red rust were evaluated. A comprehensive evaluation was made regarding the degree of damage.
■耐外面腐食性試験
上述の電着塗装が施された供試体の塗膜の上に、ポリエ
ステルタイプの中塗り塗料を使用し、３０〜４０μｍの
中塗り塗装と、同じくポリエステルタイプの上塗り塗料
を使用し、３０〜４０μｍの上塗り塗装とを施した。■ External corrosion resistance test A polyester type intermediate coating paint was used on the paint film of the test piece that had been electrocoated as described above, and a 30-40 μm intermediate coating and a polyester type top coating were applied. A top coat of 30 to 40 μm was applied.
このようにして塗膜の形成された供試体について、次に
述べる耐外面腐食性試験を施し、その結果を第１衣に併
せて示した。The specimens on which the paint film was formed in this way were subjected to the following external corrosion resistance test, and the results are shown in the first coat.
塗膜の形成された供試体にクロスカットを入れクロスカ
ットの施された供試体に対し、大気暴露試験、塩水散布
大気暴露試験を一定期間行い、クロスカット部のふくれ
程度、赤錆の発生程度について総合的に評価した。A cross-cut was made on the specimen with the coating film formed, and the specimen with the cross-cut was subjected to an atmospheric exposure test and a salt water spray atmospheric exposure test for a certain period of time, and the degree of blistering of the cross-cut area and the occurrence of red rust were determined. A comprehensive evaluation was made.
市販の亜鉛電気めっき鋼板であるめっき量４゜’ｆ ／
ｎ？ の比較用供試体ＡＩ ２、および市販の溶融亜鉛
めっき鋼板であるめっき量１２０ Ｐ／ＴＴ？ の比
較用供試体煮１３を使用して、次に述べる耐内面腐食性
試験および耐外面腐食性試験を施し、その結果を第１表
に併せて示した。The plating amount of commercially available zinc electroplated steel sheet is 4゜'f/
n? comparative specimen AI 2, and a commercially available hot-dip galvanized steel sheet with a plating amount of 120 P/TT? Using Comparative Specimen No. 13, the following internal corrosion resistance test and external corrosion resistance test were conducted, and the results are also shown in Table 1.
■耐内面腐食性試験
供試体にクロスカットを入れ、クロスカットの施された
供試体に対し、塩水噴霧試験および複合サイクル試験を
一定期間行い、クロスカット部のふくれ程度、赤錆の発
生程度について総合的に評価した。■Internal corrosion resistance test A cross cut is placed on the specimen, and the cross cut specimen is subjected to a salt spray test and a combined cycle test for a certain period of time, and the degree of blistering of the cross cut part and the degree of red rust are comprehensively evaluated. evaluated.
■耐外面腐食性試験
供試体にクロスカットを入れ、クロスカットの施された
供試体に対し、大気暴露試験、塩水散布大気暴露試験を
一定期間行い、クロスカット部のふくれ程度、赤錆の発
生程度について総合的に評価した。■ External corrosion resistance test A cross cut was placed on the specimen, and the cross cut specimen was subjected to an atmospheric exposure test and a salt water spray atmospheric exposure test for a certain period of time. A comprehensive evaluation was made.
上述した各供試体における評価基準は次の通りである。The evaluation criteria for each specimen described above are as follows.
◎印：優
○印：良
△印：やや不良
×印：不良
第１表に示すように、めっき層がＦｅ −Ｚｎ 合金層
のみからなる比較用供試体Ａ１〜７は、耐外面腐食性試
験である大気暴露試験および塩水散布大気暴露試験のい
ずれかまたは両方の結果が劣っていた。◎ mark: Good ○ mark: Good △ mark: Slightly poor The results of either or both of the atmospheric exposure test and salt water spray atmospheric exposure test were inferior.
めっき藤がＮｉ−Ｚｎ 合金層のみからなる比較用供試
体Ａ８は、塩水噴霧試験を除く他の試験結果が劣ってい
た。Comparative specimen A8, in which the plated rattan was composed of only a Ni-Zn alloy layer, had inferior test results except for the salt spray test.
めっき層が、Ｔ１をＴｉＯ２の形態で０．００５ｗｔ、
係含有するＦｅ−Ｚｎ層からなる比較用供試体Ａ９は、
大気暴露試験および塩水散布大気暴露試験の結果が劣っ
ていた。The plating layer contains 0.005wt of T1 in the form of TiO2,
Comparative specimen A9 consisting of a Fe-Zn layer containing
The results of the atmospheric exposure test and salt water spray atmospheric exposure test were poor.
めっき層が、Ａｇ ｔ Ａｌ２Ｏ３の形態で０．００６
ｗｔ、％含有するＡ／ −Ｚｎ 合金層からなる比較用
供試体Ａ１０は、大気暴露試験を除く他の試験の結果が
劣っていた。The plating layer is 0.006 in the form of Ag t Al2O3.
Comparative specimen A10, which is composed of an A/-Zn alloy layer containing A/-Zn, had poor results in all tests except the atmospheric exposure test.
めっき層が、Ｍｏ ｋ ＣａＭｏＯ４の形態で０．００
９ｗｔ、％含有するＭｏ−Ｚｎ 合金層からなる比較用
供試体Ａｌｌは、大気暴露試験を除く他の試験の結果が
劣っていた。The plating layer is in the form of Mo k CaMoO4 of 0.00
Comparative specimen All consisting of a Mo-Zn alloy layer containing 9 wt.% had poor results in all tests except the atmospheric exposure test.
市販の純亜鉛電気めっき鋼板である比較用供試体Ａ１２
は、大気暴露試験を除く他の試験の結果が劣っていた。Comparative specimen A12, which is a commercially available pure zinc electroplated steel sheet
The results of other tests except for the atmospheric exposure test were inferior.
市販の溶融亜鉛めっき鋼板である比較用供試体Ａ１３は
、塩水噴霧試験の結果が劣っていた。Comparative specimen A13, which is a commercially available hot-dip galvanized steel sheet, had poor results in the salt spray test.
これに対して、基本成分を、鉄−亜鉛とした、本発明の
供試体況１〜３．Ａ５〜８ 、 Ａ １１および１２
、 Ａ １５〜１９．Ａ２１および２２ 、’ Ａ２４
〜２６ 、 Ａ ２８〜３０および基本成分を、ニッケ
ルー亜鉛とした本発明の供試体Ａ９は耐内面腐食性試験
である塩水噴霧試験および複合サイクル試験、および、
耐外面腐食性試験である大気暴露試験および塩水散布大
気暴露試験のいずれの試験にも良好な結果を示した。On the other hand, test situations 1 to 3 of the present invention, in which the basic components were iron and zinc. A5-8, A11 and 12
, A 15-19. A21 and 22,' A24
~26, A28~30 and the specimen A9 of the present invention in which the basic component was nickel-zinc were tested for internal corrosion resistance, such as a salt spray test and a combined cycle test, and
It showed good results in both the external corrosion resistance test, the atmospheric exposure test and the salt water spray atmospheric exposure test.
基本成分を、ニッケルー亜鉛とした、本発明の供試体Ａ
４ 、１３ 、２３および２７は、耐内面腐食性試験
である塩水噴霧試験、および、耐外面腐食性試験である
大気暴露試験および塩水散布大気暴露試験に、良好な結
果を示した。Specimen A of the present invention whose basic components are nickel and zinc
Nos. 4, 13, 23, and 27 showed good results in the salt spray test, which is an internal corrosion resistance test, and the atmospheric exposure test and salt water spray atmospheric exposure test, which are external corrosion resistance tests.
基本成分を、亜鉛のみとした、本発明の供試体Ａ １０
、１４および２０は、耐外面腐食性試験である大気暴
露試験および塩水散布大気暴露試験に、良好な結果を示
した。Specimen A 10 of the present invention whose basic component was zinc only
, 14 and 20 showed good results in the atmospheric exposure test and the salt water spray atmospheric exposure test, which are external corrosion resistance tests.
以上説明したように、この発明によれば、耐外面腐食性
および耐内面腐食性に優れた、とりわけ自動車用防錆鋼
板に要求される耐外面腐食性が著しく向上した亜鉛系複
合電気めっき鋼板が得られる産業上極めて有効な効果が
得られる。As explained above, according to the present invention, there is provided a zinc-based composite electroplated steel sheet which has excellent external corrosion resistance and internal corrosion resistance, and in particular has significantly improved external corrosion resistance required for rust-proof steel sheets for automobiles. The resulting industrially extremely effective effects can be obtained.
Claims (1)
ン、アルミニウム、ストロンチウム、クロム、モリブデ
ン、マグネシウムおよびタングステンの各々の酸化物の
うちの少なくとも１つを、０．０１〜１０ｗｔ．％含有
し、残りが亜鉛からなる亜鉛系複合めつき層が形成され
ていることを特徴とする亜鉛系複合電気めつき鋼板。 ２ 鋼板の少なくとも１つの表面上に、チタン、マンガ
ン、アルミニウム、ストロンチウム、クロム、モリブデ
ン、マグネシウムおよびタングステンの各々の酸化物の
うちの少なくとも１つを０．０１〜１０ｗｔ．％含有し
、残りが亜鉛および鉄からなる亜鉛系複合めつき層が形
成されていることを特徴とする亜鉛系複合電気めつき鋼
板。 ３ 鋼板の少なくとも１つの表面上に、チタン、マンガ
ン、アルミニウム、ストロンチウム、クロム、モリブデ
ン、マグネシウムおよびタングステンの各々の酸化物の
うちの少なくとも１つを０．０１〜１０ｗｔ．％含有し
、残りが亜鉛およびニッケルからなる亜鉛系複合めつき
層が形成されていることを特徴とする亜鉛系複合電気め
つき鋼板。Claims: 1. At least one of the oxides of titanium, manganese, aluminum, strontium, chromium, molybdenum, magnesium, and tungsten is added on at least one surface of the steel plate in an amount of 0.01 to 10 wt. % and the remainder is zinc. 2. On at least one surface of the steel plate, 0.01 to 10 wt. % and the remainder is zinc and iron. 3. On at least one surface of the steel plate, 0.01 to 10 wt. % and the remainder is zinc and nickel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26978486A JPS63125698A (en) | 1986-11-14 | 1986-11-14 | Composite zinc electroplated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26978486A JPS63125698A (en) | 1986-11-14 | 1986-11-14 | Composite zinc electroplated steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63125698A true JPS63125698A (en) | 1988-05-28 |
Family
ID=17477109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26978486A Pending JPS63125698A (en) | 1986-11-14 | 1986-11-14 | Composite zinc electroplated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63125698A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54159342A (en) * | 1978-06-08 | 1979-12-17 | Nippon Steel Corp | Manufacture of corrosion resistant zinc composite- electroplated steel products |
| JPS57202866A (en) * | 1981-06-04 | 1982-12-11 | Yoshiteru Takahashi | Axially flat type motor |
| JPS6096786A (en) * | 1983-09-20 | 1985-05-30 | ベスレヘム スチ−ル コ−ポレ−シヨン | Electroplated product and its production |
| JPS61235600A (en) * | 1985-04-12 | 1986-10-20 | Sumitomo Metal Ind Ltd | Zn-ni composite plated steel sheet |
| JPS6250497A (en) * | 1985-08-28 | 1987-03-05 | Sumitomo Metal Ind Ltd | Plated steel sheet having superior workability and formability and its manufacture |
| JPS6267197A (en) * | 1985-09-19 | 1987-03-26 | Sumitomo Metal Ind Ltd | Zn-ni alloy plated steel sheet and its manufacture |
| JPS62224699A (en) * | 1986-03-26 | 1987-10-02 | Nippon Steel Corp | Steel sheet coated with zn-base layer by dispersion plating and having superior weldability |
-
1986
- 1986-11-14 JP JP26978486A patent/JPS63125698A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54159342A (en) * | 1978-06-08 | 1979-12-17 | Nippon Steel Corp | Manufacture of corrosion resistant zinc composite- electroplated steel products |
| JPS57202866A (en) * | 1981-06-04 | 1982-12-11 | Yoshiteru Takahashi | Axially flat type motor |
| JPS6096786A (en) * | 1983-09-20 | 1985-05-30 | ベスレヘム スチ−ル コ−ポレ−シヨン | Electroplated product and its production |
| JPS61235600A (en) * | 1985-04-12 | 1986-10-20 | Sumitomo Metal Ind Ltd | Zn-ni composite plated steel sheet |
| JPS6250497A (en) * | 1985-08-28 | 1987-03-05 | Sumitomo Metal Ind Ltd | Plated steel sheet having superior workability and formability and its manufacture |
| JPS6267197A (en) * | 1985-09-19 | 1987-03-26 | Sumitomo Metal Ind Ltd | Zn-ni alloy plated steel sheet and its manufacture |
| JPS62224699A (en) * | 1986-03-26 | 1987-10-02 | Nippon Steel Corp | Steel sheet coated with zn-base layer by dispersion plating and having superior weldability |
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