JPS63176490A - Surface treated steel sheet having superior corrosion resistance and suitability to phosphating - Google Patents
Surface treated steel sheet having superior corrosion resistance and suitability to phosphatingInfo
- Publication number
- JPS63176490A JPS63176490A JP751387A JP751387A JPS63176490A JP S63176490 A JPS63176490 A JP S63176490A JP 751387 A JP751387 A JP 751387A JP 751387 A JP751387 A JP 751387A JP S63176490 A JPS63176490 A JP S63176490A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- corrosion resistance
- phosphating
- phosphate
- suitability
- 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 28
- 239000010959 steel Substances 0.000 title claims abstract description 28
- 238000005260 corrosion Methods 0.000 title claims abstract description 14
- 230000007797 corrosion Effects 0.000 title claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 27
- 239000010452 phosphate Substances 0.000 claims abstract description 27
- 229910000640 Fe alloy Inorganic materials 0.000 claims abstract description 9
- 238000007747 plating Methods 0.000 claims description 17
- 239000013078 crystal Substances 0.000 abstract description 17
- 239000003973 paint Substances 0.000 abstract description 8
- 238000010422 painting Methods 0.000 abstract description 8
- 238000009713 electroplating Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052827 phosphophyllite Inorganic materials 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はＩｌｋＭ！なリン酸塩結晶皮膜が得られるＺｎ
Ｆｅ系合金電気めっき鋼板に関する。[Detailed Description of the Invention] (Industrial Application Field) The present invention is based on IlkM! Zn that provides a phosphate crystal film
This invention relates to Fe-based alloy electroplated steel sheets.
（従来技術）
Ｚｎ Ｆｅ系合金めっき鋼板は純亜鉛めっき鋼板より
めっき層の亜鉛腐食溶解速度が遅く、耐食性に優れてい
るので、従来より高度の耐食性を必要とする自動単車体
などに使用されている。このめっき鋼板は電気めっき法
または溶融めっき法により製造されているが、めっき層
組成はＦｅ含有率が重量％で１０〜３０％のものである
。これはＦｅ含有率が１０％未満であると、Ｆｅによる
亜鉛腐食溶解速度抑制効果が不十分なため、塗装しても
塗膜を↓
透過侵入しくるＨ２ＯやＣ１イオンなどによりＺｎＯや
Ｚｎ（ＯＨ）ｚなどの腐食生成物を形成して、短期間に
塗膜７クレ（ブリスター）を発生させ、塗膜剥離が生じ
やす（なり、逆に３０％を越えると鋼板の裸耐食性が劣
り、赤錆が発生しやすくなると同時にめっき層の加工性
が著しく悪くなるためである。(Prior art) Zn-Fe alloy-plated steel sheets have a slower zinc corrosion dissolution rate in the plating layer than pure galvanized steel sheets, and have excellent corrosion resistance, so they are used for automobile bodies, etc., which require higher corrosion resistance than before. There is. This plated steel sheet is manufactured by an electroplating method or a hot-dip plating method, and the composition of the plating layer has an Fe content of 10 to 30% by weight. This is because if the Fe content is less than 10%, the effect of suppressing the zinc corrosion dissolution rate by Fe is insufficient, so even if painted, the coating film will be ↓. ) Z and other corrosion products are formed, causing paint film 7 creases (blister) to occur in a short period of time, and paint film peeling is likely to occur (on the contrary, if it exceeds 30%, the bare corrosion resistance of the steel plate is poor, and red rust occurs. This is because, at the same time, the processability of the plating layer becomes significantly worse.
ところでＺｎ−Ｆｅ系合金めっき鋼板を自動単車体に使
用する場合、リン酸塩処理を施して電着塗装するが、リ
ン酸塩処理で形成される皮膜は一般に結晶が針状で粗大
なホパイト［ｔｌｏｐｉｔｅ Ｚｎｚ（ＰＯ＜）２・
４Ｈ２０］系のものより結晶の緻密なホスホフイライ
ト ［Ｐｈｏｓｐｈｏｐｈｉｌｉｔｅ Ｚｎ
２Ｆｅ（ＰＯｎ）ｚ ６ ４１１２０１ 系 のもの
の方が塗Ｉｇ！密着性に優れでいる。By the way, when Zn-Fe alloy-plated steel sheets are used for automobile bodies, they are treated with phosphate and then electrodeposited, but the film formed by phosphate treatment is generally composed of coarse hopite with needle-like crystals [ tropite Znz(PO<)2・
4H20] type, which has a denser crystal structure.
[Phosphophilite Zn
2Fe(POn)z 6 411201 series is better! Excellent adhesion.
（発明が解決しようとする問題点）
しかしながらめっき層のＦｅ含有率が上記のような層成
のめっき鋼板はＦｅ含有率が低いため、リン酸塩皮膜は
ホスホフィライト結晶のものにならず、ホバイト結晶の
ものが主であった。このため塗膜二次密着性や塗装後の
耐食性などの塗装後の性能が劣るという欠点があった。(Problems to be Solved by the Invention) However, since the Fe content of the layered plated steel sheet is low, the phosphate coating does not become a phosphophyllite crystal. The main material was hovite crystal. For this reason, there was a drawback that the performance after painting, such as the secondary adhesion of the paint film and the corrosion resistance after painting, was poor.
リン酸塩皮膜の結晶を主にホスホフィライトのものにす
るには、Ｆｅ含有率を高めればよいのであるが、Ｆｅ含
有率を高めると上記のように種々の問題が生じる。この
ためめっき層表層にさらにＦｅ系の電気めっきを施して
表層のＦｅ含有率を高める方法が提案されている６しか
しこの方法はめっき工程が２工程になるので、製造コス
トの上昇を招いてしまう。In order to make the crystals of the phosphate film mainly composed of phosphophyllite, it is sufficient to increase the Fe content, but increasing the Fe content causes various problems as described above. For this reason, a method has been proposed in which the surface layer of the plating layer is further subjected to Fe-based electroplating to increase the Fe content in the surface layer6. However, this method requires two plating steps, which increases manufacturing costs. .
以上のようなことがらＺｎ Ｆｅ系合金電気めっき鋼
板の場合、耐食性、加工性が従来と同等以上で、１工程
でめっきでき、しかもリン酸塩処理した場合がホスホフ
ィライト主成分になるものにする必要があった。As mentioned above, in the case of Zn-Fe alloy electroplated steel sheets, the corrosion resistance and workability are equal to or higher than conventional ones, it can be plated in one step, and when treated with phosphate, the main component is phosphophyllite. I needed to.
（問題点を解決するための手段）
本発明者らは上記条件を充たすＺｎ−Ｆｅ系合金めっき
鋼板を開発すべく、種々検討した結果、めっき層にＭｎ
を微量添加するとリン酸塩結晶がＩＩｋＷｊなホスホフ
ィライトが主成分のものになり、目的の鋼板が得られる
ことを見出し、本発明を完成したのである。すなわち本
発明は重量％でＦｅ含有率が１０〜３０％であるＺｎ−
Ｆｅ系合金電気めっき鋼板のめっき層にＭｎを０．０１
〜２％添加することによりリン酸塩処理性を向上させた
のである。(Means for Solving the Problems) The present inventors conducted various studies in order to develop a Zn-Fe alloy plated steel sheet that satisfies the above conditions.
They discovered that by adding a small amount of phosphate crystals, the main component is phosphophyllite with IIkWj of phosphate crystals, and the desired steel sheet can be obtained, and the present invention was completed. That is, the present invention uses Zn- with an Fe content of 10 to 30% by weight.
Adding 0.01 Mn to the plating layer of Fe-based alloy electroplated steel sheet
By adding ~2%, the phosphate treatment properties were improved.
本発明でめっき層のＦｅ含有率を１０〜３０％にしたの
は、従来のＺｎ−Ｆｅ系合金めっき鋼板の場合と同理由
であるが、Ｍｎ添加量を０．０１〜２％にしたのは、０
．０１％未満であるとリン酸塩結晶を緻密なホスホフィ
ライトる効果が小さく、２％を越えるとリン酸塩結晶の
非生成部が発生しやすくなるからである。また２％以下
にした他の理由として、電気めっきでＺｎ Ｆｅ合金
めっきする場合、浴のｐＨを３以下に管理しているが、
ｐ］１が３以下の状態でめっき層中のＭｎ含有率を２％
超になるようにするには、Ｍｎ塩を浴中に多量に溶解し
なければならず、コスト上昇を招くからである。In the present invention, the Fe content in the plating layer is set to 10 to 30% for the same reason as in the case of conventional Zn-Fe alloy plated steel sheets, but the Mn addition amount is set to 0.01 to 2%. is 0
．． If it is less than 0.01%, the effect of converting phosphate crystals into dense phosphophyllite is small, and if it exceeds 2%, non-formation areas of phosphate crystals tend to occur. Another reason for setting it below 2% is that when electroplating ZnFe alloy, the pH of the bath is controlled to below 3.
p] 1 is 3 or less, the Mn content in the plating layer is 2%
This is because, in order to make the Mn salt more concentrated, a large amount of Mn salt must be dissolved in the bath, leading to an increase in cost.
本発明のめっき鋼板を製造するのには、例えばＺｎ２＋
濃度１０−５０９／ｅ、Ｆｅ２＋濃度２０−７０９／８
、Ｍｎ２＋濃度３−４０９／ｅ、 ｐＨ３以下の酸性め
っき浴で電流密度１０〜２０〇八／ｄ鵠２、好ましくは
５０＾／ｄ箇２以上、鋼板とめつき液との相対流速０．
５１１１／ｓｅｃ以上で行えば得られる。For manufacturing the plated steel sheet of the present invention, for example, Zn2+
Concentration 10-509/e, Fe2+ concentration 20-709/8
, Mn2+ concentration 3-409/e, current density 10 to 2008/d2, preferably 50^/d2 or more in an acidic plating bath with a pH of 3 or less, and a relative flow rate between the steel plate and the plating solution 0.
This can be obtained if the speed is 5111/sec or more.
（作用）
添付図面はＺｎ−Ｆｅ系合金電気めっき鋼板のめつき屑
にＭｎを添加した場合のＭｎ添加量とリン酸塩処理性と
の関係を示したものであるが、Ｍｎを０．０１〜２％添
加するとリン酸塩処理性を向上させることができる。な
お縦軸の数字は次のようなリン酸塩結晶状態を示してい
る。(Function) The attached drawing shows the relationship between the amount of Mn added and the phosphate treatability when Mn is added to the plating scraps of Zn-Fe alloy electroplated steel sheets. Addition of ~2% can improve phosphate treatment properties. Note that the numbers on the vertical axis indicate the following phosphate crystal states.
４：均一で緻密なリン酸塩結晶生成
３：やや粗大なリン酸塩結晶生成
２：小さなリン酸塩結晶非生成部発生
１：大きなリン酸塩結晶非生成部発生
（実施例）
冷延鋼板の表面を常法により清浄化した後、下記のめっ
き浴、めっき条件でＺｎ−Ｆｅ系またはＺｎ −’
Ｆｅ−Ｍｎ系合金を電気めっきした。なおめっき層の
Ｆｅお上りＭｎｌはそれぞれＦｅ５０４−フｌｌ 、
ＯおよびＭｎ５Ｏ。4: Formation of uniform and dense phosphate crystals 3: Formation of slightly coarse phosphate crystals 2: Formation of small phosphate crystal non-formation areas 1: Formation of large phosphate crystal non-formation areas (Example) Cold rolled steel sheet After cleaning the surface using a conventional method, Zn-Fe-based or Zn-'
A Fe-Mn alloy was electroplated. Note that the Fe upstream Mnl of the plating layer is Fe504-Fll, respectively.
O and Mn5O.
の添加量により調整した。It was adjusted by the amount of addition.
浴組成 ＺｎＳＯ４・７Ｌ０ ９０９
／ ｅＦｅＳ０４・ フｕ２ｏ
１５０−２５０９ ／ｅＭｎＳＯ＜ ０又
は１０−１００９ ／ｅ。Bath composition ZnSO4・7L0 909
/ eFeS04・Fu2o
150-2509/eMnSO<0 or 10-1009/e.
Ｈａ、Ｓｏ、 ８０９／
ｅ酒石酸 ０．５９／９クエン酸
０．５９／ｅポリビニルアルコール
０．５９／ｅｐＨ２
浴温 ５０℃
電ＦＩＬ密度 ５０〜１５０＾／ｄ悼２めっき後はリン
酸塩処理、塗装を行い、リン酸塩処理性、塗膜二次密着
性および塗装後の耐食性を調査した。第１表にこの結果
を示す。なおこれらの調査は犬のような試験により行っ
た。Ha, So, 809/
eTartaric acid 0.59/9 citric acid
0.59/e Polyvinyl alcohol 0.59/epH2 Bath temperature 50℃ Electric FIL density 50-150^/d After plating, perform phosphate treatment and painting to improve phosphate treatment properties and secondary coating adhesion The properties and corrosion resistance after painting were investigated. Table 1 shows the results. These studies were conducted using dog-like tests.
（１）リン酸塩処理性試験
日本パーカーライジング（株）製のリン酸塩処理剤Ｂ、
Ｔ、３０８０で処理して、結晶のホスホフィライト状態
を電子顕微鏡で観察した。(1) Phosphate treatment test Phosphate treatment agent B manufactured by Nippon Parkerizing Co., Ltd.
The phosphophyllite state of the crystals was observed using an electron microscope.
（２）塗膜二次密着性試験
上記リン酸塩処理剤で１．８〜２．２９７Ｉ１１２の皮
膜を形成した後、日本ペイント（株）製カチオン電着塗
料ｕ−ｉｏｏを乾燥塗膜厚で２０μｌ塗装した。その後
この塗装鋼板を５０℃の蒸留水に２４０時間浸漬した後
、ｍ膜に鋼素地に達するゴバン目（２１開隔で１００個
）を入れ、テーピング剥離により塗膜剥離状況を判定し
た。(2) Paint film secondary adhesion test After forming a film of 1.8 to 2.297I112 with the above phosphate treatment agent, apply cationic electrodeposition paint u-ioo manufactured by Nippon Paint Co., Ltd. to a dry film thickness. 20 μl was applied. Thereafter, this coated steel plate was immersed in distilled water at 50° C. for 240 hours, and then gobbles (100 pieces with 21 gaps) reaching the steel substrate were placed in the M film, and the peeling status of the paint film was determined by peeling with taping.
（３）塗装後の耐食性試験
上記（２）と同要領でリン酸塩処理、塗装した塗装鋼板
の塗膜にカッターナイフで鋼素地に達するスクラッチを
入れて、塩水噴霧試験を１０００時間行った。試験後ス
クラッチ部をテーピング剥離するとともに、スクラッチ
部以外にゴパン目を上記（２）のように入れ、テーピン
グ剥離した。(3) Corrosion resistance test after painting The paint film of a painted steel plate that had been phosphate treated and painted in the same manner as in (2) above was scratched using a cutter knife to reach the steel base, and a salt water spray test was conducted for 1000 hours. After the test, the scratched portion was peeled off with taping, and a goblin was placed in the area other than the scratched portion as described in (2) above, and the taping was peeled off.
＼１、
− 、
（発明の効果）
以上のごとく本発明のめつき鋼板は従来のＺｎ−Ｆｅ系
合金めつき鋼板よりリン酸塩処理性昏こ優れており、塗
装後の性能を向上させること力Ｃできる。\1, -, (Effects of the invention) As described above, the plated steel sheet of the present invention has better phosphate treatment properties than conventional Zn-Fe alloy plated steel sheets, and improves the performance after painting. I can do force C.
また１工程でめっきできるので、コスト上昇を招かない
。Furthermore, since plating can be done in one step, there is no increase in costs.
添付図面はＺｎ−Ｆｅ系合金電気めっき鋼板のめつき層
にＭｎを添加した場合のＭｎ添加量とＩＪンｆｌｌ塩処
理性との関係を示すグラフである。The attached drawing is a graph showing the relationship between the amount of Mn added and the IJ/full salt processability when Mn is added to the plating layer of a Zn-Fe alloy electroplated steel sheet.
Claims (1)
合金電気めっき鋼板のめっき層にＭｎを０．０１〜２％
添加したことを特徴とする耐食性およびリン酸塩処理性
に優れた表面処理鋼板。Adding 0.01 to 2% Mn to the plating layer of a Zn-Fe alloy electroplated steel sheet with an Fe content of 10 to 30% by weight
A surface-treated steel sheet with excellent corrosion resistance and phosphate treatment properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP751387A JPS63176490A (en) | 1987-01-16 | 1987-01-16 | Surface treated steel sheet having superior corrosion resistance and suitability to phosphating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP751387A JPS63176490A (en) | 1987-01-16 | 1987-01-16 | Surface treated steel sheet having superior corrosion resistance and suitability to phosphating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63176490A true JPS63176490A (en) | 1988-07-20 |
Family
ID=11667860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP751387A Pending JPS63176490A (en) | 1987-01-16 | 1987-01-16 | Surface treated steel sheet having superior corrosion resistance and suitability to phosphating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63176490A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013185215A (en) * | 2012-03-08 | 2013-09-19 | Kobe Steel Ltd | High-strength hot dip galvannealed steel sheet excellent in chemical conversion property and ductility and method for producing the same |
| WO2018115413A1 (en) | 2016-12-22 | 2018-06-28 | Carl Freudenberg Kg | Aqueous, alkaline electrolyte for depositing zinc-containing layers onto surfaces of metal piece goods |
-
1987
- 1987-01-16 JP JP751387A patent/JPS63176490A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013185215A (en) * | 2012-03-08 | 2013-09-19 | Kobe Steel Ltd | High-strength hot dip galvannealed steel sheet excellent in chemical conversion property and ductility and method for producing the same |
| WO2018115413A1 (en) | 2016-12-22 | 2018-06-28 | Carl Freudenberg Kg | Aqueous, alkaline electrolyte for depositing zinc-containing layers onto surfaces of metal piece goods |
| EP3559318A1 (en) * | 2016-12-22 | 2019-10-30 | Carl Freudenberg KG | Aqueous, alkaline electrolyte for depositing zinc-containing layers onto surfaces of metal piece goods |
| US11578419B2 (en) | 2016-12-22 | 2023-02-14 | Cari, Freudenberg Kg | Aqueous, alkaline electrolyte for depositing zinc-containing layers onto surfaces of metal piece goods |
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