JPS6372887A - Production of hot dip coated steel sheet having excellent corrosion resistance and working resistance - Google Patents
Production of hot dip coated steel sheet having excellent corrosion resistance and working resistanceInfo
- Publication number
- JPS6372887A JPS6372887A JP21554886A JP21554886A JPS6372887A JP S6372887 A JPS6372887 A JP S6372887A JP 21554886 A JP21554886 A JP 21554886A JP 21554886 A JP21554886 A JP 21554886A JP S6372887 A JPS6372887 A JP S6372887A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- plating layer
- corrosion resistance
- plating
- hot
- 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
- 238000005260 corrosion Methods 0.000 title claims abstract description 20
- 230000007797 corrosion Effects 0.000 title claims abstract description 20
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 18
- 239000010959 steel Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000007747 plating Methods 0.000 claims abstract description 35
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052912 lithium silicate Inorganic materials 0.000 claims abstract description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 238000011282 treatment Methods 0.000 claims description 26
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 13
- 239000008397 galvanized steel Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 2
- -1 oxalate ions Chemical class 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005507 spraying Methods 0.000 abstract description 8
- 238000002845 discoloration Methods 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 239000002344 surface layer Substances 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 2
- 238000003618 dip coating Methods 0.000 abstract 2
- 229910007562 Li2SiO3 Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- 238000012545 processing Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 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 3
- 239000007921 spray Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000269821 Scombridae Species 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000013872 defecation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000020640 mackerel Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は溶融めっき後機械的処理加工を施したり、クロ
メート処理を施しても表面が灰黒色に変色しに（い耐食
性、耐機械的加工性に優れた溶融めっき鋼板の製造方法
に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention provides corrosion resistance and mechanical processing that prevents the surface from discoloring to grayish black even when subjected to mechanical treatment or chromate treatment after hot-dip plating. The present invention relates to a method for producing hot-dip galvanized steel sheets with excellent properties.
（従来技術）
溶融亜鉛めっ慇鋼板、溶融フルミニツムめっき鋼板など
の溶融めっき鋼板の用途は従来屋根や壁などが主であっ
たが、近年は耐久材としての需要が益々商より、内装、
器物など高度の外観、形状および加工性を必要とする方
面に用途が拡大してさている。このため溶融めっき鋼板
の製造に際しては品質向上を目的とする種々の後処理方
法が検討されている０例えばめっき後付着量を調整した
直後の未凝固めっき層にｎ状水滴を吹付けて急冷するこ
とによりスパングルをミニマイズド化して外貌を向上さ
せたり、めっき層の凝固後に種々の機械的処理加工（例
えばレベラー、スキンパス）を施して、外観、形状およ
び加工性などを向上させたりする方法などである。(Prior art) Hot-dip galvanized steel sheets, hot-dip full-miniature galvanized steel sheets, and other hot-dip galvanized steel sheets have traditionally been used mainly for roofs and walls, but in recent years demand as durable materials has increased from commercial to interior,
Applications are expanding to areas that require a high degree of appearance, shape, and workability, such as tableware. For this reason, various post-treatment methods are being considered to improve the quality when manufacturing hot-dip galvanized steel sheets. For example, spraying n-shaped water droplets onto the unsolidified coating layer immediately after adjusting the amount of coating after plating to rapidly cool it. In this way, spangles are minimized to improve the appearance, and after solidification of the plating layer, various mechanical treatments (e.g., leveler, skin pass) are applied to improve the appearance, shape, workability, etc. .
（発明が解決しようとする問題点）
しかしながらこのようにスパングルをミニマイズド化し
たものに機械的処理加工を施したり、耐食性や塗ｇｌ！
着性改善のためにクロメート処理を施すと、通常の保管
状態でも敗箇月という比較的短期間に表面が灰黒色（以
下黒変という）に変色し、銀白色の外観が失われでしま
う。(Problems to be Solved by the Invention) However, in this way, the miniaturized spangles are subjected to mechanical processing, corrosion resistance, and coating.
When chromate treatment is applied to improve adhesion, even under normal storage conditions, the surface turns grayish-black (hereinafter referred to as black discoloration) within a relatively short period of time, and the silver-white appearance is lost.
このため黒変を軽くもしくは目立たないようにするには
非クロム酸系の後処理を使用すればよいのであるが、非
クロム酸系の後処理は一般に処理費が高＜、Ｉ９！ｒ戒
的処理加工にも弱いという欠点がある。Therefore, to make the blackening lighter or less noticeable, it is possible to use a non-chromic acid-based post-treatment, but non-chromic acid-based post-treatments are generally expensive. It also has the disadvantage of being weak against harsh processing.
例えば本発明者らは先に耐黒変性、耐食性を兼ね備えた
非クロム酸系の後処理方法として、Ｎｉ。For example, the present inventors previously developed Ni as a non-chromic acid post-treatment method that has both blackening resistance and corrosion resistance.
Ｃｏ％Ｆｅイオンを１種または２種以上含む処Ｆ！！液
で溶融めっき鋼板を予め表面ｍ笹して、それらの金属を
めっき層表面に置換析出させた後、無８！系シリケーＦ
処理剤の処理液を塗布して乾燥することによりシリケー
ト皮膜を形成する方法を提案したが、この方法は工程が
！１数になるので、複雑である。また皮膜は〃ラス質の
シリケート皮膜が単にめっト層表面に付着しているのに
過ぎないので、皮膜の付着力は弱く、ロール７ｔ−ミン
グ、プレスまたは折曲げなどの加工によりしごきを受け
たりすると、皮膜は容易に破壊、剥脱してしまう。Co%F containing one or more types of Fe ions! ! After pre-coating the surface of a hot-dip plated steel plate with a liquid and displacing and precipitating those metals on the surface of the plating layer, no 8! Silica F
We proposed a method of forming a silicate film by applying a treatment solution and drying it, but this method requires several steps! It is complicated because there is only one number. In addition, since the film is simply a lath-like silicate film attached to the surface of the plating layer, the adhesion of the film is weak and cannot be easily ironed by processing such as rolling, pressing, or bending. Otherwise, the film will easily break and peel off.
このため黒変発生を抑１１Ｊするには後処理方法を安価
で、機械的処理加工に耐えるものにする必頁があった。Therefore, in order to suppress the occurrence of blackening, it was necessary to use a post-processing method that was inexpensive and resistant to mechanical processing.
（問題点を解決するための手段）
そこで本発明者らは安価で、機械的加工に耐える後処理
方法を検討した結果、めっき層が溶融状態にあるうちに
めっき層表面にシリカゾル、アルミナゾル、リチウムシ
リケートの１種または２種以上を含む水系溶液を吹付け
、めっき層表層にめっき層と一体になったがラス貿皮膜
を形成する方法およびその〃ラス質皮膜の上にクロメー
ト処理を施して、クロメート皮膜を形成する方法を開発
した。(Means for solving the problem) The present inventors investigated a post-processing method that was inexpensive and resistant to mechanical processing, and found that silica sol, alumina sol, lithium, etc. A method of spraying an aqueous solution containing one or more types of silicates to form a lath film on the surface layer of the plating layer that is integrated with the plating layer, and performing chromate treatment on the lath film, We have developed a method to form a chromate film.
本発明はこの後処理方法を溶融めっき鋼板！！遣の際利
用して耐食性、耐８！械的加工性に優れた溶融めっき鋼
板を製造するもので、鋼板に溶融めっきを施して、めっ
き付着量をｉ１ｍ！！した後、めっき層が溶融状態にあ
るうちにめっき層表面にシリカゾル、アルミナゾル、リ
チウムシリケートの１！９Ｉまたは２種以上を含む水系
溶液を吹付け、めっき層表層にＳｉＯ２、Ａｌ２Ｏ３、
ＬｉｚＳｉＯ＊の単独または混合物からなる複合酸化皮
膜を形成し、また曲記水系溶液の吹付は後クロノート処
理を施して酸化皮膜の上にクロメート皮膜を形成するの
である。The present invention applies this post-treatment method to hot-dip galvanized steel sheets! ! Corrosion resistance when used during transportation, resistance 8! We manufacture hot-dip plated steel sheets with excellent mechanical workability, and we apply hot-dip plating to steel sheets to achieve a coating weight of 1m! ! After that, while the plating layer is in a molten state, an aqueous solution containing 1!9I or two or more of silica sol, alumina sol, and lithium silicate is sprayed onto the surface of the plating layer to form SiO2, Al2O3,
A composite oxide film consisting of LizSiO* alone or as a mixture is formed, and after spraying the aqueous solution, a chromate treatment is performed to form a chromate film on the oxide film.
この方法によれば水系溶液の吹付けは従来連続溶融めっ
き設備にスパングルをミニマイズド化するのに設置しで
ある吹付は装置を使用してイテえばよいので、工程は従
来のミニマイズドスパングルの溶融めっき鋼板Ｍ造と同
じである。従って工程的には安価である。また水系溶液
はめっき層が溶融状態にあるとき吹付けるのであるから
、５ｉｎ２、＾１２０３、ＬｉｚＳｉＯ＊などのがう人
質皮膜はめっき層と一体になり、耐機械的加工に優れで
いる。According to this method, the spraying of an aqueous solution can be carried out using equipment that has been installed in conventional continuous hot-dip plating equipment to minimize spangles, so the process is similar to the conventional hot-dip plating process for minimized spangles. Same as steel plate M construction. Therefore, the process is inexpensive. Furthermore, since the aqueous solution is sprayed when the plating layer is in a molten state, the hostage film such as 5in2, ^1203, LizSiO*, etc. becomes integrated with the plating layer and has excellent mechanical processing resistance.
本発明で水系溶液に含ませるシリカゾル、アルミナゾル
、リチウムシリヶーＦは市販のものでよく、例えば８産
化学工業（株）製のスノーテックス０１スノーテツクス
Ｃ，フルミナゾル２００． リチウムシリケートＬＳＳ
３５、リチウムシリケートＬＳＳ４５などを使用すれば
よい、溶液の濃度や温度などはとくに限定はない。The silica sol, alumina sol, and lithium silica F to be included in the aqueous solution in the present invention may be commercially available products, such as Snowtex 01 Snowtex C, Fluminasol 200. Lithium silicate LSS
No. 35, lithium silicate LSS45 or the like may be used, and there are no particular limitations on the concentration or temperature of the solution.
溶液の溶融めっき鋼板への吹付けはめっき層が溶融状態
にあるうちに打うのであるが、その吹付は量は金属換算
で付着量が０．２〜２００ Ｂ７ｍ２になるようにする
。 ０．２１１１１／Ｉｌｌ”未満であると、耐食性、
黒変防止効果が不十分であり、２００ ｍｇ／＋ｓ”を
越えて付着させても、必要以上に生成した酸化皮膜の大
部分が鋼板加工の際破壊されて脱落し、製造コストが高
くなろ。The solution is sprayed onto the hot-dip plated steel sheet while the coating layer is in a molten state, and the amount of spraying is such that the coating amount is 0.2 to 200 B7m2 in terms of metal. If it is less than 0.21111/Ill”, corrosion resistance,
The effect of preventing blackening is insufficient, and even if the amount exceeds 200 mg/+s, most of the oxide film produced in excess of the necessary amount will be destroyed and fall off during processing of the steel plate, increasing manufacturing costs.
本発明では以上のようにして処理液を吹着けで、めっき
層表層に５ｉ０２、＾１□Ｏ１、Ｌｉ２５ｉＯｓの単独
または混合物からなる複合酸化皮膜を形成した後、さら
にクロメート処理を施し、酸化皮膜の上にクロメート皮
膜を形成する。クロメート処理を施すのは、金属酸化物
皮膜を形成しただけでも黒変防止も含めて長期間耐食性
を発揮するが、さらに耐食性を向上させるとともに、塗
膜密着性をも付与さるためである。In the present invention, a composite oxide film consisting of 5i02, ^1□O1, and Li25iOs alone or as a mixture is formed on the surface layer of the plating layer by spraying the treatment solution as described above, and then a chromate treatment is further performed to remove the oxide film. A chromate film is formed on top. The reason why chromate treatment is applied is that the mere formation of a metal oxide film provides long-term corrosion resistance, including prevention of blackening, but it also improves corrosion resistance and provides paint film adhesion.
使用するクロメート処理液としては、無水クロム酸を主
体に溶解したもので、Ｃｒ”◆／（Ｃｒ’◆＋Ｃｒ”）
＝０〜０．６に１１！！したちのが最も望ましい、Ｃｒ
計とＣｒ”＋とがこのような組成のクロメート処理液は
公知のクロメ−Ｆ処Ｆ！！液として知られているが、本
発明の場合そのまま使用するには問題がある場合がある
。これは公知のクロメート処理液のほとんどのものには
反応保進剤や亜鉛表面を適度にエツチングするエツチン
グ成分が添加されているため、それらにより亜鉛が溶解
されで、金Ｒ１１ｉ！化物皮膜も脱落し、耐黒変性効果
が失なわれるので、好ましくない、このため本発明で使
用するクロメ−Ｆ処理液としてはＦ−、ＣＩ−、ＳＯ４
３″、Ｎ０１− 、ＰＯ４２−１Ｃ１１，ＣＯＯ−、Ｌ
−う酸イオンなどの陰イオンからなるエツチング成分を
含有しないものを使用するのが好ましい。The chromate treatment solution used is one mainly containing chromic anhydride, Cr"◆/(Cr'◆+Cr")
= 11 to 0 to 0.6! ! Shitachi is the most desirable, Cr
A chromate treatment solution having such a composition of chromate and Cr"+ is known as the well-known chromate treatment F!! solution, but there may be problems in using it as is in the present invention. Most of the known chromate treatment solutions contain reaction preservatives and etching components that suitably etch the zinc surface, so the zinc is dissolved and the gold R11i! compound film is also removed. This is undesirable because the blackening resistance effect is lost.For this reason, the Chrome-F treatment solution used in the present invention is F-, CI-, and SO4.
3″, N01-, PO42-1C11, COO-, L
- It is preferable to use a material that does not contain etching components consisting of anions such as oxalate ions.
本発明の製造方法は溶融めっき鋼板が溶融亜鉛系、溶融
アルミニウム系、溶融亜鉛−アルミニウム系合金であっ
ても、またそれらに８１％Ｓｉ、希土類元素などを添加
したものであっても黒変を抑制できる。The manufacturing method of the present invention prevents blackening even if the hot-dip galvanized steel sheet is molten zinc-based, molten aluminum-based, molten zinc-aluminum-based alloy, or has 81% Si, rare earth elements, etc. added thereto. It can be suppressed.
以下実施例により本発明を説明する。The present invention will be explained below with reference to Examples.
（実施例）
実施例１
重量％で、＾ｌ Ｏ，１７％、Ｐｂ Ｏ，３０％、Ｆｅ
Ｏ，０３％、残部Ｚｎお上り不可避的不純物からなる
めっき浴で銅板を溶融めっきした後、気体紋り法により
めっき付着量を２００〜２５０９／輸２に調整し、＃Ｓ
１表に示す塩の水溶液を２〜３ Ｋｇ／ａｓ”の圧縮空
気でｎ化して吹付け、溶融亜鉛めっき鋼板を製造した。(Example) Example 1 In weight%, ^l O, 17%, Pb O, 30%, Fe
After hot-dipping a copper plate in a plating bath consisting of O, 0.3% and the remainder Zn as unavoidable impurities, the coating weight was adjusted to 200 to 2509/m2 by the gas patterning method, and #S
An aqueous solution of the salt shown in Table 1 was converted to n and sprayed with 2 to 3 kg/as'' compressed air to produce a hot-dip galvanized steel sheet.
その後コノ鋼板の一部をＣｒＯ＊２０９／ｅ、温ｒ１４
０℃の無水クロム酸水溶液中に５秒間浸漬して、クロメ
ート処理を施した。After that, a part of the Kono steel plate was treated with CrO*209/e at a temperature of r14.
Chromate treatment was performed by immersing it in an aqueous chromic acid anhydride solution at 0° C. for 5 seconds.
次にこれらのクロメート未処理と処理の溶融亜鉛めっき
鋼板より試験片を採取して、その一部を温度５０±１’
Ｃ１相対湿度９８％以上の雰囲気中にクロメート未処理
のものは１日間、またクロメート処理のものは３０日間
放置することにより黒変促進試験を行い、また残りの試
験片には４を曲げお上びエリク七ンＧ論論押出加工を施
した後、ＪＩＳＺ ２３７１に規定された塩水噴ｎ試験
に準じて耐食性促進試験を実施した。塩水噴霧試験はク
ロメ−Ｆ未処理のものの場合８時間、クロメート処理の
ものの場合１００時間実施した。この第１ｔｔにこの便
通試験結果を示す、なお第１表における耐食性促進試験
の７ラツト部は４を曲げお上びエリラセン６箇−押出加
工を施さない部分であり、加工部はこれらの加工を施し
た部分である。Next, test specimens were taken from these hot-dip galvanized steel sheets, untreated and treated, and some of them were heated to a temperature of 50±1'.
C1 A blackening acceleration test was performed by leaving untreated specimens in an atmosphere with a relative humidity of 98% or more for 1 day, and specimens treated with chromate for 30 days. After applying extrusion processing, an accelerated corrosion resistance test was conducted in accordance with the salt water spray test specified in JISZ 2371. The salt spray test was carried out for 8 hours in the case of untreated chromate-F and 100 hours in the case of chromate-treated ones. This 1st tt shows the results of this defecation test. In addition, the 7th rat part of the accelerated corrosion resistance test in Table 1 is the part where 4 is bent and the 6 parts are not extruded. This is the part that was applied.
なお黒変、耐食性の判定は次の基準により行った。The black discoloration and corrosion resistance were evaluated based on the following criteria.
（１）黒変促進試験
◎ 黒変せず
○ 極く薄く灰色化した
Δ 黒変の面積が全体の３０％未満
× 黒変の面積が全体の３０％以上
（２）耐食性促進試験
Ｏ錆が発生せず
Ｏ鯖の発生面積が１０％未満
Δ 錆の発生面積が全体の１０〜３０％未満× 錆の発
生面積が全体の３０％以上
実施例２
第２表に示すような組成のめっき浴で鋼板を溶融めっト
して、めっき付着量を調整した後、シリカゾル、アルミ
ナゾル、リチウムシリケートのいずれか１種を５０ｗｔ
％含む水系溶液を吹付け、しかる後に実施例１同様にク
ロメート処理して溶融めっき鋼板を製造した。その後こ
の鋼板より試験片を採取して、その一部を温度５０±１
℃、相対湿度９８％以上の雰囲気中に３０日間放置する
ことにより黒変促進試験を行った。また採取した残りの
試験片には実施例１と同様の加工を施して、同様に塩水
噴霧試験を８時間、１００時間文施した。ｔｊ４２表に
水系溶液の種類と黒変および耐食性の判定結果を示す、
なお黒変と耐食性の判定基準は実施例１と同じである。(1) Accelerated blackening test ◎ No blackening ○ Very thin graying Δ Blackening area is less than 30% of the whole × Blackening area is 30% or more of the whole (2) Accelerated corrosion resistance test O Rust No rust generation and O mackerel generation area is less than 10% Δ Rust generation area is 10 to less than 30% of the whole × Rust generation area is 30% or more of the whole Example 2 Plating bath with the composition as shown in Table 2 After hot-dipping the steel plate and adjusting the coating weight, 50wt of one of silica sol, alumina sol, and lithium silicate was applied.
% and then chromate treatment in the same manner as in Example 1 to produce a hot-dip plated steel sheet. After that, a test piece was taken from this steel plate and a part of it was heated to 50±1
A blackening acceleration test was conducted by leaving the sample in an atmosphere at a temperature of 98% or more and a relative humidity of 98% or higher for 30 days. Further, the remaining test pieces taken were processed in the same manner as in Example 1, and similarly subjected to salt spray tests for 8 hours and 100 hours. Table tj42 shows the types of aqueous solutions and the judgment results for blackening and corrosion resistance.
Note that the criteria for determining black discoloration and corrosion resistance are the same as in Example 1.
（発明の効果）
以上のごとく本発明法は非クロムｌ！ＩＭの後処理であ
るが、スパングルをミニマイズド化した溶融めっき鋼板
にクロメート処理を施しても、また機械的加工を施して
も黒変の発生を抑制することができる。また本発明法は
シリカゾル、アルミナゾル、リチウムシリケートなどを
含む水系溶液を溶融めっき直後のめっき層表面に吹付け
るだけであるので、工程は簡単で、従来のミニマイズド
スパングル溶融めっｔ＆鋼板と変わらず、安価である。(Effect of the invention) As described above, the method of the present invention is chromium-free! As for the post-treatment of IM, the occurrence of blackening can be suppressed even if a hot-dip galvanized steel sheet with minimized spangles is subjected to chromate treatment or mechanically processed. In addition, the process of the present invention is simple, as it only involves spraying an aqueous solution containing silica sol, alumina sol, lithium silicate, etc. onto the surface of the plating layer immediately after hot-dip plating, and is no different from conventional minimized spangled hot-dip plated T & steel sheets. , cheap.
さらに生成する皮膜はめっき層と一体になった酸化物皮
膜であるので、８！械的加工に対して優れている。Furthermore, the film that is formed is an oxide film that is integrated with the plating layer, so 8! Excellent for mechanical processing.
Claims (3)
した後、めっき層が溶融状態にあるうちにめっき層表面
にシリカゾル、アルミナゾル、リチウムシリケートの１
種または２種以上を含む水系溶液を吹付け、めつき層表
層にＳｉＯ＿２、Ａｌ＿２Ｏ＿３、Ｌｉ＿２ＳｉＯ＿３
の単独または混合物からなる複合酸化皮膜を形成するこ
とを特徴とする耐食性、耐加工性に優れた溶融めっき鋼
板の製造方法。(1) After applying hot-dip plating to a steel sheet and adjusting the amount of plating deposited, while the plating layer is in a molten state, a mixture of silica sol, alumina sol, and lithium silicate is applied to the surface of the plating layer.
An aqueous solution containing one or more species is sprayed onto the surface of the plating layer to form SiO_2, Al_2O_3, Li_2SiO_3.
A method for producing a hot-dip galvanized steel sheet with excellent corrosion resistance and workability, characterized by forming a composite oxide film consisting of either one or a mixture of the following.
した後、めっき層が溶融状態にあるうちにめっき層表面
にシリカゾル、アルミナゾル、リチウムシリケートの１
種または２種以上を含む水系溶液を吹付け、めっき層表
層にＳｉＯ＿２、Ａｌ＿２Ｏ＿３、Ｌｉ＿２ＳｉＯ＿３
の単独または混合物からなる複合酸化皮膜を形成し、し
かる後にクロメート処理液で処理して前記酸化物皮膜の
上にクロメート皮膜を形成することを特徴とする耐食性
、耐加工性に優れた溶融めっき鋼板の製造方法。(2) After applying hot-dip plating to a steel sheet and adjusting the amount of plating deposited, while the plating layer is in a molten state, a layer of silica sol, alumina sol, or lithium silicate is applied to the surface of the plating layer.
An aqueous solution containing one or more species is sprayed onto the surface of the plating layer to form SiO_2, Al_2O_3, Li_2SiO_3.
A hot-dip galvanized steel sheet with excellent corrosion resistance and workability, characterized by forming a composite oxide film consisting of the following alone or in combination, and then treating with a chromate treatment solution to form a chromate film on the oxide film. manufacturing method.
溶解したもので、Ｃｒ＾３＾＋／（Ｃｒ＾３＾＋＋Ｃｒ
＾６＾＋）＝０〜０．６で、かつＦ＾−、Ｃｌ＾−、Ｓ
Ｏ＿４＾２＾−、ＮＯ＿３＾−、ＰＯ＿４＾３＾−、Ｃ
Ｈ＿３ＣＯＯ＾−およびしゅう酸イオンを含有しないも
のであることを特徴とする特許請求の範囲第２項に記載
の耐食性、耐加工性に優れた溶融めっき鋼板の製造方法
。(3) As a chromate treatment liquid, it is a solution mainly containing chromic anhydride, Cr^3^+/(Cr^3^++Cr
^6^+) = 0 to 0.6, and F^-, Cl^-, S
O_4^2^-, NO_3^-, PO_4^3^-, C
The method for producing a hot-dip galvanized steel sheet with excellent corrosion resistance and workability according to claim 2, characterized in that it does not contain H_3COO^- and oxalate ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21554886A JPS6372887A (en) | 1986-09-12 | 1986-09-12 | Production of hot dip coated steel sheet having excellent corrosion resistance and working resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21554886A JPS6372887A (en) | 1986-09-12 | 1986-09-12 | Production of hot dip coated steel sheet having excellent corrosion resistance and working resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6372887A true JPS6372887A (en) | 1988-04-02 |
| JPH0533312B2 JPH0533312B2 (en) | 1993-05-19 |
Family
ID=16674254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21554886A Granted JPS6372887A (en) | 1986-09-12 | 1986-09-12 | Production of hot dip coated steel sheet having excellent corrosion resistance and working resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6372887A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2655060A1 (en) * | 1989-11-28 | 1991-05-31 | Allstars Sah | Process and compositions for improving the corrosion resistance of metals and alloys |
| FR2837218A1 (en) * | 2002-03-18 | 2003-09-19 | Dacral Sa | Anti-corrosion, lubricating and/or anti-fingerprint coating composition for zinc- or aluminum-coated metal, e.g. galvanised steel, contains sodium, potassium or lithium silicate, optionally surfactant, and water |
| BE1015823A3 (en) * | 2003-12-17 | 2005-09-06 | Ct Rech Metallurgiques Asbl | Process for coating a surface by metal layer ultrafine. |
| JP2009057587A (en) * | 2007-08-30 | 2009-03-19 | Nippon Parkerizing Co Ltd | Surface reforming method of hot-dip coated steel member, and surface-reformed hot-dip coated steel member |
| JP2011099160A (en) * | 2009-11-04 | 2011-05-19 | Daicel Finechem Ltd | Surface-treated plated steel sheet and method for production thereof |
| WO2012119973A1 (en) * | 2011-03-08 | 2012-09-13 | Thyssenkrupp Steel Europe Ag | Flat steel product, method for producing a flat steel product, and method for producing a component |
| WO2014083713A1 (en) * | 2012-11-27 | 2014-06-05 | 日新製鋼株式会社 | Method for manufacturing hot-dip zn alloy-plated steel sheet |
| CN113244881A (en) * | 2021-06-25 | 2021-08-13 | 桂林理工大学 | Method for preparing lithium orthosilicate material by taking KIT-6 as silicon source, modification and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50116331A (en) * | 1974-02-26 | 1975-09-11 | ||
| JPS5194429A (en) * | 1975-02-19 | 1976-08-19 | BISAISUPANGURUYO JUAENMETSUKIKOZAINO SEIZOHO |
-
1986
- 1986-09-12 JP JP21554886A patent/JPS6372887A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50116331A (en) * | 1974-02-26 | 1975-09-11 | ||
| JPS5194429A (en) * | 1975-02-19 | 1976-08-19 | BISAISUPANGURUYO JUAENMETSUKIKOZAINO SEIZOHO |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2655060A1 (en) * | 1989-11-28 | 1991-05-31 | Allstars Sah | Process and compositions for improving the corrosion resistance of metals and alloys |
| US7232479B2 (en) | 2002-03-18 | 2007-06-19 | Dacral | Coating composition for a metal substrate |
| FR2837218A1 (en) * | 2002-03-18 | 2003-09-19 | Dacral Sa | Anti-corrosion, lubricating and/or anti-fingerprint coating composition for zinc- or aluminum-coated metal, e.g. galvanised steel, contains sodium, potassium or lithium silicate, optionally surfactant, and water |
| WO2003078683A2 (en) * | 2002-03-18 | 2003-09-25 | Dacral | Coating composition for a metal substrate |
| WO2003078683A3 (en) * | 2002-03-18 | 2004-06-03 | Dacral | Coating composition for a metal substrate |
| US7959982B2 (en) | 2003-12-17 | 2011-06-14 | Centre de Recherches Metallurgiques ASBL—Centrum Voor Research in de Metallurgie VZW | Method for coating a metal surface with an ultrafine layer |
| WO2005059196A3 (en) * | 2003-12-17 | 2005-09-09 | Ct Rech Metallurgiques Asbl | Method for coating a metal surface with an ultrafine layer |
| BE1015823A3 (en) * | 2003-12-17 | 2005-09-06 | Ct Rech Metallurgiques Asbl | Process for coating a surface by metal layer ultrafine. |
| JP2007514865A (en) * | 2003-12-17 | 2007-06-07 | サントル ド ルシェルシュ メタリュルジク アエスベエル−セントラム ヴォール リサーチ イン デ メタルージー フェーゼットヴェー | Method for coating metal surface with ultrafine particle layer |
| JP2009057587A (en) * | 2007-08-30 | 2009-03-19 | Nippon Parkerizing Co Ltd | Surface reforming method of hot-dip coated steel member, and surface-reformed hot-dip coated steel member |
| JP2011099160A (en) * | 2009-11-04 | 2011-05-19 | Daicel Finechem Ltd | Surface-treated plated steel sheet and method for production thereof |
| EP2683848B1 (en) * | 2011-03-08 | 2020-11-04 | ThyssenKrupp Steel Europe AG | Use of a flat steel prouduct for hot pres forming into a component and method of hot press forming a component |
| WO2012119973A1 (en) * | 2011-03-08 | 2012-09-13 | Thyssenkrupp Steel Europe Ag | Flat steel product, method for producing a flat steel product, and method for producing a component |
| JP2014514436A (en) * | 2011-03-08 | 2014-06-19 | ティッセンクルップ スチール ヨーロッパ アクチェンゲゼルシャフト | Steel plate product, steel plate product manufacturing method and component manufacturing method |
| WO2014083713A1 (en) * | 2012-11-27 | 2014-06-05 | 日新製鋼株式会社 | Method for manufacturing hot-dip zn alloy-plated steel sheet |
| CN104838036A (en) * | 2012-11-27 | 2015-08-12 | 日新制钢株式会社 | Method for manufacturing hot-dip Zn alloy-plated steel sheet |
| US10167542B2 (en) | 2012-11-27 | 2019-01-01 | Nisshin Steel Co., Ltd. | Method for producing hot-dip Zn alloy-plated steel sheet |
| US10202676B2 (en) | 2012-11-27 | 2019-02-12 | Nisshin Steel Co., Ltd. | Method for producing hot-dip Zn alloy-plated steel sheet |
| AU2013350682B2 (en) * | 2012-11-27 | 2015-06-04 | Nisshin Steel Co., Ltd. | Method for manufacturing hot-dip Zn alloy-plated steel sheet |
| CN113244881A (en) * | 2021-06-25 | 2021-08-13 | 桂林理工大学 | Method for preparing lithium orthosilicate material by taking KIT-6 as silicon source, modification and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0533312B2 (en) | 1993-05-19 |
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