JPH04176878A - Galvanized steel sheet having excellent press formability and chemical conversion treataqbility - Google Patents
Galvanized steel sheet having excellent press formability and chemical conversion treataqbilityInfo
- Publication number
- JPH04176878A JPH04176878A JP2305582A JP30558290A JPH04176878A JP H04176878 A JPH04176878 A JP H04176878A JP 2305582 A JP2305582 A JP 2305582A JP 30558290 A JP30558290 A JP 30558290A JP H04176878 A JPH04176878 A JP H04176878A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- film
- zinc
- chemical conversion
- function
- 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
- 239000000126 substance Substances 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 24
- 229910001335 Galvanized steel Inorganic materials 0.000 title abstract description 15
- 239000008397 galvanized steel Substances 0.000 title abstract description 15
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 46
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 45
- 239000010959 steel Substances 0.000 claims abstract description 45
- 238000007747 plating Methods 0.000 claims abstract description 39
- 239000010410 layer Substances 0.000 claims abstract description 31
- 238000005461 lubrication Methods 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000005096 rolling process Methods 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000000084 colloidal system Substances 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 150000002926 oxygen Chemical class 0.000 claims abstract description 4
- 239000011247 coating layer Substances 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract 2
- 239000011701 zinc Substances 0.000 claims description 60
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 5
- -1 P and B and/or Si Chemical class 0.000 claims 1
- 229910001297 Zn alloy Inorganic materials 0.000 abstract description 5
- 150000004679 hydroxides Chemical class 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 5
- 230000003449 preventive effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000005238 degreasing Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 230000001050 lubricating effect Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000007591 painting process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910001444 Cr+ Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 241000275031 Nica Species 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- BKCGDVXAGFLTDN-UHFFFAOYSA-N [F].P(O)(O)(O)=O.[Zn] Chemical compound [F].P(O)(O)(O)=O.[Zn] BKCGDVXAGFLTDN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching 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
- 239000012943 hotmelt Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
- Coating With Molten Metal (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、プレス成形性、化成処理性に優れた亜鉛系め
っき鋼板に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a zinc-based plated steel sheet with excellent press formability and chemical conversion treatment properties.
亜鉛系めっき鋼板のプレス成形性を向上させる方法とし
て、例えば特開昭62−185883号公報記載の如く
、めっき鋼板表面に電解クロメート処理を施し、Cr、
O,の酸化物皮膜を生成せしめる方法や、特開昭62−
192597号公報記載の如く、鉄亜鉛合金めっきを施
す方法等の亜鉛系めっき鋼板上に硬い皮膜を形成し、プ
レス時のめっきとダイスのかじりを防止してプレスの潤
滑性の向上をはかることが開示されている。As a method for improving the press formability of zinc-based plated steel sheets, for example, as described in JP-A No. 62-185883, electrolytic chromate treatment is applied to the surface of the plated steel sheets, and Cr,
A method for producing an oxide film of O, and JP-A-62-
As described in Publication No. 192597, it is possible to form a hard film on a zinc-based plated steel sheet, such as by applying iron-zinc alloy plating, to prevent galling of the plating and die during pressing and to improve the lubricity of the press. Disclosed.
また、特開平1−136952号公報記載の如く、めっ
き鋼板の表面に有機潤滑皮膜や潤滑油等の有機物を塗布
または被覆し、プレス成形性を向上させることが開示さ
れている。Further, as described in JP-A-1-136952, it is disclosed that the surface of a plated steel sheet is coated or coated with an organic substance such as an organic lubricating film or lubricating oil to improve press formability.
しかしながら、このような製品は自動車ユーザーの使用
において、以下のような不十分な点がある。However, such products have the following disadvantages when used by automobile users.
自動車ユーザーでの使用工程の概略は、鋼板を油で洗浄
する工程、プレス工程、脱脂工程、化成処理工程、塗装
工程からなっているので、電解クロメート処理鋼板の場
合は、化成処理工程で化成処理皮膜が形成せず、また潤
滑油や潤滑皮膜などを塗布した鋼板の場合は、洗浄工程
で油が落ちるので十分な潤滑性能を発揮しない、さらに
は、化成処理前の脱脂工程に負荷がかかりコストが高く
なる。一方、亜鉛系めっき鋼板に鉄−亜鉛合金フ、ラッ
シュめっきを施したものは電解クロメート処理に比較し
て鋼板のコストが高くなる等の問題点がある。The general usage process for automobile users consists of a process of cleaning steel sheets with oil, a pressing process, a degreasing process, a chemical conversion process, and a painting process. In the case of steel sheets that do not form a film or have been coated with lubricating oil or a lubricating film, sufficient lubrication performance will not be achieved as the oil will come off during the cleaning process, and furthermore, the degreasing process before chemical conversion treatment will be burdensome and costly. becomes higher. On the other hand, zinc-plated steel sheets subjected to iron-zinc alloy flash plating have problems such as higher cost of the steel sheets compared to electrolytic chromate treatment.
本発明はかかる現状に鑑みて、低コストで、化成処理が
可能で、脱脂等の工程に負荷をかけずに製造し得るプレ
ス成形性、化成処理性に優れた亜鉛系めっき鋼板を提供
することを目的とする。In view of the current situation, it is an object of the present invention to provide a zinc-based plated steel sheet that is low in cost, can be chemically treated, and has excellent press formability and chemical conversion treatment properties that can be manufactured without adding load to processes such as degreasing. With the goal.
本発明の要旨とするところは下記のとおりである。 The gist of the present invention is as follows.
(1)めっき層表面に、プレス成形時にめっき1表面に
密着し、その変形に追随して被覆を維持する凝着防止機
能と、金型とめっき層間のコロガリ潤滑機能とを併せも
つ無機系被覆層2〜1000mg/m2(金属として)
を形成せしめたことを特徴とするプレス成形性、化成処
理性に優れた亜鉛系めっき鋼板。(1) An inorganic coating on the surface of the plating layer that has an anti-adhesion function that adheres to the surface of the plating 1 during press molding and maintains the coating by following its deformation, and a rolling lubrication function between the mold and the plating layer. Layer 2~1000mg/m2 (as metal)
A zinc-based plated steel sheet with excellent press formability and chemical conversion treatment properties.
(2)凝着防止機能をめっき層との界面に強く、コロガ
リ潤滑機能を被覆層表面に強く、傾斜被覆せしめた前項
1に記載のプレス成形性、化成処理性に優れた亜鉛系め
っき鋼板。(2) The zinc-based plated steel sheet having excellent press formability and chemical conversion treatment properties as described in the preceding item 1, which has a strong adhesion prevention function on the interface with the plating layer and a strong rolling lubrication function on the surface of the coating layer, which is coated with an inclined coating.
(3)凝着防止機能を有する皮膜がMn、 Mo、 C
o、 NiCa+ Cr、 v、 w、 h、 Aj+
Zn の1種または2種以上の金属酸化物および/
または水酸化物を主体とし、皮膜量が1〜500■/r
rr (金属として)であり、コロガリ潤滑機能を有す
る皮膜がP、Bの1種または2種の酸素酸および/また
はSx+Aj+Ti の1種または2種以上の酸化物
コロイドを主体とし、皮膜量が1〜500■/が(金属
として)である前項1または2に記載のプレス成形性、
化成処理性に優れた亜鉛系めっき鋼板。(3) The film with anti-adhesion function is made of Mn, Mo, C.
o, NiCa+ Cr, v, w, h, Aj+
One or more metal oxides of Zn and/or
Or, it is mainly composed of hydroxide, and the film amount is 1 to 500 ■/r.
rr (as a metal), and the film having a rolling lubrication function is mainly composed of one or two types of oxygen acids such as P and B and/or one or more types of oxide colloids of Sx + Aj + Ti, and the film amount is 1 Press formability according to the preceding clause 1 or 2, wherein ~500 / is (as metal);
Zinc-based plated steel sheet with excellent chemical conversion treatment properties.
本発明が対象とする亜鉛系めっき鋼板とは、例えば溶融
めっき法、電気めっき法、蒸着めっき法、溶射法などの
各種の製造方法によるものがあり、めっき組成としては
純Znの他、ZnとFe、 ZnとNi。The zinc-plated steel sheets to which the present invention is directed include those produced by various manufacturing methods such as hot-dip plating, electroplating, vapor deposition plating, and thermal spraying, and the plating composition includes not only pure Zn but also Zn and Fe, Zn and Ni.
ZnとAj、ZnとMn、 ZnとCr、 ZnとTi
、 ZnとMgなどZnを主成分として、あるいは耐食
性など諸機能の向上のためFe、 Ni+ Co +
AI、 Pb、 Sn、 Sbt Cu、 Ti+S
i、B、P、N、S、O等の1種ないし2種以上の合金
元素および不純物元素を含み、またS iOt rkl
tOsなどのセラミックス微粒子、TiO2,BaCr
0゜などの酸化物、アクリル樹脂などの有機高分子をめ
っき層中に分散させたものがあり、めっき層の厚み方向
で単一組成のもの、連続的あるいは層状に組成が変化す
るものがあり、さらに多層めっき鋼板では、最上層に、
めっき組成としては純Znの他、ZnとFe、 Znと
Ni、 ZnとAZ、ZnとMn、 ZnとCr。Zn and Aj, Zn and Mn, Zn and Cr, Zn and Ti
, Zn and Mg with Zn as the main component, or with Fe, Ni + Co + to improve various functions such as corrosion resistance.
AI, Pb, Sn, Sbt Cu, Ti+S
Contains one or more alloying elements and impurity elements such as i, B, P, N, S, O, etc., and SiOtrkl
Ceramic fine particles such as tOs, TiO2, BaCr
There are those in which oxides such as 0° and organic polymers such as acrylic resin are dispersed in the plating layer, and there are those with a single composition in the thickness direction of the plating layer, and those whose composition changes continuously or layered. , and in multilayer plated steel sheets, the top layer is
In addition to pure Zn, the plating composition includes Zn and Fe, Zn and Ni, Zn and AZ, Zn and Mn, and Zn and Cr.
ZnとTi+ ZnとMgなどZn を主成分として
、耐食性などの諸機能の向上のため1種ないし2種以上
の合金元素および不純物元素を含み、またSiO□。Mainly composed of Zn such as Zn and Ti+ Zn and Mg, containing one or more alloying elements and impurity elements to improve various functions such as corrosion resistance, and SiO□.
Altosなどのセラミックス微粒子、TiO2,Ba
CrO4などの酸化物、アクリル樹脂などの有機高分子
をめっき層中に分散させたものがある。Ceramic fine particles such as Altos, TiO2, Ba
There are some in which oxides such as CrO4 and organic polymers such as acrylic resin are dispersed in the plating layer.
例えば、溶融亜鉛めっき鋼板、蒸着亜鉛めっき鋼板、鉄
−亜鉛合金化溶融亜鉛めっき鋼板、亜鉛を主とするアル
ミニウム、鉄などの合金溶融亜鉛めっき鋼板、めっき層
断面方向で下層が合金化されている合金化溶融亜鉛めっ
き鋼板(一般にハーフアロイと称する)、片面鉄−亜鉛
合金化溶融亜鉛めっき層、他面溶融亜鉛めっき層からな
るめっき鋼板、これらのめっき層上に電気めっき、蒸着
めっき等により亜鉛、または亜鉛を主成分とし、鉄、ニ
ッケルを含有する金属をめっきした鋼板、あるいは電気
亜鉛めっき鋼板、亜鉛、ニッケル、クロム等合金電気め
っき鋼板等、さらに単一合金層または多層合金電気めっ
き鋼板、亜鉛および亜鉛含有金属の蒸着めっき鋼板等が
ある。その他、SiO2,A1z03などのセラミック
ス微粒子、TiO□酸化物微粒子および有機高分子など
を亜鉛または亜鉛合金めっき中に分散させた分散めっき
鋼板がある。For example, hot-dip galvanized steel sheets, vapor-deposited galvanized steel sheets, iron-zinc alloyed hot-dip galvanized steel sheets, hot-dip galvanized steel sheets made of zinc-based alloys such as aluminum and iron, and the lower layer is alloyed in the cross-sectional direction of the plating layer. Alloyed hot-dip galvanized steel sheet (generally referred to as half-alloy), galvanized steel sheet consisting of an iron-zinc alloyed hot-dip galvanized layer on one side and a hot-dip galvanized layer on the other side, zinc coated on these plating layers by electroplating, vapor deposition plating, etc. or steel sheets plated with metals containing zinc as the main component and iron or nickel, electrogalvanized steel sheets, zinc, nickel, chromium alloy electroplated steel sheets, etc., single alloy layer or multilayer alloy electroplated steel sheets, There are steel sheets coated with zinc and zinc-containing metals. In addition, there are dispersion-plated steel sheets in which ceramic fine particles such as SiO2 and A1z03, TiO□ oxide fine particles, and organic polymers are dispersed in zinc or zinc alloy plating.
このような亜鉛系めっき鋼板表面に、前記の如く、めっ
き金属凝着防止剤と潤滑剤を被覆することにより、プレ
ス成形性、化成処理性を向上しようとするものである。By coating the surface of such a zinc-based plated steel sheet with a plating metal adhesion inhibitor and a lubricant as described above, press formability and chemical conversion treatment properties are improved.
亜鉛系めっき鋼板は一般にめっき層が軟質なため、プレ
ス成形時に容易に塑性変形して金型の表面粗さプロフィ
ルに嵌合し、金型との真実接触面積が増加し、摩擦力が
増大する結果、めっき層がひきちぎられ、剥離しためっ
き片がバインダーとなって次々にめっき層をひきちぎり
、金型に蓄積し、遂には材料破断を引き起こす傾向が強
い。Since galvanized steel sheets generally have a soft plating layer, they easily undergo plastic deformation during press forming and fit into the surface roughness profile of the mold, increasing the actual contact area with the mold and increasing frictional force. As a result, the plating layer is torn off, and the peeled off plating pieces act as a binder, tear off the plating layer one after another, accumulate in the mold, and have a strong tendency to eventually cause material breakage.
通常は亜鉛系めっき鋼板表面に防錆油が塗布されており
、場合によってはプレス油を塗布してプレス加工される
。油膜の作用は金型とめっき表面の間に流動層を形成し
て、金属の直接接触を抑制することにあり、上記現象は
軽減されるが、金型との摺動面で油膜が切れやすく、十
分に解決されない。Usually, anti-corrosion oil is applied to the surface of the galvanized steel sheet, and in some cases, press oil is applied to the surface of the sheet for pressing. The effect of the oil film is to form a fluidized layer between the mold and the plating surface, suppressing direct contact between the metal and reducing the above phenomenon, but the oil film is easily broken on the sliding surface with the mold. , not fully resolved.
高粘度潤滑油やホットメルト型の固体潤滑油を適用して
油膜強度を高める試みも実施されており、摩擦力低減に
はそれなりの効果はあるが、成形後脱脂、化成処理、塗
装の工程で、脱脂不良を起こしたり、脱脂液を汚染して
寿命を縮め、化成皮膜がつかないか、あるいはその耐食
性能を劣化させる不利益を伴うことが問題である。Attempts have been made to increase the strength of the oil film by applying high-viscosity lubricating oils or hot-melt solid lubricating oils, and although these have some effect in reducing frictional force, they are not effective in the post-molding degreasing, chemical conversion treatment, and painting processes. Problems include poor degreasing, contamination of the degreasing solution, shortening the service life, failure to form a chemical conversion film, or deterioration of corrosion resistance.
亜鉛系めっき表面に硬い金属、例えばFe系合金をフラ
ッシュめっきする方法は軟質な亜鉛系めっきの上に被覆
することにより、複合系としての硬度を高めて金型との
真実接触面積を低下させる作用であるから、効果を発揮
するには0.5μm程度以上の厚い表層めっきをする必
要があり、コスト高となる。The method of flash plating a hard metal, such as an Fe-based alloy, on the surface of a zinc-based plating works by coating the soft zinc-based plating to increase the hardness of the composite system and reduce the actual contact area with the mold. Therefore, in order to exhibit the effect, it is necessary to perform a thick surface layer plating of about 0.5 μm or more, which increases the cost.
本発明は上記の方法とは全く異なる作用機構で働く新規
な皮膜を亜鉛系めっき鋼板上に形成させるものである。The present invention forms a novel film on a galvanized steel sheet that operates through a mechanism completely different from that of the above-mentioned methods.
即ち、亜鉛系めっき表面に1〜500■/イ(金属とし
て)の金属酸化物および/または水酸化物から主として
構成される凝着防止機能を有する皮膜と、1〜500m
g/m2(金属として)の酸素酸および/または金属酸
化物コロイドから主として構成されるコロガリ潤滑機能
を有する皮膜を形成させるものである。この皮膜は金属
−酸素結合を主体として構成される非晶質構造であって
、凝着防止機能を有する皮膜構造とコロガリ潤滑機能を
有する皮膜構造は酸素結合を介して互いに混在している
ものであって、層構造として分離できるものではなく、
プレス成形に際して機能として識別できるものである。That is, a film having an anti-adhesion function mainly composed of metal oxides and/or hydroxides of 1 to 500 cm/i (as metal) on the zinc-based plating surface, and 1 to 500 m
g/m2 (as metal) of an oxyacid and/or metal oxide colloid to form a film having a rolling lubricating function. This film has an amorphous structure mainly composed of metal-oxygen bonds, and the film structure with anti-adhesion function and the film structure with rolling lubrication function coexist with each other through oxygen bonds. However, it is not something that can be separated as a layered structure.
It can be identified as a function during press molding.
プレス加工時に非晶質金属酸素結合構造は変形する亜鉛
めっき層の新生表面に追随して酵素結合を介して亜鉛と
密着し、金型への亜鉛凝着を防止する。一方、皮膜の一
部は破壊され、粉状となって金型との摺動面でコロガリ
潤滑機能を果たすことが、極めて薄い無機系皮膜であり
ながら画期的潤滑性を示す理由であると考えられる。During press working, the amorphous metal oxygen bonding structure follows the new surface of the deformed galvanized layer and adheres to the zinc via enzyme bonds, preventing zinc from adhering to the mold. On the other hand, part of the film is destroyed and becomes powder, which performs a rolling lubrication function on the sliding surface with the mold, which is the reason why it shows revolutionary lubricity despite being an extremely thin inorganic film. Conceivable.
−例として電気亜鉛めっき鋼板にMn8■/ホ。- As an example, Mn8■/E on electrogalvanized steel sheet.
P5■/ボからなる非晶質酸化物系皮膜を形成させた電
子顕微鏡写真を第1図に示す。亜鉛めっき結晶が見える
だけで、薄い表面皮膜は全く見えない。電子プローブマ
イクロアナライザーで線分析すると、第2図に示す如(
Mn、Pの存在が確認できる。この鋼板をドロービード
摺動試験にかけた後の電子顕微鏡での表面状態を第3図
に示すが、亜鉛めっき表面は金型ビード部で擦られて元
の亜鉛結晶は痕跡もとどめない。処理をしない電気亜鉛
めっき鋼板では板破断を起こす条件であるが、本発明の
皮膜を形成させると摩擦係数は0.17であり、良好な
潤滑状態を維持している。第4図にドロービード摺動試
験後の電子プローブマイクロアナライザー線分析チャー
トを示す。皮膜のMn。FIG. 1 shows an electron micrograph showing the formation of an amorphous oxide film consisting of P5■/BO. Only the galvanized crystals are visible, and the thin surface film is not visible at all. Line analysis with an electron probe microanalyzer results in the following (as shown in Figure 2).
The presence of Mn and P can be confirmed. Figure 3 shows the surface condition of this steel plate under an electron microscope after it was subjected to a drawbead sliding test, and the zinc-plated surface was rubbed by the mold bead, leaving no trace of the original zinc crystals. In an electrogalvanized steel sheet without treatment, the condition would cause the sheet to break, but when the film of the present invention is formed, the coefficient of friction is 0.17, and a good lubrication state is maintained. FIG. 4 shows an electron probe microanalyzer line analysis chart after the drawbead sliding test. Mn of the film.
Pともに存在量は摺動試験前に比べて減少しているが、
皮膜に切れ目がなく、はぼ均一に残存している。摺動に
より新しい亜鉛面が出現しても皮膜が再構成されている
と解せられる。ここで、MnZP比に注目すると、摺動
前に比べてPが相対的に減少していることがわかる。皮
膜中のPは選択的に破壊され、粉状となってコロガリ潤
滑に寄与したと考えられる。Although the abundance of both P has decreased compared to before the sliding test,
There are no breaks in the film and it remains fairly uniform. Even if a new zinc surface appears due to sliding, it can be understood that the film is being reorganized. Here, when paying attention to the MnZP ratio, it can be seen that P is relatively reduced compared to before sliding. It is thought that P in the film was selectively destroyed and turned into powder, contributing to rolling lubrication.
凝着防止機能を有する皮膜としては、Mn、 ?IO,
−Co、 Ni、 Ca、 Cr+’V、 W、 Ti
、 Aj+ Zn 等の金属酸化物および/または水
酸化物を主体とする非晶質構造が主として機能し、コロ
ガリ潤滑機能を有する皮膜としては、P、B等からなる
酸素酸および/またはSi+ AL Tt 等からな
る酸化物コロイドが上記非晶質構造に酸素結合を媒介し
て結合している構造が主として機能すると考えられる。Films with anti-adhesion function include Mn, ? IO,
-Co, Ni, Ca, Cr+'V, W, Ti
, Aj+ Zn, etc. The film mainly has an amorphous structure mainly composed of metal oxides and/or hydroxides, and has a rolling lubrication function. It is thought that a structure in which an oxide colloid consisting of the like is bonded to the amorphous structure via an oxygen bond mainly functions.
しかしながら、皮膜の形成反応は水溶液中から界面のp
H上昇を利用して渾然一体として析出させるので、厳密
に作用機能を選別できるものではなく、皮膜の一部が凝
着防止機能を担い、他の一部がコロガリ潤滑機能を担う
と解するほうが妥当である。However, the film formation reaction occurs from the aqueous solution to the interface p.
Since it is deposited in a harmonious manner by utilizing the increase in H, it is not possible to strictly select the function, but it is better to understand that part of the film has an anti-adhesion function and the other part has a rolling lubrication function. It is reasonable.
上記皮膜構成成分は全て無機物であり、プレス後の脱脂
液には負荷をかけず、化成処理に際してはpHの低下に
よって溶解するので、化成皮膜は正常に形成できる。All of the above-mentioned film constituent components are inorganic substances, do not put any load on the degreasing solution after pressing, and are dissolved by lowering the pH during chemical conversion treatment, so that a chemical conversion film can be formed normally.
皮膜生成方法は凝着防止機能を有する皮膜成分とコロガ
リ潤滑機能を有する皮膜成分を含有する酸性水溶液に亜
鉛系めっき綱板を浸漬するか、あるいは陰極電解処理す
ることにより、確実に皮膜形成できる。浸漬処理におい
ては、Znが溶解する際に界面のpHが上昇し、その結
果皮膜成分が水酸化物あるいは酸化物となって析出する
。熔解したZnその他のめっき層成骨も皮膜中に混入す
る。The film can be formed reliably by immersing the zinc-plated steel sheet in an acidic aqueous solution containing a film component with an anti-adhesion function and a film component with a rolling lubrication function, or by cathodic electrolytic treatment. In the immersion treatment, when Zn dissolves, the pH at the interface increases, and as a result, film components precipitate as hydroxides or oxides. Melted Zn and other plating layer bones are also mixed into the film.
酸化還元反応を利用することもできる。Znの溶解は酸
化反応であり、それに対応して酸化型の金属イオンは不
熔解性の還元型酸化物となって析出する。リン酸等の酸
素酸アニオンも酸化物コロイドも界面のpH上昇によっ
て析出できる。陰極電解処理は界面のPH上昇を促進す
る効果がある。スプレー処理、コーティング処理等の水
膜の厚さ調整で界面反応を制御する試みも本発明に適用
できる。Redox reactions can also be used. The dissolution of Zn is an oxidation reaction, and correspondingly, oxidized metal ions precipitate as insoluble reduced oxides. Both oxyacid anions such as phosphoric acid and oxide colloids can be precipitated by increasing the pH at the interface. The cathodic electrolytic treatment has the effect of promoting an increase in pH at the interface. Attempts to control the interfacial reaction by adjusting the thickness of the water film, such as by spraying or coating, can also be applied to the present invention.
凝着防止機能とコロガリ潤滑機能を併せ持つ皮膜量は金
属として2〜1000■/rrfが適当である。The appropriate amount of film having both adhesion prevention function and rolling lubrication function is 2 to 1000 .mu./rrf for metal.
2■/ボ未満では明確な潤滑効果が認知できず、100
0■/イを越えると、皮膜が塊状で剥離する危険があり
、また化成処理皮膜形成に悪影響がでる場合もあるので
好ましくない。凝着防止機能とコロガリ潤滑機能を併せ
持つ被覆を形成する態様として、金属酸化物および/ま
たは水酸化物を主体とする非晶質構造皮膜と酸素酸およ
び/または金属酸化物コロイド皮膜を形成させる場合に
は、皮膜量は両者ともに金属として1〜500■/rr
fが適当である。111g/ rd未満では明確な潤滑
効果が認知できず500■/n(を越えると、皮膜が塊
状で剥離する危険があり、また化成処理皮膜形成に悪影
響がでる場合もあるので好ましくない。If it is less than 2■/bo, no clear lubricating effect can be recognized, and 100
If it exceeds 0/I, there is a risk that the film will peel off in chunks, and the formation of the chemical conversion film may be adversely affected, which is not preferable. As an embodiment of forming a coating having both adhesion prevention function and rolling lubrication function, an amorphous structure film mainly composed of metal oxide and/or hydroxide and an oxyacid and/or metal oxide colloid film are formed. The coating amount is 1 to 500 μ/rr for both metals.
f is appropriate. If it is less than 111 g/rd, no clear lubricating effect can be perceived, and if it exceeds 500 g/n, there is a risk that the film will peel off in lumps, and the formation of the chemical conversion film may be adversely affected, which is not preferable.
金WA酸化物および/または水酸化物を主体とする非晶
質構造皮膜と酸素酸および/または金属酸化物コロイド
皮膜は上記浸漬法や陰極電解処理法の如く界面の化学反
応で析出させる場合には、−般には混合皮膜として皮膜
生成される。しかるに、凝着防止機能を亜鉛めっきとの
界面により強く、コロガリ潤滑機能を皮膜の表面により
強く、傾斜機能的に皮膜形成させることも可能である。An amorphous structure film mainly composed of gold WA oxide and/or hydroxide and an oxygen acid and/or metal oxide colloid film can be deposited by a chemical reaction at the interface such as the above-mentioned immersion method or cathodic electrolytic treatment method. is generally produced as a mixed film. However, it is also possible to form a film in a functionally graded manner, with the anti-adhesion function being stronger at the interface with the zinc plating and the rolling lubrication function being stronger at the surface of the film.
かくすることにより、摩擦係数で表示される潤滑性能に
は顕著な効果は見られないが、難成形部品をプレス加工
する場合のように、亜鉛めっき鋼板の局部に高面圧がか
かるとき、カジリが発生する限界面圧が向上する効果が
ある。所謂プレス成形荷重範囲が広く採れるので、実用
上は金型設計が容易になり、プレス作業も安定するので
大きな利益を享受できる。Although this method does not have a significant effect on the lubrication performance as indicated by the coefficient of friction, it does prevent galling when localized high pressure is applied to the galvanized steel sheet, such as when pressing difficult-to-form parts. This has the effect of improving the critical surface pressure that occurs. Since the so-called press forming load range can be widened, mold design becomes easier in practical use, and pressing work becomes stable, so great benefits can be enjoyed.
傾斜機能型皮膜の生成方法は金属酸化物等の溶解度積の
相違を利用して、各成分のイオン濃度、流速、溶液温度
、電解処理の場合には電流密度等を調整することにより
、界面のイオン濃度を制御することからなる。例として
Mn、 P系皮膜の場合には、処理溶液に過マンガン
酸カリウム、リン酸、硫酸を配合し、亜鉛めっきfiI
板と反応を起こさせると、先ずZnの溶解に伴い溶解度
積の最も小さいMn酸化物が析出する。このときの界面
pHは硫酸の存在のため急上昇せず、次いでリン酸M−
nないしはZnが遅れて析出してくる。かくして形成さ
れた皮膜の厚さ方向のグロー放電分光分析を第5図に示
すが、Pが表層に冨み、Mnが下層に冨んだ傾斜機能型
皮膜になっていることがわかる。この図は電気亜鉛めっ
き鋼板上に総計Mn8■/rrf;P5■/ボの非晶質
酸化物系皮膜を傾斜機能型に形成させた皮膜の厚さ方向
の分光分析図で、皮膜厚7nm、スパッタリング時間約
0.4秒以上は亜鉛めっき層を示す。The method for producing a functionally graded film takes advantage of the differences in solubility products of metal oxides, etc., and adjusts the ion concentration of each component, flow rate, solution temperature, current density in the case of electrolytic treatment, etc. to improve the interface. It consists of controlling the ion concentration. For example, in the case of Mn and P-based coatings, potassium permanganate, phosphoric acid, and sulfuric acid are mixed in the treatment solution, and zinc plating fiI
When a reaction is caused with the plate, first, Mn oxide, which has the smallest solubility product, precipitates as Zn dissolves. At this time, the interfacial pH did not rise rapidly due to the presence of sulfuric acid, and then phosphoric acid M-
n or Zn precipitates with a delay. FIG. 5 shows a glow discharge spectroscopic analysis of the film thus formed in the thickness direction, and it can be seen that it is a functionally graded film in which P is enriched in the surface layer and Mn is enriched in the lower layer. This figure is a spectroscopic analysis diagram in the thickness direction of a functionally graded amorphous oxide film with a total of Mn8/rrf; P5/bo formed on an electrogalvanized steel sheet, with a film thickness of 7 nm, A sputtering time of about 0.4 seconds or more indicates a galvanized layer.
次に上記の如き酸化物系皮膜の生成方法としては、例え
ば、硝酸カルシウム、硝酸ニッケル、硝酸コバルト、モ
リブデン酸アンモニウムそれぞれ50〜800 g/l
にリン酸:5〜60g/lを加え、エツチング補助剤(
硫酸等)からなる水溶液に前記亜鉛系めっき鋼板を浸漬
するか、水溶液を散布するか、または水溶液中で鋼板を
陰極として電解処理することにより所望の酸化物系皮膜
を生成することができる。Next, as a method for producing the above-mentioned oxide film, for example, calcium nitrate, nickel nitrate, cobalt nitrate, and ammonium molybdate are each used at 50 to 800 g/l.
Add 5 to 60 g/l of phosphoric acid and add an etching aid (
The desired oxide film can be produced by immersing the zinc-based plated steel sheet in an aqueous solution consisting of sulfuric acid, etc., spraying the aqueous solution, or electrolytically treating the steel sheet in an aqueous solution using the steel sheet as a cathode.
(実施例) 次に本発明の実施例を比較例とともに挙げる。(Example) Next, examples of the present invention will be listed together with comparative examples.
注1)めっき鋼板 AS:合金化溶融亜鉛めっき鋼板(Fe:10%。Note 1) Plated steel sheet AS: Alloyed hot-dip galvanized steel sheet (Fe: 10%.
At : 10.25%、残Zn)、EG:電気亜鉛め
っき鋼板、G■:溶融亜鉛めっき鋼板(At : 0.
3%。At: 10.25%, residual Zn), EG: electrogalvanized steel sheet, G■: hot-dip galvanized steel sheet (At: 0.
3%.
Fe : 0.8%、Pb:0.1%、残Zn)、Zn
/Zn−Cr:下層Cr1O%含有20g/n(亜鉛合
金めっき綱板、上層zn2g/ボ、
Zn−Ni : Ni 12%残Zn含量電気合金めっ
き鋼板、Zn−Mn : Mn 40%残Zn含量電気
合金めっき鋼板、鋼板厚はいずれも0.8圓の普通網。Fe: 0.8%, Pb: 0.1%, remaining Zn), Zn
/Zn-Cr: Lower layer Cr1O% content 20g/n (zinc alloy plated steel sheet, upper layer Zn2g/n), Zn-Ni: Ni 12% residual Zn content electrical alloy plated steel sheet, Zn-Mn: Mn 40% residual Zn content electrical The alloy plated steel plate and the steel plate thickness are both 0.8 mm thick.
注2)プレス性
(摩擦係数)
サンプルサイズ:17++wnX300鵬、引張り速度
: 500 mm/1IIin 、角ビート肩R: 1
.0 /3.0mm、摺動長:200mm、塗油:ソッ
クスラスト530F−40(パーカー興産株式会社)塗
油量1g/nfの条件で、面圧を100〜600kgf
の間で数点試験を行い、引き抜き加重を測定し、面圧と
引き抜き加重の傾きから摩擦係数を求めた。Note 2) Pressability (friction coefficient) Sample size: 17++wnX300mm, Tensile speed: 500mm/1IIin, Square beat shoulder R: 1
.. 0/3.0mm, sliding length: 200mm, oiling: Socklast 530F-40 (Parker Kosan Co., Ltd.) with an oiling amount of 1g/nf, and a surface pressure of 100 to 600kgf.
A several-point test was conducted between the two, the pull-out load was measured, and the coefficient of friction was determined from the slope of the surface pressure and pull-out load.
(破断限界荷重比)
上記ドロービード試験において、引き抜き荷重が急上昇
する面圧(押え荷重)(I!を破断面圧とし、から求め
た。(Breaking limit load ratio) In the above-mentioned drawbead test, the surface pressure (presser load) at which the pullout load suddenly increases (I! is the fracture surface pressure) was determined from.
注3)凝着防止機能皮膜とコロガリ潤滑機能皮膜量は金
属量として表示。なお、めっき素地から熔出して析出し
た金属量については測定できないので表示していない。Note 3) The amount of anti-adhesion film and rolling lubrication film is expressed as the amount of metal. Note that the amount of metal melted and precipitated from the plating base is not shown because it cannot be measured.
注4)化成処理性
化成処理液(亜鉛−リン酸−弗素系処理浴)には5D5
000 (日本ペイント社製)を用い、処方どおり脱脂
、表面調整を行った後化成処理を行った。Note 4) 5D5 is used for chemical conversion treatment liquid (zinc-phosphoric acid-fluorine treatment bath).
000 (manufactured by Nippon Paint Co., Ltd.), degreasing and surface conditioning were performed according to the prescription, followed by chemical conversion treatment.
化成処理皮膜の判定は、SEM(2次電子線像)により
、均一に皮膜が形成されているものは○、部分的に皮膜
が形成されているものは△、皮膜が形成されていないも
のは×と判定した。Chemical conversion treatment films are judged by SEM (secondary electron beam image): ○ if the film is uniformly formed, △ if the film is partially formed, and △ if the film is not formed. It was judged as ×.
本発明によれば、プレス成形において摺動性が冷延鋼板
並以上に向上し、しかもプレス成形時の押庄がなくなり
、かつ化成処理皮膜も形成可能な亜鉛系めっき鋼板を提
供し得るので、従来より低コスト、高品質で、ユーザー
の工程における負荷を低減でき、プレス成形に際しての
生産性を向上させることができるなど、本発明は産業上
極めて有用である。According to the present invention, it is possible to provide a zinc-based plated steel sheet whose slidability in press forming is improved to a level higher than that of a cold rolled steel sheet, which eliminates the stress during press forming, and which can also form a chemical conversion coating. The present invention is extremely useful industrially, as it is lower in cost and higher in quality than conventional methods, can reduce the burden on the user in the process, and can improve productivity during press molding.
第1図は電気亜鉛めっき鋼板表面に形成した非晶質酸化
物系皮膜の結晶構造を示す電子顕微鏡写真、第2図は電
気亜鉛めっき鋼板表面番こ非晶質酸化物系皮膜を形成し
た表面の電子プローブマイクロアナライザー線分析図、
第3図は第1図の銅板をドロービード摺動試験にかけた
後の表面の結晶構造を示す電子顕微鏡写真、第4図は第
3図に示す鋼板の表面の電子プローブマイクロアナライ
ザー線分析図、第5図は電気亜鉛めっき鋼板表面に非晶
質酸化物系皮膜を傾斜機能型に形成した皮膜の厚さ方向
のグロー放電分光分析説明図である。
捗
第1図
第3図
)すl
−側御 に
−雨一客Figure 1 is an electron micrograph showing the crystal structure of the amorphous oxide film formed on the surface of an electrogalvanized steel sheet, and Figure 2 is the surface on which the amorphous oxide film is formed on the surface of an electrogalvanized steel sheet. Electron probe microanalyzer line analysis diagram,
Figure 3 is an electron micrograph showing the crystal structure of the surface of the copper plate shown in Figure 1 after being subjected to a drawbead sliding test; Figure 4 is an electron probe microanalyzer line analysis diagram of the surface of the steel plate shown in Figure 3; FIG. 5 is an explanatory diagram of glow discharge spectroscopic analysis in the thickness direction of a functionally gradient amorphous oxide film formed on the surface of an electrogalvanized steel sheet. Figure 1 Figure 3
Claims (3)
に密着し、その変形に追随して被覆を維持する凝着防止
機能と、金型とめっき層間のコロガリ潤滑機能とを併せ
もつ無機系被覆層2〜1000mg/m^2(金属とし
て)を形成せしめたことを特徴とするプレス成形性、化
成処理性に優れた亜鉛系めっき鋼板。(1) An inorganic coating on the surface of the plating layer that has an anti-adhesion function that adheres to the surface of the plating layer during press molding and maintains the coating by following its deformation, and a rolling lubrication function between the mold and the plating layer. A zinc-based plated steel sheet with excellent press formability and chemical conversion treatment properties, characterized by forming a layer of 2 to 1000 mg/m^2 (as metal).
ガリ潤滑機能を被覆層表面に強く、傾斜被覆せしめた請
求項1に記載のプレス成形性、化成処理性に優れた亜鉛
系めっき鋼板。(2) The zinc-based plated steel sheet with excellent press formability and chemical conversion treatment properties according to claim 1, wherein the anti-adhesion function is strong at the interface with the plating layer, and the rolling lubrication function is strong at the surface of the coating layer, and is coated with a slope. .
、Ni、Ca、Cr、V、W、Ti、Al、Znの1種
または2種以上の金属酸化物および/または水酸化物を
主体とし、皮膜量が1〜500mg/m^2(金属とし
て)であり、コロガリ潤滑機能を有する皮膜がP、Bの
1種または2種の酸素酸および/またはSi、Al、T
iの1種または2種以上の酸化物コロイドを主体とし、
皮膜量が1〜500mg/m^2(金属として)である
請求項1または2に記載のプレス成形性、化成処理性に
優れた亜鉛系めっき鋼板。(3) The film with anti-adhesion function is made of Mn, Mo, and Co.
, Ni, Ca, Cr, V, W, Ti, Al, and Zn, and the coating amount is 1 to 500 mg/m^2 (as metal). ), and the film having a rolling lubrication function is composed of one or two types of oxygen acids such as P and B and/or Si, Al, and T.
Mainly composed of one or more oxide colloids of i,
The zinc-based plated steel sheet with excellent press formability and chemical conversion treatment properties according to claim 1 or 2, wherein the coating amount is 1 to 500 mg/m^2 (as metal).
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2305582A JP2691797B2 (en) | 1990-11-10 | 1990-11-10 | Galvanized steel sheet with excellent press formability and chemical conversion treatment |
PCT/JP1990/001615 WO1991009152A1 (en) | 1989-12-12 | 1990-12-11 | Galvanized steel plate having excellent capability of press working, chemical conversion and the like, and production of said plate |
KR1019910700888A KR940001032B1 (en) | 1989-12-12 | 1990-12-11 | Galvanized steel plate-having excellent capability of press working, chemical conversion and the like, and production of said plate |
EP91900051A EP0456834B1 (en) | 1989-12-12 | 1990-12-11 | Galvanized steel plate having excellent capability of press working, chemical conversion and the like, and production of said plate |
CA002046288A CA2046288C (en) | 1989-12-12 | 1990-12-11 | Zinc-base galvanized sheet steel excellent in press-formability, phosphatability, etc. and process for producing the same |
DE69027428T DE69027428T2 (en) | 1989-12-12 | 1990-12-11 | GALVANIZED STEEL SHEET WITH EXCELLENT PRESS FORMING, CHEMICAL SURFACE CONVERSION AND SIMILAR PROPERTIES AND THE PRODUCTION OF SUCH A SHEET |
AU68889/91A AU629724B2 (en) | 1989-12-12 | 1990-12-11 | Deep drawing galvanised steel plate for press working and conversion coating |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2305582A JP2691797B2 (en) | 1990-11-10 | 1990-11-10 | Galvanized steel sheet with excellent press formability and chemical conversion treatment |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04176878A true JPH04176878A (en) | 1992-06-24 |
JP2691797B2 JP2691797B2 (en) | 1997-12-17 |
Family
ID=17946879
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2305582A Expired - Lifetime JP2691797B2 (en) | 1989-12-12 | 1990-11-10 | Galvanized steel sheet with excellent press formability and chemical conversion treatment |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2691797B2 (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05214558A (en) * | 1991-12-10 | 1993-08-24 | Nkk Corp | Galvanized steel sheet excellent in press formability and spot weldability |
JPH06116746A (en) * | 1992-10-06 | 1994-04-26 | Nkk Corp | Galvanized steel sheet excellent in spot weldability, press formability, and chemical conversion treating property and its production |
JP2004209789A (en) * | 2002-12-27 | 2004-07-29 | Jfe Steel Kk | Precoated steel plate excellent in environmental consistency and coating film peel resistance and corrosion resistance of slide part |
JP2004209791A (en) * | 2002-12-27 | 2004-07-29 | Jfe Steel Kk | Precoated steel plate excellent in environmental consistency and corrosion resistance |
US6861160B2 (en) | 2000-12-04 | 2005-03-01 | Jfe Steel Corporation | Zinc-based plated steel sheet and method for manufacturing same |
JP2006265578A (en) * | 2005-03-22 | 2006-10-05 | Jfe Steel Kk | Galvanized steel sheet for chemical conversion, its manufacturing method, and chemically treated steel sheet |
JP2009235431A (en) * | 2008-03-26 | 2009-10-15 | Jfe Steel Corp | Galvanized steel sheet and manufacturing method therefor |
WO2012004889A1 (en) | 2010-07-09 | 2012-01-12 | 新日本製鐵株式会社 | Hot-dip zinc-coated steel sheet |
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 |
TWI396773B (en) * | 2010-07-08 | 2013-05-21 | Nippon Steel & Sumitomo Metal Corp | Hot-dipped galvanized steel sheet |
TWI447261B (en) * | 2010-11-26 | 2014-08-01 | Jfe Steel Corp | Hot dip al-zn coated steel sheet |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6345383A (en) * | 1986-04-18 | 1988-02-26 | Kawasaki Steel Corp | Production of zinc electroplated steel sheet having excellent chemical conversion treatability |
JPS63274797A (en) * | 1987-05-01 | 1988-11-11 | Kawasaki Steel Corp | Production of zn or zn alloy electroplated steel sheet having superior chemical treatability |
-
1990
- 1990-11-10 JP JP2305582A patent/JP2691797B2/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6345383A (en) * | 1986-04-18 | 1988-02-26 | Kawasaki Steel Corp | Production of zinc electroplated steel sheet having excellent chemical conversion treatability |
JPS63274797A (en) * | 1987-05-01 | 1988-11-11 | Kawasaki Steel Corp | Production of zn or zn alloy electroplated steel sheet having superior chemical treatability |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05214558A (en) * | 1991-12-10 | 1993-08-24 | Nkk Corp | Galvanized steel sheet excellent in press formability and spot weldability |
JPH06116746A (en) * | 1992-10-06 | 1994-04-26 | Nkk Corp | Galvanized steel sheet excellent in spot weldability, press formability, and chemical conversion treating property and its production |
US6861160B2 (en) | 2000-12-04 | 2005-03-01 | Jfe Steel Corporation | Zinc-based plated steel sheet and method for manufacturing same |
JP2004209789A (en) * | 2002-12-27 | 2004-07-29 | Jfe Steel Kk | Precoated steel plate excellent in environmental consistency and coating film peel resistance and corrosion resistance of slide part |
JP2004209791A (en) * | 2002-12-27 | 2004-07-29 | Jfe Steel Kk | Precoated steel plate excellent in environmental consistency and corrosion resistance |
JP2006265578A (en) * | 2005-03-22 | 2006-10-05 | Jfe Steel Kk | Galvanized steel sheet for chemical conversion, its manufacturing method, and chemically treated steel sheet |
JP2009235431A (en) * | 2008-03-26 | 2009-10-15 | Jfe Steel Corp | Galvanized steel sheet and manufacturing method therefor |
TWI396773B (en) * | 2010-07-08 | 2013-05-21 | Nippon Steel & Sumitomo Metal Corp | Hot-dipped galvanized steel sheet |
JP4970632B2 (en) * | 2010-07-09 | 2012-07-11 | 新日本製鐵株式会社 | Hot-dip galvanized steel sheet |
WO2012004889A1 (en) | 2010-07-09 | 2012-01-12 | 新日本製鐵株式会社 | Hot-dip zinc-coated steel sheet |
US8852753B2 (en) | 2010-07-09 | 2014-10-07 | Nippon Steel & Sumitomo Metal Corporation | Galvanized steel sheet |
TWI447261B (en) * | 2010-11-26 | 2014-08-01 | Jfe Steel Corp | Hot dip al-zn coated steel sheet |
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 |
EP2683843A1 (en) * | 2011-03-08 | 2014-01-15 | ThyssenKrupp Steel Europe AG | Flat steel product and method for producing a flat steel product |
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 |
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 |
EP2683843B1 (en) * | 2011-03-08 | 2021-06-16 | ThyssenKrupp Steel Europe AG | Flat steel product and method for producing a flat steel product |
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