JPH01252785A - Formation of deposited zinc layer on aluminum material - Google Patents
Formation of deposited zinc layer on aluminum materialInfo
- Publication number
- JPH01252785A JPH01252785A JP7918288A JP7918288A JPH01252785A JP H01252785 A JPH01252785 A JP H01252785A JP 7918288 A JP7918288 A JP 7918288A JP 7918288 A JP7918288 A JP 7918288A JP H01252785 A JPH01252785 A JP H01252785A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- ions
- aluminum material
- layer
- acidic
- 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
- 239000011701 zinc Substances 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 36
- 229910052725 zinc Inorganic materials 0.000 title claims description 36
- 229910052782 aluminium Inorganic materials 0.000 title claims description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 23
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 239000010410 layer Substances 0.000 claims abstract description 15
- 230000002378 acidificating effect Effects 0.000 claims abstract description 14
- 239000002344 surface layer Substances 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 17
- -1 fluorine ions Chemical class 0.000 claims description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 abstract description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract description 2
- 239000011787 zinc oxide Substances 0.000 abstract description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 abstract description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 20
- 238000011282 treatment Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 238000005219 brazing Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- RCQZCHPRZSTYAX-UHFFFAOYSA-N zinc tetrahydrate Chemical compound O.O.O.O.[Zn] RCQZCHPRZSTYAX-UHFFFAOYSA-N 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はアルミニウム材の表面に亜鉛拡散処理に適した
亜鉛析出層を形成する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for forming a zinc deposited layer suitable for zinc diffusion treatment on the surface of an aluminum material.
アルミニウム材やその製品（以下アルミニウム材と称す
）は軽量性や良好な熱伝導性などの特性から熱交換機、
自動車用部品などに汎用されている。このアルミニウム
材は、普通、陽極酸化皮膜が施され、さらに封孔が行わ
れており１通常の使用条件ではこれらの処理で十分な耐
食性を得ることができる。しかし、重金属イオンや塩素
イオンを含む水に対しては耐食性が乏しく、特に孔質腐
食等を起こす欠点がある。Aluminum materials and their products (hereinafter referred to as aluminum materials) are used in heat exchangers, etc. due to their light weight and good thermal conductivity.
It is widely used in automobile parts, etc. This aluminum material is usually coated with an anodic oxide film and further sealed; 1 Under normal usage conditions, sufficient corrosion resistance can be obtained through these treatments. However, it has poor corrosion resistance against water containing heavy metal ions and chlorine ions, and has the drawback of causing porous corrosion in particular.
この対策として、特公昭６２−６７４４号公報が開示さ
れている。この先行技術は、アルミニウム材を弗化亜鉛
の無水塩または４水塩の水溶液に浸漬し、アルミニウム
材表面に亜鉛析出層を形成させるというものである。As a countermeasure against this problem, Japanese Patent Publication No. 62-6744 is disclosed. In this prior art, an aluminum material is immersed in an aqueous solution of anhydrous zinc fluoride or tetrahydrate to form a zinc deposited layer on the surface of the aluminum material.
しかし、無水塩、４水塩はいずれも水に対する溶解度が
極めて小さく、２０℃の水に１．６２％程度しか溶解し
ない。液温度をたとえば５０℃にしても、溶解度は多少
増える程度に過ぎない、このため、先行技術の手法では
、亜鉛析出量が少なくならざるを得ない。However, both the anhydrous salt and the tetrahydrate salt have extremely low solubility in water, and dissolve only about 1.62% in water at 20°C. Even if the liquid temperature is increased to, for example, 50° C., the solubility increases only to a certain degree, and therefore, in the prior art method, the amount of zinc deposited must be reduced.
そこで、亜鉛析出量を増加するため、あらかじめ加温し
た弗化亜鉛水溶液を収容した槽底に、弗化亜鉛粉末を置
き、これを攪拌手段により液中に分散したり、弗化亜鉛
粉末の微細粒子を泥しよう状にして浮遊させるなどの方
法がとられている。Therefore, in order to increase the amount of zinc precipitation, zinc fluoride powder is placed at the bottom of a tank containing a pre-warmed zinc fluoride aqueous solution, and this is dispersed in the liquid using stirring means. Methods such as suspending the particles in the form of slurry have been used.
このように未溶解の弗化亜鉛粉末を大量に使用すれば、
形式的には亜鉛析出量を増すことはできる。しかし、そ
の亜鉛析出皮膜は未溶解亜鉛粒子が付着しただけのもの
であるため、不均一であるとともにきわめて密着性が悪
く７手で軽く触っただけでも脱落してしまい、実用的な
価値は乏しかった。If you use a large amount of undissolved zinc fluoride powder like this,
Formally, it is possible to increase the amount of zinc precipitation. However, since the zinc deposited film is simply an adhesion of undissolved zinc particles, it is not uniform and has extremely poor adhesion, falling off even when touched lightly with one's hand, so it has little practical value. Ta.
本発明は前記のような問題点を解消するために創案され
たもので、その目的とするところは、アルミニウム材と
の密着性の優れた均一な亜鉛析出層を、容易に安定して
形成することができる方法を提供することにある。The present invention was devised to solve the above-mentioned problems, and its purpose is to easily and stably form a uniform zinc precipitated layer with excellent adhesion to aluminum materials. The goal is to provide a method that can be used.
上記目的を達成するため本発明は、ｐＨコントロールに
より弗化亜鉛を高い濃度で溶解できるようにしたもので
あり、すなわち、アルミニウム材を亜鉛イオンと弗素イ
オンからなるｐＨ２，５〜５゜３の酸性亜鉛系水溶液で
処理することによりアルミニウム材の表層を溶解すると
共に亜鉛析出層を形成することを特徴とするものである
。In order to achieve the above object, the present invention enables zinc fluoride to be dissolved at a high concentration by pH control. In other words, aluminum material is dissolved in an acidic solution containing zinc ions and fluoride ions with a pH of 2.5 to 5.3. It is characterized by dissolving the surface layer of the aluminum material and forming a zinc precipitated layer by treating it with a zinc-based aqueous solution.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
まず、適用されるアルミニウム材は、アミニウム合金が
一般的であるが、純アルミニウムも含まれ、形状は板、
異型材、など任意であり、押出し成形材、プレス成形材
、最終製品のいずれも含まれる。First, the aluminum material used is generally aminium alloy, but also includes pure aluminum, and the shape is plate, plate, etc.
It is optional, such as irregularly shaped materials, and includes extrusion molded materials, press molded materials, and final products.
本発明はこのアルミニウム材の処理液として、亜鉛イオ
ンと弗素イオンからなるｐＨ２，５〜５゜３の酸性亜鉛
系水溶液を用いる。すなわち、弗化亜鉛水溶液は通常２
０℃でｐＨ約５．３以上であるが、これを好ましくはｐ
）１５．２以下になるように酸を加えてｐＨを低下させ
、弗化亜鉛の濃度を大にしても溶解するようにする。In the present invention, an acidic zinc-based aqueous solution containing zinc ions and fluorine ions and having a pH of 2.5 to 5.degree. 3 is used as the treatment solution for the aluminum material. That is, zinc fluoride aqueous solution usually has 2
pH is about 5.3 or higher at 0°C, preferably pH
) Add an acid to lower the pH to 15.2 or less, so that even if the concentration of zinc fluoride is increased, it will dissolve.
まず、亜鉛イオン量は、大体０．５〜３０ｇ／Ｑが適当
であり、その供給源は、通常、酸化亜鉛、リン酸亜鉛、
水酸化亜鉛、弗化亜鉛等である。First, the appropriate amount of zinc ion is approximately 0.5 to 30 g/Q, and its source is usually zinc oxide, zinc phosphate,
These include zinc hydroxide and zinc fluoride.
ＰＨを低くするために加える酸イオンは、弗素イオンが
好適であり、これにリン酸イオンを所定割合で加えても
よい、弗素イオン量は、大体０．５〜１０ｇ／Ｑが適当
であり、その供給源は、弗化水素、酸性弗化アンモニウ
ムなどである。The acid ions added to lower the pH are preferably fluorine ions, to which phosphate ions may be added at a predetermined ratio.The amount of fluorine ions is approximately 0.5 to 10 g/Q, Its sources include hydrogen fluoride and acidic ammonium fluoride.
酸性亜鉛系水溶液のｐＨの上限を５．３としたのは、こ
れを超えると前記従来法のような問題が生ずるためであ
り、 ＰＨの下限を２．５としたのは、これを下回ると
、アルミニウム材の表面の溶解が激しくなりすぎ、亜鉛
析出層の形成が回置になるからである。The reason why the upper limit of the pH of the acidic zinc-based aqueous solution was set to 5.3 is that if it exceeds this, problems like the above-mentioned conventional method will occur, and the reason why the lower limit of pH is set to 2.5 is that if it goes below this, This is because the surface of the aluminum material becomes too violently dissolved and the formation of the zinc precipitated layer becomes dislocated.
この酸性亜鉛系水溶液による処理は、通常浸漬法が採用
され、その温度は１０〜７０℃であるが。For this treatment with an acidic zinc-based aqueous solution, a dipping method is usually adopted, and the temperature is 10 to 70°C.
本発明は常温でも十分に亜鉛析出層を形成できるため、
ことさら処理温度を高くする必要がなく、経済的である
。Since the present invention can sufficiently form a zinc precipitated layer even at room temperature,
It is economical as there is no need to particularly raise the processing temperature.
この処理により、アルミニウム材は酸性亜鉛系水溶液中
の弗素イオンにより表層が適度にエツチングされ、それ
により活性化した表層に濃度の高い亜鉛イオンが作用す
るため、密着性のすぐれた亜鉛析出層が均一に形成され
る。このときの亜鉛析出層の層厚は、酸性亜鉛系水溶液
のｐＨ１浸漬時間、液温度のいずれか１つ以上を調整す
ることにより任意にコントロールできる。従来のように
未溶解弗化亜鉛粉末やスラリーを使用しないため、複雑
な形状のアッセンブリに適用しても、酸性亜鉛系水溶液
が狭い隙間にも確実に浸透し、すみずみまで密着性にす
ぐれた亜鉛析出層を形成できる。Through this treatment, the surface layer of the aluminum material is moderately etched by fluorine ions in the acidic zinc-based aqueous solution, and as a result, highly concentrated zinc ions act on the activated surface layer, resulting in a uniform zinc deposited layer with excellent adhesion. is formed. The layer thickness of the zinc deposited layer at this time can be arbitrarily controlled by adjusting any one or more of the pH 1 immersion time of the acidic zinc-based aqueous solution and the solution temperature. Unlike conventional methods, undissolved zinc fluoride powder or slurry is not used, so even when applied to complex-shaped assemblies, the acidic zinc-based aqueous solution reliably penetrates into narrow gaps and provides excellent adhesion throughout. A zinc deposit layer can be formed.
なお、アルミニウム材は、浸漬液から引き上げた後、水
洗し、またはこれを省略して加熱炉等に装入し、析出亜
鉛を深く拡散浸透させるのが一般である。このときに、
ろう付は用フラックスを塗布し、約５５０〜６５０℃に
加熱してろう付けと同時に亜鉛拡散処理を行ってもよい
１本発明は。Note that, after the aluminum material is pulled out of the immersion liquid, it is generally washed with water or omitted and placed in a heating furnace or the like to deeply diffuse and penetrate the precipitated zinc. At this time,
One method of the present invention is to apply flux for brazing, heat it to about 550 to 650°C, and perform zinc diffusion treatment simultaneously with brazing.
ろう付は後の製品に亜鉛析出を行い、加熱して拡散させ
る場合にも用いることができる。Brazing can also be used to deposit zinc on subsequent products and diffuse it by heating.
〔実 施 例〕
■、亜鉛イオン供給源としてＺｎＦ、・４Ｈ２０、弗素
イオン供給源としてＨＦを用い、亜鉛イオン５．８ＥＩ
Ｑ、弗素イオン５．２ｇＩＱの水溶液を７Ａ整してｐＨ
４，３にした。これは十分に水溶化しており、これを酸
性亜鉛系水溶液とした。[Example] ■ Using ZnF, 4H20 as a zinc ion supply source and HF as a fluorine ion supply source, zinc ion 5.8EI
Q. Adjust the pH of an aqueous solution of 5.2 g IQ of fluorine ions to 7A.
I made it 4.3. This was sufficiently water-soluble and was used as an acidic zinc-based aqueous solution.
■、前記酸性亜鉛系水溶液を約２５℃に保ち、アルミニ
ウム板（４００Ｘ ２２ Ｘ ５ Ｘ ｍｍ）を脱脂し
て清浄した後、酸性亜鉛系水溶液に２分間浸漬した。(2) The acidic zinc-based aqueous solution was maintained at about 25° C., and an aluminum plate (400 x 22 x 5 x mm) was degreased and cleaned, and then immersed in the acidic zinc-based aqueous solution for 2 minutes.
亜鉛析出量は約３．５ｇ／ｒｒ？で、板金面にわたり均
一で、手で擦っても脱落しなかった。The amount of zinc precipitation is about 3.5g/rr? It was uniform over the sheet metal surface and did not fall off even when rubbed by hand.
■、ついでアルミニウム材を水洗後乾燥し、弗化物系の
フラックス（ＫＦ４３％、Ａｌ１．０，５７％の錯体）
をＬｏｇ／ｎ（塗布し、６００℃で２分間ろう付けした
ところ、良好なろう付けが得られた。■Then, the aluminum material was washed with water and dried, and a fluoride-based flux (a complex of 43% KF and 1.0.57% Al) was applied.
When applied with Log/n and brazed at 600° C. for 2 minutes, good brazing was obtained.
ＣＡＳＳテスト（１３００ｈｒ）を実施したところ、最
大孔食深さは０．１ｍｍ以下ときわめて良好であった。When a CASS test (1300 hr) was conducted, the maximum pitting depth was 0.1 mm or less, which was very good.
■、比較のため、亜鉛量を同じくしたＺｎＦ２・４Ｈ，
１０１５ｇ、ｌを水に泥しよう状に分散した水溶液で亜
鉛析出処理を行った。■For comparison, ZnF2・4H with the same amount of zinc,
Zinc precipitation treatment was carried out using an aqueous solution in which 1015 g, 1 of the sample was dispersed in water like slurry.
前記水溶液はＰＨ５，６で、温度２５℃で十分に攪拌し
ながら、アルミニウム板を２分間浸漬処理した。その結
果、アルミニウム表面の変化は全く見られず、亜鉛析出
量は実質的にゼロであった・
特許出願人 株式会社ケミコート
同 太田数行The aqueous solution had a pH of 5.6, and the aluminum plate was immersed for 2 minutes at a temperature of 25°C with sufficient stirring. As a result, no changes were observed on the aluminum surface, and the amount of zinc precipitation was virtually zero. Patent applicant: Kazuyuki Ota, Chemicoat Co., Ltd.
Claims (1)
２．５〜５．３の酸性亜鉛系水溶液で処理することによ
りアルミニウム材の表層を溶解すると共に亜鉛析出層を
形成することを特徴とするアルミニウム材に亜鉛析出層
を形成する方法。Aluminum material has a pH of zinc ions and fluorine ions.
A method for forming a zinc deposited layer on an aluminum material, the method comprising dissolving the surface layer of the aluminum material and forming a zinc deposited layer by treating with an acidic zinc-based aqueous solution of 2.5 to 5.3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7918288A JPH01252785A (en) | 1988-03-31 | 1988-03-31 | Formation of deposited zinc layer on aluminum material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7918288A JPH01252785A (en) | 1988-03-31 | 1988-03-31 | Formation of deposited zinc layer on aluminum material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01252785A true JPH01252785A (en) | 1989-10-09 |
Family
ID=13682835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7918288A Pending JPH01252785A (en) | 1988-03-31 | 1988-03-31 | Formation of deposited zinc layer on aluminum material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01252785A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03207885A (en) * | 1989-10-30 | 1991-09-11 | Sky Alum Co Ltd | Production of zinc type plated aluminum sheet |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50148242A (en) * | 1974-05-20 | 1975-11-27 | ||
| JPS626744A (en) * | 1985-07-02 | 1987-01-13 | Nippon Steel Corp | Continuous casting method for high-carbon steel |
-
1988
- 1988-03-31 JP JP7918288A patent/JPH01252785A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50148242A (en) * | 1974-05-20 | 1975-11-27 | ||
| JPS626744A (en) * | 1985-07-02 | 1987-01-13 | Nippon Steel Corp | Continuous casting method for high-carbon steel |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03207885A (en) * | 1989-10-30 | 1991-09-11 | Sky Alum Co Ltd | Production of zinc type plated aluminum sheet |
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