JPS63190174A - Production of aluminized steel sheet having superior oxidation resistance at high temperature and superior corrosion resistance - Google Patents
Production of aluminized steel sheet having superior oxidation resistance at high temperature and superior corrosion resistanceInfo
- Publication number
- JPS63190174A JPS63190174A JP2222887A JP2222887A JPS63190174A JP S63190174 A JPS63190174 A JP S63190174A JP 2222887 A JP2222887 A JP 2222887A JP 2222887 A JP2222887 A JP 2222887A JP S63190174 A JPS63190174 A JP S63190174A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- alkoxide
- solution
- oxidation resistance
- aluminum
- 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
- 230000003647 oxidation Effects 0.000 title claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 15
- 238000005260 corrosion Methods 0.000 title claims abstract description 6
- 230000007797 corrosion Effects 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229910000680 Aluminized steel Inorganic materials 0.000 title description 2
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 31
- 239000010959 steel Substances 0.000 claims abstract description 31
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 150000007524 organic acids Chemical class 0.000 claims description 7
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 2
- 125000005595 acetylacetonate group Chemical group 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000007747 plating Methods 0.000 description 5
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- -1 cetyl acetonate Chemical compound 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 241000894007 species Species 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
- C23C18/02—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 thermal decomposition
- C23C18/12—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- 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
- C23C18/02—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 thermal decomposition
- C23C18/12—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Chemically Coating (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６００℃以上の温度においても耐高温酸化性と
耐食性とを発揮するアルミニウム系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 relates to a method for manufacturing an aluminum-based plated steel sheet that exhibits high-temperature oxidation resistance and corrosion resistance even at temperatures of 600° C. or higher.
（従来技術）
アルミニウムめっ軽鋼板やアルミニウム合金めっき鋼板
は耐熱性に優れているので、従来上り暖房器共やＷｉＦ
ｐＩ器共の燃焼部分、自動車の排気〃ス系統などに使用
されている。これらの用途では、鋼板は６００℃以上に
加熱される場合があるので、６００℃以上の耐高温酸化
性が要求される。(Conventional technology) Aluminum-plated light steel sheets and aluminum alloy-plated steel sheets have excellent heat resistance, so they can be used with conventional heaters and Wi-Fi.
It is used in the combustion part of PI reactors and the exhaust system of automobiles. In these applications, the steel plate may be heated to a temperature of 600°C or higher, and therefore high-temperature oxidation resistance of 600°C or higher is required.
しかしながら普通鋼冷延鋼板にアルミニウムもしくはそ
の合金をめっきした鋼板の耐高温酸化性は一般に６００
℃未満であるので、上記のような用途に使用する場合は
耐高温酸化性を向上させる必要があった。However, the high-temperature oxidation resistance of cold-rolled steel sheets plated with aluminum or its alloys is generally 600.
Since the temperature is less than 0.degree. C., it is necessary to improve high-temperature oxidation resistance when used in the above-mentioned applications.
従来ニのアルミニウム系めっき鋼板の耐高温酸化性を向
上させる方法としては次のような方法が提案されている
。Conventionally, the following methods have been proposed as methods for improving the high temperature oxidation resistance of aluminum-based plated steel sheets.
（１）めっき原板の成分調整による方法（例えば特公昭
６０−１３０２７号、特公昭６０−１３０５３号、特公
昭６０−６３３６３号など）。(1) A method by adjusting the components of the plating original plate (for example, Japanese Patent Publication No. 60-13027, Japanese Patent Publication No. 60-13053, Japanese Patent Publication No. 60-63363, etc.).
（２）耐熱塗料や耐熱樹脂を塗布する方法（例えば特開
昭６１−１１１３７８号）。(2) A method of applying heat-resistant paint or heat-resistant resin (for example, JP-A-61-111378).
（３）金属アルコキシドのアルコール溶液を塗布して加
熱することにより金属酸化物ポリマーの耐酸化皮膜を形
成する方法（特開昭６１−８７８７７号）。(3) A method of forming an oxidation-resistant film of a metal oxide polymer by applying and heating an alcohol solution of a metal alkoxide (Japanese Patent Application Laid-open No. 87877/1987).
（発明が解決しようとする問題点）
しかしく１）の方法はＳｉやＣｒを多量に添加するため
、めっき性が低下してしまい、めっきのときピンホール
が多くなるという欠点がある。(Problems to be Solved by the Invention) However, method 1) has the disadvantage that, since a large amount of Si and Cr is added, the plating properties deteriorate and pinholes occur during plating.
また（２）の方法は塗膜や皮膜の耐熱温度が高々３００
℃程度であるため、耐酸化温度を６００℃以上にするこ
とが困難であった。In addition, in method (2), the heat resistance temperature of the paint film or film is at most 300°C.
℃, it was difficult to increase the oxidation resistance temperature to 600°C or higher.
さらに（３）の方法は６００℃以上の耐高温酸化性を有
するが、この方法は金属アルコキシドのアルコール溶液
に無機酸を添加して、會）７Ａアルコキシドの加水分解
により生じた金属水酸化物を加熱により脱水縮合させ、
これにより金属酸化物皮膜にするのであるため、溶液に
は１’！ｆｉ酸の添加が必要である。このためアルミニ
ウム系めっき鋼板に塗布すると無機酸によりめっき層が
腐食されてＩｌｚ〃スを発生し、皮膜にピンホールを生
じさせる。Furthermore, method (3) has high temperature oxidation resistance of 600°C or higher, but this method adds an inorganic acid to an alcoholic solution of a metal alkoxide to remove the metal hydroxide produced by hydrolysis of the 7A alkoxide. Dehydrated and condensed by heating,
This creates a metal oxide film, so the solution contains 1'! Addition of fi acid is necessary. Therefore, when applied to an aluminum-based plated steel sheet, the inorganic acid corrodes the plating layer and generates Ilz gas, causing pinholes in the coating.
本発明はこの（３）の方法１こおけるピンホール発生の
問題を解決して、６００℃以上の耐高温酸化性を有する
アルミニツム系めっき鋼板を得ることができるようにし
たものである。The present invention solves the problem of pinhole formation in method 1 of (3), and makes it possible to obtain an aluminum-based plated steel sheet having high temperature oxidation resistance of 600° C. or higher.
（問題点を解決するための手段）
本発明はアルミニウムまたはアルミニウム合金めっき鋼
板に下記（Ａ）もしくは（Ｂ）の溶液を塗布して２００
℃以上に加熱し、溶液中に含まれる金属の酸化物皮膜を
形成することにより皮膜にピンホールが発生しないよう
にした。(Means for Solving the Problems) The present invention involves coating an aluminum or aluminum alloy plated steel plate with the following solution (A) or (B).
The solution was heated to a temperature higher than 0.degree. C. to form an oxide film of the metal contained in the solution, thereby preventing the formation of pinholes in the film.
（Ａ ）Ｓｉのアルコキシドのアルコール溶液に一般式
がＣｎＨ２ｎ＋＋ Ｃ００Ｈ（但しＯ≦ｎ≦１０の整数
）で示される有機酸を添加した溶液。(A) A solution in which an organic acid having the general formula CnH2n++ C00H (where O≦n≦10, an integer) is added to an alcoholic solution of Si alkoxide.
（Ｂ ）ＳｉのアルコキシドにＴｉ５Ｚｒｘ＾１のアル
コキシドまたはアセチルアセトネート塩の１種または２
種以上を添加したアルコール溶液に一般式がＣｎ１１ｘ
ｎｆＩＣＯＯＩＩ（但し０≦ｎ≦１０の整数）で示され
る有Ｗ１ｆｌｌを添加したＳ液。(B) One or two of Ti5Zrx^1 alkoxide or acetylacetonate salt to Si alkoxide
The general formula is Cn11x in the alcohol solution to which more than one species has been added.
An S solution containing W1fll represented by nfICOOII (an integer of 0≦n≦10).
上記（Ａ）、（Ｂｌの溶液においてＳｉのアルコキシド
を必須とするのは、Ｓｉアルコキシドの溶液はＴ ｉ
ｓＺｒ、＾Ｉのアルコキシドやアセチル７セトネート塩
の溶液に比べて安定性があり、かつ溶液中のコロイド粒
子を均一にすることができて、Ｓｉアルコキシドを均一
に塗布できるからである。このため（Ｂ）溶液のように
他の金属アルコキシドや７セチル７セトネート金属塩を
添加する場合にはＳｉのアルコキシド濃度を一０１％で
７０％以上にするのが好ましい。Above (A), (the reason why Si alkoxide is essential in the solution of Bl is that the solution of Si alkoxide is Ti
This is because it is more stable than solutions of sZr, ^I alkoxides and acetyl 7cetonate salts, and the colloidal particles in the solution can be made uniform, allowing the Si alkoxide to be applied uniformly. For this reason, when other metal alkoxides or 7cetyl 7cetonate metal salts are added as in solution (B), it is preferable that the alkoxide concentration of Si is 101% or more than 70%.
溶液に添加する有機酸を一般式がＣｎＨｚｎ＋＋ Ｃ０
ＯＨにしたのは、かかる有機酸の添加ではアルミニウム
系めっき鋼板のめり外層は腐食されず、Ｈ１〃スが発生
しないため、皮膜にピンホールが発生しないためである
。また一般式Ｃｎ１ｌｚｎ＋ＩＣ０Ｏｔｌのｎを０≦ｎ
≦１０の整数にしたのは、ｎ≧１１であると酸強度が弱
くなるため、金属アルコキシドやアセチル７セトネート
金属塩の加水分解がほとんど進行しないため、金属酸化
物の皮膜形成が困難になるからである。The organic acid added to the solution has the general formula CnHzn++ C0
The reason why OH was selected is that the addition of such an organic acid does not corrode the outer layer of the aluminum plated steel sheet, does not generate H1 gas, and therefore does not generate pinholes in the film. Also, n in the general formula Cn1lzn+IC0Otl is 0≦n
The reason for choosing an integer of ≦10 is that when n≧11, the acid strength becomes weaker, and the hydrolysis of metal alkoxides and acetyl 7cetonate metal salts hardly progresses, making it difficult to form a metal oxide film. It is.
鋼板への塗布後の溶液加熱温度を２００℃以上にしたの
は、２００℃未満であるとＳｉｓ Ｔｉ、 Ｚｒｓ＾１
のアルコキシドやＴｉ％Ｚ「、＾１の７セチルアセトネ
ート塩の脱水縮合が完全に進行しないため、完全な金属
酸化物のポリマー皮膜にならないからである。Sis Ti, Zrs^1 The solution heating temperature after coating on the steel plate was set to 200 °C or higher when the temperature was lower than 200 °C.
This is because the dehydration condensation of the alkoxide of Ti%Z' and the 7cetylacetonate salt of ^1 does not proceed completely, so a complete polymer film of the metal oxide is not formed.
Ｓｉのアルコキシドとしてはエチルシリケートが安価で
好ましい、このＳｉのアルコキシドに添加するＴｉ５Ｚ
ｒｘ＾１のアルコキシドやアセチルアセトネート塩とし
ては、チタンイソプロポキシド、チタンオキシ７セチル
ア七トネート、ノルコニウムメトキシド、ノルコニウム
７セチルアセトネート、アルミニウムイソプロポキシド
、アルミニウム７セチルアセトネートなどを使用すれば
よい。As the Si alkoxide, ethyl silicate is preferable because it is inexpensive.Ti5Z added to this Si alkoxide
As the alkoxide or acetylacetonate salt of rx^1, titanium isopropoxide, titanium oxy 7-cetylacetonate, norconium methoxide, norconium 7-cetylacetonate, aluminum isopropoxide, aluminum 7-cetylacetonate, etc. may be used. Bye.
これらの化合物を希釈するアルコールは特に制限はない
が、皮Ｉ！構造の緻密化や経済性の見地から、メタノー
ル、エタノール、イソプロピルアルコール、ブタメール
など低級アルコールが好ましν１ 。There are no particular restrictions on the alcohol used to dilute these compounds, but skin I! Lower alcohols such as methanol, ethanol, isopropyl alcohol, and butamele are preferred from the viewpoint of densification of structure and economy.
溶液の鋼板への塗布は、浸漬例外上げ法、スプレー法、
スピン法、ロール−コート法など公知方法によればよい
塗布量は乾燥後の皮膜厚が０．０５μ輪以上、好ましく
は０．０５〜０．６μｍ、一般的にはｏ、ｉμ−になる
ようにする、 ０．０５μ−未満であるとピンホールが
多くなり、０．６μ−より厚くすると可撓性が低下し、
クランクや剥離が生じ易くなる。しかし０．６μ−以上
にすることを妨げるものではない。The solution can be applied to the steel plate using the immersion method, spray method,
According to a known method such as a spin method or a roll-coating method, the coating amount is such that the film thickness after drying is 0.05 μm or more, preferably 0.05 to 0.6 μm, and generally o, iμ. If it is less than 0.05μ, there will be many pinholes, and if it is thicker than 0.6μ, the flexibility will decrease.
Cracks and peeling are more likely to occur. However, this does not preclude making it 0.6μ or more.
（実施例）
実施例１
板厚０．４ｍｍの溶融アルミニウムめっき鋼板（付着１
１８０９／（至）２）を７七トンで１０分間超音波脱脂
した後、ｔｔｌの左側に示す金属アルコキシドもしくは
アセチルアセトネート金属塩のアルコール溶液に浸漬し
、３ＩｌｌＩＩ／秒の一定速度で引上げ、均一に塗布し
た。そして塗布後この鋼板を３００℃の電気炉中に１５
分間入れ、酸化物皮膜（１５１厚約０．３μ論）を形成
した。(Example) Example 1 Hot-dip aluminum plated steel plate with a plate thickness of 0.4 mm (adhesion 1
1809/(To) 2) was ultrasonically degreased at 77 tons for 10 minutes, then immersed in an alcohol solution of metal alkoxide or acetylacetonate metal salt shown on the left side of ttl, pulled up at a constant speed of 3IllII/sec, and uniformly It was applied to. After coating, this steel plate was placed in an electric furnace at 300℃ for 15 minutes.
The mixture was heated for a minute to form an oxide film (151 thickness of about 0.3 μm).
次にこの酸化物皮膜を形成した鋼板を８５０℃の雰囲気
中で４８時間加熱し、加熱前後の重量変化を測定した。Next, the steel plate on which the oxide film was formed was heated in an atmosphere of 850° C. for 48 hours, and the weight change before and after heating was measured.
この結果を８１の右側に示す。This result is shown on the right side of 81.
実施例２
［ｆｆＯ，ａｍｓの蒸着アルミニウムめっき鋼板（付着
ｆｌＬ６０９／鋤２）をエタノールで１５分間超音波脱
脂した後、前記実施例１で塗布したのと同一の金属アル
コキシドもしくはアセチル７セトネート金属塩のアルコ
ール溶液に浸漬し、 ４ ｅｎ＋７秒の一定速度で引上
げ、均一に塗布した。そして塗布後この鋼板を４００℃
の電気炉中に５分間入れ、酸化物皮ｇ！（ＷＡ厚約０．
５μ−）を形成した。Example 2 [FFO, ams vapor deposited aluminized steel plate (adhesive flL609/plow 2) was ultrasonically degreased with ethanol for 15 minutes and then treated with the same metal alkoxide or acetyl 7cetonate metal salt applied in Example 1 above. It was immersed in an alcohol solution and pulled up at a constant speed of 4 en+7 seconds to apply it uniformly. After coating, this steel plate was heated to 400°C.
Place it in an electric furnace for 5 minutes to remove the oxide skin g! (WA thickness approx. 0.
5μ-) was formed.
次にこの酸化物皮膜を形成した鋼板を７００℃の雰囲気
中で１２０時間加熱し、加熱前後の重量変化を測定した
。この結果を表２に示す。Next, the steel plate on which the oxide film was formed was heated in an atmosphere at 700° C. for 120 hours, and the weight change before and after heating was measured. The results are shown in Table 2.
実施例３
板厚０．５−の溶融アルミニウムめっ終鋼板（付着量１
００９／曽２）を７七トンで１０分間超音波脱脂した後
、表３の左側に示す金属アルコキシドもしくは７セチル
アセトネート金属塩のアルコール溶液に浸漬し、２ ｍ
ｓ／秒の一定速度で引上げ、均一に塗布した。そして塗
布後この鋼板を３５０℃の電気炉中に１０分間入れ、酸
化物皮膜（ｌＩ厚約０．２μ鋤）を形成した。Example 3 Hot-dip aluminum plated steel plate with a plate thickness of 0.5 mm (coating amount: 1
009/Zeng 2) was ultrasonically degreased at 77 tons for 10 minutes, then immersed in an alcohol solution of the metal alkoxide or 7 cetyl acetonate metal salt shown on the left side of Table 3, and heated for 2 m.
It was pulled up at a constant speed of s/sec to uniformly apply the coating. After coating, the steel plate was placed in an electric furnace at 350° C. for 10 minutes to form an oxide film (1I thickness of about 0.2 μm).
次にこの酸化物皮膜を形成した鋼板を６５０℃の雰囲気
中で８時間加熱後冷却するサイクルを１０サイクル行い
、加熱前後の重量変化を測定した。Next, the steel plate on which the oxide film was formed was heated in an atmosphere at 650° C. for 8 hours and then cooled for 10 cycles, and the weight change before and after heating was measured.
この結果を表３の右側に示す。The results are shown on the right side of Table 3.
実施例４
実施例１〜３で製造した鋼板の加熱前のものの一部を塩
水噴霧試験し、２４０時間後の白錆発生率を調査した。Example 4 Some of the steel plates manufactured in Examples 1 to 3 before heating were subjected to a salt spray test, and the incidence of white rust after 240 hours was investigated.
この結果を表４に示す。The results are shown in Table 4.
表４
（効果）
以上のごとく本発明はアルミニウム系めっ訃鋼板に金属
アルコキシドもしくはアセチル７セトネート金属塩のア
ルコール溶液を塗布して耐高温酸化性、耐食性に優れた
アルミニウム系めっき鋼板を製造する際、溶液に添加す
る酸として有機酸を使用するのであるが、有機際を使用
すればめっき層のアルミニウムを腐食しないので、皮膜
には１１２〃ス発生によるピンホールが発生しない。Table 4 (Effects) As described above, the present invention applies an alcohol solution of a metal alkoxide or acetyl 7cetonate metal salt to an aluminum plated steel plate to produce an aluminum plated steel plate with excellent high temperature oxidation resistance and corrosion resistance. An organic acid is used as the acid added to the solution, but if an organic acid is used, it will not corrode the aluminum of the plating layer, so pinholes due to 112 gas generation will not occur in the film.
Claims (2)
に下記（Ａ）もしくは（Ｂ）の溶液を塗布して２００℃
以上に加熱し、溶液中に含まれる金属の酸化物皮膜を形
成することを特徴とする耐高温酸化性および耐食性に優
れたアルミニウム系めっき鋼板の製造方法。（Ａ）Ｓｉ
のアルコキシドのアルコール溶液に一般式がＣ＿ｎＨ＿
２＿ｎ＿＋＿１ＣＯＯＨ（但し０≦ｎ≦１０の整数）で
示される有機酸を添加した溶液。 （Ｂ）ＳｉのアルコキシドにＴｉ、Ｚｒ、Ａｌのアルコ
キシドまたはアセチルアセトネート塩の１種または２種
以上を添加したアルコール溶液に一般式がＣ＿ｎＨ＿２
＿ｎ＿＋＿１ＣＯＯＨ（但し０≦ｎ≦１０の整数）で示
される有機酸を添加した溶液。(1) Apply the solution (A) or (B) below to an aluminum or aluminum alloy plated steel plate and heat it to 200°C.
A method for producing an aluminum-based plated steel sheet having excellent high-temperature oxidation resistance and corrosion resistance, the method comprising heating to the above temperature to form an oxide film of the metal contained in the solution. (A)Si
The general formula is C_nH_ in an alcoholic solution of alkoxide.
A solution containing an organic acid represented by 2_n_+_1COOH (an integer of 0≦n≦10). (B) The general formula is C_nH_2 in an alcohol solution in which one or more of Ti, Zr, and Al alkoxides or acetylacetonate salts are added to Si alkoxide.
A solution containing an organic acid represented by _n_+_1COOH (an integer of 0≦n≦10).
をｍｏｌ％で７０％以上にすることを特徴とする耐高温
酸化性および耐食性に優れたアルミニウムめっき鋼板の
製造方法。(2) A method for producing an aluminum-plated steel sheet with excellent high-temperature oxidation resistance and corrosion resistance, characterized in that the Si alkoxide concentration in the solution (B) is 70% or more by mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2222887A JPS63190174A (en) | 1987-02-02 | 1987-02-02 | Production of aluminized steel sheet having superior oxidation resistance at high temperature and superior corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2222887A JPS63190174A (en) | 1987-02-02 | 1987-02-02 | Production of aluminized steel sheet having superior oxidation resistance at high temperature and superior corrosion resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63190174A true JPS63190174A (en) | 1988-08-05 |
Family
ID=12076939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2222887A Pending JPS63190174A (en) | 1987-02-02 | 1987-02-02 | Production of aluminized steel sheet having superior oxidation resistance at high temperature and superior corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63190174A (en) |
-
1987
- 1987-02-02 JP JP2222887A patent/JPS63190174A/en active Pending
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