JP3224034B2 - Corrosion resistant film and its formation method - Google Patents
Corrosion resistant film and its formation methodInfo
- Publication number
- JP3224034B2 JP3224034B2 JP32141491A JP32141491A JP3224034B2 JP 3224034 B2 JP3224034 B2 JP 3224034B2 JP 32141491 A JP32141491 A JP 32141491A JP 32141491 A JP32141491 A JP 32141491A JP 3224034 B2 JP3224034 B2 JP 3224034B2
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- Japan
- Prior art keywords
- zinc
- corrosion
- hemimorphite
- film
- resistant film
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐食性皮膜、とくに、
水道管、下水道管等の給水または排水を目的とする配
管、温水器の配管、給湯管、冷暖房用冷温水系の循環配
管、給湯設備の貯水タンク等、水設備あるいは配管の接
液面及び自動車鋼板や屋根材等の外装鋼板表面に形成す
る耐食性皮膜およびその形成方法に関する。BACKGROUND OF THE INVENTION The present invention relates to a corrosion-resistant coating,
Pipes for water supply or drainage of water pipes, sewer pipes, etc., water heater pipes, hot water pipes, circulating pipes for cooling / heating water systems for cooling and heating, water storage tanks for hot water supply equipment, etc. The present invention relates to a corrosion-resistant film formed on the surface of an exterior steel plate such as a roof and a roof material, and a method for forming the same.
【０００２】[0002]
【従来の技術】わが国の水道水は欧米のものと比較し
て、硬質分が少なく腐食が起こり易いと言われ、これに
加えて、近年大都市部での水源の汚濁が進み、それに伴
って塩素投入量が増大しているため、水道管系における
腐食環境はますます厳しいものとなっている。一方、都
会におけるビルの老朽化に伴い、ビル内の水道系配管の
錆詰まりによる出水不良、赤水の発生、さらには漏水等
が社会問題になっている。2. Description of the Related Art It is said that tap water in Japan has less hardness and is more susceptible to corrosion than those in Europe and the United States. In addition, in recent years, water sources have become increasingly polluted in large urban areas. Corrosive environments in water pipe systems are becoming increasingly severe due to increasing chlorine inputs. On the other hand, with the aging of buildings in urban areas, poor water discharge due to rust clogging of water supply pipes in buildings, generation of red water, and water leakage have become social problems.
【０００３】この状況に鑑み、本願の発明者は、従来水
道用給水配管として最も一般的に使用されていた亜鉛め
っき鋼管の腐食機構について研究し、亜鉛の耐食性皮膜
生成と犠牲アノードの２つの防食作用の両面性につい
て、１９８９年、「腐食防食'８９」に発表し、亜鉛め
っき鋼管の耐食性は水質に著しく依存することを明らか
にした。とくに、亜鉛の腐食生成物としてヘミモルファ
イトの腐食配管断面での分布についても言及し、腐食水
道管内面の局部的に腐食した錆こぶと称する部分以外の
均一腐食部分には、ヘミモルファイトが多く存在し、こ
の層の下部には腐食が発生していないことに注目すべき
ことを発表した。In view of this situation, the inventor of the present application has studied the corrosion mechanism of galvanized steel pipe, which has been most commonly used as a conventional water supply pipe for water supply, and has developed two types of corrosion prevention, namely, formation of a corrosion-resistant film of zinc and a sacrificial anode. The two-sided action was announced in 1989 in "Corrosion and Corrosion Protection '89", and revealed that the corrosion resistance of galvanized steel pipes was significantly dependent on water quality. In particular, he mentioned the distribution of hemimorphite as a corrosion product of zinc in the cross section of corroded pipes.Hemimorphite was found to be uniformly corroded on the inner surface of corroded water pipes except for the locally corroded rust bumps. It was noted that there were many, and that there was no corrosion below this layer.
【０００４】本発明は、この現象に着眼して研究を進
め、ヘミモルファイトの防食皮膜としての積極的な利用
を思い到ったものである。このヘミモルファイトは、異
極鉱ともいわれ、地学辞典によれば、Ｚｎ4 （ＯＨ）2
Ｓｉ2 Ｏ7 ・Ｈ2 Ｏの化学式を有し、斜方晶系であっ
て、結晶は明瞭な異極像を示すものとされている。The present invention has been studied with a focus on this phenomenon, and has conceived an active use of hemimorphite as an anticorrosive film. This hemimorphite is also called hemimorphite, and according to the Geological Dictionary, Zn 4 (OH) 2
Has a Si 2 O 7 · H 2 O in the formula, a orthorhombic crystal is assumed to show a clear hemimorphic.
【０００５】従来、かかる水道系配管の耐食性の面から
ヘミモルファイトの防食機能について公表されたものは
なく、また、ヘミモルファイト自体の工業的用途とし
て、特開昭６１−１００１９号公報、特開昭６１−８６
２８４号公報、特開昭６１−１７３９８４号公報等に記
載されているように、感熱紙用充填剤をはじめ、各種樹
脂、ゴム用の充填剤、農業用充填剤、触媒用担体として
の用途に限られている。[0005] From the viewpoint of the corrosion resistance of such water system piping, there has been no publication on the anti-corrosion function of hemimorphite. Kaisho 61-86
No. 284, JP-A-61-173984, etc., as well as fillers for thermal paper, fillers for various resins, rubbers, fillers for agriculture, and as a carrier for catalysts limited.
【０００６】[0006]
【発明が解決しようとする課題】本発明において解決す
べき課題は、水道系におけるヘミモルファイトの耐食性
を利用して、これを水処理系あるいは水利用装置の耐食
性改善に積極的に利用するための方策を提供することに
ある。The problem to be solved in the present invention is to utilize the corrosion resistance of hemimorphite in a water supply system and to use it positively for improving the corrosion resistance of a water treatment system or a water utilization device. It is to provide a measure.
【０００７】[0007]
【課題を解決するための手段】本発明は、Ｚｎ4 （Ｏ
Ｈ）2 Ｓｉ2 Ｏ7 ・Ｈ2 Ｏの化学式を有する合成ヘミモ
ルファイト結晶を主体とした珪酸亜鉛化合物皮膜を基材
の接液面に均一に形成することによって、その課題を達
成した。SUMMARY OF THE INVENTION The present invention provides a method for producing Zn 4 (O
The object has been achieved by uniformly forming a zinc silicate compound film mainly composed of a synthetic hemimorphite crystal having a chemical formula of H) 2 Si 2 O 7 .H 2 O on the liquid contact surface of a substrate.
【０００８】本発明が適用できる基材として、その表面
に少なくとも亜鉛層を有するものが好適に適用できる。
ここで、亜鉛層としては基材上に亜鉛成分を表面に含有
するものであれば如何なる形態のものであっても適用で
き、例えば、亜鉛基材そのものあるいは亜鉛を合金材と
して含有する基材、亜鉛あるいは亜鉛合金めっき層、合
金化溶融亜鉛めっき層を有する基材に適用できる。[0008] As a substrate to which the present invention can be applied, a substrate having at least a zinc layer on its surface can be suitably applied.
Here, the zinc layer can be applied in any form as long as it contains a zinc component on the surface of the substrate, for example, a zinc substrate itself or a substrate containing zinc as an alloy material, It can be applied to a substrate having a zinc or zinc alloy plating layer or an alloyed hot-dip galvanized layer.
【０００９】この合成ヘミモルファイトの均一層は亜鉛
含有層を有する面を珪酸塩水溶液を用いて水熱処理する
ことにより好適に得ることができる。水熱処理するに当
たっては、亜鉛を表面層に含有する金属材料を脱脂した
後、酸化処理または水酸化処理による前処理を行って、
合成ヘミモルファイトの形成基材として、比較的、活性
状態にあるＺｎＯ層またはＺｎ（ＯＨ）2 層を形成す
る。The uniform layer of the synthetic hemimorphite can be suitably obtained by subjecting the surface having the zinc-containing layer to a hydrothermal treatment using an aqueous silicate solution. In performing the hydrothermal treatment, after degrease the metal material containing zinc in the surface layer, perform a pretreatment by an oxidation treatment or a hydroxylation treatment,
A relatively active ZnO layer or Zn (OH) 2 layer is formed as a base material for forming synthetic hemimorphite.
【００１０】この前処理としての酸化処理法による活性
ＺｎＯ層の形成は、空気中で１００〜４００℃、１〜３
時間加熱することを示し、好ましくは、例えば亜鉛の場
合、３００〜３５０℃、１〜２時間の加熱が好適に適用
できる。あまり低温では酸化速度が遅く、表面の酸化皮
膜を形成するのに時間がかかり、あまり高温では亜鉛の
融点に近づき亜鉛が軟化し、活性ＺｎＯ層の形成に悪影
響をもたらす。The formation of the active ZnO layer by the oxidation treatment as a pretreatment is performed at 100 to 400 ° C. in air at 1 to 3 ° C.
This indicates that heating is performed for an hour. For example, in the case of zinc, heating at 300 to 350 ° C. for 1 to 2 hours can be suitably applied. If the temperature is too low, the oxidation rate is slow, and it takes time to form an oxide film on the surface. If the temperature is too high, the temperature approaches the melting point of zinc, which softens the zinc and adversely affects the formation of the active ZnO layer.
【００１１】水酸化処理法による活性Ｚｎ（ＯＨ）2 層
の形成は、ｐＨ７〜１３、好ましくは、ｐＨとして８．
５〜１０．５の水酸化ナトリウム溶液中で、８０〜９５
℃で１〜６０分間煮沸処理することによって安定した水
酸化皮膜を形成する。また、水酸化処理することによっ
て、適度に表面を荒らし、表面積を増やして珪酸が吸着
し反応しやすくなる。これらの前処理によって、基材表
面に活性状態のＺｎＯまたはＺｎ（ＯＨ）2 層が基材組
織に連続して形成される。The formation of the active Zn (OH) 2 layer by the hydroxylation method is carried out at pH 7 to 13, preferably at pH 8.
80-95 in sodium hydroxide solution of 5-10.5
A stable hydroxide film is formed by boiling at 1 ° C. for 1 to 60 minutes. In addition, by performing the hydroxylation treatment, the surface is moderately roughened, the surface area is increased, and the silicic acid is adsorbed and easily reacted. By these pretreatments, an active ZnO or Zn (OH) 2 layer is continuously formed on the substrate surface in the substrate structure.
【００１２】さらに、前処理を経た後に、基材をＳｉＯ
2 濃度に換算して、５０〜１５０００ｐｐｍ、好ましく
は３００〜３０００ｐｐｍ濃度の珪酸または珪酸塩水溶
液に浸漬または塗布し、１１０〜２１０℃、好ましくは
１５０〜１９０℃で１時間以上、各温度の飽和蒸気圧力
以上という条件下において、水熱合成を行い、最終膜厚
が０．５〜５０μｍである合成ヘミモルファイトの皮膜
を生成する。ヘミモルファイト結晶で覆れた皮膜の表面
は、図２に示すように板状または柱状の単結晶が織り重
なった立体構造をしているため、あまりに薄いと皮膜の
均一性に欠け、厚すぎると母地金属との熱膨張の差によ
り皮膜にき裂が生じる場合がある。Further, after the pretreatment, the substrate is made of SiO
2 Converted to a concentration, dipped or coated in an aqueous solution of silicic acid or silicate having a concentration of 50 to 15000 ppm, preferably 300 to 3000 ppm, and saturated steam at each temperature at 110 to 210 ° C., preferably 150 to 190 ° C. for 1 hour or more. Hydrothermal synthesis is performed under the condition of a pressure or higher to produce a synthetic hemimorphite film having a final film thickness of 0.5 to 50 μm. As shown in FIG. 2, the surface of the film covered with hemimorphite crystals has a three-dimensional structure in which plate-like or columnar single crystals are woven, and if it is too thin, the film lacks uniformity and is too thick. In some cases, cracks may occur in the coating due to the difference in thermal expansion between the base metal and the base metal.
【００１３】珪酸原料としては、Ｍ2 Ｏ／ＳｉＯ2 の比
が０〜２に入る珪酸塩類等を用いることができる。ただ
し、Ｍは１価のアルカリ金属類であるＬｉ，Ｎａ，Ｋ，
Ｃｓまたは、アンモニウム及びアミンを示す。珪酸また
は珪酸塩水溶液の処理は、浸漬あるいはロールやスプレ
ー等による塗布等の手段を用いることができる。As the silicic acid raw material, silicates having a M 2 O / SiO 2 ratio of 0 to 2 can be used. Here, M is a monovalent alkali metal such as Li, Na, K,
Cs or ammonium and amine. The treatment with the aqueous solution of silicic acid or silicate can be performed by means such as immersion or application by a roll or spray.
【００１４】[0014]
【作用】亜鉛めっき等の亜鉛あるいは亜鉛含有表面を予
備処理したＺｎＯ上に連続して形成した合成ヘミモルフ
ァイトは、組織もＺｎＯと連続した組織を有し、基材と
の結合性も高く、機械的な耐剥離強度を有する。The synthetic hemimorphite formed continuously on ZnO or the zinc-containing surface pretreated with zinc such as zinc plating has a continuous structure with ZnO, and has a high bondability with the base material. It has mechanical peel strength.
【００１５】かかる合成ヘミモルファイトの形成は、珪
酸または珪酸塩水溶液に浸漬または塗布し、水熱合成す
る。この水熱合成温度は、１１０℃より低温側では皮膜
が生成できず、２１０℃以上では、亜鉛層が剥がれるた
め好ましい温度範囲は、１１０〜２１０℃で１時間以
上、各温度の飽和蒸気圧力以上という条件下において、
水熱合成を行い、最終膜厚が０．５〜５０μｍである珪
酸亜鉛化合物の皮膜を生成する。The formation of such synthetic hemimorphite is carried out by dipping or coating in an aqueous solution of silicic acid or silicate, followed by hydrothermal synthesis. As for the hydrothermal synthesis temperature, a film cannot be formed at a temperature lower than 110 ° C., and at 210 ° C. or more, the zinc layer is peeled off. Therefore, a preferable temperature range is 110 to 210 ° C. for 1 hour or more, and a saturated vapor pressure of each temperature or more. Under the condition,
Hydrothermal synthesis is performed to form a zinc silicate compound film having a final film thickness of 0.5 to 50 μm.
【００１６】この合成ヘミモルファイト層そのものは、
亜鉛層の上方に形成されたＺｎＯ層またはＺｎ（ＯＨ）
2 層と結晶構造上連続した形態をなし、その厚みが０．
５μｍ以上あれば、加熱された汚水中でも充分な耐食性
を長期にわたって維持することができる。The synthetic hemimorphite layer itself is:
ZnO layer or Zn (OH) formed above zinc layer
It has a form that is continuous with the two layers in crystal structure, and has a thickness of 0.1 mm.
If it is 5 μm or more, sufficient corrosion resistance can be maintained for a long time even in heated sewage.
【００１７】[0017]
【実施例】電気亜鉛メッキ鋼板を用いて本発明に係る合
成ヘミモルファイト耐食性皮膜を形成し、その耐食効果
を確認した。EXAMPLE A synthetic hemimorphite corrosion-resistant film according to the present invention was formed using an electrogalvanized steel sheet, and its corrosion resistance was confirmed.
【００１８】５０ｍｍ×３０ｍｍの表面積を有し、亜鉛
メッキ層の厚みが１０μｍで鋼板の厚みが１ｍｍの試料
片の表面をアセトン脱脂後、３５０℃の空気中で２時間
酸化処理し亜鉛の酸化物の皮膜を、またはｐＨ９．７の
水酸化ナトリウム水溶液中で３０分間煮沸して、亜鉛の
水酸化物の皮膜をそれぞれ形成した。次いで、この亜鉛
メッキ綱板をＳｉＯ2 濃度３００ｐｐｍまたは１０００
ｐｐｍのメタケイ酸ナトリウム水溶液１２５ミリリット
ル中に浸漬したのち、１８０℃のオートクレーブ中で６
時間または２０時間水熱処理を行った。The surface of a sample having a surface area of 50 mm × 30 mm, a galvanized layer having a thickness of 10 μm and a steel plate having a thickness of 1 mm was degreased with acetone, and then oxidized in air at 350 ° C. for 2 hours to obtain zinc oxide. Was boiled in an aqueous sodium hydroxide solution having a pH of 9.7 for 30 minutes to form a zinc hydroxide film. Next, the galvanized steel plate was subjected to SiO 2 concentration of 300 ppm or 1000 ppm.
ppm in an aqueous sodium metasilicate solution at 125 ° C.
Hydrothermal treatment was performed for 20 hours or 20 hours.
【００１９】図１は、結晶化したヘミモルファイトの形
成過程を示す模型図である。同図（ａ）は、処理前から
数分後の分子状態を示すもので、溶液中の珪酸および珪
酸イオンが、酸化亜鉛或いは水酸化亜鉛の表面に吸着す
る過程を示す。同図（ｂ）は、合成開始から数十分後の
分子状態を示すもので、酸化亜鉛或いは水酸化亜鉛が反
応して、ヘミモルファイトの前駆非晶質物質を生成した
状態を示す。同図（ｃ）は、処理開始から数百分後の分
子状態を示すもので、図（ｂ）に示すヘミモルファイト
の前駆非晶質物質からヘミモルファイト結晶の骨格が形
成されると共に、自由水が結晶水として結晶格子空間に
取り込まれた状態を示す。この状態では、結晶化したヘ
ミモルファイトは基材表面の亜鉛の酸化物と結晶構造が
一体化している。FIG. 1 is a model diagram showing the formation process of crystallized hemimorphite. FIG. 3A shows the molecular state several minutes after the treatment, and shows the process in which silicate and silicate ions in the solution are adsorbed on the surface of zinc oxide or zinc hydroxide. FIG. 2B shows the molecular state several tens of minutes after the start of the synthesis, in which zinc oxide or zinc hydroxide has reacted to produce a precursor amorphous substance of hemimorphite. FIG. 3C shows the molecular state several hundred minutes after the start of the treatment. The precursory amorphous substance of hemimorphite shown in FIG. This shows a state in which free water is taken into the crystal lattice space as crystal water. In this state, the crystallized hemimorphite has an integrated crystal structure with zinc oxide on the substrate surface.
【００２０】図２は走査型電子顕微鏡（ＳＥＭ）で観察
した合成した皮膜の表面形態を示し、基材表面が板状の
ヘミモルファイト結晶で覆われている様子がわかる。FIG. 2 shows the surface morphology of the synthesized film observed by a scanning electron microscope (SEM). It can be seen that the substrate surface is covered with plate-like hemimorphite crystals.
【００２１】図３は、Ｘ線回折による皮膜生成物の同定
結果を天然鉱物の回折パターンと比較して示す。これら
のヘミモルファイト合成皮膜の耐食性評価は、８５℃の
水道水中に１週間浸漬させた各試料表面の発錆面積を測
定して行った。その判定は、次の通りである。 FIG. 3 shows the result of identification of the film product by X-ray diffraction in comparison with the diffraction pattern of a natural mineral. The corrosion resistance of these hemimorphite synthetic films was evaluated by measuring the rusting area of each sample surface immersed in tap water at 85 ° C. for one week. The determination is as follows.
【００２２】各条件で作成した試料の耐熱試験の結果を
表１に示す。Table 1 shows the results of the heat resistance test of the samples prepared under the respective conditions.
【表１】 [Table 1]
【００２３】この結果から、本発明によって形成された
ヘミモルファイト皮膜は、その処理を行わない試料（実
施例５）や他の防食処理材料（実施例６）と比較して、
どの実施例（１〜４）においても耐熱性に優れ、防食効
果のあることがわかる。さらに、ヘミモルファイト皮膜
の耐酸、耐アルカリ性を調べるために、ヘミモルファイ
トの結晶をｐＨ３の硫酸酸性溶液、ｐＨ１２の苛性ソー
ダ溶液に２４時間浸漬したところ、酸性では溶解するが
アルカリ性では全く溶解しないことがわかった。従っ
て、ヘミモルファイト皮膜はアルカリ溶液中において安
定した保護皮膜として作用することが期待できる。ま
た、ヘミモルファイト皮膜は、雨水や塩水等に対して
も、安定であることが期待できるので、自動車や屋根材
等の外装鋼板の保護皮膜としても好適な材料である。From these results, the hemimorphite film formed according to the present invention was compared with a sample not subjected to the treatment (Example 5) and other anticorrosion-treated materials (Example 6).
It can be seen that all Examples (1 to 4) have excellent heat resistance and have an anticorrosion effect. Furthermore, in order to examine the acid resistance and alkali resistance of the hemimorphite film, the hemimorphite crystals were immersed in a sulfuric acid solution of pH 3 and a caustic soda solution of pH 12 for 24 hours. I understood. Therefore, the hemimorphite film can be expected to function as a stable protective film in an alkaline solution. Further, since the hemimorphite film can be expected to be stable against rainwater, salt water, and the like, it is a suitable material as a protective film for exterior steel plates such as automobiles and roofing materials.
【００２４】[0024]
【発明の効果】本発明によって、以下の効果を奏する。 （１）基材上に形成された合成ヘミモルファイトの均一
皮膜は、湿性大気、あるいは、水道水、下水と基材との
充分な遮断効果を有し、略半永久的な耐久性を有する。 （２）本発明に係る耐食性皮膜を家庭用水廻り製品に適
用することで、腐食のための保守作業を極端に軽減でき
る。 （３）配管、タンク内面の腐食は略永久的に防護でき、
装置として保守のための設計から解放され、設計の許容
範囲を拡大できる。According to the present invention, the following effects can be obtained. (1) The uniform film of synthetic hemimorphite formed on the base material has a sufficient barrier effect between the base material and the humid atmosphere or tap water or sewage, and has almost semi-permanent durability. (2) The maintenance work for corrosion can be extremely reduced by applying the corrosion-resistant film according to the present invention to household water-use products. (3) Corrosion of piping and tank inner surface can be almost permanently protected.
The device is freed from the maintenance design and the design tolerance can be expanded.
【図１】 オートクレーブ中の処理を１８０℃で行った
場合の結晶化したヘミモルファイトの形成過程を示す模
型図である。FIG. 1 is a model diagram showing a process of forming crystallized hemimorphite when a treatment in an autoclave is performed at 180 ° C.
【図２】 亜鉛メッキ鋼板上に合成した皮膜の、走査型
電子顕微鏡（ＳＥＭ）での結晶構造を示す。FIG. 2 shows the crystal structure of a film synthesized on a galvanized steel sheet, as measured by a scanning electron microscope (SEM).
【図３】 Ｘ線回折による皮膜生成物の同定結果を示
す。FIG. 3 shows identification results of a film product by X-ray diffraction.
フロントページの続き (56)参考文献 特開 昭54−2945（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 22/00 - 22/86 Continuation of the front page (56) References JP-A-54-2945 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C23C 22/00-22/86
Claims (8)
した、基本的にＺｎ４（ＯＨ）２Ｓｉ２Ｏ７・Ｈ２Ｏの
化学式を有する合成ヘミモルファイトを主体とした珪酸
亜鉛化合物皮膜からなる耐食性皮膜。1. A formed on the surface of the substrate having a zinc layer on the surface, essentially Zn 4 (OH) zinc silicate consisting mainly of synthetic hemi molar Fight having 2 Si 2 O 7 · H 2 O in the formula Corrosion resistant film composed of compound film.
化物層あるいは水酸化物層とＺｎ4 （ＯＨ）2 Ｓｉ2 Ｏ
7 ・Ｈ2 Ｏの化学式を有する合成ヘミモルファイトを主
体とした珪酸亜鉛化合物皮膜を連続して形成した耐食性
皮膜。2. A zinc oxide layer or a hydroxide layer on a surface of zinc or a zinc-containing alloy and Zn 4 (OH) 2 Si 2 O
7. A corrosion-resistant film formed by continuously forming a zinc silicate compound film mainly composed of synthetic hemimorphite having a chemical formula of 7 · H 2 O.
て、合成ヘミモルファイトを主体とした珪酸亜鉛化合物
皮膜が結晶化された合成ヘミモルファイトからなる耐食
性皮膜。3. A corrosion-resistant film comprising a synthetic hemimorphite obtained by crystallizing a zinc silicate compound film mainly comprising synthetic hemimorphite according to claim 1.
に有する金属基材を予備処理して、表面に活性ＺｎＯま
たはＺｎ（ＯＨ）2 皮膜を形成したのち、珪酸または珪
酸塩水溶液に浸漬または塗布し、水または水蒸気存在下
で加熱処理する合成ヘミモルファイトを主体とした珪酸
亜鉛化合物の耐食性皮膜の形成方法。4. A metal substrate having at least a zinc or zinc alloy layer on its surface is pre-treated to form an active ZnO or Zn (OH) 2 film on the surface, and then dipped or coated in a silicic acid or silicate aqueous solution. For forming a corrosion-resistant film of a zinc silicate compound mainly composed of synthetic hemimorphite which is heat-treated in the presence of water or water vapor.
気中で１００〜４００℃の加熱温度で１〜３時間保持す
る酸化処理である合成ヘミモルファイトを主体とした珪
酸亜鉛化合物の耐食性皮膜の形成方法。5. The corrosion-resistant film of a zinc silicate compound mainly composed of synthetic hemimorphite, according to claim 4, wherein the pretreatment is an oxidation treatment in which the pretreatment is performed at a heating temperature of 100 to 400 ° C. for 1 to 3 hours. Formation method.
Ｈ７〜１３の水酸化ナトリウム溶液中で、８０〜９５℃
で１〜６０分間煮沸処理する水酸化処理である合成ヘミ
モルファイトを主体とした珪酸亜鉛化合物の耐食性皮膜
の形成方法。6. The method according to claim 4, wherein the preliminary processing is p
80-95 ° C in sodium hydroxide solution of H7-13
Forming a corrosion-resistant film of a zinc silicate compound mainly composed of synthetic hemimorphite which is a hydroxylation treatment of boiling for 1 to 60 minutes.
酸水溶液の濃度が、ＳｉＯ2 換算で５０〜１５０００ｐ
ｐｍであり、加熱処理の方法が飽和蒸気圧力以上の条件
下１１０〜２１０℃で１時間以上水熱処理することを特
徴とする合成ヘミモルファイトを主体とした珪酸亜鉛化
合物の耐食性皮膜の形成方法。7. The device according to claim 4, the concentration of silicic acid or silicate aqueous solution, 50～15000P in terms of SiO 2
pm and a hydrothermal treatment at 110 to 210 ° C. for 1 hour or more under the condition that the heat treatment method is at or above the saturated vapor pressure, and wherein the zinc silicate compound is mainly composed of synthetic hemimorphite.
酸塩の原料が、Ｍを１価のアルカリ金属類であるＬｉ，
Ｎａ，Ｋ，Ｃｓ、あるいは、アンモニウムまたはアミン
としたとき、Ｍ2 Ｏ／ＳｉＯ2 の比が２以下である珪酸
塩類である合成ヘミモルファイトの耐食性皮膜の形成方
法。8. The method according to claim 7, wherein the raw material of silicic acid or silicate is Li, wherein M is a monovalent alkali metal.
A method for forming a corrosion-resistant film of synthetic hemimorphite, which is a silicate having a ratio of M 2 O / SiO 2 of 2 or less when Na, K, Cs or ammonium or amine is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32141491A JP3224034B2 (en) | 1991-11-07 | 1991-11-07 | Corrosion resistant film and its formation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32141491A JP3224034B2 (en) | 1991-11-07 | 1991-11-07 | Corrosion resistant film and its formation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05125553A JPH05125553A (en) | 1993-05-21 |
| JP3224034B2 true JP3224034B2 (en) | 2001-10-29 |
Family
ID=18132286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32141491A Expired - Fee Related JP3224034B2 (en) | 1991-11-07 | 1991-11-07 | Corrosion resistant film and its formation method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3224034B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6322687B1 (en) | 1997-01-31 | 2001-11-27 | Elisha Technologies Co Llc | Electrolytic process for forming a mineral |
| US6159552A (en) | 1999-01-14 | 2000-12-12 | Rutgers, The State University | Inorganic conversion coatings for ferrous substrate |
| DE10223022A1 (en) * | 2002-05-22 | 2003-12-11 | Christoph Schulz | Conversion layer for substrates made of zinc or alloys containing zinc |
-
1991
- 1991-11-07 JP JP32141491A patent/JP3224034B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05125553A (en) | 1993-05-21 |
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