JPH08296063A - Thin film organic composite steel sheet excellent in appearance and corrosion resistance - Google Patents
Thin film organic composite steel sheet excellent in appearance and corrosion resistanceInfo
- Publication number
- JPH08296063A JPH08296063A JP7120405A JP12040595A JPH08296063A JP H08296063 A JPH08296063 A JP H08296063A JP 7120405 A JP7120405 A JP 7120405A JP 12040595 A JP12040595 A JP 12040595A JP H08296063 A JPH08296063 A JP H08296063A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- ratio
- appearance
- film
- cro3
- 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
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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は薄膜有機被覆鋼板におけ
る外観及び耐食性の改善に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to improvement of appearance and corrosion resistance of a thin film organic coated steel sheet.
【０００２】[0002]
【従来の技術】亜鉛系めっき鋼板の上にクロメート被膜
を形成しその上に有機被膜を形成する高耐食性表面処理
鋼板として、例えば特開昭５７−１０８２９２号公報、
特開昭６０−１４９７８６号公報などが提案されてい
る。2. Description of the Related Art As a highly corrosion-resistant surface-treated steel sheet in which a chromate film is formed on a zinc-based plated steel sheet and an organic film is formed thereon, for example, JP-A-57-108292,
JP-A-60-149786 is proposed.
【０００３】これらの特許に提示されている有機被覆処
理は厚みにして５μｍ以下のクリアー被膜であることか
らその外観は下地の外観、特にクロメート処理の条件に
大きく左右される。Since the organic coating treatments proposed in these patents are clear coatings having a thickness of 5 μm or less, their appearance is greatly influenced by the appearance of the base, particularly the conditions of chromate treatment.
【０００４】特に、塗布型・反応型のクロメート処理に
おいてはクロムの付着むらが発生し易く、これに起因す
る外観不良や色調ばらつきが問題となる。Particularly, in the coating-type and reactive-type chromate treatments, uneven adhesion of chromium is apt to occur, which causes problems in appearance defects and color tone variations.
【０００５】また、こうした外観不良の発生しにくい処
理として電解型のクロメート処理が挙げられるが、その
被膜中クロムが３価であるために耐食性に劣るという欠
点がある。しかし、先に示した処理鋼板は下地のクロメ
ート処理については付着量のみ規定しておりその詳細な
処理条件について提示されたものはなく、こうした問題
に対する解決策は提示されていない。[0005] Electrolytic type chromate treatment can be mentioned as a treatment which is less likely to cause such a defective appearance, but it has a drawback that it is inferior in corrosion resistance because chromium in the coating film is trivalent. However, the above-mentioned treated steel sheet specifies only the adhesion amount for the chromate treatment of the underlayer, and no detailed treatment conditions have been presented, and no solution to such a problem has been presented.
【０００６】[0006]
【課題を解決するための手段】本発明は従来技術の課題
を解決するものであって、電気亜鉛めっき鋼板を母材と
しその表面に第１層としてＣｒ3+／全Ｃｒ比が０．１〜
０．８のクロム酸と、リン酸化合物をクロム酸に対して
重量比で０．５〜２．０含み、短径１〜１０ｎｍ、長径
１０〜１０００ｎｍで、長径／短径比が１０以上である
ことを特徴とするコロイダルシリカをクロム酸化合物と
の重量比が１以上４以下含有するクロメート被膜をＣｒ
換算で１０〜６０ｍｇ／ｍ2施し、その上層の第２層と
してシリカ含有有機被膜を０．３〜５ｇ／ｍ2有するこ
とを特徴とする外観、耐食性に優れた薄膜有機複合鋼板
である。SUMMARY OF THE INVENTION The present invention is to solve the problems of the prior art, in which an electrogalvanized steel sheet is used as a base material and the surface thereof has a Cr 3+ / total Cr ratio of 0.1 as a first layer. ~
Chromic acid of 0.8 and phosphoric acid compound in a weight ratio of 0.5 to 2.0 are included, with a minor axis of 1 to 10 nm, a major axis of 10 to 1000 nm, and a major axis / minor axis ratio of 10 or more. Chromate coating containing colloidal silica characterized in that the weight ratio with the chromic acid compound is 1 to 4 inclusive.
A thin film organic composite steel sheet excellent in appearance and corrosion resistance, characterized in that it is applied in an amount of 10 to 60 mg / m 2 in terms of conversion and has a silica-containing organic coating as a second layer above it in an amount of 0.3 to 5 g / m 2 .
【０００７】[0007]
【作用】本発明の外観、耐食性に優れた有機複合鋼板は
図１に示す被膜の構造である。即ち、薄鋼板１の上にめ
っき被膜２、クロメート被膜３、有機被膜４からなる被
膜構造である。例えば有機被膜は樹脂＋シリカ０．３〜
５ｇ／ｍ2、クロメート被膜はＣｒ3+／全Ｃｒ比が０．
１〜０．８のクロム酸と、リン酸化合物をクロム酸に対
して重量比で０．５〜２．０含み、短径１〜１０ｎｍ、
長径１０〜１０００ｎｍで、長径／短径比が１０以上で
あることを特徴とするコロイダルシリカをクロム酸化合
粒との重量比が１以上４以下含有するクロメート被覆を
Ｃｒ換算で１０〜６０ｍｇ／ｍ2、めっきは電気めっき
で得られる亜鉛めっき鋼板であり、めっき量は特に限定
する必要はなく通常使用されているめっき鋼板を用いる
ことができる。The organic composite steel sheet of the present invention having excellent appearance and corrosion resistance has the coating structure shown in FIG. That is, it is a coating structure including a plating coating 2, a chromate coating 3, and an organic coating 4 on a thin steel plate 1. For example, the organic coating is resin + silica 0.3-
5 g / m 2 , the chromate coating has a Cr 3+ / total Cr ratio of 0.1.
Chromic acid of 1 to 0.8 and a phosphoric acid compound in a weight ratio of 0.5 to 2.0 with respect to chromic acid, and a minor axis of 1 to 10 nm,
Chromate coating containing colloidal silica having a major axis / minor axis ratio of 10 or more and a major axis / minor axis ratio of 10 or more in a weight ratio of 1 to 4 inclusive with chromium oxide compound particles is 10 to 60 mg / m in terms of Cr. 2. The plating is a galvanized steel sheet obtained by electroplating, and the plating amount is not particularly limited, and a commonly used galvanized steel sheet can be used.
【０００８】以下に本発明の特徴について記す。The features of the present invention will be described below.
【０００９】本発明の特徴は有機被覆の下地クロメート
処理に白色で美麗な外観を有し、かつ被膜密着性に優れ
た処理を採用したことにある。以下、クロメート処理の
詳細について述べる。A feature of the present invention is that the undercoating chromate treatment of the organic coating employs a treatment which has a white and beautiful appearance and is excellent in coating adhesion. The details of the chromate treatment will be described below.
【００１０】部分還元クロム酸はクロム酸水溶液に公知
の方法で還元剤を加えて作る。還元率はＣｒ3+／全Ｃｒ
比が０．８超では液の安定性に問題があり、０．１未満
では十分な白色度が得られない。シリカゾルの長径／短
径比は１０未満であると上層の潤滑被膜との密着性に劣
化が認められるため１０以上が望ましい。また、その含
有量はＣｒＯ3換算１に対し１以上４以下が望ましい。
１未満では耐食性が十分ではなく４超においては上層の
有機被覆との加工時の密着性に劣化が認められるためで
ある。リン酸の添加量は０．５〜１．５である。１．５
超では上層の有機被覆との加工時の密着性に劣化が認め
られ、０．５未満では十分な白色度が得られない。ここ
でクロメート付着量としてはＣｒ換算で１０〜４０ｍｇ
／ｍ2であり、１０ｍｇ／ｍ2未満では十分な耐食性が得
られず、４０ｍｇ／ｍ2以上では上層の有機被覆との加
工時の密着性に劣化が認められる。The partially reduced chromic acid is prepared by adding a reducing agent to a chromic acid aqueous solution by a known method. Reduction rate is Cr 3+ / total Cr
If the ratio exceeds 0.8, there is a problem in the stability of the liquid, and if it is less than 0.1, sufficient whiteness cannot be obtained. If the major axis / minor axis ratio of the silica sol is less than 10, deterioration of adhesion with the lubricating coating of the upper layer is observed, so 10 or more is desirable. Further, the content is preferably 1 or more and 4 or less with respect to 1 in terms of CrO 3 .
This is because if it is less than 1, the corrosion resistance is not sufficient, and if it exceeds 4 the adhesion to the upper organic coating is deteriorated during processing. The amount of phosphoric acid added is 0.5 to 1.5. 1.5
If it exceeds 0.5, the adhesiveness with the upper organic coating during processing is deteriorated, and if it is less than 0.5, sufficient whiteness cannot be obtained. Here, the amount of chromate attached is 10 to 40 mg in terms of Cr.
/ M 2 , and if it is less than 10 mg / m 2 , sufficient corrosion resistance cannot be obtained, and if it is 40 mg / m 2 or more, the adhesiveness during processing with the upper organic coating is deteriorated.
【００１１】クロメートの白色化機構は下地めっきの亜
鉛とクロメート液中のＣｒ6+の反応がリン酸イオンによ
って加速され、有色のＣｒ6+がＣｒ3+に還元される点と
イオン化した亜鉛イオンが界面のｐＨ上昇に伴い水に対
して不溶性でリン酸塩（白色）、または縮合リン酸塩
（無色）を形成、被膜中のＣｒ6+、Ｃｒ3+も界面の反応
に伴うｐＨ上昇により不溶性クロミウムクロメート（無
色ないし薄緑）を形成することによる。The mechanism of whitening of chromate is that the reaction between zinc of the undercoat and Cr 6+ in the chromate solution is accelerated by phosphate ions, and colored Cr 6+ is reduced to Cr 3+ , and ionized zinc ion. Is insoluble in water and forms a phosphate (white) or condensed phosphate (colorless) as the pH of the interface rises, and Cr 6+ and Cr 3+ in the coating also increase due to the pH increase due to the reaction of the interface. By forming insoluble chromium chromate (colorless to light green).
【００１２】さらに、クロメート処理層の上層にシリカ
含有有機被膜を０．３〜５ｇ／ｍ2形成する。Further, a silica-containing organic film is formed in an amount of 0.3 to 5 g / m 2 on the chromate-treated layer.
【００１３】シリカ含有有機被膜の組成はエポキシ樹脂
およびエポキシ樹脂をアミン変成したもの、ウレタン樹
脂、アクリル樹脂およびこれらをエポキシ変成させたも
の等であり、含有するシリカは粒系３〜３０ｎｍで被膜
中に１０〜４０％の割合で含有されている。また、０．
３ｇ／ｍ2以下では十分な潤滑加工性、耐食性が得られ
ないことからこれを下限とし、５ｇ／ｍ2以上では安定
した加工性等の性能が得られないことからこれを上限と
した。The composition of the silica-containing organic coating includes an epoxy resin, an epoxy resin modified with an amine, a urethane resin, an acrylic resin, and an epoxy modified of these, and the like, and the silica contained in the coating has a particle size of 3 to 30 nm. It is contained in the ratio of 10 to 40%. Also, 0.
If it is 3 g / m 2 or less, sufficient lubricating workability and corrosion resistance cannot be obtained, so this is the lower limit, and if it is 5 g / m 2 or more, stable workability and other performance cannot be obtained, so this was made the upper limit.
【００１４】[0014]
【実施例】以下その実施例について述べる。EXAMPLES Examples will be described below.
【００１５】各種亜鉛めっき鋼板に本発明の処理を施し
た鋼板と、従来法に基づいた処理を施した鋼板の作成例
を表１に示す。Table 1 shows examples of steel sheets obtained by subjecting various galvanized steel sheets to the treatment of the present invention and steel sheets subjected to the treatment according to the conventional method.
【００１６】次に表２にこの鋼板の性能評価結果につい
て記す。各評価方法は次の通りである。 〔外観〕鋼板作成後、３０ｃｍ×３０ｃｍの鋼板サンプ
ルについて目視にて以下の基準に基づいて外観の評点づ
けを行った。 ◎ 色調差、むらなく美麗 ○ 若干色調差あるが美麗 △ 色調差、またはむらあり × 激しい色調差、色むらあり 〔裸耐食性〕鋼板作成後、試験片をそのままの状態で塩
水噴霧試験（ＪＩＳ−Ｚ−２３７１）で行い、塩水噴霧
開始後、１０００時間目で試験片の錆発生状態を下記基
準に基づき評点づけを行った。 ◎ 白錆発生２０％未満 ○ 白錆発生２０〜７０％ △ 白錆発生７０〜１００％ × 赤錆発生あり 〔潤滑被膜密着性〕８ｍｍエリクセン押し出し加工後、
セロテープを加工部に貼り付けた後、剥離を行い、メチ
ルバイオレットにて染色し潤滑被膜の剥離状態を確認。 ◎ 剥離なし ○ 剥離５％未満 △ 剥離５〜３０％ × 剥離３０％以上Next, Table 2 shows the results of performance evaluation of this steel sheet. Each evaluation method is as follows. [Appearance] After the steel sheet was produced, a steel sheet sample of 30 cm × 30 cm was visually evaluated for the appearance based on the following criteria. ◎ Color difference, evenly beautiful ○ Some color difference but beautiful △ Color difference or unevenness × Extreme color difference, uneven color [Bare corrosion resistance] After the steel sheet was prepared, the test piece was left in a salt spray test (JIS- Z-2371), and the rust generation state of the test piece was rated 1000 hours after the start of salt spraying based on the following criteria. ◎ White rust occurrence less than 20% ○ White rust occurrence 20-70% △ White rust occurrence 70-100% × Red rust occurrence [Lubricating film adhesion] 8mm Erichsen After extrusion,
After sticking the cellophane tape to the processed part, peel it off and dye it with methyl violet to check the peeled state of the lubricating coating. ◎ No peeling ○ Peeling less than 5% △ Peeling 5-30% × Peeling 30% or more
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【表２】 [Table 2]
【００１９】[0019]
【発明の効果】以上説明した通り、本発明はいずれも外
観、耐食性、潤滑被膜密着性とも良好であり、比較例と
して挙げた従来処理に対して優れた性能を有しているこ
とが分かる。As described above, it can be seen that all of the present inventions have good appearance, corrosion resistance, and lubricating film adhesion, and have excellent performance over the conventional treatments given as comparative examples.
【図１】本発明の一実施例の主要構成を示す図である。FIG. 1 is a diagram showing a main configuration of an embodiment of the present invention.
１ 鋼板 ２ めっき被膜 ３ クロメート被膜 ４ 有機被膜 1 Steel plate 2 Plating film 3 Chromate film 4 Organic film
Claims (1)
に第１層としてＣｒ3+／全Ｃｒ比が０．１〜０．８のク
ロム酸と、リン酸化合物をクロム酸に対して重量比で
０．５〜２．０含み、短径１〜１０ｎｍ、長径１０〜１
０００ｎｍで、長径／短径比が１０以上であるコロイダ
ルシリカをクロム酸化合物との重量比が１以上４以下含
有するクロメート被膜をＣｒ換算で１０〜６０ｍｇ／ｍ
2施し、その上層の第２層としてシリカ含有有機被膜を
０．３〜５ｇ／ｍ2有することを特徴とする外観、耐食
性に優れた薄膜有機複合鋼板。1. A chromic acid having a Cr 3+ / total Cr ratio of 0.1 to 0.8 as a first layer on an electrogalvanized steel sheet as a base material and a phosphoric acid compound relative to chromic acid. The ratio is 0.5 to 2.0, the minor axis is 1 to 10 nm, and the major axis is 10 to 1.
Chromate coating containing colloidal silica having a major axis / minor axis ratio of 10 or more at 000 nm in a weight ratio of 1 to 4 with a chromic acid compound is 10 to 60 mg / m in terms of Cr.
2. A thin-film organic composite steel sheet excellent in appearance and corrosion resistance, which is characterized by having a silica-containing organic coating of 0.3 to 5 g / m 2 as a second layer on top of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7120405A JPH08296063A (en) | 1995-04-24 | 1995-04-24 | Thin film organic composite steel sheet excellent in appearance and corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7120405A JPH08296063A (en) | 1995-04-24 | 1995-04-24 | Thin film organic composite steel sheet excellent in appearance and corrosion resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08296063A true JPH08296063A (en) | 1996-11-12 |
Family
ID=14785407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7120405A Pending JPH08296063A (en) | 1995-04-24 | 1995-04-24 | Thin film organic composite steel sheet excellent in appearance and corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08296063A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998057804A1 (en) * | 1997-06-18 | 1998-12-23 | Certek Ltd. | Coated part, coating and method of coating |
-
1995
- 1995-04-24 JP JP7120405A patent/JPH08296063A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998057804A1 (en) * | 1997-06-18 | 1998-12-23 | Certek Ltd. | Coated part, coating and method of coating |
| US6103362A (en) * | 1997-06-18 | 2000-08-15 | Certek Ltd. | Coated part, coating and method of coating |
| US6517898B1 (en) | 1997-06-18 | 2003-02-11 | Certek Ltd. | Method of coating |
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