GB2163456A - Method of forming a coloured hard coating - Google Patents
Method of forming a coloured hard coating Download PDFInfo
- Publication number
- GB2163456A GB2163456A GB08517461A GB8517461A GB2163456A GB 2163456 A GB2163456 A GB 2163456A GB 08517461 A GB08517461 A GB 08517461A GB 8517461 A GB8517461 A GB 8517461A GB 2163456 A GB2163456 A GB 2163456A
- Authority
- GB
- United Kingdom
- Prior art keywords
- coating
- coloured
- coatings
- hard coating
- ion
- 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
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
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C27/00—Making jewellery or other personal adornments
- A44C27/001—Materials for manufacturing jewellery
- A44C27/005—Coating layers for jewellery
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B37/00—Cases
- G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
- G04B37/223—Materials or processes of manufacturing pocket watch or wrist watch cases metallic cases coated with a nonmetallic layer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Physical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemically Coating (AREA)
Abstract
A coloured hard coating for an eye-glass frame, a wrist-watch or the like is formed by depositing a hard transparent coating on a layer of coloured coating by ion-plating. The hard coating may be TiN, TiC, oxides of Al, B, Si, In, Ti, Zr, Ta or other ceramics.
Description
SPECIFICATION
Method of forming a coloured hard coating
Description
This invention relates to a method of forming a coloured hard coating, more particularly to a method of forming a wear-resistant, corrosion-resistant and coloured hard coating comprising a combination of a coloured coating selected from conventional electro-plated colour coatings, chemically coloured coatings and ion-plated colour coatings and a hard coating, which is transparent at least in a thin coating and selected from coatings of titanium nitride, carbide or a mixture thereof, coatings of oxides of aluminium, boron, silicon, indium, titanium, zirconium and tantalum and other ceramic coatings.
A number of products having electro-plated colour coatings or chemically coloured coatings are in increasing demand due to their beautiful and highgrade image. However, such coatings are inferior in their wear-resistance, so that their usage is limited to applications that cause little or no frictional wear. Consequently, a coating for a product, such as an eye-glass frame, a wrist watch or the like subjected to frequent frictional contact must be protected by an additional plastic coating thereon.
Even so the coating remains imperfect in its durability, so that a product of high grade still cannot be obtained.
A method of forming a coloured coating has been developed, in which a highly wear-resistant coloured coating of titanium compound may be formed by an ion-plating technique directly onto a material to be processed. However, such type of coating is poor in colour and brittle in practical use. Further, a practical method of forming a highly wear-resistant coloured coating by a flame spray technique has been developed but still has many problems in that a material to be processed must be resistant to a high temperature and that a surface-grinding treatment must be applied after the flame spraying process. Since the products having coloured coatings have recently been in increased demand, it is desired to develop a practical method of forming a highly wear-resistant coloured coating at a relatively low cost.
The object of the invention is to provide a method of forming a highly wear-resistant and corrosion resistant coloured beautiful coating at a relatively low cost.
According to the invention there is provided a method of forming a coloured hard coating on a substrate, in which a layer of coloured coating is provided thereon with a hard coating, which is transparent at least in a thin coating, in a thickness of 0.0005 to 3y by means of ion-plating.
It has now been found that a coating of oxides of aluminium, boron, silicon, indium, titanium zirconium, tantalum or other ceramic materials by the ion-plating procedure, or a coating of substantially titanium compound by the ion-plating procedure is hard and highly corrosion-resistant and may be used for forming a highly wear-resistant and corrosion-resistant coloured hard coating, when combined with a conventional electro-plated or chemically coloured coating.
Further, it has been found that a combination of the coloured coating selected from electro-plated coloured coatings, ion-plated colour coatings or chemically coloured coatings with a transparent hard coating in a thickness of 0.0005 to 3 > selected from coatings of substantially titanium nitride, titanium carbide or a mixture thereof, coatings of oxides of aluminium, boron, silicon, indium, titanium, zirconium, tantalum or other ceramic materials may provide an excellent wear-resistant and corrosion-resistant coloured coating by means of the ion-plating procedure.
In accordance with the invention the conventional coloured coating is provided on the substrate with the thin, transparent and hard coating in a thickness of 0.0005 to 31l preferably at a temperature of 200 to 500"C by the ion-plating procedure. Thus, the porous coloured coating, such as electro-plated or chemically coloured coating, may be integrated with the transparent hard coating, such as hard oxide compound, to enhance denseness and wear-resistance of the final coating. Furthermore, a thin coating of 0.0005 to 3,uW thickness results in a low cost.A thickness of less than 0.0005 cannot provide a satisfactory effect, while a thickness of more than 3 gives the colour of the hard coating itself to the final coating so that the colour of the prime-coating is masked. A coating of titanium compound alone without the prime coating is weak and poor in wear-resistance.
A thickness of more than 1 E is acceptable, provided that the colour of the prime coating is visible through the outer hard coating. Further, as the substrate, there may be used any metal, such as stainless steel, iron, copper, copper-zinc alloy, aluminium, cadmium, zinc, silver, nickel-chrome alloy and nickel-based alloy.
The invention will now be further described with reference to the following non-limiting Examples.
EXAMPLES
Example 1
A wrist watch band of stainless steel (SUS304) was cleansed and then cathodically electrolysed in a solution of 3v/v% sulphuric acid and 15Wlv% citric acid for 2 minutes under a current density of SAl dm2. Then, it was activated, washed and electroplated in a commercially available black chromeplating liquor, CHEMICRON CR (supplied from
MURATA Chemicals Co., Limited.) for 10 minutes under a current density of 30A/dm2 to form a coloured coating layer of black chrome plating of 1.2 > thickness.
Thereafter, 300ml/min. of an acetylene gas was passed thereon, while aluminium oxide (A120s) was ion-plated in an ion-plating apparatus (Shinko Seiki
Model AIH-16110SB) for 30 minutes under a condition of a gas pressure of 5x103 Torr, an ionizing voltage of 40V and current of 10A, a base voltage of 1.5KV and a base current of 300A to form an aluminium oxide coating of 0.004pew thickness, which did not affect the black colour of the prime chrome-coating.
Then, the coating thus formed was compared with the coating of black chrome-plating alone for their wear-resistance by rubbing them ten times with a force of 10Kg using a commercially available grinding cloth (Silbo Blue from SILBO & CO.) to find out that the chrome coating alone was worn out to expose the stainless steel material, while the coating with additional aluminium oxide coating was not affected by the rubbing test.
Example 2
An eye-glass frame of Cu-Zn-Ni alloy was cleansed, nickel-plated and then subjected to the black chrome plating for 15 minutes under the same condition as in Example 1.
Thus, a black chrome plated layer of 1.5 to 1.7so was obtained. Then, 250ml/min. of an acetylene gas and 40mllmin. of a nitrogen gas were passed thereon, while silicon oxide (SiO2) was ion-plated in the same ion-plating apparatus as in Example 1 for 40 minutes under a condition of a gas pressure of 4x10-3 Torr, an ionizing voltage and current of 35V and 1oA, respectively, as well as a base voltage and current of 1.7KV and 500A, respectively, to form a silicon oxide coating of 0.005 thickness, which did not affect the black colour of the prime chrome-coating.
Then, the coating thus formed was compared with the prime coating alone for their wear-resistance by the same procedure as in Example 1 to find out that the prime coating alone was worn out to expose the nickel plating layer, while the coating with the ion-plated silicon coating was not affected by the rubbing test. Further, the coating thus formed was subjected to a corrosion-resistance test for 168 hours using an artifical sweat, but was not affected thereby.
Example 3
Usual chrome-plating were applied on a stainless steel directly and on Cu-Zn-Ni alloy after nickelplated under the same condition for ion-plating as in Examples 1 and 2. Then, silicon oxide was ionplated thereon to form a silicon oxide coating of the same thickness as in Examples 1 and 2.
The resulting coatings were subjected to the corrosion test to find no deterioration therefrom.
However, the colour was grayish and dull, so that a high grade image could not be observed. In order to provide the high grade image, more amounts of acetylene gas was passed for ion-plating to increase the black colour. In this way, the colour itself was improved similarly to those in Examples 1 and 2, but the wear-resistance and the corrosion-resistance became inferior to those in
Examples 1 and 2, as well as the previous grayish coating.
Example 4
A gold-palladium alloy was plated on the same material as in Example 1, and then ion-plated with boron oxide (B2O3) under the same condition as in
Example 1 to obtain a coating of beautiful brown colour. The coating of boron oxide had a thickness of 0.00411 and showed very good results in the wear-and corrosion-resistance tests.
Example 5
A cobalt plating was chemically applied on the same material as in Example 2, and then ion-plated with boron oxide under the same condition as in
Example 2 to obtain a coating keeping colour of the chemical cobalt plating. The coating of the boron oxide had a thickness of 0.0051l and showed very good results in the wear- and corrosion-resistance tests.
Example 6
Aluminium oxide was ion-plated on the ionplated coloured coating layer under the same condition as in Example 1 to obtain very good results as in Example 1.
As the hard coating of oxide compound, there were used oxides of indium, titanium, zirconium, tantalum and other ceramic materials to form respective coatings, which showed very good results as in Example 1.
Example 7
The same coloured coating layer was formed on the same material as in Example 1, and thereon 300ml/min of acetylene gas was passed, while titanium was ion-plated in the same apparatus as in
Example 1 for 30 minutes under a condition of a gas pressure of 5x10-3 Torr, ionizing voltage and current of 40V and 10A, as well as base voltage and current of 0.8KV and 300A to form a coating of substantially titanium compound having a thickness of 0.4u and keeping the colour of black chrome.
Thus, very good results could be obtained as in
Example 1.
Example 8
Instead of silicon oxide, titanium was ion-plated for 40 minutes, using the same materials under the same conditions as in Examples 2 and 3 to obtain a coating, which showed the same good results as in Examples 2 and 3.
Example 9
Instead of boron oxide, titanium was ion-plated on the same materials under the same conditions as in Examples 4 and 5 to obtain a coating, which showed the same good results as in Examples 4 and 5.
As described hereinabove, in accordance with the invention the layer of coloured coating is provided thereon with the hard coating, which is transparent at least in a thin coating, in a thickness of 0.0005 to 3FL by means of the ion-plating technique, so that the colour of the prime coating may be maintained and the beautiful final coating of high wear- and corrosion-resistance may be readily obtained in a low cost.
Claims (9)
1. A method of forming a coloured hard coating on a substrate characterised in that a layer of coloured coating is provided thereon with a hard coating which is transparent at least in a thin coating, in a thickness of 0.0005 to 311 by means of ionplating.
2. A method according to claim 1, wherein the coloured coating is selected from electro-plated colour coatings, ion-plated colour coatings, and chemically coloured coatings.
3. A method according to claim 1 or 2, wherein the hard coating is selected from coatings of substantially titanium nitride, carbide or a mixture thereof, and coatings of oxides of aluminium, boron, silicon, indium, titanium zirconium or tantalum and other ceramic coatings.
4. A method as claimed in claim 1, 2 or 3 wherein the ion-plating is carried out at 200 to 500"C.
5. A method as claimed in any one of claims 1 to 4 wherein the hard coating has a thickness of 1 to 3It.
6. A method as claimed in any one of claims 1 to 5 wherein the substrate is a metal.
7. A method as claimed in claim 6 wherein the metal is selected from stainless steel, iron, copper, copper-zinc alloy, aluminium, cadmium, zinc, silver, nickel-chrome alloy and nickel-based alloy.
8. A method of forming a coloured hard coating on a substrate substantially as hereinbefore described with reference to any one of the Examples.
9. A coloured hard coating produced by a method as claimed -in any one of claims 1 to 8.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59145330A JPS6126769A (en) | 1984-07-13 | 1984-07-13 | Formation of colored hard film |
Publications (3)
Publication Number | Publication Date |
---|---|
GB8517461D0 GB8517461D0 (en) | 1985-08-14 |
GB2163456A true GB2163456A (en) | 1986-02-26 |
GB2163456B GB2163456B (en) | 1987-07-15 |
Family
ID=15382671
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB08517461A Expired GB2163456B (en) | 1984-07-13 | 1985-07-10 | Method of forming a coloured hard coating |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPS6126769A (en) |
KR (1) | KR860001216A (en) |
GB (1) | GB2163456B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3727279A1 (en) * | 1986-09-02 | 1988-03-03 | Seikosha Kk | BLACK SILVER COATING FOR ARTICLES |
US5356661A (en) * | 1990-11-21 | 1994-10-18 | Sumitomo Electric Industries, Ltd. | Heat transfer insulated parts and manufacturing method thereof |
EP0714615A1 (en) * | 1994-11-30 | 1996-06-05 | TWALLJE Co., Ltd. | Accessorial device |
CN108505001A (en) * | 2018-04-09 | 2018-09-07 | 苏州市彩衣真空镀膜有限公司 | A kind of composite wear-resistant layer and preparation method thereof |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01116083A (en) * | 1987-10-29 | 1989-05-09 | Nippon Chem Ind Co Ltd | Modified electroless-plated powder |
JPH03761U (en) * | 1989-05-25 | 1991-01-08 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1342071A (en) * | 1970-04-17 | 1973-12-25 | Wilkinson Sword Ltd | Razor blades |
GB1342072A (en) * | 1971-04-19 | 1973-12-25 | Wilkinson Sword Ltd | Razor blades |
GB1420941A (en) * | 1972-04-08 | 1976-01-14 | Wilkinson Sword Ltd | Razor blades |
GB2075068A (en) * | 1980-05-02 | 1981-11-11 | Sumitomo Electric Industries | Articles coated with hard materials |
GB2123039A (en) * | 1982-03-23 | 1984-01-25 | Atomic Energy Authority Uk | Coatings for cutting implements |
GB2129835A (en) * | 1982-10-29 | 1984-05-23 | Citizen Watch Co Ltd | A method for providing a bi- coloured pattern on a metal ornamental article by coating |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56112473A (en) * | 1980-02-08 | 1981-09-04 | Dairiyuu Denshi Sangyo Kk | Metallic film for decoration of stainless steel |
-
1984
- 1984-07-13 JP JP59145330A patent/JPS6126769A/en active Pending
-
1985
- 1985-07-10 GB GB08517461A patent/GB2163456B/en not_active Expired
- 1985-07-13 KR KR1019850005010A patent/KR860001216A/en not_active Application Discontinuation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1342071A (en) * | 1970-04-17 | 1973-12-25 | Wilkinson Sword Ltd | Razor blades |
GB1342072A (en) * | 1971-04-19 | 1973-12-25 | Wilkinson Sword Ltd | Razor blades |
GB1420941A (en) * | 1972-04-08 | 1976-01-14 | Wilkinson Sword Ltd | Razor blades |
GB2075068A (en) * | 1980-05-02 | 1981-11-11 | Sumitomo Electric Industries | Articles coated with hard materials |
GB2123039A (en) * | 1982-03-23 | 1984-01-25 | Atomic Energy Authority Uk | Coatings for cutting implements |
GB2129835A (en) * | 1982-10-29 | 1984-05-23 | Citizen Watch Co Ltd | A method for providing a bi- coloured pattern on a metal ornamental article by coating |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3727279A1 (en) * | 1986-09-02 | 1988-03-03 | Seikosha Kk | BLACK SILVER COATING FOR ARTICLES |
US5356661A (en) * | 1990-11-21 | 1994-10-18 | Sumitomo Electric Industries, Ltd. | Heat transfer insulated parts and manufacturing method thereof |
EP0714615A1 (en) * | 1994-11-30 | 1996-06-05 | TWALLJE Co., Ltd. | Accessorial device |
CN108505001A (en) * | 2018-04-09 | 2018-09-07 | 苏州市彩衣真空镀膜有限公司 | A kind of composite wear-resistant layer and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
JPS6126769A (en) | 1986-02-06 |
GB2163456B (en) | 1987-07-15 |
KR860001216A (en) | 1986-02-24 |
GB8517461D0 (en) | 1985-08-14 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |