CA2870523A1 - Colored graphic artworks on titanium surfaces - Google Patents
Colored graphic artworks on titanium surfaces Download PDFInfo
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- CA2870523A1 CA2870523A1 CA2870523A CA2870523A CA2870523A1 CA 2870523 A1 CA2870523 A1 CA 2870523A1 CA 2870523 A CA2870523 A CA 2870523A CA 2870523 A CA2870523 A CA 2870523A CA 2870523 A1 CA2870523 A1 CA 2870523A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/22—Removing surface-material, e.g. by engraving, by etching
- B44C1/227—Removing surface-material, e.g. by engraving, by etching by etching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44D—PAINTING OR ARTISTIC DRAWING, NOT OTHERWISE PROVIDED FOR; PRESERVING PAINTINGS; SURFACE TREATMENT TO OBTAIN SPECIAL ARTISTIC SURFACE EFFECTS OR FINISHES
- B44D5/00—Surface treatment to obtain special artistic surface effects or finishes
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- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/04—Treatment of selected surface areas, e.g. using masks
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- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
- C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied
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- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/80—After-treatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/106—Other heavy metals refractory metals
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
A graphic artwork that has multicolor appearance due to the interference phenomena taking place at the air-oxide-metal interfaces comprises titanium oxide films in which the color controlling factor, thickness, is manipulated by oxidation or etching processes on titanium based surfaces.
Description
COLORED GRAPHIC ARTWORKS ON TITANIUM SURFACES
Inventor: Xiaojiang Zhang Company: Electron Brush Studio Ltd.
Address: Unit #107, 9020-Jasper Ave. Edmonton, AB, Canada T5H 3S8 Emails: xiaojiangalbertzhanggmail.com (main); infoelectronbrushstudio.com Description Of The Invention The present invention relates to multicolored and/or multidimensional artworks including designs, drawings, images, and pictures on oxidized titanium surfaces, and the process to manufacturing the artworks. In particular, this invention relates to a novel solution for permanently employing ultraviolet (UV) and water stable colors for titanium-based artworks.
Titanium is a highly corrosion resistant and human body compatible metal which has been widely used for various ranges of applications such as in medical and biological industries. The coloration of titanium is achieved by surface oxidation: due to interference phenomena which take place at the air-oxide-titanium interfaces, an oxidized titanium surface acquires particular colour tones depending on the thickness of the oxide layer.
Heretofore, using conventional methods to produce graphic artwork objects such painting and color-printed pictures have many known disadvantages. For example, the materials used for visual art including paint, paper, wood, fabrics, and plastic degrade
Inventor: Xiaojiang Zhang Company: Electron Brush Studio Ltd.
Address: Unit #107, 9020-Jasper Ave. Edmonton, AB, Canada T5H 3S8 Emails: xiaojiangalbertzhanggmail.com (main); infoelectronbrushstudio.com Description Of The Invention The present invention relates to multicolored and/or multidimensional artworks including designs, drawings, images, and pictures on oxidized titanium surfaces, and the process to manufacturing the artworks. In particular, this invention relates to a novel solution for permanently employing ultraviolet (UV) and water stable colors for titanium-based artworks.
Titanium is a highly corrosion resistant and human body compatible metal which has been widely used for various ranges of applications such as in medical and biological industries. The coloration of titanium is achieved by surface oxidation: due to interference phenomena which take place at the air-oxide-titanium interfaces, an oxidized titanium surface acquires particular colour tones depending on the thickness of the oxide layer.
Heretofore, using conventional methods to produce graphic artwork objects such painting and color-printed pictures have many known disadvantages. For example, the materials used for visual art including paint, paper, wood, fabrics, and plastic degrade
2 under ultraviolet irradiation and hence are not suitable for permanent outdoor applications. Heavy metals such as lead, chromium, cobalt, and mercury, etc.
in the paint and chemicals used have raised concerns due to their toxicity at high levels of exposure including touching and inhaling. Paper or fabrics have an additional disadvantage that they are not water proof. Said materials used in graphic artworks have also suffered from high temperature, pressure, and humidity sensitivities.
There is a growing demand in the fine art industry for a solution to create permanent color effects on a water proof medium such as metal; and the sales and marketing of multicolored art products for outdoor applications has been increasingly expanding. In recent years, artworks on metals have become very popular because the metallic effect is attractive to the consumer. However, most of these artworks are color-printed designs on a polymer-coated lightweight metal substrate such as aluminium and are not truly UV or water stable since conventional water-soluble or polymeric paint are still used.
Coating the metal surface after employing colors with a transparent material is a solution but the objects are lack of the attractive metallic look. Other related industrial approaches to produce a mono-colored pattern on a metal substrate such as copper include chemical etching and laser engraving.
The present invention, by contrast with the above-noted processes, is directed to providing a permanent multicolor effect solution for a graphic artwork on titanium surfaces which is hard and resists to scratching or wearing, is UV and water stable, is tolerant to extreme display or storage conditions, is non-toxic to human, and does not require the use of paint.
in the paint and chemicals used have raised concerns due to their toxicity at high levels of exposure including touching and inhaling. Paper or fabrics have an additional disadvantage that they are not water proof. Said materials used in graphic artworks have also suffered from high temperature, pressure, and humidity sensitivities.
There is a growing demand in the fine art industry for a solution to create permanent color effects on a water proof medium such as metal; and the sales and marketing of multicolored art products for outdoor applications has been increasingly expanding. In recent years, artworks on metals have become very popular because the metallic effect is attractive to the consumer. However, most of these artworks are color-printed designs on a polymer-coated lightweight metal substrate such as aluminium and are not truly UV or water stable since conventional water-soluble or polymeric paint are still used.
Coating the metal surface after employing colors with a transparent material is a solution but the objects are lack of the attractive metallic look. Other related industrial approaches to produce a mono-colored pattern on a metal substrate such as copper include chemical etching and laser engraving.
The present invention, by contrast with the above-noted processes, is directed to providing a permanent multicolor effect solution for a graphic artwork on titanium surfaces which is hard and resists to scratching or wearing, is UV and water stable, is tolerant to extreme display or storage conditions, is non-toxic to human, and does not require the use of paint.
3 The oxidation of a titanium surface by thermal or electrical chemical methods generates a thin titanium oxide layer which is only up to a few micrometers thick. It is a principal object of the present invention to provide a solution for efficiently fabricating, with controlled surface oxidation, a multicolored image or design on titanium or its alloys.
To achieve the aforementioned purpose, it is critical to manipulate the oxide layer by either increasing or decreasing the thickness. The methods of the invention comprise the steps of:
"Bottom-up" method (1) Preparing a titanium artwork surface before employing multicolor by either (a) removing the native oxide layer on the titanium substrate, or (b) coating an object such as metal, silicon, glass, polymer, rubber or ceramic, etc.
with a titanium layer using a method such as sputter deposition;
(2) Applying cleaning and drying procedures on the titanium surface;
(3) Applying an initial oxidation on the cleaned and dried titanium surface using thermal or electrical chemical methods; the oxidation process is controlled by monitoring the surface color;
To achieve the aforementioned purpose, it is critical to manipulate the oxide layer by either increasing or decreasing the thickness. The methods of the invention comprise the steps of:
"Bottom-up" method (1) Preparing a titanium artwork surface before employing multicolor by either (a) removing the native oxide layer on the titanium substrate, or (b) coating an object such as metal, silicon, glass, polymer, rubber or ceramic, etc.
with a titanium layer using a method such as sputter deposition;
(2) Applying cleaning and drying procedures on the titanium surface;
(3) Applying an initial oxidation on the cleaned and dried titanium surface using thermal or electrical chemical methods; the oxidation process is controlled by monitoring the surface color;
(4) Applying a first layer of resist material to selected areas of the oxidized titanium surface thereby preventing the selected areas from further oxidation;
the resist material is preferably a polymer that has good affinity with titanium surface and can withstand thermal or electrical chemical oxidation processes; the resist is applied by painting, masking, stenciling, sputtering, etching, or printing;
the resist material is preferably a polymer that has good affinity with titanium surface and can withstand thermal or electrical chemical oxidation processes; the resist is applied by painting, masking, stenciling, sputtering, etching, or printing;
(5) Applying a second controlled oxidation on the partially sealed surface;
the thickness of oxide layer is increased except the areas where the surface has been covered with resist;
the thickness of oxide layer is increased except the areas where the surface has been covered with resist;
(6) Applying a second layer of resist material, without removing previously applied resist, to selected areas of the oxidized titanium surface;
(7) Applying further oxidations and layers of resist material;
(8) After employing the final color, all the resist on the surface is physically or chemically removed and the titanium artwork is cleaned and dried.
"Top-down" method (1) Preparing a titanium artwork surface for employing multicolor by either (a) removing the native oxide layer on the titanium substrate, or (b) coating an object such as metal, silicon, glass, polymer, rubber or ceramic, etc. with a titanium layer using a method such as sputter deposition;
(2) Applying cleaning and drying procedures on the titanium surface;
(3) Applying an initial oxidation on the cleaned and dried titanium surface using thermal or electrical chemical methods; the oxidation process is controlled by monitoring the surface color;
(4) Applying a first layer of resist material to selected areas of the oxidized titanium surface thereby preventing the selected areas from etching; the resist material is preferably a polymer that has good affinity with titanium surface and can withstand physical or electrical chemical etching processes; the resist is applied by painting, masking, stenciling, sputtering, etching, or printing;
(5) Applying a first controlled etching on titanium artwork surface by using plasma, laser, electrochemical, or photo electrochemical methods; the thickness of oxide layer is reduced except the areas where the surface has been covered with resist;
(6) Applying a second layer of resist material, without removing previously applied resist, to selected areas of the artwork surface;
(7) Applying a second controlled etching on titanium artwork surface;
(8) Applying further masking and etching procedures;
"Top-down" method (1) Preparing a titanium artwork surface for employing multicolor by either (a) removing the native oxide layer on the titanium substrate, or (b) coating an object such as metal, silicon, glass, polymer, rubber or ceramic, etc. with a titanium layer using a method such as sputter deposition;
(2) Applying cleaning and drying procedures on the titanium surface;
(3) Applying an initial oxidation on the cleaned and dried titanium surface using thermal or electrical chemical methods; the oxidation process is controlled by monitoring the surface color;
(4) Applying a first layer of resist material to selected areas of the oxidized titanium surface thereby preventing the selected areas from etching; the resist material is preferably a polymer that has good affinity with titanium surface and can withstand physical or electrical chemical etching processes; the resist is applied by painting, masking, stenciling, sputtering, etching, or printing;
(5) Applying a first controlled etching on titanium artwork surface by using plasma, laser, electrochemical, or photo electrochemical methods; the thickness of oxide layer is reduced except the areas where the surface has been covered with resist;
(6) Applying a second layer of resist material, without removing previously applied resist, to selected areas of the artwork surface;
(7) Applying a second controlled etching on titanium artwork surface;
(8) Applying further masking and etching procedures;
(9) After employing the final etching, all the resist on the surface is physically or chemically removed and the titanium artwork is cleaned and dried.
In the drawings:
Figure 1 illustrates a multicolored titanium artwork substrate having an oxidized layer;
Figure 2 is a perspective cross-sectional view of the multicolored titanium artwork substrate, on smaller scale than Figure 1;
Figure 3 illustrates the principle of the "bottom-up" method to increase the thickness of the oxide layer on titanium surface;
Figure 4 illustrates the principle of the "top-down" method to decrease the thickness of the oxide layer on titanium surface;
Figure 5 illustrates the procedures used in the "bottom-up" method, Figure 6 illustrates the procedures used in the "top-down" method;
Figure 1 and 2 generally illustrate the structure of an artwork article with multicolored image on a titanium surface; while Figure 3-6 generally illustrate the process of "bottom-up" and "top-down" methods for making a multicolored graphic artwork of the present invention.
Figure 1 illustrates a substrate 1 with a titanium-based surface 2 on which has been formed a multicolored artwork image 3, and Figure 2 illustrates the cross-section of the article of Figure 1. In Figure 2, the thickness of the oxide layer 4 is directly related to the surface color. Generally the following order of surface colors can be achieved by increasing the thickness of the oxide layer: light brown, brown, purple, blue, light blue, silver, light yellow, yellow, pink, cobalt, and green. The appearance of the resulting color such as the brightness is also influenced by the surface finish of the titanium substrate.
The manipulating of the surface color is accomplished by two methods called "bottom-up" and "top-down", respectively, as shown in Figure 3-6. In the bottom-up method, the surface is partially covered by a resist material 5 and the thickness of the oxide layer of the uncovered areas is increased in a controlled manner during oxidation process 6; in the top-down method, the surface is partially covered by a resist material 5 and the thickness of the oxide layer of the uncovered areas is reduced in a controlled manner during an etching process 7.
The growth or etching of oxide layer on a titanium article is manipulated by interrupting the oxidation process and selecting target areas, as described in detail above, in the color generation procedure of the present invention. Hereinafter, the present invention will be further illustrated with reference to the following three examples.
Example 1 A five inch by one inch grade 2 titanium sheet was mechanically or electrochemically polished on one side to remove the native oxide on the surface. The titanium sheet was then degreased with liquid soap and rinsed with hot water (150 F) followed by drying in an air flow.
The pattern to be created on the titanium sheet was three separated boxes with a brown, blue, and yellow color, respectively; while the background color was green.
An electrical chemical anodization solution was prepared in a rectangular polyethylene container by dissolving 16.8 g sodium bicarbonate in 2 L distilled water at room temperature.
As shown in Figure 5, to employ multicolor on the titanium surface using the bottom-up method, the titanium sheet was placed in the anodization solution and the polished side was anodically oxidized at 25 V for 30 seconds to achieve an initial brown color layer 8 for the first box 15. The color was monitored by using portable spectrophotometers.
The oxidized titanium sheet was removed from the solution, followed by rinsing and drying in an air flow. The resulting oxidized surface was then partially covered by a resist polymer layer 9 upon the area of the first box 15 (brown).
Proceeding as before, the titanium sheet was immersed in the anodization solution and anodically oxidized at 45 V for 30 seconds to achieve a blue color layer 10 for the second box 16 expect the previously polymer-covered area.
The oxidized titanium sheet was removed from the solution, followed by rinsing and drying in an air flow. A second polymer layer 11 was applied to cover the area of the second box 16 (blue).
Similarly, the titanium sheet was immersed in the anodization solution for the third time and anodically oxidized at 65 V for 30 seconds to achieve a yellow color layer 12 for the third box 17 expect the previously polymer-covered areas.
The oxidized titanium sheet was removed from the solution, followed by rinsing and drying in an air flow. A third polymer layer 13 was applied to cover the area of the third box 17 (yellow).
Finally, the titanium sheet was immersed in the anodization solution and anodically oxidized at 90 V for 30 seconds to achieve a green color layer 14 upon the uncovered background areas 18.
The sheet was then immersed in an organic solution and ultrasonication was applied to remove all the polymer resists. The titanium artwork was then cleaned by rinsing with ethanol and dried in air.
Example 2 A five inch by one inch grade 2 titanium sheet was mechanically or electrochemically polished on one side to remove the native oxide on the surface. The titanium sheet was then degreased with liquid soap and rinsed with hot water (150 F) followed by drying in an air flow.
The pattern to be created on the titanium sheet was three separated boxes with a brown, blue, and yellow color, respectively; while the background color was green.
A chemical etching solution containing HF, NH4F, and H202 was prepared in a rectangular polyethylene container at room temperature.
As shown in Figure 6, to employ multicolor on the titanium surface using the top-down method, the titanium sheet was anodically or thermally oxidized to achieve an initial green color layer 19 for the background. The color was monitored by using portable spectrophotometers.
The oxidized titanium surface was then partially covered by a resist polymer layer 20 upon the background area 18 of the design.
The titanium sheet was then immersed in the etching solution to achieve a yellow color layer 21 for the third box 17.
The etched artwork was then removed from the etching solution, followed by rinsing in distilled water and drying in an air flow. A second polymer layer 22 was applied to cover the area of the third box 17.
The titanium sheet was immersed in the etching solution again to achieve a blue color layer 23 for the second box 16.
The etched artwork was removed from the solution, followed by rinsing in distilled water and drying in an air flow. A third polymer layer 24 was applied to cover the area of the second box 16.
The titanium sheet was immersed in the etching solution and etched to a brown color layer 25 upon the uncovered areas for the first box 15.
The artwork was then removed from the etching solution, rinsed in distilled water, and dried in an air flow. An organic solution and ultrasonication were used to remove all the polymer resists. The titanium artwork was then cleaned in water and dried.
Example 3 A five inch by one inch grade 2 titanium sheet was mechanically or electrochemically polished on one side to remove the native oxide on the surface. The titanium sheet was then degreased with liquid soap and rinsed with hot water (150 F) followed by drying in an air flow.
The same design pattern in Example 1 and 2 was used.
The titanium surface was initially oxidized to achieve a green color layer for the background. The color was monitored by using portable spectrophotometers.
The oxidized surface was then etched at different energy level using a laser engraving machine to achieve the multicolored effect: one brown box, one blue box, and one yellow box, by manipulating the oxide layer thickness.
The etched artwork was removed from the working chamber of the engraving machine, rinsed with ethanol and dried in air.
In the drawings:
Figure 1 illustrates a multicolored titanium artwork substrate having an oxidized layer;
Figure 2 is a perspective cross-sectional view of the multicolored titanium artwork substrate, on smaller scale than Figure 1;
Figure 3 illustrates the principle of the "bottom-up" method to increase the thickness of the oxide layer on titanium surface;
Figure 4 illustrates the principle of the "top-down" method to decrease the thickness of the oxide layer on titanium surface;
Figure 5 illustrates the procedures used in the "bottom-up" method, Figure 6 illustrates the procedures used in the "top-down" method;
Figure 1 and 2 generally illustrate the structure of an artwork article with multicolored image on a titanium surface; while Figure 3-6 generally illustrate the process of "bottom-up" and "top-down" methods for making a multicolored graphic artwork of the present invention.
Figure 1 illustrates a substrate 1 with a titanium-based surface 2 on which has been formed a multicolored artwork image 3, and Figure 2 illustrates the cross-section of the article of Figure 1. In Figure 2, the thickness of the oxide layer 4 is directly related to the surface color. Generally the following order of surface colors can be achieved by increasing the thickness of the oxide layer: light brown, brown, purple, blue, light blue, silver, light yellow, yellow, pink, cobalt, and green. The appearance of the resulting color such as the brightness is also influenced by the surface finish of the titanium substrate.
The manipulating of the surface color is accomplished by two methods called "bottom-up" and "top-down", respectively, as shown in Figure 3-6. In the bottom-up method, the surface is partially covered by a resist material 5 and the thickness of the oxide layer of the uncovered areas is increased in a controlled manner during oxidation process 6; in the top-down method, the surface is partially covered by a resist material 5 and the thickness of the oxide layer of the uncovered areas is reduced in a controlled manner during an etching process 7.
The growth or etching of oxide layer on a titanium article is manipulated by interrupting the oxidation process and selecting target areas, as described in detail above, in the color generation procedure of the present invention. Hereinafter, the present invention will be further illustrated with reference to the following three examples.
Example 1 A five inch by one inch grade 2 titanium sheet was mechanically or electrochemically polished on one side to remove the native oxide on the surface. The titanium sheet was then degreased with liquid soap and rinsed with hot water (150 F) followed by drying in an air flow.
The pattern to be created on the titanium sheet was three separated boxes with a brown, blue, and yellow color, respectively; while the background color was green.
An electrical chemical anodization solution was prepared in a rectangular polyethylene container by dissolving 16.8 g sodium bicarbonate in 2 L distilled water at room temperature.
As shown in Figure 5, to employ multicolor on the titanium surface using the bottom-up method, the titanium sheet was placed in the anodization solution and the polished side was anodically oxidized at 25 V for 30 seconds to achieve an initial brown color layer 8 for the first box 15. The color was monitored by using portable spectrophotometers.
The oxidized titanium sheet was removed from the solution, followed by rinsing and drying in an air flow. The resulting oxidized surface was then partially covered by a resist polymer layer 9 upon the area of the first box 15 (brown).
Proceeding as before, the titanium sheet was immersed in the anodization solution and anodically oxidized at 45 V for 30 seconds to achieve a blue color layer 10 for the second box 16 expect the previously polymer-covered area.
The oxidized titanium sheet was removed from the solution, followed by rinsing and drying in an air flow. A second polymer layer 11 was applied to cover the area of the second box 16 (blue).
Similarly, the titanium sheet was immersed in the anodization solution for the third time and anodically oxidized at 65 V for 30 seconds to achieve a yellow color layer 12 for the third box 17 expect the previously polymer-covered areas.
The oxidized titanium sheet was removed from the solution, followed by rinsing and drying in an air flow. A third polymer layer 13 was applied to cover the area of the third box 17 (yellow).
Finally, the titanium sheet was immersed in the anodization solution and anodically oxidized at 90 V for 30 seconds to achieve a green color layer 14 upon the uncovered background areas 18.
The sheet was then immersed in an organic solution and ultrasonication was applied to remove all the polymer resists. The titanium artwork was then cleaned by rinsing with ethanol and dried in air.
Example 2 A five inch by one inch grade 2 titanium sheet was mechanically or electrochemically polished on one side to remove the native oxide on the surface. The titanium sheet was then degreased with liquid soap and rinsed with hot water (150 F) followed by drying in an air flow.
The pattern to be created on the titanium sheet was three separated boxes with a brown, blue, and yellow color, respectively; while the background color was green.
A chemical etching solution containing HF, NH4F, and H202 was prepared in a rectangular polyethylene container at room temperature.
As shown in Figure 6, to employ multicolor on the titanium surface using the top-down method, the titanium sheet was anodically or thermally oxidized to achieve an initial green color layer 19 for the background. The color was monitored by using portable spectrophotometers.
The oxidized titanium surface was then partially covered by a resist polymer layer 20 upon the background area 18 of the design.
The titanium sheet was then immersed in the etching solution to achieve a yellow color layer 21 for the third box 17.
The etched artwork was then removed from the etching solution, followed by rinsing in distilled water and drying in an air flow. A second polymer layer 22 was applied to cover the area of the third box 17.
The titanium sheet was immersed in the etching solution again to achieve a blue color layer 23 for the second box 16.
The etched artwork was removed from the solution, followed by rinsing in distilled water and drying in an air flow. A third polymer layer 24 was applied to cover the area of the second box 16.
The titanium sheet was immersed in the etching solution and etched to a brown color layer 25 upon the uncovered areas for the first box 15.
The artwork was then removed from the etching solution, rinsed in distilled water, and dried in an air flow. An organic solution and ultrasonication were used to remove all the polymer resists. The titanium artwork was then cleaned in water and dried.
Example 3 A five inch by one inch grade 2 titanium sheet was mechanically or electrochemically polished on one side to remove the native oxide on the surface. The titanium sheet was then degreased with liquid soap and rinsed with hot water (150 F) followed by drying in an air flow.
The same design pattern in Example 1 and 2 was used.
The titanium surface was initially oxidized to achieve a green color layer for the background. The color was monitored by using portable spectrophotometers.
The oxidized surface was then etched at different energy level using a laser engraving machine to achieve the multicolored effect: one brown box, one blue box, and one yellow box, by manipulating the oxide layer thickness.
The etched artwork was removed from the working chamber of the engraving machine, rinsed with ethanol and dried in air.
Claims (24)
The Embodiments Of The Invention In Which An Exclusive Property Or Privilege Is Claimed Are Defined As Follows:
1. An article having colored graphics, said article comprising a titanium or titanium alloy based surface and an oxide layer comprising titanium oxide formed or modified on said surface with a controlled manner for achieving said colored graphics.
2. The article according to claim 1, wherein said titanium or titanium alloy is in the form comprising foil, sheet, plate, block, or a machined shape.
3. The article according to claim 1, wherein said titanium or titanium alloy is formed, coated or deposited on a substrate comprising metal, glass, silicon, wood, fabric, ceramic, and polymer.
4. The article according to any one of claims 1 to 3, wherein said oxide layer comprises amorphous titanium oxide.
5. The article according to any one of claims 1 to 3, wherein said oxide layer comprises crystallized titanium oxide.
6. The article according to any one of claims 1 to 5, wherein said oxide layer comprises titanium oxide nanostructures.
7. The article according to any one of claims 1 to 6, wherein said oxide layer is deposited, coated or plated with copper, silver, gold, platinum, cobalt, nickel, iron, iridium, cadmium, silicon, and silica.
8. The article according to any one of claims 1 to 7, wherein said oxide layer is coated or covered with at least one optically transparent material including polymer, sapphire, quartz, and glass.
9. The article according to any one of claims 1 to 8, wherein the appearance of said colored graphics including brightness and contrast is adjusted by surface treatment of said surface comprising etching, sanding, milling, engraving, and polishing.
10. A method for applying colored graphics on a titanium or titanium alloy based surface. Said method comprising the steps of: (a) providing a cleaned titanium or titanium alloy based surface or substrate, (b) applying oxidation on said surface, (c) monitoring said color and manipulating the thickness of the oxide layer comprising interrupting the oxidation process, protecting selected areas using resists, and applying further oxidation on said surface, and (d) removing resists, cleaning and drying said surface.
11. The method according to claim 10, in which the oxidation is applied by using anodic or electrical chemical process.
12. The method according to claim 10, in which the oxidation is applied by using thermal process.
13. The method according to claim 10, in which the oxidation is applied by using chemical process.
14. The method according to claims 11 to 13 , in which the oxidation is applied by a combination of said processes.
15. The method according to any one of claims 10 to 14, in which the resist is polymer-based and is applied using an approach comprising printing, spraying, sputtering, painting, and coating.
16. The method according to any one of claims 10 to 14, in which the resist is inorganic material-based and is applied using an approach comprising printing, spraying, sputtering, painting, and coating.
17. A method for applying colored graphics on a titanium or titanium alloy based surface. Said method comprising the steps of: (a) providing a cleaned titanium or titanium alloy based surface or substrate, (b) applying oxidation on said surface, (c) monitoring said color and manipulating the thickness of the oxide layer comprising interrupting the oxidation process, protecting selected areas using resists, and applying further etching on said surface, and (d) removing resists, cleaning and drying said surface.
18. The method according to claim 17, in which the etching is applied by using chemical process.
19. The method according to claim 17, in which the etching is applied by using electrical-chemical process.
20. The method according to claim 17, in which the etching is applied by using photo-chemical process.
21. The method according to claim 17, in which the etching is applied by using photo-electrical-chemical process.
22. The method according to claim 17, in which the etching is applied by using processes comprising laser etching, plasma etching, milling, sanding, and polishing.
23. The method according to claim 22, in which said resist is not applied.
24. The method according to claims 18 to 23, in which the etching is applied by a combination of said processes.
Priority Applications (1)
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CA2870523A CA2870523A1 (en) | 2014-11-03 | 2014-11-03 | Colored graphic artworks on titanium surfaces |
Applications Claiming Priority (1)
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CA2870523A CA2870523A1 (en) | 2014-11-03 | 2014-11-03 | Colored graphic artworks on titanium surfaces |
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CA2870523A1 true CA2870523A1 (en) | 2016-05-03 |
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CA2870523A Pending CA2870523A1 (en) | 2014-11-03 | 2014-11-03 | Colored graphic artworks on titanium surfaces |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106676606A (en) * | 2016-11-21 | 2017-05-17 | 广西大学 | Method for preparing ceramic oxidation films in different colors on surface of titanium alloy |
US20210115550A1 (en) * | 2019-10-22 | 2021-04-22 | Korea Institute Of Science And Technology | Non-metal member with colored surface and method of coloring non-metal surface |
FR3117132A1 (en) * | 2020-12-09 | 2022-06-10 | Safran Aircraft Engines | SURFACE TREATMENT METHOD BY SELECTIVE REMOVAL OF A BONDING PRIMER ON A TITANIUM OR TITANIUM ALLOY SUBSTRATE |
-
2014
- 2014-11-03 CA CA2870523A patent/CA2870523A1/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106676606A (en) * | 2016-11-21 | 2017-05-17 | 广西大学 | Method for preparing ceramic oxidation films in different colors on surface of titanium alloy |
CN106676606B (en) * | 2016-11-21 | 2019-03-01 | 广西大学 | The method that titanium alloy surface prepares different colours ceramic coating |
US20210115550A1 (en) * | 2019-10-22 | 2021-04-22 | Korea Institute Of Science And Technology | Non-metal member with colored surface and method of coloring non-metal surface |
US11753725B2 (en) * | 2019-10-22 | 2023-09-12 | Korea Institute Of Science And Technology | Non-metal member with colored surface and method of coloring non-metal surface |
FR3117132A1 (en) * | 2020-12-09 | 2022-06-10 | Safran Aircraft Engines | SURFACE TREATMENT METHOD BY SELECTIVE REMOVAL OF A BONDING PRIMER ON A TITANIUM OR TITANIUM ALLOY SUBSTRATE |
WO2022123141A1 (en) * | 2020-12-09 | 2022-06-16 | Safran Aircraft Engines | Method for surface treatment by selective removal of a bonding primer on a titanium or titanium alloy substrate |
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