EP1199385A2 - Method of coloring titanium and its alloys through anodic oxidation - Google Patents
Method of coloring titanium and its alloys through anodic oxidation Download PDFInfo
- Publication number
- EP1199385A2 EP1199385A2 EP01124684A EP01124684A EP1199385A2 EP 1199385 A2 EP1199385 A2 EP 1199385A2 EP 01124684 A EP01124684 A EP 01124684A EP 01124684 A EP01124684 A EP 01124684A EP 1199385 A2 EP1199385 A2 EP 1199385A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- titanium
- alloys
- acid
- electrolytic bath
- potential
- 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
- 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
Definitions
- This invention concerns a method of coloring titanium and titanium alloys through anodic oxidation.
- the invention also deals with the use of this method to color articles made of titanium and or titanium alloys, providing them with particular chromatic properties and resistance to corrosion.
- the film of titanium oxide produced on its surface takes on a variety of interference colours which change according to the potential applied-and thus to the thickness of the film- in a chromatic scale which goes from yellow to purple to blue, and back to yellow, then to pink, cobalt and green.
- This behaviour has been recognized for decades, and anodically colored titanium has been used in a wide variety of fields, with applications in, for example: decorative panels for interior and exterior use, furnishings, architecture, painting, monuments, costume jewellery, ornaments, precious jewellery, eyeglasses, the biomedical area, etc.
- a titanium sample is immersed in an electrolytic solution and connected to the positive plug of a direct current power supply whose negative plug is connected to a metallic counter-electrode made, for example, of stainless steel.
- a metallic counter-electrode made, for example, of stainless steel.
- the titanium plate behaves as anode and the oxide film formed has a thickness, and thus a tint, which depends on the potential applied.
- electrolytic solutions may be used: for example diluted phosphoric or sulphuric acids (1-5% by weight), sulphamic acid (1-15% by weight) or ammonium sulphate or sodium bicarbonate solutions (1-15% by weight).
- the extension of colours can be controlled by limiting the area to be oxidised with screens or laquers or through the use of special electrochemical brushes adapted with a cathodic ring to carry the current.
- a current density in the range of 1-100 A/m2 is normally used and the potential applied is higher than that used in galvanics: depending on the color desired, potential varying from a few Volt to more than 100 Volt are applied.
- US Patent N° 5160599 describes a method of coloring titanium, including two separate stages of anodization at constant current density, by which many shades of color are obtained.
- the procedure in this invention is characterized by the fact that the titanium or its alloy undergoes a preliminary anodic treatment at constant potential in a first electrolytic solution consisting of hydrohalogen acids or salts, fluoboric, fluosilic, acetic, oxalic, tartaric, nitric, phosphoric acids and their mixtures, possibly in the presence of oxidizing agents.
- titanium acts anodically in certain baths, even for very brief periods (from a few thousandths of a second and up), the potential remaining constant and contained within a well-defined interval, its surface is modified so that when it is subsequently oxidized with the usual solutions and techniques, it takes on colors which are particularly intense and more resistant than those traditionally obtained.
- Coloration carried out on such pre-treated titanium not only differs in appearance and in its corrosion resistance in solutions (such as sulphuric-hydrchloric and phosphoric nitric-hydrofluoric, or organic acids) but can also be distinguished from traditional coloring at a microscopic level: observations made under a metallographic microscope show that all the crystalline grains of the metal are colored equally and uniformly, while this does not happen in traditional coloring.
- the potential to be applied depends on the type of bath used, and runs from 2 to 15 Volt. Hydrochloric acid or nitric acid / hydrofluoric acid are the solutions of choice.
- the electrolytic bath consists of an aqueous solution of hydrochloric acid, at a concentration of, for example, 10%, the potential is normally between 3.0 and 5.0 V, and preferably between 3.5 and 4.0 V.
- the potential may run from 4.0 to 8.0 V.
- the treatment time may vary widely, for example from 1/1000 sec. to 60 seconds or more.
- Pre-treatment is carried out by immersing the pickled titanium in one of baths mentioned, at a potential within the critical interval cited, then rinsing it in water and drying it. If, at some time during immersion, the potential rises or falls outside the critical interval, for example if a pulsating potential is applied, the treatment will be valid only for those portions of the surface that come into contact with the bath at the moment the potential applied lies within the critical interval. Thus a subsequent oxidation will allow intense colours to be obtained only in those regions.
- the second oxidation instead, is carried out in any of the electrolytic baths utilized for traditional anodic oxidation of titanium-and, that is, for example, diluted phosphoric or sulphuric acids (1-5% by weight), solutions of sulphamic acid (1-15% by weight) or solutions of ammonium sulphate or sodium bicarbonate (1-15% by weight), etc., with a current density, in general, between 1 and 100 A/m 2 .
- a titanium plate is pickled in a bath of nitric and hydrofluoric acid (35%-5% by weight). After being rinsed in water, the plate is dried and then dipped in a bath of hydrochloric acid (10%) under an anodic potential of 4 Volt until it is completely immersed. The treatment is continued for 5-15 seconds, after which it is interrupted. After being rinsed in water, the plate is then oxidized according to the traditional techniques.
- Example 2 The same procedure of Example 1 is used, applying a pulsating anodic potential as follows: 4 Volt for 1 second, 0 Volt the following second, 4 Volt the third second, and so on, for a variable number of cycles.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Heat Treatment Of Nonferrous Metals Or Alloys (AREA)
- Electrochemical Coating By Surface Reaction (AREA)
Abstract
Description
Claims (8)
- A method of coloring titanium and its alloys through anodic oxidation in an electrolytic bath characterized in that titanium or its alloys undergoes an anodic pre-treatment at constant potential in a first electrolytic bath consisting of hydrohalogen acids or salts, fluoboric acid, fluosilic acid, acetic acid, oxalic acid, tartaric acid, nitric acid, phosphoric acid and their mixtures, optionally in the presence of oxidizing agents.
- A method according to claim 1, in which titanium or its alloys, pickled and dried, are connected to the electrode before immersion in the first electrolytic bath.
- A method, according to claim 1 or 2, in which the constant anodic potential is between 2.0 and 15.0 Volts.
- A method, according to claim 3, in which the first electrolytic bath consists of an aqueous solution of hydrochloric acid, and the constant anodic potential is between 3.0 and 5.0 Volts.
- A method, according to claim 4, in which the constant anodic potential is between 3.0 and 4.0 Volts.
- A method, according to claim 3, in which the first electrolytic bath consists of an aqueous solution of fluohydric and nitric acid and the constant anodic potential between 4.0 and 8.0 Volts.
- A method, according to any of claims 1 to 6, in which the pre-treatment is carried out for periods of time ranging from 1/1000 second to 30 seconds.
- Articles of titanium or its alloys colored using the methods according to any one of claims 1 to 6.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMI002263 | 2000-10-19 | ||
ITMI20002263 IT1319225B1 (en) | 2000-10-19 | 2000-10-19 | METHOD OF COLORING OF TITANIUM OR ITS ALLOYS BY ANODIC OXIDATION. |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1199385A2 true EP1199385A2 (en) | 2002-04-24 |
EP1199385A3 EP1199385A3 (en) | 2004-02-04 |
EP1199385B1 EP1199385B1 (en) | 2012-07-25 |
Family
ID=11445997
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20010124684 Expired - Lifetime EP1199385B1 (en) | 2000-10-19 | 2001-10-16 | Method of coloring titanium and its alloys through anodic oxidation |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP1199385B1 (en) |
IT (1) | IT1319225B1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102115902A (en) * | 2009-12-30 | 2011-07-06 | 沈阳天贺新材料开发有限公司 | Surface anodization coloring treatment method for titanium and titanium alloy |
CN109346727A (en) * | 2018-08-27 | 2019-02-15 | 广州倬粤动力新能源有限公司 | The edge-locking method of grid |
CN111155159A (en) * | 2020-01-16 | 2020-05-15 | 广东安特齿科有限公司 | Anodic oxidation liquid and coloring method of implant abutment |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5160599A (en) | 1989-07-07 | 1992-11-03 | Kenzo Kobayashi | Process for coloring titanium and its alloys |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE559886A (en) * | 1956-08-08 | |||
SU850764A1 (en) * | 1979-04-05 | 1981-07-30 | Казанский Инженерно-Строитель-Ный Институт | Solution for electrochemical polishing of titanium |
JPH01240696A (en) * | 1988-03-18 | 1989-09-26 | Nkk Corp | Anodic oxidation for titanium or titanium alloy |
JPH02250981A (en) * | 1989-03-23 | 1990-10-08 | Nippon Stainless Steel Co Ltd | Pretreatment of titanium material before coloring with molten salt |
-
2000
- 2000-10-19 IT ITMI20002263 patent/IT1319225B1/en active
-
2001
- 2001-10-16 EP EP20010124684 patent/EP1199385B1/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5160599A (en) | 1989-07-07 | 1992-11-03 | Kenzo Kobayashi | Process for coloring titanium and its alloys |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102115902A (en) * | 2009-12-30 | 2011-07-06 | 沈阳天贺新材料开发有限公司 | Surface anodization coloring treatment method for titanium and titanium alloy |
CN109346727A (en) * | 2018-08-27 | 2019-02-15 | 广州倬粤动力新能源有限公司 | The edge-locking method of grid |
CN111155159A (en) * | 2020-01-16 | 2020-05-15 | 广东安特齿科有限公司 | Anodic oxidation liquid and coloring method of implant abutment |
Also Published As
Publication number | Publication date |
---|---|
EP1199385A3 (en) | 2004-02-04 |
IT1319225B1 (en) | 2003-09-26 |
ITMI20002263A1 (en) | 2002-04-19 |
EP1199385B1 (en) | 2012-07-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Grubbs | Anodizing of aluminum | |
US5674371A (en) | Process for electrolytically treating aluminum and compositions therefor | |
KR100733478B1 (en) | Method for marking character and figure on aluminum article | |
DE10393234T5 (en) | Surface treatment of magnesium and its alloys | |
US6379523B1 (en) | Method of treating surface of aluminum blank | |
US3284321A (en) | Manufacture of aluminum articles with anodized surfaces presenting multicolor effects | |
AU633132B2 (en) | Improved electrolytic method for coloring anodized aluminum | |
US4019970A (en) | Process for making titanium-supported lead electrode | |
US20030057100A1 (en) | Method of producing bright anodized finishes for high magnesium, aluminum alloys | |
US4043880A (en) | Method for producing green-colored anodic oxide film on aluminum or aluminum base alloy articles | |
EP1199385B1 (en) | Method of coloring titanium and its alloys through anodic oxidation | |
US4877495A (en) | Electrolytic coloring of anodized aluminum | |
US4430169A (en) | Method of producing green coatings on aluminum and aluminum alloys | |
JPS6210299A (en) | Formation of colored coated film for titanium or titanium alloy | |
US4632735A (en) | Process for the electrolytic coloring of aluminum or aluminum alloys | |
US5288372A (en) | Altering a metal body surface | |
GB1598939A (en) | Electrolytic colouring of aluminium and alloys thereof | |
CN216585268U (en) | Anodized aluminum alloy rim | |
JPH06235091A (en) | Pretreatment of colored titanium material by anodization and production of colored titanium material | |
US4917780A (en) | Process for coloring anodized aluminum by AC electrolysis | |
CN109652838A (en) | A kind of method of titanium-niobium alloy surface anodization coloring | |
TWI845291B (en) | Surface coloring method of magnesium alloy article and magnesium alloy article with colored surface | |
US3897278A (en) | Oxidizing process and composition for aluminum | |
KR950000313B1 (en) | Method for impartation of blue color to aluminum or aluminum alloy | |
JPS63199894A (en) | Method for electrolytically developing color on titanium and titanium alloy |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
|
17P | Request for examination filed |
Effective date: 20040728 |
|
AKX | Designation fees paid |
Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
17Q | First examination report despatched |
Effective date: 20060413 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Ref country code: AT Ref legal event code: REF Ref document number: 567764 Country of ref document: AT Kind code of ref document: T Effective date: 20120815 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 60146851 Country of ref document: DE Effective date: 20120920 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20120725 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 567764 Country of ref document: AT Kind code of ref document: T Effective date: 20120725 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120725 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120725 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120725 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120725 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20121026 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20121126 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120725 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120725 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20121105 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120725 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121031 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120725 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20121025 |
|
26N | No opposition filed |
Effective date: 20130426 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20130628 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130501 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121016 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121031 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121031 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121025 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60146851 Country of ref document: DE Effective date: 20130501 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 60146851 Country of ref document: DE Effective date: 20130426 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20120725 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121016 |