US20050218004A1 - Process for making a composite aluminum article - Google Patents
Process for making a composite aluminum article Download PDFInfo
- Publication number
- US20050218004A1 US20050218004A1 US10/995,527 US99552704A US2005218004A1 US 20050218004 A1 US20050218004 A1 US 20050218004A1 US 99552704 A US99552704 A US 99552704A US 2005218004 A1 US2005218004 A1 US 2005218004A1
- Authority
- US
- United States
- Prior art keywords
- salt
- low friction
- friction material
- substrate
- article
- 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.)
- Abandoned
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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
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
Definitions
- the present invention relates to a process for the preparation of a stain-resistant composite aluminum article, such as cookware, and to stain-resistant cookware.
- Aluminum articles having treated oxidized surfaces are commonly used due to the low friction and high corrosion resistance of their surfaces.
- Anodized aluminum articles have a thin layer of porous, irregular, coarsely crystalline aluminum oxide formed on their surfaces. Additionally, it is known to apply a thin coating to seal the porous oxide. The coating adheres very strongly and tenaciously to the aluminum substrate and thus making the substrate highly abrasion resistant.
- Processes for anodizing and sealing aluminum include U.S. Pat. Nos. 4,861,440 and 4,784,732, the respective disclosures of which are hereby incorporated by reference in their entirety.
- Coated anodized aluminum surfaces may be used in a variety of applications. In particular, they enjoy wide use in the production of cookware due to their strength, hardness and corrosion resistance. Notwithstanding these benefits, anodized cookware may be susceptible to sticking or staining. Further, acidic food may react with the surface of anodized aluminum cookware and may corrode the hard anodized surface.
- the invention relates to a process for making a composite aluminum article comprising:
- the invention relates to a process for making a composite aluminum article comprising:
- sealing is performed with an aqueous solution or suspension containing at least one salt having an anion, a cation, or both of a divalent metal or a trivalent metal thereby producing a sealed, anodized aluminum substrate, wherein the salt solution or suspension substantially saturates the low friction material-treated substrate.
- the salt used may be a nickel salt and/or a cobalt salt.
- a nickel salt is used. More preferably, the nickel salt is nickel acetate.
- sealing may be accomplished by immersion in near-boiling water (e.g., water at 200° F.-210° F.).
- the low friction material that may be used is a blend of food grade polymers.
- Other types of low-friction materials may also be used.
- the treatment of the low friction material-treated substrate with an aqueous solution or suspension containing at least one salt having an anion, a cation, or both of a divalent metal or a trivalent metal is performed at a temperature of 170-180° F.
- the pH of the solution is between 5.7 and 6.0 and the treatment is conducted for 6 to 15 minutes.
- cookware is made according to the above-described process.
- Various types of cookware contemplated include, by way of example, kettles, dutch ovens, pots, pans, skillets, griddles and waffle irons.
- Cookware according to the invention exhibit improved durability, corrosion resistance and stain resistance.
- a composite aluminum article is prepared in four steps from an aluminum substrate.
- the aluminum substrate can be pure aluminum or an aluminum alloy and can be wrought, cast or forged.
- the four steps may be summarized as follows: (i) anodizing; (ii) sealing; (iii) treating with a “low friction material,” preferably a blend of food-grade polymers; and (iv) a second sealing with a solution containing the salt of a di- or tri-valent metal.
- the first three of these steps have been found to result in anodized surfaces with good strength and corrosion resistance.
- the added sealing treatment with the salt of a di- or tri-valent metal significantly and unexpectedly improved the stain resistance of the resulting composite aluminum substrate.
- This process delivers better performance than achieved with a single sealing step of the anodized aluminum substrate, even where the single sealing step took place over a longer total duration.
- Conventional wisdom would have predicted that treating the low friction material-treated substrate with a solution containing the salt of a di- or tri-valent metal would not have any impact on the stain-resistance of the resulting composite aluminum substrate.
- an aluminum oxide layer is formed electrolytically on the surface of the aluminum substrate.
- Anodization methods well known to the skilled artisan including, for example, those disclosed in detail in U.S. Pat. Nos. 4,861,440 and 4,784,732 may be used.
- This step produces an aluminum oxide surface that is integral with the base aluminum and is irregular, coarsely crystalline and highly porous.
- the aluminum oxide layer can be “grown” on the aluminum substrate by electrolytic treatment while the aluminum substrate is immersed in an oxidizing acid bath.
- the substrate serves as the anode, and high voltages and current densities are used to form a highly porous aluminum oxide layer.
- an aluminum substrate is immersed in a non-etching acid bath for electrolytically growing aluminum oxide crystals.
- aqueous sulfuric acid comprising about 120-310 g/L concentrated sulfuric acid may be used.
- Other components known in the art may also be used in the bath.
- the acid bath used for anodizing be highly agitated.
- this is performed by air agitation or mechanical means well known in the art.
- a conventional wetting agent such as an alkylaryl polyether alcohol, can also be added to the bath wetting agent.
- the bath is preferably maintained at a temperature of about 25°-80° F., particularly about 26°-36° F., and the temperature of the bath is not allowed to rise substantially during the electrolytic formation of the oxide layer, particularly when high current densities are used.
- the voltage between anode and cathode is increased gradually from the start to the finish of the process.
- Different voltage ramp schedules based on current density may be used in accordance with techniques known in the art and will vary depending on the application. (See, e.g., Tool and Manufacturing Engineers Handbook, 4 th Edition, Volume 3, which indicates that current densities should be maintained at 20-50 amps per square foot). Preferably, a current density of 20-25 amps per square foot is used.
- the voltage schedule is preferably increased from 20 volts to 100 volts over the cycle time of the anodizing process, preferably 25 volts up to 80 volts at equal time increment. Particular cycle times may vary depending on the specific article to be anodized desired characteristics of the process.
- the aluminum oxide crystal structure thus formed has a thickness of up to 2 mils, preferably about 1.5 mils.
- the anodization process may take from about 15 minutes to about 60 minutes, depending upon the desired thickness of the aluminum oxide crystal structure and the aluminum alloy composition, as well as the current density, as understood in the art.
- these process parameters are merely illustrative, and can be varied to suit particular applications.
- the resulting anodized aluminum substrate is then rinsed thoroughly with deionized, preferably distilled water, to remove any residue on its surfaces from the acid bath.
- deionized preferably distilled water
- the anodized aluminum substrate produced in the anodization step is then “sealed” or “pre-sealed.”
- Sealing may be performed, for example, by treating the anodized aluminum substrate with an aqueous solution or suspension containing one or more salts with an anion, a cation or both of a divalent or trivalent metal, wherein each of the salt(s) is absorbed into the crystal lattice of the aluminum oxide.
- Other sealing processes may be used instead of such treatment.
- the anodized aluminum substrate may be sealed with near boiling water.
- the anodized aluminum substrate preferably is dipped into a bath containing the solution, or a suspension containing the salt or salts, for about 20 minutes.
- salts that can be used to seal the anodized aluminum substrate are the lower alkanoates (e.g., acetate or formate) of nickel, cobalt, lead, zinc and copper and the ammonium, alkali metal and alkaline earth metal dichromates and molybdates, as well as other conventional salts used for sealing aluminum surfaces.
- a nickel salt such as nickel acetate, is used to seal the anodized aluminum substrate.
- anodized aluminum substrate may be sealed more than once. Further, (a) mixtures of salts may be used in each sealing step, and (b) each sealing step may employ a different salt or mixture of salts than the previous sealing step.
- anodized aluminum substrate in water that is near boiling (e.g., 200-210° F.) for a sufficient period of time, preferably, about 5 minutes.
- the anodized, sealed aluminum substrate is treated with a lubricant or low friction material, thereby producing a low friction material-treated substrate.
- lubricants/low friction materials include, but are not limited to, graphite, silicone, molybdenum disulfide, polymers and the like.
- the anodized, sealed aluminum substrate is treated with a blend of food grade polymers by dipping the anodized, sealed aluminum substrate in a bath containing the mixture of polymers for about 5 minutes.
- One blend of food grade polymers that is preferred is an HCR-F® blend provided from General Magnaplate, Linden, N.J.
- the resulting low friction material-treated substrate is then rinsed thoroughly with deionized water, preferably hot, distilled water, before performing the fourth step of the process of a preferred embodiment of the present invention.
- deionized water preferably hot, distilled water
- the use of hot water heats the substrate to facilitate more rapid evaporation of the water, but such heating may not be necessary.
- the low friction material-treated substrate is baked so as to remove any residual water that may be found in the lubricant/low friction material.
- baking takes place at a temperature from about 500° F. to about 700° F., most preferably at about 680° F. Baking takes place for an appropriate time to cure, typically at least 6 to 90 minutes, depending, for example, on temperature.
- the resulting low friction material-treated substrate is again sealed or “post-sealed” with an aqueous solution or suspension containing one or more salts with an anion, a cation or both of a divalent or trivalent metal, as described above.
- the low friction material-treated substrate is dipped in a nickel acetate solution for an immersion time of about 6-15 minutes, at a temperature of 170° F.-180° F., wherein the pH of the nickel acetate solution is between 5.7 and 6.0.
- This final step produces a composite aluminum article with improved characteristics.
- this final step can be used advantageously to produce hard anodized cookware with markedly improved stain resistance.
- the composite aluminum article comprises two protective layers when the low friction material-treated substrate is subsequently treated with the above-mentioned salt solution: a first protective layer that is formed by the low friction material; and a second protective layer that is formed when the salt(s) is absorbed into the pores of the low friction material (particularly when the low friction material is a polymer or blend of polymers). While not wishing to be bound by theory, it is believed that these two protective layers, in combination, provide the composite aluminum article with the observed enhanced stain resistance. The resulting article further exhibits superior strength, hardness and corrosion resistance.
- the surface of the composite aluminum article produced by the process described herein is ideal for the production of pieces of cookware (e.g., kettles, dutch ovens, pots, pans, skillets, griddles, waffle irons, and the like), where stain-resistance, as well as enhanced strength, enhanced hardness and corrosion resistance are important.
- the surface of the composite aluminum article exhibits excellent stain-resistance.
- the surface of the composite aluminum article exhibits excellent acid resistance and easier cleaning.
- the fourth step in the process for the production of the composite aluminum article of the preferred embodiments of the present invention significantly and unexpectedly improved the stain resistance of the resulting composite aluminum substrate to blueberry paste, curry paste, cooking oil and tomato.
- the composite aluminum article of a preferred embodiment may be produced using the four steps described above (i.e., anodization, pre-seal, lubricant/low friction material treatment, post-seal), starting with an aluminum substrate that is not anodized. It will be appreciated, however, that the composite aluminum article of a preferred embodiment may be produced starting with an anodized aluminum substrate that may be obtained, for example, from a third-party source. The anodized aluminum substrate would then be pre-sealed using the methods disclosed (or methods well known in the art), treated with a lubricant or low friction material and post-sealed according to the methods disclosed above.
- a process according to another embodiment of the invention may involve providing a sealed, anodized aluminum substrate and sealing the sealed, anodized aluminum substrate according to the methods disclosed above.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cookers (AREA)
- Laminated Bodies (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/995,527 US20050218004A1 (en) | 2003-11-26 | 2004-11-24 | Process for making a composite aluminum article |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US52490703P | 2003-11-26 | 2003-11-26 | |
US10/995,527 US20050218004A1 (en) | 2003-11-26 | 2004-11-24 | Process for making a composite aluminum article |
Publications (1)
Publication Number | Publication Date |
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US20050218004A1 true US20050218004A1 (en) | 2005-10-06 |
Family
ID=34885926
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US10/995,527 Abandoned US20050218004A1 (en) | 2003-11-26 | 2004-11-24 | Process for making a composite aluminum article |
Country Status (2)
Country | Link |
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US (1) | US20050218004A1 (zh) |
CN (1) | CN1644760B (zh) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2046174A1 (en) * | 2006-07-18 | 2009-04-15 | Thermolon Korea Co., Ltd | Structure of coating layer for heat-cooker |
US7622197B2 (en) | 2006-11-20 | 2009-11-24 | Ferroxy-Aled, Llc | Seasoned ferrous cookware |
US20120088033A1 (en) * | 2010-10-07 | 2012-04-12 | Michael Sheehy | Sealed anodized aluminum components and process for their manufacture |
WO2012061872A1 (en) * | 2010-11-08 | 2012-05-18 | Mezurx Pty Ltd | Sample analyser |
US8814863B2 (en) | 2005-05-12 | 2014-08-26 | Innovatech, Llc | Electrosurgical electrode and method of manufacturing same |
US9260792B2 (en) | 2010-05-19 | 2016-02-16 | Sanford Process Corporation | Microcrystalline anodic coatings and related methods therefor |
US9630206B2 (en) | 2005-05-12 | 2017-04-25 | Innovatech, Llc | Electrosurgical electrode and method of manufacturing same |
US10214827B2 (en) | 2010-05-19 | 2019-02-26 | Sanford Process Corporation | Microcrystalline anodic coatings and related methods therefor |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8512872B2 (en) * | 2010-05-19 | 2013-08-20 | Dupalectpa-CHN, LLC | Sealed anodic coatings |
Citations (20)
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US3563785A (en) * | 1965-10-09 | 1971-02-16 | Sumitomo Electric Industries | Method of resin coating of the metal and resin-coated metal product therefor |
US3717555A (en) * | 1970-11-27 | 1973-02-20 | Fentron Ind Inc | Method of producing an electrolytic coating on aluminum and the product thereof |
US3959090A (en) * | 1974-07-31 | 1976-05-25 | Swiss Aluminium Ltd. | Continuous electrolyte coloring of a pre-anodised aluminum foil or strip |
US4022671A (en) * | 1976-04-20 | 1977-05-10 | Alcan Research And Development Limited | Electrolytic coloring of anodized aluminum |
US4179342A (en) * | 1978-06-28 | 1979-12-18 | Reynolds Metals Company | Coating system method for coloring aluminum |
US4193848A (en) * | 1973-08-13 | 1980-03-18 | Swiss Aluminium Ltd. | Process for the production of composite material |
US4251330A (en) * | 1978-01-17 | 1981-02-17 | Alcan Research And Development Limited | Electrolytic coloring of anodized aluminium by means of optical interference effects |
US4559114A (en) * | 1984-11-13 | 1985-12-17 | Kaiser Aluminum & Chemical Corporation | Nickel sulfate coloring process for anodized aluminum |
US4571287A (en) * | 1980-12-27 | 1986-02-18 | Nagano Prefecture | Electrolytically producing anodic oxidation coat on Al or Al alloy |
US4784732A (en) * | 1986-07-24 | 1988-11-15 | Covino Charles P | Electrolytic formation of an aluminum oxide layer |
US4861440A (en) * | 1986-07-24 | 1989-08-29 | Covino Charles P | Electrolytic formation of an aluminum oxide surface |
US5330635A (en) * | 1993-03-25 | 1994-07-19 | Lockheed Corporation | Protective coating process for aluminum and aluminum alloys |
US5374347A (en) * | 1993-09-27 | 1994-12-20 | The United States Of America As Represented By The Secretary Of The Navy | Trivalent chromium solutions for sealing anodized aluminum |
US5374455A (en) * | 1991-04-09 | 1994-12-20 | Sandoz Ltd. | Process for sealing aluminum oxide films |
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US5419970A (en) * | 1991-08-19 | 1995-05-30 | Mitsubishi Jukogyo Kabushiki Kaisha | Method for making a composite aluminum article |
US5472788A (en) * | 1994-07-14 | 1995-12-05 | Benitez-Garriga; Eliseo | Colored anodized aluminum and electrolytic method for the manufacture of same |
US5674371A (en) * | 1989-11-08 | 1997-10-07 | Clariant Finance (Bvi) Limited | Process for electrolytically treating aluminum and compositions therefor |
US5804253A (en) * | 1995-07-17 | 1998-09-08 | Kanegafuchi Chemical Ind. Co., Ltd. | Method for adhering or sealing |
US20030075452A1 (en) * | 2001-10-24 | 2003-04-24 | Che-Yuan Hsu | Process of surface treating aluminum articles |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9422952D0 (en) * | 1994-11-14 | 1995-01-04 | Secr Defence | Corrosion inhibitor |
JP4359001B2 (ja) * | 2001-03-02 | 2009-11-04 | 本田技研工業株式会社 | 陽極酸化膜改質方法、陽極酸化膜構造及びアルミニウム合金製船外機 |
-
2004
- 2004-11-24 US US10/995,527 patent/US20050218004A1/en not_active Abandoned
- 2004-11-26 CN CN200410095468XA patent/CN1644760B/zh not_active Expired - Fee Related
Patent Citations (21)
Publication number | Priority date | Publication date | Assignee | Title |
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US3563785A (en) * | 1965-10-09 | 1971-02-16 | Sumitomo Electric Industries | Method of resin coating of the metal and resin-coated metal product therefor |
US3717555A (en) * | 1970-11-27 | 1973-02-20 | Fentron Ind Inc | Method of producing an electrolytic coating on aluminum and the product thereof |
US4193848A (en) * | 1973-08-13 | 1980-03-18 | Swiss Aluminium Ltd. | Process for the production of composite material |
US3959090A (en) * | 1974-07-31 | 1976-05-25 | Swiss Aluminium Ltd. | Continuous electrolyte coloring of a pre-anodised aluminum foil or strip |
US4022671A (en) * | 1976-04-20 | 1977-05-10 | Alcan Research And Development Limited | Electrolytic coloring of anodized aluminum |
US4251330A (en) * | 1978-01-17 | 1981-02-17 | Alcan Research And Development Limited | Electrolytic coloring of anodized aluminium by means of optical interference effects |
US4179342A (en) * | 1978-06-28 | 1979-12-18 | Reynolds Metals Company | Coating system method for coloring aluminum |
US4571287A (en) * | 1980-12-27 | 1986-02-18 | Nagano Prefecture | Electrolytically producing anodic oxidation coat on Al or Al alloy |
US4559114A (en) * | 1984-11-13 | 1985-12-17 | Kaiser Aluminum & Chemical Corporation | Nickel sulfate coloring process for anodized aluminum |
US4861440A (en) * | 1986-07-24 | 1989-08-29 | Covino Charles P | Electrolytic formation of an aluminum oxide surface |
US4784732A (en) * | 1986-07-24 | 1988-11-15 | Covino Charles P | Electrolytic formation of an aluminum oxide layer |
US5674371A (en) * | 1989-11-08 | 1997-10-07 | Clariant Finance (Bvi) Limited | Process for electrolytically treating aluminum and compositions therefor |
US5403975A (en) * | 1990-08-17 | 1995-04-04 | Olin Corporation | Anodized aluminum electronic package components |
US5374455A (en) * | 1991-04-09 | 1994-12-20 | Sandoz Ltd. | Process for sealing aluminum oxide films |
US5419970A (en) * | 1991-08-19 | 1995-05-30 | Mitsubishi Jukogyo Kabushiki Kaisha | Method for making a composite aluminum article |
US5439712A (en) * | 1991-08-19 | 1995-08-08 | Mitsubishi Jukogyo Kabushiki Kaisha | Method for making a composite aluminum article |
US5330635A (en) * | 1993-03-25 | 1994-07-19 | Lockheed Corporation | Protective coating process for aluminum and aluminum alloys |
US5374347A (en) * | 1993-09-27 | 1994-12-20 | The United States Of America As Represented By The Secretary Of The Navy | Trivalent chromium solutions for sealing anodized aluminum |
US5472788A (en) * | 1994-07-14 | 1995-12-05 | Benitez-Garriga; Eliseo | Colored anodized aluminum and electrolytic method for the manufacture of same |
US5804253A (en) * | 1995-07-17 | 1998-09-08 | Kanegafuchi Chemical Ind. Co., Ltd. | Method for adhering or sealing |
US20030075452A1 (en) * | 2001-10-24 | 2003-04-24 | Che-Yuan Hsu | Process of surface treating aluminum articles |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9630206B2 (en) | 2005-05-12 | 2017-04-25 | Innovatech, Llc | Electrosurgical electrode and method of manufacturing same |
US8814863B2 (en) | 2005-05-12 | 2014-08-26 | Innovatech, Llc | Electrosurgical electrode and method of manufacturing same |
US8814862B2 (en) | 2005-05-12 | 2014-08-26 | Innovatech, Llc | Electrosurgical electrode and method of manufacturing same |
US10463420B2 (en) | 2005-05-12 | 2019-11-05 | Innovatech Llc | Electrosurgical electrode and method of manufacturing same |
US11246645B2 (en) | 2005-05-12 | 2022-02-15 | Innovatech, Llc | Electrosurgical electrode and method of manufacturing same |
EP2046174A4 (en) * | 2006-07-18 | 2012-08-08 | Thermolon Korea Co Ltd | COATING LAYER STRUCTURE FOR HEAT COOKING APPARATUS |
EP2046174A1 (en) * | 2006-07-18 | 2009-04-15 | Thermolon Korea Co., Ltd | Structure of coating layer for heat-cooker |
US7622197B2 (en) | 2006-11-20 | 2009-11-24 | Ferroxy-Aled, Llc | Seasoned ferrous cookware |
US9260792B2 (en) | 2010-05-19 | 2016-02-16 | Sanford Process Corporation | Microcrystalline anodic coatings and related methods therefor |
US10214827B2 (en) | 2010-05-19 | 2019-02-26 | Sanford Process Corporation | Microcrystalline anodic coatings and related methods therefor |
US20120088033A1 (en) * | 2010-10-07 | 2012-04-12 | Michael Sheehy | Sealed anodized aluminum components and process for their manufacture |
US9187839B2 (en) * | 2010-10-07 | 2015-11-17 | Michael Sheehy | Process for the manufacture of sealed anodized aluminum components |
WO2012061872A1 (en) * | 2010-11-08 | 2012-05-18 | Mezurx Pty Ltd | Sample analyser |
Also Published As
Publication number | Publication date |
---|---|
CN1644760A (zh) | 2005-07-27 |
CN1644760B (zh) | 2011-04-13 |
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Legal Events
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AS | Assignment |
Owner name: CALPHALON CORPORATION, ILLINOIS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CHARLES, KEVIN C.;REEL/FRAME:016707/0873 Effective date: 20050511 |
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STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |