EP0955394A2 - Procédé de fabrication d'une couche protectrice sur la surface intérieure d'un tuyau en cuivre - Google Patents
Procédé de fabrication d'une couche protectrice sur la surface intérieure d'un tuyau en cuivre Download PDFInfo
- Publication number
- EP0955394A2 EP0955394A2 EP99107792A EP99107792A EP0955394A2 EP 0955394 A2 EP0955394 A2 EP 0955394A2 EP 99107792 A EP99107792 A EP 99107792A EP 99107792 A EP99107792 A EP 99107792A EP 0955394 A2 EP0955394 A2 EP 0955394A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- copper
- copper tube
- water
- protective layer
- carbonate
- 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
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/63—Treatment of copper or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
Definitions
- the invention relates to methods for producing a protective layer which limits copper solubility in water on the inner surface of copper pipes.
- DE 195 33 410 A1 also includes a process for producing a protective layer which limits copper solubility in water from malachite (CuCO 3 Cu [OH] 2 ) or atakamite (CuCl 2 3Cu [OH] 2 ).
- a synthetic drawing agent modified with CO 2 or with substances that form CO 2 and O 2 is used, to which halogen-organic or other chlorine / halogen-containing compounds have been added.
- the invention is therefore based on the object of enabling a technically efficient production of a protective layer on the inner surface of copper pipes.
- a first solution to this problem consists in the measures of claim 1, with which a protective layer of basic copper carbonates is produced on the inner surface of copper pipes.
- the main idea is the oxidative treatment of the inner surface of the pipe with solutions of oxidants and carbonate-containing salts at elevated temperatures.
- the inner surface of the copper tube is expediently cleaned. This is particularly useful for degreasing.
- the degreasing can be carried out chemically by treatment with commercially available degreasing agents or by pickling, for example with sulfuric acid or nitric acid. Mechanical treatment such as sandblasting can also be carried out.
- the tube is then filled with an aqueous oxidation solution.
- the oxidation solution remains in the copper tube for a period between 0.1 hours and 48 hours, with a temperature between 10 ° C and 95 ° C is maintained.
- the copper tube is then rinsed with water and then dried. To remove loosely adhering copper carbonate particles, the tube can be blown out with compressed air.
- the oxidizing solution contains oxidants and salts of carbonic acid as well as optional salts of other acids.
- the pH of the oxidation solution is in the range between 3 and 12.
- the consistency of the oxidation solution can be changed by adding wetting agents or thickeners and adapted to the respective conditions of use.
- wetting agents and / or thickeners of a known type are used. They are added to the oxidation solution up to a proportion of 50 g / l each.
- an oxidation solution is used from oxidants such as hydrogen peroxide, potassium permanganate, potassium chlorate, sodium chlorite or mixtures thereof in a concentration between 5 g / l and 500 g / l and salts of carbonic acid such as sodium carbonate, potassium carbonate, ammonium carbonate, copper (I ) carbonate, copper (II) carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate or mixtures thereof in a concentration between 5 g / l and 500 g / l.
- oxidants such as hydrogen peroxide, potassium permanganate, potassium chlorate, sodium chlorite or mixtures thereof in a concentration between 5 g / l and 500 g / l and salts of carbonic acid such as sodium carbonate, potassium carbonate, ammonium carbonate, copper (I ) carbonate, copper (II) carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate or mixtures thereof in a concentration between 5 g
- the protective layer produced according to the invention reduces the release of copper ions, particularly in carbonated and / or acidic drinking water.
- the factory production ensures above all a copper ion release in the first years after commissioning a new copper pipe installation.
- a second solution to the problem consists in a method in which the inner surface of the copper tube is wetted with a copper ammonium chloride solution and then brought into contact with an oxygen-containing gas.
- the inner surface of the copper pipe should also first be cleaned and degreased.
- the copper ammonium chloride solution preferably consists of distilled water in which 80 g copper ammonium chloride are dissolved per liter. To wet the inner surface of the copper tube, it is advisable to rinse the copper tube with the copper ammonium chloride solution, a contact time between 1 sec and 10 sec, preferably between 1 sec and 3 sec, being sufficient (claim 7).
- Air or other oxygen-containing gases can be used as the reaction gas.
- the wetted inner surface is brought into contact with an oxygen-containing gas for a period between 10 min and 20 min at a temperature between 15 ° C and 70 ° C.
- a contact time of 15 minutes and a temperature of 20 ° C are considered to be particularly advantageous.
- the inner surface of the tube is allowed to dry. This can be accelerated by hot air (claim 9), preferably at a temperature of 65 ° C, which is passed through the copper pipes by means of a fan.
- Non-adhering particles of the protective layer can additionally be cleaned mechanically, in particular by blowing them out with compressed air.
- the protective layer is preferably deposited from an electrolyte solution in the form of a mixture of water, sodium hydrogen carbonate NaHCO 3 and sodium sulfate Na 2 SO 4 , the proportion of sodium hydrogen carbonate being 60 g and the proportion of sodium sulfate being 40 g per liter of water.
- the electrolytic deposition can be carried out using an inner electrode, for example in the form of a wire. After the copper tube has been filled with the electrolyte solution, the copper tube is polarized anodically and the inner electrode is cathodically polarized. It is also possible to apply the electrodes at the beginning or end of the pipe.
- the indicated solutions to the problem on which the invention is based are based on the idea of producing a protective layer on the inner surface of a copper tube in the factory.
- the technological connection consists of surface corrosion, which is defined in the factory and leads to the formation of protective layers from copper corrosion products. This ensures a reliable minimization of the copper ion release to the drinking water.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Protection Of Pipes Against Damage, Friction, And Corrosion (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Laminated Bodies (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19819925 | 1998-05-05 | ||
| DE19819925A DE19819925A1 (de) | 1998-05-05 | 1998-05-05 | Verfahren zur Erzeugung einer Schutzschicht auf der inneren Oberfläche eines Kupferrohrs |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0955394A2 true EP0955394A2 (fr) | 1999-11-10 |
| EP0955394A3 EP0955394A3 (fr) | 2000-04-12 |
| EP0955394B1 EP0955394B1 (fr) | 2005-01-19 |
Family
ID=7866663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99107792A Expired - Lifetime EP0955394B1 (fr) | 1998-05-05 | 1999-04-20 | Procédé de fabrication d'une couche protectrice sur la surface intérieure d'un tuyau en cuivre |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0955394B1 (fr) |
| AT (1) | ATE287460T1 (fr) |
| DE (2) | DE19819925A1 (fr) |
| DK (1) | DK0955394T3 (fr) |
| ES (1) | ES2236985T3 (fr) |
| PT (1) | PT955394E (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2795678A1 (fr) * | 1999-06-30 | 2001-01-05 | Hiroaka Environmental Science | Methode de formation artificielle de patine sur cuivre |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007055446A1 (de) * | 2007-11-12 | 2009-05-14 | Hansgrohe Ag | Bereitstellung von wasserführenden Bauteilen aus Messinglegierungen mit verringerter Metallionenfreisetzung |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB599971A (en) * | 1944-11-04 | 1948-03-25 | Jacob Finley Buckman | Improvements in and relating to the colouring of copper and copper-alloy surfaces |
| US3497401A (en) * | 1967-09-20 | 1970-02-24 | Intern Copper Research Ass Inc | Patination of copper |
| US3544389A (en) * | 1967-12-18 | 1970-12-01 | Bell Telephone Labor Inc | Process for surface treatment of copper and its alloys |
| FR2064465A5 (en) * | 1969-09-12 | 1971-07-23 | Trefimetaux | Artificial patina prodn on copper (alloy)objects |
| JPS53122641A (en) * | 1977-04-01 | 1978-10-26 | Mitsubishi Metal Corp | Method of electrolytically generating verdigris on surface of copper or copper alloy |
| JPS53142935A (en) * | 1977-05-20 | 1978-12-13 | Mitsubishi Metal Corp | Formation of patina on copper or copper alloy surface by electrolysis |
| JPS5638477A (en) * | 1979-09-04 | 1981-04-13 | Nippon Peroxide Co Ltd | Formation of cupric oxide coating |
| JPS56139680A (en) * | 1980-03-31 | 1981-10-31 | Matsushita Electric Works Ltd | Composition for oxidizing solution |
| LU83165A1 (fr) * | 1981-02-25 | 1982-09-10 | Liege Usines Cuivre Zinc | Tubes pour condenseurs ou echangeurs de chaleur en alliages de cuivre resistant a la corrosion et procede pour leur fabrication |
| JPS60200973A (ja) * | 1984-03-23 | 1985-10-11 | Hitachi Cable Ltd | 耐食性表面処理銅管 |
| JPS61221378A (ja) * | 1985-03-27 | 1986-10-01 | Toho Gas Kk | 銅溶解防止方法 |
| DE3827353A1 (de) * | 1988-08-12 | 1990-02-22 | Kabelmetal Ag | Innenoxidierte rohre |
| DE4334536A1 (de) * | 1993-10-09 | 1995-04-13 | Kabelmetal Ag | Verfahren zur Herstellung von nahtlos gezogenen halbharten/harten Installationsrohren |
| GB9407778D0 (en) * | 1994-04-20 | 1994-06-15 | Sandoz Ltd | Improvements in or relating to organic compounds |
| DE19533410B4 (de) * | 1995-09-09 | 2005-11-24 | Km Europa Metal Ag | Verfahren zur Erzeugung einer Schutzschicht an der inneren Oberfläche eines Kupferrohrs sowie Verwendung von Ziehmitteln |
-
1998
- 1998-05-05 DE DE19819925A patent/DE19819925A1/de not_active Withdrawn
-
1999
- 1999-04-20 DE DE59911465T patent/DE59911465D1/de not_active Expired - Lifetime
- 1999-04-20 EP EP99107792A patent/EP0955394B1/fr not_active Expired - Lifetime
- 1999-04-20 AT AT99107792T patent/ATE287460T1/de active
- 1999-04-20 PT PT99107792T patent/PT955394E/pt unknown
- 1999-04-20 ES ES99107792T patent/ES2236985T3/es not_active Expired - Lifetime
- 1999-04-20 DK DK99107792T patent/DK0955394T3/da active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2795678A1 (fr) * | 1999-06-30 | 2001-01-05 | Hiroaka Environmental Science | Methode de formation artificielle de patine sur cuivre |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0955394A3 (fr) | 2000-04-12 |
| ES2236985T3 (es) | 2005-07-16 |
| EP0955394B1 (fr) | 2005-01-19 |
| DK0955394T3 (da) | 2005-05-23 |
| ATE287460T1 (de) | 2005-02-15 |
| PT955394E (pt) | 2005-03-31 |
| DE59911465D1 (de) | 2005-02-24 |
| DE19819925A1 (de) | 1999-11-11 |
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