DE19819925A1 - Process for creating a protective layer on the inner surface of a copper pipe - Google Patents
Process for creating a protective layer on the inner surface of a copper pipeInfo
- Publication number
- DE19819925A1 DE19819925A1 DE19819925A DE19819925A DE19819925A1 DE 19819925 A1 DE19819925 A1 DE 19819925A1 DE 19819925 A DE19819925 A DE 19819925A DE 19819925 A DE19819925 A DE 19819925A DE 19819925 A1 DE19819925 A1 DE 19819925A1
- Authority
- DE
- Germany
- Prior art keywords
- copper
- solution
- 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.)
- Withdrawn
Links
- 239000010949 copper Substances 0.000 title claims abstract description 51
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 50
- 239000011241 protective layer Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 19
- 239000000243 solution Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 copper ammonium chloride Chemical compound 0.000 claims abstract description 6
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- JMRJRCGXPDVLIZ-UHFFFAOYSA-L copper(1+);carbonate Chemical compound [Cu+].[Cu+].[O-]C([O-])=O JMRJRCGXPDVLIZ-UHFFFAOYSA-L 0.000 claims description 2
- 229910000009 copper(II) carbonate Inorganic materials 0.000 claims description 2
- 239000011646 cupric carbonate Substances 0.000 claims description 2
- 235000019854 cupric carbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 4
- 235000002639 sodium chloride Nutrition 0.000 claims 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- 239000011780 sodium chloride Substances 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 239000011736 potassium bicarbonate Substances 0.000 claims 1
- 235000015497 potassium bicarbonate Nutrition 0.000 claims 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims 1
- 235000011181 potassium carbonates Nutrition 0.000 claims 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 4
- 229940116318 copper carbonate Drugs 0.000 abstract description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 abstract description 2
- 238000009736 wetting Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000003651 drinking water Substances 0.000 description 5
- 235000020188 drinking water Nutrition 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000907663 Siproeta stelenes Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 229940059913 ammonium carbonate Drugs 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (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 And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Die Erfindung betrifft Verfahren zur Erzeugung einer die Kupferlöslichkeit in Wasser begrenzenden Schutzschicht auf der inneren Oberfläche von Kupferrohren.The invention relates to methods for producing a copper solubility in water protective layer on the inner surface of copper pipes.
Für Installationsrohre, insbesondere zum Einsatz bei der Trinkwasserversorgung, werden nahtlos gezogene Kupferrohre eingesetzt. Hierbei handelt es sich vorwie gend um Kupferrohre aus sauerstofffreien Kupfersorten, sogenannten SF-Cu-Roh ren. Zur Gewährleistung einer für den menschlichen Verbrauch geeigneten Was serqualität gemäß der Trinkwasserverordnung ist man bestrebt, die Kupfer-Ionenab gabe an das Wasser zu minimieren. Der gesetzlich geforderte Richtwert liegt derzeit für Installationen, die älter als zwei Jahre sind, bei 3 mg/l nach zwölf Stunden Stagnation in der Rohrleitung. Im Rahmen der Revision der europäischen Trinkwas serdirektive ist beabsichtigt, diesen Richtwert in einen Grenzwert von 2 mg/l um zuwandeln, der dann auch für Installationen gilt, die jünger als zwei Jahre sind. Man versucht daher, generell den unmittelbaren Kontakt zwischen Kupfer und Wasser durch eine Innenbeschichtung zu vermeiden.For installation pipes, especially for use in drinking water supply, seamless drawn copper pipes are used. This is how around copper pipes made of oxygen-free copper types, so-called SF-Cu-Roh Ren. To ensure a suitable for human consumption Water quality in accordance with the Drinking Water Ordinance strives to reduce the copper ion surrender to the water. The legally required guideline is currently for installations older than two years, at 3 mg / l after twelve hours of stagnation in the pipeline. As part of the revision of European drinking water serdirective is intended to convert this benchmark into a limit of 2 mg / l change, which then also applies to installations that are less than two years old. Man therefore generally tries to make direct contact between copper and water to avoid by an inner coating.
Aus der EP 0 299 408 B1 ist es bekannt, die Rohrinnenoberfläche mit Kunstharz zu beschichten. Solche Beschichtungen sind jedoch meist nicht diffusionsdicht. Auch können sie durch die Temperaturbelastung bei Lötvorgängen beschädigt bzw. zerstört werden.It is known from EP 0 299 408 B1 to cover the inner surface of the pipe with synthetic resin coat. However, such coatings are usually not diffusion-tight. Also can be damaged or damaged by the temperature load during soldering processes be destroyed.
Ein anderer gebräuchlicher Weg ist die Innenverzinnung von Kupferrohren, wie sie beispielsweise aus der DE 43 21 244 A1 hervorgeht. Zur Erzeugung einer Innenbe schichtung aus Zinnoxid wird die innere Oberfläche eines Kupferrohrs zunächst chemisch verzinnt, anschließend unter inerter Atmosphäre diffusionsgeglüht, woran sich eine oxidierende thermische Innenoberflächenbehandlung mit einem Gasge misch anschließt. Another common way is the internal tinning of copper pipes, like them for example from DE 43 21 244 A1. To create an interior Layering of tin oxide is the inner surface of a copper pipe chemically tinned, then diffusion annealed under an inert atmosphere an oxidizing thermal interior surface treatment with a gas ge mix connects.
Zum Stand der Technik gehört durch die DE 195 33 410 A1 ferner ein Verfahren zur Erzeugung einer die Kupferlöslichkeit in Wasser begrenzenden Schutzschicht aus Malachit (CuCO3Cu[OH]2) oder Atakamit (CuCl23Cu[OH]2). Hierzu wird beim Zie hen eines Kupferrohrs ein mit CO2 bzw. mit CO2 und O2 bildenden Stoffen modifi ziertes synthetisches Ziehmittel eingesetzt, dem halogenorganische oder andere chlor-/halogenhaltige Verbindungen zugesetzt sind.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 ). For this purpose, when drawing a copper pipe, a synthetic drawing agent modified with CO 2 or with CO 2 and O 2- forming substances is used, to which halogen-organic or other chlorine / halogen-containing compounds have been added.
Das Verfahren hat sich grundsätzlich bewährt und begrenzt die Kupferlöslichkeit auf ein sehr niedriges unbedenkliches Niveau von ca. 1 mg/l nach zwölf Stunden Stagnation. Jedoch ist die Einbindung der Schutzschichtherstellung in den Ziehvorgang des Kupferrohrs nicht immer möglich.The method has proven itself in principle and limits the copper solubility a very low safe level of approx. 1 mg / l after twelve hours of stagnation. However, the integration of the protective layer production in the drawing process of the copper pipe is not always possible.
Der Erfindung liegt daher ausgehend vom Stand der Technik die Aufgabe zugrunde, eine verfahrenstechnisch effiziente werksseitige Herstellung einer Schutzschicht auf der inneren Oberfläche von Kupferrohren zu ermöglichen.Based on the prior art, the invention is therefore based on the object a technically efficient factory production of a protective layer to allow the inner surface of copper pipes.
Eine erste Lösung dieser Aufgabe besteht in den Maßnahmen des Anspruchs 1, womit eine Schutzschicht aus basischen Kupfercarbonaten auf der inneren Oberflä che von Kupferrohren erzeugt wird.A first solution to this problem consists in the measures of claim 1, with a protective layer of basic copper carbonates on the inner surface surface of copper pipes.
Kerngedanke ist die oxidative Behandlung der Rohrinnenoberfläche mit Lösungen von Oxidantien und carbonathaltigen Salzen bei erhöhten Temperaturen.The main idea is the oxidative treatment of the inside of the pipe with solutions of oxidants and salts containing carbonate at elevated temperatures.
Vor dem Einbringen der Oxidationslösung wird die innere Oberfläche des Kupfer rohrs zweckmäßigerweise gereinigt. Dies dient insbesondere zur Entfettung. Das Entfetten kann chemisch durch Behandlung mit handelsüblichen Entfettungsmitteln oder durch Beizen, z. B. mit Schwefelsäure oder Salpetersäure erfolgen. Auch eine mechanische Behandlung wie Sandstrahlen kann durchgeführt werden. Before introducing the oxidation solution, the inner surface of the copper appropriately cleaned pipes. This is particularly useful for degreasing. The Degreasing can be done chemically by treatment with commercially available degreasing agents or by pickling, e.g. B. with sulfuric acid or nitric acid. Also one mechanical treatment such as sandblasting can be carried out.
Das Rohr wird dann mit einer wässerigen Oxidationslösung befüllt. Die Oxidations lösung verbleibt im Kupferrohr für einen Zeitraum zwischen 0,1 Stunden und 48 Stunden, wobei eine Temperatur zwischen 10°C und 95°C gehalten wird. Im An schluß daran wird das Kupferrohr mit Wasser gespült und anschließend getrocknet. Zur Entfernung locker anhaftender Kupfercarbonatpartikel kann das Rohr noch mit Druckluft ausgeblasen werden.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, maintaining a temperature between 10 ° C and 95 ° C. In the An finally the copper tube is rinsed with water and then dried. The pipe can also be used to remove loosely adhering copper carbonate particles Compressed air are blown out.
Bestandteil der Oxidationslösung sind Oxidantien und Salze der Kohlensäure sowie wahlweise Salze anderer Säuren. Der pH-Wert der Oxidationslösung liegt im Be reich zwischen 3 und 12. Die Oxidationslösung kann durch den Zusatz von Netzmit teln oder Verdickern in ihrer Konsistenz verändert und auf die jeweiligen Einsatz bedingungen abgestimmt werden. Hierbei kommen Netzmittel und/oder Verdicker bekannter Art zum Einsatz. Sie werden der Oxidationslösung bis zu einem Anteil von je 50 g/l zugesetzt.Part of the oxidation solution are oxidants and salts of carbonic acid as well optionally salts of other acids. The pH of the oxidation solution is in the loading rich between 3 and 12. The oxidation solution can be added by adding Netzmit thickening or thickening changed in their consistency and to the respective application conditions. Here come wetting agents and / or thickeners known type to use. You will get up to a share of the oxidation solution 50 g / l added.
Gemäß der Maßnahme des Anspruchs 2 wird eine Oxidationslösung verwendet aus Oxidantien wie Wasserstoffperoxid, Kaliumpermanganat, Kaliumchlorat, Natri umchlorit oder Mischungen hiervon in einer Konzentration zwischen 5 g/l und 500 g/l und Salzen der Kohlensäure wie Natriumcarbonat, Kaliumcarbonat, Ammo niumcarbonat, Kupfer(I)carbonat, Kupfer(II)carbonat, Natriumhydrogencarbonat, Ka liumhydrogencarbonat, Ammoniumhydrogencarbonat oder Mischungen hiervon in einer Konzentration zwischen 5 g/l und 500 g/l.According to the measure of claim 2, an oxidation solution is used Oxidants such as hydrogen peroxide, potassium permanganate, potassium chlorate, natri umchlorite 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, ammo nium carbonate, copper (I) carbonate, copper (II) carbonate, sodium hydrogen carbonate, Ka lium bicarbonate, ammonium bicarbonate or mixtures thereof in a concentration between 5 g / l and 500 g / l.
Die erfindungsgemäß hergestellte Schutzschicht verringert die Kupferionenabgabe, insbesondere in kohlensäurereichen und/oder sauren Trinkwässern. Durch die werksseitige Herstellung wird vor allem eine Kupferionenabgabe in den ersten Jahren nach Inbetriebnahme einer neuen Kupferrohrinstallation gewährleistet.The protective layer produced according to the invention reduces the release of copper ions, especially in carbonated and / or acidic drinking water. Through the Factory production will primarily be a copper ion release in the first Years after commissioning a new copper pipe installation.
Eine zweite Lösung der Aufgabe besteht nach Anspruch 6 in einem Verfahren, bei dem die innere Oberfläche des Kupferrohrs mit einer Kupferammoniumchlorid-Lö sung benetzt und anschließend mit einem sauerstoffhaltigen Gas in Kontakt ge bracht wird. A second solution to the problem is according to claim 6 in a method in which the inner surface of the copper tube with a copper ammonium chloride solder solution wetted and then in contact with an oxygen-containing gas is brought.
Hierdurch findet ein Oxidationsvorgang statt und es wird eine flächige gut haftende Schutzschicht aus Kupferchlorid an der inneren Oberfläche eines Kupferrohrs er zeugt. In einem Vorbehandlungsschritt sollte die innere Oberfläche des Kupferrohrs ebenfalls zunächst gereinigt und entfettet werden.As a result, an oxidation process takes place and it becomes a flat, adherent one Protective layer of copper chloride on the inner surface of a copper pipe testifies. In a pretreatment step, the inner surface of the copper pipe should also be cleaned and degreased first.
Die Kupferammoniumchlorid-Lösung besteht vorzugsweise aus destilliertem Was ser, in dem je Liter 80 g Kupferammoniumchlorid gelöst sind. Zur Benetzung der inneren Oberfläche des Kupferrohrs empfiehlt es sich, das Kupferrohr mit der Kupferammoniumchlorid-Lösung zu spülen, wobei eine Kontaktzeit zwischen 1 sec und 10 sec, vorzugsweise zwischen 1 sec und 3 sec, ausreicht (Anspruch 7).The copper ammonium chloride solution preferably consists of distilled water water in which 80 g of copper ammonium chloride are dissolved per liter. For wetting the inner surface of the copper pipe, it is recommended to use the copper pipe with the Rinse copper ammonium chloride solution, with a contact time between 1 sec and 10 sec, preferably between 1 sec and 3 sec, is sufficient (claim 7).
Als Reaktionsgas können Luft oder andere sauerstoffhaltige Gase verwendet wer den. Gemäß der Maßnahme des Anspruchs 8 wird die benetzte innere Oberfläche während eines Zeitraums zwischen 10 min und 20 min bei einer Temperatur zwi schen 15°C und 70°C mit einem sauerstoffhaltigen Gas in Kontakt gebracht. Für die Praxis wird eine Kontaktzeit von 15 min und eine Temperatur von 20°C als be sonders vorteilhaft angesehen.Air or other oxygen-containing gases can be used as the reaction gas the. According to the measure of claim 8, the wetted inner surface for a period between 10 min and 20 min at a temperature between 15 ° C and 70 ° C in contact with an oxygen-containing gas. For the practice will be a contact time of 15 min and a temperature of 20 ° C viewed particularly advantageous.
Nach Abschluß der Behandlung läßt man die innere Oberfläche des Rohrs trocknen. Dies kann durch heiße Luft beschleunigt werden (Anspruch 9), vorzugsweise mit einer Temperatur von 65°C, die mittels eines Gebläses durch die Kupferrohre geführt wird.After the treatment is complete, the inner surface of the tube is allowed to dry. This can be accelerated by hot air (claim 9), preferably with a temperature of 65 ° C, which is blown through the copper pipes to be led.
Nicht haftende Teilchen der Schutzschicht können zusätzlich mechanisch, insbe sondere durch Ausblasen mit Druckluft, abgereinigt werden.Non-adhering particles of the protective layer can additionally mechanically, in particular especially by blowing out with compressed air.
Schließlich besteht eine weitere Lösung der erfindungsgemäßen Aufgabe in einem Verfahren gemäß Anspruch 10. Finally, a further solution to the problem according to the invention is one A method according to claim 10.
Dieses sieht vor, die Schutzschicht nach der Reinigung der inneren Oberfläche des Kupferrohrs elektrolytisch aus einer Elektrolyt-Lösung in Form von basischen Kup fercarbonaten abzuscheiden, anschließend das Kupferrohr mit Wasser zu spülen und zu trocknen.This provides the protective layer after cleaning the inner surface of the Copper pipe electrolytically from an electrolyte solution in the form of basic copper Separate ferocarbonates, then rinse the copper pipe with water and dry.
Vorzugsweise wird die Schutzschicht aus einer Elektrolyt-Lösung in Form einer Mischung aus Wasser, Natriumhydrogencarbonat NaHCO3 und Natriumsulfat Na2SO4 abgeschieden, wobei der Anteil von Natriumhydrogencarbonat 60 g und der Anteil von Natriumsulfat 40 g je Liter Wasser ist.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.
Die elektrolytische Abscheidung kann unter Verwendung einer Innenelektrode, bei spielsweise in Form eines Drahts, erfolgen. Nach dem Befüllen des Kupferrohrs mit der Elektrolyt-Lösung wird das Kupferrohr anodisch und die Innenelektrode katho disch polarisiert. Möglich ist es ferner, die Elektroden am Rohranfang bzw. -ende anzulegen.The electrodeposition can be carried out using an internal electrode for example in the form of a wire. After filling the copper pipe with the electrolyte solution, the copper tube becomes anodic and the inner electrode catho Disch polarized. It is also possible to have the electrodes at the beginning or end of the tube to create.
Die aufgezeigten Lösungen der der Erfindung zugrundeliegenden Aufgabe ist der Gedanke gemein, eine Schutzschicht auf der inneren Oberfläche eines Kupferrohrs werksseitig zu erzeugen. Der technologische Zusammenhang besteht in einer werksseitig definiert erzeugten Flächenkorrosion, welche zur Bildung von Schutz schichten aus Kupfer-Korrosionsprodukten führt. Hierdurch wird eine zuverlässige Minimierung der Kupferionenabgabe an das Trinkwasser realisiert.The indicated solutions of the object on which the invention is based is Common thought, a protective layer on the inner surface of a copper pipe generated at the factory. The technological connection is one Factory-defined surface corrosion, which is used to form protection layers of copper corrosion products. This will make it reliable Minimized copper ion release to drinking water.
Claims (11)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19819925A DE19819925A1 (en) | 1998-05-05 | 1998-05-05 | Process for creating a protective layer on the inner surface of a copper pipe |
| PT99107792T PT955394E (en) | 1998-05-05 | 1999-04-20 | PROCESS FOR PRODUCING A PROTECTIVE LAYER ON THE INTERIOR SURFACE OF A COPPER TUBE |
| DE59911465T DE59911465D1 (en) | 1998-05-05 | 1999-04-20 | Method for producing a protective layer on the inner surface of a copper tube |
| AT99107792T ATE287460T1 (en) | 1998-05-05 | 1999-04-20 | METHOD FOR PRODUCING A PROTECTIVE LAYER ON THE INNER SURFACE OF A COPPER TUBE |
| EP99107792A EP0955394B1 (en) | 1998-05-05 | 1999-04-20 | Process for producing a protective coating on the interior surface of a copper pipe |
| DK99107792T DK0955394T3 (en) | 1998-05-05 | 1999-04-20 | Method of forming a protective layer on the inner surface of a copper tube |
| ES99107792T ES2236985T3 (en) | 1998-05-05 | 1999-04-20 | PROCEDURE FOR THE FORMATION OF A PROTECTION LAYER ON THE INTERIOR SURFACE OF A COPPER TUBE. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19819925A DE19819925A1 (en) | 1998-05-05 | 1998-05-05 | Process for creating a protective layer on the inner surface of a copper pipe |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19819925A1 true DE19819925A1 (en) | 1999-11-11 |
Family
ID=7866663
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19819925A Withdrawn DE19819925A1 (en) | 1998-05-05 | 1998-05-05 | Process for creating a protective layer on the inner surface of a copper pipe |
| DE59911465T Expired - Lifetime DE59911465D1 (en) | 1998-05-05 | 1999-04-20 | Method for producing a protective layer on the inner surface of a copper tube |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE59911465T Expired - Lifetime DE59911465D1 (en) | 1998-05-05 | 1999-04-20 | Method for producing a protective layer on the inner surface of a copper tube |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0955394B1 (en) |
| AT (1) | ATE287460T1 (en) |
| DE (2) | DE19819925A1 (en) |
| DK (1) | DK0955394T3 (en) |
| ES (1) | ES2236985T3 (en) |
| PT (1) | PT955394E (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4121217B2 (en) * | 1999-06-30 | 2008-07-23 | 株式会社スーパーブラストシステムズ | Artificial patina generation method |
| DE102007055446A1 (en) * | 2007-11-12 | 2009-05-14 | Hansgrohe Ag | Provision of water-bearing components from brass alloys with reduced metal ion release |
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 (en) * | 1981-02-25 | 1982-09-10 | Liege Usines Cuivre Zinc | TUBES FOR CONDENSERS OR HEAT EXCHANGERS OF CORROSION RESISTANT COPPER ALLOYS AND METHOD FOR THE PRODUCTION THEREOF |
| JPS60200973A (en) * | 1984-03-23 | 1985-10-11 | Hitachi Cable Ltd | Surface-treated corrosion resistant copper pipe |
| JPS61221378A (en) * | 1985-03-27 | 1986-10-01 | Toho Gas Kk | Method for preventing dissolution of copper |
| DE3827353A1 (en) * | 1988-08-12 | 1990-02-22 | Kabelmetal Ag | INTERNAL OXIDIZED TUBES |
| DE4334536A1 (en) * | 1993-10-09 | 1995-04-13 | Kabelmetal Ag | Process for the production of seamless drawn semi-hard / hard installation pipes |
| GB9407778D0 (en) * | 1994-04-20 | 1994-06-15 | Sandoz Ltd | Improvements in or relating to organic compounds |
| DE19533410B4 (en) * | 1995-09-09 | 2005-11-24 | Km Europa Metal Ag | Method for producing a protective layer on the inner surface of a copper pipe and use of drawing agents |
-
1998
- 1998-05-05 DE DE19819925A patent/DE19819925A1/en not_active Withdrawn
-
1999
- 1999-04-20 ES ES99107792T patent/ES2236985T3/en not_active Expired - Lifetime
- 1999-04-20 EP EP99107792A patent/EP0955394B1/en not_active Expired - Lifetime
- 1999-04-20 AT AT99107792T patent/ATE287460T1/en active
- 1999-04-20 DE DE59911465T patent/DE59911465D1/en not_active Expired - Lifetime
- 1999-04-20 PT PT99107792T patent/PT955394E/en unknown
- 1999-04-20 DK DK99107792T patent/DK0955394T3/en active
Also Published As
| Publication number | Publication date |
|---|---|
| EP0955394A3 (en) | 2000-04-12 |
| DE59911465D1 (en) | 2005-02-24 |
| EP0955394B1 (en) | 2005-01-19 |
| ATE287460T1 (en) | 2005-02-15 |
| DK0955394T3 (en) | 2005-05-23 |
| ES2236985T3 (en) | 2005-07-16 |
| PT955394E (en) | 2005-03-31 |
| EP0955394A2 (en) | 1999-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1888819B1 (en) | Method for preparing metallic workpieces for cold forming | |
| DE3728993A1 (en) | MIX FOR ALUMINUM CORROSION FASTENING | |
| EP0045110A1 (en) | Method for the production of phosphate coatings on iron and steel surfaces, and its use | |
| DE60213131T2 (en) | PREPARATION OF STEEL SURFACES FOR GALVANIZING IN ALUMINUM ZINC BATH | |
| EP0578670A1 (en) | METHOD FOR PHOSPHATATION OF METAL SURFACES. | |
| KR890001379B1 (en) | Manufacturing process of metal products including oxide scale formation control and descaling | |
| EP0603921B1 (en) | Process for forming phosphate coatings | |
| DE19819925A1 (en) | Process for creating a protective layer on the inner surface of a copper pipe | |
| DE1421994A1 (en) | Process, device and means for cleaning metal surfaces | |
| DE1496915A1 (en) | Process for applying a zinc phosphate coating containing metallic zinc to an iron surface | |
| DE102006047713B3 (en) | Electrolyte for electro-polishing surfaces of metal and metal alloys used in the production of gas turbines contains methane sulfonic acid and ammonium difluoride | |
| DE19931820C2 (en) | Process for descaling titanium material and descaled titanium material | |
| DE1771689B2 (en) | Process for the production of aluminum welding wire with a thin oxide layer | |
| DE102011055644B4 (en) | Process for producing a black oxide ceramic surface layer on a light metal alloy component | |
| DE19542410A1 (en) | Building material quickly forming natural patina | |
| US3348979A (en) | Process for treating aluminum weld wire | |
| DE2627837A1 (en) | ELECTRIC CLEANING PROCEDURES | |
| DE2540685C2 (en) | Process for the production of phosphate coatings | |
| DE1496906A1 (en) | Process for the electrolytic descaling of iron and steel | |
| US3595985A (en) | Conversion coated aluminum conductor and method for preparation thereof | |
| EP0359736A1 (en) | Method of electrolytically pickling special steel | |
| DE10017187A1 (en) | Use of a liquid solution of hydrogen fluoride to treat the surface of aluminum and titanium alloys to improve the oxidation resistance of the alloys | |
| DE887138C (en) | Process for the production of firmly adhering coatings on stainless steel to facilitate drawing processes | |
| DE2034863B2 (en) | Process for the surface treatment of zirconium and zirconium alloys for fuel elements or other nuclear reactor components | |
| DE2402051B2 (en) | METAL PHOSPHATING METHOD |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8110 | Request for examination paragraph 44 | ||
| 8130 | Withdrawal |