EP1541710B1 - Verfahren zur Beschichtung von Rohren - Google Patents
Verfahren zur Beschichtung von Rohren Download PDFInfo
- Publication number
- EP1541710B1 EP1541710B1 EP04028988A EP04028988A EP1541710B1 EP 1541710 B1 EP1541710 B1 EP 1541710B1 EP 04028988 A EP04028988 A EP 04028988A EP 04028988 A EP04028988 A EP 04028988A EP 1541710 B1 EP1541710 B1 EP 1541710B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tin
- coating
- coating solution
- tube
- solution
- 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.)
- Not-in-force
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 116
- 239000011248 coating agent Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 34
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 63
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 32
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 8
- 238000010979 pH adjustment Methods 0.000 claims description 8
- 229910001432 tin ion Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 3
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical group [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims 1
- 239000000243 solution Substances 0.000 description 76
- 239000010410 layer Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 229910052728 basic metal Inorganic materials 0.000 description 3
- 150000003818 basic metals Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- OBBXFSIWZVFYJR-UHFFFAOYSA-L tin(2+);sulfate Chemical compound [Sn+2].[O-]S([O-])(=O)=O OBBXFSIWZVFYJR-UHFFFAOYSA-L 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1614—Process or apparatus coating on selected surface areas plating on one side
- C23C18/1616—Process or apparatus coating on selected surface areas plating on one side interior or inner surface
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1675—Process conditions
- C23C18/1676—Heating of the solution
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1675—Process conditions
- C23C18/1678—Heating of the substrate
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1675—Process conditions
- C23C18/1682—Control of atmosphere
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/54—Contact plating, i.e. electroless electrochemical plating
Definitions
- the invention relates to a method according to claim 1 for coating the inner surface of a tube made of copper or copper alloy.
- Copper tubes are known to be coated internally by tin that provides a cathodic protection for copper. Specific quality requirements are set for tin-coated tubes with respect to strength, purity and coating porosity.
- chemical tin coating the process is known to be distinguished as two or three separate process steps comprising the activation of the surface to be coated, precoating and the coating step proper with the tin coating.
- the surface to be coated is treated by certain chemicals in order to make the coating succeed.
- the solution is usually composed of an acidic solution, in which there is dissolved both a complexing agent participating in the coating reactions, as well as the tin source proper.
- the function of the precoating step is to form tin nuclei on the surface to be coated.
- a tin coating layer is deposited onto the tin nuclei.
- the actual coating step may be carried out either in an acidic or an alkaline solution.
- Chemical tin coating is known to be carried out as an ion-exchange reaction, in which copper ions are dissolved from the basic metal, and simultaneously on the surface of the basic metal, from the tin coating solution there is deposited an equivalent quantity of tin ions on the basis of the tension between the tin coating solution and copper.
- An increased quantity of dissolved copper in the solution with respect to the quantity of tin slows down the ion exchange reaction. Consequently, also according to the quantity of deposited tin, the solution must from time to time be subjected to tin source regulation.
- the ion exchange reaction is slowed down and finally stops.
- tin coating becomes nonhomogeneous during the tin coating process, this may later result in that tin ions are disengaged for example to household water.
- the working life of a tin coating solution can be raised by adding so-called stabilizers into the solution. It is well known that the tin coating process is carried out in two separate steps, so that the solution of the first step is only used for transmission, and the solution of the second step is used for accumulating the tin layer.
- a plating method has been known to coat the inner surface of a copper alloy pipe with Sn by means of a chemical plating solution.
- the plating method is carried out by using Tin(II)-chloride, Thiourea and Tartaric acid as the plating solution which is caused to flow through the copper pipe.
- a coating method for a copper tube is disclosed which method is based on the same principal to let a chemical tin-solution flow through the pipe.
- method is divided into two method steps which differ in the temperature of the solution to be fed through the pipe, respectively. Accordingly, one has to begin with a low temperature within the range of 35°C - 45°C. which first method step is followed by the second one using a temperature between 70°C and 85° C at the maximum temperature. At least it is proposed to alter the temperature during the plating process to realize the effect of the double-step process.
- the object of the present invention is to introduce a novel solution that is more advantageous than the prior art for coating the inner wall of a tube made of copper or copper alloy with a tin layer, particularly so that the coating is carried out in one coating step.
- the invention is characterized by what is set forth in the characterizing part of claim 1.
- Other preferred embodiments of the invention are characterized by what is set forth in the rest of the claims.
- the tin coating process of the interior tube wall is made more rapid, and the quantity of used chemicals is remarkably reduced in comparison with conventional tin coating.
- the invention there is formed a tin layer according to the regulations on the inner surface of a tube made of copper or copper alloy by carrying out the coating in one coating step, so that the tin layer is formed as the tin coating solution circulates on the inner tube surface.
- the one coating step according to the invention means that the coating solution is circulated to the inner tube surface at one end of the tube, and it is made to flow out of the other end of the tube, during which time there is created a tin layer by means of chemical tin coating according to an ion exchange reaction.
- the multi-step activation of the inner tube surface, the precoating and the coating are made to take place by means of one and the same coating solution and essentially in one coating step, while the coating solution circulates on the inner tube surface.
- the coating solution according to the invention includes at least pH adjustment agent, to the extent that the pH of the coating solution ⁇ 1, tin source for creating bivalent tin ions (Sn 2+ ) in the coating solution and complexing agent.
- the employed tin source is tin chloride (SnCl 2 )
- the employed complexing agent is thiourea (NH 2 ) 2 CS, in which case the ratio of the contents of tin chloride and thiourea in the coating solution is 1:(1-10), preferably, however, 1:4.
- the employed pH adjustment agent is hydrochloric acid (HCI).
- the employed tin source can be for example tin (II) sulfate or some other tin source, by using which the tin ion can be made to be present as bivalent (Sn 2+ ) in the above mentioned coating solution.
- the employed pH adjustment agent is sulfuric acid (H 2 SO 4 ).
- the content of thiourea in the coating solution is 2 - 20 percentages by weight (w-%), preferably 10 percentages by weight. When the content of thiourea in the coating solution is relatively low, the tubes are easier to clean after coating.
- the complexing agent participates in the tin coating reactions as a complexing agent at least by binding free copper ions in said coating solution.
- the inner tube surface is also cleaned of possible impurities that are accumulated on the inner surface in earlier treatments of the inner tube surface.
- the use of many other chemicals such as for example stabilizers, can be completely avoided.
- the further treatment of the coating solution is remarkably cheaper.
- harmful sedimentation of the solution at high temperatures can be avoided.
- the coating reaction time is remarkably shortened at the achieved high temperatures.
- the solution expenses are reduced, and the time required for preparing the solution remains short in comparison with the manufacturing of multi-step coating solutions.
- the use of rinsing waters circulated between various steps can be avoided, and savings can be achieved in the further treatment expenses of the solution.
- the temperature of the coating solution is adjusted to be within the range 35 - 100oC when feeding the coating solution onto the inner tube surface.
- the tube is preheated before coating, which further enhances a successful coating. Preheating can be carried out from outside the tubes, or for instance by rinsing the inside of the tube by warm water or warm compressed air.
- the coating circulates on the inner tube surface for less than 30 minutes.
- the coating is carried out in an oxygen-free atmosphere, so that the coating solution and the coating equipment are insulated against the effects of oxygen, for example by arranging them in oxygen-free protective gas and by preventing the access of oxygen into the coating solution.
- oxygen is removed from the coating solution, for instance before coating or during the coating step, in which case the effects of oxygen contained in the various ingredients of the solution can be avoided.
- Tin oxidation binds tin as a component, which means that the quantity of free tin ions in the solution is reduced.
- the stabilizer can thus be advantageously replaced by various equipment arrangements.
- the function of the stabilizer is to prevent the oxidation of tin ions (Sn 2+ ) in the solution.
- the inner tube surface is cleaned of solution residues, for example by means of rinsing by air and water.
- the inner surface of the tube to be coated can be either treated or untreated.
- the inner surface of the tube to be coated is oxidized, in which case the tube can be semi-hard or soft.
- both pickling and coating are carried out in the same coating solution.
- the tube to be coated is hard.
- the tube can also be pickled.
- the tube to be coated can be a tube coil, or a straight tube, and can have a length of even 1,000 meters.
- the tube to be coated is a semi-hard, straight tube with an oxidized inner surface.
- the coating for forming the tin layer can be carried out by feeding the coating solution simultaneously either onto the inner surfaces of several tubes, or to one tube at a time. Onto the inner tube surface, there is fed coating solution from a separate solution tank by pressurizing the coating solution into the tube.
- the coating solution contains hydrochloric acid (HCI) as the pH adjustment, tin chloride (SnCl 2 ) as the tin source, and thiourea ((NH 2 ) 2 CS) as the complexing agent.
- pH adjustment agent is added into pure water to that extent that the acidity (pH) in the coating solution is below 1, whereafter thiourea is added so that the content of thiourea in the final coating solution is 10 percentages by weight.
- Tin chloride is added to the coating solution to the extent that the ratio of the tin chloride and thiourea contents in the coating solution is 1:4, i.e. the quantity of thiourea is 4 times as much as the quantity of tin chloride.
- tin is present in ion form (Sn 2+ ). According to the example, the temperature of the coating solution is 75 oC, when it is fed onto the inner tube surface.
- the solution tank and the rest of the equipment are protected so that the access of oxygen into the coating solution is prevented for example by protective gas.
- oxygen is removed from the coating solution.
- the temperature of the coating solution kept in the solution tank is maintained constant.
- the tubes are rinsed by warm liquid.
- the coating solution is fed into the preheated tube at a turbulent speed. The coating solution circulates on the inner tube surface for about 20 minutes, during which time a tin layer is formed.
- the tin layer grows on the inner surface according to the ion exchange reaction, so that metallic copper is dissolved from the inner tube surface to the tin coating solution to ions, and the tin ion contained in the coating solution is deposited on the inner tube surface, forming a metallic coating.
- the tin layer is formed as a homogeneous layer with a thickness of about 1 - 2 micrometers.
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- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Chemically Coating (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemical Treatment Of Metals (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Claims (15)
- Verfahren zum Beschichten der Innenfläche eines aus Kupfer oder einer Kupferlegierung gefertigten Rohres mit einer Zinnschicht, gemäß welchem Verfahren die Zinnschicht mittels einer chemischen Zinnbeschichtung gebildet wird, und die an der Innenrohrfläche zirkulierte Beschichtungslöschung zumindest ein pH-Reguliermittel enthält, in dem Maße, dass der pH der Beschichtungslösung < 1 ist, ferner eine Zinn-Stammquelle zur Bildung von bivalenten Zinn-Ionen (Sn2+) in der Beschichtungslösung, ferner einen Komplexbildner,
dadurch gekennzeichnet, dass die zu beschichtende Innenfläche des Rohres oxidiert wird und dass die Beschichtung der Innenrohrfläche in einem einzelnen Beschichtungsschritt mit Hilfe der Beschichtungslösung ausgeführt wird, wobei das Verfahren in einem sauerstofffreien Schutzgas durchgeführt wird, und die Zinnschicht gebildet wird, wenn die Beschichtungslösung eine Temperatur innerhalb des Bereiches von 35 - 100°C hat und auf der Innenrohrfläche für weniger als 30 Minuten zirkuliert. - Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass die verwendete Zinn-Stammquelle Zinnchlorid ist. - Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass der verwendete Komplexbildner Thiocarbamid ist. - Verfahren nach Anspruch 2 oder 3,
dadurch gekennzeichnet, dass das Verhältnis von Zinnchlorid und den Thiocarbamid-Anteilen in der Beschichtungslösung ist 1 : (1-10). - Verfahren nach Anspruch 4,
dadurch gekennzeichnet, dass das Verhältnis von Zinnchlorid und den Thiocarbamid-Bestandteilen in der Beschichtungslösung vorzugsweise 1 : 4 ist. - Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass das verwendete pH-Reguliermittel Salzsäure ist. - Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass das eingesetzte pH-Reguliermittel Schwefelsäure ist. - Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass die verwendete Zinnstammquelle Zinnsulfat ist. - Verfahren nach Anspruch 3, 4 oder 5,
dadurch gekennzeichnet, dass der Anteil an Thiocarbamid in der Beschichtungslösung 2 - 20 Gewichtsprozent beträgt. - Verfahren nach Anspruch 9,
dadurch gekennzeichnet, dass der Anteil an Thiocarbamid in der Beschichtungslösung vorzugsweise 10 Gewichtsprozent beträgt. - Verfahren nach einem der vorangehenden Ansprüche,
dadurch gekennzeichnet, dass der Rohr vor dem Beschichten erwärmt wird. - Verfahren nach einem der vorangehenden Ansprüche,
dadurch gekennzeichnet, dass die Innenrohrfläche nach dem Beschichten gereinigt wird. - Verfahren nach Anspruch 1 - 12,
dadurch gekennzeichnet, dass das zu beschichtende Rohr halbhart ist. - Verfahren nach Anspruch 1-12,
dadurch gekennzeichnet, dass das zu beschichtende Rohr weich ist. - Verfahren nach Anspruch 1-14,
dadurch gekennzeichnet, dass das zu beschichtende Rohr gebeizt ist.
Priority Applications (1)
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PL04028988T PL1541710T3 (pl) | 2003-12-12 | 2004-12-07 | Sposób powlekania rur |
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FI20031821A FI120268B (fi) | 2003-12-12 | 2003-12-12 | Menetelmä putken pinnoittamiseksi |
FI20031821 | 2003-12-12 |
Publications (3)
Publication Number | Publication Date |
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EP1541710A2 EP1541710A2 (de) | 2005-06-15 |
EP1541710A3 EP1541710A3 (de) | 2006-08-02 |
EP1541710B1 true EP1541710B1 (de) | 2009-11-04 |
Family
ID=29763516
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP04028988A Not-in-force EP1541710B1 (de) | 2003-12-12 | 2004-12-07 | Verfahren zur Beschichtung von Rohren |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP1541710B1 (de) |
AT (1) | ATE447631T1 (de) |
DE (1) | DE602004023913D1 (de) |
EA (1) | EA008451B1 (de) |
ES (1) | ES2336103T3 (de) |
FI (1) | FI120268B (de) |
PL (1) | PL1541710T3 (de) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN109576703A (zh) * | 2018-12-29 | 2019-04-05 | 烟台南山学院 | 一种非标铜管的手工镀锡方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2282511A (en) * | 1940-03-20 | 1942-05-12 | American Brass Co | Coating cupreous surfaces with tin |
DE3800918A1 (de) * | 1988-01-14 | 1989-07-27 | Siemens Ag | Bad zur stromlosen zinnabscheidung |
RU2061790C1 (ru) * | 1992-07-10 | 1996-06-10 | Екатеринбургский завод по обработке цветных металлов | Способ получения серебряных покрытий |
DE19501274A1 (de) * | 1995-01-18 | 1996-07-25 | Km Europa Metal Ag | Verfahren zur Herstellung eines Installationsrohrs aus Kupfer |
WO1996028686A1 (fr) * | 1995-03-16 | 1996-09-19 | Kabushiki Kaisha Kobe Seiko Sho | Tuyau en alliage de cuivre pour eau froide ou eau chaude equipe d'un film protecteur sur sa face interne, production de ce tuyau et echangeur de chaleur pour la production d'eau chaude |
AU2792697A (en) * | 1996-06-05 | 1998-01-05 | Sumitomo Light Metal Industries, Ltd. | Internally tin-plated copper pipe manufacturing method |
DE19653765A1 (de) * | 1996-12-23 | 1998-06-25 | Km Europa Metal Ag | Innen verzinntes Kupferrohr und Verfahren zur Beschichtung eines Kupferrohrs |
JP3277846B2 (ja) * | 1997-05-19 | 2002-04-22 | 日立電線株式会社 | 内面SnまたはSn合金めっき管のめっき方法 |
-
2003
- 2003-12-12 FI FI20031821A patent/FI120268B/fi not_active IP Right Cessation
-
2004
- 2004-12-07 ES ES04028988T patent/ES2336103T3/es active Active
- 2004-12-07 AT AT04028988T patent/ATE447631T1/de not_active IP Right Cessation
- 2004-12-07 DE DE602004023913T patent/DE602004023913D1/de active Active
- 2004-12-07 PL PL04028988T patent/PL1541710T3/pl unknown
- 2004-12-07 EP EP04028988A patent/EP1541710B1/de not_active Not-in-force
- 2004-12-10 EA EA200401489A patent/EA008451B1/ru not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
ES2336103T3 (es) | 2010-04-08 |
FI120268B (fi) | 2009-08-31 |
EA200401489A1 (ru) | 2005-06-30 |
PL1541710T3 (pl) | 2010-04-30 |
FI20031821A (fi) | 2005-06-13 |
EP1541710A2 (de) | 2005-06-15 |
FI20031821A0 (fi) | 2003-12-12 |
DE602004023913D1 (de) | 2009-12-17 |
EP1541710A3 (de) | 2006-08-02 |
ATE447631T1 (de) | 2009-11-15 |
EA008451B1 (ru) | 2007-06-29 |
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