ES2374817T3 - METHOD FOR COVERING COPPER WITH PATH. - Google Patents
METHOD FOR COVERING COPPER WITH PATH. Download PDFInfo
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- ES2374817T3 ES2374817T3 ES04797943T ES04797943T ES2374817T3 ES 2374817 T3 ES2374817 T3 ES 2374817T3 ES 04797943 T ES04797943 T ES 04797943T ES 04797943 T ES04797943 T ES 04797943T ES 2374817 T3 ES2374817 T3 ES 2374817T3
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- patina
- copper
- resting
- weight
- temperature
- 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.)
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- 238000000034 method Methods 0.000 title claims abstract description 51
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000010949 copper Substances 0.000 title claims abstract description 33
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 21
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 4
- 241001311547 Patina Species 0.000 claims description 56
- 230000000284 resting effect Effects 0.000 claims description 16
- 238000004378 air conditioning Methods 0.000 claims description 11
- 230000035800 maturation Effects 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 238000005422 blasting Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims 2
- 150000005323 carbonate salts Chemical class 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 230000005070 ripening Effects 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 238000007790 scraping Methods 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 3
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- -1 chlorine ions Chemical class 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- 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
- C23C22/68—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 solutions with pH between 6 and 8
-
- 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
- C23C22/73—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 characterised by the process
- C23C22/77—Controlling or regulating of the coating process
-
- 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
- C23C22/78—Pretreatment of the material to be coated
-
- 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
- C23C22/82—After-treatment
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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)
- Chemical Treatment Of Metals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Physical Vapour Deposition (AREA)
- Paints Or Removers (AREA)
- Chemically Coating (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
Description
Método para cubrir cobre con pátina Method to cover copper with patina
La invención se refiere a un procedimiento para la generación de una pátina sobre objetos de cobre o aleaciones de cobre. The invention relates to a process for the generation of a patina on copper objects or copper alloys.
Se sabe, en general, que sobre la superficie de piezas de cobre se forma una capa verdosa que posee, entre otras cosas, una función de protección, cuando esta capa está expuesta a la intemperie durante mucho tiempo. Esta capa se designa como pátina de cobre. En nuestras latitudes dura normalmente entre diez y quine años hasta que una superficie de cobre está recubierta totalmente con la capa verde. Con objeto de reducir este periodo de tiempo largo han sido desarrollados diferentes procedimientos en el pasado, con el objetivo de imitar una pátina natural sobre superficies de cobre o, en cambio, generarla de forma favorable. It is known, in general, that a greenish layer is formed on the surface of copper pieces that has, among other things, a protective function, when this layer is exposed to the weather for a long time. This layer is designated as copper patina. In our latitudes it normally lasts between ten and fifteen years until a copper surface is completely covered with the green layer. In order to reduce this long period of time, different procedures have been developed in the past, with the aim of imitating a natural patina on copper surfaces or, instead, generating it favorably.
Así, por ejemplo, el documento US-3.497.401-A publica un procedimiento y una solución de reacción para la fabricación de una pátina. En este caso, a temperatura ambiente, se sumerge una pieza de cobre en una solución acuosa ácida con porciones de clorato potásico y sulfato de cobre. También el documento US-5.160.381-A describe la generación de una pátina sobre un objeto de cobre. En el procedimiento de varias fases descrito allí, la pieza de cobre sobre la que debe aplicarse la capa de pátina es tratada, después de la limpieza, con una solución acuosa, que contiene iones de cobre, de sodio, de acetato, de cloro, de sulfato de H+ y de OH-. Después de la limpieza y secado cuidadosos, se tra5ta la pieza de cobre en una segunda etapa de trabajo con una solución acuosa de carbonato de cobre, de cloruro de amonio, de acetato de cobre, de trióxido de arsénico, de nitrato de cobre y de ácido clorhídrico. También el documento EP 0 943 701 A1 se ocupa de la generación de una pátina, de nuevo a través de tratamiento de un objeto de cobre con una solución salina acuosa de cobre. Este procedimiento es especialmente adecuado para superficies de cobre pre-oxidadas. Thus, for example, US-3,497,401-A publishes a process and a reaction solution for the manufacture of a patina. In this case, at room temperature, a piece of copper is immersed in an acidic aqueous solution with portions of potassium chlorate and copper sulfate. Also US-5,160,381-A describes the generation of a patina on a copper object. In the multistage process described there, the piece of copper on which the patina layer should be applied is treated, after cleaning, with an aqueous solution, containing copper, sodium, acetate, chlorine ions, of H + sulfate and OH-. After careful cleaning and drying, the copper piece is treated in a second working stage with an aqueous solution of copper carbonate, ammonium chloride, copper acetate, arsenic trioxide, copper nitrate and hydrochloric acid. Also EP 0 943 701 A1 deals with the generation of a patina, again through treatment of a copper object with an aqueous saline solution of copper. This procedure is especially suitable for pre-oxidized copper surfaces.
Los documentos EP 0 492 466 y GB 697294 se refieren de la misma manera a procedimientos para la generación de una pátina artificial. De acuerdo con ello, sobre la superficie de un objeto de cobre o de una aleación de cobre se aplica una solución acuosa de sales de cobre. Los objetos tratados de esta manera son almacenados a continuación en temperatura y humedad del aire definidas. EP 0 492 466 and GB 697294 refer in the same way to procedures for the generation of an artificial patina. Accordingly, an aqueous solution of copper salts is applied to the surface of a copper object or a copper alloy. Objects treated in this way are then stored in defined air temperature and humidity.
El documento JP 08120460 publica un procedimiento similar con una soluciona de pátina que contiene cinc. JP 08120460 publishes a similar procedure with a patina solution containing zinc.
De acuerdo con el documento JP 09067681, para la generación de una página artificial, se conduce un objeto de cobre o de una aleación de cobre a través de una solución salina de cobre oxidante. El objeto tratado de esta manera se humedecido a continuación y es tratado posteriormente con un agente oxidante en forma de gas. According to JP 09067681, for the generation of an artificial page, a copper object or a copper alloy is conducted through an oxidizing copper salt solution. The object treated in this way is then moistened and subsequently treated with an oxidizing agent in the form of gas.
No obstante, los procedimientos conocidos presentan una serie de inconvenientes. Así, por ejemplo, durante la fabricación de algunas soluciones de pátina conocidas se utilizan componentes tóxicos y nocivos para la salud, como por ejemplo el trióxido de arsénico mencionado al principio. Por razones de protección del medio ambiente así como por razones sanitarias es deseable evitar el empleo de tales ingredientes. Otros procedimientos presentan limitaciones en la aplicabilidad. Así, por ejemplo, muchos procedimientos son, en general, menos adecuados para la aplicación de la capa de pátina sobre superficies de cobre no tratadas, puesto que requieren una oxidación previa de las piezas de cobre a cubrir con pátina. However, known procedures have a number of drawbacks. Thus, for example, during the manufacture of some known patina solutions toxic and harmful components for health are used, such as the arsenic trioxide mentioned at the beginning. For reasons of environmental protection as well as for sanitary reasons it is desirable to avoid the use of such ingredients. Other procedures have limitations in applicability. Thus, for example, many procedures are, in general, less suitable for the application of the patina layer on untreated copper surfaces, since they require a previous oxidation of the copper pieces to be covered with patina.
También con respecto a las propiedades cualitativas, tanto desde aspectos ópticos como también desde aspectos mecánicos, se pueden reconocer deficiencias en muchas capas de pátina generadas artificialmente. Con frecuencia, poseen propiedades adhesivas insuficientes, es decir, que la capa de protección artificial revienta ya en caso de carga mecánica ligera. Also with respect to qualitative properties, both from optical and mechanical aspects, deficiencies in many artificially generated patina layers can be recognized. Often, they have insufficient adhesive properties, that is, the artificial protection layer already bursts in case of light mechanical loading.
De acuerdo con ello, la invención tiene el cometido de preparar un procedimiento, que evita los inconvenientes del estado de la técnica y en este caso soluciona el mayor número posible de los problemas descritos. Accordingly, the invention has the task of preparing a procedure, which avoids the inconveniences of the state of the art and in this case solves the greatest possible number of the problems described.
Este cometido se soluciona por medio del procedimiento con las características de la reivindicación 1. Las formas de realización preferidas de este procedimiento se describen en las reivindicaciones dependientes. This task is solved by means of the process with the features of claim 1. Preferred embodiments of this process are described in the dependent claims.
De acuerdo con el procedimiento según la invención objetos de cobre o de una aleación de cobre son tratados con una solución de pátina con preferencia acuosa, que contiene iones de cobre y a continuación son sometidos a un llamado proceso de maduración. According to the process according to the invention, copper or copper alloy objects are treated with a preferably aqueous patina solution containing copper ions and then subjected to a so-called maturation process.
El proceso de maduración contiene etapas de maduración individuales, que comprenden una selección de humedades del aire y de temperaturas. El ajuste y el control de los dos parámetros temperatura y humedad del aire se puede realizar bien especialmente en una cámara de climatización prevista para ello. The maturation process contains individual maturation stages, which comprise a selection of air humidity and temperatures. The adjustment and control of the two parameters temperature and humidity of the air can be done well especially in an air conditioning chamber provided for it.
El proceso de maduración contiene las siguientes etapas de maduración. Después del tratamiento del objeto con la solución de pátina, en particular después de la aplicación de la solución de pátina sobre el objeto a cubrir con pátina, sigue una permanencia en reposo del objeto a una primera temperatura de reposo y a una primera humedad del aire The maturation process contains the following stages of maturation. After treatment of the object with the patina solution, in particular after the application of the patina solution on the object to be covered with patina, a rest remains of the object at a first resting temperature and at a first air humidity
de reposo durante un primer periodo de tiempo de reposo. A continuación se realiza una humidificación con agua del objeto, al menos una vez, a una temperatura de humidificación y a una humedad del aire de humidificación durante un periodo de tiempo de humidificación, después de lo cual sigue de nuevo una permanencia en reposo a una segunda temperatura de reposo y a una segunda humedad del aire de reposo durante un segundo periodo de tiempo de reposo. of rest during a first period of rest time. A humidification is then carried out with water of the object, at least once, at a humidification temperature and a humidity of the humidification air for a period of humidification time, after which a rest remains again at a second time. resting temperature and a second humidity of the resting air for a second period of resting time.
Durante la primera permanencia en reposo, la temperatura especialmente en la cámara de climatización está entre 20 ºC y 70 ºC, en particular entre 25 ºC y 55 ºC (primera temperatura de reposo). La humedad del aire está en el intervalo entre 30 % y 90 %, en particular entre 40 % y 50 % (primera humedad del aire de reposo). Estos intervalos preferidos para la temperatura y la humedad del aire, indicados para la primera fase de reposo, corresponden también a los intervalos preferidos para la segunda temperatura de reposo y la segunda humedad del aire de reposo. During the first time at rest, the temperature especially in the air conditioning chamber is between 20 ° C and 70 ° C, in particular between 25 ° C and 55 ° C (first resting temperature). The humidity of the air is in the range between 30% and 90%, in particular between 40% and 50% (first humidity of the resting air). These preferred intervals for the temperature and humidity of the air, indicated for the first resting phase, also correspond to the preferred intervals for the second resting temperature and the second humidity of the resting air.
Durante el proceso de humidificación, la temperatura en la cámara de climatización está entre 20 ºC y 70 º, en particular entre 25 ºC y 55 ºC. La humedad del aire se mantiene durante el proceso de humidificación en el intervalo entre 30 % y 95 %, en particular en el intervalo entre 65 % y 80 %. Habitualmente la humidificación de realiza a través de una pulverización del objeto tratado con agua. Este proceso se repite con preferencia de cuatro a cinco veces en un intervalo de tiempo de 90 minutos a 2 horas. During the humidification process, the temperature in the air conditioning chamber is between 20 ° C and 70 ° C, in particular between 25 ° C and 55 ° C. Air humidity is maintained during the humidification process in the range between 30% and 95%, in particular in the range between 65% and 80%. Usually humidification is carried out by spraying the object treated with water. This process is preferably repeated four to five times in a time interval of 90 minutes to 2 hours.
La primera duración de reposo alcanza hasta una semana, pero se prefiere un periodo de tiempo de dos a tres días. Lo mismo se aplica para la segunda duración de reposo. La duración de la humidificación no es mayor que un día, pero con preferencia está entre 5 horas y 10 horas. The first rest period is up to one week, but a period of two to three days is preferred. The same applies to the second rest period. The duration of humidification is not longer than one day, but preferably it is between 5 hours and 10 hours.
Como ya se ha mencionado, en la solución de pátina empleada se trata de una solución que contiene iones de cobre, cuya composición preferida se tratará más adelante. Además, debe subrayarse que es especialmente preferido que el objeto a cubrir con pátina sea limpiado antes de la aplicación de la solución de pátina y/o su superficie sea raspada. Los restos de grasa o de aceite eventualmente presentes o bien otras contaminaciones sobre las superficies influyen negativamente sobre la página resultante. Esto se soluciona especialmente a través de desengrase químico y/o chorreado de la superficie s cubrir con pátina con bolas de cristal rotas. De manera alternativa, se puede emplear, por ejemplo, también una afiladora de excéntrica o una afiladora de cinta. As already mentioned, in the patina solution used it is a solution containing copper ions, the preferred composition of which will be discussed later. In addition, it should be stressed that it is especially preferred that the object to be covered with patina be cleaned before the application of the patina solution and / or its surface is scraped off. The remains of grease or oil that may be present or other contamination on the surfaces negatively influence the resulting page. This is especially solved through chemical degreasing and / or blasting of the surface s covered with patina with broken glass balls. Alternatively, an eccentric grinder or a tape grinder can also be used, for example.
El objeto a cubrir con pátina es sometido, dado el caso de un tratamiento previo opcional descrito, al proceso de maduración, con preferencia es transferido a la cámara de climatización ya mencionada. No es forzoso, pero es preferido que la aplicación de la solución de pátina se realice en la cámara. The object to be covered with patina is subjected, in the case of an optional prior treatment described, to the maturation process, preferably it is transferred to the aforementioned air conditioning chamber. It is not forced, but it is preferred that the patina solution is applied to the chamber.
La solución de pátina se aplica con preferencia en forma finamente distribuidas, de manera especialmente preferida es pulverizada. La temperatura (con preferencia en la cámara de climatización) está en este caso con preferencia entre 30 ºC y 70 ºC, en particular está entre 40 ºC y 55 ºC. Normalmente, la aplicación de la solución de pátina se lleva a cabo en al menos dos, con preferencia en cuatro a cinco etapas de tratamiento, en particular a intervalos de aproximadamente 1 hora. The patina solution is preferably applied in finely distributed form, especially preferably it is sprayed. The temperature (preferably in the air conditioning chamber) is in this case preferably between 30 ° C and 70 ° C, in particular it is between 40 ° C and 55 ° C. Normally, the application of the patina solution is carried out in at least two, preferably in four to five treatment stages, in particular at intervals of approximately 1 hour.
De manera sorprendente se ha constatado que en oposición a los procedimientos clásicos para la aplicación de pátina sobre piezas de cobre, que están constituidas esencialmente por un tratamiento una o varias veces con una solución salina de cobre acuosa y un secado al aire siguiente, el empleo de un proceso de maduración, en particular en una cámara de climatización, ofrece grandes ventajas especialmente en lo que se refiere a la óptica y a la calidad de la pátina fabricada. La pátina artificial resultante ofrece una impresión de color uniforme e intensiva. Surprisingly it has been found that in opposition to the classical procedures for the application of patina on copper pieces, which are essentially constituted by a treatment once or several times with an aqueous copper saline solution and an air-drying afterwards, the use A maturation process, in particular in an air conditioning chamber, offers great advantages especially in regard to the optics and quality of the manufactured patina. The resulting artificial patina offers a uniform and intensive color impression.
Opcionalmente, se puede realizar todavía un tratamiento siguiente de la superficie recién cubierta con pátina. Es posible aclarar u oscurecer la superficie. En caso conveniente, se puede sellar también la superficie, puesto que la pátina no sellada puede reaccionar posteriormente en determinadas circunstancias bajo influencias naturales de la intemperie. Optionally, a subsequent treatment of the surface just covered with patina can still be carried out. It is possible to lighten or darken the surface. If appropriate, the surface can also be sealed, since the unsealed patina can subsequently react under certain circumstances under natural weather influences.
El procedimiento descrito está previsto para la cobertura con pátina de material de panel, de cinta o de ripia de cobre. No obstante, en principio, se puede aplicar sobre todas las piezas moldeadas u objetos de cobre o de aleaciones de cobre. También se pueden realizar coberturas parciales con pátina de piezas moldeadas como por ejemplo canelones de tejado. Así, por ejemplo, en el caso de canalones de tejado se puede cubrir fuertemente con pátina la zona del cordón, mientras que el lado exterior de la circulación del agua solamente se oxida. De esta manera, se consigue la impresión óptica de que la pieza de cobre ha estado expuesta durante años y decenios a influencias atmosféricas. Tales efectos se emplean con frecuencia en la configuración óptica de edificios nuevos, pero en particular en la restauración o reparación de monumentos más antiguos conservados, para obtener la impresión histórica general. The procedure described is intended for covering with patina of panel material, tape or copper shingle. However, in principle, it can be applied to all molded parts or objects made of copper or copper alloys. You can also make partial coverings with patina of molded parts such as roof cannelloni. Thus, for example, in the case of roof gutters, the cord area can be heavily covered with patina, while the outer side of the water circulation only oxidizes. In this way, the optical impression is achieved that the copper piece has been exposed for years and decades to atmospheric influences. Such effects are frequently used in the optical configuration of new buildings, but in particular in the restoration or repair of older preserved monuments, to obtain the general historical impression.
Como otras características, la pátina producida de acuerdo con el procedimiento de la invención posee una resistencia buena frente a carga mecánica y propiedades adhesivas excelentes. Like other features, the patina produced according to the process of the invention has a good resistance to mechanical loading and excellent adhesive properties.
Estas propiedades positivas se pueden atribuir también a la solución de pátina empleada con preferencia, que es These positive properties can also be attributed to the patina solution used preferably, which is
igualmente objeto de esta invención. Está constituida por una solución acuosa, en la que está contenida una sal de cobre, con preferencia nitrato de cobre, en una proporción de hasta 20 % en peso, en particular en una proporción de 3 % en peso a 5 % en peso. Adicionalmente, en la solución está contenida adicionalmente una sal de cinc, en particular cloruro de cinc, con preferencia en una proporción de 0,1 % en peso a 5 % en peso, en particular en una proporción de 0,2 % en peso a 1 % en peso. Por lo demás, la solución puede contener diversos aditivos de cloruro y de carbonato, entre ellos especialmente cloruro de sodio, cloruro de amonio, cloruro de calcio y carbonato de amonio. El valor pH de la solución de pátina está con preferencia en la zona básica, en particular en la zona ligeramente básica en pH 7 – 10. also object of this invention. It consists of an aqueous solution, in which a copper salt, preferably copper nitrate, is contained in a proportion of up to 20% by weight, in particular in a proportion of 3% by weight to 5% by weight. Additionally, a zinc salt, in particular zinc chloride, is preferably contained in the solution, preferably in a proportion of 0.1% by weight to 5% by weight, in particular in a proportion of 0.2% by weight a 1% by weight. Otherwise, the solution may contain various chloride and carbonate additives, including especially sodium chloride, ammonium chloride, calcium chloride and ammonium carbonate. The pH value of the patina solution is preferably in the basic zone, in particular in the slightly basic zone at pH 7-10.
Entre los componentes contenidos en la solución de pátina de acuerdo con la invención, hay que resaltar especialmente la proporción de sal de cinc. De manera más sorprendente se ha constatado que la adición de sal de cinc repercute positivamente sobre las propiedades adhesivas de la pátina resultante. Además, tal adición provoca una aclaración óptica tirando a verde. La pátina presenta normalmente un espesor de capa de 0,02 mm a 0,06 mm, en particular de 0,03 mm a 0,05 mm. Among the components contained in the patina solution according to the invention, the proportion of zinc salt must be especially emphasized. More surprisingly, it has been found that the addition of zinc salt has a positive effect on the adhesive properties of the resulting patina. In addition, such addition causes an optical clarification by pulling green. The patina normally has a layer thickness of 0.02 mm to 0.06 mm, in particular 0.03 mm to 0.05 mm.
Otras características de la invención se deducen a partir de los ejemplos siguientes en combinación con las reivindicaciones dependientes. En este caso, las características y propiedades representadas se pueden realizar por sí solas o agrupadas en combinación entre sí. Other features of the invention are deduced from the following examples in combination with the dependent claims. In this case, the characteristics and properties represented can be performed by themselves or grouped in combination with each other.
Ejemplo Example
Para la preparación de la solución de pátina se disolvieron en un litro de agua los siguientes componentes: For the preparation of the patina solution, the following components were dissolved in a liter of water:
- --
- 40 g de nitrato de cobre-(II) 40 g of copper nitrate- (II)
- --
- 3 g de cloruro de cinc 3 g zinc chloride
- --
- 8 g de cloruro de calcio 8 g calcium chloride
- --
- 2 g de cloruro potásico 2 g potassium chloride
- --
- 20 g de cloruro de amonio 20 g of ammonium chloride
La cámara de climatización tenía un área de aproximadamente 3 x 2,5 m. Una chapa de cobre, cuya superficie fue rectificada a fondo con una afiladora de excéntrica y que estaba libre de grasa y de otras contaminaciones, se colocó en la cámara de climatización. La temperatura en la cámara de climatización se ajustó a 50 ºC. A esta temperatura, se pulverizó la solución de pátina cuatro veces a un intervalo respectivo de una hora sobre la superficie de la pieza de cobre. Durante la primera duración de reposo siguiente ahora se mantuvo la temperatura en 45 ºC aproximadamente. La humedad del aire se reguló a 45 % aproximadamente. Después de tres días en permanencia en reposo siguió una humidificación varias veces de la pieza de cobre tratada. En total, se pulverizó cinco veces a un intervalo respectivo de 90 minutos con agua. La humedad del aire en la cámara de climatización era en este intervalo de tiempo 75 % aproximadamente, la temperatura era aproximadamente 50 ºC durante el tratamiento con solución de pátina. A continuación se redujeron los parámetros humedad del aire y temperatura de nuevo a 45 % y 45 ºC, respectivamente y se dejó reposar la chapa de cobre de nuevo durante 3 días. De esta manera se terminó la aplicación de la capa de pátina. La chapa de cobre estaba revestida de manera absolutamente uniforme por la capa de protección artificial. The air conditioning chamber had an area of approximately 3 x 2.5 m. A copper plate, whose surface was thoroughly ground with an eccentric grinder and free of grease and other contamination, was placed in the air conditioning chamber. The temperature in the air conditioning chamber was set at 50 ° C. At this temperature, the patina solution was sprayed four times at a respective interval of one hour on the surface of the copper piece. During the first first rest period the temperature was now maintained at approximately 45 ° C. Air humidity was regulated at approximately 45%. After three days at rest, a humidification followed several times of the treated piece of copper. In total, it was sprayed five times at a respective interval of 90 minutes with water. The humidity of the air in the air conditioning chamber was in this time interval approximately 75%, the temperature was approximately 50 ° C during the patina solution treatment. The air humidity and temperature parameters were then reduced again to 45% and 45 ° C, respectively, and the copper plate was allowed to stand again for 3 days. In this way the application of the patina layer was terminated. The copper plate was absolutely uniformly coated by the artificial protection layer.
Claims (17)
- --
- dejar en reposo el objeto tratado a una temperatura de reposo entre 20 ºC y 70 ºC y a una humedad del aire de reposo entre 30 % y 90 % durante una primera duración de reposo de hasta una semana, leave the treated object at rest at a resting temperature between 20 ° C and 70 ° C and at a resting air humidity between 30% and 90% for a first resting period of up to one week,
- - -
- humedecer con agua al menos una vez el objeto tratado a una temperatura de humidificación entre 20 ºC y 70 ºC y a una humedad del aire de humidificación en el intervalo de 30 % a 95 % durante un periodo de humidificación de hasta un día, y wet the treated object at least once with water at a humidification temperature between 20 ° C and 70 ° C and at a humidification air humidity in the range of 30% to 95% during a humidification period of up to one day, and
- --
- dejar en reposo el objeto tratado a una temperatura de reposo entre 20 ºC y 70 ºC y a una humedad del aire de reposo entre 30 % y 90 % durante una segunda duración de reposo de hasta una semana, leave the treated object at rest at a resting temperature between 20 ° C and 70 ° C and at a resting air humidity between 30% and 90% for a second resting period of up to one week,
Applications Claiming Priority (3)
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|---|---|---|---|
| DE10354527 | 2003-11-17 | ||
| DE10354527A DE10354527B4 (en) | 2003-11-17 | 2003-11-17 | Process for patination of copper |
| PCT/EP2004/013009 WO2005049889A1 (en) | 2003-11-17 | 2004-11-17 | Method for covering copper with patina |
Publications (1)
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| ES2374817T3 true ES2374817T3 (en) | 2012-02-22 |
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| ES04797943T Expired - Lifetime ES2374817T3 (en) | 2003-11-17 | 2004-11-17 | METHOD FOR COVERING COPPER WITH PATH. |
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| US (1) | US20070079906A1 (en) |
| EP (1) | EP1685273B1 (en) |
| JP (1) | JP2007511668A (en) |
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| KR100890607B1 (en) * | 2007-07-02 | 2009-03-27 | 김부현 | Method of manufacturing copper oxide copper plate |
| KR101143687B1 (en) * | 2011-12-07 | 2012-05-09 | 김부현 | A oxidized verdigris copper manufacture method |
| US10119038B2 (en) | 2015-05-08 | 2018-11-06 | PatinaNow, LLC | Patina solution, method for producing patina on object, and patina kit |
| JP6354814B2 (en) | 2016-09-30 | 2018-07-11 | ダイキン工業株式会社 | Manufacturing method of piping and forming method of oxide film on inner surface of copper pipe |
| JP6421892B1 (en) * | 2017-10-26 | 2018-11-14 | 住友化学株式会社 | Thermoplastic resin composition |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB697294A (en) * | 1950-09-05 | 1953-09-16 | Ici Ltd | Improvements in or relating to the colouring of copper and its alloys |
| US3497401A (en) * | 1967-09-20 | 1970-02-24 | Intern Copper Research Ass Inc | Patination of copper |
| US3669766A (en) * | 1969-11-28 | 1972-06-13 | Mitsunosuke Fukawa | Formation of coating on copper containing materials |
| US3725138A (en) * | 1971-03-15 | 1973-04-03 | Anaconda American Brass Co | Production of synthetic patina |
| JPS52110235A (en) * | 1976-03-03 | 1977-09-16 | Nippon Paint Co Ltd | Industrial process for forming patina |
| JPH06102837B2 (en) * | 1990-02-14 | 1994-12-14 | 日鉱金属株式会社 | How to form patina |
| DE4041854A1 (en) * | 1990-12-24 | 1992-06-25 | Kabelmetal Ag | METHOD FOR PRODUCING A GREEN PATINA ON A SEMI-PRODUCT CONSTRUCTED FROM COPPER |
| JPH04329884A (en) * | 1991-05-02 | 1992-11-18 | Kanebo Ltd | Artificial verdigris liquid |
| US5160381A (en) * | 1991-06-26 | 1992-11-03 | Fumigation Maritime Ltee | Method for forming artificially and rapidly patina on copper, products thereof and solutions therefor |
| JPH0718485A (en) * | 1993-07-01 | 1995-01-20 | Furukawa Electric Co Ltd:The | Material forming patina and method of manufacturing the same |
| JP2640432B2 (en) * | 1994-10-20 | 1997-08-13 | 三井金属鉱業株式会社 | Chemical conversion solution for artificial patina and artificial patina treatment method |
| JP2920610B2 (en) * | 1995-08-31 | 1999-07-19 | 元旦ビューティ工業株式会社 | Method and apparatus for forming patina film |
| DE19809904A1 (en) * | 1998-03-07 | 1999-09-09 | Km Europa Metal Ag | Process and reaction solution to create a patina |
| JP3696139B2 (en) * | 2001-09-14 | 2005-09-14 | 元旦ビューティ工業株式会社 | Cyan blue coloring composition and patina formation method |
-
2003
- 2003-11-17 DE DE10354527A patent/DE10354527B4/en not_active Expired - Fee Related
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2004
- 2004-11-17 DK DK04797943.0T patent/DK1685273T3/en active
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- 2004-11-17 WO PCT/EP2004/013009 patent/WO2005049889A1/en not_active Ceased
- 2004-11-17 PL PL04797943T patent/PL1685273T3/en unknown
- 2004-11-17 EP EP04797943A patent/EP1685273B1/en not_active Expired - Lifetime
- 2004-11-17 AU AU2004291674A patent/AU2004291674B2/en not_active Ceased
- 2004-11-17 US US10/579,550 patent/US20070079906A1/en not_active Abandoned
- 2004-11-17 SI SI200431789T patent/SI1685273T1/en unknown
- 2004-11-17 PT PT04797943T patent/PT1685273E/en unknown
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- 2004-11-17 ES ES04797943T patent/ES2374817T3/en not_active Expired - Lifetime
- 2004-11-17 CN CNA2004800404245A patent/CN1906328A/en active Pending
- 2004-11-17 CA CA2548291A patent/CA2548291C/en not_active Expired - Fee Related
- 2004-11-17 JP JP2006538826A patent/JP2007511668A/en active Pending
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- 2011-11-25 CY CY20111101159T patent/CY1112119T1/en unknown
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| AU2004291674A1 (en) | 2005-06-02 |
| EP1685273A1 (en) | 2006-08-02 |
| DE10354527B4 (en) | 2008-08-28 |
| BRPI0416664A (en) | 2007-01-16 |
| SI1685273T1 (en) | 2012-01-31 |
| PT1685273E (en) | 2011-11-03 |
| US20070079906A1 (en) | 2007-04-12 |
| WO2005049889A1 (en) | 2005-06-02 |
| KR20060107784A (en) | 2006-10-16 |
| EP1685273B1 (en) | 2011-10-05 |
| JP2007511668A (en) | 2007-05-10 |
| DE10354527A1 (en) | 2005-06-23 |
| CY1112119T1 (en) | 2015-11-04 |
| ATE527396T1 (en) | 2011-10-15 |
| CN1906328A (en) | 2007-01-31 |
| CA2548291A1 (en) | 2005-06-02 |
| CA2548291C (en) | 2012-03-13 |
| DK1685273T3 (en) | 2012-01-16 |
| AU2004291674B2 (en) | 2009-08-27 |
| PL1685273T3 (en) | 2012-03-30 |
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