EP1144724B1 - Heat exchanger with a reduced tendency to produce deposits and method for producing same - Google Patents

Heat exchanger with a reduced tendency to produce deposits and method for producing same Download PDF

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Publication number
EP1144724B1
EP1144724B1 EP99964672A EP99964672A EP1144724B1 EP 1144724 B1 EP1144724 B1 EP 1144724B1 EP 99964672 A EP99964672 A EP 99964672A EP 99964672 A EP99964672 A EP 99964672A EP 1144724 B1 EP1144724 B1 EP 1144724B1
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European Patent Office
Prior art keywords
metal
polymer
phosphorus
layer
polymer dispersion
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EP99964672A
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German (de)
French (fr)
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EP1144724A2 (en
Inventor
Stephan Hüffer
Axel Franke
Stephan Scholl
Hans Mueller-Steinhagen
Qi Zhao
Bernd Diebold
Peter Dillmann
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BASF SE
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BASF SE
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • F28F19/06—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of metal
    • 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
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • 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
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • 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
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • 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
    • C23C18/38—Coating with copper
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00—Coatings; Surface treatments
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12944—Ni-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the invention relates to a method for producing Heat exchangers, the electroless chemical deposition of a metal-polymer dispersion layer includes.
  • the invention further relates to heat exchanger according to the invention.
  • the invention further relates to the Use of a metal-polymer dispersion layer as a permanent incrustation inhibitor.
  • the deposits whose formation is to be prevented are inorganic salts such as calcium and barium sulfate, calcium and Magnesium carbonate, inorganic phosphates, silicas and silicates, Corrosion products, particulate deposits, for example alluvial sand (River and sea water), as well as organic deposits such as bacteria, algae, Proteins, mussels or mussel larvae, polymers, oils and resins as well as the biomineralized composites consisting of the aforementioned substances.
  • inorganic salts such as calcium and barium sulfate, calcium and Magnesium carbonate, inorganic phosphates, silicas and silicates, Corrosion products, particulate deposits, for example alluvial sand (River and sea water), as well as organic deposits such as bacteria, algae, Proteins, mussels or mussel larvae, polymers, oils and resins as well as the biomineralized composites consisting of the aforementioned substances.
  • the object of the present invention is to provide a method for producing a Specify heat exchanger, on the one hand, the inclination of the reduces heat transfer surfaces, solids to form Deposits and on the other hand with high durability (e.g. against heat, corrosion and undermining) to a negligible Thermal resistance leads.
  • the process should treated surfaces have a satisfactory durability.
  • the procedure is supposed to be cost-effective to use even on hard-to-reach areas.
  • a heat exchanger is a device which has surfaces designed for heat exchange (heat transfer surfaces). Heat exchangers which exchange heat with fluids, in particular with liquids, are preferred. Heating elements and heat exchangers, in particular plate heat exchangers and spiral heat exchangers, are preferred versions of heat exchangers.
  • a halogenated polymer is a fluorinated or a chlorinated polymer; fluorinated polymers, in particular perfluorinated, are preferred. Examples of perfluorinated polymers are polytetrafluoroethylene (PTFE) and perfluoroalkoxy polymers (PFA, according to DIN 7728, Part 1, January 1988).
  • This object of the invention is a method for Electroless chemical deposition of metal-polymer dispersion phases which is known per se (W. Riedel: Functional nickel plating, publisher Eugen Leize, Saulgau, 1989 pages 231 to 236, ISBN 3-750480-044-x).
  • a Metal-polymer dispersion phase comprises a polymer, in the context of the invention a halogenated polymer dispersed in a metal alloy.
  • the Metal alloy is preferably a metal-phosphor alloy.
  • the surfaces treated according to the invention allow good heat transfer, although the coatings have a can have a not inconsiderable thickness of 1 to 100 ⁇ m.
  • the Surfaces treated according to the invention also have a satisfactory Shelf life, which also appear useful from 1 to 100 ⁇ m leaves; 3 to 20 ⁇ m, in particular 5 to 16 ⁇ m, are preferred.
  • the polymer content the dispersion coating is 5 to 30% by volume, preferably 15 to 25% by volume, especially 19 to 21 vol.%.
  • coatings are relatively inexpensive and can also be opened Apply hard-to-reach areas. These areas can be any heat transfer surfaces such as inner pipe surfaces, surfaces of electrical heating elements and surfaces of plate heat exchangers etc. act for the heating or cooling of fluids in industrial plants, in Private households, in food processing or in plants for Electricity production or water treatment can be used.
  • Heat transfer means the heat transfer from the inside of the Heat exchanger to a possibly existing, facing the fluid Coating, the heat conduction within the coating layer and the Heat transfer from the coating layer to a fluid (e.g. a saline solution).
  • a fluid e.g. a saline solution
  • the metal-phosphorus alloy of the metal-polymer dispersion layer around copper phosphorus or nickel phosphorus is preferred Nickel-phosphorus.
  • the nickel polymer dispersion layer is a dispersion layer Nickel-phosphorus polytetrafluoroethylene.
  • Suitable polymers such as perfluoro-alkoxy polymers (PFA, copolymers of Tetrafluoroethylene and perfluoroalkoxy vinyl ether e.g. Perfluorovinyl propyl ether). Should the heat exchanger be operated at a comparatively low temperature then the use of chlorinated polymers is also conceivable.
  • the Metal-polymer dispersion layer with a spherical polymer particle average diameter (number average) from 0.1 ⁇ m to 1.0 ⁇ m, especially from 0.1 ⁇ m to 0.3 ⁇ m.
  • the coating is done by immersing the workpiece in a metal electrolyte solution that has been mixed with a stabilized polymer dispersion beforehand.
  • the tempering period is generally 5 minutes to 3 hours, preferably 35 to 45 minutes.
  • Ni II , hypophosphite, carboxylic acids and fluoride and optionally deposition moderators such as Pb 2+ can be used as metal solutions.
  • metal solutions are sold, for example, by Riedel, Galvano- und Filtertechnik GmbH, Halle, Westphalia and Atotech GmbH, Berlin.
  • PTFE dispersions polytetrafluoroethylene dispersions
  • PTFE dispersions with a solids content of 35 to 60% by weight and an average particle diameter (number average) of 0.1 ⁇ m to 1 ⁇ m, in particular of 0.1 ⁇ m to 0.3 ⁇ m, are preferred, the particles of which have a spherical morphology and which have a neutral detergent (for example polyglycols, alkylphenol ethoxylate or possibly mixtures of the substances mentioned, 80 to 120 g of neutral detergent per liter) and an ionic detergent (for example alkyl and haloalkyl sulfonates, alkylbenzenesulfonates, alkylphenol ether sulfates, tetraalkylammonium salts or optionally Mixtures of the substances mentioned, 15 to 60 g of ionic detergent per liter).
  • a neutral detergent for example polyglycols, alkylphenol ethoxylate or possibly mixtures of the substances mentioned, 80 to 120 g of neutral detergent per liter
  • Dip baths with a pH of around 5 and about 27 g / l NiSO 4 x 6 H 2 O and about 21 g / l NaH 2 PO 2 x H 2 O with a PTFE content of 1 to 25 g are typical / l included.
  • the polymer content of the dispersion coating is mainly influenced by the amount of polymer dispersion added and the choice of detergents.
  • Another object of the invention is a method for producing a heat exchanger, which has a particularly adhesive, durable and heat-resistant coating and therefore solves the problem of the invention in a special way.
  • This method is based on a method for producing a heat exchanger, characterized by the electroless chemical deposition of a metal-polymer dispersion coating, in which the polymer is halogenated, on a heat transfer surface.
  • This method is additionally characterized in that a 1 to 15 ⁇ m thick metal-phosphor layer is applied by electroless chemical deposition before the metal-polymer dispersion layer is applied
  • Electroless chemical application of a 1 to 15 ⁇ m thick metal-phosphor layer to improve adhesion takes place through the already described metal electrolyte baths, but in this case no stabilized polymer dispersion is added.
  • On tempering at this time preferably dispensed with, since this adversely affects the adhesion of the subsequent metal-polymer dispersion layer generally adversely affected.
  • To Deposition of the metal-phosphor layer will place the workpiece in the top brought immersion bath, which in addition to the metal electrolyte also a stabilized polymer dispersion. This forms the metal-polymer dispersion layer.
  • an annealing at 200 to 400 °, in particular at 315 to 325 ° C performed.
  • the tempering period is generally 5 minutes to 3 hours, preferably 35 to 45 minutes.
  • the Metal-phosphor layer on a thickness of 1 to 5 microns.
  • it is the metal-phosphor alloy of the metal-polymer dispersion layer and the metal-phosphor layer around nickel-phosphorus or copper-phosphorus.
  • the metal-polymer dispersion layer is a dispersion layer Nickel-phosphorus polytetrafluoroethylene.
  • Another object of the invention is one by an inventive Method of producing heat exchangers. Production is preferably carried out of the heat exchanger according to the invention by using a inventive method.
  • the aforementioned is according to the invention Heat exchangers for transferring heat to fluids, in particular to Liquids, designed. All heating elements come into question here Transfer heat to fluids. Furthermore, heat exchangers, in particular Plate heat exchangers and spiral heat exchangers, preferred examples of such Heat exchangers.
  • Another object of the invention is the use of a coating, produced by electroless chemical deposition of a metal-polymer dispersion layer, where the polymer is halogenated to reduce the Inclination of the coated surfaces, solids from fluids to form To deposit deposits.
  • the fluids are preferably Liquids.
  • Fig. 1 shows the decrease in the heat transfer coefficient ( ⁇ [W / m 2 K]) due to CaSO 4 deposits as a function of time (t [min], abscissa) for different heat exchangers, which differ in the nature of their surfaces.
  • Reference number 1 refers to the measured values of the coating according to the invention of example (* 7).
  • Reference number 2 denotes the measured values for an electropolished steel surface.
  • the area-related output is 200 kW / m 2
  • the concentration of the CaSO 4 solution is 1.6 g / l and has a temperature that corresponds to the boiling point.
  • Fig. 2 shows the measured decrease in the heat transfer coefficient ( ⁇ [W / m 2 K]) due to CaSO 4 deposits as a function of time (t [min], abscissa) for different heat exchangers, which differ in the nature of their surfaces.
  • Reference number 1 is the coating according to the invention of example (* 7).
  • the reference number 3 indicates an untreated steel surface.
  • the power based on the area of the heat exchanger is 100 kW / m 2 .
  • a CaSO 4 solution with a concentration of 2.5 g / l flows past the heat exchanger at a speed of 80 cm / s and a temperature of 80 ° C.
  • Table 1 contains a comparison of the measured values of surface roughness, surface energy and wetting angle of the examined heating surfaces, as well as the relative decrease in the measured heat transfer coefficients within the first 100 hours of the test. It can be seen that the heat exchangers according to the invention provide a very low surface energy, a very large contact angle and very good heat transfer behavior.
  • Table 2 compares surface energy, contact angle and bacteria deposited per area (Streptococcus Thermophilus) of the heat exchangers according to the invention with the heat exchangers of the prior art.
  • Surface energy [mJ / m 2 ]
  • Contact angle [°]
  • Log10 cells / cm 2 * 9 untreated (steel) 84 65 5.7
  • Electropolished steel 86 62 5.5 Steel implanted with Si ions 39 80 4.9 F-ion implanted steel 37 82 5.5 Steel DLC sputtered 36 85 5.0 Steel CrC sputtered 34 87 4.1 Steel / Ni-PTFE 25 100 3.9
  • Concentration [g / l] pH NiSO 4 x6H 2 O 27 4.8 NaH 2 PO 2 xH 2 O 21 CH 3 CHOHCOOH 20 C 2 H 5 COOH 3 Na citrate; 5 NaF 1 PTFE (50%) 2-50

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemically Coating (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polymerisation Methods In General (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Laminated Bodies (AREA)
  • Pretreatment Of Seeds And Plants (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

The present invention relates to a process for coating apparatuses and apparatus parts for chemical plant construction-which are taken to mean, for example, apparatus, tank and reactor walls, discharge devices, valves, pumps, filters, compressors, centrifuges, columns, dryers, comminution machines, internals, packing elements and mixing elements-wherein a metal layer or a metal/polymer dispersion layer is deposited in an electroless manner on the apparatus(es) or apparatus part(s) to be coated by bringing the parts into contact with a metal electrolyte solution which, in addition to the metal electrolyte, comprises a reducing agent and optionally the polymer or polymer mixture to be deposited in dispersed form, where at least one polymer is halogenated.

Description

Die Erfindung bezieht sich auf ein Verfahren zur Herstellung von Wärmeübertragern, das das stromlose chemische Abscheiden einer Metall-Polymer-Dispersionschicht umfaßt. Die Erfindung bezieht sich ferner auf erfindungsgemäße Wärmeüberträger. Ferner betrifft die Erfindung die Verwendung einer Metall-Polymer-Dispersionschicht als Permanent-Inkrustierungsinhibitor.The invention relates to a method for producing Heat exchangers, the electroless chemical deposition of a metal-polymer dispersion layer includes. The invention further relates to heat exchanger according to the invention. The invention further relates to the Use of a metal-polymer dispersion layer as a permanent incrustation inhibitor.

Während der letzten Jahrzehnte litten faßt alle Industriezweige unter Ablagerung in Wärmetauschern (Steinhagen et al. (1982), Problems and Costs Due to Heat Exchanger Fouling in New Zealand Industies, Heat Transfer Eng., 14(1), Seiten 19-30). Bei der Berechnung von Wärmetauschern muß ein aufgrund von Ablagerungen (Fouling) ansteigender Reibungsdruckverlust und Wärmeübertragungswiderstand mit einbezogen werden. Dies führt zur Überdimensionierung von Wärmeüberträgern um 10 bis 200 %.Over the past few decades, all industries have suffered from deposition in heat exchangers (Steinhagen et al. (1982), Problems and Costs Due to Heat Exchanger Fouling in New Zealand Industries, Heat Transfer Eng., 14 (1), pages 19-30). When calculating heat exchangers, a due to Deposits (fouling) increasing friction pressure loss and Heat transfer resistance should be included. This leads to Oversizing heat exchangers by 10 to 200%.

Die Entwicklung von Anti-Fouling-Verfahren hat deswegen einen hohen Stellenwert eingenommen.
Mechanische Lösungen haben den Nachteil, daß sie auf relativ große Wärmetauscher beschränkt sind und zudem erhebliche Mehrkosten verursachen. Chemische Additive können zu einer unerwünschten Kontamination des Produktes führen und belasten zum Teil die Umwelt.
Aus diesen Gründen wird in letzter Zeit nach Möglichkeiten gesucht, die Fouling-Neigung durch Modifizierung der Wärmeübertragungsflächen zu reduzieren. Oberflächenbeschichtungen mit organischen Polymeren wie Polytetrafluorethylen (PTFE) reduzieren zwar die Neigung, Ablagerung zu bilden, jedoch führen die bekannten Beschichtungen selbst zu einem bemerkenswerten zusätzlichen Wärmedurchgangswiderstand. Zugleich ist aus Gründen der Haltbarkeit der Schichtdicke eine untere Grenze gesetzt. Ähnliche Probleme werden auch bei Verfahren beobachtet, die die Aufbringung von Monolayer-Silanschichten auf die zu schützende Oberfläche umfassen (Polym. Mater. Sci. and Engineering, Proceedings of the ACS Division of Polymeric Materials Science and Engineering (1990), Band 62, Seiten 259 bis 263).The development of anti-fouling processes has therefore taken on a high priority.
Mechanical solutions have the disadvantage that they are limited to relatively large heat exchangers and also cause considerable additional costs. Chemical additives can lead to an undesirable contamination of the product and sometimes pollute the environment.
For these reasons, possibilities have recently been sought to reduce the tendency to fouling by modifying the heat transfer surfaces. Surface coatings with organic polymers such as polytetrafluoroethylene (PTFE) reduce the tendency to form deposits, but the known coatings themselves lead to a remarkable additional thermal resistance. At the same time, a lower limit is set for reasons of durability of the layer thickness. Similar problems are also observed in processes which involve the application of monolayer silane layers to the surface to be protected (Polym. Mater. Sci. And Engineering, Proceedings of the ACS Division of Polymeric Materials Science and Engineering (1990), volume 62, pages 259 to 263).

Die mit der Verwendung von Polymerbeschichtungen einhergehenden Probleme treten bei einem in WO 97/16692 beschriebenen Verfahren nicht auf. Bei diesem Verfahren wird durch Ionenimplantation oder durch Sputter-Techniken die Hydrophobizität der Oberfläche erhöht. Dies führt zwar zu einer Verringerung der Fouling-Neigung, jedoch ist die Anwendung dieser stets Vakuumtechniken erfordernden Verfahren sehr teuer. Zudem sind die beschriebenen Verfahren nicht geeignet, um schwer zugängliche oder komplex geformte Flächen oder Bauteile mit einer gleichmäßigen Schicht zu vergüten.The problems associated with the use of polymer coatings do not occur in a method described in WO 97/16692. With this The procedure is carried out by ion implantation or by sputtering techniques Surface hydrophobicity increased. This leads to a reduction in A tendency to foul, but the use of these is always vacuum techniques required procedures very expensive. In addition, the methods described are not Suitable for difficult to access or complex shaped surfaces or components to be coated with an even layer.

Bei den Ablagerungen, deren Bildung verhindert werden soll, handelt es sich um anorganische Salze wie Calcium- und Bariumsulfat, Calcium- und Magnesiumcarbonat, anorganische Phosphate, Kieselsäuren und Silicate, Korrosionsprodukte, partikelförmige Ablagerungen, zum Beispiel Schwemmsand (Fluß- und Meerwasser), sowie organische Ablagerungen wie Bakterien, Algen, Proteine, Muscheln bzw. Muschellarven, Polymere, Öle und Harze sowie die biomineralisierten Komposite, die aus den vorgenannten Substanzen bestehen.The deposits whose formation is to be prevented are inorganic salts such as calcium and barium sulfate, calcium and Magnesium carbonate, inorganic phosphates, silicas and silicates, Corrosion products, particulate deposits, for example alluvial sand (River and sea water), as well as organic deposits such as bacteria, algae, Proteins, mussels or mussel larvae, polymers, oils and resins as well as the biomineralized composites consisting of the aforementioned substances.

Aufgabe der vorliegenden Erfindung ist es, ein Verfahren zur Herstellung eines Wärmeüberträgers anzugeben, das einerseits die Neigung der wärmeübertragenden Flächen herabsetzt, Feststoffe unter Bildung von Ablagerungen anzulagern und das andererseits bei hoher Beständigkeit (z.B. gegenüber Wärme, Korrosion und Unterspülung) zu einem vernachlässigbaren Wärmedurchgangswiderstand führt. Dabei sollen die verfahrensgemäß behandelten Flächen eine befriedigende Haltbarkeit aufweisen. Das Verfahren soll auch auf schwer zugängliche Flächen kostengünstig anwendbar sein.The object of the present invention is to provide a method for producing a Specify heat exchanger, on the one hand, the inclination of the reduces heat transfer surfaces, solids to form Deposits and on the other hand with high durability (e.g. against heat, corrosion and undermining) to a negligible Thermal resistance leads. The process should treated surfaces have a satisfactory durability. The procedure is supposed to be cost-effective to use even on hard-to-reach areas.

Die erfindungsgemäße Aufgabe wird gelöst durch ein Verfahren zur Herstellung eines Wärmeüberträgers, gekennzeichnet durch das stromlose chemische Abscheiden einer Metall-Polymer-Dispersionsschicht, bei der das Polymer halogeniert ist, auf einer Wärmeübertragungsoberfläche.
Ein Wärmeüberträger ist im Rahmen der Erfindung eine Vorrichtung, die für den Wärmeaustausch ausgestaltete Flächen (Wärmeübertragungsoberflächen) aufweist. Bevorzugt sind Wärmeüberträger, die Wärme mit Fluiden, insbesondere mit Flüssigkeiten, austauschen.
Heizelemente und Wärmetauscher, insbesondere Plattenwärmetauscher und Spiralwärmetauscher, sind bevorzugte Ausführungen von Wärmeüberträgern.
Ein halogeniertes Polymer ist ein fluoriertes oder ein chloriertes Polymer; bevorzugt sind fluorierte Polymere, insbesondere perfluorierte. Beispiele für perfluorierte Polymere sind Polytetrafluorethylen (PTFE) und Perfluor-Alkoxy-Polymere (PFA, nach DIN 7728, Tl. 1, Jan. 1988).The object of the invention is achieved by a method for producing a heat exchanger, characterized by the electroless chemical deposition of a metal-polymer dispersion layer, in which the polymer is halogenated, on a heat transfer surface.
In the context of the invention, a heat exchanger is a device which has surfaces designed for heat exchange (heat transfer surfaces). Heat exchangers which exchange heat with fluids, in particular with liquids, are preferred.
Heating elements and heat exchangers, in particular plate heat exchangers and spiral heat exchangers, are preferred versions of heat exchangers.
A halogenated polymer is a fluorinated or a chlorinated polymer; fluorinated polymers, in particular perfluorinated, are preferred. Examples of perfluorinated polymers are polytetrafluoroethylene (PTFE) and perfluoroalkoxy polymers (PFA, according to DIN 7728, Part 1, January 1988).

Dieser erfindungsgemäßen Lösung der Aufgabe liegt ein Verfahren zur stromlosen chemischen Abscheidung von Metall-Polymer-Dispersionsphasen zugrunde, das an sich bekannt ist (W. Riedel: Funktionelle Vernickelung, Verlag Eugen Leize, Saulgau, 1989 Seite 231 bis 236, ISBN 3-750480-044-x). Eine Metall-Polymer-Dispersionsphase umfaßt ein Polymer, im Rahmen der Erfindung ein halogeniertes Polymer, das in einer Metall-Legierung dispergiert ist. Bei der Metall-Legierung handelt es sich bevorzugt um eine Metall-Phosphor-Legierung.This object of the invention is a method for Electroless chemical deposition of metal-polymer dispersion phases which is known per se (W. Riedel: Functional nickel plating, publisher Eugen Leize, Saulgau, 1989 pages 231 to 236, ISBN 3-750480-044-x). A Metal-polymer dispersion phase comprises a polymer, in the context of the invention a halogenated polymer dispersed in a metal alloy. In the Metal alloy is preferably a metal-phosphor alloy.

Die bisher zur Verminderung der Inkrustierungsneigung eingesetzten Verfahren führten zu Oberflächen, die größere Rauhigkeit aufwiesen als elektropolierter Stahl (siehe Tabelle 1). Es wurde nun gefunden, daß eine mit einer Verminderung der Rauhigkeit einhergehende Beschichtung den gleichen Zweck erfüllt. The methods previously used to reduce the tendency towards incrustation resulted in surfaces that had greater roughness than electropolished ones Steel (see table 1). It has now been found that one with a diminution the roughness associated coating serves the same purpose.

Außerdem wurde gefunden, daß der Einfluß des Polymeranteils bei der Verminderung der Inkrustierungsneigung entscheidend ist, obwohl der Polymeranteil in der Dispersionsschicht mit 5 bis 30 Vol.% eher gering ist.It was also found that the influence of the polymer content in the Decreasing the incrustation tendency is crucial, though Polymer content in the dispersion layer with 5 to 30 vol.% Is rather low.

Außerdem wurde festgestellt, daß die erfindungsgemäß behandelten Oberflächen einen guten Wärmedurchgang ermöglichen, obwohl die Beschichtungen eine nicht unerhebliche Dicke von 1 bis 100 µm aufweisen können. Die erfindungsgemäß behandelten Oberflächen weisen ferner eine befriedigende Haltbarkeit auf, die auch Schichtdicken von 1 bis 100 µm sinnvoll erscheinen läßt; bevorzugt sind 3 bis 20 µm, insbesondere 5 bis 16 µm. Der Polymeranteil der Dispersionsbeschichtung beträgt 5 bis 30 Vol.%, bevorzugt 15 bis 25 Vol.%, vor allem 19 bis 21 Vol.%. Ferner sind die erfindungsgemäß verwendeten Beschichtungen verfahrensbedingt relativ preiswert und lassen sich auch auf schwer zugängliche Flächen aufbringen. Bei diesen Flächen kann es sich um beliebige Wärmeübertragungsflächen wie Rohrinnenflächen, Oberflächen von elektrischen Heizelementen und Oberflächen von Plattenwärmetauschern etc. handeln, die zur Beheizung oder Kühlung von Fluiden in industriellen Anlagen, in Privathaushalten, bei der Lebensmittelverarbeitung oder in Anlagen zur Stromherstellung bzw. Wasseraufbereitung verwendet werden.It was also found that the surfaces treated according to the invention allow good heat transfer, although the coatings have a can have a not inconsiderable thickness of 1 to 100 µm. The Surfaces treated according to the invention also have a satisfactory Shelf life, which also appear useful from 1 to 100 µm leaves; 3 to 20 μm, in particular 5 to 16 μm, are preferred. The polymer content the dispersion coating is 5 to 30% by volume, preferably 15 to 25% by volume, especially 19 to 21 vol.%. Furthermore, those used according to the invention Due to the process, coatings are relatively inexpensive and can also be opened Apply hard-to-reach areas. These areas can be any heat transfer surfaces such as inner pipe surfaces, surfaces of electrical heating elements and surfaces of plate heat exchangers etc. act for the heating or cooling of fluids in industrial plants, in Private households, in food processing or in plants for Electricity production or water treatment can be used.

"Wärmedurchgang" bezeichnet den Wärmeübergang von dem Inneren des Wärmeüberträgers auf eine ggf. vorhandene, dem Fluid zugewandte Beschichtung, die Wärmeleitung innerhalb der Beschichtungsschicht und den Wärmeübergang von Beschichtungsschicht auf ein Fluid (z.B. eine Salzlösung)."Heat transfer" means the heat transfer from the inside of the Heat exchanger to a possibly existing, facing the fluid Coating, the heat conduction within the coating layer and the Heat transfer from the coating layer to a fluid (e.g. a saline solution).

In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens handelt es sich bei der Metall-Phosphor-Legierung der Metall-Polymer-Dispersionsschicht um Kupfer-Phosphor oder Nickel-Phosphor; bevorzugt ist Nickel-Phosphor. In a preferred embodiment of the method according to the invention it is the metal-phosphorus alloy of the metal-polymer dispersion layer around copper phosphorus or nickel phosphorus; is preferred Nickel-phosphorus.

In einer weiteren Ausführungsform des erfindungsgemäßen Verfahrens handelt es sich bei der Nickel-Polymer-Dispersionsschicht um eine Dispersionsschicht aus Nickel-Phosphor-Polytetrafluorethylen. Es sind aber auch andere fluorierte Polymere geeignet wie Perfluor-Alkoxy-Polymere (PFA, Copolymerisate von Tetrafluorethylen und Perfluoralkoxyvinylether z.B. Perfluorvinylpropylether). Soll der Wärmeüberträger bei vergleichsweise geringer Temperatur betrieben werden, dann ist der Einsatz von chlorierten Polymeren ebenfalls denkbar.In a further embodiment of the method according to the invention the nickel polymer dispersion layer is a dispersion layer Nickel-phosphorus polytetrafluoroethylene. But there are also other fluorinated ones Suitable polymers such as perfluoro-alkoxy polymers (PFA, copolymers of Tetrafluoroethylene and perfluoroalkoxy vinyl ether e.g. Perfluorovinyl propyl ether). Should the heat exchanger be operated at a comparatively low temperature then the use of chlorinated polymers is also conceivable.

In einer weiteren Ausführungsform des erfindungsgemäßen Verfahrens weist die Metall-Polymer-Dispersionsschicht sphärische Polymerpartikel mit einem mittleren Durchmesser (Zahlenmittel) von 0,1 µm bis 1,0 µm, insbesondere von 0,1 µm bis 0,3 µm, auf.In a further embodiment of the method according to the invention, the Metal-polymer dispersion layer with a spherical polymer particle average diameter (number average) from 0.1 µm to 1.0 µm, especially from 0.1 µm to 0.3 µm.

Im Gegensatz zur galvanischen Abscheidung werden bei der chemischen oder autokatalytischen Abscheidung des Nickel-Phosphors die dazu nötigen Elektronen nicht durch eine äußere Stromquelle zur Verfügung gestellt, sondern durch chemische Umsetzung im Elektrolyten selbst erzeugt (Oxidation eines Reduktionsmittels). Die Beschichtung erfolgt durch Eintauchen des Werkstückes in eine Metall-Elektrolytlösung, die mit einer stabilisierten Polymerdispersion zuvor gemischt wurde. Vorzugsweise wird im Anschluß an den Tauchvorgang eine Temperung bei 200 bis 400°, vor allem bei 315 bis 325 °C, durchgeführt. Die Temperierungsdauer beträgt im allgemeinen 5 Minuten bis 3 Stunden, bevorzugt 35 bis 45 Minuten. Als Metallösungen können z.B. handelsübliche Nickelelektrolytlösungen eingesetzt werden, die NiII, Hypophosphit, Carbonsäuren und Fluorid und ggf. Abscheidungsmoderatoren wie Pb2+ enthalten. Solche Lösungen werden zum Beispiel von der Riedel, Galvano- und Filtertechnik GmbH, Halle, Westfalen und der Atotech Deutschland GmbH, Berlin vertrieben. Als Polymer können z.B. handelsübliche Polytetrafluorethylen-Dispersionen (PTFE-Dispersionen) verwandt werden. Bevorzugt werden PTFE-Dispersionen mit einem Feststoffanteil von 35 bis 60 Gew.% und einem mittleren Partikeldurchmesser (Zahlenmittel) von 0,1 µm bis 1 µm, insbesondere von 0,1 µm bis 0,3 µm, eingesetzt, deren Partikel eine sphärische Morphologie aufweisen und die ein neutrales Detergens (zum Beispiel Polyglykole, Alkylphenolethoxylat oder ggf. Gemische aus den genannten Stoffen, 80 bis 120 g neutrales Detergens pro Liter) und ein ionischen Detergens (zum Beispiel Alkyl- und Haloalkylsulfonate, Alkylbenzolsulfonate, Alkylphenolethersulfate, Tetraalkylammoniumsalze oder ggf. Gemische aus den genannten Stoffen, 15 bis 60 g ionisches Detergens pro Liter) enthalten. Typisch sind Tauch-Bäder die einen pH-Wert um 5 aufweisen und etwa 27 g/l NiSO4 x 6 H2O und etwa 21 g/l NaH2PO2 x H2O bei einem PTFE-Gehalt von 1 bis 25 g/l enthalten.
Der Polymeranteil der Dispersionsbeschichtung wird hauptsächlich durch die Menge der zugesetzten Polymerdispersion und die Wahl der Detergentien beeinflußt.In contrast to electrodeposition, chemical or autocatalytic deposition of nickel phosphorus does not provide the electrons required for this through an external power source, but rather through chemical conversion in the electrolyte itself (oxidation of a reducing agent). The coating is done by immersing the workpiece in a metal electrolyte solution that has been mixed with a stabilized polymer dispersion beforehand. An annealing at 200 to 400 °, especially at 315 to 325 ° C, is preferably carried out after the dipping process. The tempering period is generally 5 minutes to 3 hours, preferably 35 to 45 minutes. For example, commercially available nickel electrolyte solutions which contain Ni II , hypophosphite, carboxylic acids and fluoride and optionally deposition moderators such as Pb 2+ can be used as metal solutions. Such solutions are sold, for example, by Riedel, Galvano- und Filtertechnik GmbH, Halle, Westphalia and Atotech Deutschland GmbH, Berlin. For example, commercially available polytetrafluoroethylene dispersions (PTFE dispersions) can be used as the polymer. PTFE dispersions with a solids content of 35 to 60% by weight and an average particle diameter (number average) of 0.1 μm to 1 μm, in particular of 0.1 μm to 0.3 μm, are preferred, the particles of which have a spherical morphology and which have a neutral detergent (for example polyglycols, alkylphenol ethoxylate or possibly mixtures of the substances mentioned, 80 to 120 g of neutral detergent per liter) and an ionic detergent (for example alkyl and haloalkyl sulfonates, alkylbenzenesulfonates, alkylphenol ether sulfates, tetraalkylammonium salts or optionally Mixtures of the substances mentioned, 15 to 60 g of ionic detergent per liter). Dip baths with a pH of around 5 and about 27 g / l NiSO 4 x 6 H 2 O and about 21 g / l NaH 2 PO 2 x H 2 O with a PTFE content of 1 to 25 g are typical / l included.
The polymer content of the dispersion coating is mainly influenced by the amount of polymer dispersion added and the choice of detergents.

Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung eines Wärmeüberträgers, der eine besonders haftfeste, haltbare und wärmebeständige Beschichtung aufweist und deshalb die erfindungsgemäße Aufgabe in besonderer Weise löst.
Dieses Verfahren geht aus von einem Verfahren zur Herstellung eines Wärmeüberträgers, gekennzeichnet durch das stromlose chemische Abscheiden einer Metall-Polymer-Dispersions-Beschichtung, bei der das Polymer halogeniert ist, auf eine Wärmeübertragungsoberfläche.
Dieses Verfahren ist zusätzlich dadurch gekennzeichnet, daß vor dem Aufbringen der Metall-Polymer-Dispersionsschicht eine 1 bis 15 µm dicke Metall-Phosphor-Schicht durch stromloses chemisches Abscheiden aufgebracht wirdAnother object of the invention is a method for producing a heat exchanger, which has a particularly adhesive, durable and heat-resistant coating and therefore solves the problem of the invention in a special way.
This method is based on a method for producing a heat exchanger, characterized by the electroless chemical deposition of a metal-polymer dispersion coating, in which the polymer is halogenated, on a heat transfer surface.
This method is additionally characterized in that a 1 to 15 µm thick metal-phosphor layer is applied by electroless chemical deposition before the metal-polymer dispersion layer is applied

Das stromlose chemische Aufbringen einer 1 bis 15 µm dicken Metall-Phosphor-Schicht zur Haftverbesserung erfolgt durch die schon beschriebenen Metall-Elektrolytbäder, denen jedoch in diesem Fall keine stabilisierte Polymer-Dispersion zugesetzt wird. Auf eine Temperung wird zu diesem Zeitpunkt vorzugsweise verzichtet, da diese die Haftfähigkeit der nachfolgenden Metall-Polymer-Dispersionsschicht im allgemeinen negativ beeinflußt. Nach Abscheidung der Metall-Phosphor-Schicht wird das Werkstück in das oben beschriebene Tauchbad gebracht, das neben dem Metall-Elektrolyt auch eine stabilisierte Polymer-Dispersion umfaßt. Hierbei bildet sich die Metall-Polymer-Dispersionsschicht. Vorzugsweise wird anschließend eine Temperung bei 200 bis 400°, insbesondere bei 315 bis 325 °C, durchgeführt. Die Temperierungsdauer beträgt im allgemeinen 5 Minuten bis 3 Stunden, bevorzugt 35 bis 45 Minuten.Electroless chemical application of a 1 to 15 µm thick metal-phosphor layer to improve adhesion takes place through the already described metal electrolyte baths, but in this case no stabilized polymer dispersion is added. On tempering at this time preferably dispensed with, since this adversely affects the adhesion of the subsequent metal-polymer dispersion layer generally adversely affected. To Deposition of the metal-phosphor layer will place the workpiece in the top brought immersion bath, which in addition to the metal electrolyte also a stabilized polymer dispersion. This forms the metal-polymer dispersion layer. Subsequently, an annealing at 200 to 400 °, in particular at 315 to 325 ° C, performed. The tempering period is generally 5 minutes to 3 hours, preferably 35 to 45 minutes.

In einer weiteren Ausführungsform des erfindungsgemäßen Verfahrens weist die Metall-Phosphor-Schicht eine Dicke von 1 bis 5 µm auf.In a further embodiment of the method according to the invention, the Metal-phosphor layer on a thickness of 1 to 5 microns.

In einer weiteren Ausführungsform der erfindungsgemäßen Verfahren handelt es sich bei der Metall-Phosphor-Legierung der Metall-Polymer-Dispersionsschicht und der Metall-Phosphor-Schicht um Nickel-Phosphor oder Kupfer-Phosphor.In a further embodiment of the method according to the invention, it is the metal-phosphor alloy of the metal-polymer dispersion layer and the metal-phosphor layer around nickel-phosphorus or copper-phosphorus.

In einer weiteren Ausführungsform des erfindungsgemäßen Verfahrens handelt es sich bei der Metall-Polymer-Dispersionsschicht um eine Dispersionsschicht aus Nickel-Phosphor-Polytetrafluorethylen.In a further embodiment of the method according to the invention the metal-polymer dispersion layer is a dispersion layer Nickel-phosphorus polytetrafluoroethylene.

Ein weiterer Gegenstand der Erfindung ist ein durch ein erfindungsgemäßes Verfahren herstellbarer Wärmeüberträger. Vorzugsweise erfolgt die Herstellung des erfindungsgemäßen Wärmeüberträgers durch Anwendung eines erfindungsgemäßen Verfahrens.Another object of the invention is one by an inventive Method of producing heat exchangers. Production is preferably carried out of the heat exchanger according to the invention by using a inventive method.

In einer weiteren Ausführungsform ist der vorgenannte erfindungsgemäße Wärmeüberträger zur Übertragung von Wärme auf Fluide, insbesondere auf Flüssigkeiten, ausgestaltet. Hierbei kommen alle Heizelemente in Frage, die Wärme auf Fluide übertragen. Ferner sind Wärmetauscher, insbesondere Plattenwärmetauscher und Spiralwärmetauscher, bevorzugte Beispiele solcher Wärmeüberträger. In a further embodiment, the aforementioned is according to the invention Heat exchangers for transferring heat to fluids, in particular to Liquids, designed. All heating elements come into question here Transfer heat to fluids. Furthermore, heat exchangers, in particular Plate heat exchangers and spiral heat exchangers, preferred examples of such Heat exchangers.

Ein weiterer Gegenstand der Erfindung ist die Verwendung einer Beschichtung, hergestellt durch das stromlose chemische Abscheiden einer Metall-Polymer-Dispersionsschicht, bei der das Polymer halogeniert ist, zur Verringerung der Neigung der beschichteten Flächen, Feststoffe aus Fluiden unter Bildung von Ablagerungen anzulagern. Bei den Fluiden handelt es sich bevorzugt um Flüssigkeiten. Die Ablagerungen, deren Bildung erfindungsgemäß verhindert wird, sind bereits beschrieben worden.Another object of the invention is the use of a coating, produced by electroless chemical deposition of a metal-polymer dispersion layer, where the polymer is halogenated to reduce the Inclination of the coated surfaces, solids from fluids to form To deposit deposits. The fluids are preferably Liquids. The deposits, the formation of which prevents according to the invention have already been described.

Einige Vorteile der erfindungsgemäßen Wärmeüberträger bzw. deren Beschichtungen werden durch die anliegende Zeichnung aufgezeigt. Es zeigt

Fig. 1
die zeitliche Veränderung des Wärmedurchgangskoeffizienten durch die Grenzschicht unter Einbeziehung einer ggf. vorhandenen Beschichtungsschicht bei Kontakt von verschiedenen Wärmetauscherflächen mit einer siedenden Salzlösung.
Fig. 2
die zeitliche Veränderung des Wärmedurchgangskoeffizienten durch die Grenzschicht unter Einbeziehung einer ggf. vorhandenen Beschichtungsschicht bei Kontakt von verschiedenen Wärmetauscherflächen mit einer vorbeiströmenden warmen Salzlösung.
Some advantages of the heat exchangers according to the invention or their coatings are shown by the attached drawing. It shows
Fig. 1
the change over time of the heat transfer coefficient through the boundary layer, including any coating layer that may be present when different heat exchanger surfaces come into contact with a boiling salt solution.
Fig. 2
the change over time of the heat transfer coefficient through the boundary layer, including any coating layer that may be present when different heat exchanger surfaces come into contact with a warm saline solution flowing past.

Fig. 1 zeigt die Abnahme des Wärmedurchgangskoeffizienten (α [W/m2K]) infolge von CaSO4-Ablagerungen als Funktion der Zeit (t [min], Abszisse) für verschiedene Wärmeüberträger, die sich in der Beschaffenheit ihrer Oberflächen unterscheiden. Die Bezugsziffer 1 verweist auf die Meßwerte der erfindungsgemäßen Beschichtung des Beispiels (*7), Die Bezugsziffer 2 bezeichnet die Meßwerte für eine elektropolierte Stahloberfläche. Die flächenbezogene Leistung beträgt 200 kW/m2, die Konzentration der CaSO4-Lösung beträgt 1,6 g/l und weist eine Temperatur auf, die dem Siedepunkt entspricht.Fig. 1 shows the decrease in the heat transfer coefficient (α [W / m 2 K]) due to CaSO 4 deposits as a function of time (t [min], abscissa) for different heat exchangers, which differ in the nature of their surfaces. Reference number 1 refers to the measured values of the coating according to the invention of example (* 7). Reference number 2 denotes the measured values for an electropolished steel surface. The area-related output is 200 kW / m 2 , the concentration of the CaSO 4 solution is 1.6 g / l and has a temperature that corresponds to the boiling point.

Fig. 2 zeigt die gemessene Abnahme des Wärmedurchgangskoeffizienten (α [W/m2K]) infolge von CaSO4-Ablagerungen als Funktion der Zeit (t [min], Abszisse) für verschiedene Wärmeüberträger, die sich in der Beschaffenheit ihrer Oberflächen unterscheiden. Bei der Bezugsziffer 1 handelt es sich um die erfindungsgemäße Beschichtung des Beispiels (*7). Die Bezugsziffer 3 verweist auf eine unbehandelte Stahloberfläche. Die auf die Fläche des Wärmeüberträgers bezogene Leistung beträgt 100 kW/m2. Eine CaSO4-Lösung einer Konzentration von 2,5 g/l strömt mit einer Geschwindigkeit von 80 cm/s und einer Temperatur von 80°C an dem Wärmeüberträger vorbei.Fig. 2 shows the measured decrease in the heat transfer coefficient (α [W / m 2 K]) due to CaSO 4 deposits as a function of time (t [min], abscissa) for different heat exchangers, which differ in the nature of their surfaces. Reference number 1 is the coating according to the invention of example (* 7). The reference number 3 indicates an untreated steel surface. The power based on the area of the heat exchanger is 100 kW / m 2 . A CaSO 4 solution with a concentration of 2.5 g / l flows past the heat exchanger at a speed of 80 cm / s and a temperature of 80 ° C.

Beispielexample

In Laboruntersuchungen wurden die Vorteile der erfindungsgemäß beschichteten Heizflächen gegenüber entsprechend unbeschichteten Heizflächen, elektropolierten Flächen und ionen-implantierten bzw. gesputterten Flächen ermittelt. Tabelle 1 enthält einen Vergleich der Meßwerte von Oberflächenrauhigkeit, Oberflächenenergie und Benetzungswinkel der untersuchten Heizflächen, sowie die relative Abnahme der gemessenen Wärmedurchgangskoeffizienten innerhalb der ersten 100 Stunden Versuchsdauer. Es zeigt sich, daß die erfindungsgemäßen Wärmeüberträger eine sehr geringen Oberflächenenergie, einen sehr großen Randwinkel und ein sehr gutes Wärmeübertragungsverhalten liefert. Oberflächenenergie [mJ/m2] * Randwinkel [°] ** Rauhigkeit, µm **** α100/α0 *** unbehandelt (Stahl) 84 65 0,14 0,4 Stahl elektropoliert 86 62 0,08 0,65 Stahl Si-Ionenimplantiert *5 39 80 0,14 0,75 Stahl F-Ionenimplantiert *5 37 82 0,14 0,9 Stahl DLC―gesputtert *6 36 85 0,13 0,85 Stahl TiNF―gesputtert *6 34 87 0,14 0,9 Stahl / Ni-PTFE *7 25 100 0,1 0,9 The advantages of the heating surfaces coated according to the invention compared to correspondingly uncoated heating surfaces, electropolished surfaces and ion-implanted or sputtered surfaces were determined in laboratory tests. Table 1 contains a comparison of the measured values of surface roughness, surface energy and wetting angle of the examined heating surfaces, as well as the relative decrease in the measured heat transfer coefficients within the first 100 hours of the test. It can be seen that the heat exchangers according to the invention provide a very low surface energy, a very large contact angle and very good heat transfer behavior. Surface energy [mJ / m 2 ] * Contact angle [°] ** Roughness, µm **** α 100 / α 0 *** untreated (steel) 84 65 0.14 0.4 Electropolished steel 86 62 0.08 0.65 Steel Si ion implanted * 5 39 80 0.14 0.75 Steel F-ion implanted * 5 37 82 0.14 0.9 Steel DLC ― sputtered * 6 36 85 0.13 0.85 Steel TiNF ― sputtered * 6 34 87 0.14 0.9 Steel / Ni-PTFE * 7 25 100 0.1 0.9

In Tabelle 2 werden Oberflächenenergie, Randwinkel und pro Fläche abgelagerte Bakterien (Streptococcus Thermophilus) der erfindungsgemäßen Wärmeüberträger mit den Wärmeüberträgern des Standes der Technik verglichen. Oberflächenenergie [mJ/m2] Randwinkel [°] Log10 Zellen/cm2 *9 unbehandelt (Stahl) 84 65 5,7 Stahl elektropoliert 86 62 5,5 Stahl Si-Ionenimplantiert 39 80 4,9 Stahl F-Ionen-implantiert 37 82 5,5 Stahl DLC -gesputtert 36 85 5,0 Stahl CrC-gesputtert 34 87 4,1 Stahl / Ni-PTFE 25 100 3,9 Konzentration [g/l] pH NiSO4x6H2O 27 4,8 NaH2PO2xH2O 21 CH3CHOHCOOH 20 C2H5COOH 3 NaCitrat; 5 NaF 1 PTFE (50%) 2-50 Table 2 compares surface energy, contact angle and bacteria deposited per area (Streptococcus Thermophilus) of the heat exchangers according to the invention with the heat exchangers of the prior art. Surface energy [mJ / m 2 ] Contact angle [°] Log10 cells / cm 2 * 9 untreated (steel) 84 65 5.7 Electropolished steel 86 62 5.5 Steel implanted with Si ions 39 80 4.9 F-ion implanted steel 37 82 5.5 Steel DLC sputtered 36 85 5.0 Steel CrC sputtered 34 87 4.1 Steel / Ni-PTFE 25 100 3.9 Concentration [g / l] pH NiSO 4 x6H 2 O 27 4.8 NaH 2 PO 2 xH 2 O 21 CH 3 CHOHCOOH 20 C 2 H 5 COOH 3 Na citrate; 5 NaF 1 PTFE (50%) 2-50

Claims (7)

  1. A process for the production of a heat transfer device for exchange of heat with fluids, characterized in that
    a) a metal/phosphorus layer with a thickness of from 1 to 5 µm is applied to a heat transfer surface by electroless chemical deposition, and
    b) a metal/polymer dispersion layer in which the polymer is halogenated is subsequently applied by electroless chemical deposition atop the metal/phosphorus layer produced under a), the polymer content in the metal/polymer dispersion layer being from 5 to 30% by volume.
  2. A process as claimed in claim 1, characterized in that the metal/phosphorus alloy of the metal/polymer dispersion layer and of the metal/phosphorus layer is nickel/phosphorus or copper/phosphorus, preferably nickel/phosphorus.
  3. A process as claimed in claim 1 or 2, characterized in that the metal/polymer dispersion layer is a dispersion layer of nickel/phosphorus/polytetrafluoroethylene.
  4. A process as claimed in any of claims 1 to 3, characterized in that the polymer content in the metal/polymer dispersion layer is from 15 to 25% by volume and especially from 19 to 21% by volume.
  5. A process as claimed in any of claims 1 to 4, characterized in that the metal/polymer dispersion layer comprises spherical polymer particles having a mean diameter of from 0.1 µm to 0.3 µm.
  6. A heat transfer device which is produced by the process of any of claims 1 to 5.
  7. The use of a coating produced by the process of any of claims 1 to 5, for reducing the tendency of the coated surfaces to accumulate solids from fluids, causing fouling.
EP99964672A 1998-12-30 1999-12-24 Heat exchanger with a reduced tendency to produce deposits and method for producing same Expired - Lifetime EP1144724B1 (en)

Applications Claiming Priority (3)

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DE19860526A DE19860526A1 (en) 1998-12-30 1998-12-30 Heat exchangers with reduced tendency to form deposits and processes for their production
DE19860526 1998-12-30
PCT/EP1999/010368 WO2000040773A2 (en) 1998-12-30 1999-12-24 Heat exchanger with a reduced tendency to produce deposits and method for producing same

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EP1144724B1 true EP1144724B1 (en) 2002-11-06

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US (3) US6617047B1 (en)
EP (3) EP1144725B1 (en)
JP (3) JP2002534606A (en)
KR (3) KR20010100013A (en)
CN (3) CN1636305A (en)
AT (3) ATE227360T1 (en)
CA (2) CA2358099A1 (en)
DE (4) DE19860526A1 (en)
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DE59906313D1 (en) 2003-08-21
JP2002534605A (en) 2002-10-15
DE59903362D1 (en) 2002-12-12
WO2000040775A3 (en) 2000-11-09
JP2002534606A (en) 2002-10-15
ATE237006T1 (en) 2003-04-15
WO2000040773A3 (en) 2000-11-09
EP1144723B1 (en) 2003-04-09
US6513581B1 (en) 2003-02-04
CA2358097A1 (en) 2000-07-13
KR20010100013A (en) 2001-11-09
KR20010103724A (en) 2001-11-23
WO2000040774A3 (en) 2002-09-26
DE59905005D1 (en) 2003-05-15
DE19860526A1 (en) 2000-07-06
WO2000040773A2 (en) 2000-07-13
ATE227360T1 (en) 2002-11-15
JP2003511551A (en) 2003-03-25
KR20010100009A (en) 2001-11-09
CN1338008A (en) 2002-02-27
ES2197710T3 (en) 2004-01-01
US6617047B1 (en) 2003-09-09
EP1144725A2 (en) 2001-10-17
ES2204184T3 (en) 2004-04-16
CA2358099A1 (en) 2000-07-13
CN1332810A (en) 2002-01-23
US6509103B1 (en) 2003-01-21
CN1636305A (en) 2005-07-06
EP1144723A3 (en) 2002-11-13
EP1144723A2 (en) 2001-10-17
WO2000040774A2 (en) 2000-07-13
EP1144724A2 (en) 2001-10-17
ATE245210T1 (en) 2003-08-15
WO2000040775A2 (en) 2000-07-13

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