Classifications

• • 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, which comprises the electroless chemical deposition of a metal-polymer dispersion layer.
• the invention further relates to heat exchangers according to the invention.
• the invention further relates to the use of a metal-polymer dispersion layer as a permanent incrustation inhibitor.
• Heat exchangers are limited and also cause considerable additional costs.
• 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, which consist 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, which consist of the aforementioned substances.
• the object of the present invention is to provide a method for producing a heat exchanger which, on the one hand, reduces the tendency of the heat-transferring surfaces to deposit solids with the formation of deposits and, on the other hand, is negligible with high resistance (for example to heat, corrosion and undermining) Thermal resistance leads.
• the surfaces treated according to the process should have a satisfactory durability.
• the method should also be cost-effective to use on hard-to-reach areas.
• 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.
• 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
• 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 perfluoro-alkoxy
• a metal-polymer dispersion phase comprises a polymer, in the context of the invention a halogenated polymer which is dispersed in a metal alloy.
• the metal alloy is preferably a metal-phosphor alloy.
• the surfaces treated according to the invention enable good heat transfer, although the coatings can have a not inconsiderable thickness of 1 to 100 ⁇ m.
• the surfaces treated according to the invention also have a satisfactory durability, which also makes layer thicknesses of 1 to 100 ⁇ m appear reasonable; 3 to 20 ⁇ m, in particular 5 to 16 ⁇ m, are preferred.
• the polymer content of the dispersion coating is 5 to 30% by volume, preferably 15 to 25% by volume, especially 19 to 21% by volume.
• the coatings used according to the invention are relatively inexpensive due to the process and can also be applied to hard-to-reach areas.
• These surfaces can be any heat transfer surfaces, such as inner pipe surfaces, surfaces of electrical heating elements and surfaces of plate heat exchangers, etc., which are used for heating or cooling fluids in industrial plants, in private households, in food processing or in plants for power production or water treatment become.
• Heat transfer refers to the heat transfer from the interior of the heat exchanger to an optionally present coating facing the fluid, 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 is copper-phosphorus or nickel-phosphorus; nickel phosphorus is preferred.
• the nickel polymer dispersion layer is a dispersion layer made of nickel-phosphorus-polytetrafluoroethylene.
• fluorinated polymers are also suitable, such as perfluoroalkoxy polymers (PFA, copolymers of tetrafluoroethylene and perfluoroalkoxy vinyl ether, for example perfluorovinyl propyl ether). If the heat exchanger is to be operated at a comparatively low temperature, the use of chlorinated polymers is also conceivable.
• the metal-polymer dispersion layer has spherical polymer particles with an average diameter (number average) of 0.1 ⁇ m to 1.0 ⁇ m, in particular of 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.
• nickel electrolyte solutions which contain Ni 11 , 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 are preferred Particle diameter (number average) from 0.1 ⁇ m to 1 ⁇ m, in particular from 0.1 ⁇ m to 0.3 ⁇ m, is used, the particles of which have a spherical morphology and which have a neutral detergent (for example polyglycols, alkylphenol ethoxylate or, if appropriate, 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,
• a neutral detergent for example polyglycols, alkylphenol ethoxylate or, if appropriate, mixtures of the substances mentioned, 80 to 120 g of neutral detergent per liter
• an ionic detergent for example alkyl and haloalkyl sulfonates, alkylbenzen
• 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 according to 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
• the electroless chemical application of a 1 to 15 ⁇ m thick metal-phosphor layer to improve adhesion takes place through the metal electrolyte baths already described, to which, however, no stabilized polymer dispersion is added in this case.
• Tempering is preferably dispensed with at this point in time, since this affects the adherence of the subsequent metal Polymer dispersion layer generally adversely affected.
• the workpiece is placed in the immersion bath described above, which in addition to the metal electrolyte also comprises a stabilized polymer dispersion. This forms the metal-polymer dispersion layer.
• Annealing is then preferably carried out at 200 to 400 ° C., in particular at 315 to 325 ° C.
• the tempering period is generally 5 minutes to 3 hours, preferably 35 to 45 minutes.
• the metal-phosphor layer has a thickness of 1 to 5 ⁇ m.
• the metal-phosphorus alloy of the metal-polymer dispersion layer and the metal-phosphorus layer is nickel-phosphorus or copper-phosphorus.
• the metal-polymer dispersion layer is a dispersion layer made of nickel-phosphorus-polytetrafluoroethylene.
• Another object of the invention is a heat exchanger that can be produced by a method according to the invention.
• the heat exchanger according to the invention is preferably produced by using a method according to the invention.
• the aforementioned heat exchanger according to the invention is designed to transfer heat to fluids, in particular to liquids. All heating elements that transfer heat to fluids can be used. Furthermore, heat exchangers, in particular plate heat exchangers and spiral heat exchangers, are preferred examples of such heat exchangers.
• Another object of the invention is the use of a coating, produced by the electroless chemical deposition of a metal-polymer dispersion layer, in which the polymer is halogenated, to reduce the tendency of the coated surfaces to deposit solids from fluids with the formation of deposits.
• the fluids are preferably liquids. The deposits, the formation of which is prevented according to the invention, have already been described.
• Fig. 1 shows the change over time in the heat transfer coefficient through the boundary layer, including any existing
• Heat exchanger surfaces with a boiling salt solution are heat exchanger surfaces with a boiling salt solution.
• Fig. 2 shows the change over time in the heat transfer coefficient by
• Boundary layer including a possibly existing coating layer when different ones come into contact
• the reference number 1 shows the decrease in the heat transfer coefficient ( ⁇ [W / m 2 K]) as a result of CaSO 4 deposits as a function of time (t [min], abscissa) for different heat exchangers which differ in the nature of their surfaces.
• the reference number 1 refers to the measured values of the coating according to the invention of example (* 7).
• the reference number 2 designates the measured values for an electropolished steel surface.
• the area-related power is 200 kW / m 2
• the concentration of the CaSO - Solution is 1.6 g / 1 and has a temperature that corresponds to the boiling point.
• Reference number 1 is the coating according to the invention of example (* 7).
• the reference number 3 indicates an untreated steel surface.
• the power related to the surface of the heat exchanger is 100 kW / m.
• a CaSO 4 solution with a concentration of 2.5 g / 1 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 heating surfaces examined, 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 1:
• Table 2 compares surface energy, contact angle and bacteria deposited per surface (Streptococcus Thermophilus) of the heat exchangers according to the invention with the heat exchangers of the prior art.
• Ni-phosphor-PTFE dispersion coating was then produced in an immersion bath, consisting of a mixture of a chemically electroless nickel electrolyte solution and a detergent-stabilized PTFE Dispersion.
• the deposition of nickel-phosphorus-polytetrafluoroethylene was carried out at 87 to 89 ° C, that is below 90 ° C and at a pH of the electrolyte solution of 4.6 to 5.0.
• the deposition rate was 10 ⁇ m h, the layer thickness 15 ⁇ m.
• the composition of the electroless nickel electrolyte PTFE solution is shown in Table 3.
• Electroless nickel electrolyte solutions are commercially available (Riedel, Galvano- und Filtertechnik GmbH, Halle, Westphalia and Atotech GmbH, Berlin). After the nickel-phosphorus-PTFE layer had been applied, the workpiece was annealed at 300 ° C. for 20 minutes. The proportion of polymer and phosphorus in the dispersion layer was 20% by volume of PTFE, corresponding to 6% by weight of PTFE and 7% of phosphorus.
• the PTFE dispersions are commercially available.
• the solids content and average particle size were 50% by weight and 0.2 ⁇ m, respectively.
• the dispersion was made using a neutral detergent (50 g / 1 alkylphenol ethoxylate from the Lutensol® brand, 50 g / 1 alkylphenol ethoxylate from the Emulan® brand, both detergents are manufactured by BASF AG, Ludwigshafen) and an ionic detergent (15 g / 1 alkylsulfonate from the brand) Lutensit®, BASF AG, Ludwigshafen, 8 g / 1 perfluoro-C 3 -C 8 -alkyl sulfonate of the brand Zonyl®, DuPont, Wilmington, USA) stabilized.
• the concentration specification 2-50 g / 1 refers to the amount of dispersion solution added.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (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)
• Processes Of Treating Macromolecular Substances (AREA)
• Pretreatment Of Seeds And Plants (AREA)
• Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
• Laminated Bodies (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
• Separation By Low-Temperature Treatments (AREA)
• Paints Or Removers (AREA)

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• 1998
  • 1998-12-30 DE DE19860526A patent/DE19860526A1/de not_active Withdrawn
• 1999
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  • 1999-12-24 AT AT99965554T patent/ATE245210T1/de not_active IP Right Cessation
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