EP0679853A1 - Coating for end plates and heat exchanger tubes for cooling medium - Google Patents
Coating for end plates and heat exchanger tubes for cooling medium Download PDFInfo
- Publication number
- EP0679853A1 EP0679853A1 EP94106304A EP94106304A EP0679853A1 EP 0679853 A1 EP0679853 A1 EP 0679853A1 EP 94106304 A EP94106304 A EP 94106304A EP 94106304 A EP94106304 A EP 94106304A EP 0679853 A1 EP0679853 A1 EP 0679853A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- coolant
- tube
- tube sheet
- layer
- 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.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 165
- 239000011248 coating agent Substances 0.000 title claims abstract description 156
- 239000002826 coolant Substances 0.000 title claims abstract description 73
- 239000004033 plastic Substances 0.000 claims abstract description 21
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 239000006223 plastic coating Substances 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000003082 abrasive agent Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000005422 blasting Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims 2
- 239000000843 powder Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 description 22
- 230000007797 corrosion Effects 0.000 description 22
- 230000007704 transition Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 231100000241 scar Toxicity 0.000 description 5
- 208000032544 Cicatrix Diseases 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 239000004848 polyfunctional curative Substances 0.000 description 4
- 230000037387 scars Effects 0.000 description 4
- 241000195493 Cryptophyta Species 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 229920006360 Hostaflon Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010002 mechanical finishing Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- F28F19/04—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of rubber; of plastics material; of varnish
Definitions
- the invention relates to a coating for tube sheets and coolant tubes for heat exchangers, in particular steam condensers, based on hardening plastic mixtures, which are cleaned by cleaning the surfaces provided for coating with the aid of abrasive agents; Closing the pipe inlets and outlets with removable plugs; Applying at least one layer of a hardening plastic coating to the tube sheet; Allowing the coating to harden so that further mechanical processing can take place and processing the surface; Removing the plugs from the pipe inlets and outlets and introducing at least one layer of a hardening plastic coating at least into the entrance area of the coolant pipes and allowing them to harden; is available, as well as a method for coating tube sheets and coolant tubes of steam condensers.
- tube sheets of steam condensers such as are used, for example, in plants for generating electrical energy, with a plastic coating in order to counteract signs of corrosion.
- Pipe trays and the coolant pipes emanating from them are exposed to a large number of external influences, in particular mechanical, chemical and electromechanical stresses. Mechanical stress occurs due to solid particles entrained by the coolant, such as sand.
- the temperature difference between the cooling medium and the steam to be condensed which can exceed 100 ° C., causes expansion in the roll-in area of the coolant tubes on the tube plate.
- Electrochemical or galvanic corrosion is the one that occurs due to the formation of galvanic elements at metallic interfaces, in particular at the transitions from the tube sheet to the coolant tube, and which are strongly promoted by electrically conductive liquids, such as sea water.
- the functionality of a tube sheet is impaired by the deposition of undesirable substances, algae formation, etc. on its surface, which are promoted in particular by roughness, such as that caused by corrosion.
- the signs of corrosion and deposits accelerate with the age of a tube sheet, because there are increasing starting points for corrosion and deposits.
- the invention has for its object to provide tube sheets and adjacent coolant tube inlets and outlets with a coating that integrates both, which provides long-term resistance to the mechanical stresses acting at the transition points and at the same time is suitable for chemical stresses caused by the Resist coolant in the long term.
- This object is achieved with a coating of the type mentioned at the outset, in which the coating of the coolant tubes is reactively connected to the tube sheet coating by means of a time-coordinated application, and in which the coating of the coolant tubes has a greater elasticity than the tube sheet coating with an at least 2% , based on the elongation at break of the tube sheet coating, has greater elongation at break according to DIN 53152.
- the timing of the coating processes on the tube sheet and in the coolant tubes it is achieved that crosslinking occurs across the coating limits from the coating in the tubes to the coating on the tube sheet, so that a particularly resilient chemical bond is given.
- the relatively greater elasticity of the coolant pipe coating results in better resistance to mechanical stress in the entrance and exit area of the pipes, where there is galvanic corrosion. It has been shown that an increase in the elongation at break by 2% according to DIN 53152 is generally sufficient to bring about an improvement in the coating composite, with an elongation at break of the tube sheet coating of less than 5% and that of the coolant tube coating of less than 10%. is assumed to ensure the hardness, abrasion resistance and compressive strength required for the durability of the coating. On the other hand, the elongation at break should not be less than 2% for the tube sheet coating in order to avoid brittleness.
- each layer on the still reactive surface of the underlying one Layer is applied to achieve chemical crosslinking.
- two or three layers are applied both to the tube sheet and in the coolant tubes, which can be colored differently in order to be able to check the remaining layer thickness on the basis of the color during inspections which take place from time to time.
- the minimum layer thickness of the entire coating for the inner coating of the tubes is at least about 80 ⁇ m and for the tube sheet at least 2000 ⁇ m. Layer thicknesses of 20 mm and more are easily possible without sacrificing strength. This is a particular advantage when it comes to coating heavily corroded tube sheets that have deep corrosion scars.
- the cleaned surfaces of the tube sheet and the coolant tubes with a primer before the actual coating is applied, which is generally sprayed on with a lower viscosity and penetrates into corrosion cavities and scars. As a result, the surfaces are leveled, better adaptation to unevenness and overall better adhesion of the actual coating.
- the actual coating on the surface can additionally be provided with a seal, in order in particular to achieve a smoother surface which prevents the adherence of algae, dirt particles and the like. The like prevented.
- the seal in the tube sheet area is preferably set to be more elastic than the tube sheet coating, whereby it should comply with the elongation at break values indicated above for the coolant tube coatings. In general, it is advisable to provide two primer and two sealing layers. Sealing in the pipe area is generally not necessary.
- Preferred materials for the coating according to the invention are cold-curing epoxy resins which are processed together with an amine hardener. These resin compositions contain common fillers and dyes, adjusting agents, stabilizers and. a. Common additives to ensure the properties you want, especially processability and durability. These are customary plastic blends, as they can also be used for other purposes - the decisive factor for the coating according to the invention is less the type of the hardening plastic mass than its corrosion resistance and elasticity after curing. In addition to epoxy resins, other cold-curing plastic mixtures that meet these requirements can also be used. However, epoxy / amine systems are preferred for the purposes of the invention.
- the plastic mixtures used for the tube sheets and in particular the coolant tubes expediently contain a proportion of powdered polytetrafluoroethylene (PTFE) in an amount of at least about 5% by weight in order to achieve the desired elasticity and strength values. It has been shown that an addition of PTFE in the range from 5 to 20% by weight, in particular about 10% by weight, significantly improves the durability of the coating in the area of the pipe entries and exits.
- PTFE additive for example Hostaflon (R) from Hoechst, should have a grain size of ⁇ 50 ⁇ m and in particular in the range from 10 to 30 ⁇ m. It forms a matrix that fills, stabilizes and improves the elasticity and in particular also serves to set the desired elasticity.
- a content of> 30% by weight of mineral additives in the mixture is expedient.
- the coatings according to the invention have shown that they have to meet certain criteria with regard to their mechanical strength.
- the hardness of the coating finally achieved should reach a value of at least about 75 according to DIN 53153 (Barcol hardness), preferably at least 80.
- a value of at least about 95 is appropriate for the tube sheet coating.
- the adhesive strength of the coating on the substrate should be at least about 4 N / mm2 according to DIN / ISO 4624, preferably at least about 5 N / mm2 and in particular at least 7 N / mm2. According to the invention, adhesive strengths of more than 10 / mm2 for the tube sheet coating and more than 5 N / mm2 for the coolant tube coating and primer are achieved.
- the compressive strength and abrasion resistance are essential for the stability of the coatings according to the invention.
- values of more than 50 N / mm2 for the coolant tube coating and more than 100 N / mm2 for the tube sheet coating should be achieved, with the abrasion resistance according to DIN 53233 (case A) values of more than 40 mg or more than 55 mg .
- the invention further relates to a method for applying the coating described above, in which the surfaces intended for coating are first cleaned with the aid of abrasive agents, the tube inlets and outlets are closed by removable plugs, at least one layer of a hardening plastic coating on the tube sheet is applied, the coating is allowed to harden so that further mechanical processing can take place, but reactive spots remain on the surface, after which the surface is processed mechanically.
- the tube plugs are then removed from the tube inlets and outlets and at least one layer of a hardening plastic coating is introduced at least into the entrance area of the coolant tubes, forming a reactive connection with the tube sheet coating, the plastic mixtures being selected such that the coolant tube coating is one in comparison to the tube sheet coating greater elasticity with an elongation at break greater by at least 2%, based on the elongation at break of the tube sheet coating according to DIN 53152.
- the surfaces provided for the coating are thoroughly abrasively cleaned in order to create a firm and uniform surface.
- the mass intended for the tube sheet coating should be prevented from penetrating into the pipe inlets, and on the other hand the tube sheet coating on the course of the coolant pipes adjusted and a corresponding profiling are carried out, for which purpose shaped plugs are used.
- the pipe inlet has a streamlined design and ensures that the coolant pipe coating can be attached to the pipe bottom coating without any problems.
- the surfaces provided for coating are preferably cleaned by blasting with an abrasive agent, for example by sandblasting.
- the pipe inlets are closed with the plugs provided.
- a primer is then preferably applied, in particular a primer with a coating composition which achieves the elastic properties of the coating provided for the coolant tubes. Since it is expedient to apply the primer by spraying, the corresponding plastic mixtures should have an appropriate viscosity, also with regard to the penetration into corrosion scars in the metal surface.
- the layer thickness should be at least about 80 ⁇ m.
- the drying time for epoxy resins is about 8 hours to a few days at 20 ° C., during which time it is ensured that a reactive connection to the next layer can be formed. However, a rolling process can also be selected for the order.
- One to three layers of the plastic mass intended for the tube sheet are applied to the primer, especially with spatulas to ensure penetration into depressions, to eliminate voids and to avoid the formation of pores and bubbles.
- the drying time for further processing is about 24 hours up to 4 days for epoxy resins.
- the surface is mechanically smoothed, especially by working with abrasive materials.
- the smoothing process is expedient because it achieves a more uniform surface that offers less resistance to the coolant hitting the tube sheet and offers fewer starting points for mechanical erosion corrosion and growth by, for example, algae.
- a seal is expediently applied to the leveled coating, usually in two layers.
- the material used for this is an elastically adjusted plastic mixture based on the underlying coating, for example a mixture as described here for the coating of the coolant tubes.
- the layer thicknesses for each individual layer are at least 40 ⁇ m, in total at least about 80 ⁇ m, and the drying times in epoxy / amine systems are 6 hours until they are tack-free.
- the seal in particular when it is sprayed on or rolled up, brings about a further smoothing of the surface due to the running of the plastic mass, which therefore offers fewer starting points for corrosion damage and growth.
- the seal is expediently only applied when the coolant tubes are coated, the at least last application layer the coolant tube coating is seamlessly extended to the tube sheet coating.
- the entire coating can be subjected to mechanical and chemical loads after a curing temperature of 20 ° C after about 7 days.
- the plugs are removed from the tube inlets in the next step.
- the coolant tube coating is applied to the cleaned surface, at least in its entrance area, but expediently in its entire course, expediently in several layers. Spraying has proven to be particularly suitable for the application, starting with a suitable nozzle that emits to the sides at the end facing away from the tube sheet and is coated toward the tube sheet.
- the coating can also be rolled in with a brush soaked with the coating material, the brush rotating and the material being thrown against the pipe wall. The plastic mixes used for this are adjusted to spray viscosity, while at the same time ensuring the greatest possible penetration and immediate adhesion without tear formation.
- a primer in one or two layers on the metal surface, which hardens with epoxy resins for 8 hours to 8 days, and then the actual coating in one or more layers, with a curing time of 6 hours up to 4 Days. Reworking is not absolutely necessary for the coolant pipe coating. As described above, at least the last layer of the pipe coating is in also applied to the tube sheet coating where it serves as a seal.
- the individual layers of the pipe coating and sealing are applied in a layer thickness of at least approximately 40 ⁇ m, the total dry layer thickness for permanent corrosion protection being at least approximately 80 ⁇ m.
- the total dry layer thickness for permanent corrosion protection being at least approximately 80 ⁇ m.
- the coolant pipe coating can also be chemically and mechanically loaded after about 7 days. The times given refer to epoxy resin / amine hardener systems and 20 ° C.
- the coating in the coolant tubes is not continuous, it should run out layer by layer, so that the coating gradually flats out. It is expedient to go further into the coolant tube with the outer layer and onto the bare metal, so that the layer underneath is completely covered by the layer above.
- the respective outer layer can also start further out than the one underneath.
- FIG. 1 (a) A tube plate 1 with a coolant tube 2 is shown in detail in FIG. 1 (a).
- the pipe protrusion 3 is bent or flared to the sides.
- the tube sheet In the upper half of the figure (also in FIGS. 2 (b) and (c)), the tube sheet has an intact smooth surface 4, which is practically only available in new condition without special protection.
- the surface of the tube sheet In the lower half of the picture, the surface of the tube sheet is considerably damaged by signs of corrosion, particularly in the area of the inlet of the coolant tube, with deep corrosion scars being caused by galvanic corrosion.
- the blackened parts in the area of the tube sheet surface 4 provide a coating 6 with a coating therefor suitable cold-curing plastic mixture.
- the coating 6 merges into the coolant tube coating.
- the corrosion scar 5 is completely filled by the coating. Since the coating composition itself is practically chemically inert, the tube sheet 1 as well as the tube 2 are completely shielded from the cooling water which burns on. This largely prevents galvanic corrosion.
- FIG. 2 shows the layered structure of the coating according to the invention. Details of the tube sheet coating and the tube coating can be found in sections A and B.
- the tube sheet 1 itself has a primer 8 underneath the actual coating 6, which also fills in small unevenness.
- the smoothed surface of the coating 6 is additionally protected with a seal 9 which extends into the tube and forms the outer layer within the tube coating.
- the wall 2 of the coolant tube is first provided with a primer 11 on the cleaned metal surface.
- the actual coolant tube coating 7, which is elastically set with respect to the tube sheet coating, is applied to this primer 11.
- the coolant tube 2 is not coated over its entire length, but only in the entrance area, the coating tapering overall (section B), ie the layers lying thereon each further into the tube protrude than the one below.
- the last layer of the coolant tube coating 9 is at the same time the seal 9 of the tube sheet coating 6.
- the curved outlet of the tube coating (11, 7, 9) shown in section A is predetermined by the contour of the stopper provided in the coating of the tube sheet, which before the coating of the Coolant pipe is removed.
- the total thickness of all layers in the area of the tube sheet is> 2000 ⁇ m and in the area of the tube walls> 80 ⁇ m; greater layer thicknesses can easily be achieved.
- Epoxy resins which are processed with an amine as hardener have proven to be particularly suitable for the coatings according to the invention. These are commercially available systems that can be set to be solvent-free. Suitable products are, for example, epoxides based on glyidyl ethers and epoxides derived from bisphenol A, which are cured with a customary modified polyamine.
- the epoxy and hardener components contain common additives that regulate processability, chemical and storage stability and resistance.
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Abstract
Description
Die Erfindung betrifft eine Beschichtung für Rohrböden und davon ausgehende Kühlmittelrohre von Wärmetauschern, insbesondere Dampfkondensatoren, auf Basis von härtenden Kunststoffabmischungen, die durch Reinigen der zur Beschichtung vorgesehenen Flächen mit Hilfe abrasiv wirkender Mittel; Verschließen der Rohrein- und -auslässe durch entfernbare Stopfen; Auftragen wenigstens einer Schicht einer härtenden Kunststoffbeschichtung auf den Rohrboden; Aushärtenlassen der Beschichtung, so daß eine weitere mechanische Bearbeitung erfolgen kann, und Bearbeiten der Oberfläche; Entfernen der Stopfen von den Rohrein- und -auslässen sowie Einbringen wenigstens einer Schicht einer härtenden Kunststoffbeschichtung wenigstens in den Eingangsbereich der Kühlmittelrohre und Aushärtenlassen; erhältlich ist, sowie ein Verfahren zum Beschichten von Rohrböden und davon ausgehenden Kühlmittelrohren von Dampfkondensatoren.The invention relates to a coating for tube sheets and coolant tubes for heat exchangers, in particular steam condensers, based on hardening plastic mixtures, which are cleaned by cleaning the surfaces provided for coating with the aid of abrasive agents; Closing the pipe inlets and outlets with removable plugs; Applying at least one layer of a hardening plastic coating to the tube sheet; Allowing the coating to harden so that further mechanical processing can take place and processing the surface; Removing the plugs from the pipe inlets and outlets and introducing at least one layer of a hardening plastic coating at least into the entrance area of the coolant pipes and allowing them to harden; is available, as well as a method for coating tube sheets and coolant tubes of steam condensers.
Es ist bekannt, Rohrböden von Dampfkondensatoren, wie sie beispielsweise in Anlagen zur Erzeugung elektrischer Energie eingesetzt werden, mit einer Kunststoffbeschichtung zu versehen, um Korrosionserscheinungen entgegenzuwirken. Rohrböden und die davon ausgehenden Kühlmittelrohre sind einer Vielzahl von äußeren Einflüssen ausgesetzt, insbesondere mechanischen, chemischen und elektromechanischen Beanspruchungen. Mechanische Beanspruchungen treten auf durch vom Kühlmittel mitgerissene feste Partikel, beispielsweise Sand. Außerdem treten durch die Temperaturdifferenz zwischen dem Kühlmedium und dem zu kondensierenden Dampf, die 100° C übersteigen kann, Ausdehnungen im Einwalzbereich der Kühlmittelrohre am Rohrboden auf.It is known to provide tube sheets of steam condensers, such as are used, for example, in plants for generating electrical energy, with a plastic coating in order to counteract signs of corrosion. Pipe trays and the coolant pipes emanating from them are exposed to a large number of external influences, in particular mechanical, chemical and electromechanical stresses. Mechanical stress occurs due to solid particles entrained by the coolant, such as sand. In addition, the temperature difference between the cooling medium and the steam to be condensed, which can exceed 100 ° C., causes expansion in the roll-in area of the coolant tubes on the tube plate.
Chemische Beanspruchungen ergeben sich aus der Natur des Kühlmediums, beispielsweise aus dessen Befrachtung mit Salzen oder sauren Substanzen. Insbesondere wäre hier die bekannte Korrosionswirkung von zu Kühlzwecken verwandtem Meerwasser oder stark belastetem Flußwasser zu nennen. Unter elektrochemischer oder galvanischer Korrosion ist diejenige zu nennen, die durch die Ausbildung von galvanischen Elementen an metallischen Grenzflächen, insbesondere an den Übergängen von Rohrboden zu Kühlmittelrohr, auftreten und die durch elektrisch leitende Flüssigkeiten, etwa Meerwasser, stark gefördert werden. Hinzu kommen Beeinträchtigungen der Funktionsfähigkeit eines Rohrbodens durch Ablagerung unerwünschter Stoffe, Algenbildung, etc. an dessen Oberfläche, die insbesondere durch Rauhigkeiten gefördert werden, wie sie durch Korrosionserscheinungen entstehen. Dies hat zur Folge, daß sich die Korrosions- und Ablagerungserscheinungen mit dem Alter eines Rohrbodens beschleunigen, weil sich zunehmend Ansatzpunkte für Korrosion und Ablagerungen bilden.Chemical stresses arise from the nature of the cooling medium, for example from its loading with salts or acidic substances. In particular, the known corrosion effect of seawater used for cooling purposes or heavily polluted river water should be mentioned here. Electrochemical or galvanic corrosion is the one that occurs due to the formation of galvanic elements at metallic interfaces, in particular at the transitions from the tube sheet to the coolant tube, and which are strongly promoted by electrically conductive liquids, such as sea water. In addition, the functionality of a tube sheet is impaired by the deposition of undesirable substances, algae formation, etc. on its surface, which are promoted in particular by roughness, such as that caused by corrosion. As a result, the signs of corrosion and deposits accelerate with the age of a tube sheet, because there are increasing starting points for corrosion and deposits.
Schon frühzeitig ist man deshalb dazu übergegangen, Rohrböden mit einer korrosionsmindernden Beschichtung aus Kunststoffmaterialien zu versehen. Insbesondere wurden hier Epoxidharz-Dickbeschichtungen eingesetzt, die mit bestimmten Techniken an die Rohrein- und -auslässe angepaßt wurden, beispielsweise durch die Verwendung von Formstopfen während der Aufbringung. Auf diese Weise kann die Beschichtung des Rohrbodens zunächst nahtlos an die Rohrein- und -austritte angepaßt werden, wobei auf eine Innenbeschichtung der zumeist überstehenden oder im Bereich der Beschichtung endenden Rohren aus korrosionsbeständigem Material zumeist verzichtet wurde. Aber auch bei derartigen Lösungen konnte auf Dauer das Eindringen von Kühlwasser durch Mikrorisse und dadurch bedingt die Ausbildung von galvanischen Elementen nicht verhindert werden, mit der Folge zunehmender Korrosionserscheinungen nach Ausbildung der ersten Risse. Selbst die Einbeziehung der Kühlmittelrohre in die beschichtete Fläche zumindestens in ihrem Eintritts- und Austrittsbereich brachte hier nur geringe Besserung, da die in diesem Bereich herrschenden extremen thermischen und mechanischen Beanspruchungen zur Ausbildung von Haarrissen gerade im empfindlichen Übergangsbereich von Rohrboden zu Kühlmittelrohr führt. Ist aber an diesen Stellen der Verbund aus Rohrboden- und Rohrbeschichtung einmal durchbrochen, wird die Schutzwirkung der Beschichtung zunehmend gestört.It was therefore adopted early on to provide tube sheets with a corrosion-reducing coating made of plastic materials. In particular, epoxy resin thick coatings were used here, which were adapted to the pipe inlets and outlets using certain techniques, for example by using molded plugs during the application. In this way, the coating of the tube sheet can first be seamlessly adapted to the tube inlets and outlets, an internal coating of the mostly protruding tubes or ends of the tube made of corrosion-resistant material mostly ending in the area of the coating. But even with such solutions, the penetration of cooling water through microcracks and thus caused the Formation of galvanic elements can not be prevented, with the consequence of increasing signs of corrosion after formation of the first cracks. Even the inclusion of the coolant pipes in the coated surface, at least in their entry and exit areas, brought little improvement, since the extreme thermal and mechanical stresses in this area lead to the formation of hairline cracks, especially in the sensitive transition area from the tube sheet to the coolant tube. However, if the composite of tube sheet and tube coating is broken at these points, the protective effect of the coating is increasingly disrupted.
Maßnahmen der vorstehend genannten Art sind beispielsweise aus GB-A-1 175 157, DE-U-1 939 665, DE-U-7 702 562 sowie EP-A-0 236 388 bekannt.Measures of the type mentioned above are known, for example, from GB-A-1 175 157, DE-U-1 939 665, DE-U-7 702 562 and EP-A-0 236 388.
In Anbetracht der vorstehend aufgezeigten Probleme liegt der Erfindung die Aufgabe zugrunde, Rohrböden und daran angrenzende Kühlmittelrohrein- und -auslässe mit einer beide integrierenden Beschichtung zu versehen, die den an den Übergangsstellen wirkenden mechanischen Beanspruchungen langfristig Widerstand entgegensetzt und gleichzeitig geeignet ist, chemischer Beanspruchung durch das Kühlmittel langfristig zu widerstehen.In view of the problems outlined above, the invention has for its object to provide tube sheets and adjacent coolant tube inlets and outlets with a coating that integrates both, which provides long-term resistance to the mechanical stresses acting at the transition points and at the same time is suitable for chemical stresses caused by the Resist coolant in the long term.
Diese Aufgabe wird mit einer Beschichtung der eingangs genannten Art gelöst, bei der die Beschichtung der Kühlmittelrohre durch zeitlich aufeinander abgestimmten Auftrag reaktiv an die Rohrbodenbeschichtung angeschlossen ist, und bei der die Beschichtung der Kühlmittelrohre eine im Vergleich zur Rohrbodenbeschichtung größere Elastizität mit einer um wenigstens 2 %, bezogen auf die Reißdehnung der Rohrbodenbeschichtung, größeren Reißdehnung nach DIN 53152 aufweist. Mit der zeitlichen Abstimmung der Beschichtungsvorgänge am Rohrboden und in den Kühlmittelrohren aufeinander wird erreicht, daß eine Vernetzung über die Beschichtungsgrenzen von der Beschichtung in den Rohren zur Beschichtung auf dem Rohrboden hin entsteht, so daß ein besonders belastbarer chemischer Verbund gegeben ist. Gleichzeitig und zusätzlich bewirkt die relativ größere Elastizität der Kühlmittelrohrbeschichtung eine bessere Beständigkeit gegen mechanische Beanspruchung im Eingangs- und Ausgangsbereich der Rohre, dort wo es zur galvanischen Korrosion kommt. Dabei hat sich gezeigt, daß eine Erhöhung der Reißdehnung um 2 % nach DIN 53152 im allgemeinen ausreichend ist, um die Verbesserung des Beschichtungsverbundes zu bewirken, wobei von einer Reißdehnung der Rohrbodenbeschichtung von weniger als 5 % und einer solchen der Kühlmittelrohrbeschichtung von weniger als 10 % ausgegangen wird, um die für die Dauerhaftigkeit der Beschichtung erforderliche Härte, Abriebfestigkeit und Druckfestigkeit zu gewährleisten. Andererseits sollte für die Rohrbodenbeschichtung eine Reißdehnung von 2 % nicht unterschritten werden, um Sprödigkeit zu vermeiden. Als besonders geeignet haben sich Materialien gezeigt, die eine Reißdehnung nach DIN 53152 von 2 bis 4 % für den Rohrboden und 4 bis 9 % für die Kühlmittelrohre aufweisen. Besonders bevorzugt sind Beschichtungen mit Reißdehnungen von mehr als 3 % beim Rohrboden und mehr als 5 % bei den Kühlmittelrohren.This object is achieved with a coating of the type mentioned at the outset, in which the coating of the coolant tubes is reactively connected to the tube sheet coating by means of a time-coordinated application, and in which the coating of the coolant tubes has a greater elasticity than the tube sheet coating with an at least 2% , based on the elongation at break of the tube sheet coating, has greater elongation at break according to DIN 53152. With the timing of the coating processes on the tube sheet and in the coolant tubes, it is achieved that crosslinking occurs across the coating limits from the coating in the tubes to the coating on the tube sheet, so that a particularly resilient chemical bond is given. At the same time and in addition, the relatively greater elasticity of the coolant pipe coating results in better resistance to mechanical stress in the entrance and exit area of the pipes, where there is galvanic corrosion. It has been shown that an increase in the elongation at break by 2% according to DIN 53152 is generally sufficient to bring about an improvement in the coating composite, with an elongation at break of the tube sheet coating of less than 5% and that of the coolant tube coating of less than 10%. is assumed to ensure the hardness, abrasion resistance and compressive strength required for the durability of the coating. On the other hand, the elongation at break should not be less than 2% for the tube sheet coating in order to avoid brittleness. Materials which have an elongation at break according to DIN 53152 of 2 to 4% for the tube sheet and 4 to 9% for the coolant tubes have proven to be particularly suitable. Coatings with elongations at break of more than 3% for the tube sheet and more than 5% for the coolant tubes are particularly preferred.
Um die für einen dauerhaften Betrieb über mehrere Jahre erforderlichen Schichtdicken aufzutragen und gleichzeitig die Qualität hinsichtlich Haftung, Poren- und Haarrißfreiheit zu gewährleisten, ist es zweckmäßig, die erfindungsgemäße Beschichtung in mehreren Schichten aufzutragen, wobei jede Schicht auf die noch reaktive Oberfläche der darunterliegenden Schicht aufgebracht wird, um eine chemische Vernetzung zu erzielen. Zweckmäßigerweise werden sowohl auf den Rohrboden als auch in den Kühlmittelrohren zwei oder drei Schichten aufgebracht, die unterschiedlich gefärbt sein können, um bei von Zeit zu Zeit stattfindenden Inspektionen die noch verbliebene Schichtdicke anhand der Färbung überprüfen zu können. Dabei beträgt die Mindestschichtdicke der gesamten Beschichtung für die Innenbeschichtung der Rohre wenigstens etwa 80 µm und für den Rohrboden wenigstens 2000 µm. Schichtstärken von 20 mm und mehr sind ohne weiteres möglich, ohne daß es zu Einbußen bei der Festigkeit kommt. Dies ist ein besonderer Vorteil, wenn es um die Beschichtung bereits stark korrodierter Rohrböden geht, die tiefe Korrosionsnarben aufweisen.In order to apply the layer thicknesses required for permanent operation over several years and at the same time to ensure the quality in terms of adhesion, freedom from pores and hairline cracks, it is expedient to apply the coating according to the invention in several layers, each layer on the still reactive surface of the underlying one Layer is applied to achieve chemical crosslinking. Appropriately, two or three layers are applied both to the tube sheet and in the coolant tubes, which can be colored differently in order to be able to check the remaining layer thickness on the basis of the color during inspections which take place from time to time. The minimum layer thickness of the entire coating for the inner coating of the tubes is at least about 80 µm and for the tube sheet at least 2000 µm. Layer thicknesses of 20 mm and more are easily possible without sacrificing strength. This is a particular advantage when it comes to coating heavily corroded tube sheets that have deep corrosion scars.
Es hat sich als sehr zweckmäßig erwiesen, die gereinigten Flächen des Rohrbodens und der Kühlmittelrohre vor der Aufbringung der eigentlichen Beschichtung mit einer Grundierung zu versehen, die in der Regel niedriger viskos aufgespritzt wird und in Korrosionsmulden und -narben eindringt. Hierdurch wird eine Einebnung der Flächen, eine bessere Anpassung an Unebenheiten und eine insgesamt bessere Haftung der eigentlichen Beschichtung erreicht. Ebenso kann die eigentliche Beschichtung an der Oberfläche zusätzlich mit einer Versiegelung versehen werden, um insbesondere eine glattere Oberfläche zu erzielen, die das Anhaften von Algen, Schmutzteilchen u. dgl. verhindert. Die Versiegelung im Rohrbodenbereich ist vorzugsweise elastischer eingestellt als die Rohrbodenbeschichtung, wobei sie die vorstehend für die Kühlmittelrohrbeschichtungen ausgewiesenen Reißdehnungswerte einhalten sollte. Im allgemeinen ist es zweckmäßig, je zwei Grundierungs- und Versiegelungsschichten vorzusehen. Eine Versiegelung im Rohrbereich ist im allgemeinen nicht erforderlich.It has proven to be very expedient to provide the cleaned surfaces of the tube sheet and the coolant tubes with a primer before the actual coating is applied, which is generally sprayed on with a lower viscosity and penetrates into corrosion cavities and scars. As a result, the surfaces are leveled, better adaptation to unevenness and overall better adhesion of the actual coating. Likewise, the actual coating on the surface can additionally be provided with a seal, in order in particular to achieve a smoother surface which prevents the adherence of algae, dirt particles and the like. The like prevented. The seal in the tube sheet area is preferably set to be more elastic than the tube sheet coating, whereby it should comply with the elongation at break values indicated above for the coolant tube coatings. In general, it is advisable to provide two primer and two sealing layers. Sealing in the pipe area is generally not necessary.
Bevorzugte Materialien für die erfindungsgemäße Beschichtung sind kalthärtende Epoxidharze, die mit einem Aminhärter zusammen verarbeitet werden. Diese Harzmassen enthalten übliche Füllstoffe und Farbstoffe, Stellmittel, Stabilisatoren u. a. übliche Zusätze, um die von ihnen gewünschten Eigenschaften, insbesondere Verarbeitbarkeit und Haltbarkeit, sicherzustellen. Es handelt sich dabei um übliche Kunststoffabmischungen, wie sie auch für andere Zwecke eingesetzt werden können - entscheidend für die erfindungsgemäße Beschichtung ist weniger die Art der härtenden Kunststoffmasse als vielmehr ihre Korrosionsbeständigkeit und Elastizität nach der Aushärtung. Außer Epoxidharzen können somit auch andere kalthärtende Kunststoffabmischungen eingesetzt werden, die diesen Anforderungen genügen. Epoxid/Amin-Systeme sind jedoch für die erfindungsgemäßen Zwecke bevorzugt.Preferred materials for the coating according to the invention are cold-curing epoxy resins which are processed together with an amine hardener. These resin compositions contain common fillers and dyes, adjusting agents, stabilizers and. a. Common additives to ensure the properties you want, especially processability and durability. These are customary plastic blends, as they can also be used for other purposes - the decisive factor for the coating according to the invention is less the type of the hardening plastic mass than its corrosion resistance and elasticity after curing. In addition to epoxy resins, other cold-curing plastic mixtures that meet these requirements can also be used. However, epoxy / amine systems are preferred for the purposes of the invention.
Die für die Rohrböden und insbesondere die Kühlmittelrohre verwandten Kunststoffabmischungen enthalten zweckmäßigerweise einen Anteil an pulverförmigen Polytetrafluorethylen (PTFE) in einer Menge von wenigstens etwa 5 Gew.-%, um die gewünschten Elastizitäts- und Festigkeitswerte zu erzielen. Es hat sich gezeigt, daß ein PTFE-Zusatz im Bereich von 5 bis 20 Gew.-%, insbesondere etwa 10 Gew.-% die Dauerhaftigkeit der Beschichtung im Bereich der Rohrein- und -austritte deutlich verbessert. Der PTFE-Zusatz, beispielsweise Hostaflon (R) von Hoechst, sollte eine Körnung von < 50 µm und insbesondere im Bereich von 10 bis 30 µm haben. Er bildet eine Matrix, die füllt, stabilisiert und eine Elastizitätsverbesserung bewirkt und insbesondere auch dazu dient, die gewünschte Elastizität einzustellen.The plastic mixtures used for the tube sheets and in particular the coolant tubes expediently contain a proportion of powdered polytetrafluoroethylene (PTFE) in an amount of at least about 5% by weight in order to achieve the desired elasticity and strength values. It has been shown that an addition of PTFE in the range from 5 to 20% by weight, in particular about 10% by weight, significantly improves the durability of the coating in the area of the pipe entries and exits. The PTFE additive, for example Hostaflon (R) from Hoechst, should have a grain size of <50 µm and in particular in the range from 10 to 30 µm. It forms a matrix that fills, stabilizes and improves the elasticity and in particular also serves to set the desired elasticity.
Zur Erhöhung der Widerstandsfähigkeit insbesondere der Rohrbodenbeschichtung ist ein Gehalt von > 30 Gew.-% mineralischen Zuschlägen in der Abmischung zweckmäßig.To increase the resistance, in particular of the tube sheet coating, a content of> 30% by weight of mineral additives in the mixture is expedient.
Zur weiteren Verbesserung der Beständigkeit der erfindungsgemäßen Beschichtung im Bereich des Übergangs von Kühlmittelrohr zu Rohrboden kann es zweckmäßig sein, im Bereich des Übergangs zum Rohrboden in die Beschichtung eine Kunststoffhülse einzubringen, die einen zusätzlichen Stabilisationseffekt bewirkt.To further improve the durability of the coating according to the invention in the area of the transition from the coolant tube to the tube sheet, it may be expedient to introduce a plastic sleeve into the coating in the area of the transition to the tube sheet, which brings about an additional stabilizing effect.
Bei den erfindungsgemäßen Beschichtungen hat es sich gezeigt, daß sie gewisse Kriterien bezüglich ihrer mechanischen Beanspruchbarkeit erfüllen müssen. So sollte die schließlich erreichte Härte der Beschichtung einen Wert von wenigstens etwa 75 nach DIN 53153 (Barcol-Härte) erreichen, vorzugsweise wenigstens 80. Für die Rohrbodenbeschichtung ist ein Wert von wenigstens etwa 95 zweckmäßig.The coatings according to the invention have shown that they have to meet certain criteria with regard to their mechanical strength. The hardness of the coating finally achieved should reach a value of at least about 75 according to DIN 53153 (Barcol hardness), preferably at least 80. A value of at least about 95 is appropriate for the tube sheet coating.
Des weiteren sollte die Haftfestigkeit der Beschichtung auf dem Untergrund wenigstens etwa 4 N/mm² nach DIN/Iso 4624 betragen, vorzugsweise wenigstens etwa 5 N/mm² und insbesondere wenigstens 7 N/mm². Erfindungsgemäß werden Haftfestigkeiten von mehr als 10/mm² für die Rohrbodenbeschichtung und mehr als 5 N/mm² für die Kühlmittelrohrbeschichtung und Grundierung erreicht.Furthermore, the adhesive strength of the coating on the substrate should be at least about 4 N / mm² according to DIN / ISO 4624, preferably at least about 5 N / mm² and in particular at least 7 N / mm². According to the invention, adhesive strengths of more than 10 / mm² for the tube sheet coating and more than 5 N / mm² for the coolant tube coating and primer are achieved.
Wesentlich für die Standfestigkeit der erfindungsgemäßen Beschichtungen sind deren Druckfestigkeit und Abriebfestigkeit. Bezüglich der Druckfestigkeit sollten Werte von mehr als 50 N/mm² für die Kühlmittelrohrbeschichtung und mehr als 100 N/mm² für die Rohrbodenbeschichtung erreicht werden, bei der Abriebfestigkeit nach DIN 53233 (Fall A) Werte von mehr als 40 mg bzw. mehr als 55 mg.The compressive strength and abrasion resistance are essential for the stability of the coatings according to the invention. With regard to the compressive strength, values of more than 50 N / mm² for the coolant tube coating and more than 100 N / mm² for the tube sheet coating should be achieved, with the abrasion resistance according to DIN 53233 (case A) values of more than 40 mg or more than 55 mg .
Die Erfindung betrifft ferner ein Verfahren zur Aufbringung der vorstehend beschriebenen Beschichtung, bei dem zunächst die zur Beschichtung vorgesehenen Flächen mit Hilfe abrasiv wirkender Mittel gereinigt werden, die Rohrein- und -auslässe durch entfernbare Stopfen verschlossen werden, wenigstens eine Schicht einer härtenden Kunststoffbeschichtung auf den Rohrboden aufgetragen wird, die Beschichtung aushärten gelassen wird, so daß eine weitere mechanische Bearbeitung erfolgen kann, jedoch noch reaktive Stellen an der Oberfläche zurückbleiben, wonach die Oberfläche mechanisch bearbeitet wird. Anschließend werden die Rohrstopfen von den Rohrein- und -auslässen entfernt sowie wenigstens eine Schicht einer härtenden Kunststoffbeschichtung wenigstens in den Eingangsbereich der Kühlmittelrohre unter Ausbildung einer reaktiven Verbindung mit der Rohrbodenbeschichtung eingebracht, wobei die Kunststoffabmischungen so gewählt sind, daß die Kühlmittelrohrbeschichtung im Vergleich zur Rohrbodenbeschichtung eine größere Elastizität mit einer um wenigstens 2 %, bezogen auf die Reißdehnung der Rohrbodenbeschichtung nach DIN 53152 größere Reißdehnung aufweist.The invention further relates to a method for applying the coating described above, in which the surfaces intended for coating are first cleaned with the aid of abrasive agents, the tube inlets and outlets are closed by removable plugs, at least one layer of a hardening plastic coating on the tube sheet is applied, the coating is allowed to harden so that further mechanical processing can take place, but reactive spots remain on the surface, after which the surface is processed mechanically. The tube plugs are then removed from the tube inlets and outlets and at least one layer of a hardening plastic coating is introduced at least into the entrance area of the coolant tubes, forming a reactive connection with the tube sheet coating, the plastic mixtures being selected such that the coolant tube coating is one in comparison to the tube sheet coating greater elasticity with an elongation at break greater by at least 2%, based on the elongation at break of the tube sheet coating according to DIN 53152.
Für das erfindungsgemäße Verfahren ist es wichtig, daß die zur Beschichtung vorgesehenen Oberflächen gründlich abrasiv gereinigt werden, um einen festen und einheitlichen Untergrund zu schaffen. Das Verschließen der Rohrein- und -auslässe durch entfernbare Stopfen, das an und für sich bekannt ist, hat zwei Gründe: Zum einen soll das Eindringen der für die Rohrbodenbeschichtung vorgesehenen Masse in die Rohreinlässe verhindert werden, zum anderen die Rohrbodenbeschichtung an den Verlauf der Kühlmittelrohre angeglichen und eine entsprechende Profilierung vorgenommen werden, wozu entsprechend geformte Stopfen verwandt werden. Auf diese Weise wird insbesondere der Rohreinlauf strömungsgünstig ausgebildet und ein problemloser Ansatz der Kühlmittelrohrbeschichtung an die Rohrbodenbeschichtung gewährleistet. Es kann dabei - vor allem bei älteren Rohrböden - sinnvoll sein, die Kühlmittelrohre am Ein- und Austritt entsprechend anzudornen, um einen glatten Übergang an die Einbettung der Rohreinsätze in die Rohrbodenbeschichtung zu gewährleisten (DE-U-7 702 562). Hierdurch wird insbesondere erreicht, daß der Übergang Rohrboden/Kühlmittelrohr nicht mit dem Übergang Rohrbodenbeschichtung/Kühlmittelrohrbeschichtung zusammenfällt, was die Lebensdauer der Beschichtung erhöht.For the process according to the invention it is important that the surfaces provided for the coating are thoroughly abrasively cleaned in order to create a firm and uniform surface. There are two reasons for closing the pipe inlets and outlets by removable plugs, which are known per se: on the one hand, the mass intended for the tube sheet coating should be prevented from penetrating into the pipe inlets, and on the other hand the tube sheet coating on the course of the coolant pipes adjusted and a corresponding profiling are carried out, for which purpose shaped plugs are used. This way in particular the pipe inlet has a streamlined design and ensures that the coolant pipe coating can be attached to the pipe bottom coating without any problems. It can make sense - especially with older tube sheets - to appropriately thorn the coolant tubes at the inlet and outlet to ensure a smooth transition to the embedding of the tube inserts in the tube sheet coating (DE-U-7 702 562). This ensures in particular that the transition from the tube sheet to the coolant tube does not coincide with the transition from the tube sheet coating to the coolant tube coating, which increases the service life of the coating.
Das Reinigen der zur Beschichtung vorgesehenen Flächen erfolgt vorzugsweise durch Strahlen mit einem abrasiven Mittel, beispielsweise durch Sandstrahlen. Im darauffolgenden Schritt werden die Rohreinlässe mit den dafür vorgesehenen Stopfen verschlossen. Danach wird vorzugsweise eine Grundierung aufgebracht, insbesondere eine Grundierung mit einer Beschichtungsmasse, die die Elastizitätseigenschaften der für die Kühlmittelrohre vorgesehenen Beschichtung erreicht. Da es zweckmäßig ist, die Grundierung im Spritzverfahren aufzubringen, sollten die entsprechenden Kunststoffabmischungen eine entsprechende Viskosität aufweisen, auch im Hinblick auf das Eindringvermögen in Korrosionsnarben in der Metalloberfläche. Die Schichtdicke sollte wenigstens etwa 80 µm betragen. Die Trocknungszeit beträgt für Epoxyharze etwa 8 Stunden bis einige Tage bei 20° C, wobei innerhalb dieses Zeitraums sichergestellt ist, daß noch eine reaktive Verbindung zur nächstfolgenden Schicht ausgebildet werden kann. Es kann aber auch ein Rollverfahren für den Auftrag gewählt werden.The surfaces provided for coating are preferably cleaned by blasting with an abrasive agent, for example by sandblasting. In the next step, the pipe inlets are closed with the plugs provided. A primer is then preferably applied, in particular a primer with a coating composition which achieves the elastic properties of the coating provided for the coolant tubes. Since it is expedient to apply the primer by spraying, the corresponding plastic mixtures should have an appropriate viscosity, also with regard to the penetration into corrosion scars in the metal surface. The layer thickness should be at least about 80 µm. The drying time for epoxy resins is about 8 hours to a few days at 20 ° C., during which time it is ensured that a reactive connection to the next layer can be formed. However, a rolling process can also be selected for the order.
Auf die Grundierung werden ein bis drei Schichten der für den Rohrboden vorgesehenen Kunststoffmasse aufgebracht, insbesondere durch Spachteln, um das Eindringen in Vertiefungen sicherzustellen, Hohlräume zu beseitigen und die Ausbildung von Poren und Blasen zu vermeiden. Hierzu hat es sich als zweckmäßig erwiesen, zur Erzielung der erforderlichen Schichtdicken von 20 mm oder mehr mehrere Schichten nacheinander aufzutragen. Die Trocknungszeit bis zur weiteren Bearbeitung beträgt für Epoxyharze etwa 24 Stunden bis zu 4 Tage. Nach der Aushärtung wird die Oberfläche mechanisch geglättet, insbesondere durch Bearbeiten mit abrasiven Materialien. Der Glättungsvorgang ist deshalb zweckmäßig, weil damit eine einheitlichere Oberfläche erzielt wird, die dem auf den Rohrboden auftreffenden Kühlmittel weniger Widerstand entgegenbringt und weniger Ansatzpunkte für die mechanische Erosionskorrosion und Anwachsungen durch beispielsweise Algen bietet. Es ist beim Auftrag sicherzustellen, daß die einzelnen Schichten reaktiv miteinander verbunden sind.One to three layers of the plastic mass intended for the tube sheet are applied to the primer, especially with spatulas to ensure penetration into depressions, to eliminate voids and to avoid the formation of pores and bubbles. For this purpose, it has proven to be expedient to apply several layers in succession in order to achieve the required layer thicknesses of 20 mm or more. The drying time for further processing is about 24 hours up to 4 days for epoxy resins. After curing, the surface is mechanically smoothed, especially by working with abrasive materials. The smoothing process is expedient because it achieves a more uniform surface that offers less resistance to the coolant hitting the tube sheet and offers fewer starting points for mechanical erosion corrosion and growth by, for example, algae. When applying, make sure that the individual layers are reactively connected.
Auf die aufgespachtelte Beschichtung wird zweckmäßigerweise eine Versiegelung aufgebracht, üblicherweise in zwei Schichten. Als Material hierfür dient eine elastisch eingestellte Kunststoffabmischung auf der Basis der darunterliegenden Beschichtung, beispielsweise eine Abmischung, wie sie hier für die Beschichtung der Kühlmittelrohre beschrieben ist. Die Schichtdicken betragen für jede einzelne Schicht wenigstens 40 µm, insgesamt wenigstens etwa 80 µm, die Trocknungszeiten bei Epoxid/Amin-Systemen 6 Stunden bis zur Klebfreiheit. Die Versiegelung bringt insbesondere dann, wenn sie aufgespritzt oder aufgerollt ist, durch das Verlaufen der Kunststoffmasse eine weitere Glättung der Oberfläche mit sich, die damit weniger Ansatzpunkte für Korrosionsschäden und Anwachsungen bietet. Zweckmäßigerweise wird die Versiegelung erst aufgebracht, wenn die Kühlmittelrohre beschichtet werden, wobei die wenigstens letzte Auftragsschicht der Kühlmittelrohrbeschichtung nahtlos auf die Rohrbodenbeschichtung ausgedehnt wird.A seal is expediently applied to the leveled coating, usually in two layers. The material used for this is an elastically adjusted plastic mixture based on the underlying coating, for example a mixture as described here for the coating of the coolant tubes. The layer thicknesses for each individual layer are at least 40 μm, in total at least about 80 μm, and the drying times in epoxy / amine systems are 6 hours until they are tack-free. The seal, in particular when it is sprayed on or rolled up, brings about a further smoothing of the surface due to the running of the plastic mass, which therefore offers fewer starting points for corrosion damage and growth. The seal is expediently only applied when the coolant tubes are coated, the at least last application layer the coolant tube coating is seamlessly extended to the tube sheet coating.
Die Gesamtbeschichtung ist bei einer Aushärtungstemperatur von 20° C nach etwa 7 Tagen mechanisch und chemisch belastbar.The entire coating can be subjected to mechanical and chemical loads after a curing temperature of 20 ° C after about 7 days.
Nach dem Aufbringen der Rohrbodenbeschichtung auf die Grundierung und der mechanischen Nachbearbeitung werden im nächsten Schritt die Stopfen von den Rohreinlässen entfernt. Anschließend wird in die Rohre wenigstens in deren Eingangsbereich, zweckmäßigerweise aber in deren ganzen Verlauf, auf die gereinigte Oberfläche die Kühlmittelrohrbeschichtung aufgebracht, zweckmäßigerweise in mehreren Schichten. Als besonders geeignet für das Aufbringen hat sich das Aufspritzen erwiesen, wobei mit einer hierfür geeigneten, zu den Seiten abstrahlenden Düse am vom Rohrboden abgewandten Ende begonnen wird und zum Rohrboden hin beschichtet wird. Alternativ kann die Beschichtung auch mit einer mit der Beschichtungsmasse getränkten Bürste eingerollt werden, wobei die Bürste rotiert und die Masse gegen die Rohrwandung geschleudert wird. Die dafür verwandten Kunststoffabmischungen sind auf Spritzviskosität eingestellt, wobei gleichzeitig auf größstmögliches Eindringvermögen und sofortiges Haftvermögen ohne Tränenbildung geachtet wird. Zweckmäßigerweise werden auch hier mehrere Schichten aufgebracht, zunächst eine Grundierung in ein oder zwei Schichten auf die Metalloberfläche, die bei Epoxidharzen 8 Stunden bis 8 Tage aushärtet, und darauf die eigentliche Beschichtung in einer oder mehreren Schichten, mit einer Aushärtungszeit von 6 Stunden bis zu 4 Tagen. Eine Nachbearbeitung ist bei der Kühlmittelrohrbeschichtung nicht unbedingt erforderlich. Wie oben beschrieben, wird wenigstens die letzte Schicht der Rohrbeschichtung in einem Zug auch auf die Rohrbodenbeschichtung aufgebracht, wo sie als Versiegelung dient.After applying the tube sheet coating to the primer and mechanical finishing, the plugs are removed from the tube inlets in the next step. Subsequently, the coolant tube coating is applied to the cleaned surface, at least in its entrance area, but expediently in its entire course, expediently in several layers. Spraying has proven to be particularly suitable for the application, starting with a suitable nozzle that emits to the sides at the end facing away from the tube sheet and is coated toward the tube sheet. Alternatively, the coating can also be rolled in with a brush soaked with the coating material, the brush rotating and the material being thrown against the pipe wall. The plastic mixes used for this are adjusted to spray viscosity, while at the same time ensuring the greatest possible penetration and immediate adhesion without tear formation. Expediently, several layers are also applied here, first a primer in one or two layers on the metal surface, which hardens with epoxy resins for 8 hours to 8 days, and then the actual coating in one or more layers, with a curing time of 6 hours up to 4 Days. Reworking is not absolutely necessary for the coolant pipe coating. As described above, at least the last layer of the pipe coating is in also applied to the tube sheet coating where it serves as a seal.
Die einzelnen Schichten der Rohrbeschichtung und Versiegelung werden in einer Schichtdicke von wenigstens etwa 40 µm aufgetragen, wobei die Gesamttrockenschichtdicke für einen dauerhaften Korrosionsschutz wenigstens etwa 80 µm betragen sollte. Bei der Aufbringung mehrerer Schichten ist es wichtig, auf den zeitlichen Ablauf zu achten: Sowohl der Übergang zur Rohrbodenbeschichtung als auch die individuellen Schihten der Kühlmittelrohrbeschichtung müssen in einem solchen zeitlichen Rahmen aufgetragen werden, daß es zu einer chemischen Vernetzung mit der darunterliegenden Schicht kommt.The individual layers of the pipe coating and sealing are applied in a layer thickness of at least approximately 40 μm, the total dry layer thickness for permanent corrosion protection being at least approximately 80 μm. When applying several layers, it is important to pay attention to the chronological sequence: Both the transition to the tube sheet coating and the individual layers of the coolant tube coating must be applied in such a time frame that there is chemical crosslinking with the layer below.
Auch die Kühlmittelrohrbeschichtung ist nach etwa 7 Tagen chemisch und mechanisch belastbar. Die angegebenen Zeiten beziehen sich auf Epoxidharz/Aminhärter-Systeme und 20° C.The coolant pipe coating can also be chemically and mechanically loaded after about 7 days. The times given refer to epoxy resin / amine hardener systems and 20 ° C.
Die Beschichtung in den Kühlmittelrohren sollte, wenn sie nicht durchgängig ist, Schicht für Schicht auslaufen, so daß sich ein allmähliches Abflachen der Beschichtung ergibt. Dabei ist es zweckmäßig, mit der jeweils äußeren Schicht weiter in das Kühlmittelrohr hinein- und auf das blanke Metall zu gehen, so daß die darunterliegende Schicht von der darüberliegenden vollständig abgedeckt wird. Die jeweils äußere Schicht kann aber auch weiter außen ansetzen als die darunterliegende.If the coating in the coolant tubes is not continuous, it should run out layer by layer, so that the coating gradually flats out. It is expedient to go further into the coolant tube with the outer layer and onto the bare metal, so that the layer underneath is completely covered by the layer above. The respective outer layer can also start further out than the one underneath.
Bei allen Beschichtungen ist es zweckmäßig, die einzelnen Schichten unterschiedlich einzufärben, um den Zustand der Beschichtung und ihre Dicke kontrollieren zu können. Bei einer grauen Grundierung und darauf sich abwechselnden roten und weißen Schichten der Gesamtbeschichtung ist es ohne weiteres möglich, anhand der Färbung die verbliebene Beschichtungsdicke optisch zu kontrollieren und beispielsweise festzustellen, wann die vorletzte und letzte Schicht erreicht ist. Auf diese Art und Weise ist ein volles Ausnutzen der Lebensdauer der Beschichtung möglich wie auch gezielte Reparaturen an besonders von Korrosion oder Erosion betroffenen Stellen, die sich durch ihre unterschiedliche Färbung gegenüber ihrer Umgebung auszeichnen.With all coatings, it is advisable to color the individual layers differently in order to be able to control the condition of the coating and its thickness. With a gray primer and alternating red and white layers of the overall coating, it is easily possible use the color to visually check the remaining coating thickness and, for example, determine when the penultimate and last layer has been reached. In this way, a full exploitation of the life of the coating is possible, as well as targeted repairs to areas particularly affected by corrosion or erosion, which are distinguished by their different coloration from their surroundings.
Die Erfindung wird durch die beiliegenden Abbildungen näher erläutert. Von diesen zeigt
- Fig. 1
- im Schnitt den mit Kühlmittelrohreintritt eines Rohrbodens in nicht korrodiertem und korrodiertem Zustand, jeweils mit Beschichtung, in drei Varianten (a) bis (c); und
- Fig. 2
- die erfindungsgemäße Beschichtung eines Rohrbodens und eintretenden Kühlmittelrohrs in ihrem schichtförmigen Aufbau.
- Fig. 1
- on average, with the coolant pipe entering a tube sheet in a non-corroded and corroded state, each with a coating, in three variants (a) to (c); and
- Fig. 2
- the coating according to the invention of a tube sheet and entering coolant tube in their layered structure.
In Fig. 1 (a) ist ausschnittsweise ein Rohrboden 1 mit einem Kühlmittelrohr 2 dargestellt. Im Bereich des Kühlmittelrohreintritts ist der Rohrüberstand 3 zu den Seiten hin aufgebogen bzw. aufgedornt. In der oberen Bildhälfte (auch in Fig. 2 (b) und (c)) weist der Rohrboden eine intakte glatte Oberfläche 4 auf, wie sie ohne besonderen Schutz praktisch nur im Neuzustand gegeben ist. In der unteren Bildhälfte ist die Rohrbodenoberfläche durch Korrosionserscheinungen insbesondere im Bereich des Eintritts des Kühlmittelrohrs erheblich geschädigt, wobei durch galvanische Korrosion tiefe Korrosionsnarben entstanden sind.A tube plate 1 with a
Die geschwärzten Teile im Bereich der Rohrbodenoberfläche 4 stellen eine Beschichtung 6 mit einer dafür geeigneten kalthärtenden Kunststoffabmischung dar. Die Beschichtung 6 geht in die Kühlmittelrohrbeschichtung über. Die Korrosionsnarbe 5 ist durch die Beschichtung vollständig ausgefüllt. Da die Beschichtungsmasse selbst chemisch praktisch inert ist, wird der Rohrboden 1 wie auch das Rohr 2 vollständig gegen das anbrandende Kühlwasser abgeschirmt. Die galvanische Korrosion wird damit weitgehend unterbunden.The blackened parts in the area of the
Fig. 1 (b) und (c) zeigen gängige Varianten des Kühlmittelrohransatzes mit bündigem Abschluß (1b) und Überstand ohne Aufdornung (1c), wobei in allen Fällen (1a bis 1c) der Rohransatz 3 vollständig in die Beschichtung 6, 7 integriert ist.1 (b) and (c) show common variants of the coolant pipe attachment with a flush end (1b) and a protrusion without a thorn-out (1c), the
Fig. 2 zeigt den schichtförmigen Aufbau der erfindungsgemäßen Beschichtung. Details der Rohrbodenbeschichtung und der Rohrbeschichtung ergeben sich aus den Ausschnitten A und B.2 shows the layered structure of the coating according to the invention. Details of the tube sheet coating and the tube coating can be found in sections A and B.
Der Rohrboden 1 selbst weist unterhalb der eigentlichen Beschichtung 6 eine Grundierung 8 auf, die auch kleinere Unebenheiten ausfüllt. Die geglättete Oberfläche der Beschichtung 6 ist zusätzlich mit einer Versiegelung 9 geschützt, die in das Rohr hinein verläuft und innerhalb der Rohrbeschichtung die äußere Schicht bildet.The tube sheet 1 itself has a
Die Wand 2 des Kühlmittelrohres ist zunächst mit einer Grundierung 11 auf der gereinigten Metalloberfläche versehen. Auf diese Grundierung 11 ist die eigentliche, gegenüber der Rohrbodenbeschichtung elastisch eingestellte Kühlmittelrohrbeschichtung 7 aufgebracht. Im dargestellten Fall ist das Kühlmittelrohr 2 nicht über seine gesamte Länge beschichtet, sondern nur im Eingangsbereich, wobei die Beschichtung insgesamt konisch ausläuft (Ausschnitt B), d. h. die aufliegenden Schichten jeweils weiter in das Rohr hineinragen, als die jeweils darunterliegende. Die letzte Schicht der Kühlmittelrohrbeschichtung 9 ist zugleich die Versiegelung 9 der Rohrbodenbeschichtung 6. Der in Ausschnitt A dargestellte gekrümmte Auslauf der Rohrbeschichtung (11, 7, 9) ist durch die Kontur des bei der Beschichtung des Rohrbodens vorgesehenen Stopfens vorgegeben, der vor der Beschichtung des Kühlmittelrohrs entfernt wird.The
Die Gesamtdicke aller Schichten beträgt im Bereich des Rohrbodens > 2000 µm und im Bereich der Rohrwandungen > 80 µm; größere Schichtdicken können ohne weiteres erzielt werden.The total thickness of all layers in the area of the tube sheet is> 2000 µm and in the area of the tube walls> 80 µm; greater layer thicknesses can easily be achieved.
Als besonders geeignet für die erfindungsgemäßen Beschichtungen haben sich Epoxidharze erwiesen, die mit einem Amin als Härter verarbeitet werden. Es handelt sich dabei um handelsübliche Systeme, die lösungsmittelfrei eingestellt sein können. Geeignete Produkte sind beispielsweise Epoxide auf Basis von Glyidylethern und von Bis-phenol A abgeleitete Epoxide, die mit einem üblichen modifizierten Polyamin gehärtet werden. Die Epoxid- wie die Härterkomponente enthalten übliche Zusätze, die die Verarbeitbarkeit, chemische und Lagerstabilität und Widerstandsfähigkeit regeln.Epoxy resins which are processed with an amine as hardener have proven to be particularly suitable for the coatings according to the invention. These are commercially available systems that can be set to be solvent-free. Suitable products are, for example, epoxides based on glyidyl ethers and epoxides derived from bisphenol A, which are cured with a customary modified polyamine. The epoxy and hardener components contain common additives that regulate processability, chemical and storage stability and resistance.
Claims (19)
dadurch gekennzeichnet,
daß die Beschichtung der Kühlmittelrohre durch zeitlich aufeinander abgestimmten Auftrag reaktiv an die Rohrbodenbeschichtung angeschlossen ist und die Beschichtung der Kühlmittelrohre im Vergleich zur Beschichtung des Rohrbodens eine größere Elastizität mit einer um wenigstens 2 %, bezogen auf die Reißdehnung der Rohrbodenbeschichtung nach DIN 53152, größeren Reißdehnung aufweist.Coating for tube sheets and coolant tubes for heat exchangers, in particular steam condensers, based on hardening plastic mixtures, obtainable by cleaning the surfaces provided for coating with the aid of abrasive agents; Closing the pipe inlets and outlets with removable plugs; Applying at least one layer of a hardening plastic coating to the tube sheet; Allowing the coating to harden so that further mechanical processing can take place and processing the surface; Removing the plugs from the pipe inlets and outlets and introducing at least one layer of a hardening plastic coating at least into the entrance area of the coolant pipes and allowing them to harden;
characterized,
that the coating of the coolant tubes is reactively connected to the tube sheet coating by means of a time-coordinated application and that the coating of the coolant tubes has greater elasticity than the coating of the tube sheet, with an elongation at break greater by at least 2%, based on the elongation at break of the tube sheet coating according to DIN 53152 .
Priority Applications (17)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE59404431T DE59404431D1 (en) | 1994-04-22 | 1994-04-22 | Coating for tube sheets and coolant tubes of heat exchangers |
ES94106304T ES2108902T3 (en) | 1994-04-22 | 1994-04-22 | COATING OF TUBE PLATES AND COOLING TUBES OF HEAT EXCHANGERS. |
DK94106304.2T DK0679853T3 (en) | 1994-04-22 | 1994-04-22 | Coatings for pipes and refrigerants for heat exchangers |
AT94106304T ATE159585T1 (en) | 1994-04-22 | 1994-04-22 | COATING FOR TUBE BASE AND COOLANT PIPES OF HEAT EXCHANGERS |
EP94106304A EP0679853B1 (en) | 1994-04-22 | 1994-04-22 | Coating for end plates and heat exchanger tubes for cooling medium |
US08/330,629 US5820931A (en) | 1994-04-22 | 1994-10-28 | Coating tube plates and coolant tube |
CA002141069A CA2141069C (en) | 1994-04-22 | 1995-01-25 | Coating tube plates and coolant tube |
PL95312222A PL177572B1 (en) | 1994-04-22 | 1995-04-04 | Coating for perforated walls and coolant carrying pipes of heat exchangers |
CZ19953368A CZ292699B6 (en) | 1994-04-22 | 1995-04-04 | Coating for tube plates and heat exchanger coolant tubes extending therefrom as well as process for its preparation |
MXPA/A/1996/000023A MXPA96000023A (en) | 1994-04-22 | 1995-04-04 | Coating for pipe plates, and cooling pipes in ac exchangers |
PCT/EP1995/001228 WO1995029375A1 (en) | 1994-04-22 | 1995-04-04 | Coating for tube bases and coolant tubes of heat exchangers |
RU96102032A RU2138752C1 (en) | 1994-04-22 | 1995-04-04 | Coat for tube sheets and cooling tubes of heat exchangers and method: of obtaining coat |
RO95-02263A RO116028B1 (en) | 1994-04-22 | 1995-04-04 | Protective coating method for hollow plates and cooling pipes of heat exchangers |
AU22153/95A AU681513B2 (en) | 1994-04-22 | 1995-04-04 | Coating for tube bases and coolant tubes of heat exchangers |
ZA953198A ZA953198B (en) | 1994-04-22 | 1995-04-20 | A coating for tube plates and coolant tubes in heat exchangers |
FI956189A FI106744B (en) | 1994-04-22 | 1995-12-21 | Coating for pipe plates and coolant pipes in heat exchanger |
US09/102,047 US6254930B1 (en) | 1994-04-22 | 1998-06-22 | Coating tube plates and coolant tube |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94106304A EP0679853B1 (en) | 1994-04-22 | 1994-04-22 | Coating for end plates and heat exchanger tubes for cooling medium |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0679853A1 true EP0679853A1 (en) | 1995-11-02 |
EP0679853B1 EP0679853B1 (en) | 1997-10-22 |
Family
ID=8215881
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94106304A Expired - Lifetime EP0679853B1 (en) | 1994-04-22 | 1994-04-22 | Coating for end plates and heat exchanger tubes for cooling medium |
Country Status (15)
Country | Link |
---|---|
US (1) | US5820931A (en) |
EP (1) | EP0679853B1 (en) |
AT (1) | ATE159585T1 (en) |
AU (1) | AU681513B2 (en) |
CA (1) | CA2141069C (en) |
CZ (1) | CZ292699B6 (en) |
DE (1) | DE59404431D1 (en) |
DK (1) | DK0679853T3 (en) |
ES (1) | ES2108902T3 (en) |
FI (1) | FI106744B (en) |
PL (1) | PL177572B1 (en) |
RO (1) | RO116028B1 (en) |
RU (1) | RU2138752C1 (en) |
WO (1) | WO1995029375A1 (en) |
ZA (1) | ZA953198B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19654736A1 (en) * | 1996-12-30 | 1997-06-19 | Hans Dieter Treptow | Component for sealing pipe plate rear side and pipe ends |
DE102005026294A1 (en) * | 2005-06-08 | 2006-12-14 | Behr Gmbh & Co. Kg | Automotive radiator has horizontal cooling pipes soldered to end-tank under plastic coating in transition zone |
DE102010047589A1 (en) | 2010-10-07 | 2012-04-12 | Techno-Coat Sa | Apparatus for internal treatment of pipes |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000202363A (en) | 1999-01-19 | 2000-07-25 | Jsr Corp | Coating film formation and hardened body obtained thereby |
CA2635085A1 (en) | 2007-06-22 | 2008-12-22 | Johnson Controls Technology Company | Heat exchanger |
IT1396816B1 (en) | 2009-12-04 | 2012-12-14 | Gma S R L | PROCEDURE FOR COATING A MECHANICAL ORGAN, AND MECHANICALLY COVERED ORGAN |
DE102014219401A1 (en) * | 2014-09-25 | 2016-03-31 | Mahle International Gmbh | Arrangement for a tempering device and tempering device |
DE102017100946A1 (en) * | 2017-01-18 | 2018-07-19 | Techno-Coat Sa | Use of SiO2 coatings in water-carrying cooling systems |
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DE7702562U1 (en) * | 1900-01-01 | Dipl.-Ing. Ernst Kreiselmaier Wasser- Und Metall-Chemie Kg, 4660 Gelsenkirchen- Buer | ||
DE2515007A1 (en) * | 1975-04-07 | 1976-10-21 | Wessels Gerhard | Synthetic cladding for heat exchangers and exchanger pipes - three-component layer provides smooth, very highly resistant surface |
WO1987001437A1 (en) * | 1985-08-31 | 1987-03-12 | Dipl.-Ing. Ernst Kreiselmaier Gmbh & Co. Wasser- U | Process for coating tube-sheets or similar for condensers, coolers, heat exchangers or similar with an anti-corrosion agent |
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GB1175157A (en) * | 1966-03-19 | 1969-12-23 | Ernst Kreiselmaier | Improvements in or relating to Steam Condensers |
DE1939665A1 (en) * | 1969-08-05 | 1971-02-25 | Exxon Research Engineering Co | Ammonia synthetsis iron-alkali metal-carrier- - catalyst |
US3689311A (en) * | 1970-11-06 | 1972-09-05 | Ler Son Co Inc | Method for external coating of cylindrical objects |
-
1994
- 1994-04-22 ES ES94106304T patent/ES2108902T3/en not_active Expired - Lifetime
- 1994-04-22 DK DK94106304.2T patent/DK0679853T3/en active
- 1994-04-22 EP EP94106304A patent/EP0679853B1/en not_active Expired - Lifetime
- 1994-04-22 AT AT94106304T patent/ATE159585T1/en not_active IP Right Cessation
- 1994-04-22 DE DE59404431T patent/DE59404431D1/en not_active Expired - Lifetime
- 1994-10-28 US US08/330,629 patent/US5820931A/en not_active Expired - Lifetime
-
1995
- 1995-01-25 CA CA002141069A patent/CA2141069C/en not_active Expired - Lifetime
- 1995-04-04 RU RU96102032A patent/RU2138752C1/en not_active IP Right Cessation
- 1995-04-04 WO PCT/EP1995/001228 patent/WO1995029375A1/en active IP Right Grant
- 1995-04-04 RO RO95-02263A patent/RO116028B1/en unknown
- 1995-04-04 AU AU22153/95A patent/AU681513B2/en not_active Ceased
- 1995-04-04 CZ CZ19953368A patent/CZ292699B6/en not_active IP Right Cessation
- 1995-04-04 PL PL95312222A patent/PL177572B1/en not_active IP Right Cessation
- 1995-04-20 ZA ZA953198A patent/ZA953198B/en unknown
- 1995-12-21 FI FI956189A patent/FI106744B/en not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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DE7702562U1 (en) * | 1900-01-01 | Dipl.-Ing. Ernst Kreiselmaier Wasser- Und Metall-Chemie Kg, 4660 Gelsenkirchen- Buer | ||
DE2515007A1 (en) * | 1975-04-07 | 1976-10-21 | Wessels Gerhard | Synthetic cladding for heat exchangers and exchanger pipes - three-component layer provides smooth, very highly resistant surface |
WO1987001437A1 (en) * | 1985-08-31 | 1987-03-12 | Dipl.-Ing. Ernst Kreiselmaier Gmbh & Co. Wasser- U | Process for coating tube-sheets or similar for condensers, coolers, heat exchangers or similar with an anti-corrosion agent |
EP0236388A1 (en) * | 1985-08-31 | 1987-09-16 | Kreiselmaier Ernst | Process for coating tube-sheets or similar for condensers, coolers, heat exchangers or similar with an anti-corrosion agent. |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19654736A1 (en) * | 1996-12-30 | 1997-06-19 | Hans Dieter Treptow | Component for sealing pipe plate rear side and pipe ends |
DE19654736C2 (en) * | 1996-12-30 | 1999-08-05 | Hans Dieter Treptow | Sealing element for sealing the back of the tube plate and the tube ends against the medium in the jacket space (space around the tubes) in heat exchangers |
DE102005026294A1 (en) * | 2005-06-08 | 2006-12-14 | Behr Gmbh & Co. Kg | Automotive radiator has horizontal cooling pipes soldered to end-tank under plastic coating in transition zone |
DE102010047589A1 (en) | 2010-10-07 | 2012-04-12 | Techno-Coat Sa | Apparatus for internal treatment of pipes |
Also Published As
Publication number | Publication date |
---|---|
CA2141069C (en) | 1999-11-16 |
EP0679853B1 (en) | 1997-10-22 |
FI956189A (en) | 1996-02-15 |
ES2108902T3 (en) | 1998-01-01 |
FI106744B (en) | 2001-03-30 |
CZ292699B6 (en) | 2003-11-12 |
FI956189A0 (en) | 1995-12-21 |
RO116028B1 (en) | 2000-09-29 |
US5820931A (en) | 1998-10-13 |
MX9600023A (en) | 1998-11-30 |
DE59404431D1 (en) | 1997-11-27 |
AU2215395A (en) | 1995-11-16 |
ZA953198B (en) | 1996-01-03 |
AU681513B2 (en) | 1997-08-28 |
WO1995029375A1 (en) | 1995-11-02 |
PL312222A1 (en) | 1996-04-01 |
CZ336895A3 (en) | 1996-07-17 |
DK0679853T3 (en) | 1998-05-25 |
ATE159585T1 (en) | 1997-11-15 |
CA2141069A1 (en) | 1995-10-23 |
RU2138752C1 (en) | 1999-09-27 |
PL177572B1 (en) | 1999-12-31 |
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