WO1995029375A1 - Beschichtung für rohrböden und kühlmittelrohre von wärmetauschern - Google Patents
Beschichtung für rohrböden und kühlmittelrohre von wärmetauschern Download PDFInfo
- Publication number
- WO1995029375A1 WO1995029375A1 PCT/EP1995/001228 EP9501228W WO9529375A1 WO 1995029375 A1 WO1995029375 A1 WO 1995029375A1 EP 9501228 W EP9501228 W EP 9501228W WO 9529375 A1 WO9529375 A1 WO 9529375A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating
- tube
- coolant
- tube sheet
- elongation
- Prior art date
Links
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 the coolant tubes of heat exchangers, in particular steam condensers, based thereon on the basis of hardening plastic mixtures which are obtained 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 systems for generating electrical energy, with a plastic coating in order to counteract corrosion phenomena.
- Tube sheets and the coolant tubes resulting therefrom are exposed to a large number of external influences, in particular mechanical, chemical and electromechanical stresses. Mechanical stresses occur due to solid particles entrained by the coolant, for example sand.
- mechanical stresses occur due to solid particles entrained by the coolant, for example sand.
- expansion occurs in the roll-in area of the coolant tubes on the tube sheet.
- Chemical stresses arise from the nature of the cooling medium, for example from its loading with salts or acidic substances.
- Electrochemical or galvanic corrosion is to be mentioned that which 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 signs of corrosion. The consequence of this is that the signs of corrosion and deposits accelerate with the age of a tube sheet, because starting points for corrosion and deposits form increasingly.
- the object of the invention is 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 is simultaneously suitable, chemi ⁇ to withstand long-term stress from the coolant.
- 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 is more elastic than the tube sheet coating with a greater elongation at break according to DIN 53152 by at least 2%, based on the elongation at break of the tube sheet coating.
- the relatively greater elasticity of the coolant tube coating results in better resistance to mechanical stress in the entrance and exit area of the tubes, 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 for the tube sheet coating should not be less than 2% in order to avoid brittleness.
- each layer on the still reactive surface of the underlying layer Layer is applied to achieve chemical crosslinking.
- two or three layers are applied both to the tube sheet and in the coolant tubes, which layers 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 the coating of already heavily corroded tube sheets which 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.
- 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 algae, dirt particles and the like from adhering. 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.
- 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 customary fillers and dyes, adjusting agents, stabilizers and other usual additives in order to ensure the properties desired, in particular processability and durability. These are customary plastic mixtures, as they can also be used for other purposes - what is decisive for the coating according to the invention is less the type of the hardening plastic mass than rather 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 inlets and outlets.
- the PTFE additive for example Hostafion (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 final hardness of the coating 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 / mm 'according to DIN / ISO 4624, preferably at least about 5 N / mm ⁇ and in particular at least 7 N / mm. According to the invention, adhesive strengths of more than 10 / mm ⁇ for the tube sheet coating and more than 5
- the compressive strength and abrasion resistance are essential for the stability of the coatings according to the invention.
- values of more than 50 N / mm ⁇ should be achieved for the coolant tube coating and more than 100 N / mm * 'for the tube bottom coating, 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 pipe inlets and outlets are closed by removable plugs, at least one layer of a hardening plastic coating is applied to the tube bottom, the coating is allowed to harden so that further mechanical processing can take place, but reactive areas remain on the surface, after which the surface is mechanically processed.
- 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 inlet 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 in the Compared to the tube sheet coating, it has 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 pipes the floor coating is adjusted to the course of the coolant pipes and a corresponding profiling is 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., it being ensured within this period 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. brings, especially by spatulas to ensure penetration into wells, 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 smoothed mechanically, in particular by working with abrasive materials.
- the smoothing process is expedient because it achieves a more uniform surface which 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 coating underneath, 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 particularly 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 base layer of the coolant tube coating is seamlessly extended to the tube sheet coating.
- the entire coating can be subjected to mechanical and chemical loads at a curing temperature of 20 ° C. after about 7 days.
- the plugs are removed from the tube inlets in the next step.
- the coolant pipe coating is then applied to the pipes, at least in their entrance area, but expediently in their entire course, onto the cleaned surface, advantageously 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 tube wall. The plastic mixtures 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 for 8 hours to 8 days in the case of epoxy resins, and then the actual coating in one or more layers, with a curing time from 6 hours to 4 days.
- Post-processing is not absolutely necessary for the coolant tube coating.
- at least the last layer of the pipe coating is in a train 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 about 40 ⁇ m, the total dry layer thickness for permanent corrosion protection being at least about 80 ⁇ m.
- the total dry layer thickness for permanent corrosion protection being at least about 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 below is completely covered by the layer above.
- the respective outer layer can also start further out than the one underneath.
- FIG. 2 shows the coating according to the invention of a tube sheet and incoming coolant tube in its layered structure.
- 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 figure, 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 one for it 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 result from the sections A and B.
- the tube sheet 1 itself has a primer 8 underneath the actual coating 6, which also fills up minor unevenness.
- the smoothed surface of the coating 6 is additionally protected with a seal 9 which runs 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 elastic in relation to the tube sheet coating, is applied to this primer 11.
- the coolant tube 2 is not coated over its entire length, but rather only in the entrance area, the overall coating tapering (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 which 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 customary additives which regulate the processability, chemical and storage stability and resistance.
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
- Thermal Insulation (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL95312222A PL177572B1 (pl) | 1994-04-22 | 1995-04-04 | Sposób powlekania ścian sitowych i wychodzących z nich rur na chłodziwo w wymiennikach ciepła |
RO95-02263A RO116028B1 (ro) | 1994-04-22 | 1995-04-04 | Metoda de acoperire de protectie pentru placile tubulare si pentru tevile de racire ale schimbatoarelor de caldura |
AU22153/95A AU681513B2 (en) | 1994-04-22 | 1995-04-04 | Coating for tube bases and coolant tubes of heat exchangers |
RU96102032A RU2138752C1 (ru) | 1994-04-22 | 1995-04-04 | Покрытие для трубных досок и охлаждающих труб теплообменников и способ получения покрытия |
FI956189A FI106744B (fi) | 1994-04-22 | 1995-12-21 | Pinnoitus putkialustoja ja jäähdytysputkia varten lämmönvaihtimissa |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94106304.2 | 1994-04-22 | ||
EP94106304A EP0679853B1 (de) | 1994-04-22 | 1994-04-22 | Beschichtung für Rohrböden und Kühlmittelrohre von Wärmetauschern |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995029375A1 true WO1995029375A1 (de) | 1995-11-02 |
Family
ID=8215881
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1995/001228 WO1995029375A1 (de) | 1994-04-22 | 1995-04-04 | Beschichtung für rohrböden und kühlmittelrohre von wärmetauschern |
Country Status (15)
Country | Link |
---|---|
US (1) | US5820931A (de) |
EP (1) | EP0679853B1 (de) |
AT (1) | ATE159585T1 (de) |
AU (1) | AU681513B2 (de) |
CA (1) | CA2141069C (de) |
CZ (1) | CZ292699B6 (de) |
DE (1) | DE59404431D1 (de) |
DK (1) | DK0679853T3 (de) |
ES (1) | ES2108902T3 (de) |
FI (1) | FI106744B (de) |
PL (1) | PL177572B1 (de) |
RO (1) | RO116028B1 (de) |
RU (1) | RU2138752C1 (de) |
WO (1) | WO1995029375A1 (de) |
ZA (1) | ZA953198B (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6440569B1 (en) | 1999-01-19 | 2002-08-27 | Jsr Corporation | Method of making coating layers containing photocatalyst and a photocatalyst coating glass formed thereby |
WO2018134302A1 (de) | 2017-01-18 | 2018-07-26 | Techno-Coat Sa | Verwendung von sio2-beschichtungen in wasserführenden kühlsystemen |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19654736C2 (de) * | 1996-12-30 | 1999-08-05 | Hans Dieter Treptow | Abdichtungselement zur Abdichtung der Rohrplattenrückseite und der Rohrenden gegen das Medium im Mantelraum (Raum um die Rohre) in Wärmetauschern |
DE102005026294A1 (de) * | 2005-06-08 | 2006-12-14 | Behr Gmbh & Co. Kg | Wärmetauscher für ein Kraftfahrzeug und Verfahren zu seiner Herstellung |
CA2635085A1 (en) * | 2007-06-22 | 2008-12-22 | Johnson Controls Technology Company | Heat exchanger |
IT1396816B1 (it) * | 2009-12-04 | 2012-12-14 | Gma S R L | Procedimento per rivestire un organo meccanico, ed organo meccanico cosi' rivestito |
DE102010047589A1 (de) | 2010-10-07 | 2012-04-12 | Techno-Coat Sa | Vorrichtung zur Innenbehandlung von Rohren |
DE102014219401A1 (de) * | 2014-09-25 | 2016-03-31 | Mahle International Gmbh | Anordnung für eine Temperiereinrichtung sowie Temperiereinrichtung |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE7702562U1 (de) * | 1900-01-01 | Dipl.-Ing. Ernst Kreiselmaier Wasser- Und Metall-Chemie Kg, 4660 Gelsenkirchen- Buer | ||
DE2515007A1 (de) * | 1975-04-07 | 1976-10-21 | Wessels Gerhard | Kunststoffbeschichtung fuer waermeaustauscher und rohre fuer waermeaustauscher |
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 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1175157A (en) * | 1966-03-19 | 1969-12-23 | Ernst Kreiselmaier | Improvements in or relating to Steam Condensers |
DE1939665A1 (de) * | 1969-08-05 | 1971-02-25 | Exxon Research Engineering Co | Katalysator fuer die Ammoniak-Synthese und Verfahren zu seiner Herstellung |
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/es not_active Expired - Lifetime
- 1994-04-22 EP EP94106304A patent/EP0679853B1/de not_active Expired - Lifetime
- 1994-04-22 DE DE59404431T patent/DE59404431D1/de not_active Expired - Lifetime
- 1994-04-22 AT AT94106304T patent/ATE159585T1/de not_active IP Right Cessation
- 1994-04-22 DK DK94106304.2T patent/DK0679853T3/da active
- 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 WO PCT/EP1995/001228 patent/WO1995029375A1/de active IP Right Grant
- 1995-04-04 AU AU22153/95A patent/AU681513B2/en not_active Ceased
- 1995-04-04 CZ CZ19953368A patent/CZ292699B6/cs not_active IP Right Cessation
- 1995-04-04 RU RU96102032A patent/RU2138752C1/ru not_active IP Right Cessation
- 1995-04-04 PL PL95312222A patent/PL177572B1/pl not_active IP Right Cessation
- 1995-04-04 RO RO95-02263A patent/RO116028B1/ro unknown
- 1995-04-20 ZA ZA953198A patent/ZA953198B/xx unknown
- 1995-12-21 FI FI956189A patent/FI106744B/fi not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE7702562U1 (de) * | 1900-01-01 | Dipl.-Ing. Ernst Kreiselmaier Wasser- Und Metall-Chemie Kg, 4660 Gelsenkirchen- Buer | ||
DE2515007A1 (de) * | 1975-04-07 | 1976-10-21 | Wessels Gerhard | Kunststoffbeschichtung fuer waermeaustauscher und rohre fuer waermeaustauscher |
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 (de) * | 1985-08-31 | 1987-09-16 | Kreiselmaier Ernst | Verfahren zur beschichtung von rohrböden od.dgl. von kondensatoren, kühlern, wärmetauschern od.dgl. mit einem korrosionsschutzmittel. |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6440569B1 (en) | 1999-01-19 | 2002-08-27 | Jsr Corporation | Method of making coating layers containing photocatalyst and a photocatalyst coating glass formed thereby |
WO2018134302A1 (de) | 2017-01-18 | 2018-07-26 | Techno-Coat Sa | Verwendung von sio2-beschichtungen in wasserführenden kühlsystemen |
US11708497B2 (en) * | 2017-01-18 | 2023-07-25 | Coattech Sa | Use of SiO2 coatings in water-carrying cooling systems |
Also Published As
Publication number | Publication date |
---|---|
CA2141069C (en) | 1999-11-16 |
ATE159585T1 (de) | 1997-11-15 |
DE59404431D1 (de) | 1997-11-27 |
CZ292699B6 (cs) | 2003-11-12 |
ES2108902T3 (es) | 1998-01-01 |
RU2138752C1 (ru) | 1999-09-27 |
FI956189A0 (fi) | 1995-12-21 |
AU681513B2 (en) | 1997-08-28 |
PL177572B1 (pl) | 1999-12-31 |
FI956189A (fi) | 1996-02-15 |
RO116028B1 (ro) | 2000-09-29 |
PL312222A1 (en) | 1996-04-01 |
CZ336895A3 (en) | 1996-07-17 |
AU2215395A (en) | 1995-11-16 |
CA2141069A1 (en) | 1995-10-23 |
DK0679853T3 (da) | 1998-05-25 |
US5820931A (en) | 1998-10-13 |
ZA953198B (en) | 1996-01-03 |
EP0679853A1 (de) | 1995-11-02 |
MX9600023A (es) | 1998-11-30 |
EP0679853B1 (de) | 1997-10-22 |
FI106744B (fi) | 2001-03-30 |
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