Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/01—Selective coating, e.g. pattern coating, without pre-treatment of the material to be coated
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C24/00—Coating starting from inorganic powder
  • C23C24/02—Coating starting from inorganic powder by application of pressure only
  • C23C24/04—Impact or kinetic deposition of particles
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
  • C23C4/06—Metallic material
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
  • C23C4/06—Metallic material
  • C23C4/08—Metallic material containing only metal elements
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
  • C23C4/14—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
  • C23C4/16—Wires; Tubes
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
  • C23C4/18—After-treatment
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F24—HEATING; RANGES; VENTILATING
  • F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
  • F24H1/00—Water heaters, e.g. boilers, continuous-flow heaters or water-storage heaters
  • F24H1/10—Continuous-flow heaters, i.e. heaters in which heat is generated only while the water is flowing, e.g. with direct contact of the water with the heating medium
  • F24H1/12—Continuous-flow heaters, i.e. heaters in which heat is generated only while the water is flowing, e.g. with direct contact of the water with the heating medium in which the water is kept separate from the heating medium
  • F24H1/14—Continuous-flow heaters, i.e. heaters in which heat is generated only while the water is flowing, e.g. with direct contact of the water with the heating medium in which the water is kept separate from the heating medium by tubes, e.g. bent in serpentine form
  • F24H1/142—Continuous-flow heaters, i.e. heaters in which heat is generated only while the water is flowing, e.g. with direct contact of the water with the heating medium in which the water is kept separate from the heating medium by tubes, e.g. bent in serpentine form using electric energy supply
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01C—RESISTORS
  • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
  • H01C17/22—Apparatus or processes specially adapted for manufacturing resistors adapted for trimming
  • H01C17/24—Apparatus or processes specially adapted for manufacturing resistors adapted for trimming by removing or adding resistive material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01C—RESISTORS
  • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
  • H01C17/22—Apparatus or processes specially adapted for manufacturing resistors adapted for trimming
  • H01C17/24—Apparatus or processes specially adapted for manufacturing resistors adapted for trimming by removing or adding resistive material
  • H01C17/245—Apparatus or processes specially adapted for manufacturing resistors adapted for trimming by removing or adding resistive material by mechanical means, e.g. sand-blasting, cutting or ultrasonic treatment
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B3/00—Ohmic-resistance heating
  • H05B3/40—Heating elements having the shape of rods or tubes
  • H05B3/42—Heating elements having the shape of rods or tubes non-flexible
  • H05B3/46—Heating elements having the shape of rods or tubes non-flexible heating conductor mounted on insulating base
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49002—Electrical device making
  • Y10T29/49082—Resistor making
  • Y10T29/49083—Heater type
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49002—Electrical device making
  • Y10T29/49082—Resistor making
  • Y10T29/49099—Coating resistive material on a base

Definitions

• the invention initially relates to a method for producing an electrically conductive resistance layer, in which an electrically conductive material is applied to a non-conductive substrate by means of thermal spraying.
• Such a method is known from DE 198 10 848 AI.
• This describes a heating element which is produced by applying strip-shaped layers of an electrically conductive and resistance-forming material to surfaces of a substrate by means of arc sputtering or in the plasma spraying process.
• a separating layer is previously applied to the substrate by means of a printing process.
• the separating layer is made of a material such that the electrically conductive material does not adhere to those points on the substrate where the separating layer is present.
• the known method has the disadvantage that it is relative is complex and therefore the parts with the electrically conductive resistance layers are comparatively expensive. In addition, only more or less flat parts can be provided with an electrically conductive layer using the known method.
• the object of the present invention is therefore to develop a method of the type mentioned at the outset in such a way that the production of an electrically conductive layer on a substrate is simpler and less expensive, and even complex-shaped objects can be provided with such an electrically conductive resistance layer.
• the electrically conductive material from which the resistance layer is made becomes flat and in Generally applied evenly on the non-conductive surface.
• the application by means of thermal spraying ensures that the electrically conductive material adheres to the non-conductive surface.
• a wide variety of materials can be applied quickly and very evenly to the non-conductive surface in this way.
• the applied electrically conductive material is then removed at certain points by means of a suitable device. This also enables a complex shaping of the electrically conductive layer in only two work steps.
• the material When using laser radiation, the material is heated to such an extent that it evaporates.
• the use of a laser beam has the advantage that very high energies can be coupled into the electrically conductive material very quickly, so that it evaporates immediately. This instantaneous vaporization of the electrical conductive material ensures that only comparatively little heat is injected into the subsurface beneath the electrically conductive material. This is therefore not damaged in the method according to the invention. Evaporation has the advantage over burning that essentially no residues remain in the evaporated areas on the substrate and their insulating effect is very good.
• Appropriate optics of the device which emits the laser beam, can be directed onto the workpiece to be produced in almost any way.
• any complex contours can be evaporated out of the sprayed-on electrically conductive material, so that correspondingly complex contoured electrical resistance layers can be produced.
• workpieces can also be machined that are themselves three-dimensionally complex. An electrically conductive resistance layer with complex geometry can thus be produced in a total of only two work steps.
• the electrical resistance of the electrically conductive resistance layer is at least indirectly detected during the removal of the material layer in regions. In this way, precise quality control is possible directly during the production of the electrically conductive layer.
• an actual value of the electrical resistance of the electrically conductive resistance layer is compared with a target value and that the electrical resistance of the electrically conductive layer is changed by removing additional electrically conductive material in regions such that the difference between the actual value and the target value is reduced.
• Such deviations can arise, for example, from the fact that when the thermally conductive material is sprayed, different amounts of the electrically conductive material reach the substrate in some areas, so that the resulting electrically conductive layer has a different thickness at one point than at another point.
• deviations of the actual value of the electrical resistance of the electrically conductive layer from the target value can be compensated with an accuracy of +/- 1%.
• the removal of additional electrically conductive material in certain areas can include shortening or lengthening the electrically conductive layer and / or changing the width of the electrically conductive layer.
• the material layer be removed in such a way that a desired melting point in the sense of a fuse is created at at least one point on the electrically conductive layer.
• a desired melting point in the sense of a fuse is created at at least one point on the electrically conductive layer.
• the material layer is removed in such a way that the electrically conductive resistance layer is at least partially mutually shaped. This enables the formation of the longest possible electrically conductive resistance layer on a small area.
• the electrically conductive material preferably comprises bismuth, tellurium, germanium, silicon and / or gallium arsenide. These materials have proven to be particularly favorable for application by means of thermal spraying and subsequent processing using laser radiation. In addition, the relevant known technical effects can be realized with these materials.
• Plasma spraying, high-speed flame spraying, arc spraying, oxy-fuel spraying, laser spraying or cold gas spraying have proven to be favorable for the application of the electrically conductive material to the substrate.
• the electrically conductive material be applied and the material layer removed in some areas and include such a material that an electrical heating or an electrical cooling layer is formed.
• the "Peltier effect" is advantageously used in the production of an electrical cooling layer.
• the local electrical resistance of the electrically conductive resistance layer is set by a local heat treatment.
• oxides can be introduced locally into the layer, which affects the local electrical conductivity of the material. This enables a particularly precise and fine adjustment of the electrical resistance.
• the electrically conductive resistance layer is sealed. This has advantages above all in the case of a porous substrate (for example metal with an A1203 intermediate layer). Sealing reduces the risk of electrical breakdown due to air humidity, especially at high voltages. Silicone, polyimide, or water glass, the latter based on sodium or potassium, is suitable as the material for the seal. It can be applied by dipping, spraying, brushing, etc. The tightness of the seal is best when the sealing layer is applied under vacuum.
• Glass or glass ceramic can also be used as a non-conductive substrate.
• the electrical resistance layer can then be applied permanently, above all by plasma spraying.
• the good insulating properties of glass make earthing unnecessary when the resistance layer is in operation.
• the invention also relates to a heating and / or cooling device with a non-conductive base and an electrically conductive resistance layer applied to the substrate by thermal spraying.
• the manufacturing costs for such a heating and / or cooling device can be reduced if the resistance layer comprises an electrically conductive material which was initially applied to the surface by thermal spraying and which was subsequently removed in regions by means of laser radiation and thus brought into a desired shape.
• Figure 1 is a perspective view of a tube onto which an electrically conductive material is sprayed;
• Figure 2 shows the tube of Fig. 1, the electrically conductive
• Material layer is processed by means of laser radiation
• Figure 3 is a side view of the tube of Figure 2 after processing
• Figure 4 is a plan view of a plate-shaped part a meandering electrically conductive resistance layer
• FIG. 5 shows two diagrams, one diagram showing the time course of the electrical resistance and the other diagram the time course of the length of the electrically conductive resistance layer from FIG. 4 during its manufacture;
• FIG. 6 shows a section through a plate-shaped part with two electrically conductive resistance layers arranged one above the other.
• FIG. 1 and 2 show the production of a tubular instantaneous water heater: an electrically conductive material layer 14 is applied to a tube 12 made of a material which is resistant to high temperatures and forms an electrical insulator (FIG. 1).
• the application takes place by means of a device 16 with which germanium particles 18 are sprayed onto the tube 12. It is applied by cold gas spraying (also called “gas dynamic powder coating").
• the unmelted germanium particles are moved at speeds of approximately 300 - Accelerated 1,200 m / s and sprayed onto the tube 12.
• the germanium particles 18 and also the surface of the tube 12 deform.
• the impact breaks up surface oxides on the surface of the tube 12. Micro-friction due to the impact increases the temperature at the contact surface and leads to micro-welding.
• the germanium particles 18 are accelerated by means of a conveying gas, the temperature of which can be slightly increased. However, since the germanium powder 18 never reaches its melting temperature, the temperatures arising on the surface of the tube 12 are relatively moderate, so that, for example, a comparatively inexpensive plastic material can be used for the tube 12.
• the coating of the tube 12 with the germanium particles 18 is initially carried out in such a way that the entire Surface of the tube 12 is covered with the material layer 14 made of germanium (see FIG. 1).
• this material layer 14 does not yet have the desired shape: in order to be able to produce a tubular instantaneous water heater, an electrically conductive resistance layer must be produced, which extends in the manner of a spiral in the circumferential direction around the tube 12.
• a laser beam 22 is directed onto the still "informal" material layer 14 by means of a laser device 20 in such a way that an area 24, which extends in a spiral shape around the tube 12, is created, in which the sprayed-on electrically conductive material 14 is no longer available.
• the laser device 20 on the one hand, and a device, not shown in the figure, with which the tube 12 is held, are moved in such a way that a continuous working process by the laser device 20 is possible.
• FIG. 4 shows a plan view of a flat heating plate 28.
• This consists of a non-conductive base which is not visible in this plan view and on which is analogous to that shown in FIGS. 1 and 2, a flat material layer 14 was first applied, from which areas 24 were subsequently evaporated by means of a laser beam (for reasons of illustration, only one area 24 is provided with reference numerals).
• the material layer 14 from which the electrically conductive resistance layer 26 is made has been evaporated in such a way that the conductor track 26 has a cross-sectional constriction. This creates a fuse 30, by which the operation of the heating plate 28 is secured.
• a second special feature is that the heating power or the heat flow density of the electrically conductive resistance layer was corrected during its manufacture so that it corresponds to the desired heating power and the desired heat flow density with very high precision. This is done in the following way: An electrical voltage is applied to end regions 32 and 34 of the electrically conductive resistance layer 26 during the evaporation of the regions 24, so that the electrical resistance of the electrically conductive layer 26 can be measured continuously during this evaporation.
• the material layer 14 is only evaporated with the laser beam in initially very narrow areas 24. The evaporated areas 24 running horizontally in FIG. 4 thus initially only run from an edge 36 shown in dashed lines in FIG.
• the material layer 14 is first processed by the laser beam in such a way that the lower electrical end region 34 in FIG. 4 is relatively wide. This is also represented by a dashed line with the reference symbol 40.
• the electrically conductive resistance layer 26 is lengthened by a dimension d1 (cf. FIGS. 4 and 5) and the actual electrical resistance WIST then increases until it approximately corresponds to the desired resistance WSOLL.
• the final position of the boundary line of the lower electrical connection 34 is designated by the reference symbol 42 in FIG. 4.
• a plate-shaped heating device is shown in section. In contrast to the exemplary embodiments described above, it comprises not only one electrically conductive resistance layer, but two electrically conductive resistance layers 26a and 26b. An electrically non-conductive intermediate layer 46 is present between these.
• This electrical heating plate 28 is produced as follows: First, as in the above exemplary embodiments, an electrically conductive material is applied to a plate-shaped carrier 12. The application takes place over a large area by thermal spraying in such a way that the material layer resulting therefrom initially has essentially no desired shape. Subsequently, the material layer is partially evaporated by means of laser radiation (reference numeral 24a) in such a way that an electrically conductive resistance layer 26a is produced which has the desired shape.
• the electrically insulating intermediate layer 46 is applied to the finished electrically conductive resistance layer 26a in the further course of the manufacturing process. Then the process described above is repeated, i. H. again electrically conductive material is applied to the non-conductive intermediate layer 46 by thermal spraying in such a way that a second material layer resulting therefrom does not yet have the desired shape. This is then processed by means of laser radiation and partially evaporated (reference numeral 24b) in such a way that a second electrically conductive resistance layer (26b) is produced in the desired shape.
• the material of the electrically conductive layer is selected so that an electrical instead of an electrical heating layer Cooling layer is formed.
• the temperature of the heating layer is monitored by a ceramic switch.
• a ceramic switch This is understood to mean a non-mechanical switch which has an element whose conductivity depends to a considerable extent on its temperature.
• a bimetal switch can also be used.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Physics & Mathematics (AREA)
• Plasma & Fusion (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Manufacturing & Machinery (AREA)
• Thermal Sciences (AREA)
• Combustion & Propulsion (AREA)
• General Engineering & Computer Science (AREA)
• Apparatuses And Processes For Manufacturing Resistors (AREA)
• Coating By Spraying Or Casting (AREA)
• Resistance Heating (AREA)
• Conductive Materials (AREA)
• Laser Beam Processing (AREA)

Priority Applications (1)

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• 2001
  • 2001-12-19 DE DE10162276.7A patent/DE10162276C5/de not_active Expired - Lifetime
• 2002
  • 2002-12-16 EP EP20080015360 patent/EP2009648B1/fr not_active Revoked
  • 2002-12-16 AT AT02796639T patent/ATE414321T1/de active
  • 2002-12-16 PT PT80153604T patent/PT2009648E/pt unknown
  • 2002-12-16 DE DE50213016T patent/DE50213016D1/de not_active Expired - Lifetime
  • 2002-12-16 ES ES02796639T patent/ES2314125T3/es not_active Expired - Lifetime
  • 2002-12-16 EP EP02796639A patent/EP1459332B1/fr not_active Expired - Lifetime
  • 2002-12-16 ES ES08015360T patent/ES2452325T3/es not_active Expired - Lifetime
  • 2002-12-16 WO PCT/EP2002/014310 patent/WO2003052776A2/fr not_active Ceased
  • 2002-12-16 CA CA 2471268 patent/CA2471268C/fr not_active Expired - Lifetime
  • 2002-12-16 PT PT02796639T patent/PT1459332E/pt unknown
• 2004
  • 2004-06-21 US US10/872,752 patent/US7361869B2/en not_active Expired - Lifetime
• 2006
  • 2006-01-09 US US11/328,469 patent/US20060108354A1/en not_active Abandoned
• 2013
  • 2013-05-28 US US13/903,710 patent/US9029742B2/en not_active Expired - Lifetime
• 2015
  • 2015-03-26 US US14/669,836 patent/US9758854B2/en not_active Expired - Fee Related

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