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
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/28—Sensitising or activating
  • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22C—FOUNDRY MOULDING
  • B22C9/00—Moulds or cores; Moulding processes
  • B22C9/06—Permanent moulds for shaped castings
  • B22C9/061—Materials which make up the mould
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
  • B22F3/115—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by spraying molten metal, i.e. spray sintering, spray casting
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
  • B22F3/12—Both compacting and sintering
  • B22F3/1208—Containers or coating used therefor
  • B22F3/1258—Container manufacturing
  • B22F3/1283—Container formed as an undeformable model eliminated after consolidation
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1646—Characteristics of the product obtained
  • C23C18/165—Multilayered product
  • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
  • C23C18/2013—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by mechanical pretreatment, e.g. grinding, sanding
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/22—Roughening, e.g. by etching
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/28—Sensitising or activating
  • C23C18/285—Sensitising or activating with tin based compound or composition
• • 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
  • C23C4/185—Separation of the coating from the substrate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y80/00—Products made by additive manufacturing
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T50/00—Aeronautics or air transport
  • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft

Definitions

• the present invention relates to a method for producing injection molding, forming, stamping and casting tools.
• the conventional way of producing investment casting models, injection, forming and punching tools as well as prototypes is to manufacture the prototypes or the tools and models according to drawings on cutting and / or eroding machines.
• Processes including stereolithography, the method of laminated object production, fixed deposition modeling and laser sintering.
• a common feature of these processes is that a 3D CAD model is first created.
• the 3D CAD constructions are converted into volume data in the CAD system.
• the 3D volume model for rapid prototyping is then divided into cross sections on the PC. These cross sections have a layer thickness of approximately 0.1 to 0.2 millimeters. After the data has been transferred to a rapid prototyping machine, the original shape is created layer by layer from polymer plastics, paper, powdered metal or similar.
• the prototypes produced in this way can often only be used to assess functionality and design.
• the rapid prototyping processes can be used in part for the processes for producing the tools.
• the prototype / model is poured out in a mold with a clay or ceramic mass.
• the resulting negative impressions are dried in ovens. Liquid metal is then introduced into the dried mold.
• Rapid prototyping technology is applied to the manufacture of tools.
• a laser melts a ceramic powder, for example zirconium silicate, in layers around the model into a casting mold.
• Another method of producing molding, injection and pressing tools is to measure the prototype on a measuring machine and to pass the data on to a CNC machine.
• CAD data can also be used. Due to the tool and scanning head geometry, it is often not possible to produce an exact tool. A tool manufactured in this way has to be manufactured for use by extensive post-processing.
• the more modern methods such as stereolithography or laser sintering, also require the model or prototypes to be divided into segments that are later combined to form the tool. be set because the machines do not exceed a certain size (approx. 400 mm x 600 mm).
• US Pat. No. 6,257,309 B1 describes a method for producing an injection mold which can be produced by thermal spraying.
• a disadvantage of this method is that the positive impression of the model must be made of a material whose melting or softening temperature is above the temperature of the material applied by thermal spraying.
• a mold made of tool steel can only be produced in accordance with the methods presented in US Pat. No. 6,257,309 B1 if the models used have a melting or softening temperature of more than 1600 ° C. In this case, only ceramic models can be used. The production of such ceramic models is, however, very complex. Therefore, this method is hardly suitable for the production of models with small tolerances.
• a method is known in which a mold is produced by thermal spraying using a model which is produced by milling a soft metal block. After milling, i.e. before thermal spraying, a copper layer is applied to the soft metal.
• the disadvantage of this method is the very complex production of the model. Due to the necessity of the machining manufacturing process, it is not possible to produce models with fine surface contours or corresponding molded parts. In addition, the production of larger models requires a considerable amount of time, which could be a reason why this method has not yet been used economically.
• EP 0 781 625 A1 discloses a method for producing mold tools for the automotive industry, in which a negative model is first generated by stereolithography. A ceramic impression is then made from this negative model. print manufactured. In order to comply with the tolerances necessary for the automotive industry, this molding process is very complex. The molds must first be frozen and then fired ceramic. The sintered ceramic mold is then coated with tool steel by thermal spraying. In addition to the very complex manufacturing process, the fact that no larger molds can be produced with this process is part of the problem with this process, since such larger molds would have flaking or cracks in the ceramic model due to the high thermal energy.
• the invention is therefore based on the object of providing a method with which casting, injection, shaping and stamping tools can be produced quickly and precisely.
• the tools produced should be suitable for small series as well as for production.
• This object is achieved according to the invention by a process for the production of injection, forming, stamping and / or casting tools and prototypes, starting from
• step iii. or step iv. be backfilled.
• step iii. or step iv. is on a corresponding mass is applied to the covering in order to ensure the rigidity of the mold, to ensure absorption into the press and, on the other hand, to evenly dissipate the energy generated during the pressing or forming.
• the backfill can either be made of the same material as is applied by thermal spraying. But it is also possible to use other materials, if necessary
• step iii. or iv. it is also possible, after step iii. or iv. to remove the intermediate layer. Before that, of course, the model has to be detached from the manufactured shape. This process variant should be selected if the applied intermediate layer made of copper or nickel would behave disadvantageously when using the corresponding tools.
• the thickness of the coating does not play a decisive role.
• the covering has an average thickness of at least 4 mm.
• the method according to the invention makes it possible for the first time to easily produce dimensionally accurate casting tools from tool steel.
• the covering has a hardness of at least 35 HRC, in particular 50 HRC.
• the model can be made from all common materials.
• plastic preferably from CKF, polyamide, polymer resin, polyethylene, polypropylene, PMMA, GFK, polyvinyl chloride, polystyrene, epoxy resin, polyether ether ketone, polyether imide, polycarbonate, polyphenyl sulfone, polyurethane, NBR, SBR, polytetrafluoroethylene and phenolic resin ,
• This plastic model can preferably be laminated by stereolithography
• LOM Object Manufacturing
• LOM laminated object manufacturing
• the roughening of the surface of the model is carried out using an abrasive, preferably using silicon arbide with the P80 grit.
• the surface pretreatment can be carried out, for example, with a modified pressure jet system.
• the blasting system is operated at a pressure of 4 bar.
• a boron carbide nozzle with a diameter of 8 mm can be used as the jet nozzle.
• the average beam duration is 4.6 s. However, it can also be between 1 s and 15 s.
• SiC with a grain size of P80 with an average grain diameter of 200 to 300 ⁇ m is preferably used as the abrasive.
• blasting media that can be used are glass balls, broken glass, ceramics, high-grade corundum, mixed corundum, normal corundum, cast steel, wire grit, chilled cast iron, Alusat, shell granulate or dry-strip.
• two pressure circuits can be installed, one each for the transport of the blasting medium and the actual acceleration process. This modification results in a very constant volume flow and a large pressure range.
• a stream of compressed air transports the abrasive to the lowest possible pressure
• the flow conditions ensure, caused by a high volume flow of the blasting medium and a low proportion of compressed air, a low wear of the system and the blasting medium.
• the cross section is only reduced at the end of the transport hose in front of the mixing nozzle in order to set the desired volume flow.
• a constant volume flow of 1 l / min is preferably specified. However, volume flows between 0.1 l / min and 3 l / min can also be selected.
• compressed air volume flow 1 flows up to the nozzle, which can be continuously adjusted within a pressure range of 0.2-7 bar.
• the blasting medium which is conveyed into the mixing nozzle at a very low flow rate, is then accelerated by the high flow rate of the compressed air flow.
• the intermediate layer is coated with copper or nickel using an external currentless chemical process.
• the component is immersed in a colloidal solution (active bath).
• a colloidal solution active bath
• the palladium nuclei that are necessary for metallization and are already present in the activator solution are adsorbed on the plastic surface.
• the tin-II or tin-IV oxide hydrate additionally formed when immersed in the colloidal solution is dissolved by rinsing in an alkaline, aqueous solution (conditioning) and the palladium seed is thereby exposed.
• chemical reduction baths can be used to nickel or copper.
• the deposition of nickel is dealt with here as an example.
• the germinated and conditioned plastic surface is immersed in a nickel metal salt bath, which allows a chemical reaction in a temperature range between 82 ° C and 94 ° C.
• the electrolyte is generally a weak acid with a pH between 4.4 and 4.9.
• the intermediate layer applied without external current in particular by electrolytic processes.
• the thin copper or nickel coatings applied without external current can be reinforced with an electrolytically deposited metal layer.
• Coating components with layer thicknesses> 25 ⁇ m is not economical due to the low deposition rate of chemical coating processes.
• only a few coating materials can be deposited with the chemical coating processes, so that it is advantageous to use electrolytic processes for other technically important coating materials.
• Another important point is the Different properties of chemically and electrolytically deposited layers with layer thicknesses> 25 ⁇ m, for example leveling, hardness and gloss.
• the basics of electrolytic metal deposition can be found in B. Gaida, "Introduction to Electroplating", EG Leuze-Verlag, Saulgau, 1988 or in H. Simon, M. Thoma, "Applied Surface Technology for Metallic Materials", C. Hanser- Verlag, Kunststoff (1985).
• Plastic parts that have an electrically conductive layer due to an electroless coating process differ only slightly from those of the metals with regard to electrolytic metallization. Nevertheless, some points should not be neglected in the electrolytic metallization of metallized plastics. Due to the mostly low conductive layer thickness, the current density must be reduced at the beginning of the electrolytic deposition. If this point is not observed, the conductive layer may peel off and burn. Furthermore, care should be taken to ensure that annoying tarnish layers are removed with specially suitable decapitation baths. Furthermore, residual stresses can destroy the layer. When nickel layers are deposited from an ammoniacal bath, tensile stresses of the order of 400 to 500 MPa, for example, can occur.
• Additives such as saccharin and butynediol can change the structure of the nickel coatings in the form of a changed grain size and form microdeformations to promote the reduction of internal stresses, which can have a positive effect on a possible premature coating failure.
• a layer made of aluminum, titanium or their alloys is applied to the metallic layer of the molding tool or prototype produced using the method according to the invention, the surface of which is anodically oxidized or ceramized.
• Such anodically oxidized or ceramicized layers of aluminum, titanium or their alloys are known on metallic objects and are sold for example under the name Hart-Coat ® or Kepla-Coat ® by the company AHC endurentechnik GmbH & Co. OHG. These layers are characterized by a particularly high hardness and a high operating resistance and by mechanical stress.
• One or more further metallic layers can be arranged between the metallic layer deposited without external current and the layer of aluminum, titanium or their alloys.
• the further metallic layers arranged between the electrolessly deposited layer and the aluminum layer are selected depending on the intended use.
• the choice of such intermediate layers is well known to the person skilled in the art and is described, for example, in the book “The AHC Surface - Manual for Construction and Manufacturing", 4th extended edition 1999.
• Foreign ion storage is black colored, ceramic oxide layer made of aluminum, titanium or their alloys.
• the ceramic oxide layer made of aluminum, titanium or their alloys, colored black by foreign ions, is of particular interest for high-quality optical elements, especially in the aerospace industry.
• the model provided with the intermediate layer can be positioned and fixed in a frame.
• This variant should be selected if the external dimensions of the part to be manufactured are to be specified. This reduces mechanical rework.
• the covering can be filled in or backfilled within this frame. Thermal spraying or pouring out with an epoxy resin which may contain metal particles or with aluminum-containing foams are particularly suitable.
• the coating applied by thermal spraying is an alloyed tool steel. This makes it easy to make high-strength and extremely wear-resistant
• Manufacture tools in less time is thermal spraying using a wettable powder, which preferably consists of 30-50% by weight of molybdenum powder and 70-50% by weight of steel powder. It is particularly preferably such a powder which consists of 50% by weight of molybdenum powder and 50% by weight of steel powder.
• the tools produced in this way are suitable for normal use in production, ie their resilience is in no way inferior to that of a tool manufactured in a conventional manner from the same material. This makes it possible for the first time to produce a production-ready tool in a very short time, which also has significant advantages in terms of dimensional accuracy.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Manufacturing & Machinery (AREA)
• Physics & Mathematics (AREA)
• Plasma & Fusion (AREA)
• Other Surface Treatments For Metallic Materials (AREA)
• Coating By Spraying Or Casting (AREA)
• Moulds For Moulding Plastics Or The Like (AREA)

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• 2004
  • 2004-04-15 JP JP2006500366A patent/JP2006523769A/ja active Pending
  • 2004-04-15 WO PCT/IB2004/050463 patent/WO2004091907A1/de not_active Application Discontinuation
  • 2004-04-15 US US10/553,356 patent/US20060188650A1/en not_active Abandoned
  • 2004-04-15 CA CA002522504A patent/CA2522504A1/en not_active Abandoned
  • 2004-04-15 EP EP04727650A patent/EP1615767A1/de not_active Withdrawn

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