WO2010133216A2 - Procédé de fabrication d'un élément en matériau composite - Google Patents

Procédé de fabrication d'un élément en matériau composite Download PDF

Info

Publication number
WO2010133216A2
WO2010133216A2 PCT/DE2010/000569 DE2010000569W WO2010133216A2 WO 2010133216 A2 WO2010133216 A2 WO 2010133216A2 DE 2010000569 W DE2010000569 W DE 2010000569W WO 2010133216 A2 WO2010133216 A2 WO 2010133216A2
Authority
WO
WIPO (PCT)
Prior art keywords
component
cavity
fiber
fibers
components
Prior art date
Application number
PCT/DE2010/000569
Other languages
German (de)
English (en)
Other versions
WO2010133216A3 (fr
Inventor
Caren Mueller
Rico Tscharntke
Original Assignee
Biostructure Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Biostructure Gmbh filed Critical Biostructure Gmbh
Priority to DE112010002052T priority Critical patent/DE112010002052A5/de
Publication of WO2010133216A2 publication Critical patent/WO2010133216A2/fr
Publication of WO2010133216A3 publication Critical patent/WO2010133216A3/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/44—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using isostatic pressure, e.g. pressure difference-moulding, vacuum bag-moulding, autoclave-moulding or expanding rubber-moulding
    • B29C70/443—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using isostatic pressure, e.g. pressure difference-moulding, vacuum bag-moulding, autoclave-moulding or expanding rubber-moulding and impregnating by vacuum or injection
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/02—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising combinations of reinforcements, e.g. non-specified reinforcements, fibrous reinforcing inserts and fillers, e.g. particulate fillers, incorporated in matrix material, forming one or more layers and with or without non-reinforced or non-filled layers
    • B29C70/021—Combinations of fibrous reinforcement and non-fibrous material
    • B29C70/025—Combinations of fibrous reinforcement and non-fibrous material with particular filler
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B29C70/86—Incorporated in coherent impregnated reinforcing layers, e.g. by winding

Definitions

  • the invention relates to a method for producing a component from a composite material which consists of at least one matrix material and a plurality of fibers embedded therein.
  • Such a component is lightweight and is said to replace metal, wood, plastic, concrete and other composites without reducing application parameters. This is to be achieved by fibers can be fixed according to a load profile of the component according to any position within the component. Thus, a component is to be created, which is adapted to the intended use of the component occurring loads and compared to alternative designs with the same strength is significantly easier.
  • EP 0 402 708 A1 discloses a lightweight composite material having a duromer matrix in which fibers are preferably initially present in prefabricated fabric layers and these individual fabric layers are stacked on top of one another and surrounded by the thermoset or duromeric resin.
  • the invention is therefore based on the problem of providing a method which overcomes the disadvantages mentioned above and allows the provision of a component made of a fibrous composite, in which an adaptation of the spatial structure of the fibers during the manufacturing process is possible without access on the fibers from the outside is necessary.
  • a method of manufacturing a composite component comprising at least one matrix material and a plurality of fibers embedded therein, the method comprising the steps of:
  • cellular structures can be produced with the method according to the invention. This makes it possible to realize insights from bionics and geometry practically and industrially. Furthermore, when constructing a fiber structure within the component, measures can be taken which specifically locally modify the physical properties of the matrix material.
  • It can be monolithic components manufactured, which are composed of a fiber-reinforced foam.
  • the fibers are here dissipatively in the component before.
  • the component is thus formed from a homogeneous material, which can be freely modified by functional groups in its physical behavior.
  • Expandable component components can consist of different functional groups in any mixing ratios. They preferably form a core structure for a cellular structure of a fiber foam, of which the .Bauteil consists.
  • Fillers for influencing the mechanical properties of the component to be produced, which surround at least the component components and / or the fibers in sections; are preferably poured in (loose);
  • Carrier components to create a supporting structure which is conductive within the component to be produced and at least partially surrounded by component components and fibers; their cores may be surrounded by frictionally bonded fibers, typically characterized by high volume and low weight;
  • Additives chemical / crystallographic substances which react with the matrix material and which are used to influence the properties of the solidified resin matrix and thus to influence the material properties of the component to be produced;
  • Expander filled with gas and / or carrier components and gas-tight closed hollow body as expandable component components that increase their volume under relative negative pressure. Typically, they are surrounded or coated with an elastomer or latex.
  • gas-filled expandable component components or expander can be arranged together with the fibers and carrier components in a first step within the cavity.
  • the expandable component components preferably form the core for building cellular structures within the component.
  • Component components that push surrounding fibers and carrier components outward i. they e.g. move away from a mid-point of the respective expander.
  • the component component or the expander formed with them can be designed such that they can expand only at defined locations and thus not in certain, predetermined spatial directions. Preferably, however, the component components or expander expand in the evacuation of the cavity in all directions almost uniformly.
  • component components and expander may have almost any geometric shape, both are preferably made spherical.
  • Particularly suitable starting materials for the production of the expanders are elastomers, natural rubber, e.g. Latex, so that the gas trapped in them or in the component component inside it can expand under a relatively low pressure.
  • expanders are, for example, gas-filled balloons or have gas-storing cores, e.g. Styrofoam, but can also - as already stated above - be enclosed by elastomers carrier components.
  • gas-storing cores e.g. Styrofoam
  • expanders allow a stable volume under normal pressure, which allows a more precise structure of the fiber architecture.
  • the expandable component components with the carrier components form cores of the cellular structures.
  • Such cores can have any spatial dimensions but are always fixed.
  • Fiber filaments connected non-positively to them can bond with filaments of adjacent expandable component components.
  • fiber filaments can be produced in a specific manner in the form of bonded or mechanically bonded short and long cut fibers and together with fillers. page 5
  • the expandable component components can be embedded in fiber layers, fiber hoses, mats, etc. or fillers. They thus form a basis of a spatially cellular structure.
  • seeds of plants or their replicas can be used as expansion-capable component components. These allow for filling of the matrix material by irradiation with micro or infrared waves, a (second) expansion stage within the component. This can also be done in an embodiment variant as an additional process step after the introduction of the matrix material. Consequently, the expansion of these component components to their final size would take place only within the component produced or at least already having the matrix material. In this way, the desired fiber structures within the component to be produced can optionally be adjusted even better, avoiding undesired voids within the matrix material or pressing excess resin out of the component.
  • a resin is used as a matrix material and cured by a resin injection or infusion process with the fiber (inner) structure to the component.
  • the process of the present invention implements parts of a "vacuum assisted resin injection” (VARI) or “resin transfer molding” (RTM) process ("vacuum assisted resin injection” or “resin transfer molding” process) and their advancements in which in each case a negative pressure is built up in a cavity.
  • VARI vacuum assisted resin injection
  • RTM refsin transfer molding
  • the component to be produced can be equipped by applying the method according to the invention with functional assemblies. These allow, among other things, property modifications of a fiber foam in the component.
  • the introduction of one or more continuous hoses can also allow the transport of liquids and gases through the component. These can also continue to allow filling with functional gases and liquids or the evacuation of such fluids, resulting in further property extensions for the component to be produced.
  • the fiber volume fraction between the expandable component parts and fibers and to an outer shape defined by the cavity is due to the pressure Page 6 from the component components or expanders specifically regulated. It is possible to define the amount, size, internal pressure and material of the expandable component parts to adjust the fiber volume fraction.
  • a targeted adaptation of the fiber profile is ensured by the expandable component components or by their embodiment as expanders, which may optionally also be capable of different expansion by the use of different materials.
  • the fibers can be positioned in the direction of a force occurring in the intended use of the component and are preferably connected three-dimensionally in the entire component to be produced in the method according to the invention.
  • the fiber volume fraction of the component to be produced is between 15-90%.
  • the fibers used in the process according to the invention are understood as meaning, for example, textile fibers, glass fibers, metal fibers or carbon fibers.
  • microstructured and all organic fibers can be used.
  • any solid or flexible negative mold is understood, which determines the later outer shape of the component to be produced. It may be this particular Page 7 is a rigid shell, a closed injection mold or a vacuum bag with flexible lateral surfaces.
  • the fibers may already rest directly on the not yet expanded component components or initially be placed loosely within the cavity. This means that the expandable component components may already be at least partially surrounded by fibers prior to their placement in the cavity, and e.g. are wrapped with fibers.
  • ordered or disordered loose fibers can be arranged separately from the expandable component components in the cavity and, for example, the expandable component components can be introduced loosely or in a specific pattern into a fiber material already in the cavity.
  • the arrangement of the expandable component components within the cavity is carried out according to a predefined pattern, by the delimited functional areas arise in the finished component, which are each optimized for the loads or forces occurring in the intended use of the component.
  • predefined regions of the component to be produced are combined to form functional groups which serve to absorb defined loads such as impact, tension or rotation. Accordingly, these regions can have fibers in the necessary density and / or orientation, wherein a desired, final fiber profile can be adjusted and adjusted by means of the expandable component components.
  • the component is therefore structurable in itself and almost arbitrarily according to performance parameters.
  • the fibers are three-dimensionally twisted / sewn together and / or positively connected with each other or with each other.
  • the component components, expanders and / or fibers can be treated with fillers and additives.
  • Embodiment arranged in at least one prefabricated Faserumhüllung and / or on a fiber surface.
  • This fiber cladding or fiber surface is in each case made of fibers, in particular of fiber filaments, fiber rovings, fiber layers, individual fiber mats or at least one fiber hose.
  • expandable component components are arranged within at least one fiber sheath formed from a fiber tube or a fiber sheath consisting of a plurality of individual chambers.
  • This fiber sheath is placed within the cavity and thus already constitutes a basic structure for the fiber structure to be realized within the component to be produced, before the cavity is evacuated and the matrix material is introduced.
  • expandable component components are arranged on a substantially flat, spread-out fiber surface with fiber material which is wound in such a way that the components arranged thereon are located inside the wound-up fiber surface and the wound-up fiber surface is arranged in the cavity before the matrix material is introduced into the cavity.
  • the entire inner and outer structure of the component is unwound into the fiber surface.
  • the fiber surface is provided with expandable component parts, e.g. partly in the form of expanders and optionally with functional ingredients, e.g. Fillers and / or additives, coated and then rolled until the fiber surface is in the form of a coil. This is introduced into the cavity, which is closed and evacuated. In the process, the component components or expander expand and press the outer layer of the wound fiber surface against the inner walls of the cavity and establish the structure present within the fiber surface.
  • expandable component components can be arranged on a fiber surface, which, regardless of whether this is wound or not, consists of individual surface-connected fiber mats.
  • fillers in the cavity are preferably before the evacuation of the cavity Page 9 arranged, which surround the expandable component components at least in sections.
  • the fiber volume fraction can be regulated and the specification of the physical properties of the matrix controlled.
  • an expansion of the component components within the cavity takes place in a through the
  • Carrier components and fibers are compressed by the expanding component components or expander.
  • matrix material are then already by the expandable component components, fibers and
  • Fillers formed supporting structures fixed in the component.
  • the fillers may furthermore be introduced into / on the prefabricated fiber sheathings and / or at least partially surround the prefabricated fiber sheathings. Likewise, fillers may be introduced into interstices or chambers of a fiber surface discussed above, the interstices being formed by area of the fiber surface in which the fiber mats making up the fiber surface are not interconnected.
  • fillers may be added to the resin matrix prior to injection / infusion.
  • Fillers are for example fiber-needle, plate or particulate and / or mineral substances, in particular carbon fibers, glass fibers, glass beads, amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, powdered Quartz, mica, barium sulfate, feldspar, aramid fibers, potassium titanate fibers, acicular wollastonite, talc, boehmite, bentonite, montmorillonite, vermicullite, hectorite or laponite, etc.
  • Particles of rubber, metal powders, dyes, pigments and their binders and adhesion promoters, organic fillers such as wood flour can be used.
  • the fillers to be applied may, for example, also be carbon nanotubes ("CNTs") contained in a solvent, or micorbalons, etc., which are sprayed onto the expandable component components, fibers and / or fillers.
  • CNTs carbon nanotubes
  • the bond between fibers and resin matrix or matrix material takes place physically. Adhesive forces connect fibers and matrix. In addition, surface defects of the fibers and the therein e.g. resinous matrix material for increased friction between fibers and matrix. These properties can be regulated by the fillers, the surface structure of the fibers and the viscosity of the resin.
  • the introduction of the matrix material preferably takes place after the evacuation of the cavity so that already expanded component components are present when the matrix material, for example a resin, is supplied.
  • the negative pressure can be regulated during and after the filling of the resin.
  • an expansion of the component components is realized only after the complete or partial filling of the cavity with matrix material. In such a case, therefore, the component components would at least partially already be within a liquid matrix material as they expand.
  • the method according to the invention can be supplemented by a gas injection into the component before and / or after hardening of the matrix material.
  • a gas injection into the component before and / or after hardening of the matrix material This is understood to mean, for example, that gas is injected locally into the expanded expander. This is a third way to regulate the cavity pressure and thus the fiber volume fraction.
  • these expander can be used by their physical connection to the outside of the component even after curing functionally for the transport or storage of substances.
  • additives are applied to the component components, to fibers and fillers in one embodiment prior to introduction of the matrix material into the cavity.
  • additives are understood as meaning, in particular, additives which influence the crystallization of the matrix material, for example of a resin.
  • Part of the present invention is, inter alia, that the properties of the resin matrix in the monolithic component in a single casting can be controlled dynamically targeted.
  • the additives By spraying or generally applying the additives to the preform, the additives are already at the location of the desired property in the component. However, this can be applied in all fiber composite techniques.
  • a matrix of resin from the matrix material by incorporating additives but also localized fillers (crystallization, density, length of the polymer chains and their unfolding, physical and chemical behavior, duration and position of the glass transition point).
  • additives and / or introducing fillers are applied to the preform, i. in particular, the fiber architecture or the already arranged in the cavity components of the composite, applied before evacuation.
  • a progressing resin front of the introduced matrix material absorbs the additives at design-determined positions and locally determines the properties of the resin solidified there. This makes the component relatively complex with e.g. defined mechanical properties. With additives, however, the resin can still be foamed in the marketplace at specified points.
  • the matrix material a resin can be used.
  • the matrix material may comprise a duromer, an elastomer or a thermoplastic.
  • the matrix material may also comprise a biopolymer which is essentially obtained from renewable raw materials.
  • thermoset mainly epoxy (EP) resins unsaturated polyester (UP) resins and vinyl ester (VE) resins are used.
  • UP unsaturated polyester
  • VE vinyl ester
  • PF phenol
  • polyamides and bismaleimides can be used.
  • Uncrosslinked polymers are vulcanized with sulfur to elastomers, which can be used in particular for the production of the expander.
  • the starting material is rubber, which, inter alia, in the form of natural rubber, isoprene rubber Page 12 and butadiene rubber is used.
  • the spatially crosslinked elastomers there are the thermoplastic elastomers. Used are, for example, styrene-butadiene-styrene triblock copolymers, polyurethanes, elastomer thermoplastic blends (eg EPDM / PP, NR / PP).
  • thermoplastics In the field of thermoplastics, semi-crystalline materials such as polypropylene (PP), polyamide (PA) and amorphous thermoplastics such as polystyrene (PS), polycarbonate (PC) are used. Particularly suitable as the matrix are polypropylene (PE), the saturated polyesters, polybutylene terephthalate (PBT) and polyethylene terephthalate (PET) and polyamides (PA).
  • High heat-resistant thermoplastic matrix materials include polysulfone (PSU), polyethersulfone (PES), polyphenylene sulfide (PPS), as well as polyetheretherketone (PEEK) and polyetherimide (PEI).
  • suitable starting materials are preferably the natural fats and oils of rapeseed, sunflower, soy, flax, hemp, castor, coconuts, oil palms,
  • Oil palm kernels and olive trees are those by the same
  • thermosets For the preparation of oleochemical thermosets, the following classes of compounds are particularly suitable:
  • Amine fatty substances (meth) acrylate-functional fatty substances preferably prepared by esterification of (meth) acrylic acid with hydroxide functionalized fats and oils, or by ring-opening reaction of epoxidized fatty substances with olefinically unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid or their mixture.
  • the most important representatives of the epoxidized fats and oils are the expoxidized linseed and soybean oil and the epoxidized rapeseed oil as well as the epoxidized sunflower oil.
  • the expandable component components or the expanders made from or with them include elastomers, polyamides, or latex, or are made from the foregoing materials to define their expandability.
  • Another aspect of the present invention is a component made according to the proposed method of the invention.
  • Conceivable are components for vehicle construction, i. the automotive industry, rail vehicle construction, aircraft construction, the manufacture of body parts and interior fittings.
  • an inventive component in the construction industry for insulation materials and structural elements in window construction for the construction of window frames, door frames and doors, in the furniture industry for the production of panels, multi-shell wall systems, furniture parts and furniture, in the electrical / energy industry for the production of computers , Home appliances, hi-fi, PA enclosures, blades and rotor blades of blowers or wind turbines.
  • the production of machine parts and panels are procedurally feasible.
  • the inventive method for the production of components and bodies whose applications are under water and in space.
  • the components according to the invention can be used for the production of bottles, hollow bodies, molded parts and technical packaging.
  • such a component can be used as a container or case or in scaffolding and stage construction.
  • a further aspect of the present invention is therefore also the use of a component made of a composite material according to the method of the invention for providing therewith at least one diffusion layer for an isobaric tank for storing a gaseous fluid, e.g. Hydrogen, produce.
  • a gaseous fluid e.g. Hydrogen
  • Such an isobaric tank has at least a first and a second diffusion layer and a jacket, wherein the first diffusion layer in the interior of the isobaric tank completely encloses a first cavity for receiving the fluid, the second diffusion layer completely encloses a second cavity in which the first cavity is completely accommodated and the shell completely encloses the second diffusion layer to seal the isobaric tank from an exterior space. Furthermore, the first and second diffusion layers are permeable to the fluid from a threshold value for the pressure applied to the respective diffusion layer by the gaseous fluid received in the isobaric tank.
  • a multi-layer Isobarentank can be constructed, which is filled with the gas to be stored at high pressure.
  • the outermost cavity of the isobaric tank, in which several other cavities are located with the fluid under the highest pressure.
  • the fluid would diffuse through the individual diffusion layers from outside to inside.
  • the permissible diffusion between the adjoining cavities via the respective diffusion layer can be adjusted specifically.
  • the permissible diffusion between the adjoining cavities via the respective diffusion layer can be adjusted specifically.
  • the material properties of the diffusion layer, the permeability of a diffusion layer is already set during production.
  • the active principle of the isobaric tank described here is not necessarily bound to the use of a component for one of the diffusion layers, which was produced by the method according to the invention.
  • FIG. 1 is a flowchart which schematically illustrates the sequence of a method according to the invention
  • FIG. 2 shows an exemplary embodiment of a component produced by the method according to the invention
  • Fig. 3 shows schematically a fiber tube in the expansible
  • FIGS. 4A-4D show various views of a fiber architecture to be arranged in a cavity, which is wound up, in which inter alia, expandable component components and functional assemblies are located in their interior, in various stages of the method;
  • Fig. 5A schematically several, provided with individual chambers
  • Fiber cladding are to be filled in the expandable component components and fillers, within a cavity for the component to be produced; Page 16
  • FIG. 5B a detail of a fiber surface consisting of a plurality of hexagonal fiber mats with expandable component components and fillers;
  • 6A-6B are sectional views of two embodiments of an isobaric tank according to the invention with a plurality of diffusion layers.
  • FIG. 1 shows schematically a possible sequence of the method according to the invention for producing a component from a composite material, in which fibers are embedded within a matrix material, for example a resin.
  • a cavity in which the components forming the component to be produced are arranged or introduced.
  • the outer shape defined by the cavity determines the later final shape of the component to be produced.
  • a cavity may, for example, be a matrix provided with a solid core or a simple hollow shape without an inner core.
  • a cavity in the form of a flexible (vacuum) bag or a combination of outer form and vacuum bag.
  • a fiber architecture is built up within the cavity in the subsequent steps.
  • This is characterized by an arrangement of fibers, fiber rovings, fiber fabrics, fiber hoses and / or mats or tiles and the arrangement of expandable component components and fillers in the cavity according to design specifications for the component to be manufactured, as provided in a step B of Figure 1 is.
  • the said components to be arranged in the cavity in particular the expansion-capable component components, can be in the form of the expander and carrier components already explained in the introduction.
  • the expandable component components may already be individually surrounded by fibers. But they can also be used in already introduced in the cavity fibers that are loose or disordered or targeted within the cavity aligned or arranged.
  • the fiber material may also be loose and present as rovings, yarns, tubes, knitted fabrics, knits, prepegs.
  • process can be additionally connected with fibers from micro to endless.
  • the aim is to surround the expandable component components or the expander with ordered and / or disordered fibers, so that the fibers within the cavity can be specifically aligned with a subsequent expansion of the component components or expander or at least the already built in the cavity shape stabilized and fixed.
  • the expander are preferably designed as filled with gas and / or carrier components hollow body made of an elastomer, so that in an evacuation of the cavity by the resulting negative pressure, an expansion of such hollow body can take place.
  • More load-bearing support structures are primarily formed by surrounding with fibers selectively expanded component components and possibly additionally filled and non-expandable carrier components. Such carrier components are preferably such that they allow a frictional connection of their surface and fibers.
  • expandable component components are inserted into a fiber tube formed from interwoven individual fibers before an arrangement of the component components takes place within the cavity.
  • Such an exemplified fiber tube can thus be designed within the cavity along a desired course.
  • a profile of a fiber tube for example, be rectilinear within the cavity, so that a kind of pressure rod is realized within the component to be produced.
  • this pressure rod is formed by the fibers of the fiber tube embedded within the later-introduced matrix material and the components accommodated therein (in particular expanders, carrier components and fillers explained below) and, with the support structure provided with it, provides a larger (tensile) area along its course. Strength within the finished component.
  • the carrying capacity and load capacity of the component not exclusively on the introduced fibers and the expandable component components and to provide greater rigidity of the support structure to be created are in a step B.2 additionally Fillers added to the cavity.
  • expansion-capable component components are preferably positioned or placed within the cavity, in one embodiment of the method according to the invention it is entirely possible to introduce additional fillers, at least partially surrounding the component components, loosely into the cavity in order to produce the fiber architecture.
  • fillers can be arranged in prefabricated Faserumhüllept, such as a fiber hose described above (see also Figure 3), together with the expandable component components.
  • prefabricated Faserumhüllept such as a fiber hose described above (see also Figure 3)
  • Component components always cause a displacement of the fibers and the fillers against each other and in the direction of the outer walls defining the cavity.
  • Fibers arranged expansionsdayen component components form after hardening of the introduced matrix material prestressed support structures in the manufactured component.
  • the fillers may include crosslinking agents, or additional crosslinking agents may be added to the fillers.
  • crosslinking agents are substances which can also be referred to as additives.
  • the additives added to the fillers can thus specifically (chemically) influence the crosslinking properties of the resin matrix.
  • crosslinking agents are also intended for the crosslinking of fibers which form lateral surfaces of fiber cladding or fiber surfaces. Although individual fibers can always be connected to each other mechanically, for example by sewing, twisting or weaving together. However, it is also possible to use the cross-linking agents in a simple manner to achieve a three-dimensional coupling of the fibers in the component at the chemical level. Page 19
  • additives can in principle be introduced into the cavity in process step B.2 during the production of the fiber architecture.
  • additives of this type for example materials which are in a solvent and influence the crystallization of the resin matrix, can preferably be sprayed or applied onto component components already surrounded by fibers.
  • additives serve e.g. volatile solvents e.g. Toluene Toluene, common name after IUPAC also toluene, methylbenzene, phenylmethane, called by the IUPAC nomenclature methylbenzene, is a colorless, characteristic smelling, volatile liquid that resembles benzene in many of its properties.
  • Toluene is an aromatic hydrocarbon, often replacing the toxic benzene as a solvent.
  • an air turbulence may be previously provided according to method step B.3.
  • Luftverwirbelung present loose fibers are mechanically linked together within the cavity.
  • the expander expand and thus define the desired inner support structure consisting of expansion-capable component components as well as fibers, fillers and additives within the cavity.
  • the shape of the expander stabilizes the fiber architecture and provides the necessary in-mold pressure.
  • the matrix material for example a resin, in particular a duromer, an elastomer or a thermoplastic
  • the matrix material can be heated to increase the viscosity.
  • VARI Vacuum Assisted Resin Injection
  • RTM Resin Transfer Molding
  • Expander is thereby created within the component made of the composite material a stabilizing and in particular three-dimensionally networked support structure, which is adapted to the loads occurring at a proper use of the manufactured component.
  • Such functional components can also be incorporated in the production of the fiber architecture prior to closing the cavity (step C of the embodiment of FIG. 1).
  • Such functional components may be, for example, any pipes or even electronic components such as sensors.
  • FIG. 2 shows a component 1 produced by the process according to the invention in the form of a mast, which is shown in cross-section in FIG.
  • the component 1 is substantially cylindrical and has a circular base.
  • fiber-surrounded expanders (component components) 20 and 21 as well as particulate fillers 3 embedded in an additive-provided cured matrix material.
  • a single expander (or even a single component component 20) is centrally located within a cavity, not shown, so that it forms an amplified center of the component 1 to be produced.
  • Longitudinal direction of the component 1 extend and each have a length which corresponds to almost a total length of the component 1. However, it is preferred if in each case a plurality of central expanders 20 and a plurality of
  • Component components 21 along the longitudinal direction of the component 1 are arranged one behind the other, wherein a central expander 20 is each surrounded by a plurality of expandable component components 21 and / or fillers.
  • the expander 20 and expansion-capable component components 21 and the surrounding carrier components and fillers 3 have been arranged within the component 1 just in functional areas 6.0 and 6.1 according to a predefined pattern to the produced component 1 targeted to these functional areas with an adapted physical To provide behavior.
  • the functional groups formed thereby are surrounded by supporting cell structures, which in turn are built up from expanders, carrier components, fibers and fillers.
  • cell structures are constructed in such a way that forces acting on each spatial dimension counteract a large number of neutral lines.
  • FIG. 3 shows a prefabricated fiber sheath in the form of a fiber tube 5 into which expandable component components 2 and surrounding fillers 3 have been introduced.
  • Such a fiber tube 5 is arranged as already fully formed Faserumhüllung in a cavity and thus allows a comparatively easy-to-hand specification of a desired fiber structure or - together with the accommodated within the fiber tube 5 expandable component components 2 and the fillers 3 - the direct specification of a defined Support structure within the component to be produced.
  • the fiber tube 5 of Figure 3 here consists of interwoven fibers F, which are then pressed upon expansion of the possibly filled with gas spherical expander or component components 2 to the outside, as indicated by the arrows for an expander 2.
  • FIG. 3 illustrates two different variants.
  • the individual fibers F of the fiber tube 5 all run parallel to each other and transversely to the direction of extension of the fiber tube 5.
  • the individual fibers F thus form a fiber structure 50 * in the form of a Unidirectional Geleges.
  • Page 22 In a subsequent expansion of Page 22
  • Component component or of the expander 2 and the associated increase in surface area of the component component or of the expander 2 the individual fibers F and the fiber structure 50 * are significantly charged to train in the fiber direction and thus biased.
  • a force acting perpendicular to the fiber direction in the pressure rod force leads to a bulge and thus to an increase in the diameter of the ball-like or cylindrical shape. This deformation counteract the loaded on train fibers until collapse.
  • the optimum performance parameters of the fibers are exploited spatially. This makes it possible to translate a compressive load for the tensile optimized fibers.
  • a further improvement can be produced by Multiaxialgelege, as they are also illustrated in Figure 3 (at a left end of the illustrated fiber tube 5).
  • a plurality of fiber layers extend as fiber structures 50, 51 and 52, each with parallel individual fibers F at different angles to one another.
  • the fiber tube 5 is defined here by a plurality of fiber bundles of individual fibers F, wherein the individual fiber bundles defining the fiber structures 50 - 52 are each inclined relative to one another or run along different directions.
  • a defined functional component can already be created in the fiber architecture of the component to be produced with such a fiber sheath in which already expandable component components 2 and / or fillers 3 are arranged.
  • This functional assembly then forms the desired and adjustable expansion of the component components 2 a desired support structure in a functional area of the finished component, which is adapted to the loads occurring during normal use.
  • FIGS. 4A to 4D show, in different views and at different stages, a further embodiment variant for the arrangement of expansion-capable component components and fillers with fibers F prior to the arrangement within a cavity.
  • FIG. 4B a fiber mat designed as a fiber base surface 6 is first of all shown in a state in which the fiber base surface 6 is opened by folding it upwards
  • Folding line L outgoing was once opened by a delivery state shown in Figure 4A delivery.
  • a lateral surface 60 thus visible in FIG. 4B forms in the later coiled state of the fiber base surface 6 (see FIG.
  • Component components 200, fillers 3 and optionally additives are included.
  • FIG. 4C shows the fiber base surface 6 in a further unwound state resulting from the unfolding of the fiber base surface 6 starting from the state of FIG. 4B.
  • the thus processed length and width of the newly spread fiber base 6 thus exceeds many times the dimensions of the unwound surface of the component to be produced.
  • FIG. 4C the sections of the fiber base 6 still wound up in FIG. 4B are thus also visible, which are designated as functional regions 61.
  • Functional regions 61 of the fiber base surface 6 are formed by shoulders, recesses and / or cuts in the fiber base surface 6 consisting of fibers F.
  • the specific configuration of the functional regions 61 of the fiber base 6 takes place on the basis of design specifications, in particular on the basis of expected or calculated forces acting on the component to be manufactured during its intended use.
  • the arrangement of the expandable component components 200 and any fillers and additives on the unfolded or unwound functional areas 61 is further carried out on the basis of the force flows occurring within the finished component along predetermined patterns 201 and 202.
  • the fiber base 6 is rewound or rolled up.
  • the fiber materials arranged in the functional areas 61 and expandable component components 200 as well as any fillers and additives are then wrapped or rolled in, so that a coil formed by the fiber base surface 6 is formed, in the interior of which Page 24 components are present and each separated by the individual winding layers of the fiber base 6 from each other.
  • the coiled fiber base 6 is shown in Figure 4D in a cross section.
  • This wound-up fiber base surface 6 is then introduced into the cavity and optionally surrounded with further fibers, expandable component components and / or fillers. With the evacuation of the cavity, the expandable component components 200 expand and so define the final shape of the internal structure of the component to be manufactured prior to the introduction of the matrix material.
  • the lateral surface 60 of the wound-up fiber base surface 6 with the components located therein adjoin an outer wall of the cavity and thus compress the lateral surface 60 during expansion of the expandable component components 200 against this outer wall or against the cavity itself.
  • the inner layers of the fiber base surface 6 are pressed upwards or downwards, that is to say essentially perpendicular to the outer surface 60.
  • the inner structure of the wound fiber base 6 is directed to or is pressed outwards.
  • FIGS. 5A and 5B further illustrate an embodiment variant for the method according to the invention, in which prefabricated fiber structures
  • a centered hexagon in which all edge lengths and rays are of equal length to the center span a surface that does not want to be deformed into the third spatial dimension. This deformation would trigger a complex tensile-pressure behavior, which the hexagonal fiber structure defies.
  • This area is a homeostatic area.
  • the variant embodiment of the method according to the invention provides a hybrid fiber architecture according to these basic geometric rules
  • the hexagonal mat consists of at least two fiber mats as the outer layer.
  • An application-oriented mix of expandable component components, fillers and additives is applied over a wide area.
  • the cutting takes place with individual fibers, rovings and yarns and forms the basic geometric structure.
  • the chambers are fixed with their contents.
  • a CNC sewing machine With the help of the fabric holder, a CNC sewing machine, the diagonal sewing system and the robot-assisted single- and double-sided sewing technology, high accuracy and reproducibility of the products are achieved.
  • the sewing machine parameters such as needle geometry, needle thickness, sewing thread tension and sewing speed, affect the mechanical properties of the end product, as well as the nature of an optional fiber material entrained on the outer sides.
  • the hexagonal mats can be used for the construction of arched surfaces.
  • the angle of suturing is modified or the tension of the entrained fiber material is changed in order to adapt the shape of the triangles dynamically to the curved surfaces in the sense of triangulation of surfaces.
  • a structure is built according to the principle of action of a geodesic dome.
  • a shingle-like structure (not shown) is selected, that is to say the seams do not have to be designed vertically.
  • FIG. 5A Shown schematically in FIG. 5A is a cavity V, in which a plurality of (in the present case two shown) fiber sheathings 5 * are arranged. These fiber sheaths 5 * are Page 26 cylindrical and each have a hexagonal base. This hexagonal base is divided into six sections by six substantially identical triangles, each forming a triangular base for the six six chambers 5a-5f located within the fiber sheaths 5 * .
  • the individual chambers 5a-5f of the fiber cladding 5 * are bounded in each case by three chamber walls W1, W2 and W3, so that the individual chambers 5a-5f are open at the two end faces of the cylindrical fiber cladding 5 * .
  • a chamber 5a-5f is preferably made of a single fiber mat which forms the individual chamber walls W1-W3 by corresponding folding and stitching along seams N.
  • the seams N preferably also connect the chambers 5a-5f with one another in order to form the individual fiber sheathings 5 * .
  • the expandable component components as well as any fillers and optionally additional fibers (not shown here) are arranged.
  • the expandable component components By projecting loose fiber bundles or loose fibers F L , with which the individual chambers 5a - 5f are sewn together, also a connection to another adjacent Faserumhüllung 5 * is possible.
  • adjoining fiber sheathings 5 * are non-positively connected to each other by twisting, stitching or interweaving and thus produce a complex, three-dimensional load-bearing structure within the component to be produced from fibers F, F L , fillers and expandable component components.
  • each chamber wall W1, W2, W3 both radially after Pressed on the outside 27, as well as by the associated with her and also outwardly depressed chamber wall W2, W3; W1, W3 or W1, W2 prevented.
  • a chamber wall W1, which defines a part of an outer surface would be pressed outward as well as such an expansion of the chamber wall W1 would be counteracted by an adjacent chamber wall W1-W3 of an adjacent fiber sheath 5 * .
  • FIG. 5B illustrates another prefabricated fiber structure in the form of a fiber surface 7.
  • This fiber surface 7 is made of several mutually hexagonal sewn fiber mats 7a - 7d.
  • the individual fiber mats 7a-7d are each connected to at least one further fiber mat 7a-7f at the corners of the regular hexagon formed by them so that there is a gap between each of three interconnected fiber mats 7a, 7b and 7c or 7b, 7c and 7d 8 is formed.
  • expansion component components 2 and 200 can be filled or arranged according to the preceding figures, in particular a complex geometric support structure with fibers, fillers and Page 28 to create expandable component components within the component to be produced.
  • a fiber surface 7 according to FIG. 5B is suitable for creating shell-like components in which at least one of the fiber surfaces 7 or also a plurality of fiber surfaces 7 are arranged to create a complex three-dimensional fiber structure within the cavity.
  • the individual fiber mats 7a-7d extend along the hexagonal one Form defining edges and along the seam N fibers F L , which can produce a frictional connection, for example by twisting, sewing or weaving to other fibers F, F L.
  • the chambers are designed to be open to allow direct contact of the fiber filaments and to be fixed as the matrix hardens.
  • FIGS. 6A and 6B illustrate two exemplary embodiments for using a component which has been produced from a composite material according to a method according to the invention.
  • FIGS. 6A and 6B each show a section through an isobaric tank T or T * , which has a plurality of individual diffusion layers D1-D3 or D1 * -D3 * produced according to the invention.
  • a cavity H1, which is defined by the (first) diffusion layer D1 forms an innermost cavity of the isobaric tank T, which lies within the respective larger cavities H2 and H3.
  • the next larger cavity H2, which is defined by the (second) diffusion layer D2 is accordingly within the next larger cavity H3, which is defined by the outermost (third) diffusion layer D3.
  • the isobaric tank T is designed for storage or storage of a gaseous fluid, for example of hydrogen, which is preferably in the innermost cavity H1 Page 29 is filled under high pressure.
  • the individual diffusion layers D1, D2 and D3 are produced by means of the method according to the invention. Due to the possible with the inventive method specific adjustment of the material properties based on the expandable component components are the diffusion layers D1, D2 and D3 from a certain (possibly different from each other) threshold or limit value for a pressure on the respective diffusion layer D1, D2 or D3 is applied, designed to be permeable to the fluid received. In other words, the individual diffusion layers D1, D2 and D3 are open to diffusion at a certain pressure value.
  • the gaseous fluid received therein may at least partially diffuse through the diffusion layer D1 into the adjacent cavity H2 so as to provide relief to the cavity H1.
  • part of the gaseous fluid to be stored within the isobaric tank T is also present in the cavity H2 at a pressure. If this pressure in the second cavity H2 increases by further diffusion through the diffusion layer D1 beyond a further (second) threshold, which is defined for the diffusion layer D2, then the gaseous fluid can move from the cavity H2 via the diffusion layer D2 into the next larger one Reach cavity H3.
  • this illustrated principle of diffusing through the individual diffusion layers D1-D3 of an isobaric tank T can be supplemented almost arbitrarily by further diffusion layers, so that such an isobaric tank has more than the three diffusion layers D1-D3 shown.
  • the outermost diffusion layer (the diffusion layer D3 in FIG. 6A) is separated by a jacket from an outer space of the isobaric tank T, which completely encloses the outermost diffusion layer (here D3) and seals against the outside space.
  • a jacket is not shown in FIGS. 6A and 6B.
  • FIG. 6B also shows a multilayer isobaric tank T * , which has three diffusion layers DT-D3 * of different sizes.
  • the diffusion layers D1 * , D2 * and D3 * are identical in their properties to the diffusion layers D1, D2 and D3 of the isobaric tank T, but have a different shape.
  • the diffusion layers D1 * -D3 * do not enclose a cylindrical cavity with a circular base, but in each case a cuboid cavity HT, H2 * or H3 * .
  • the size of the individual cavities is valid: H3 * > H2 * > H1 * .
  • FIG. 6B illustrates, with the exemplary diffusion directions S 12 and S 23, the diffusion of the gaseous fluid within the isobaric tank T * when the individual set (pressure) threshold values of the diffusion layers D 1 * , D 2 * and D3 * can be achieved.
  • This is further illustrated by the pressures P 1 , p 2 and p 3 in the cavities H1 * , H2 * and H3 * which are plotted in FIG. 6B, p 1 > p 2 > p 3 being valid in this exemplary embodiment.
  • FIGS. 6A and 6B also illustrates the advantages of the method according to the invention, in which specific functionalities, in particular diffusibility and the targeted conduction of components, fillers and additives within a fiber structure for a component produced from a composite material are easily achieved Force flows, recorded and can be adjusted during the manufacture of the component.
  • the thermal conductivity of the component to be produced can be adjusted comparatively easily and in almost any degree of detail.

Abstract

La présente invention concerne un procédé de fabrication d'un élément (1) en matériau composite comprenant au moins un matériau formant matrice (4) dans lequel sont incorporées une pluralité de fibres (F, FL), le procédé présentant les étapes suivantes: préparation d'une cavité (V) donnant forme pour l'élément (1) à fabriquer, disposition de composants (2, 2*, 20, 21, 200, 200*) expansibles de l'élément dans la cavité (V) et de fibres (F, FL) entourant au moins en partie les composants (2, 2*, 20, 21, 200, 200*) expansibles, fermeture de la cavité (V) et mise sous vide de la cavité (V) de manière à permettre l'expansion des composants (2, 2*, 20, 21, 200, 200*) expansibles, expansion des composants (2, 2*, 20, 21, 200, 200*) expansibles, apport du ou des matériaux formant matrice (4), sous forme d'un fluide, dans la cavité (V) et retrait de l'élément (1) formé par le matériau formant matrice (4) durci, les composants (2, 2*, 20, 21, 200, 200*) expansibles et les fibres (F, FL), les composants de (2, 2*, 20, 21, 200, 200*) expansibles et les fibres (F, FL) étant incorporés dans le matériau formant matrice (4). De cette façon, les composants (2, 2*, 20, 21, 200, 200*) expansibles peuvent être disposés avec les fibres (F, FL) dans la cavité (V) lors d'une première étape et c'est seulement après la mise de la cavité (V) sous vide que se forment les tracés et les structures de fibres, lorsque les composants (2, 2*, 20, 21, 200, 200*) pressent vers l'extérieur les fibres (F, FL) qui les entourent, c'est-à-dire les éloignent d'un point central des composants (2, 2*, 20, 21, 200, 200*) respectifs.
PCT/DE2010/000569 2009-05-20 2010-05-19 Procédé de fabrication d'un élément en matériau composite WO2010133216A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE112010002052T DE112010002052A5 (de) 2009-05-20 2010-05-19 Verfahren zur Herstellung eines Bauteils aus einem Faserverbundwerkstoff und dadurch hergestellter Isobarentank

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009022774.1 2009-05-20
DE102009022774A DE102009022774A1 (de) 2009-05-20 2009-05-20 Verfahren zur Herstellung eines Bauteils aus einem Verbundwerkstoff

Publications (2)

Publication Number Publication Date
WO2010133216A2 true WO2010133216A2 (fr) 2010-11-25
WO2010133216A3 WO2010133216A3 (fr) 2011-06-23

Family

ID=43028365

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2010/000569 WO2010133216A2 (fr) 2009-05-20 2010-05-19 Procédé de fabrication d'un élément en matériau composite

Country Status (2)

Country Link
DE (2) DE102009022774A1 (fr)
WO (1) WO2010133216A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012083971A1 (fr) 2010-12-23 2012-06-28 Bonnen Jesper Supports de revêtements de sol de combles

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011101853A1 (de) * 2011-05-18 2012-11-22 Marco Schaal Surfboard Carbon Nose Protector
DE102012023065A1 (de) * 2012-11-26 2014-05-28 Volkswagen Aktiengesellschaft Druckbehälter und Kraftfahrzeug

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0402708A1 (fr) 1989-06-13 1990-12-19 Bayer Ag Matériau léger et aggloméré avec une matrice thermodurcissable

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2235785A1 (en) * 1973-07-06 1975-01-31 Desplat Marie Light weight plastic moulded article has encapsulated hollow bodies - wrapped in fibrous matting
US4720244A (en) * 1987-05-21 1988-01-19 Hudson Products Corporation Fan blade for an axial flow fan and method of forming same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0402708A1 (fr) 1989-06-13 1990-12-19 Bayer Ag Matériau léger et aggloméré avec une matrice thermodurcissable

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012083971A1 (fr) 2010-12-23 2012-06-28 Bonnen Jesper Supports de revêtements de sol de combles

Also Published As

Publication number Publication date
DE112010002052A5 (de) 2012-06-06
WO2010133216A3 (fr) 2011-06-23
DE102009022774A1 (de) 2010-12-02

Similar Documents

Publication Publication Date Title
DE102010003497B4 (de) Verfahren zur Herstellung eines Aufprallschutzelementes
DE102005059933B4 (de) Flechttechnisch hergestelltes Faserverbundbauteil
DE102010043645B4 (de) Drucktankverbund
EP2429803B1 (fr) Élément structural et procédé de fabrication
DE602005005364T2 (de) Energieaufnehmer und Methode zu dessen Herstellung
EP3150363B1 (fr) Procédé de fabrication en sandwich d'une pièce pour éolienne
EP3023236B1 (fr) Procédé de fabrication de pièces composites en fibres et pre-produit
DE102013226017B4 (de) Blaskern für Faserverbundbauteile komplexer Geometrie
EP2650094A1 (fr) Procédé de fabrication d'une préforme
DE60106283T2 (de) Formverfahren
WO2010133216A2 (fr) Procédé de fabrication d'un élément en matériau composite
WO2015055614A1 (fr) Pièce munie d'une partie fixation permettant un assemblage par vis et pièce moulée et élément de fixation
EP1626859B1 (fr) Procede de production d'une piece et produit intermediaire pour la mise en oeuvre dudit procede
EP3843981A1 (fr) Produit semi-fini composite en fibres, pièce structurale composite en fibres, élément de pale pour rotor, pale pour rotor et éolienne ainsi que procédé de production d'un produit semi-fini composite en fibres et procédé de production d'une pièce structurale composite en fibres
EP3291972B1 (fr) Composite hybride à matériaux multiples renforcé par un textile et son procédé de fabrication
DE102013020871A1 (de) Strukturbauteil für ein Kraftfahrzeug
DE102017130341A1 (de) Verfahren zur herstellung von sandwichbauteilen mit faserverstärkten decklagen
DE102014017809B4 (de) Verfahren zur Herstellung eines Strukturbauteils
EP3030781B1 (fr) Élément composite et procédé de fabrication d'un élément composite
WO2019020703A1 (fr) Procédé de fabrication d'un ressort hélicoïdal
EP3460114A2 (fr) Structure composite renforcée par fibres, noeuds de raccordement destinés à la construction de bâtiments et procédé de fabrication de noeuds de raccordement destinés à la construction de bâtiments
EP3023235A1 (fr) Procede de fabrication d'elements composites fibreux et element composite fibreux
DE102017113928A1 (de) Faserverbundbauteil sowie eine Vorrichtung und ein Verfahren zur Herstellung eines Faserverbundbauteils
DE102016210180B4 (de) Verfahren und Vorrichtung zur Herstellung eines Schaumkerns in einem faserverstärkten Kunststoffbauteil und Kunststoffbauteil
DE2853464A1 (de) Kernschicht fuer leichtbauteile

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10743007

Country of ref document: EP

Kind code of ref document: A2

WWE Wipo information: entry into national phase

Ref document number: 112010002052

Country of ref document: DE

Ref document number: 1120100020523

Country of ref document: DE

REG Reference to national code

Ref country code: DE

Ref legal event code: R225

Ref document number: 112010002052

Country of ref document: DE

Effective date: 20120606

122 Ep: pct application non-entry in european phase

Ref document number: 10743007

Country of ref document: EP

Kind code of ref document: A2