EP2153159B1 - Verfahren zur herstellung eines verbundstoffes, insbesondere eines kugelsicheren verbundstoffes, und damit erhalter verbundstoff - Google Patents

Verfahren zur herstellung eines verbundstoffes, insbesondere eines kugelsicheren verbundstoffes, und damit erhalter verbundstoff Download PDF

Info

Publication number
EP2153159B1
EP2153159B1 EP20080805945 EP08805945A EP2153159B1 EP 2153159 B1 EP2153159 B1 EP 2153159B1 EP 20080805945 EP20080805945 EP 20080805945 EP 08805945 A EP08805945 A EP 08805945A EP 2153159 B1 EP2153159 B1 EP 2153159B1
Authority
EP
European Patent Office
Prior art keywords
yarns
layer
composite material
composite
fabric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP20080805945
Other languages
English (en)
French (fr)
Other versions
EP2153159A1 (de
EP2153159B9 (de
Inventor
François BOUSSU
Virginie Begus
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ensait
Original Assignee
Ensait
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 Ensait filed Critical Ensait
Publication of EP2153159A1 publication Critical patent/EP2153159A1/de
Publication of EP2153159B1 publication Critical patent/EP2153159B1/de
Application granted granted Critical
Publication of EP2153159B9 publication Critical patent/EP2153159B9/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41WEAPONS
    • F41HARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00Armour; Armour plates
    • F41H5/02Plate construction
    • F41H5/04Plate construction composed of more than one layer
    • F41H5/0471Layered armour containing fibre- or fabric-reinforced layers
    • F41H5/0485Layered armour containing fibre- or fabric-reinforced layers all the layers being only fibre- or fabric-reinforced layers
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/27Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]

Definitions

  • the present invention is in the technical field of composite materials for structuring applications, and more particularly for ballistic protection.
  • the low energy impact is the impact of handgun and shotgun ammunition using non-perforating soft core bullets ranging in size from about 0.22 inches to 0.44 inches.
  • the structures mainly used against this type of impact are called flexible protections. They are built of a succession of fabric layers, UD (UniDirectional) or nonwoven linked by seams in the form of checkerboard, rhombus or cross.
  • the high-energy impact corresponds to the impacts caused by ammunition of weapons of war, such as assault rifles Famas and Kalashnikov (caliber 5.56 mm, 7.62 mm, ...) or heavy machine guns (caliber 12.7 mm) ) Equipping aircraft, tanks, ....
  • weapons of war such as assault rifles Famas and Kalashnikov (caliber 5.56 mm, 7.62 mm, ...) or heavy machine guns (caliber 12.7 mm) ) Equipping aircraft, tanks, ....
  • the so-called "perforating" balls have an internal warhead made of very hard and very dense metal (tungsten, hardened steel for example).
  • Ballistic protection for weapons and piercing weapons ammunition requires the use of two types of hard protectors: monolayer shield consisting of a composite material alone and the bilayer shield consisting of a composite associated with a ceramic or composite plate and a steel plate. Ceramics are used in the field of ballistic protection for their low surface density compared to that of metal plates and their high hardness.
  • the composite material absorbs the kinetic energy by the deformation of its fibrous structure, ie its reinforcement, and intercepts the fragments.
  • the projectiles considered may be bullets, rockets or fragments of them.
  • projectiles armored, perforating, expansive bullets, ...) which are differentiated by their mass, shape (ogive, spherical, %), the material constituting them (lead, hardened steel %) and in particular their speed of impact.
  • composite materials for ballistic protection are formed of the superposition of textile layers (knit, fabric, nonwoven, Uni Directional reinforcement, "Non Crimp Fabric” or NCF corresponding to non-wetted fabrics) optionally with inorganic layers, embedded in a matrix, such as an epoxy resin.
  • the matrix in these materials is incorporated by liquid means, for example by the process "RTM” (Resin Transfer Molding), or by gas.
  • RTM Resin Transfer Molding
  • the textile reinforcements used can also be pre-impregnated, so-called prepegs.
  • the textile reinforcements of the composite materials are oriented in a single direction in order to eliminate the cross points.
  • These are unidirectional reinforcements in which the long fibers, arranged parallel to each other and in the same plane, are embedded in a matrix. It is also possible to orient the layers relative to each other according to different angles (0 °, 45 °, 90 °, ...) to improve the distribution and transfer of energy in the composite.
  • the UD folds proposed in the composites on the market are oriented at 0 ° / 90 °.
  • a composite is also known whose textile reinforcement comprises folds of fabric obtained according to an orthogonal weaving technique developed by the company 3Tex® and described in US Pat. EP 1.386.028 B1 .
  • This weaving technique makes it possible to attenuate the delamination observed in laminated composites of 2D or UD plies, and to reduce the number of pleats required.
  • EP 0424216 A describes a method of manufacturing a composite material forming part of the state of the art with regard to the present invention.
  • the subject of the present invention is a method for manufacturing a composite material making it possible to obtain a composite material having an improved delamination behavior, a weight per unit area lower than the density of the composites on the market with equivalent performance, less expensive and simpler to manufacture.
  • the subject of the present invention is a method for manufacturing a composite material, comprising a textile reinforcement and a polymer matrix, for ballistic protection,
  • 2.5D weaving refers to the weaving technique for obtaining fabrics called "warp interlock" or 2.5D, which can be performed on a conventional loom and to introduce son in the thickness of a multi-layered fabric.
  • the warp interlock fabric is in the form of a multi-layer fabric whose connection between the layers is provided by the warp son.
  • the weaving technique used is that of multichain weaving on a warp and weft loom in which the opening of the shed is unidirectional unlike weaving in 3 dimensions.
  • Interlocks fabrics can be woven on all types of looms adapted to receive the layers of warp son required for the manufacture of said fabrics.
  • the number of layers of warp threads is a function of the number of blades available on the loom and the fitting width of the chosen armor.
  • 2.5D fabrics are suitable for the manufacture of thin structures because there are no inter-layer cavities such as in a three-dimensional (3D) fabric. This arrangement makes it possible to optimize the quantity of polymer matrix and promotes the production of lightweight composite materials.
  • a 2.5D fabric is a multilayer fabric having at least three layers or plies.
  • the temperature T 0 of the heat treatment is preferably between the melting temperature of the second son T f2 and the melting temperature of the first son T f1 , T f1 being greater than T f2 , so that the first son are not altered .
  • the second son can be inserted in warp or weft, and this over the entire thickness, width and length of the interlock fabric, so that during said heat treatment the resulting molten polymer said second son impregnate heart said first son, and despite the sometimes significant thickness of the interlock fabric.
  • Said first son are impregnated at the core and on the surface of the polymer matrix.
  • the selected weave, the number of layers of the interlock fabric and the nature of the second threads are determined depending on the application of the composite material.
  • the second son may be multi-component yarns, gimped, fiber yarns and / or multi-filament yarns.
  • the first yarns are preferably monofilaments or multi-filament yarns in a high performance polymer.
  • the incorporation of the polymer matrix in the form of hot melt threads during the weaving step eliminates the step of incorporating the matrix by liquid or gaseous subsequent to the textile reinforcement forming step in the state of the technique.
  • the quality of the impregnation is not with these techniques satisfactory for composite materials of large thickness, of the order for example of 20-25 mm for the composite materials forming the back layer of the composite assemblies for the shielding, several textile pleats are then impregnated individually and glued together.
  • the 2.5D weave making it possible to obtain an interlock fabric having a thickness of up to several tens of millimeters, these superposition and bonding stages of the various plies they are removed, which represents a considerable saving of time and money.
  • the pressure exerted on the composite material under vacuum makes it possible to compact it and thus improve the impregnation of the first son.
  • the manufacturing process can be carried out continuously by arranging the means necessary for said heat treatment at the output of the 2.5D weaving step.
  • the composite materials obtained according to the present invention for ballistic protection are very resistant to delamination, which is particularly advantageous in the case of multi-impact shots.
  • said interlock fabric comprises first threads impregnated at the core and at the surface in the direction of its thickness which maintain the cohesion of the structure of said material under an impact, and thereby reduce the delamination effects that it is usually observed in the laminates of the state of the art.
  • the delamination must, however, be retained so that the composite material after an impact does not fall apart completely.
  • the folds of the fibrous reinforcement delaminate progressively while sliding relative to one another in a controlled manner so that one fold adjacent to another fold is ultimately offset relative to to this other fold but always in solidarity with it. It is indeed possible to decompose the behavior of said composite material in three successive steps following impact.
  • a first step the fibers at the periphery of the composite material are sheared and cut.
  • the shock wave propagates in the adjacent folds causing the elongation of the fibers until their breaks.
  • the composite material generally behaves like a spring and the projectile sinks into the thickness of the composite material forming a tunnel.
  • the composite material thus has excellent resistance to delamination while allowing the composite material to delaminate in a controlled manner, which is particularly advantageous in the case of a multi-impact shot.
  • the folds of a 2.5D fabric are bound by the warp threads and not by the weft threads by definition. It is thus possible to exert prestressing on the warp or weft threads during the weaving operation in order to position the threads in a better working configuration as a function of the mechanical stress envisaged during the use of said composite material. .
  • the fact of exerting a prestressing on the weft threads if possible equal to that exerted on the warp threads for a number of warp threads substantially equal to the number of threads weft, makes it possible to obtain a rear deformation of the iso-directional composite material.
  • Said manufacturing method makes it possible to obtain composite materials for ballistic protection, particularly in the following fields: protection of persons by means of vests, breastplates, helmets, and armor of land vehicles (tanks, combat vehicles, etc.), air (helicopters, transport planes ..) and marine (assault boats type cruiser and destroyer, aircraft carriers, submarines, ).
  • the composite material obtained can also be used for the manufacture of structural parts having improved mechanical performance, particularly in aeronautics and aerospace.
  • the composite materials obtained according to the present invention can be used alone, not used in composite assemblies, for protection against non-perforating bullets or against attacks with a blade.
  • High performance yarns are understood to mean yarns having a toughness substantially greater than 60 cN / Tex. This value makes it possible to distinguish the high-performance yarns from the conventional yarns used in particular in the field of clothing whose toughness is generally less than or equal to 60 cN / Tex.
  • the first yarns are preferably selected from the following families of polymers, alone or as a mixture: aromatic polyamides such as para-aramid (poly-p-phenylene terephthalamide), meta-aramid (poly-m-phenylene isophthalamide), and para-aramid copolymers; aromatic polyimides; high performance polyesters, high density polyethylene (HDPE); polybenzoxazoles such as PBO (p-phenylene benzobisoxazole) and PIPD (polypyridobisimidasole); polybenzothiazoles; and glass, in particular of the S-2® brand marketed by AGY®.
  • aromatic polyamides such as para-aramid (poly-p-phenylene terephthalamide), meta-aramid (poly-m-phenylene isophthalamide), and para-aramid copolymers
  • aromatic polyimides such as para-aramid (poly-p-phenylene terephthalamide), meta-aramid (poly-m-pheny
  • the first threads for ballistic protection are high density polyethylene yarns or S-2® brand glass fibers.
  • the HDPE yarns have a density of less than 1 g / cm 3 ensuring their buoyancy, and in particular a high elastic modulus, high tenacity and good resistance to abrasion.
  • S-2® glass fibers have a very high transverse compression modulus, unlike organic fibers, which gives them good ability to break up piercing projectiles.
  • the first HDPE yarns are based on the UHMWPE polymer ("Ultra High Molecular Weight PE”), and have a toughness greater than 2N / Tex, or more than 3N / Tex depending on the grades.
  • the first threads have a toughness greater than 1 Newton / Tex.
  • the second son are in one or more families of polymers: polypropylene, low density polyethylene, polyester and polyamide.
  • the weave is of the diagonal type, in particular of the diagonal type 5-4.
  • the so-called diagonal armor ensures good dimensional stability to the textile reinforcement, especially during an impact.
  • All Weaving armors, especially of the diagonal type, favoring the floats and thus making it possible to minimize the points of connection between the layers of the interlock fabric, also known as crisscross points are preferred.
  • the shock wave propagates in the son by coupling to the crossing points.
  • the waves are reflected and superimposed causing the elongation of the first son forming the textile reinforcement until they break.
  • Textile reinforcements having a limited number of cross points have better resistance to delamination and impact.
  • the temperature T 0 of the heat treatment is in the range [T f2 +
  • the manufacturing method according to the invention comprises an intermediate step, between the 2.5D weaving step and the heat treatment as described above, during which the reinforcement is superimposed in this order: textile obtained after said 2.5D weaving step, a first layer in a fusible polymer material, a second layer, preferably a para-aramid fabric layer, a third layer in a fusible polymer material a fourth layer, especially in a ceramic-based material; and in that during the heat treatment said first and third layers melt and bond the obtained composite material with said second and fourth layers so as to form a composite assembly for ballistic protection.
  • Said first and third layers are preferably a polyurethane film.
  • Said second layer is preferably a fabric, such as a fabric, based on para-aramid yarns. Said second layer is preferably calendered with a low density polyethylene film.
  • the fourth ceramic layer may be monolithic or formed of small tiles, flat or curved.
  • Said composite material forms, in the composite assembly for ballistic protection, in particular for shielding, the rear layer, that is to say the layer disposed in said assembly as close as possible to the element to be protected, the human body for example in the case of bulletproof vest.
  • the subject of the present invention is, according to a second aspect, a composite material obtained by implementing the manufacturing method described above, the 2,5 D woven fabric reinforcement comprising high performance yarns chosen from the families of organic polymers.
  • aromatic polyamides such as para-aramid (poly-p-phenylene terephthalamide), meta-aramid (poly-m-phenylene isophthalamide), and para-aramid copolymers
  • aromatic polyimides high performance polyesters, high density polyethylene (HDPE); polybenzoxazoles such as PBO (p-phenylene benzobisoxazole) and PIPD (polypyridobisimidasole); polybenzothiazoles; or among the following fibers: glass, in particular of the S-2® brand, carbon, alumina, silicon carbide, boron carbide.
  • the first son forming the textile reinforcement for ballistic protection are high density polyethylene yarns or S-2® brand glass fibers.
  • the polymer matrix is thermoplastic, and represents by weight less than 30%, preferably less than 20%, of the total basis weight of said composite material.
  • the insertion technique by weaving the polymer matrix into the interlock fabric makes it possible to optimize the quantity of matrix required.
  • This arrangement makes it possible to lighten the mass per unit area of the composite material according to the invention compared to that of the composite materials of the state of the art to equal performance.
  • the degree of reinforcement is thus very high, of the order of at least 70%, preferably at least of the order of 80%, and makes it possible to confer high mechanical performances on the structuring parts comprising said composite material.
  • the polymer matrix is in one or more families of polymers: low density polyethylene, polypropylene, polyamide, polyethylene terephthalate, and especially in low density polyethylene.
  • said textile reinforcement is typically formed of a single fold of fabric.
  • the method according to the invention advantageously makes it possible to obtain an interlock fabric in a single weaving operation having an adjustable weight / m 2 and thickness as well as a polymer matrix disposed at heart by virtue of said second woven threads.
  • said composite material is not formed of the superposition of several folds, each fold being formed by an individual textile, but formed of a textile reinforcement comprising only one fold comprising a multi-layer fabric.
  • the object of the present invention is, according to a third aspect, a composite assembly for ballistic protection, the rear layer of which is formed of a composite material as described above.
  • the composite material according to the invention is used as a rear layer in a composite assembly, the front layer of said assembly preferably comprising a material having properties fragmentation of said balls.
  • back layer is meant that the composite material is disposed in said assembly so as to be closer to the element to be protected, for example oriented towards the interior of the cockpit of a helicopter in the case of shielding of air vehicles.
  • Said composite assembly is used for the shielding used in personal equipment and in particular in soft vests, bibs and helmets, or in the structuring panels forming the land vehicles (tanks, combat vehicles, etc %), air (helicopters, have transport, etc %) and sailors (aircraft carriers, etc ).
  • the composite assembly comprises from behind forwards: a composite material, a first layer made of a fusible polymer-based material, a second layer, preferably comprising a layer of para-aramid fabric, a third layer in a fusible polymer-based material, a fourth layer, especially in a ceramic-based material.
  • the fourth layer is arranged so as to directly face a possible impact when said composite assembly is used, and has the function of fragmenting the hard core munitions of the perforating bullets and reducing the impact kinetic energy.
  • the composite material has a basis weight of the order of less than 11 000 g / m 2 .
  • the applicant has developed a composite material used as a back layer in a composite assembly for the shielding having a basis weight of the order of 10% less than the equivalent performance-based composite weights of composite materials. This provision has a considerable saving in energy especially for the protection of air vehicles, and preserves the wear of mechanical parts (shock absorbers, ...) of land vehicles.
  • the loom 1 partially represented in the figure 1 5.
  • the interlock fabric 5 is formed in this example of five layers 2 of warp and weft son 6. These layers 2 are themselves linked to each other by warp son.
  • the weft threads 6 are inserted into the thickness e 0 of the interlock fabric 5.
  • the basic tack A 1/1 shown in the figure 2 is a 5-4 diagonal with 3 out of 3.
  • the off-set is the shift from one pick to another.
  • the number of layers of warp yarns is equal to the number of blades available on a loom divided by the fitting width of the armor chosen.
  • the loom used in this embodiment, and not shown, comprises 24 blades.
  • the blades are the frames supporting the rails.
  • the interlock fabric 7, obtained by using the basic armor A 1/1 and shown in FIG. figure 4 thus comprises eight layers of CH1 to CH8 warp yarns woven with nine T1 to T9 yarns, including three yarns of woven chains per layer.
  • the warp threads C 1 to C 3 correspond to the layer CH 1 of the interlock fabric 7 according to the table represented in FIG.
  • FIG 3 and more particularly are woven according to the armor A 1/1 also represented in the figure 2 .
  • the diagonal armors allow to have a height connection, here nine, much larger than the connection width, here three, if the uncheck divides the fitting height.
  • This type of armor makes it possible to approach the structure of unidirectional textile reinforcements by minimizing the number of binding points.
  • the warp C 1 passes over the T 1 to T 5 and then under the T 6 to T 9 .
  • the chain wire C1 crosses only four picks, between T 5 and T 6 and T 9 and T 1 , on nine picks, which corresponds to two binding points or crossing points out of nine, ie about 22% tie points. . It is the same for the C2 and C3 chain son.
  • the interlock fabric 7 thus comprises a low tying rate of the order of 22%. This binding rate makes it possible to ensure good dimensional stability to the interlock fabric 7 used as a textile reinforcement during an impact. In addition, it reduces the coupling at the crossing points of the shock waves following an impact and thus improves the resistance to delamination, particularly in the case of multi-impact shots.
  • the abbreviations LM and BM at the intersection of the boxes comprising the abbreviations CH1 to CH8 for the chain layers one to eight and the frame son T 1 to T 9 correspond to Lifting Mass and Lowering Mass, respectively.
  • the term Lift Mass and Lower Mass respectively means lifting and lowering frames supporting the rails.
  • the figure 4 represents the interlock fabric 7 in a longitudinal section.
  • the CH1 layer of said fabric 7 is formed of C1 to C3 chain son, and is bonded to the CH2 layer by these same warp son.
  • the ability of a wire to propagate a wave is very important in the field of ballistic protection since it allows to dissipate the kinetic energy due to (x) shock (s) more or less quickly.
  • Yarns with a velocity of more than 10,000 m / s are high-density polyethylene yarns; the para-aramid yarns and the glass yarns, in particular of the S-2® brand, have a very interesting propagation speed since they exceed 8000 m / s.
  • the chain son C 1 to C 24 are the first son and are preferably high density polyethylene son, such as those marketed under the Spectra® brand by HoneyWell®.
  • the first yarns respectively show toughness, tensile strength and an elastic modulus of 2.52 GPa, 2.31 GPa, and 62 GPa.
  • the second hot-melt yarns are inserted in weft, and preferably one yarn on four of the weft yarns T 1 to T 9 is a second hot-melt yarn.
  • the second yarns are of low density polyethylene, and have by way of example a tensile strength, an elongation at break and a Young's modulus respectively of 8 MPa, 200% and 170 MPa.
  • the titration of the first and second yarns is determined so that the interlock fabric 7 has a basis weight of the order of 3660 g / m 2, including 2930 g / m 2 for the first yarns formed by the HDPE yarns and 730g / m 2 for the second son formed by hot melt son LDPE.
  • the weight per second son is of the order of 20% of the total mass per unit area of the interlock fabric 7.
  • the interlock fabric at the end of the loom has a thickness e1 of the order of 7 mm.
  • the composite assembly 14 shown in FIG. figure 5 is used for the shielding, that is to say in protection of piercing ammunition as described above. It comprises a composite material 8 formed in this order of three plies p1, p2 and p3 each comprising a layer of interlock fabric 7 and interposed with a hot melt film 9 for their adhesion.
  • the composite material 8 forms the rear layer of the composite assembly 14.
  • the composite assembly 14 also comprises, disposed on the fold p3: a first layer 10 in a fusible polymer-based material, a second layer 11 in a fabric made of calendered para-aramid with a LDPE film, a third layer 12 in a fusible polymer-based material, a fourth ceramic layer 13.
  • Layers 9, 10 and 12 are in a thermofusible polyurethane film.
  • the fourth layer 13 is formed of four alumina tiles arranged in staggered rows, not shown.
  • the composite set 14 then undergoes a marouflage step of having on the set 14 a felt then a self-removing film and a not shown tarpaulin. Once said tarpaulin is sealed by means known in the state of the art, the evacuation of the assembly is performed and is intended to compact the assembly including the pleats p1 to p3 with the ceramic tiles.
  • the assembly 14 is then subjected to a heat treatment having a treatment temperature of between 100 ° C.
  • the treatment temperature is lower than the glass transition temperature of the high density polyethylene son in order not to degrade them.
  • the composite assembly 14 once cooked is removed from the mold.
  • the composite material 8 has a surface density of the order of 11 000 g / m 2 , the polymer matrix formed by the second melted wires represents 20% of the total basis weight of the composite material 8.
  • the three plies p1 to p3 each formed a layer of interlock fabric 7 and interposed with the films 9 have a thickness of the order of 20 mm.
  • the temperature T 0 of the heat treatment is determined so as to obtain the fusion of the second son without altering the first son.
  • T 0 is in the range [T f2 +
  • the layer 13 is the one disposed impacted first by an impact when the composite assembly 14 is used, the composite material 8 facing the element to be protected.
  • the composite assembly 14 was impacted according to MIL-PRF-46103E with a 12.7 mm bore (weight: 43 g).
  • the speed of the ball must be of the order of 610 m / s according to the aforementioned standard.
  • the impact formed a hole whose diameter is between 120 and 150 mm and the depth is between 20 and 25 mm.
  • the impact left on the surface of the ply p3 on the composite material 8 is very clear compared to that left on the composite assembly of reference consisting of 48 folds UD superimposed in HDPE and glued with LDPE films.
  • the impacted surface once the ceramic de-fragmentation layer has been removed, has exploded wires and highly deformed areas.
  • there is observed in the thickness of the composite material 8 a slight delamination between the plies p1, p2 and p3 sufficient to absorb the kinetic energy due to the impact but limited in order to minimize any dislocation of the composite material 8.
  • the delamination behavior of the composite material 8 is improved by directly weaving an interlock fabric having a surface density of the order of 11 000 g / m 2, of which 20% is formed by second hot melt threads.
  • the back layer of the reference composite assembly has a surface density of the order of 10% greater than that of the composite material 8.

Landscapes

  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Aiming, Guidance, Guns With A Light Source, Armor, Camouflage, And Targets (AREA)
  • Woven Fabrics (AREA)
  • Laminated Bodies (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Reinforced Plastic Materials (AREA)

Claims (13)

  1. Verfahren zur Herstellung eines Verbundwerkstoffes (8), umfassend eine textile Verstärkung (7) und eine Polymermatrix für ballistischen Schutz, umfassend:
    a) einen Schritt der Bildung der textilen Verstärkung (7) durch Weben in 2,5D von ersten Fäden mit zweiten Fäden nach einer bestimmten Bindung (A1/1), wobei die zweiten Fäden aus einem wärmeschmelzenden Polymer und die ersten Fäden Hochleistungsfäden sind, um ein Interlock-Gewebe (7) zu erhalten, das in Form eines mehrschichtigen Gewebes vorhanden ist, dessen Verbindung zwischen den übereinander liegenden Schichten durch Kettfäden gewährleistet ist,
    b) gefolgt von einer Wärmebehandlung, während der das Interlock-Gewebe (7) bestimmten Temperatur- und Druckbedingungen unterzogen wird, um die zweiten Fäden zu schmelzen, um die Polymermatrix ohne Beeinträchtigung der ersten Fäden zu bilden.
  2. Herstellungsverfahren nach Anspruch 1, dadurch gekennzeichnet, daß die ersten Hochleistungsfäden eine Reißfestigkeit von über 1 Newton/Tex haben.
  3. Herstellungsverfahren nach dem einen oder dem anderen der Ansprüche 1 und 2, dadurch gekennzeichnet, daß die zweiten Fäden aus einer oder mehreren der folgenden Polymerfamilien stammen: Polypropylen, Polyethylen mit geringer Dichte, Polyester und Polyamid.
  4. Herstellungsverfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Webbindung diagonalen Typs ist, insbesondere diagonalen Typs 5-4 (A1/1).
  5. Herstellungsverfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Temperatur T0 der Wärmebehandlung in dem Intervall [Tf2 + |Tf1 - Tf2|/2; Tf1] liegt, wobei die Schmelztemperatur der zweiten Fäden Tf2 geringer als die Schmelztemperatur der ersten Fäden Tf1 ist, um die Viskosität der geschmolzenen zweiten Fäden zu verringern und die Imprägnierung der ersten Fäden zu verbessern.
  6. Verfahren nach einem der Ansprüche 1 bis 5 zur Herstellung einer Verbundeinheit (14) für ballistischen Schutz, dadurch gekennzeichnet, daß es einen Zwischenschritt zwischen dem Webschritt in 2,5D und der Wärmebehandlung umfaßt, während dessen in folgender Reihenfolge: die nach dem Webschritt in 2,5D erhaltene textile Verstärkung (7), eine erste Schicht aus einem Material auf Basis von schmelzbarem Polymer (10), eine zweite Schicht (11), die vorzugsweise eine Gewebeschicht aus Para-Amid umfaßt, eine dritte Schicht (12) aus einem Material auf Basis von schmelzbarem Polymer, eine vierte Schicht (13) insbesondere aus einem Material auf Keramikbasis übereinander gelegt werden, und daß bei der Wärmebehandlung die ersten und dritten Schichten schmelzen und das erhaltene Verbundmaterial (8) mit der zweiten (11) und vierten Schicht (13) verbinden, um die Einheit (14) zu bilden.
  7. Verbundwerkstoff (8), der mit dem Herstellungsverfahren nach einem der Ansprüche 1 bis 5 erhalten wurde, dadurch gekennzeichnet, daß die in 2,5D gewebte textile Verstärkung (7) Hochleistungsfäden umfaßt, die in den folgenden Familien von organischen Polymeren ausgewählt werden, und zwar alleine oder im Gemisch: die aromatischen Polyamide, wie Para-Amid (Poly-p-phenylenterephtalamid), Meta-Aramid (Poly-m-phenylenisophtalamid), und die Copolymere von Para-Amiden; die aromatischen Polyimide, die Hochleistungspolyester, hochdichtes Polyethylen (PEHD); die Polybenzoxazole, wie das PBO (p-phenylenbenzobisoxazol) und das PIPD (Polypyridobisimidasol); die Polybenzothiazole; oder Glasfasern.
  8. Verbundwerkstoff (8) nach Anspruch 7, dadurch gekennzeichnet, daß die Polymermatrix ein Thermoplast ist und im Gewicht weniger als 30 %, vorzugsweise weniger als 20 % der Gesamtoberflächenmasse des Verbundwerkstoffes (8) darstellt.
  9. Verbundwerkstoff (8) nach dem einen oder dem anderen der Ansprüche 7 und 8, dadurch gekennzeichnet, daß die Polymermatrix zu einer oder mehreren der folgenden Polymerfamilien gehört: Polyethylen mit geringer Dichte, Polypropylen, Polyamid, Polyethylenterephtalat, und insbesondere Polyethylen geringer Dichte.
  10. Verbundwerkstoff (8) nach einem der Ansprüche 7 bis 9, dadurch gekennzeichnet, daß die textile Verstärkung (7) aus einer einzigen Gewebsfalte (7) gebildet ist.
  11. Verbundeinheit (14) für ballistischen Schutz, deren hintere Schicht aus einem Verbundwerkstoff (8) nach einem der Ansprüche 7 bis 10 gebildet ist.
  12. Verbundeinheit (14) nach Anspruch 11, dadurch gekennzeichnet, daß sie von hinten nach vorne umfaßt: einen Verbundwerkstoff (8), eine erste Schicht (10) aus einem Material auf Basis von schmelzbarem Polymer, eine zweite Schicht (11) die vorzugsweise eine Gewebsschicht aus Para-Amid umfaßt, eine dritte Schicht (12) aus einem Material aus schmelzbarem Polymer, eine vierte Schicht (13) insbesondere aus einem Material auf Basis von Keramik.
  13. Verbundeinheit (14) nach dem einen oder dem anderen der Ansprüche 11 und 12, dadurch gekennzeichnet, daß der Verbundwerkstoff (8) eine Oberflächenmasse von ungefähr oder kleiner als 11 000 g/m2 aufweist.
EP20080805945 2007-06-06 2008-06-05 Verfahren zur herstellung eines verbundstoffes, insbesondere eines kugelsicheren verbundstoffes, und damit erhalter verbundstoff Not-in-force EP2153159B9 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0755511A FR2917099B1 (fr) 2007-06-06 2007-06-06 Procede de fabrication d'un materiau composite, notamment pour la protection balistique, et materiau composite obtenu.
PCT/FR2008/051009 WO2008152337A1 (fr) 2007-06-06 2008-06-05 Procédé de fabrication d'un matériau composite, notamment pour la protection balistique, et matériau composite obtenu

Publications (3)

Publication Number Publication Date
EP2153159A1 EP2153159A1 (de) 2010-02-17
EP2153159B1 true EP2153159B1 (de) 2010-12-08
EP2153159B9 EP2153159B9 (de) 2011-04-06

Family

ID=38896778

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20080805945 Not-in-force EP2153159B9 (de) 2007-06-06 2008-06-05 Verfahren zur herstellung eines verbundstoffes, insbesondere eines kugelsicheren verbundstoffes, und damit erhalter verbundstoff

Country Status (7)

Country Link
US (1) US20100215953A1 (de)
EP (1) EP2153159B9 (de)
AT (1) ATE491131T1 (de)
CA (1) CA2710861A1 (de)
DE (1) DE602008003924D1 (de)
FR (1) FR2917099B1 (de)
WO (1) WO2008152337A1 (de)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8555472B2 (en) * 2009-03-04 2013-10-15 The United States Of America As Represented By The Secretary Of The Navy Crimp-imbalanced protective fabric
US9212437B2 (en) * 2011-11-02 2015-12-15 GM Global Technology Operations LLC One-piece fiber reinforcement for a reinforced polymer combining aligned and random fiber layers
US9867414B2 (en) * 2013-03-14 2018-01-16 The United States of America, as representedy by the Secretary of the Navy Flat panel test hardware and technology for assessing ballistic performance of helmet personnel protective equipment
CN104878507B (zh) * 2015-05-29 2016-06-08 中材科技股份有限公司 一种环向和/或轴向加筋的圆管状层连织物及其制备方法
FR3041343B1 (fr) * 2015-09-18 2021-04-02 Snecma Piece en materiau composite
US10012482B1 (en) * 2016-05-18 2018-07-03 Blake Terence Williams Sheet material for use as a curtain for capturing and retaining firearm-discharged pellets and method for recovery of firearm-discharged pellets therewith
CN106048858A (zh) * 2016-08-08 2016-10-26 建德鑫鼎纤维材料有限公司 一种2.5d异型织物的整体编织方法
CN107912840B (zh) * 2017-12-15 2021-04-27 浙江伟星实业发展股份有限公司 一种防泼水布带和防泼水拉链
CN112873872B (zh) * 2019-11-29 2022-06-17 福建省晋江陶瓷编织工艺厂 一种陶瓷粒编织复合工艺
CN111791551A (zh) * 2020-08-10 2020-10-20 中国人民解放军军事科学院国防工程研究院 一种快凝快硬高强水泥基防弹板
CN113232328B (zh) * 2021-03-31 2022-05-06 成都飞机工业(集团)有限责任公司 一种基于2.5d编织的复合材料s型进气道筒体制造方法
US12055369B2 (en) 2021-11-09 2024-08-06 Trelleborg Sealing Solutions Albany, Inc. Lightweight composite armor
CN115946369B (zh) * 2023-03-15 2023-06-30 天津工业大学 一种防弹复合材料及其制备方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2610951B1 (fr) * 1987-02-17 1989-05-05 Aerospatiale Armature tissee pour materiau composite
FR2653141B1 (fr) * 1989-10-16 1992-04-17 Chaignaud Ind Materiau composite et son procede de realisation.
GB9104781D0 (en) * 1991-03-07 1991-04-17 Ward Ian M Polymer materials
US5437905A (en) * 1994-05-17 1995-08-01 Park; Andrew D. Ballistic laminate structure in sheet form
JP2001508003A (ja) * 1997-01-06 2001-06-19 オウェンス コーニング 耐衝撃性および耐破壊性を有するパネル
US6846548B2 (en) * 1999-02-19 2005-01-25 Honeywell International Inc. Flexible fabric from fibrous web and discontinuous domain matrix
FR2819804B1 (fr) 2001-01-24 2003-04-25 Eads Launch Vehicles Procede de fabrication d'une piece en carbone/carbone
US6315007B1 (en) 2001-03-23 2001-11-13 3Tex, Inc. High speed three-dimensional weaving method and machine
EP1396698A1 (de) * 2002-09-06 2004-03-10 Teijin Twaron GmbH Penetrationsresistentes Material und daraus hergestellte Gegenstände
GB0423948D0 (en) * 2004-10-28 2004-12-01 Qinetiq Ltd Composite materials
US20060248623A1 (en) * 2005-05-03 2006-11-09 Patriot Performance Materials, Inc. Armor for ballistic-resistant headgear

Also Published As

Publication number Publication date
FR2917099A1 (fr) 2008-12-12
ATE491131T1 (de) 2010-12-15
CA2710861A1 (fr) 2008-12-18
EP2153159A1 (de) 2010-02-17
WO2008152337A1 (fr) 2008-12-18
EP2153159B9 (de) 2011-04-06
US20100215953A1 (en) 2010-08-26
FR2917099B1 (fr) 2010-03-19
DE602008003924D1 (de) 2011-01-20

Similar Documents

Publication Publication Date Title
EP2153159B1 (de) Verfahren zur herstellung eines verbundstoffes, insbesondere eines kugelsicheren verbundstoffes, und damit erhalter verbundstoff
EP0544561B1 (de) Beschussfeste Panzerung für dem Körper
EP0221794B1 (de) Verformbare und aus Modulen aufgebaute Panzerung
JP5368312B2 (ja) 間隔を置いて配置された軽量複合材料防護物品
US7964267B1 (en) Ballistic-resistant panel including high modulus ultra high molecular weight polyethylene tape
KR101420107B1 (ko) 제어된 흉갑, 자동차 장갑판 및 헬멧
US11536540B2 (en) Rigid ballistic composites having large denier per filament yarns
US20070283801A1 (en) Armor apparatus and method
KR102046682B1 (ko) 강성 복합 탄도 장갑을 위한 원단
CN101820785A (zh) 含聚乙烯纤维的头盔
KR101349709B1 (ko) 전단농화유체를 이용한 방탄복합재, 그 제조방법 및 그를 이용한 방탄복
KR101723936B1 (ko) Cnt 함유 방탄섬유 복합체를 포함하는 방탄헬멧
FR2697626A1 (fr) Blindage de protection balistique, et son application.
EP3837487B1 (de) Mehrschichtige ballistische schutzplatte
FR2469277A1 (fr) Dispositif de protection contre les chocs et les explosions constitues de materiaux stratifies a base de fibres et de resine viscoelastique
Boussu et al. Experimental and high velocity impact studies on hybrid armor using metallic and 3D textile composites
FR2494832A1 (fr) Blindage a structure multidirectionnelle
FR2685074A1 (fr) Blindage stratifie.
WO1991019951A1 (fr) Structures composites multicouches de protection contre les projectiles et/ou eclats d'armes a feu
WO2023143875A1 (fr) Renfort textile pour materiau composite et materiau composite obtenu
BR112021001640B1 (pt) Painel compósito blindado compreendendo uma parede de blindagem, painel de proteção balística multicamadas e processo de produção deste

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20091202

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

RIN1 Information on inventor provided before grant (corrected)

Inventor name: BOUSSU, FRANCOIS

Inventor name: BEGUS, VIRGINIE

RIN1 Information on inventor provided before grant (corrected)

Inventor name: BEGUS, VIRGINIE

Inventor name: BOUSSU, FRANCOIS

RIN1 Information on inventor provided before grant (corrected)

Inventor name: BOUSSU, FRANCOIS

Inventor name: BEGUS, VIRGINIE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ENSAIT

RIN1 Information on inventor provided before grant (corrected)

Inventor name: BOUSSU, FRANCOIS

Inventor name: BEGUS, VIRGINIE

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 602008003924

Country of ref document: DE

Date of ref document: 20110120

Kind code of ref document: P

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20101208

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110308

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20101208

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110308

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110408

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110319

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110408

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110309

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

26N No opposition filed

Effective date: 20110909

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

BERE Be: lapsed

Owner name: ENSAIT

Effective date: 20110630

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602008003924

Country of ref document: DE

Effective date: 20110909

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110630

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120630

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110605

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101208

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: MC

Payment date: 20140623

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20140711

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20140717

Year of fee payment: 7

Ref country code: FR

Payment date: 20140611

Year of fee payment: 7

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602008003924

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150630

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20150605

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20160229

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150605

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150630