[go: up one dir, main page]

WO2013008178A1 - Composite stratifié de protection balistique - Google Patents

Composite stratifié de protection balistique Download PDF

Info

Publication number
WO2013008178A1
WO2013008178A1 PCT/IB2012/053523 IB2012053523W WO2013008178A1 WO 2013008178 A1 WO2013008178 A1 WO 2013008178A1 IB 2012053523 W IB2012053523 W IB 2012053523W WO 2013008178 A1 WO2013008178 A1 WO 2013008178A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoplastic polymer
laminated
polymer layer
composite
layer
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.)
Ceased
Application number
PCT/IB2012/053523
Other languages
English (en)
Inventor
Hubert Simon
Dominique BURR
Muege Deniz YUEKSEK
Gabrielle MILLET
François Finck
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.)
Von Roll Isola France SA
Original Assignee
Von Roll Isola France SA
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 Von Roll Isola France SA filed Critical Von Roll Isola France SA
Priority to EP12750487.6A priority Critical patent/EP2732234B1/fr
Publication of WO2013008178A1 publication Critical patent/WO2013008178A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F41H5/0471—Layered armour containing fibre- or fabric-reinforced layers
    • F41H5/0485—Layered armour containing fibre- or fabric-reinforced layers all the layers being only fibre- or fabric-reinforced layers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F41H5/0471—Layered armour containing fibre- or fabric-reinforced layers
    • F41H5/0478—Fibre- or fabric-reinforced layers in combination with plastics layers

Definitions

  • the present invention relates, generally, to the field of ballistic protection using bulletproof panels. More particularly, the present invention relates to a composite for ballistic protection and the manufacturing process thereof.
  • references between parentheses [ ] refer to the list of references presented at the end of the text.
  • Bulletproof materials intended for body protection are typically designed according to criteria of mechanical strength, ballistic properties, permissible residual deformation and/or lightness.
  • Aromatic polyamide (aramid) organic fibres such as Kevlar®
  • Kevlar® Aromatic polyamide (aramid) organic fibres
  • the drawback of bulletproof materials made of aramid fibres lies in the fact that although the projectile is stopped, the residual deformation at the point of impact (also referred to as "trauma") remains too large.
  • One of the solutions would be to increase the number of layers of Kevlar® in the bulletproof material, but this would increase the weight and the thickness of the personal protection.
  • layers of materials made of thermoplastic organic fibres have been added to the layers of Kevlar® in the bulletproof materials as described in patent application GB 2 234 156 [1] and international application WO 2006/136323 [2] .
  • Patent application GB 2 234 156 describes the use of polypropylene fibres, which make it possible to absorb the kinetic energy during the impact of the projectile.
  • a laminated composite is an assembly of one or more layers of at least two immiscible materials.
  • this invention describes the assembling, within the panel, of at least one layer of impact-resistant aramid organic fibres, such as Kevlar®, and of at least one layer of glass fibres that make it possible to absorb the kinetic energy during the impact of the projectile.
  • This bulletproof laminated composite is sold under the trade mark PARA-LITE®.
  • thermoset material in the form of a laminated composite of "sandwich” type, or simply in the form a thermoplastic polymer layer adhesively bonded, on one of its faces, to a laminated thermoset material layer, truly makes it possible to meet all of these requirements.
  • thermoplastic polymer is understood to mean a polymer that reversibly softens under the action of heat and hardens on cooling.
  • thermoplastic polymers are made up of filiform linear macromolecules that are not joined together. They are especially characterized by their plastic formability when they are heated beyond their softening point.
  • thermoset material is understood to mean a material which, under the action of heat, gradually hardens to achieve an irreversible solid state. They are typically crosslinked materials (three-dimensional macromolecules). During the conversion thereof, the final structure of the macromolecules is obtained by irreversible chemical reactions. Once hardened, their shape can no longer be modified.
  • a lightweight composite possessing improved ballistic and mechanical properties, and having an advantageous limitation of the trauma.
  • residual deformation at the point of impact or “trauma” is understood to mean the visible deformation of the material after the impact of the projectile on the opposite face to that of the impact face. It is measured in cm and is a result of the absorption of kinetic energy during the impact of the projectile on the material.
  • the present invention proposes a laminated hybrid composite (la, lb) for ballistic protection, characterized in that it comprises a thermoplastic polymer layer (2) which comprises, at least on one of its faces, a laminated thermoset material layer (3), depending on the final application of the product or on the desired properties.
  • the thermoplastic polymer layer (2) is a solid layer.
  • the thermoplastic polymer layer (2) is advantageously not hollow, or does not contain voids, such as a honeycomb structure.
  • the term “comprise” and variations of the term, such as “ comprising” and “comprises,” will be understood to imply the inclusion of other components or layers but not the exclusion of of other components or layers. However, it will be understood that the term “comprise” and variations of the term, such as “ comprising” and “comprises,” encompasses the variant “consist of and variations of that term, such as " consisting of " and " consists of.
  • a laminated hybrid composite (la) for ballistic protection characterized in that it comprises a central thermoplastic polymer layer (2) sandwiched between two laminated thermoset material layers (3).
  • a laminated hybrid composite (la) for ballistic protection characterized in that it comprises one central thermoplastic polymer layer (2) sandwiched between two laminated thermoset material layers (3), excluding other occurrences of a thermoplastic polymer layer and laminated thermoset material layers (in other words, the laminated hybrid composite (la) comprises only one central thermoplastic polymer layer (2) and two laminated thermoset material layers (3), in a sandwich configuration, the other components of the laminated hybrid composite (la) being different from a thermoplastic polymer layer and a laminated thermoset material layer).
  • a laminated hybrid composite (la) for ballistic protection characterized in that it consists of a central thermoplastic polymer layer (2) sandwiched between two laminated thermoset material layers (3).
  • the central thermoplastic polymer layer (2) may be a solid layer.
  • the central thermoplastic polymer layer (2) is advantageously not hollow, or does not contain voids, such as a honeycomb structure.
  • a laminated hybrid composite (lb) for ballistic protection characterized in that it comprises a thermoplastic polymer layer (2) adhesively bonded, on one of its faces, to a laminated thermoset material layer (3).
  • a laminated hybrid composite (la) for ballistic protection characterized in that it comprises one thermoplastic polymer layer (2) adhesively bonded, on one of its faces, to a laminated thermoset material layer (3), excluding other occurrences of a thermoplastic polymer layer and a laminated thermoset material layers (in other words, the laminated hybrid composite (lb) comprises only one central thermoplastic polymer layer (2) and one laminated thermoset material layer (3), adhesively bonded to each other, the other components of the laminated hybrid composite (la) being different from a thermoplastic polymer layer and a laminated thermoset material layer).
  • a laminated hybrid composite (lb) for ballistic protection characterized in that it consists of a thermoplastic polymer layer (2) adhesively bonded, on one of its faces, to a laminated thermoset material layer (3).
  • the thermoplastic polymer layer (2) may be a solid layer.
  • the thermoplastic polymer layer (2) is advantageously not hollow, or does not contain voids, such as a honeycomb structure.
  • a laminated hybrid composite for ballistic protection, characterized in that it comprises: a) a central thermoplastic polymer layer (2) sandwiched between two laminated thermoset material layers (3); wherein the central thermoplastic polymer layer (2) is a solid layer; or b) a thermoplastic polymer layer (2) adhesively bonded, on one of its faces, to a laminated thermoset material layer (3); wherein the thermoplastic polymer layer (2) is a solid layer.
  • the thermoplastic polymer layer (2) may be produced from any thermoplastic polymer, copolymer or mixture of polymers.
  • it may be made up of polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyaramid, polyamide, polycarbonate, polyester, polyimide, or a mixture of at least two of these polymers.
  • thermoplastic polymer layer (2) may be made up of polyethylene, polypropylene, polyamide, or a mixture of at least two of these polymers.
  • thermoplastic polymer layer (2) may be made up of polyethylene or polypropylene, very particularly polyethylene.
  • a laminated hybrid composite for ballistic protection, characterized in that it comprises: a) a central thermoplastic polymer layer (2) sandwiched between two laminated thermoset material layers (3); wherein the central thermoplastic polymer layer (2) is a solid layer; or b) a thermoplastic polymer layer (2) adhesively bonded, on one of its faces, to a laminated thermoset material layer (3); wherein the thermoplastic polymer layer (2) is a solid layer; wherein the thermoplastic polymer layer (2) may be made up of polyethylene, polypropylene, polyamide, or a mixture of at least two of these polymers.
  • the thermoplastic polymer may be in the form of a ply, that is to say a unidirectional or two-dimensional arrangement of thermoplastic polymer yarns forming a flat surface. These yarns may be woven in certain cases in order to form a fabric.
  • the thermoplastic polymer ply may be in the form of a woven or nonwoven thermoplastic polymer sheet.
  • the weaving method may correspond, for example, to a weaving of taffeta weave or twill weave type.
  • the thermoplastic polymer ply may be in the form of a symmetrical fabric (i.e. same number of polymer yarns in the weft and warp direction), or a unidirectional (UD) fabric, that is to say a fabric containing a different number of polymer yarns in the weft and in the warp.
  • the thermoplastic polymer ply may be pre-impregnated with an adhesive, enabling the good cohesion of the polymer yarns forming the ply.
  • Such plies may, for example, be obtained from HPPE (High Performance Polyethylene) like for instance from Honeywell (Spectra®) and DSM (Dyneema®).
  • HPPE High Performance Polyethylene
  • DSM Denseema®
  • Dyneema® BT10 and Dyneema® HB26 products which are woven and laminated sheets of ultra-high-molecular- weight polyethylene (UHMWPE).
  • the thermoplastic polymer layer (2) may be produced from 5 to 200 thermoplastic polymer plies. In particular, these thermoplastic polymer plies may be stacked and compressed at high temperature in order to form a compact and uniform layer, the thickness and the ballistic properties of which are determined by the nature and the number of thermoplastic polymer plies used. Thus, the thermoplastic polymer layer (2) may be a solid layer.
  • the thermoplastic polymer layer (2) may be formed from 5 to 150, 5 to 100, 5 to 75, 5 to 50, 5 to 30, 5 to 20 or 5 to 15 thermoplastic polymer plies as a function of the desired ballistic properties and thickness (weight).
  • the laminated thermoset material layer (3) may be produced from a material having advantageous mechanical strength properties. For example, it may be produced from carbon fibres.
  • the laminated thermoset material layer (3) may comprise a stack of carbon fibre fabric plies (4), which plies may be pre-impregnated by a varnish in order to enable the formation of the laminated thermoset material layer (3) by hot pressing of said stack of carbon fibre fabric plies (4).
  • carbon fibre fabric ply is understood in the present text to mean a two-dimensional arrangement of carbon fibres forming a fabric.
  • the carbon fibre fabric plies may be in the form of woven carbon fibre sheets.
  • the weaving method may correspond, for example, to a weaving of taffeta weave, twill weave or satin weave type, preferably taffeta weave or twill weave type.
  • the carbon fibre fabric plies may or may not be in the form of a symmetrical fabric (i.e., same number of woven yarns in the weft and warp direction) or they may be in the form of a unidirectional (UD) fabric, that is to say a fabric containing a different number of woven yarns in the weft and in the warp.
  • UD unidirectional
  • Each yarn may comprise at least 3000 carbon fibrils and at most 48 000 carbon fibrils.
  • they may be carbon yarns containing 3000, 6000, 12 000, 24 000 or 48 000 carbon fibrils.
  • the carbon fibre fabric plies may be symmetrical (i.e., containing the same number of carbon yarns/cm in the weft and warp direction), or asymmetrical, that is to say a fabric made from yarns containing a different number of carbon yarns/cm in the weft and in the warp.
  • the carbon fibre fabric plies (4) may be carbon fibre fabric plies conventionally used in aeronautics, namely carbon fibre fabric plies in which the yarns contain 3000 to 6000 carbon fibrils.
  • the laminated thermoset material layer (3) may comprise a stack of 5 to 30 carbon fibre fabric plies (4) (or 5 to 30 woven carbon fibre sheets) pre-impregnated by a varnish.
  • these carbon fibre fabric plies (4) pre-impregnated by a varnish may be stacked and compressed at high temperature in order to form a laminated thermoset material layer (3), the thickness and the mechanical properties of which are determined by the nature and the number of carbon fibre fabric plies used.
  • the laminated thermoset material layer (3) may be formed from 5 to 30, 5 to 25, 5 to 20 or 5 to 15 carbon fibre fabric plies (4), as a function of the desired mechanical properties.
  • the pre-impregnating varnish may be any epoxy resin known in the field.
  • the techniques for preparing pre-impregnated fabrics are well known in the field. Reference could be made, for example, to the following work: "Materiaux composites a matrice organique” [Composites containing an organic matrix], 1986, Gilbert Chretien, Publisher: Technique et Documentation, 11 rue Lavoisier, F-75384b Paris Cedex [6] .
  • the impregnating varnish may contain a resin, a hardener, a catalyst and a solvent.
  • the resin may be bisphenol A diglycidyl ether, a "novo lac” epoxy resin (such as bisphenol F, phenol-novolac resins, cresol-novolac resins, phenol- formaldehyde novolac resins or cresol-formaldehyde novolac resins), a resin based on tetraphenylolethane and triphenylolmethane glycidyl ethers, an epoxy resin based on aromatic amines (such as methylenediamine tetraglycidyl ether), an epoxy resin based on /?ara-aminophenol (such as /?ara-aminophenol triglycidyl ether), a cycloaromatic resin (such as 3,4-epoxycyclohexylmethyl or bis(2,3- epoxycyclopentyl)ether), a flexible epoxy resin
  • the hardener may be a catalytic hardener such as an aliphatic, alicyclic or aromatic primary or secondary amine.
  • a catalytic hardener such as an aliphatic, alicyclic or aromatic primary or secondary amine.
  • it may be ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, trimethylhexamethylenediamine, cyandiamine, N-aminoethylpiperazine, isophorone diamine, 4,4'-diaminodiphenylmethane, m-phenylenediamine, methylenedianiline or diaminodiphenylsulphone.
  • the hardener may be a coreactive hardener such as an acid anhydride.
  • phthalic anhydride tetrahydrophthalic anhydride
  • hexahydrophthalic anhydride methyl nadic anhydride
  • tetrapropenyl succinic anhydride trimellitic anhydride or pyromellitic anhydride.
  • the catalyst may be an imidazole, a phenol or a tertiary amine. It may be, for example, benzyldimethylamine, tris(dimethylaminomethyl)phenol, 2-ethyl-4- methylimidazole or the boron trifluoride/monoethylamine complex.
  • the hardener HT 973® from Huntsman (boron trifluoride/ethylamine complex) may be used.
  • the solvent may be, for example, methyl ethyl ketone, l-methoxy-2-propanol, or a mixture thereof.
  • the solvent may be a 50/50 methyl ethyl ketone/ 1 -methoxy-2-propanol mixture.
  • methyl ethyl ketone from Celanese may be used.
  • the varnish may optionally contain a diluent, that is to say a liquid product typically added to epoxy resins in order to lower the viscosity thereof and enable easier processing.
  • a diluent that is to say a liquid product typically added to epoxy resins in order to lower the viscosity thereof and enable easier processing.
  • a reactive or non-reactive diluent mention may be made, for example, of n-butyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, 1,4-butanediol diglycidyl ether or l,2-epoxy-4-(epoxyethyl)cyclohexane.
  • non-reactive diluents mention may be made, for example, of dibutyl phthalate and benzyl and furfuryl alcohols.
  • the laminated hybrid composite (la) may comprise a central thermoplastic polymer layer (2) as defined above, sandwiched between two laminated thermoset material layers (3) as defined above.
  • the laminated hybrid composite (la) for ballistic protection may comprise one central thermoplastic polymer layer (2) sandwiched between two laminated thermoset material layers (3), excluding other occurrences of a thermoplastic polymer layer and laminated thermoset material layers (in other words, the laminated hybrid composite (la) comprises only one central thermoplastic polymer layer (2) and two laminated thermoset material layers (3), in a sandwich configuration, the other components of the laminated hybrid composite (la) being different from a thermoplastic polymer layer and a laminated thermoset material layer).
  • the laminated hybrid composite (la) for ballistic protection consists of a central thermoplastic polymer layer (2) sandwiched between two laminated thermoset material layers (3).
  • the laminated hybrid composite (lb) may comprise a thermoplastic polymer layer (2) as defined above, adhesively bonded on one of its faces to a laminated thermoset material layer (3) as defined above.
  • the laminated hybrid composite (lb) for ballistic protection comprises one thermoplastic polymer layer (2) adhesively bonded, on one of its faces, to a laminated thermoset material layer (3), excluding other occurrences of a thermoplastic polymer layer and a laminated thermoset material layers (in other words, the laminated hybrid composite (lb) comprises only one central thermoplastic polymer layer (2) and one laminated thermoset material layer (3), adhesively bonded to each other, the other components of the laminated hybrid composite (la) being different from a thermoplastic polymer layer and a laminated thermoset material layer).
  • the laminated hybrid composite (lb) for ballistic protection consists of a thermoplastic polymer layer (2) adhesively bonded, on one of its faces, to a laminated thermoset material layer (3).
  • the thermoplastic polymer layer (2) (whether it be central as in variant (la) or not as in variant (lb)) may be a solid layer.
  • the thermoplastic polymer layer (2) is advantageously not hollow, or does not contain voids, such as a honeycomb structure.
  • the laminated thermoset material layers (3) may be identical or different.
  • they may each contain:
  • carbon fibre fabric plies (4) i.e., symmetrical or asymmetrical carbon fibre plies
  • - carbon fibre fabric plies (4) having the same type or a different type of weaving method i.e. taffeta weave, twill weave or satin weave
  • weaving method i.e. taffeta weave, twill weave or satin weave
  • the laminated hybrid composite (la) is symmetrical, that is to say that the two laminated thermoset material layers (3) constituting it are identical. This renders the use of the laminated hybrid composite (la) as bulletproof or antishrapnel protection easier and safer (i.e. the user can equally well use one or the other face of the laminated hybrid composite panel (la) towards the source of projectiles or shrapnel when it is a symmetrical panel).
  • the expression "material for ballistic protection” is understood to mean a material suitable for immobilizing a bullet fired by a firearm, such as for example for a small calibre (handgun) the 357 or 44 Magnum, or for a larger calibre (assault rifle) the AK47 (7.62x39) or Nato Ball (7.62x51), or other weapon with a 0.3 FSP calibre, in tests like for instance according to the norm MIL STD 662F.
  • the laminated hybrid composite (la) is asymmetrical (that is to say that the two laminated thermoset material layers (3) constituting it are different, for example, in terms of the number of carbon fibre fabric plies (4) of which they are constituted), one face of the laminated hybrid composite (la) is advantageously marked in order to identify that which is intended to be exposed to the source of projectiles or shrapnel.
  • the laminated hybrid composite (la) may be assembled by adhesively bonding a laminated thermoset material layer (3) to each of the two surfaces of the central thermoplastic polymer layer (2), so that said central thermoplastic polymer layer (2) is sandwiched between two laminated thermoset material layers (3).
  • the laminated hybrid composite (lb) may be assembled by adhesively bonding one laminated thermoset material layer (3) to one of the two surfaces of the thermoplastic polymer layer (2).
  • the thermoplastic polymer layer (2) may be a solid layer.
  • the adhesive used may be any adhesive capable of providing an assembly that is solid, durable and resistant to delamination. For example, it may be an epoxy adhesive or a silicone adhesive.
  • an epoxy adhesive for example such as that defined in the various embodiments described above for the pre-impregnating varnish. Mention could be made, for example, of the epoxy adhesive of Araldite®, Lopox®, Lekutherm® or Eporex/Uranox® type.
  • the Araldite® 2011 adhesive may be used.
  • the surface of the laminated thermoset material layer (3) and/or of the thermoplastic polymer layer (2) could be pretreated in order to increase the roughness thereof. This may be accomplished, for example, via mechanical means such as sanding with sandpaper.
  • the roughness may also be introduced during the preparation of the laminated thermoset material layers (3) and/or the thermoplastic polymer layer (2): in the press used, the element in contact with the outer surface of the laminated thermoset material layer (3) and/or the thermoplastic polymer layer (2) may contain, on its surface, a pattern in relief that makes it possible to imprint/etch this pattern into said layers (2) and/or (3). This increased roughness makes it possible to provide bonding that is more resistant to delamination.
  • the laminated hybrid composite (la, lb) makes it possible to attain a minimum ballistic limit V50 of 555 m/s at 0 degree of obliquity according to the MIL STD 662 standard with a 0.3 FSP calibre.
  • V50 minimum ballistic limit
  • the laminated hybrid composite (la, lb) according to the invention is tested according to the aforementioned standard, no perforation is observed.
  • the laminated hybrid composite (la, lb) according to the invention is tested according to the NIJ 0101.06 standard with for instance ammunition of 7.62x51 NB or 7.62x39 MSC AK47 type, the residual deformation at the point of impact ("trauma") is between 0 and 3 cm.
  • the deformation or trauma is generally evaluated using a material used for modelling known as plastilin.
  • a material used for modelling known as plastilin.
  • plastilin a material used for modelling known as plastilin.
  • the NIJ 0101.06 standard describes this method.
  • the laminated hybrid composite (la, lb) according to the invention has a perpendicular flexural strength from 50 to 130 MPa, measured according to the ISO 178 standard.
  • - Flexural modulus of elasticity in perpendicular flexion :
  • the laminated hybrid composite (la, lb) according to the invention has a flexural modulus of elasticity, in perpendicular flexion, between 20 000 MPa and 30 000 MPa, measured according to the ISO 178 standard.
  • the laminated hybrid composite (la, lb) according to the invention has a density between 0.8 g/cm 3 and 1.5 g/cm 3 (measured according to the ISO 1183 standard).
  • the laminated hybrid composite (la, lb) according to the invention weighs between 10 and 13 kg per square metre for a thickness of 10 to 12 mm for a panel tested according to MIL STD 662 with a 0.3 FSP fragment projectile. Other thicknesses and weights of panels may be needed for protection against other threats.
  • a process for manufacturing a laminated hybrid composite (la) comprising the assembling, using an adhesive, of a central thermoplastic polymer layer (2) sandwiched between two laminated thermoset material layers (3).
  • the central thermoplastic polymer layer (2) may be a solid layer.
  • a process for manufacturing a laminated hybrid composite (lb) comprising the assembling, using an adhesive, of a thermoplastic polymer layer (2) with a laminated thermoset material layer (3).
  • the thermoplastic polymer layer (2) may be a solid layer. It is understood that all the variants presented above for the laminated hybrid composite, and its components (e.g., thermoplastic polymer layer (2), laminated thermoset material layers (3), adhesive, etc.) are applicable mutadis mutandis to the process of the invention, even though they are not explicitly reiterated here.
  • thermoplastic polymer layer (2) is made up of polyethylene, polypropylene, , polyamide, or a mixture of at least two of these polymers.
  • the adhesive is as defined in any one of the embodiments described in section "3.
  • it may be an epoxy or silicone adhesive, preferably an epoxy adhesive.
  • the thermoplastic polymer layer (2) may be obtained by stacking thermoplastic polymer plies under a pressure of between 2 MP a (20 bar) and 20 MPa (200 bar) at a temperature between 80°C and 160°C.
  • the thermoplastic polymer plies are as defined in any one of the embodiments described in section "1.
  • they may be polyethylene or polypropylene plies, advantageously polyethylene plies.
  • the thermoplastic polymer layer (2) may be obtained by stacking from 5 to 200 thermoplastic polymer plies, as defined previously.
  • the thermoplastic polymer layer (2) may be formed from 5 to 150, 5 to 100, 5 to 75, 5 to 50, 5 to 30, 5 to 20 or 5 to 15 thermoplastic polymer plies, as a function of the desired ballistic properties and thickness (weight).
  • the temperature is maintained at a value below the glass transition temperature of the thermoplastic polymer.
  • the process for preparing the thermoplastic polymer layer (2) may be carried out by stacking polyethylene plies under a pressure of between 2 MPa (20 bar) and 20 MPa (200 bar) at a temperature between 120°C and 130°C.
  • thermoplastic polymer plies are polypropylene plies
  • the process for preparing the thermoplastic polymer layer (2) may be carried out by stacking polypropylene plies under a pressure of between 2 MPa (20 bar) and 20 MPa (200 bar) at a temperature between 145°C and 155°C.
  • a person skilled in the art will know how to define the temperature range to be used as a function of the thermoplastic polymer used.
  • the laminated thermoset material layer (3) may be obtained by stacking at least 5 carbon fibre fabric plies (4) that are pre-impregnated with a varnish, under a pressure of between 2 MPa (20 bar) and 5 MPa (50 bar) at a temperature between 140°C and 200°C.
  • the varnish is as defined in any one of the embodiments described in section "2.
  • Laminated thermoset material layer (3) above.
  • it may be an epoxy resin as defined previously.
  • the laminated thermoset material layer (3) may be formed from 5 to 30, 5 to 25, 5 to 20 or 5 to 15 carbon fibre fabric plies (4), as a function of the desired mechanical properties and thickness (weight).
  • the varnish may be premixed in a tank (5), and a carbon fibre fabric ply (4) may be dipped into this varnish, before being passed into an oven (6) (or drying tower).
  • the main role of the oven (6) is advantageously to evaporate the solvent, so as to avoid obtaining a tacky carbon fibre fabric ply (4).
  • the oven (6) is maintained at a temperature so as to evaporate almost all of the solvent contained in the carbon fibre fabric ply (4) pre- impregnated with the varnish.
  • a person skilled in the art will know how to define the temperature range to be used as a function of the solvent contained in the varnish. For example, when the varnish contains a 50/50 methyl ethyl ketone/1- methoxy-2-propanol mixture, the oven (6) may be maintained at a temperature from 150°C to 200°C.
  • the laminated thermoset material layer (3) may be obtained via a process in which the carbon fibre fabric plies (4) pre-impregnated with a varnish are obtained by dipping said carbon fibre fabric plies (4) into an impregnating varnish containing a resin, a hardener, a catalyst and a solvent; followed by evaporation of said solvent.
  • the laminated hybrid composite (la) may be assembled by adhesively bonding a laminated thermoset material layer (3) to each of the two surfaces of the central thermoplastic polymer layer (2), so that said central thermoplastic polymer layer (2) is sandwiched between two laminated thermoset material layers (3).
  • the laminated hybrid composite (lb) may be assembled by adhesively bonding a laminated thermoset material layer (3) to one of the two surfaces of the thermoplastic polymer layer (2).
  • the thermoplastic polymer layer (2) may be a solid layer.
  • the adhesive used may be any adhesive capable of providing an assembly that is solid, durable and resistant to delamination.
  • it may be an epoxy adhesive or a silicone adhesive.
  • it could be an epoxy adhesive, for example such as that defined in the various embodiments described above for the pre- impregnating varnish.
  • the surface of the laminated thermoset material layer (3) and/or of the thermoplastic polymer layer (2) could be pretreated in order to increase the roughness thereof. This may be accomplished, for example, via mechanical means such as sanding with sandpaper.
  • the roughness may also be introduced during the preparation of the laminated thermoset material layers (3) and/or the thermoplastic polymer layer (2): in the press used, the element in contact with the outer surface of the laminated thermoset material layer (3) and/or the thermoplastic polymer layer (2) may contain, on its surface, a pattern in relief that makes it possible to imprint/etch this pattern into said layers (2) and/or (3). This increased roughness makes it possible to provide bonding that is more resistant to delamination.
  • a bulletproof or antishrapnel protective device comprises a laminated hybrid composite (la, lb) as defined previously.
  • the invention relates to the use of a laminated hybrid composite (la, lb) as defined previously as bulletproof or antishrapnel protection.
  • the laminated hybrid composite (la, lb) according to the invention may find an application in any device for ballistic protection.
  • it may be applied to buildings, civilian or military vehicles, shelters temporary or permanent shelters intended for police or military forces, or personal protection such as bulletproof or antishrapnel helmets, shields, vests or inserts/chest protectors.
  • the laminated hybrid composite (la, lb) according to the invention may therefore be in various forms, depending on the envisaged application.
  • it may be in the form of a panel having a thickness between 1.5 and 100 cm, of a moulded article (for example for a helmet) or of an insert (for application in bulletproof or antishrapnel vests).
  • the laminated hybrid composite (la, lb) according to the invention is particularly suitable for the manufacture of a safety zone in the form of an armoured booth of the type of that presented in Figure 3 and enabling weapons to be discharged in complete safety in shooting ranges and police stations and armouries.
  • FIG. 3 shows a bulletproof booth 16, comprising several panels 1 in accordance with any one of the embodiments of the laminated hybrid composite (la, lb) of the invention and preferably in accordance with the embodiments described in Figure 1.
  • the panel 1 may also be used as separating partitions in a building. This is directly related to the high mechanical properties that exhibit the panels according to the present invention.
  • Another application relates to inserts for personal protection.
  • Composite parts for ballistic protection are generally inserted into textile materials of the vest type in order to give protection to the individual and to their vital organs (for example chest protection).
  • the laminated hybrid composite according to the present invention makes it possible to advantageously reduce the trauma.
  • Another application example relates to panels for ballistic protection in order to protect vehicles and their passengers.
  • the present invention makes it possible to produce bodywork parts that have high mechanical strengths without being combined with metal and metal bodywork parts, and while guaranteeing ballistic protection, having a weight much lower than the equivalent protective parts which are generally combinations of composites with metal.
  • the laminated hybrid composite (la, lb) according to the invention takes advantage of the advantageous mechanical properties of carbon fibres, and of the ballistic properties of thermoplastic polymers such as polyethylene or polypropylene.
  • thermoset material makes it possible to reduce the density of the composite while increasing its ballistic performance, by enabling, in particular, the composite to absorb more energy during the impact of the bullet.
  • the thermoset material itself also contributes to the lightening of the structure (since it is constituted of carbon fibres) and also gives the composite according to the invention high mechanical strength properties, in particular a flexural modulus of elasticity, in perpendicular flexion, between 20 000 MPa and 30 000 MPa, typically greater than 25 000 MPa (measured according to the ISO 178 standard).
  • thermoplastic polymer layer (2) contributes to lightening the bulletproof or antishrapnel panel.
  • This laminated bulletproof or antishrapnel structure thus makes it possible to progressively absorb the kinetic energy of the projectile in order to contribute to the progressive slowdown thereof within the panel thus preventing a risk of the projectile ricocheting.
  • a panel according to the invention for partitions or vehicles is two to three times lighter than a conventional armour based on steel or concrete having a similar level of protection.
  • Figure 1A represents a cross section of a laminated hybrid composite (la) for ballistic protection according to one variant of the invention
  • Figure IB represents a cross section of a laminated hybrid composite (lb) for ballistic protection according to one variant of the invention
  • - Figure 2 represents an example of an implementation device for preparing prepreg carbon fibre fabric plies (4) according to the invention
  • Figure 3 shows a bulletproof booth formed of several panels of laminated hybrid composite (la, lb) according to the invention, this booth forming a secured zone for enabling a person in the booth to handle firearms.
  • the bulletproof or antishrapnel laminated hybrid composite according to the present invention and the preparation thereof may be understood with the aid of the following examples, which illustrate certain methods via which this composite may be prepared or used. It will be noted, however, that these examples are given by way of illustration and are not meant to be limiting.
  • thermoplastic polymer used is UHMWPE Dyneema® ultra-performance polyethylene.
  • woven sheets of ultra-performance polyethylene sold under the trade mark Dyneema® BT 10, are used.
  • the number of plies of Dyneema® BT 10 polyethylene determines the final thickness of the central thermoplastic polymer layer (2), and of the laminated hybrid composite (la).
  • the final thickness of the central thermoplastic polymer layer (2) is 9.5 mm.
  • the central thermoplastic polymer layer (2) is a solid layer.
  • Carbon fibre fabric plies (4) sold under the name 3K carbon by Porcher Industrie are used.
  • the formation of the laminated thermoset material layers (3) is similar to that of the central thermoplastic polymer layer (2), and requires a preliminary step of impregnating the carbon fibre fabric plies with a varnish.
  • the prepreg carbon fibre fabric plies are obtained by dipping carbon fibre fabric plies into an impregnating varnish containing a resin, a hardener, a catalyst and a solvent.
  • the resin is EPON® resin 828
  • the hardener is DDS (diaminodiphenylsulphone)
  • the catalyst is the boron trifluoride/ethylamine complex.
  • the solvent used is a mixture of methyl ethyl ketone and l-methoxy-2-propanol (50/50).
  • the solvent is then evaporated by drying the prepreg carbon fibre fabric plies in an oven set at 150°C to 200°C for 5 to 10 minutes.
  • the laminated hybrid composite (la) is assembled using a two-part epoxy adhesive, comprising an epoxy resin and a hardener, sold under the trade mark Araldite®.
  • the adhesive is applied uniformly over the whole of the two outer faces of the central thermoplastic polymer layer (2).
  • the two laminated thermoset material layers (3) are affixed to each side of the central thermoplastic polymer layer (2).
  • the assembly is then placed in a press (e.g. a Sechmy press) under 5 bars for a duration of 4 hours at a temperature of 60°C. II. Mechanical tests
  • the flexural strength and the flexural modulus of elasticity, in perpendicular flexion, of the composite described previously are determined according to the ISO 178 standard.
  • the flexural test results in a value of the flexural strength equal to 100 MPa and a value of the flexural modulus of elasticity, in perpendicular flexion, equal to 25 000 MPa.

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)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne, d'une manière générale, le domaine de la protection balistique au moyen de panneaux de protection balistique. Plus particulièrement, la présente invention concerne un composite hybride stratifié (1a, 1b) de protection balistique, caractérisé en ce qu'il comprend une couche centrale (2) de polymère thermoplastique solide qui comprend, au moins sur l'une de ses faces, une couche stratifiée (3) de matériau thermodurcissable. L'invention concerne également un procédé de fabrication du composite selon l'invention, le procédé comprenant le collage, au moyen d'un adhésif, d'une couche stratifiée de matériau thermodurcissable sur l'une et l'autre face d'une couche de polymère thermoplastique solide ou sur au moins une des faces d'une couche de polymère thermoplastique solide. En outre, l'invention concerne un dispositif de protection pare-balles ou anti-shrapnel comprenant le composite selon l'invention. De plus, l'invention concerne l'utilisation dudit composite comme protection pare-balles ou anti-shrapnel.
PCT/IB2012/053523 2011-07-11 2012-07-10 Composite stratifié de protection balistique Ceased WO2013008178A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12750487.6A EP2732234B1 (fr) 2011-07-11 2012-07-10 Composite stratifié de protection balistique

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201161506362P 2011-07-11 2011-07-11
FR1156296 2011-07-11
FR1156296A FR2977933B1 (fr) 2011-07-11 2011-07-11 Materiau composite stratifie pour protection balistique
US61/506,362 2011-07-11

Publications (1)

Publication Number Publication Date
WO2013008178A1 true WO2013008178A1 (fr) 2013-01-17

Family

ID=45319218

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2012/053523 Ceased WO2013008178A1 (fr) 2011-07-11 2012-07-10 Composite stratifié de protection balistique

Country Status (3)

Country Link
EP (1) EP2732234B1 (fr)
FR (1) FR2977933B1 (fr)
WO (1) WO2013008178A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103884238A (zh) * 2014-02-28 2014-06-25 北京同益中特种纤维技术开发有限公司 一种复合防弹单元材料及其制备方法
CN104848746A (zh) * 2015-04-23 2015-08-19 北京勤达远致新材料科技股份有限公司 一种混杂纤维弹性织物复合材料防弹插板及其制备方法
WO2016007718A1 (fr) * 2014-07-10 2016-01-14 Isola Usa Corp. Films minces de résine et leur utilisation dans des empilements
JP2018021718A (ja) * 2016-08-04 2018-02-08 スターライト工業株式会社 防刃防突刺し用保護材及びそれを用いた防護用具
WO2020127187A1 (fr) 2018-12-21 2020-06-25 Dsm Ip Assets B.V. Article moulé pare-balles
US20220136805A1 (en) * 2020-10-29 2022-05-05 William B. McMurray Flexible vault ballistic panel and ballistic panel accessories
WO2022126216A1 (fr) * 2020-12-17 2022-06-23 Coplatex Indústria E Comércio De Tecidos Ltda Agencement structural pour composite balistique
CN116294817A (zh) * 2023-03-24 2023-06-23 江苏奥神新材料股份有限公司 一种聚酰亚胺纤维防弹抗冲击复合板及其制备方法
WO2024033778A1 (fr) * 2022-08-07 2024-02-15 Technology Innovation Institute – Sole Proprietorship LLC Composition de nanoparticules légères pour un appareil de protection et procédé de fabrication

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1594543A (fr) * 1966-12-23 1970-06-08
GB2234156A (en) 1989-06-08 1991-01-30 Craig Antony Mills Anti-ballistic body armour
WO2006136323A1 (fr) 2005-06-23 2006-12-28 Teijin Aramid Gmbh Stratifie pare-balles et garniture de protection contre les traumatismes
EP1847796A1 (fr) 2006-04-20 2007-10-24 Fernando Héctor Andujar Couche pour utilisation dans un matériau ballistique et matériau ballistique comprenant une telle couche
WO2008109629A1 (fr) 2007-03-05 2008-09-12 Agy Holding Corp. Tissus balistiques
WO2008135685A1 (fr) 2007-03-28 2008-11-13 Von Roll Isola France Panneaux de cloison pare-balles
WO2009032585A1 (fr) * 2007-08-29 2009-03-12 Supracor, Inc. Blindage léger et appareil de défense contre un projectile balistique
US20090084256A1 (en) * 2007-09-28 2009-04-02 Lucent Technologies Inc. Initial strike-face layer for armor, a method of constructing an armor plate and armor
US7601654B2 (en) * 2006-03-30 2009-10-13 Honeywell International Inc. Molded ballistic panel with enhanced structural performance
US20100297388A1 (en) * 2006-02-03 2010-11-25 The University Of Maine System Board Of Trustees Composite panel for blast and ballistic protection

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1594543A (fr) * 1966-12-23 1970-06-08
GB2234156A (en) 1989-06-08 1991-01-30 Craig Antony Mills Anti-ballistic body armour
WO2006136323A1 (fr) 2005-06-23 2006-12-28 Teijin Aramid Gmbh Stratifie pare-balles et garniture de protection contre les traumatismes
US20100297388A1 (en) * 2006-02-03 2010-11-25 The University Of Maine System Board Of Trustees Composite panel for blast and ballistic protection
US7601654B2 (en) * 2006-03-30 2009-10-13 Honeywell International Inc. Molded ballistic panel with enhanced structural performance
EP1847796A1 (fr) 2006-04-20 2007-10-24 Fernando Héctor Andujar Couche pour utilisation dans un matériau ballistique et matériau ballistique comprenant une telle couche
WO2008109629A1 (fr) 2007-03-05 2008-09-12 Agy Holding Corp. Tissus balistiques
WO2008135685A1 (fr) 2007-03-28 2008-11-13 Von Roll Isola France Panneaux de cloison pare-balles
WO2009032585A1 (fr) * 2007-08-29 2009-03-12 Supracor, Inc. Blindage léger et appareil de défense contre un projectile balistique
US20090084256A1 (en) * 2007-09-28 2009-04-02 Lucent Technologies Inc. Initial strike-face layer for armor, a method of constructing an armor plate and armor

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
C.P. KOCH ET AL.: "Response of a high-strength flexible laminate to dynamic tension", INTERNATIONAL JOURNAL OF IMPACT ENGINEERING, vol. 35, no. 6, 2008, pages 559 - 568, XP022475913, DOI: doi:10.1016/j.ijimpeng.2007.04.010
F. LARSSON; L. SVENSSON: "Carbon, polyethylene and PBO hybrid fibre composites for structural lightweight armour", COMPOSITES PART A: APPLIED SCIENCE AND MANUFACTURING, vol. 33, no. 2, 2002, pages 221 - 231, XP004320155, DOI: doi:10.1016/S1359-835X(01)00095-1
GILBERT CHRETIEN: "Materiaux composites a matrice organique", 1986, TECHNIQUE ET DOCUMENTATION
J. RODRIGUEZ ET AL.: "High strain rate properties of aramid and polyethylene woven fabric composites", COMPOSITES PART B: ENGINEERING, vol. 27, no. 2, 1996, pages 147 - 154

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103884238A (zh) * 2014-02-28 2014-06-25 北京同益中特种纤维技术开发有限公司 一种复合防弹单元材料及其制备方法
US10697738B2 (en) 2014-02-28 2020-06-30 Beijing Tongyizhong Specialty Fibre Technology & Development Co., .Td Composite ballistic-resistant unit material and preparation method for same
WO2016007718A1 (fr) * 2014-07-10 2016-01-14 Isola Usa Corp. Films minces de résine et leur utilisation dans des empilements
CN104848746A (zh) * 2015-04-23 2015-08-19 北京勤达远致新材料科技股份有限公司 一种混杂纤维弹性织物复合材料防弹插板及其制备方法
JP2018021718A (ja) * 2016-08-04 2018-02-08 スターライト工業株式会社 防刃防突刺し用保護材及びそれを用いた防護用具
WO2020127187A1 (fr) 2018-12-21 2020-06-25 Dsm Ip Assets B.V. Article moulé pare-balles
US20220136805A1 (en) * 2020-10-29 2022-05-05 William B. McMurray Flexible vault ballistic panel and ballistic panel accessories
WO2022126216A1 (fr) * 2020-12-17 2022-06-23 Coplatex Indústria E Comércio De Tecidos Ltda Agencement structural pour composite balistique
WO2024033778A1 (fr) * 2022-08-07 2024-02-15 Technology Innovation Institute – Sole Proprietorship LLC Composition de nanoparticules légères pour un appareil de protection et procédé de fabrication
US12350908B2 (en) 2022-08-07 2025-07-08 Technology Innovation Institute—Sole Proprietorship LLC Lightweight nanoparticle composition for a protective apparatus and method of making
CN116294817A (zh) * 2023-03-24 2023-06-23 江苏奥神新材料股份有限公司 一种聚酰亚胺纤维防弹抗冲击复合板及其制备方法

Also Published As

Publication number Publication date
FR2977933B1 (fr) 2015-01-16
FR2977933A1 (fr) 2013-01-18
EP2732234A1 (fr) 2014-05-21
EP2732234B1 (fr) 2018-04-11

Similar Documents

Publication Publication Date Title
EP2732234B1 (fr) Composite stratifié de protection balistique
CN104677194B (zh) 一种模块化多维复合防弹板及其制备方法
US6703104B1 (en) Panel configuration composite armor
Salman et al. Ballistic impact resistance of plain woven kenaf/aramid reinforced polyvinyl butyral laminated hybrid composite
US6825137B2 (en) Lightweight ballistic resistant rigid structural panel
CN115127398B (zh) 基于高韧性异质界面层的轻质防弹抗爆多相复合装甲材料
CN110103556B (zh) 一种柔性防弹防刺材料及其制备方法
US20150082976A1 (en) Light-weight semi-rigid composite anti-ballistic systems with engineered compliance and rate-sensitive impact response
JP2009523083A (ja) 複合積層板とその製法
Samir et al. Preparation and characterization of bullet-proof vests based on polyamide fibers
EP2109530A1 (fr) Article moulé résistant aux balles et procédé de fabrication d'un tel article
CN108955385B (zh) 一种局部强化的复合材料防弹头盔
Walsh et al. The development of a hybrid thermoplastic ballistic material with application to helmets
CN105667019A (zh) 一种抵御机枪弹侵彻的复合结构防弹装甲及其制备方法
CN114872390A (zh) 一种陶瓷/纤维增强复合防护装甲结构
CN105172256A (zh) 一种增强材料不同叠层比例的防弹板材的制备方法
KR20150003471A (ko) 방탄용 복합재료 및 이를 이용하여 제조된 방탄헬멧
CN114957989B (zh) 一种防弹复合材料及其制备方法
JP4869915B2 (ja) 複合防弾板
CN102632665B (zh) 一种芳纶纤维增强树脂基防刺复合材料
CN110861382A (zh) 无溶剂型芳纶防弹预浸料及其复合材料
Dimeski et al. Advanced prepreg ballistic composites for military helmets
Folgar et al. Thermoplastic matrix combat helmet with graphite-epoxy skin
CN111703088B (zh) 一种破片收敛型防弹复合材料的制备方法
GB2276933A (en) Composite ballistic armour

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: 12750487

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012750487

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE