WO2016169691A1 - Structure ayant un tissu respirant pour la production de protections résistant aux balles et aux coups de couteau - Google Patents

Structure ayant un tissu respirant pour la production de protections résistant aux balles et aux coups de couteau Download PDF

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Publication number
WO2016169691A1
WO2016169691A1 PCT/EP2016/054948 EP2016054948W WO2016169691A1 WO 2016169691 A1 WO2016169691 A1 WO 2016169691A1 EP 2016054948 W EP2016054948 W EP 2016054948W WO 2016169691 A1 WO2016169691 A1 WO 2016169691A1
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WO
WIPO (PCT)
Prior art keywords
structure according
resin
polymer
fibers
textile element
Prior art date
Application number
PCT/EP2016/054948
Other languages
English (en)
Inventor
Giorgio Citterio
Filippo Citterio
Original Assignee
Societa' Per Azioni Fratelli Citterio
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 Societa' Per Azioni Fratelli Citterio filed Critical Societa' Per Azioni Fratelli Citterio
Publication of WO2016169691A1 publication Critical patent/WO2016169691A1/fr

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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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/042—Acrylic polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/12—Permeability or impermeability properties
    • D06N2209/121—Permeability to gases, adsorption
    • D06N2209/123—Breathable

Definitions

  • the present invention relates to a structure for the production of ballistic stab resistant/awl-resistant protections, in particular a structure with breathable fabric.
  • Violent actions performed by means of cold weapons are more and more common, especially in situations in which a gun can be difficult to obtain (for example because of restrictive regulations in this matter).
  • a cutting weapon is easily available and even simple kitchen knives can become efficacious.
  • the bullet-proof and/or stab resistant jackets are obtained by the superimposition of layers of fabric composed of highly resistant fibers, if necessary covered with polymeric matrices.
  • the fabric stops the bullet, since it deforms the incident bullet; actually, the deformed bullet has a larger surface and a smaller specific energy per unit of surface area and therefore it is easier to stop.
  • the stab resistant jackets a very small part of the blade is deformed and the stopping is caused mainly by the mechanical action of the friction between the blade and highly resistant fibers and by the "barrier" action caused by the type of the surface of fabric.
  • the densely beaten stab-resistant fabrics are described for example in the patents US6737368, US6133169, US7340779; these are fabrics obtained by means of weaving processes, in which the ratio between the dimension of the fibers and the weight of the fabric layer, known as titer, is greater than a prefixed threshold value.
  • the Patent US8067317 describes a double protection fabric (stab- and bullet- resistant), obtained by a densifying treatment.
  • Patent US7354875 describes a fabric, in which a densification of threads is obtained by mechanical processes of the finished product.
  • the impregnated stab-resistant fabrics an evolution of the densely beaten stab- resistant fabrics, use polymer resins, whose function is to obtain compact fabrics without the need to use structures having high density of threads; the second solution is cheaper than the first one since the resins are cheaper than the fibers.
  • Fabrics of this type are described for example in the Patent US8450222.
  • a third structure aimed at stopping the blades is the so-called chain mail; this involves metallic rings connected one to another so as to form an open structure. It is the same solution used in the Middle Ages by the horse fighters and therefore widely known. Since it is made of interlinked rings, this type of armor is not suitable for stopping awls or pointed tools if the dimension of the awls is smaller than the dimension of the chain. Another disadvantage derives from the fact that they are extremely heavy and rather uncomfortable to wear.
  • the protective jackets are formed by superimposing numerous layers of fabric kept in containing covers.
  • the jacket user wears it for many hours in places which can be hot and humid; thus the comfort offered by the jacket is very important and consequently very strongly felt about.
  • the densely beaten and impregnated fabrics present a very low breathability and consequently, they do not allow the air to circulate between the outer surface of the jacket and the clothes, thus causing strong sweating and uncomfortable situations. In addition, they are very rigid.
  • the metallic meshes do not protect against pointed tools, such as ice-picks or others, since such tools insert in the rings of the mesh without finding any resistance.
  • the main object of the present invention is to propose an element for ballistic protection and against cutting weapons, which reduces the disadvantages of the prior art solutions.
  • a structure comprising at least one textile element including fibers having a negative axial Coefficient of Thermal Expansion (CTE), the textile element being coupled with a polymer layer by means of a process comprising a step of pressing, the polymer layer comprising at least a first resin having a positive CTE, a value of elongation at break lower than 5% and a hardness greater than 75 Shore D.
  • CTE negative axial Coefficient of Thermal Expansion
  • the at least first polymer resin includes one or more of the following polymers: Butyl Acrylate and Methyl Methacrylate, possibly mixed together.
  • the at least one polymer resin includes a copolymer Butyl Acrylate - Methyl Methacrylate.
  • the at least one polymer resin includes 5-cloro-2-metil-2H-isotiazol-3-one and/or 2-metil-2H-isotiazol-3-one, possibly mixed together.
  • the polymer comprising butyl acrylate or methyl methacrylate also in the form of the copolymer can be cross- linked for example with the addition of isocyanates, blocked isocyanates, melamine, peroxides or the like.
  • the polymers or copolymers are non-melting, less exposed to attack by organic solvents and with a higher hardness compared to non-cross-linked polymers, with a further increase of the mechanical characteristics e therefore with a better resistance to penetration to spikes or sharp blades.
  • the structure of the present invention makes it possible to obtain a flexible and breathable bullet-proof, stab resistant and awl resistant protection, in which the presence of holes and a polymeric deposit constituted by microfractures provide at the same time breathableness, protection against blades and pointed objects,without giving up a valid protection against bullets.
  • the fact that the resin placed on the fiber adheres to the interface resin/fiber is not due to the chemical bonds, but results from interlacing of the matrix around the filaments composing the fiber.
  • the axial CTE of the fibers of the textile element is between -20x10 "6 /°C and 0/°C, preferably in the range of - 20x10 "6 to -0,1x10 "6 per degree centigrade, while the CTE of the first resin is included between 0 and 200x10 "6 /°C.
  • the polymer layer after the treatment presents a structure with discontinuities which let air pass through. Such discontinuities can be micropores having dimensions in the range of 10 to 300 ⁇ .
  • the polymer layer comprises a second resin mixed with the first resin, the second resin having a hardness lower than 80 Shore A and elongation greater than 300%.
  • the textile element of the structure according to a preferred embodiment of the present invention comprises fibers of one of the following groups: para-aramid, co- poly-aramid, polyethylenic, etc.
  • a production process which facilitates the adhesion matrix/fiber; the process according to an embodiment of the present invention includes the following steps: - application of the resin to the textile element according to one of the many techniques available in the state of the art; the characteristics of the fabric and resin are those described above;
  • the temperature is selected so as to respect the following relation:
  • CTE F is the Coefficient of Thermal Expansion of the fibers of the textile element
  • T P is the pressing temperature
  • T A is the ambient temperature
  • CTER is the coefficient of expansion of the resin.
  • the CTE of the fabric is negative, while the CTE of the resin is positive.
  • the temperature Tp is preferably in the range of 20 to 200°C, the pressure is in the range of 5 to 200 bar and the pressing time is greater than 5s.
  • the textile element comprises polyethylene fibers, and the temperature TP is below the melting temperature of the polyethylene fibers and the polymer matrix.
  • the present invention makes it possible to obtain an element of ballistic protection, which is particularly effective both against bullets fired by a gun or rifle and against the attack with a cutting weapon and which at the same time has breathable characteristics.
  • a ballistic/stab-resistant protection in accordance with the present invention comprises a structure with one or more textile elements ET constituted by the intertwining of yarns composed of fibers which usually have a tensile strength greater than 8 cN/dtex, preferably greater than 18 cN/dtex, our example 20 cN/dtex, a modulus greater than 20 GPa and an elongation at break greater than 1 %.
  • fabrics we designate: weft/warp fabrics, knitted fabrics, unidirectional fabrics, semi-unidirectional fabrics, three-dimensional fabrics, biaxial fabrics, multi- axial fabrics, felts, non-woven fabrics, continuous filament felts etc. or combinations thereof.
  • the fibers forming the textile element ET have a negative axial Coefficient of Thermal
  • Expansion preferably in the range between -20x10 "6 /°C e 0.
  • the fibers of the textile element ET are partially or totally pre-impregnated with matrixes (resins) that can be of polymeric, organic or inorganic nature; in the case polymers, thermoplastic or thermosetting materials are known with plastomeric or elastomeric behavior, with liquid or solid nature, possibly with viscoelastic properties also in liquid nature.
  • matrixes resins
  • thermoplastic or thermosetting materials are known with plastomeric or elastomeric behavior, with liquid or solid nature, possibly with viscoelastic properties also in liquid nature.
  • the impregnation process of the fabric fibers include total or partial immersion treatment, coating on one or two sides, spraying, deposition by PVD, CVD, joining films, polymeric networks or web or combinations thereof.
  • the polymer forming the positive matrix (or resin) must have a positive Coefficient of Thermal Expansion (CTE), preferably in the range between 0 and 200x10 "6 /°C.
  • CTE Coefficient of Thermal Expansion
  • the same fibers that form the fabrics can be partially or totally pre-impregnated with the polymers described above.
  • the fabrics or the fibers may possibly be printed in continuous or discontinuous way.
  • the manufacturing process according to a preferred embodiment of the present invention facilitates the matrix/fiber adhesion; the process includes the following steps:
  • drying the textile element with the resin joined thereto also this step can be performed using one of the techniques available from the state of the art;
  • the temperature is selected so as to respect the following relation:
  • CTE F is the expansion (negative) Coefficient of the fibers of the textile element
  • T P is the pressing temperature
  • T A is the ambient temperature
  • CTER is the expansion (positive) Coefficient of the polymer resin.
  • the pressing temperature used was 80°C at a room temperature of 20°C (and thus with a difference (T P -T A ) of 60°C)
  • the resin used must have very specific characteristics.
  • the resin must be rigid with a hardness greater than 75 Shore D.
  • the resin contains one or two of the following polymers: Butyl Acrylate and Methyl methacrylate. Possibly the two polymers are mixed together or can even form a copolymer Butyl Acrylate - Methyl methacrylate.
  • Acrilem 7105 acrylic resin produced by ICAP SIRA is used.
  • Acrilem 7105 resin contains a copolymer Butyl Acrylate - Methyl methacrylate; more specifically it includes the following components mixed together: 5-cloro-2-metil-2H- isotiazol-3-one [EC no. 247-500-7] and 2-metil-2H-isotiazol-3-one [EC no. 220-239- 6].
  • the polymer comprising butyl acrylate or methyl methacrylate also in the form of the copolymer can be cross-linked for example with the addition of isocyanates, blocked isocyanates, melamine, peroxides or the like.
  • the polymers or copolymers are non-melting, less exposed to attack by organic solvents and with a higher hardness compared to non-cross-linked polymers, with a further increase of the mechanical characteristics e therefore with a better resistance to penetration to spikes or sharp blades.
  • micro-discontinuities small holes
  • a high ratio coefficient of cohesion/coefficient of adhesion
  • the application of the resin is preferably carried out by means of a processing adjuvant, which is responsible for spreading the polymer onto the fabric.
  • a processing adjuvant which is responsible for spreading the polymer onto the fabric.
  • this consists of solvents which may or may not be water-based.
  • the polymer tends to adhere to the fiber (adhesion) and to itself (cohesion); if the coefficient of cohesion/coefficient of adhesion ratio is above a certain value, the polymer will tend to adhere to itself and not to occupy areas where it has no support, typically at the warp and woof intersections. In these areas the polymer withdraws until it forms a hole/opening, which will then be responsible for the breathability of the fabric.
  • the micro-cracks present on the resin that impregnates the fabric are instead due to a high coefficient of shrinkage which creates a naturally wavy surface in which the polymer islands touch each other in correspondence of their perimeters.
  • these are fabrics for which the ratio is between 0.09 (g/m 2 )dtex and 0.5
  • (g/m 2 )/dtex preferably between 0.14 (g/m 2 )/dtex and 0.3 (g/m 2 )/dtex and more preferably of 0.15 to 0.28 (g/m 2 )/dtex.
  • the textile element ET includes polyethylene fibers, in particular UHMW polyethylene fibers, such as fibers of the Dyneema® o Spectra® type.
  • the textile element ET is made with para-aramid fibers, such as fibers of Kevlar®, Twaron® or Artec® and mixtures thereof.
  • Beaten tissue typically with values greater than 0.5 (g/m 2 )/dtex do not offer spaces to the withdrawal of the matrix, and less beaten tissue, typically with values lower than 0.09 (g/m 2 )/dtex, allow the formation of holes, but are not effective against blades and awls because these holes become too large.
  • the size of the holes can vary from 10 microns up to about 300 microns, preferably from 20 to 100 microns, more preferably from 30 to 60 microns; this dimension is at most influenced by the coefficient of cohesion/coefficient of adhesion of the polymer ratio.
  • the resin (matrix) used in the product and in the process described above may comprise a mixture of two resins, in order to improve the anti-ballistic characteristics (bullet protection) in addition to those of the shear strength (or resistance to attack by awls).
  • the impact speed of a cutting weapon e.g. a blade
  • a protective structure typically a maximum of 10 m/s are reached by a blade attack and 200 m/s are exceeded by a bullet; the same applies to the energies involved: max 80 Joules for a blade and more than 300 Joules per a bullet.
  • the bullet induces a deformation that on the cover (Trauma or Back Face Deformation) is much greater than the deformation induced by a blade.
  • the polymers suitable to impregnate fabrics that stop bullets have low toughness, low modulus and high.
  • the polymer suitable to stop the blade must instead have a very high modulus, high hardness and high resistance to compression and should absorb energy with smaller deformations as compared to those induced by bullets.
  • an engineered resin intended to stop a bullet may not be suitable to stop a blade.
  • the first harder, low adhesion resin is used to stop a blade with low speed load application conforming with the limited deformations that occur during this event 2.
  • the second low-hardness, high adhesion resin with low cohesion and high elongation is instead suitable to stop the bullet as it conforms with the highest deformations typical of this ballistic event
  • the very hard resins such as the cut-resistant resin of the present invention, have a reduced elongation and thus tend to detach from the textile support which is rather soft and flexible.
  • Mixing with the second resin allows the hard resin to adhere to the fiber surface in a flexible way, thus avoiding separation from the fiber surface. In this way, a further advantage of ensuring a high flexibility of the textile support while impregnating it with a hard resin can be obtained.
  • the stab-awl-bullet resistant resin is made from the mixture of two resins: one with tg > 50C° and one with tg ⁇ -30C°; the first one with hardness greater than 75 Shore D and the second one with hardness lower than 80 Shore A.
  • the tg of the stab-awl resistant resin should be above the test temperature of the protection structure while the tg of the bullet-resistant resin should be substantially lower than the test temperature of the protection structure.
  • the elongation at break of the cut-resistant resin is lower than 5% while the one of the bullet-resistant resin is greater than 300%.
  • preventive treatments may be implemented to promote mutual adhesion between the textile element ET fibers and the matrix (resin).
  • To promote adhesion processes are known for activation of the surface of the textile element ET by washing treatments, corona treatments, plasma treatments or combination thereof, etc.
  • Treatments that normally follow the impregnations may provide molding at temperatures above the melting/softening temperature of the resin, in order to promote fluidization of the matrix and a better penetration of the resin in the composite.
  • the penetration of the resin between the fibers is obtained through an impregnation process in which the resin/solvent solution often wets the fibers taking advantage from a low viscosity;
  • the resin/fibers adhesion is substantially improved through a process of molding at a temperature below the melting point temperature of the resin and of the fiber. More preferably, at a temperature lower than the melting temperature of the resin but around the softening temperature of the polyethylene fiber. Precisely during the final molding operation the surface of the fiber polyethylene, while softening, adheres intimately to the resin thus improving the stab-awl-bullet resistant properties of the protective structure.
  • polymer refers to a polymeric material, as well as to natural or synthetic resins and their mixtures.
  • fiber refers to elongated bodies, whose longitudinal dimension is much longer than the transversal dimension.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

La présente invention concerne une structure pour la réalisation de protections résistant aux balles et aux coups de couteau, comprenant au moins un élément textile accouplé à une couche polymère au moyen d'un procédé comprenant une étape de pression à une température déterminée en fonction des caractéristiques de l'élément textile et de la couche polymère. La structure obtenue à l'aide du procédé selon la présente invention garantit des caractéristiques de respirabilité qui rendent les protections réalisées avec la structure particulièrement confortables.
PCT/EP2016/054948 2015-04-21 2016-03-08 Structure ayant un tissu respirant pour la production de protections résistant aux balles et aux coups de couteau WO2016169691A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI2015A000572(102015902345518) 2015-04-21
ITMI20150572 2015-04-21

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WO2016169691A1 true WO2016169691A1 (fr) 2016-10-27

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5124195A (en) 1990-01-10 1992-06-23 Allied-Signal Inc. Flexible coated fibrous webs
EP0572965A1 (fr) * 1992-06-01 1993-12-08 AlliedSignal Inc. Blindage composite anti-balistique
EP0658589A1 (fr) * 1993-10-29 1995-06-21 AlliedSignal Inc. Composite de haute résistance
US6133169A (en) 1998-03-20 2000-10-17 E. I. Du Pont De Nemours And Company Penetration-resistant ballistic article
US6737368B2 (en) 2001-12-19 2004-05-18 E. I. Du Pont De Nemours And Company Multiple threat penetration resistant articles
WO2007044041A2 (fr) * 2004-12-29 2007-04-19 Honeywell International Inc. Articles et fibres pbo resistants a l’humidite et procede de fabrication de ceux-ci
US7340779B2 (en) 2003-07-01 2008-03-11 E.I. Du Pont De Nemours And Company Flexible spike/ballistic penetration-resistant articles
US7354875B2 (en) 2002-02-08 2008-04-08 Teijin Twaron Gmbh Stab resistant and anti-ballistic material and method of making the same
US8450222B2 (en) 2007-03-26 2013-05-28 Barrday Inc. Coated multi-threat materials and methods for fabricating the same

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5124195A (en) 1990-01-10 1992-06-23 Allied-Signal Inc. Flexible coated fibrous webs
EP0572965A1 (fr) * 1992-06-01 1993-12-08 AlliedSignal Inc. Blindage composite anti-balistique
EP0658589A1 (fr) * 1993-10-29 1995-06-21 AlliedSignal Inc. Composite de haute résistance
US6133169A (en) 1998-03-20 2000-10-17 E. I. Du Pont De Nemours And Company Penetration-resistant ballistic article
US6737368B2 (en) 2001-12-19 2004-05-18 E. I. Du Pont De Nemours And Company Multiple threat penetration resistant articles
US7354875B2 (en) 2002-02-08 2008-04-08 Teijin Twaron Gmbh Stab resistant and anti-ballistic material and method of making the same
US8067317B2 (en) 2002-02-08 2011-11-29 Teijin Aramid Gmbh Stab resistant and anti-ballistic material and method of making the same
US7340779B2 (en) 2003-07-01 2008-03-11 E.I. Du Pont De Nemours And Company Flexible spike/ballistic penetration-resistant articles
WO2007044041A2 (fr) * 2004-12-29 2007-04-19 Honeywell International Inc. Articles et fibres pbo resistants a l’humidite et procede de fabrication de ceux-ci
US8450222B2 (en) 2007-03-26 2013-05-28 Barrday Inc. Coated multi-threat materials and methods for fabricating the same

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