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WO2025010346A1 - Matériaux de blindage transparents - Google Patents

Matériaux de blindage transparents Download PDF

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Publication number
WO2025010346A1
WO2025010346A1 PCT/US2024/036752 US2024036752W WO2025010346A1 WO 2025010346 A1 WO2025010346 A1 WO 2025010346A1 US 2024036752 W US2024036752 W US 2024036752W WO 2025010346 A1 WO2025010346 A1 WO 2025010346A1
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melanin
resins
armor
transparent
group
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Steven Baranowitz
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • 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
    • F41H5/0407—Transparent bullet-proof laminatesinformative reference: layered products essentially comprising glass in general B32B17/06, e.g. B32B17/10009; manufacture or composition of glass, e.g. joining glass to glass C03; permanent multiple-glazing windows, e.g. with spacing therebetween, E06B3/66
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F1/00—Shielding characterised by the composition of the materials
    • G21F1/02—Selection of uniform shielding materials
    • G21F1/10—Organic substances; Dispersions in organic carriers
    • G21F1/103—Dispersions in organic carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Definitions

  • transparent armors are typically constructed of individual sheets or blocks of polymers such as polycarbonate (PC) or polymethylmethacrylate (PMMA), or laminated versions of these polymers with each other, and/or with ballistic nylons and related materials. There are also a few ceramic transparent armor materials in use. (Crouch, 2016).
  • PC and PMMA each have their own strengths and weaknesses and the use of combinations of the two somewhat mitigates their individual weaknesses for armor, e.g., PC is generally tougher and more resistant to projectiles and heat than PMMA, but it has relatively poorer resistance to abrasion and ultraviolet light compared to PMMA, which can also "spread the impact area" better (Crouch, 2016).
  • Melanin is known to have high abrasion resistance (Moses, 2006). Melanin has been reported to have the capacity to absorb gases (Mostert, A. B. et al. 2010). Price (1972) reported that melanin can absorb shellfish toxin. Melanin has reported anti-infective properties (e.g. Sidibe S. et al., 1996). Melanin nanoparticles were reported to moderately improve the robustness of thin films of another polymer, polyvinyl alcohol (Wang et al., 2015, 2016). The inventor has discovered that melanins and melanin derivatives have the surprising effect of markedly enhancing, for example, the ballistic protective properties of polymers such as PC and PMMA while maintaining transparency at a useful level. Remarkably, even small percentages of melanin or its derivatives in these polymers, such as 0.5%-5%, have been now discovered to substantially improve these transparent polymers' robustness to attack by projectiles, heat, radiation, and chemical and biological weapons.
  • the present disclosure relates to lightweight melanin composite transparent materials, which are useful as, for example, transparent armor.
  • Lightweight melanin composite transparent armor materials may be useful, for example, in the construction and automotive industries, law enforcement, as well as in military applications.
  • the present disclosure also relates to transparent armor made of polymeric material incorporating melanins and melanin derivatives for ballistic protection such as armor, including body armor.
  • the transparent armor made of polymeric material incorporating melanins and melanin derivatives of the present disclosure substantially increase the level of ballistic protection available to military and law enforcement personnel without increasing equipment weight.
  • the present disclosure further relates to light-weight transparent materials for ballistic protection, including materials for eye and face protection, that has ballistic impact resistance properties comparable to present non-transparent fiber reinforced polymer composite materials.
  • the transparent armor made of polymeric material incorporating melanins and melanin derivatives of the present disclosure have optical properties comparable to commercially available transparent polymers presently used for eye and face protection.
  • PC polycarbonates
  • PMMA polymethylmethacrylates
  • the present disclosure relates generally to lightweight melanin composite transparent materials such as, for example, polymers, ceramics, fibrous sheets and/or laminated plies.
  • melanin composite transparent materials such as, for example, polymers, ceramics, fibrous sheets and/or laminated plies.
  • the inventor has appreciated that by combining certain melanin materials and non-melanin materials into for example, ceramics, laminar configurations, and composites with advantages not attainable by either component separately can be achieved. In some cases, the resulting composite, synergistic interactions between the polymeric materials and melanin materials may arise.
  • melanin can be doped with metal to enhance its desirable protective capabilities.
  • multiple different types of metals can be applied to a single piece of melanin to surprisingly enhance these properties.
  • melanosomes can be doped with metal. The manufacturing methods as disclosed herein for improving melanin's properties will lead to a variety of desirable properties regarding protective effect, which can be adjusted and tuned to particular applications.
  • Melanin composites may take many forms and have many different useful advantages. Melanin composites comprising mechanically strong melanin materials are particularly usefill. In some embodiments, melanin composites are particularly well-suited as multilayer insulation (MLI) with better thermal performance than the melanin material by itself. In some embodiments, melanin composites with good flexibility may serve as useful insulation for garments. In other embodiments, lightweight melanin composite transparent materials are highly effective ballistic materials useful for, for example, armor, bullet-proof vests, ballistic protective windows and visors, armored vehicle cladding, and energetic flames or jets. In some embodiments, lightweight melanin composite transparent materials may be useful in space applications including micrometeoroid/ space debris protection and vehicle reentry shielding.
  • melanin material containing composites may serve as high stiffness-to-weight ratio materials suitable for lightweight structures, aircraft and automotive parts, and high-performance sports equipment.
  • the melanin composite transparent materials exhibit the following features: 1. Ultra-light- weight; 2. Flexibility to fit various vehicle bodies and contours; 3. Superior impact energy absorption capability; 4. Superior strength for structural integrity; 5. Capability to resist heat and flame; 6. Ease of manufacture, maintenance and repair, and low life-cycle cost; 7. Applicability to other military applications and to commercial vehicle systems.
  • the new melanin material containing composite material can also be used, with minimum modifications, to protect commercial vehicles when necessary.
  • the melanin material containing composite can be further extended for other usages, for example, in a windshield to protect driver and passengers, or law enforcement protect officers, or even as a personal armor.
  • the melanins comprise a family of biopolymer pigments. Progress understanding the structure, functions, chemical and physical properties of melanins has been slow, sporadic and fragmented among many different scientific disciplines, including biology, chemistry, physics, and electronics.
  • melanin The definition and nomenclature of melanin remains unsettled and problematic, since workers in various scientific disciplines differ somewhat in their use of the term. For instance, chemists can produce different synthetic melanins using different pathways, but vary in how they characterize the resulting substances. Also, biologists sometimes struggle with the exact definition of melanin, since many melanins extracted from different organisms have similar chemical and physical properties, but remain largely insoluble in most common solvents, and resist many types of chemical and physical analysis.
  • lightweight melanin composite transparent armor materials that are easy to fabricate into final armor components, at reasonable cost, yet still offer ballistic protection properties on par with heavier armor materials.
  • Such materials would find ready use in a number of applications, including comprises protective eyewear, a face shield, a window or a vision block for a combat vehicle or an armored vehicle, a ballistic shield window, an aircraft transparency, a sensor window, am infrared dome for a missile, a laser ignition windows for medium and large caliber cannons, a law enforcement vehicle window or armor for executive protection, helmets, visors, safety goggles, body armor, ballistic shields, windows, vehicle windows, portholes, vehicle armor, aircraft armor, watercraft armor, structure armor, equipment housing, blast protection panels, transparent armor panels, phone screens, and cargo containers.
  • the disclosure provides a transparent material comprising: at least one transparent polymer; at least one melanin material; optionally, at least one additional non-melanin material selected from the group consisting of lead, zinc, magnesium, bismuth, and combinations thereof; and optionally, at least one binder.
  • the disclosure provides a transparent material wherein said transparent polymer is selected from the group consisting of polyethylene, polypropylene, polystyrene, poly-propylene copolymers, Polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), PET copolymers, polyacrylates, polyaciylate copolymers, cyclic olefin copolymers (COC), polyamides, polyamide co-polymers, polybutylene terephthalate (PBT), polycarbonate (PC), polyetherimides (PEI) and polyethersulfones (PES) with melting or softening point temperatures between 100 and 350° C, or said heat fusible coating layer polymer is selected from the group consisting of ethylene vinyl acetates (EVA), polymeric ionomers, polyethylenes, polyethylene copolymerized with olefins, amorphous polyesters, ethylene-acrylic acid (EAA) copolymers, ethylene-methacrylic acid
  • the disclosure provides a transparent material wherein said transparent polymer is selected from the group consisting of Polymethyl methacrylate (PMMA), Polycarbonate (PC), and combinations thereof.
  • PMMA Polymethyl methacrylate
  • PC Polycarbonate
  • the disclosure provides a transparent material natural, synthetic, extracted from plant sources, from bioreactors, from bacterial sources, from fungal sources, extracted from animal sources, and combinations thereof.
  • the disclosure provides a transparent material wherein the melanin material is genetically modified.
  • the disclosure provides a transparent material wherein the melanin material is present in the composition at a range of about 0.5% - about 5% w/w.
  • the disclosure provides a transparent material wherein the melanin material comprises metal selected from the group consisting of: bismuth linked to the carboxyl groups of melanin; lead linked to the carboxyl groups of melanin; zinc linked to the carboxyl groups of melanin; iron linked to the hydroxyl groups of melanin; copper linked to the hydroxyl groups of melanin; magnesium linked to the hydroxyl groups of melanin; and combinations thereof.
  • the melanin material comprises metal selected from the group consisting of: bismuth linked to the carboxyl groups of melanin; lead linked to the carboxyl groups of melanin; zinc linked to the carboxyl groups of melanin; iron linked to the hydroxyl groups of melanin; copper linked to the hydroxyl groups of melanin; magnesium linked to the hydroxyl groups of melanin; and combinations thereof.
  • non-melanin material further comprises at least one other polymer independently selected from the group consisting of polyimides, polyetherimides, polyimideamides, polysulfones, epoxy resins, bismaleimide resins, bis benzocyclobutene resins, phthalonitrile resins, polyaryletherketones, polyetherketones, liquid crystal polymers, oligomeric cyclic polyester precursors, polybenzbisoxazoles, polybenzbisthiazoles, polybenzbisimidazoles, acetylene endcapped thermosetting resins, polysulfones, polyaramides, Poly-paraphenylene terephthalamide, polyamides, polycarbonates, polyethylenes, and polyesters.
  • polyimides polyetherimides, polyimideamides, polysulfones, epoxy resins, bismaleimide resins, bis benzocyclobutene resins, phthalonitrile resins, polyaryletherketones, polyetherketones, liquid crystal polymers, oligo
  • the disclosure provides a transparent material wherein the binder is present and is selected from the group consisting of phenolic resins, ureaformaldehyde resins, melamine formaldehyde resins, hide glue, aminoplast resins, epoxy resins, acrylate resins, latexes, polyester resins, urethane resins, and mixtures thereof may be used as a binder.
  • Suitable binders include glue, varnish, epoxy resins, phenolic resins, polyurethane resins, and combinations thereof.
  • the disclosure provides a transparent material further comprising at least one additive material selected from the group consisting of process aids, modifiers, colorants, fibers, adhesion promoters, fillers, and combinations thereof.
  • the disclosure provides a transparent material wherein the transparent material is manufactured in a form selected from the group consisting of particles, nanoparticles, dust, beads, fibers that are woven, fibers that are non-woven, sheets, laminates, films, slabs, plates, bricks, chars, spheres, nodules, balls, graphite-like sheets and shards, liquids, gels, solids, thermoplastic solids, and thermoset solids.
  • the disclosure provides a transparent material wherein the non-melanin material and the melanin material combine to synergistically increase the impact resistance of the transparent material compared to the non-melanin materials and melanin material alone.
  • the disclosure provides a transparent material wherein the transparent material is resistant to attack by attack by projectiles, heat, radiation, chemical and biological weapons, and combinations thereof.
  • the disclosure provides a transparent material wherein the transparent material is formed into an article which is an item selected from the group consisting of helmets, visors, safety goggles, body armor, ballistic shields, windows, vehicle windows, portholes, vehicle armor, aircraft armor, watercraft armor, structure armor, equipment housing, blast protection panels, transparent armor panels, phone screens, and cargo containers.
  • the disclosure provides an impact-resistant article formed from the transparent material as disclosed herein.
  • the disclosure provides an impact-resistant article wherein said article is an automotive part, polymeric laminate for ballistic protection, or an explosive blast barrier.
  • the disclosure provides an impact-resistant article wherein said article is transparent.
  • the disclosure provides an impact-resistant article wherein said article is a vehicle body armor panel, a personnel armor system, or a ballistic shield.
  • the disclosure provides an impact-resistant article wherein said article is transparent and is selected from the group consisting of protective eyewear, a face shield, a window or a vision block for a combat vehicle or an armored vehicle, a ballistic shield, a ballistic shield window, an aircraft transparency, a sensor window, a phone screen, a computer screen, an infrared dome for a missile, a laser ignition window for medium and large caliber cannons, a law enforcement vehicle window or armor for executive protection, helmets, visors, safety goggles, body armor, windows, vehicle windows, portholes, vehicle armor, aircraft armor, watercraft armor, structure armor, equipment housing, blast protection panels, transparent armor panels, and cargo containers.
  • the disclosure provides a method for forming a transparent material comprising mixing: at least one transparent polymer; at least one melanin material; optionally, at least one additional non-melanin material selected from the group consisting of lead, zinc, magnesium, bismuth, and combinations thereof; and optionally, at least one binder; and optionally shaping the resultant material into an article.
  • the disclosure provides a method wherein said transparent polymer is selected from the group consisting of polyethylene, polypropylene, polystyrene, poly-propylene copolymers, Polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), PET copolymers, polyacrylates, polyacrylate copolymers, cyclic olefin copolymers (COC), polyamides, polyamide co-polymers, polybutylene terephthalate (PBT), polycarbonate (PC), polyetherimides (PEI) and polyethersulfones (PES) with melting or softening point temperatures between 100 and 350° C, or said heat fusible coating layer polymer is selected from the group consisting of ethylene vinyl acetates (EVA), polymeric ionomers, polyethylenes, polyethylene copolymerized with olefins, amorphous polyesters, ethylene-acrylic acid (EAA) copolymers, ethylene-methacrylic acid (EMA
  • the disclosure provides a method wherein said transparent polymer is selected from the group consisting of Polymethyl methacrylate (PMMA), Polycarbonate (PC), and combinations thereof.
  • PMMA Polymethyl methacrylate
  • PC Polycarbonate
  • the disclosure provides a method wherein the melanin material is natural, synthetic, extracted from plant sources, from bioreactors, from bacterial sources, from fungal sources, extracted from animal sources, and combinations thereof.
  • the disclosure provides a method wherein the melanin material is genetically modified.
  • the disclosure provides a method wherein the melanin material is present in the composition at a range of about 0.5% - about 5% w/w.
  • the melanin material comprises metal selected from the group consisting of: bismuth linked to the carboxyl groups of melanin; lead linked to the carboxyl groups of melanin; zinc linked to the carboxyl groups of melanin; iron linked to the hydroxyl groups of melanin; copper linked to the hydroxyl groups of melanin; magnesium linked to the hydroxyl groups of melanin; and combinations thereof.
  • non-melanin material further comprises at least one other polymer independently selected from the group consisting of polyimides, polyetherimides, polyimideamides, polysulfones, epoxy resins, bismaleimide resins, bis benzocyclobutene resins, phthalonitrile resins, polyaryletherketones, polyetherketones, liquid crystal polymers, oligomeric cyclic polyester precursors, polybenzbisoxazoles, polybenzbisthiazoles, polybenzbisimidazoles, acetylene endcapped thermosetting resins, polysulfones, polyaramides, Poly-paraphenylene terephthalamide, polyamides, polycarbonates, polyethylenes, and polyesters.
  • polyimides polyetherimides, polyimideamides, polysulfones, epoxy resins, bismaleimide resins, bis benzocyclobutene resins, phthalonitrile resins, polyaryletherketones, polyetherketones, liquid crystal polymers, oligo
  • the disclosure provides a method wherein the binder is present and is selected from the group consisting of phenolic resins, ureaformaldehyde resins, melamine formaldehyde resins, hide glue, aminoplast resins, epoxy resins, acrylate resins, latexes, polyester resins, urethane resins, and mixtures thereof may be used as a binde, glue, varnish, epoxy resins, phenolic resins, polyurethane resins, and combinations thereof.
  • the disclosure provides a method further comprising at least one additive material selected from the group consisting of process aids, modifiers, colorants, fibers, adhesion promoters, fillers, and combinations thereof.
  • the disclosure provides a method wherein the transparent material is manufactured in a form selected from the group consisting of particles, nanoparticles, dust, beads, fibers that are woven, fibers that are non-woven, sheets, laminates, films, slabs, plates, bricks, chars, spheres, nodules, balls, graphite-like sheets and shards, liquids, gels, solids, thermoplastic solids, and thermoset solids.
  • the disclosure provides a method wherein the non-melanin material and the melanin material combine to synergistically increase the impact resistance of the transparent material compared to the non-melanin materials and melanin material alone.
  • the disclosure provides a method wherein the transparent material is resistant to attack by attack by projectiles, heat, radiation, chemical and biological weapons, and combinations thereof.
  • the disclosure provides a method wherein the transparent material is formed into an article which is an item selected from the group consisting of protective eyewear, a face shield, a window or a vision block for a combat vehicle or an armored vehicle, a ballistic shield, a ballistic shield window, an aircraft transparency, a sensor window, a phone screen, a computer screen, an infrared dome for a missile, a laser ignition window for medium and large caliber cannons, a law enforcement vehicle window or armor for executive protection, helmets, visors, safety goggles, body armor, windows, vehicle windows, portholes, vehicle armor, aircraft armor, watercraft armor, structure armor, equipment housing, blast protection panels, transparent armor panels, and cargo containers.
  • melanins and their derivatives have the surprising effect of markedly enhancing, for example, the ballistic protective properties of polymers such as PC and PMMA while maintaining transparency at a useful level.
  • polymers such as PC and PMMA
  • melanin or its derivatives in these polymers such as 0.5%-5%, have been now discovered to substantially improve these transparent polymers' robustness to attack by projectiles, heat, radiation, and chemical and biological weapons.
  • small amounts of melanin and melanin derivatives can surprisingly and substantially increase the resistance of armor, including transparent armor, to acids and alkalis.
  • Melanins are known to be unaffected by harsh acids or alkalis (Prota, 1992).
  • armor composed of melanin or metal-melanin polymer composites will be highly resistant to harsh chemical attack (e.g. by acids or alkalis) or environmental chemical degradation depending on the porosity of the composite and the ability of the chemical to diffuse in the composite, or if the composite is lined on its outside faces with sheets of melanin or metal-melanin polymers that are a higher percentage of the melanin (or metal-melanin) than the bulk of the block.
  • melanin and melanin derivatives can surprisingly and substantially increase the resistance to diverse chemical attacks.
  • toxic chemicals such as mustard gas or shellfish toxin can be absorbed by melanin containing armor, including transparent armor, to protect.
  • metal-melanin composites Ballistic armor composed of melanin or metal-melanin polymer composites has the capacity to absorb toxic gases, depending on the porosity of the composite and the ability of the chemical to diffuse in the composite, or if the composite is lined on its outside faces with sheets of melanin or metal-melanin polymers that are a higher percentage of the melanin (or metal-melanin) than the bulk of the block.
  • melanin (or metal-melanin) polymer composites can be used in armor against certain bioweapons, depending on the porosity of the composite and the ability of the bioweapon agent to diffuse in the composite, or if the composite is lined on its outside faces with sheets of melanin or metal-melanin polymers that are a higher percentage of the melanin (or metal-melanin) than the bulk of the block.
  • incorporation of melanin and melanin derivatives will sufficiently strengthen polyvinyl alcohol polymer so that it can be used as transparent armor alone or as a lamella in layered armor structures with other polymers such as PC and PMMA.
  • the melanins comprise a family of biopolymer pigments.
  • a frequently used chemical description of melanin is that it is comprised of “heteropolymers of 5-6-dihydroxy indole and 5- 6- dihydroxyindole-2-carboxylic acid” (Bettinger et al., 2009).
  • Melanins are polymers produced by polymerization of reactive intermediates.
  • the polymerization mechanisms include, but are not limited to, autoxidation, enzyme-catalyzed polymerization and free radical initiated polymerization.
  • the reactive intermediates are produced chemically, electrochemically, or enzymatically from precursors.
  • Suitable enzymes include, but are not limited to, peroxidases, catalases, polyphenol oxidases, tyrosinase, tyrosine hydroxylases, and laccases.
  • the precursors that are connected to the reactive intermediates are hydroxylated aromatic compounds.
  • Suitable hydroxylated aromatic compounds include, but are not limited to 1) phenols, polyphenols, aminophenols and thiophenols of aromatic or polycyclicaromatic hydrocarbons, including, but not limited to, phenol, tyrosine, pyrogallol, 3 -aminotyrosine, thiophenol and a-naphthol; 2) phenols, polyphenols, aminophenols, and thiophenols of aromatic heterocyclic or heteropoly cyclic hydrocarbons such as, but not limited to, 2-hydroxypyrrole,4-hydroxy-l,2-pyrazole, 4- hydroxypyridine, 8-hydroxyquinoline, and 4,5-dihydroxybenzothiazole.
  • melanin includes naturally occurring melanin polymers as well as melanin analogs as defined below. Naturally occurring melanins include eumelanins, phaeomelanins, neuromelanins and allomelanins.
  • melanin refers to melanins, melanin precursors, melanin analogs, melanin variants, melanin derivatives, melanin-like pigments, and/or melanosomes, unless the context dictates otherwise.
  • the term “melanin-like” also refers to hydrogels with melanin-like pigmentation and quinoid electrophilicity. This electrophilicity can be exploited for facile coupling with biomolecules.
  • melanin analog refers to a melanin in which a structural feature that occurs in naturally-occurring or enzymatically -produced melanins is replaced by a substituent divergent from substituents traditionally present in melanin.
  • a substituent is a selenium, such as selenocysteine, in place of sulfur.
  • the term “melanin derivative” refers to any derivative of melanin which is capable of being converted to either melanin or a substance having melanin activity.
  • An example of a melanin derivative is melanin attached to a dihydrotrigonelline carrier such as described in Bodor, N., Ann. N.Y. Acad. Sci. 507, 289 (1987), which enables the melanin to cross the bloodbrain barrier.
  • melanin derivatives is also intended to include chemical derivatives of melanin, such as an esterified melanin.
  • the term “melanin variant” refers to various subsets of melanin substances that occur as families of related materials. Included in these subsets, but not limited thereto, are:
  • Melanin-like substances refers to heteropolymers of 5-6- dihydroxyindole and 5-6-dihydroxyindole-2-carboxylic acid which have one or more properties usually associated with natural melanins, such as UV absorption or semiconductor behavior.
  • Melanin Sources Melanin and Melanin-like compounds can be obtained:
  • cephalopods such as cuttlefish (e.g. Sepia) or squid (e.g. Loligo), bird feathers (e.g. from species with black strains such as Silkie chickens);
  • Cephalopod inks are natural composites of melanin with other materials, including peptidoglycans, amino acids, proteins, metals, and chemicals and enzymes (such as tyrosinase) which are involved in the synthesis of melanin, and other materials.
  • Cephalopod inks include cuttlefish (such as Sepia), squid, and octopus inks. There is some variation among different species of the percentages of these components. Reports of cephalopod ink components include: Derby, C.D. 2014 Cephalopod Ink: Production, Chemistry, Functions and Applications Marine Drugs 12, 2700-2730; doi: 10.3390/mdl2052700, and Magarelli M, Passamonti P, Renieri C. 2010. Purification, characterization and analysis of sepia melanin from commercial sepia ink (Sepia Officinalis) . Rev CES Med Vet Zootec; Vol 5 (2): 18-28.
  • Melanin and melanin-like compounds can be manufactured as particles, nanoparticles, dust, beads, or fibers that sire woven or non-woven e.g. by methods as described by (Greiner and Wendorff, 2007), sheets e.g. (Meredith et al., 2005), films (daSilva et al., 2004), plates, bricks, chars, spheres, nodules, balls, graphite-like sheets and shards, liquids, gels, or solids (e.g. thermoplastic or thermoset), and by common chemical engineering molding and fabrication methods or custom methods.
  • Sheets can range from one molecular layer to several millimeters.
  • Fibers can range from nanometers to several millimeters.
  • the melanin material may be natural or synthetic, with natural pigments being extracted from plant and animal sources, such as squid, octopus, mushrooms, cuttlefish, and the like. In some cases, it may be desirable to genetically modify or enhance the plant or animal melanin source to increase the melanin production. Melanins are also available commercially from suppliers. The following procedure describes an exemplary technique for the extraction of melanin from cuttlefish (Sepia Officinalis). 100 gm of crude melanin are dissected from the ink sac of 10 cuttlefish and washed with distilled water. The melanin is collected after each wash by centrifugation (200 x g for 30 minutes).
  • the melanin granules are then stirred in 800 ml of 8 M Urea for 24 hours to disassemble the melanosomes.
  • the melanin suspension is spun down at 22,000xg for 100 minutes and then washed with distilled water (5x400 ml).
  • the pellet is washed with 50% aqueous DMF (5x400 ml) until a constant UV baseline is achieved from the washes.
  • Synthetic melanins may be produced by enzymatic conversion of suitable starting materials, as described in more detail hereinbelow.
  • the melanins may be formed in situ within the porous particles or may be preformed with subsequent absorption into the porous particles.
  • Suitable melanin precursors include but are not limited to tyrosine, 3,4-dihydroxy phenylalanine (dopa), D-dopa, catechol, 5-hydroxyindole, tyramine, dopamine, m-aminophenol, oaminophenol, p-aminophenol, 4-aminocatechol, 2-hydroxyl-l,4-naphthaquinone (henna), 4- m ethyl catechol, 3,4- dihydroxybenzylamine, 3,4-dihydroxybenzoic acid, 1,2- dihydroxynaphthalene, gallic acid, resorcinol, 2-chloroaniline, p-chloroanisole, 2-amino-p-cresol, 4,5-dihydroxynaphthalene 2,7- disulfonic acid, o-cresol, m-cresol, p-cresol, and other related substances which are capable of being oxidized to tan, brown, or black
  • the melanin precursor is dissolved in an aqueous solution, typically at an elevated temperature to achieve complete solution.
  • a suitable amount of the enzyme tyrosinase (EC 1.14.18.1) is added to the solution, either before or after the melanin precursor.
  • the concentration of tyrosinase is not critical, typically being present in the range from about 50 to about 5000 U/ml.
  • the solution is buffered with an acetate, phosphate, or other suitable buffer, to a pH in the range from about 3 to 10, usually in the range from about 5 to 8, more usually being about 7.
  • Melanin like pigments can be obtained using suitable precursors even in the absence of an enzyme just by bubbling oxygen through a solution of a precursor for an adequate period of time.
  • Melanin material may be obtained by treatment of, e.g, cuttlefish ink or squid ink in a microwave, optionally with mixing.
  • the inventor has found that microwaving can be used for the preparation of melanin formulations.
  • the compositions and methods as disclosed herein may be produced and practiced using a variety of heating techniques, such as, for example, infrared heating, microwave heating, convection heating, laser heating, sonic heating, or optical heating.
  • heating techniques such as, for example, infrared heating, microwave heating, convection heating, laser heating, sonic heating, or optical heating.
  • it was found that drying melanin in a microwave oven made possible the preparation of large amount of melanin from cuttlefish ink in a very short period of time.
  • cuttlefish ink at was placed at 40°C in a conventional oven and required 18 days to reduce the material to 40% of its original weight. In a 900 watt microwave oven, the same degree of drying was achieved in 12 minutes.
  • the disclosure provides a method for production of melanin and melanin derivatives in a bioreactor, which is a device or system used to create and control an optimal environment for the growth and cultivation of biological organisms, such as cells, bacteria, or fungi, to carry out specific biochemical processes.
  • Bioreactors provide the necessary conditions for the organisms to thrive, including temperature, pH, nutrient supply, oxygenation, and agitation.
  • Bioreactors provide conditions such as temperature, pH, oxygen supply, and nutrient availability to support their growth and metabolism.
  • the bioreactor design can vary depending on the specific requirements of the organisms and the desired output.
  • cells, bacteria, or fungi are engineered or selected based on their ability to efficiently produce the desired melanin or melanin derivate substances.
  • the disclosure provides a method for formulation of melanin by applying a hydraulic press to melanin partially dried in a microwave oven.
  • hydraulic presses for this use may range in capacity from, for example, about 1 ton/sq. in. to about 500 tons/ sq.in. approximately.
  • the disclosure provides a method wherein the hydraulic press applies compression of approximately 500 tons/sq. in.
  • commercial cuttlefish ink was dried in a 900 watt microwave oven so that the product was 30% or 35% of the initial weight.
  • a blender was used to mix and grind the melanin.
  • a variety of formulations were made. In one formulation, the 30% preparation was mixed with 7% iron filings, and then the blender was used to mix again.
  • the disclosure provides for the use of formulations of melanin produced by, for example, microwaving and hydraulic press compression to reduce penetration of bullets and other projectiles.
  • the melanin produced by the methods of the disclosure proved effective in reducing the penetration of a bullet.
  • two slabs of melanin were produced by placing cuttlefish ink at 40°C in a conventional oven and dried for 18 days to reduce the material to 40% of its original weight.
  • cuttlefish ink was placed in a 900 watt microwave oven, and dried for 12 minutes to form two slabs. Each slab was approximately 3.5 in square. One slab was 1 inch thick and 1 slab was 0.5 in. thick. Both slabs were placed together in a wood frame to create a 1.5 inch thick sample of melanin.
  • Several blocks of ballistic clay, approximately 3.5 in. square were placed behind the melanin sample. A control was created separately where the melanin sample was replaced by a (dummy) ballistic clay block. 9 mm bullets were fired at approximately 1200 fit/sec.
  • the bullet penetrated the melanin and then went a depth of approximately 6 cm into the clay.
  • the bullet penetrated the initial (dummy) clay block, and then penetrated 12 cm into the clay. This demonstrated that the melanin formulation showed effectiveness in reducing the bullet's penetration compared to the clay control.
  • the disclosure provides for the use of elemental metals mixed with melanin to create new formulations of melanin with novel properties.
  • the metals may be, for example, iron, copper, zinc, magnesium, manganese, bismuth, calcium, enamel, cesium, radium, strontium, thorium, uranium, or combinations thereof.
  • elemental iron was mixed with melanin in the form of dried cuttlefish ink resulted in unexpected hardness of the material while it remains somewhat flexible. Under scanning electron microscopy it was demonstrated that the new formulation of melanin had organized into stacks of lamellae, which appeared to be composed of melanosomes.
  • cuttlefish ink was dried using a microwave oven to 40% of its original weight. Iron filings were added so that they comprised 0.5% of the final formulation. The material felt harder than a similar sample without the 0.5% iron filings. Scanning electron microscopy revealed multiple areas where sharply defined lamellae with 90° comer angles were seen in stacks.
  • the disclosure provides a practical method for formulating melanin to be placed into pharmaceutical or dietary supplement capsules, and other containers.
  • a novel method was developed to enable formulation of melanin (e.g., from cephalopod ink) into capsules or other containers for pharmaceutical, dietary supplement, and other uses.
  • melanin e.g., from cephalopod ink
  • cuttlefish ink was dried using a microwave oven to 40% of its original weight.
  • Cab-O-Sil a pharmaceutical preparation of the excipient micronized silicon dioxide, was mixed to comprise 40% of the final mixture with the 40% dried cuttlefish ink. This mixture was placed in a hard size zero pharmaceutical capsule. After seven days the capsule became weak and flaccid and would be unsuitable for use.
  • the mixture of silicon dioxide and cuttlefish ink was dried for several days in a conventional oven at 40°C, then placed in the capsule and observed, the capsule remained intact and is suitable for human and animal use.
  • melanins are incorporated into other materials and used for many useful applications, such as:
  • Melanin and melanin-like compounds can be incorporated into: polymers, metals, salts, ceramics of many types, clothing, construction materials, existing armor materials including Kevlar and ceramics, other natural materials or their synthetic mimics, materials for implantation into human or mammalian living beings.
  • melanin confers new or improved properties on resultant material: Another aspect of the present disclosure is that small amounts of melanin and of melanin like substances will impart to a mixture of melanin with other substances, such as a matrix or polymer, properties which are unexpected. Generally, 1 to 5% of melanin will impart desired properties to a mixture or composite, whereas small incremental improvement in properties will be gained by increasing up to 35%.
  • melanin may be present at about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, at a range of about 1% to about 10%, at a range of about 2% to about 8%, at a range of about 3% to about 7%, at a range of about 1% to about 4%, at a range of about 2% to about 5%.
  • Hydration effects and control It is another aspect of the present disclosure that the control and maintenance of hydration of melanin and melanin like substances (or non-water solvent or matrix concentration for melanins made from organic solvents) is critical for the applications described above, including armor and shielding. Published research describes the effect of hydration on electrical conductivity, and on the ability to absorb radiation from the electromagnetic spectrum.
  • the present disclosure includes the aspect that when melanin or melanin-like substances are extracted or synthesized, manufactured or fabricated, incorporated in any way with other substances, whether by mixtures, impregnation, layering, compositing, that control and maintenance of desired levels of hydration (and non-water solvent concentration for melanins made from organic solvents) may be critical to achieving and preserving the desired combination of properties.
  • melanin or melanin-like substances are extracted or synthesized, manufactured or fabricated, incorporated in any way with other substances, whether by mixtures, impregnation, layering, compositing, that control and maintenance of desired levels of hydration (and non-water solvent concentration for melanins made from organic solvents) may be critical to achieving and preserving the desired combination of properties.
  • melanin or melanin-like substances are extracted or synthesized, manufactured or fabricated, incorporated in any way with other substances, whether by mixtures, impregnation, layering, compositing, that control and maintenance
  • the present disclosure includes recognition that for the purposes set forth in this disclosure, such as armor and shielding, hydration and control of hydration may be critical for the properties desired in the final material, and the use of highly desiccated or lyophilized melanin may in many instances be undesirable. However, in certain aspects of the disclosure, desiccated or lyophilized melanin may be appropriate.
  • Oxygenation effects and control It is another aspect of the present disclosure that the control and maintenance of oxygenation, or of lack of access to oxygen, by incorporating melanin into materials that control this factor, or by restricting use to environments that control or restrict this factor, may be critical for certain characteristics to be achieved for shielding, armor, flame retardancy, heat resistance, and cold resistance.
  • compositions and methods of the disclosure may be produced or practiced using molding techniques such as transfer molding, resin film infusion, resin transfer molding, and structural reaction injection molding (SRIM).
  • SRIM structural reaction injection molding
  • the compositions and methods of the disclosure may be produced or practiced using molding techniques such as a vacuum assisted resin transfer molding process (VARTM).
  • VARTM vacuum assisted resin transfer molding process
  • Composites Process aids and modifiers are materials commonly used to facilitate polymer fabrication, to help compatibilize the mixture of polymers, ceramics, and other additives, and the like, to increase fire resistance, or to modify other properties, other than primary ballistic protection properties. Any of these materials that are desirable for fabricating or using the new lightweight transparent armor materials may be incorporated into the current disclosure, including but not limited to materials such as silicones, phthalates, bromides, and the like.
  • additives present in amounts not exceeding 10% by weight, if any, may also be included.
  • These materials may include, but are not limited to adhesion aides, colorants, fibers (carbon, polyaramid, polyethylene, etc.), fillers (talc, sand, microballoons) that further serve to modify the process-ability, stability, durability, or appearance of the objective transparent armor materials.
  • any suitable ceramic materials may be used in the composite composition in accordance with the current disclosure.
  • the ceramic powders or particles may be selected from the group consisting of alumina, boron carbide, boron nitride, mullite, silica, silicon carbide, silicon nitride, magnesium boride, multi-walled carbon nanotubes, single walled carbon nanotubes, group IVB, VB and VIB metal sulfide nanotubes, titanium boride, titanium carbide, and diamond.
  • the current disclosure is also directed to methods of preparing transparent armor materials.
  • the transparent armor material is formed by a simple process of mixing the starting materials without melt processing prior to the final molding step. This simplifies the processing, as it is not necessary to undertake the possibly complicated step of melt processing with its accompanying difficulties in dispersion and equipment wear.
  • any suitable standard machinery such as single and twin-screw extruders (both co- and counter-rotating), Henschel mixers, cokneaders, etc.
  • An additional technique that can be used is solvent mixing in which the ceramic and the polymer are mixed while the polymer is dissolved in the appropriate solvent. In such an embodiment any suitable solvent may be utilized.
  • Transparent armor materials of the present disclosure may be fabricated into any suitable article, including but not limited to sheets, slabs, disks, or more complex shapes, of varying thicknesses and sizes.
  • the transparent armor materials of the present disclosure may be used together with other ballistic materials, including but not limited to woven ballistic fabrics (such as but not limited to polyaramid or polyethylene fabrics), metals, ceramics, and the like to form transparent armor articles, such as, for example, helmets, sheets or panels, or body armor.
  • body armor using the inventive material may be fabricated by first forming a woven fiber vest containing pockets then sewing flat or curved panels or tiles comprising the composite into the pockets.
  • the sheets or panels may also be incorporated into a number of blast or ballistic shields or armor, such as, for example, blast/ballistics shields or armor for vehicles, aircraft and watercraft like cars, trucks, vans, personnel carriers, limousines, trailers, helicopters, cargo planes, rail cars, boats and ships; armor or blast/transparent armor for small buildings, especially military command posts and mobile headquarters; armor or blast/transparent armor for cargo containers; armor or blast/transparent armor for equipment housing, such as, for example, computers, communications equipment; and generally mobile or stationary blast or transparent armor panels.
  • blast/ballistics shields or armor for vehicles, aircraft and watercraft like cars, trucks, vans, personnel carriers, limousines, trailers, helicopters, cargo planes, rail cars, boats and ships
  • armor or blast/transparent armor for small buildings, especially military command posts and mobile headquarters armor or blast/transparent armor for cargo containers
  • armor or blast/transparent armor for equipment housing such as, for example, computers, communications equipment
  • generally mobile or stationary blast or transparent armor panels such as, for
  • a structure in an embodiment, includes bonded alternating layers of at least a melanin material and at least one of a for example, fibrous sheet, a plastic sheet, a plastic plate, a ceramic sheet, a ceramic plate, and a multilayer ply, the multilayer ply comprising multiple fibrous sheets bonded together.
  • a structure in another embodiment, includes alternating layers of melanin material wherein said layers are bonded to each other. In another embodiment, a structure is provided. The structure includes alternating layers of melanin material wherein said layers are joined to each other by an array of oriented nanostructures.
  • a method for fabricating a melanin composite includes providing a first layer, the layer comprising at least a fibrous sheet or a multilayer laminate; applying a second layer to the first layer, the layer comprising an melanin material; applying a third layer to the second layer, the layer comprising another fibrous sheet or multilayer laminate; bonding or joining the first layer to the second layer; and bonding or joining the second layer to the third layer.
  • a method for fabricating a melanin composite includes providing a first layer, the layer comprising at least a fibrous sheet or a multilayer laminate; applying a second layer to the first layer, the layer comprising a liquid-phase gel precursor; applying a third layer to the second layer, the layer comprising another fibrous sheet or multilayer laminate; bonding or joining the first layer to the second layer; and bonding or joining the second layer to the third layer.
  • a method for fabricating a melanin composite includes providing two layers of melanin material, and bonding the two layers together.
  • a method for fabricating a melanin composite is provided. The method includes providing a liquid-phase; forming a gel from the liquid-phase precursor; and optionally forming a second gel in contact with the first gel.
  • a composition in an embodiment, includes melanin and nonmelanin material and embedding the melanin material within the non-melanin material.
  • the non-melanin material and the melanin material are present in a ratio selected from the group consisting of about 1 to about 15, about 15 to about 1, about 1 to about 10, about 10 to about 1, about 1 to about 5, about 5 to about 1, about 2 to about 98, about 5 to about 95, about 20 to about 80, about 30 to about 70, about 40 to about 60, about 50 to about 50, about 60 to about 40 about 70 to about 30 about 80 to about 20, about 95 to about 5, about 98 to about 2 (percent by weight).
  • melanin is rather unique among armor-like materials in the following respect.
  • Melanin has multiple functional groups (e.g. potential chemical binding locations) which can bind metals (Hong, L. and Simon, J.D., 2004, Photochem. Photobiol., 80:477-481).
  • Many melanins have been demonstrated to possess at least four functional groups with regard to binding of metals: carboxyl, hydroxyl, phenolic, and amine.
  • Metals can be linked, either covalently or non-covalently, absorbed, adsorbed, or chelated to specific functional groups with multiple beneficial effects including: strengthening the bonds between the atoms in the melanin polymer, adding properties of each individual metal dopant, such as density, weight, resistance to penetration or abrasion or radiation, etc. Additionally, some metals can bind to more than one functional group, and conditions such as pH and temperature can determine the preference of a metal for one or the other functional group.
  • a second metal can be applied, in some instances, without dislodging the first metal (Hong, L. and Simon, J.D., 2007, J. Phys. Chem. B il l :7938-7947).
  • more than one metal can simultaneously be used to dope melanin to enhance its impact-resistance and other protective properties.
  • the metals bismuth and/or zinc can be linked to, for example, melanin’s carboxyl group, and then copper could be linked to, for example, melanin’s hydroxyl group.
  • some of the sites of one specific functional group can be loaded with one metal, while other unoccupied sites of the same functional group can then be loaded with a another metal.
  • biological polymer it is understood collagen and its derivatives, hyaluronic acid, its salts and its derivatives, alginates, synthetic polymers, elastin and biological polymers, and mixtures thereof.
  • the biological polymer may comprises compounds chosen from collagen, collagen of porcine origin, collagen of bovine origin, crosslinked collagens, hyaluronic acid, its salts and its derivatives, lactic acid polymers, methacrylate derivatives, calcium phosphate derivatives, polyacrylamides, polyurethanes, polyalkylimide gels, polyvinyl microspheres, silicones, silica (SiO2) polymers, and mixtures thereof.
  • Collagen is a fibrous protein, of approximately 300 kDa, which makes up the connective tissue in the animal kingdom. It may be of human or nonhuman origin, in particular of porcine or bovine origin. Collagen derivatives include, inter alia, crosslinked collagens.
  • the composites of the disclosure may be formed from a wide variety of polymers, including natural polymers such as carboxylmethylcellulose, cellulose acetate phthalate, ethylcellulose, methylcellulose, arabinogalactan, nitrocellulose, propylhydroxycellulose, and succinylated gelatin; and synthetic polymers such as polyvinyl alcohol, polyethylene, polypropylene, polystyrene, polyacrylamide, polyether, polyester, polyamide, polyurea, epoxy, ethylene vinyl acetate copolymer, polyvinylidene chloride, polyvinyl chloride, polyacrylate, polyacrylonitrile, chlorinated polyethylene, acetal copolymer, polyurethane, polyvinyl pyrrolidone, poly(p-xylene), polymethylmethacrylate, polyvinyl acetate, polyhydroxyethyl methacrylate, and combinations thereof.
  • natural polymers such as carboxylmethylcellulose, cellulose acetate phthalate, ethylcellulose
  • melanin and composite materials incorporating melanin can be used for shielding from biological, chemical, radiological and nuclear weapons.
  • melanin and composites materials incorporating melanin can be used for shielding from impact due to bullets or other projectiles or explosives, including shaped charges.
  • the current disclosure is directed to a transparent armor material composition comprising one or more type of, e.g., ceramic powders or particles mixed with one or more type of melanin materials.
  • other polymeric materials may be further selected from the group consisting of rigid- rod polymers, semi-rigid-rod polymers, polyimides, polyetherimides, polyimideamides, polysulfones, epoxy resins, bismaleimide resins, bis-benzocyclobutene resins, phthalonitrile resins, polyaryletherketones, polyetherketones, liquid crystal polymers, oligomeric cyclic polyester precursors, polybenzbisoxazoles, polybenzbisthiazoles, polybenzbisimidazoles, acetylene endcapped thermosetting resins, PrimoSpire® polymers, polysulfones, polyaramides, poly-paraphenylene terephthalamide, polyamides, polycarbonates, polyethylenes, polyesters, polyphenols and polyurethanes.
  • the composition further comprises one or more types of process aids, modifiers, colorants, fibers, adhesion promoters and fillers.
  • ceramic powders or particles are selected from the group consisting of alumina, boron carbide, boron nitride, mullite, silica, silicon carbide, silicon nitride, magnesium boride, multi-walled carbon nanotubes, single walled carbon nanotubes, group IVB, VB and VIB metal sulfide nanotubes, titanium boride, titanium carbide, and diamond.
  • ceramic powders or particles provide 10% to 98% of the total mass, in a preferred embodiment the ceramic powders or particles provide 20% to 95% of the total mass, and in a most preferred embodiment the ceramic powders or particles provide at least 50% of the total mass.
  • ceramic powders or particles have particle size in the range of 10 nanometers to 100 microns; and in a preferred embodiment the ceramic powders or particles have particle size in the range of 100 nanometers to 10 microns.
  • the melanin material or materials provide 2% to 95% of the total mass, and in a preferred embodiment the melanin material or materials provide less than 50% of the total mass.
  • the transparent armor materials are used together with other ballistic materials, including, but not limited to woven ballistic fabrics (such as but not limited to polyaramid or polyethylene fabrics), metals, ceramics, and the like.
  • the transparent armor materials are incorporated into an article selected from the group consisting of: a transparent armor article, a helmet, a sheet or panel, such as a vehicle or blast protection panel, body armor, and cargo containers.
  • melanin and composite materials including melanin can be used for shielding from lasers.
  • melanin The ability of melanin to resist degradation by chemicals of all types, including strong acids (such as hydrochloric acid) and bases (such as sodium hydroxide), was reviewed by (Prota, 1992).
  • strong acids such as hydrochloric acid
  • bases such as sodium hydroxide
  • the present disclosure includes the discovery that melanin can be used alone, or in composites with other materials such as metals and polymers, to resist destruction by chemicals including strong acids and strong bases, for shielding, armor, and aerospace applications such as airplane and space vehicle construction parts.
  • melanin absorbs beta particles, gamma rays, X-rays, infrared, visible, ultraviolet, and the remainder of the electromagnetic spectrum.
  • the present disclosure includes the discovery that melanin can be used alone, or in composites with other materials such as lead and polymers, to absorb and prevent destruction by radiation, e.g. for shielding, armor, and aerospace applications such as airplane and space vehicle construction parts.
  • the disclosed manufacturing method of doping melanin and/or melanosomes with multiple metals will also enable melanin to be enhanced with regard to its protective capabilities against radiation, both ionizing and electromagnetic.
  • bismuth or lead can be linked to the carboxyl groups of melanin.
  • the linking of bismuth or lead linked to the carboxyl groups of melanin will absorb many types of ionizing radiation such as a gamma rays, and/or magnesium, copper, or iron can be linked to the hydroxyl groups of melanin to absorb, for example, a different range of ionizing and/or electromagnetic radiation.
  • the melanin composite lends itself to materials that have both offensive as well as defensive properties. It should be noted that radioactive substances are classified as metals, e.g., in the periodic table. The ability of melanin to bind to radioactive substances, as it does with other metals, is well documented. (Taylor, G.N. and Mays, C.W. 1964, Radiation Research 21 : 285- 298; Bruenger, F.W. et al., 1967, Radiation Research 32: 1-12.)
  • the present disclosure includes the discovery that melanin can be used alone, or in composites with other materials for: a. shielding of radiation from sources like uranium and radium, b. to degrade, encapsulate and shield from living and non-living radioactive particles in sizes from nanometers to millimeters, c. to shield personnel and equipment from radiation from depleted uranium used in weaponry or armor.
  • melanin can be used alone, or in composites with other materials not only by covering a human or other organism by melanin and melanin-like compounds, alone or in mixture with other materials: It can be accomplished by ingestion, injection, or other internal administration of these compounds or composites. Furthermore, the melanin or melanin-like compounds, can be used to mitigate the destructive biological effects of radiation, even if the radiation has been absorbed. For instance, radiation creates free radicals in biological tissues which creates great damage in the hematopoietic and gastrointestinal systems. Melanin and melanin-like compounds are known to absorb such free radicals and mitigate such damage.
  • melanin can be used alone, or in composites with other materials to form a physical barrier against microorganisms and infectious agents of all types including: bacteria, fungi, parasites, viruses.
  • the present disclosure includes the discovery that melanin can be used alone, or in composites with other materials to form shielding from adherent substances for applications where Teflon and similar materials are currently used. Protection from Sensors
  • the present disclosure includes the discovery that melanin can be used alone, or in composites with other materials to form shielding from electromagnetic, sound, ultrasound, and radar sensors.
  • melanin has been reported to be hard (Majerus, 1998) and to resist abrasion (Majerus, 1998; Moses et al., 2006)
  • the present disclosure includes the discovery that melanin can be used alone, or in composites with other materials to form body armor, vehicle armor, and other applications, including aerospace use, where desirable characteristics include hardness, resistance to abrasion, resistance to indentation, resistance to cutting, flexibility, shock absorption, and sound and ultrasound absorption.
  • melanin can be used alone, or in composites with other materials, in harsh environments such as the vacuum and extreme cold of space where the following listed properties are desirable or necessary:
  • An example of a metal composite with both offensive and defensive properties enhanced by multiple metal bindings would be the following.
  • An outer melanin layer facing the environment, that is impregnated with radioactive substances, would be joined to an inner layer, impregnated with radiation absorbing or reflecting metals, which protects the person or tank wearing the composite from the radiation. This would have several applications, as described below.
  • the composite suit would sterilize a zone around the wearer or tank in a short period of time. This would enhance the safety of the suit or tank against the epidemic dangerous organisms, for example when a researcher or rescuer needs to enter a contaminated zone.
  • such a composite could be used to avoid the possibility of contamination from organisms that might exist in space, such as tardigrades, or alien life forms, should they exist.
  • Transparent polymers which may be utilized in the methods and compositions as disclosed herein may be, for example:
  • PMMA Polymethyl methacrylate
  • Acrylic Acrylic
  • PMMA is a widely used transparent polymer known by trade names such as Plexiglas, Lucite, or Acrylite. It has excellent transparency, high impact resistance, and weatherability. It is often used as a substitute for glass in applications such as windows, lenses, signage, and displays.
  • PC Polycarbonate
  • Polycarbonate is a transparent thermoplastic polymer known for its high impact strength and heat resistance. It is commonly used in applications where both transparency and toughness are required, such as safety goggles, bulletproof windows, and automotive parts.
  • PET Polyethylene terephthalate
  • PVA Polyvinyl Alcohol
  • PVA is a synthetic polymer that is water-soluble and has a variety of industrial and commercial applications. It is derived from the polymerization of vinyl acetate followed by the hydrolysis of the acetate groups. The resulting material is a white or creamy white solid that is odorless and non-toxic.
  • PVA possesses several unique properties, including high tensile strength, flexibility, and film-forming ability. It has excellent adhesion to various surfaces, making it widely used as an adhesive in a range of industries. PVA films are also transparent, making them suitable for applications where visibility is required.
  • PVC Polyvinyl chloride
  • PS Polystyrene
  • PE Polyethylene
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • Polypropylene can be formulated to have transparency. Transparent polypropylene is used in applications such as packaging, stationery products, and medical devices.
  • PEN Polyethylene naphthalate
  • PET Polyethylene Terephthalate
  • Amorphous Copolyester forms when modifications are made to polyesters, which are combinations of diacids and diols.
  • Amorphous copolyesters such as PETG offer versatility to meet a wide range of applications.
  • Amorphous copolyester combines excellent clarity and toughness with outstanding heat and chemical resistance.
  • Cyclic Olefin Copolymer is an amorphous, transparent thermoplastic produced by chain copolymerization of cyclic monomers with ethane.
  • Transparent polymers which may be utilized in the methods and compositions as disclosed herein may be, for example: polyethylene, polypropylene, polystyrene, poly-propylene copolymers, polyethylene terephthalate (PET), PET copolymers, Polyvinyl Alcohol (PVA), polyacrylates, polyacrylate copolymers, cyclic olefin copolymers (COC), polyamides, polyamide co-polymers, polybutylene terephthalate (PBT), polycarbonates (PC), polyetherimides (PEI) and polyethersulfones (PES) with melting or softening point temperatures between 100 and 350° C, or said heat fusible coating layer polymer is selected from the group consisting of ethylene vinyl acetates (EVA), polymeric ionomers, polyethylenes, polyethylene copolymerized with olefins, amorphous polyesters, ethylene-acrylic acid (EAA) copolymers, ethylene-methacrylic
  • Transparent polymers which may be utilized in the methods and compositions as disclosed herein may be, for example:
  • the core polymer film layers and heat fusible coating layer films may be non-oriented, unidirectionally or biaxially oriented.
  • any polymer capable of forming a unidirectionally or biaxially oriented film can be used.
  • Polymers suitable for use as core polymer film layers include polyethylene, polypropylene and its copolymers, polyethylene terephthalate (PET) and its copolymers, polyacrylates, polystyrene, including polymethylmethacrylate (PMMA), and their copolymers, cyclic olefin copolymers (COC), polyamides and their copolymers, polybutylene terephthalate (PBT), polycarbonates (PC), polyether-imides (PEI), polyethersulfones (PES), all of which having melting or softening point temperatures between 100 and 350° C.
  • Preferred heat fusible coating layer polymers include ethylene vinyl acetates (EVA), ethylene acrylic acid (EAA) copolymers, ethylene-methacrylic acid (EMA) copolymers, polymeric ionomers, polyethylenes, including low density polyethylene (LDPE), very low density polyethylenes (VLDPE), ultra low density polyethylenes (ULDPE) and polyethylene copolymerized with olefins such as butane, hexane or octene, polypropylene copolymers, including copolymers with olefin monomers, polyethylene terephthalate (PET) copolymers, amorphous polyesters, polyurethanes, copolyesters, polyvinyl butyral (PVB), polyacrylates, including thermal and UV curable acrylic resins, , all of which having melting or softening point temperatures between 65 and 265° C.
  • EVA ethylene vinyl acetates
  • EAA ethylene acrylic acid
  • EMA
  • any polymer capable of being directionally oriented is suitable for use in the present disclosure.
  • suitable core layer polymers include polyethylene, such as Hostalen® GD9555 from Basell Polyolefins, polypropylene, such as Moplen® from Basell Polyolefins, polypropylene copolymers, such as Moplen® HP520 from Basell Polyolefins, polyethylene terephthalates (PET) and its copolymers, such as Invista® 3301 from Invista, polyacrylates and their copolymers, including polymethylmethacrylates (PMMA), such as EG920 PMMA from LG Chemical, cyclic olefin copolymers (COC), such as Topas® 6013F-04 from Topas Advanced Polymers, polycarbonates (PC) and their copolymers, such as Makrolon® 1239 from Bayer Material Science, poly etherimides (PEI), such as Ultem® 8015 from SABIC Innovative Plastics, polyethersulfones (PE
  • the core polymer film layers and heat fusible coating layer films may be non-oriented, unidirectionally or biaxially oriented. Essentially any polymer capable of forming a unidirectionally or biaxially oriented film can be used.
  • Polymers suitable for use as core polymer film layers include polyethylene, polypropylene and its copolymers, polyethylene terephthalate (PET) and its copolymers, polyacrylates, polystyrene, including polymethyl-methacrylate (PMMA), and their copolymers, cyclic olefin copolymers (COC), polyamides and their copolymers, polybutylene terephthalate (PBT), polycarbonates (PC), polyether-imides (PEI), polyethersulfones (PES), all of which having melting or softening point temperatures between 100 and 350° C.
  • a spall layer which entraps and/or catches shattering material, may be polycarbonate, polymethyl-methacrylate, or preferably a laminate of polycarbonate and polymethyl-methacrylate bound together via a polymer interlayer.
  • a spall layer is preferably from about 10-20 mm thick.
  • Polymethyl methacrylate (PMMA), or poly (methyl 2-methylpropenoate) is the polymer of methyl methacrylate.
  • the thermoplastic and transparent plastic is sold by the trade names PLEXIGLASS®, PLEXIGLAS-G®, R-CAST®, PERSPEX®, PLAZCRYL®, LIMACRYL®, ACRYLEX®, ACRYLITE®, ACRYLPLAST®, ALTUGLAS®, POLYCAST® and LUCITE®. It is often also commonly called acrylic glass or simply acrylic.
  • Polycarbonate is lightweight and highly fracture resistant particularly when compared to silica glass. This polymer also is highly transparent to visible light and is sold by the trade names LEXAN® from General Electric, CALIBRE® from Dow Chemicals, MAKROLON® from Bayer and PANLITE® from Teijin Chemical Limited.
  • the spall layer is a laminate of polycarbonate and polymethyl-methaciylate bound together via a polymer interlayer. The polycarbonate layer provides a stretchable support to the PMMA layer, which undergoes stiffening/hardening at high strain rates.
  • the laminates are formed from core polymer film layers consisting of the same polymer.
  • hybrid laminates are provided in which core polymer film layers of two or more different polymers are employed.
  • One hybrid laminate according to this aspect of the present disclosure consists of core polymer film layers in which layers of different core polymers alternate within the laminate, so that no two adjacent core polymer film layers consist of the same polymer.
  • Another hybrid laminate according to this aspect of the present disclosure consists of a plurality of sub-laminates, wherein each sub-laminate consists of a plurality of core polymer film layers of the same polymer and sub-laminates of different polymers alternate within the laminate, so that no two adjacent sub-laminates con-sist of the same polymer.
  • adjacent core polymer film layers of the same or different polymer are bonded together by heat fusible coating layers.
  • Laminates according to one embodiment of the present disclosure consist of plural layers of the same core polymer.
  • hybrid film laminates are provided in which core polymer film layers of two or more different polymers are employed.
  • One hybrid film laminate according to this embodiment of the present disclosure consists of core polymer film layers in which core layers of different polymers alternate within the laminate (alternate film stacking), so that no two adjacent polymer film core layers consist of the same polymer.
  • Polymer precursor coating processes include applying a UV or thermally curable acrylic coating onto a core film. After a plurality of surface coated films are consolidated under heat and pressure to form the bonded laminate, the laminate is subsequently exposed to heat or UV radiation to form a cross-linked polymer network between two adjacent heat fusible layers to create a much stronger bond.
  • the UV cured coating layer can be very hard and highly scratch resistance. Such surfaces are preferably applied to the outermost core polymer layer of a film laminate to improve the scratch and abrasion resistance for transparent applications, such as eye wear or face shields, thereby extending service life.
  • Preferred polymer precursor coating processes apply a UV curable fusible acrylic or polyurethane resin onto oriented core film layers.
  • a -cross-linked polymer network between two adjacent heat fusible layers is formed upon exposure of the bonded laminate to UV radiation.
  • Binders are useful in fabricating materials from non or loosely assembled matter. For example, binders enable two or more surfaces to become united.
  • nonmelanin material may be included in the compositions and methods of the disclosure and may be a binder.
  • any adhesive material such as phenolic resins, ureaformaldehyde resins, melamine formaldehyde resins, hyde glue, aminoplast resins, epoxy resins, acrylate resins, latexes, polyester resins, urethane resins, and mixtures thereof may be used as a binder.
  • Suitable binders include glue, varnish, epoxy resins, phenolic resins, polyurethane resins.
  • the binder may be, for example, glue, which may be selected from the group consisting of Clear Weld, LOCTITE® Heavy Duty Epoxy, LOCTITE® Epoxy Metal/Concrete, LOCTITE INSTANT-MIX®, LOCTITE®, LOCTITE® BULLDOG, LOCTITE® PL Marine Adhesive Sealant, E6000®, (E6000 STITCHLESS®, E6000 EXTREME TACK®, E6000 FABRI-FUSE®, PRO-POXY® 20, TITEBOND III®, TITEBOND III ULTIMATE WOOD GLUE®, FIBER FIX SUPER TAPE, ELMER’S SCHOOL GLUE NATURALS®, ELMER'S GLUE-ALL®, Elmer's Multi Purpose All Glue, KRAZY GLUE®, LIQUID NAILS®, PRODUTY ® HEAVY DUTY CONSTRUCTION ADHESIVE, Firmo Li
  • Thermally curable resins suitable for use in accordance with the compositions and methods of the disclosure are preferably selected from the group consisting of phenolic resins, urea formaldehyde resins, melamine-formaldehyde resins, epoxy resins, acrylate resins, urethane resins, melamine resins, alkyd resins, and polyimide resins, isocyanate, isocyanurate, and combinations thereof.
  • Multifunctional acrylates are preferably selected from trimethylolpropane triacrylate, glycerol triacylate, pentaerythritol triacrylate and methacrylate, pentaerythritol tetraacrylate and methacrylate, dipentaerythritol pentaacrylate, sorbitol triacrylate, and sorbital hexaacrylate.
  • Thermoplastic binders comprise a variety of polymerized materials such as polyvinyl acetate, polyvinyl butyral, polyvinyl alcohol, and other polyvinyl resins; polystyrene resins; acrylic and methacrylic acid ester resins; cyanoacrylates; and various other synthetic resins such as polyisobutylene polyamides, courmarone-idene products, and silicones.
  • Suitable functionalized acrylics, alkyds, polyurethanes, polyesters, and epoxies can be obtained from a number of commercial sources.
  • Useful acrylics are sold under the ACRYLOIDTM trade name (Rohm & Haas, Co., Pennsylvania); useful epoxy resins are sold under the EPONTM trade name (Resolution Specialty Materials, LLC, Illinois); useful polyester resins are sold under the CYPLEX® trade name (Cytec Industries, New Jersey); and useful vinyl resins are sold under the UCARTM trade name (The Dow Chemical Company, Michigan).
  • Illustrative of useful high modulus or rigid binder materials are polycarbonates; polyphenylenesulfides; polyphenylene oxides; polyester carbonates; polyesterimides; polyimides; and thermoset resins such as epoxy resins, phenolic resins, modified phenolic resins, allylic resins, alkyd resins, unsaturated polyesters, aromatic vinylesters as for example the condensation produced of bisphenol A and methacrylic acid diluted in a vinyl aromatic monomer (e.g. styrene or vinyl toluene), urethane resins and amino (melamine and urea) resins.
  • the major criterion is that such material holds the composition together and maintains the geometrical integrity of the composite under the desired use conditions.
  • the binder can be included in the composition in any suitable amount.
  • the binder can be included in an amount from about 5 wt. % to about 100 wt. % by weight (on a solids basis) of the wet composition, such as from about 20 wt. % to about 80 wt. %, from about 30 wt. % to about 70 wt. %, from about 40 wt. % to about 60 wt. %, etc.
  • compositions and methods as disclosed herein include law enforcement vehicle windows, ballistic shields, including as replacements for the ballistic shields currently employed in banks and other commercial enterprises, and executive protection armor configurations, protective eyewear, a face shield, a window or a vision block for a combat vehicle or an armored vehicle, a ballistic shield window, an aircraft transparency, a sensor window, an infrared dome for a missile, a laser ignition windows for medium and large caliber cannons, a law enforcement vehicle window or armor for executive protection, helmets, visors, safety goggles, body armor, ballistic shields, windows, vehicle windows, portholes, vehicle armor, aircraft armor, watercraft armor, structure armor, equipment housing, blast protection panels, transparent armor panels, phone screens, computer screens, and cargo containers.
  • the lightweight melanin composite transparent materials of the present disclosure can be further laminated with other polymeric and/or non-polymeric sheets or plates to further enhance impact resistance for opaque armor applications, such as vehicle or aircraft armor, or ballistic shield applications, such as ballistic panels for portable shelters.
  • Polymeric sheet materials include polymethyl-methacrylate (PMMA), polycarbonates (PC), polyetherimides (PEI), polyethersulfones (PES), thermoplastic or thermosetting polymeric composites (such as glass or carbon fiber reinforced epoxy composites), and the like.
  • Nonpolymeric sheet materials include glass (both annealed and heat treated), ceramics and metal (such as high strength steel or aluminum).
  • the lightweight melanin composite transparent materials in this disclosure have much higher mechanical properties than those of monolithic sheets of the same core polymer made by conventional techniques (such as extrusion or injection molding), and thus can also be used, with or without further forming, in structural or semi-structural applications, such as impact-resistant panels or other articles in the construction and automotive industries.
  • the present disclosure thus includes impact-resistant automotive parts formed from the opaque and transparent laminates of the present disclosure, as well as impact-resistant industrial, structural, semi-structural or decorative panels or other articles formed from the opaque of transparent laminates of the present disclosure.
  • Example 1 Melanin and metal-melanin polymer composites to resist projectiles (including bullets and shrapnel)
  • Natural cephalopod melanin e.g., from cuttlefish, squid, or octopus
  • distilled water 5-7 times at 14,000g in an ultracentrifuge and then dehydrated to a powder.
  • Bismuth-melanin is prepared as per Baranowitz (See WO 2022/15556).
  • Purified melanin or bismuth melanin is mixed into PMMA at the 3% level by melt compounding in a twin-screw DSM microcompounder at 100 rpm for 10 minutes, at 220°C, with a dry nitrogen purge.
  • Example 2 Enhancement of resistance to chemical weapons and bioweapons a. Resistance to Acids and Alkalis
  • Melanin or bismuth-melanin is prepared and incorporated into PMMA as in Example 1. It is formulated as a 4 inch x 4 inch tile with the bismuth-melanin-PMMA internally and purified melanin as an external coat for a tank armor plate. Boiling hydrochloric acid is poured on the tile and it has no effect and the tile displays no degradation. b. Resistance to diverse chemical attacks including toxic gas
  • Melanin or Bismuth melanin is prepared and incorporated into PMMA as in Example 1. It is formulated as a 6 inch x 4 inch tile with the bismuth-melanin-PC internally and purified melanin as an external coat for a tank armor plate. Under controlled conditions, the tile is exposed to mustard gas and measurements show the mustard gas is absorbed by the external melanin coat. c. Resistance to bioweapons
  • Melanin or Bismuth melanin is prepared and incorporated into PMMA as in Example 1. It is formulated as a 3 inch x 3 inch tile with the bismuth-melanin-PC internally and purified melanin as an external coat for a body armor plate. Methyl Paraban 0.01% and Propyl Paraban 0.005% are added to the external melanin coat by blending for 15 minutes, before it is applied, to enhance its anti-infective qualities. A culture medium solution containing HIV virus is poured on the plate. Viability tests show that the absorbed virus particles are non-infectious.
  • Example 3 Enhancement of resistance to heat.
  • Example 4 Enhancement of resistance to radiation.
  • a. Bismuth-melanin is prepared and incorporated into PMMA as in Example 1. A comparator sample of an equal weight of lead is incorporated into PMMA. Measurements show that the ability to absorb gamma-radiation of the bismuth-melanin-PMMA sample is substantially greater than that of the lead-PMMA sample.
  • b. Bismuth-melanin is prepared and incorporated into PC. A comparator sample of an equal weight of bismuth nitrate is incorporated into PC. Measurements show that the ability to absorb gamma-radiation of the bismuth-melanin-PC sample is substantially greater than that of the bismuth nitrate-PC sample.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne des matériaux comprenant un polymère et de la mélanine, qui sont transparents et également suffisamment résistants pour résister à une attaque par des projectiles, de la chaleur, un rayonnement et d'autres agents nocifs, et qui sont hautement souhaitables à la fois à des fins militaires et civiles.
PCT/US2024/036752 2023-07-06 2024-07-03 Matériaux de blindage transparents Pending WO2025010346A1 (fr)

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US202363525175P 2023-07-06 2023-07-06
US63/525,175 2023-07-06

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6103777A (en) * 1998-12-18 2000-08-15 Bayer Corporation Thermoplastic composition suitable for optical applications having low haze values
CN111574733A (zh) * 2020-05-29 2020-08-25 浙江大学 一种高透明性紫外屏蔽膜的制备方法
US20220072763A1 (en) * 2018-12-21 2022-03-10 The Johns Hopkins University Melanin based bio-composites for 3d printing
KR20220102075A (ko) * 2021-01-12 2022-07-19 아주대학교산학협력단 생분해성 기능성 고분자 및 이의 생합성 방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6103777A (en) * 1998-12-18 2000-08-15 Bayer Corporation Thermoplastic composition suitable for optical applications having low haze values
US20220072763A1 (en) * 2018-12-21 2022-03-10 The Johns Hopkins University Melanin based bio-composites for 3d printing
CN111574733A (zh) * 2020-05-29 2020-08-25 浙江大学 一种高透明性紫外屏蔽膜的制备方法
KR20220102075A (ko) * 2021-01-12 2022-07-19 아주대학교산학협력단 생분해성 기능성 고분자 및 이의 생합성 방법

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