Methods for producing biomineral compositions and uses thereof

Abstract

Biomineral particle and products thereof are presented, along with methods for manufacturing calcareous organisms into a particulate phase of various granulometry. In addition to calcium carbonate, other trace minerals as well as organic and inorganic compounds can be present in the calcareous organisms, making these organisms a valuable source for raw materials. Processing includes receiving, drying, comminuting and surface-modifying the calcareous organisms to produce biomineral particles with a variety of properties, compositions, and functions. The resulting biomineral particles can be utilized in part or in full as a raw material, in the manufacture of biomineral materials and product applications.

Description

[0001] METHODS FOR PRODUCING BIOMINERAL COMPOSITIONS AND USES THEREOF

[0002] Technical Field

[0003] [1] The present invention relates to biomineral particles, particularly to those derived from calcareous organisms, and methods for their processing and use.

[0004] Background

[0005] [2] Processing methods to produce materials from calcareous organisms have been researched with commercial applications in niche, low value markets such as dietary supplements or animal feed from eggshell, agricultural soil amendment from oyster, mussel or scallop, and crushed shell aggregate for landscaping.

[0006] [3] Processes can involve cleaning, mechanical grinding or crushing to reduce raw material into aggregate or particle, followed by thermal calcination to remove organic matter. The result has been a particle that is sanitized and recycled from otherwise waste material for use as agricultural product or dietary supplement, but are low value or undifferentiated, with narrow application scope, and not uses that provide enhanced functional properties or novel applications.

[0007] Summary

[0008] [4] In an aspect, the disclosure relates to a biomineral and process of manufacturing biominerals from the skeletal elements of calcareous organisms, such as the endo- and exo- skeletons of invertebrates, into a particulate phase of various granulometry. These compositions can be further processed with thermosetting polymers, thermoplastic polymers, cementitious binders, and biopolymers that are derived from natural, biological, synthetic, or hybrid origins. The biomineral compositions have a high content of calcium carbonate and other trace minerals making them suitable for the manufacture of many products including, for example, engineered stone composites, 3D printing filament, films, viscosity modifiers or toughening agents in polymer composite systems, as well as an efficient intermediates for natural pigment extraction. Processing can include harvesting, drying, treating of invertebrates and / or their skeletons followed by comminuting to impart a specified granulometry. The resulting biomineral compositions can be further treated with surface modifier compounds to enhance their processibility, binder compatibility, shelflife, physical, mechanical, optical, chemical, and thermal characteristics.

[0009] [5] Minerals derived from calcareous organisms such as marine organisms (mollusks, coccolithophores, echinoderms, foraminifera), eggshells, coral skeletons, and other organisms, are produced through a process of biomineralization that exhibit distinctivemorphological, crystallographic, and surface properties, with structures that often incorporate organic matrix proteins, polysaccharides, and other biomolecules, that differentiate them significantly from its geological counterparts. The effective utilization of biologically derived calcium carbonate requires sophisticated processing methods that can preserve the beneficial characteristics while adapting the material for specific application requirements. The complex hierarchical structures and organic component integration that provide functional advantages also present unique processing challenges, including the need for gentle purification and particle size reduction methods that maintain structural integrity, microstructure, and morphology, controlled thermal treatments that preserve desired organic compounds and crystalline phases, and surface modification techniques that can functionalize surfaces for range of applications.

[0010] [6] The utilization of bio-derived minerals represents a paradigm shift toward more sustainable and environmentally responsible material processing approaches.

[0011] Traditional mining and processing of geological deposits involve significant environmental impacts, including habitat destruction, energy-intensive extraction processes, and substantial carbon emissions from calcination operations. In contrast, biologically derived sources can often be obtained from renewable biological waste streams, such as waste mollusk shells from aquaculture operations, invasive or overpopulated species, eggshells from food processing, or marine organism debris from natural accumulation sites.

[0012] [7] The development of innovative processing methods that can efficiently convert diverse calcareous organisms into a wide range of functional, value-added, and application-tailored biominerals and compounds in a scalable manner represents a critical technological gap that limits the broader adoption of these sustainable alternatives. Owing to their physicochemical properties, biomineral particles can be incorporated into material systems for use in a range of applications, for example, with binders that are thermosetting polymers, thermoplastic polymers, gels and emulsions, biopolymers, or cementitious produced from natural, synthetic, or hybrid origins. When incorporated, they can function as fillers and / or additives for additive manufacturing, flexible films, composite materials and construction materials such as geopolymers, concrete, engineered stone; as abrasives in polishing and surface finishing; as catalysts, anti-oxidants, or catalyst supports in chemical processing; as pigments and opacifiers in ceramics and paper manufacturing; as rheology modifiers in cosmetics and skincare; as reinforcing agents in elastomers and polymers; as adsorbents for water purification and environmental remediation; and as additives andfunctional components in sensors, smart materials, pharmaceuticals, water purification, soil amendments, nutraceuticals, food, agriculture, packaging, biomedical and drug delivery devices.

[0013] [8] Due to the presence of organic matrix proteins, polysaccharides, and other biomolecules contained in calcareous organisms, the byproducts of the biomineral production process can yield other compounds of interest, or biominerals themselves can be used as efficient intermediates for biomolecule extraction. In an aspect, the disclosure relates to a biomineral and method of processing a set of calcareous organisms into a particulate phase of various granulometry, to produce a useful output product. The method can include receiving the set of calcareous organisms; drying the received calcareous organisms; comminuting the dried calcareous organisms to produce a biomineral particle (BMA); and modifying the surface thereof to produce the surface-treated biomineral particle. When BMA is used in an output product, BMA can provide functional benefits, that make them advantageous for certain applications, for example: enhance manufacturing processability such as flow characteristics, interfacial adhesion and matrix / binder compatibility, working time, pot life; rheological properties such as storage and loss modulus, viscosity, and tan 6, dispersion; extend service life and shelflife such as color stability, lightfastness, UV-resi stance, thermo-oxidative resistance, color brilliance, anti-microbial resistance, chemical resistance; impart new properties and functions such as fluorescence, refractive index, opacity, odor, pH sensing, oxygen sensing, UV sensing, hydrogen peroxide sensing; enhance performance of bulk properties such as impact resistance, fracture toughness, compressive modulus, compressive yield strength, hardness, temperature resistance, scratch resistance, and thermal conductivity.

[0014] Brief Description of the Drawings

[0015] [9] FIG. l is a flow diagram for a general procedure for manufacturing a surface-treated calcareous biomineral particle in accordance with an embodiment of the present invention.

[0016]

[0010] FIG. 2 is a flow diagram for a general procedure for manufacturing a calcareous biomineral particle in accordance with an embodiment of the present invention.

[0017]

[0011] FIG. 3 is a flow diagram illustrating processes for use in manufacturing of biomineral particles and surface-treated biomineral particles in accordance with embodiments of the present invention.

[0012] FIG. 4 is a flow diagram illustrating processes for use in manufacturing of biomineral particles and surface-treated biomineral particles into biomineral materials and product applications in accordance with an embodiment of the present invention.

[0018]

[0013] FIG. 5 is a plot of thermogravimetric analysis data in accordance with embodiments of the present invention, showing various types of BMA derived from purple sea urchin, compared with commercial calcium carbonate in accordance with an embodiment of the present invention.

[0019]

[0014] FIG. 6 is an image of compounds extracted from sea urchin providing purple, red, and orange pigments, a biomineral material application that is manufactured from a type of biomineral particle (BMA) using the methods described in accordance with an embodiment of the present invention.

[0020]

[0015] FIG. 7 is an image of films, a biomineral material application, manufactured from a type of biomineral particle (BMA) using the methods described in accordance with an embodiment of the present invention.

[0021]

[0016] FIG. 8 is an image of biocalcite engineered stone composites providing a diversity of colors including patterned, speckled, and terrazzo designs, a biomineral material application, manufactured from a type of biomineral particle (BMA) using the methods described in accordance with an embodiment of the present invention.

[0022]

[0017] FIG. 9 is an image of 3D printing filament, a biomineral material application, manufactured from a type of biomineral particle (BMA) using the methods described in accordance with an embodiment of the present invention.

[0023]

[0018] FIG. 10 are scanning electron micrographs of one type of BMA particle produced from the shell (or test) of purple sea urchin, highlighting the preservation of unique microstructural morphology using the methods described in accordance with an embodiment of the present invention.

[0024]

[0019] FIG. 11 are scanning electron micrographs of one type of BMA particle produced from the spine of purple sea urchin, highlighting the preservation of unique microstructural morphology using the methods described in accordance with an embodiment of the present invention.

[0025]

[0020] FIG. 12 is a plot of the particle size distribution of one type of BMA, produced using the methods described in accordance with an embodiment of the present invention.Detailed Description

[0026]

[0021] Before the various embodiments are described, it is to be understood that the teachings of this disclosure are not limited to the particular embodiments described, and as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present teachings will be limited only by the appended claims.

[0027]

[0022] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present teachings, some exemplary methods and materials are now described.

[0028]

[0023] As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which can be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present teachings. Any recited method can be carried out in the order of events recited or in any other order which is logically possible.

[0029]

[0024] As used in this specification and the appended claims, the singular forms “a”, “an” and “the” include plural referents unless the context clearly indicates otherwise. Thus, for example, reference to “an particle” includes more than one particle.

[0030]

[0025] The section headings used herein are for organizational purposes only and not to be construed as limiting the subject matter described.

[0031] Definitions

[0032]

[0026] As used in this description and the accompanying claims, the following terms shall have the meanings indicated, unless the context otherwise requires:

[0033]

[0027] A “set” includes at least one member.

[0034]

[0028] “ Calcareous organisms” refers to any organism, or taxonomic grouping that biologically synthesizes, secretes, or incorporates calcium carbonate (CaCCh) as a structural or functional component of its anatomy, through the endogenous biological process of biomineralization.

[0035]

[0029] A “biomineral particle” or “BMA” is a dried and comminuted form of calcareous organism that contains a combination of calcium carbonate and other organic and inorganic compounds that may vary depending on the source calcareous organism. BMA canalso be referred to as biomineral, biocalcite, mineral, biomineral mixture, mineral additive, biomineral additive, filler, biofiller, particle, or dust.

[0036]

[0030] A “surface-treated biomineral particle” is a biomineral particle that has been treated to modify its surface characteristics.

[0037]

[0031] “Biocalcite” is a biomineral particle that is entirely or partially composed of a calcite form of calcium carbonate that is biologically derived.

[0038]

[0032] A “matrix material” or “binder” is any material that encapsulates a biomineral particle or serves as a binder to create a singular material. The material can be a thermosetting polymer or resin or plastic, thermoplastic polymer or resin or plastic, gel, biopolymer, concrete, and cement produced from natural, biological, synthetic, or hybrid sources.

[0039]

[0033] A “biomineral material” is a material that has been generated as a result of mostly or partially utilizing biomineral particles whether surface-treated or un-treated, as a raw material in the manufacture of a product. It may be combined as an additive or filler with other materials such as binders that are thermosetting polymer or resin or plastic, thermoplastic polymer or resin or plastic, gel, biopolymer, concrete, and cement produced from natural, biological, synthetic, or hybrid sources.

[0040]

[0034] A “product application” is a product that uses BMA or biomineral materials that use BMA, to fulfill a particular function or set of functions in a use case. A product application can use BMA in isolation or in combination with other raw materials.

[0041]

[0035] A “moisture target” or “moisture content” is the amount of residual moisture present in a material, as expressed in percentage of a material’s mass.

[0042]

[0036] A “BMA composite mixture” is a material combination that comprises an unreacted thermoset matrix that encapsulates BMAs and is mixed such that the BMAs are uniformly distributed throughout the matrix.

[0043] Biomineral Particle (BMA)

[0044]

[0037] BMA is made from organisms that biologically synthesize, secrete or incorporate calcium carbonate as a structural or functional component of its anatomy. These calcareous organisms can include, for example, sea urchin, oyster, gastropod, mussel, clam, snail, scallop, whelk, coral, coccolithophores, diatom, shellfish, foraminifera, nautilus, echinoderm, starfish, abalone, cowrie, limpet, conch, periwinkle, barnacle, chiton, sand dollar, bivalve, cockle, paua, perlemoen, kina, pearl oyster, razor clam, pipi, giant clam, etc. A range of species can be used including, for example, purple sea urchin, red sea urchin,green sepaa urchin, ezo sea urchin, murasaki urchin, long-spined sea urchin, kina, Chilean red urchin, diadema sea urchin, sand dollar, Pacific oyster, eastern oyster, mangrove oyster, West African oyster, European flat oyster, Japanese pearl oyster, Chilean oyster, blood cockle, common cockle, Manila clam, hard clam, pismo clam, surf clam, razor clam, greenshell mussel, blue mussel, brown mussel, Mediterranean mussel, thick-shell mussel, Chilean mussel, bay scallop, Pacific scallop, Japanese scallop, Iceland scallop, king scallop, Chilean scallop, sea scallop, giant clam, pearl oyster, pipi, Venus clam, red abalone, Pacific abalone, Japanese abalone, paua, blacklip abalone, perlemoen, green abalone, pink abalone, channeled whelk, common whelk, ivory shell, sea snail, common periwinkle, giant periwinkle, common limpet, Chilean conch, conch, Strombus conch, Baja conch, acanthaster planci, achatina fulica, anadara broughtonii, archachatina marginata, arctica islandica, argopecten irradians, asterias amurensis, austrominius modestus, bativentosa angulata, bradybaena similaris, busycon carica, busycotypus canaliculatus, bythotrephes longimanus, callinectes sapidus, carcinus maenas, caulerpa taxifolia, chlamys nobilis, cipangopaludina chinensis, cipangopaludina japonica, corbicula fluminea, cornu aspersum, crassostrea gigas, crassostrea virginica, diadema antillarum, dreissena bugensis, dreissena polymorpha, echinus esculentus, ensis leei, eriocheir sinensis, euglandina rosea, faxonius rusticus, haliotis asinina, haliotis discus hannai, haliotis laevigata, haliotis midae, haliotis rubra, haliotis tuberculata, hedleyella falconeri, heliocidaris erythrogramma, helix lucorum, helix pomatia, hemicentrotus pulcherrimus, hemigrapsus sanguineus, homarus americanus, homarus gammarus, limnoperna fortunei, littorina littorea, lobatus gigas, mesocentrotus franciscanus, mesocentrotus nudus, metacar cinus magister, mizuhopecten yessoensis, mnemiopsis leidyi, mytilus edulis, mytilus galloprovincialis, orconectes rusticus, ostrea edulis, otala lactea, pacifastacus leniusculus, panopea generosa, panulirus argus, panulirus interruptus, paralithodes camtschaticus, perna canaliculus, perna viridis, pinctada albina, pinctada fucata, pinctada margaritifera, pinctada maxima, pinctada radiata, placopecten magellanicus, pomacea canaliculata, pomacea maculata, portunus pelagicus, portunus trituberculatus, potamopyrgus antipodarum, procambarus virginalis, rangia cuneata, rapana venosa, ruditapes decussatus, saccostrea glomerata, saxidomus gigantea, scylla serrata, spisula solidissima, strombus gigas, strongylocentrotus droebachiensis, strongylocentrotus franciscanus, strongylocentrotus purpuratus, tachypleus tridentatus, tegillarca granosa, triplofusus giganteus, tripneustes gratilla, venerupis philippinarum, viviparus georgianus, zachrysia provisoria.

[0038] The substances contained in the structures of calcareous organisms are used to make BMA, and can contain up to 90%, 95%, 98% or 99% calcium carbonate. Calcium carbonate can be in the crystalline polymorphic forms of calcite, aragonite, or vaterite, or in the form of amorphous calcium carbonate (ACC). Structures can also contain organic content of up to 30%, up to 20% non-CACO3 minerals, up to 20% proteins, up to 10% proteins, up to 5% proteins, up to 2% nitrogen, up to 0.5% phosphorus, up to 1% potassium, up to 3% chlorine, or up to 10% sodium wherein these supplemental elements constitute inorganic and organic contents contained in the calcareous organism and its biological calcium carbonate structure which imparts a unique morphology (Weber, Jon, et al. Journal of ultrastructure research 26.5-6 (1969): 355-366, which is incorporated by reference in its entirety for all purposes) that differs from mined or precipitated calcium carbonate. Geologically formed calcareous minerals exhibit relatively simple crystalline structures, while minerals in calcareous organisms demonstrate sophisticated hierarchical architectures which often incorporate organic matrix proteins, polysaccharides, and other biomolecules that can act as natural templates and modifiers, resulting in enhanced mechanical properties, controlled porosity, and tailored surface chemistries. The presence of residual organic components and the specific crystalline polymorphs (aragonite, vaterite, or calcite) commonly found in biological systems can be leveraged to achieve targeted functionalities. These characteristics can enable precise control over optical properties for pigmentary applications, improved dispersion stability in suspensions and gels, and enhanced interfacial adhesion in composite materials. Additionally, they can contain unique morphology with complex three-dimensional architectures that makes them advantageous for tailored particle-matrix interactions. For example, sea urchins are echinoderms that possess a round rigid endoskeleton known as a test, composed of calcium carbonate, with spines distributed over the surface of the test. The spines are cylindrical, mineralized structures composed of calcite, amorphous calcium carbonate (ACC)(e.g., Alberic, et al. Cryst. Growth Des. 18.4 (2018): 2189-2201, DOI: 10.102 l / acs.cgd.7b01622, which is incorporated by reference in its entirety for all purposes), water and intra-crystalline organic molecules (e.g., Alberic, et al. J. Struct. Biol. X 1 (2019): 100004, DOI: 10.1016 / j.yjsbx.2019.100004, which is incorporated by reference in its entirety for all purposes). The surface of sea urchin calcium carbonate is more hydrophilic than commercial sources and also has a longer range order than mined calcium carbonate (e.g., Towe, et al. Science 157.3792 (1967): 1048-1050, http: / / www.jstor.org / stable / 1722224, which is incorporated by reference in its entirety for all purposes).

[0039] The calcareous feedstock may contain spinochrome pigments, chitin, nacre or other organic compounds which provide performance enhancing benefits such as UV protection, color enhancement / stability, or mechanical property improvements (e.g., Grossert, J. S. Chemical Society Reviews 1.1 (1972): 1-25, which is incorporated by reference in its entirety for all purposes). The BMA can contain natural antioxidants and UV stabilizers (Fedorey ev, Sergey A., et al. Marine drugs 16.12 (2018): 509.) to facilitate the use of biomineral materials containing these additives in outdoor applications.

[0045]

[0040] The calcareous feedstock can be dried until the moisture content in the feedstock drops below 50%, 30%, 10%, 5%, and 1% depending on the application. Some applications, such as cementitious composites are more tolerant to moisture presence, or may even benefit from it, whereas thermoset or thermoplastic matrix composites typically require minimal moisture content to ensure optimal mechanical performance is achieved.

[0046]

[0041] The calcareous feedstock can be comminuted to impart specific granulometry. Different product applications will require BMA to have particular particle size, shape, chemistry, color, or particle size distribution to meet target function, performance, and properties. Thus, the comminuting process must consider the process route, and its tradeoffs including, for example, heat generation, throughput, particle size distribution, equipment contamination, feed size, wet vs. dry processing capabilities, particle shape and uniformity, and embodied energy, in order to maximize the desirable characteristics for the BMA produced. BMA described herein can have particle size distributions or particle mixtures with desired particle size distributions for specific biomineral materials and product applications. The particle size distributions can be tuned to be made suitable for applications to enable efficient particle packing, viscosity modification, and / or the bulk properties performance of biomineral materials and product applications. BMA can have particle size distributions particles have a size distribution wherein the D90 is between 0.001 pm to 0.1 pm, or 0.1 pm to 1 pm, or 0.001 pm to 2 mm, or 0.001 pm to 1 mm, or 0.01 pm to 1 mm, or 0.01 pm to 2 mm, or 100 pm to 50 mm, or between 0.001 pm to 2 inches, and / or wherein the D50 is between 0.001 pm to 0.1 pm, or 0.1 pm to 1 pm, or 0.001 pm to 2 mm, or 0.001 pm to 1 mm, or 0.01 pm to 1 mm, or 0.01 pm to 2 mm, or 100 pm to 50 mm, and / or wherein the D10 is between 0.001 pm to 0.1 pm, or 0.1 pm to 1 pm, or 0.001 pm to 2 mm, or 0.001 pm to 1 mm, or 0.01 pm to 1 mm, or 0.01 pm to 2 mm, or 100 pm to 50 mm. For example, by incorporating a range of particle sizes, the viscosity of the same composition of particles in suspension can be reduced (Parkinson, C., S. Matsumoto, and P. Sherman. Journal of colloidand interface science 33.1 (1970): 150-160, which is incorporated by reference in its entirety for all purposes). This enhances processibility by reducing viscosity and increases the maximum particle loading that can be processed. Particle size distribution can be controlled to allow high filler loading up to 95% in thermoset or thermoplastic polymer matrices (Sudduth, Richard D. Journal of applied polymer science 48.1 (1993): 37-55, which is incorporated by reference in its entirety for all purposes.). BMA loading can be from 0.01-5% or 5-10% or 20-30% or up to 40% in thermoplastic polymer matrices. In one embodiment, the particle size distribution (PSD) for type A BMA is 30 to 45 pm for D97, 10 to 20 pm for D50, 2 to 5 pm for D10. The PSD for type B BMA is 35 to 50pm for D97, 15 to 25 pm for D50, and 5 to 10 pm for D10. In another embodiment, the particle size distribution (PSD) for type A BMA is 30 to 45 pm for D97, 10 to 20 pm for D50, 2 to 5 pm for D10. The PSD for type B BMA is 35 to 50pm for D97, 15 to 25 pm for D50, and 5 to 10 pm for D10.

[0047]

[0042] Surface-treating of the BMA can be made for example, to promote flow characteristics, dispersion, color stability, brilliance, lightfastness, anti-microbial properties, and shelflife; as well as functional benefits, for example, enhance manufacturing processability such as flow characteristics, interfacial adhesion and matrix compatibility, working time, pot life; rheological properties such as storage and loss modulus, viscosity, and tan 6, dispersion; extend service life and shelflife such as color stability, lightfastness, UV-resistance, color brilliance, anti-microbial resistance, chemical resistance; impart new properties and functions such as fluorescence, refractive index, opacity, odor, pH sensing, oxygen sensing, UV sensing, hydrogen peroxide sensing; enhance performance of bulk properties such as impact resistance, fracture toughness, compressive strength, compressive yield strength, hardness, temperature resistance, scratch resistance. BMA can be treated to provide a surface-treated BMA by applying a compound or mixture of compounds by way of, for example, mechanofusion, hybridization, ball milling, high-energy milling, electrostatic dry powder coating, triboelectric coating, resin bonding, thermal fusion, fluidized bed coating, wurster process, pan coating, drum coating, solution coating, slurry coating, sol-gel coating, layer-by-layer assembly, coacervation, phase separation, polymer precipitation coating, spray drying with coating agents, hot-melt coating, extrusion coating, thermal plasma coating, chemical vapor deposition, atomic layer deposition, physical vapor deposition, protein coating, polysaccharide coating, enzymatic crosslinking, spray chilling, spray congealing, microencapsulation, nanoencapsulation, etc. Surface-treating can provide anti-microbial properties by using, for example, a 0.01 - 10 wt% solution of silver nitrate,chitosan hydrochloride, quaternary ammonium silane, zinc oxide nanoparticles, glycerol carbonate, triethylene glycol, beta cyclodextrin, copper sulfate pentahydrate, tannic acid, cetyltrimethylammonium bromide, chitosan oligosaccharide, polyhexamethylene biguanide, defensins, 11-37, povidone iodine, thymol, eugenol, cinnamaldehyde, probiotic surface sprays, silver nanoparticles, copper oxide, benzalkonium chloride, sodium hypochlorite, graphene oxide, titanium dioxide nanoparticles, chlorhexidine digluconate, titanium dioxide, glycerol carbonate, beta cyclodextrin, triethylene glycol, lignosulphonate, activated charcoal, metal oxides, zeolites, terpenes, titanium dioxide anatase, limonene, pinene, ethanol, silver sulfadiazine, copper nanoparticles, bismuth subgallate, zinc pyrithione, triclosan, chloroxylenol, benzethonium chloride, guanidine derivatives, gallium nitrate, nitric oxide donors, biguanides, phytic acid, polyhexamethylene guanidine, flavonoids such as quercetin, curcumin, graphene quantum dots, selenium nanoparticles, tea tree oil, cinnamon aldehyde, methylglyoxal, plant-derived alkaloids such as berberine, antimicrobial dendrimers, amphiphilic polymers with cationic groups, polymer-bound iodine, etc. Surface-treating can promote matrix or binder compatibility by using, for example, a 0.01 - 10 wt% solution of silane coupling agents, titanium dioxide, glycerol carbonate, beta cyclodextrin, triethylene glycol, lignosulphonate, activated charcoal, metal oxides, zeolites, terpenes, titanium dioxide anatase, limonene, pinene, ethanol, styrene butadiene rubber latex, polyacrylic acid, polycarboxylate ether, lignosulphonate, maleic anhydride copolymers, citric acid, tartaric acid, ethylenediaminetetraacetic acid, sodium gluconate, polyvinyl alcohol, lignosulfonates, hydroxypropyl methylcellulose, carboxymethyl cellulose, sodium polyacrylate, acrylic latex, polyethylene glycol, polyaspartic acid, triethanolamine, sodium naphthalene sulfonate, maleic anhydride grafted polypropylene, decanoic acid, dodecanoic acid, tetradecaonic acid, hexadecanoic acid, octadecanoic acid, icosanoic acid, titanate coupling agents, zirconate coupling agents, polyethyleneimine, acrylic acid, succinic anhydride, epoxidized soybean oil, glycidyl methacrylate, polylactic acid, polycaprolactone, isocyanate functional silanes, methacryloxypropyltrimethoxysilane, aminopropyltriethoxysilane, styrene maleic anhydride copolymer, lignin sulfonate, cellulose nanofibers, polysiloxanes, epoxidized vegetable oils, acidic monomers such as benzoic acid, polycarbonate esters, epoxy resins, urethane prepolymers, polyamide resins, chlorinated polyolefins, ethylene-vinyl acetate copolymers, polyisobutylene, maleated ethylene-propylene copolymers, alkyd resins, block copolymers like styrene-isoprene-styrene, bisphenol a diglycidyl ether, phenolic resins, melamine formaldehyde, urea formaldehyde, linseed oil, modified starches, casein, shellac, siloxane-polyether copolymers, hydrophobic wax dispersions, latex binders, polyester-polyol blends, etc. Surface-treating can deodorize or alter the odor of BMA, selectively or in its entirety, by using for example, a 0.01 - 10 wt% solution of activated charcoal, baking soda, zinc ricinoleate, cyclodextrins, sodium bicarbonate, calcium hydroxide, potassium permanganate, chlorophyllin, essential oils, tea tree oil, titanium dioxide, glycerol carbonate, beta cyclodextrin, triethylene glycol, lignosulphonate, activated charcoal, metal oxides, zeolites, terpenes, titanium dioxide anatase, limonene, pinene, ethanol, eucalyptus oil, sodium percarbonate, hydrogen peroxide, citric acid, vinegar, tannic acid, bentonite clay, zeolite, alum, chlorine dioxide, copper sulfate, silver ions, bioenzymes, neem extract, thyme oil, rosemary oil, sodium hypochlorite, ozone, magnesium oxide, lactic acid, ethanol, isopropyl alcohol, acetic acid, surfactants such as sodium lauryl sulfate, enzymatic cleaners containing protease and lipase, activated manganese dioxide, protease, lipase, amylase, urease, laccase, peroxidase, oxidase, esterase, papain, bromelain, subtilisin, alcalase, pepsin, trypsin, catalase, chymotrypsin, deaminase, monoamine oxidase, diamine oxidase, tyrosinase, glutathione peroxidase, methionine gamma-lyase, trimethylamine oxidase, etc. Surface-treating can enhance or stabilize the color of BMA or extracted compounds or pigments, by using for example, a 0.01 - 10 wt% solution of ascorbic acid, citric acid, sodium citrate, sodium metabisulfite, potassium sorbate, rosemary extract, tocopherol, butylated hydroxytoluene, butylated hydroxyanisole, sorbic acid, sorbate-benzoate, sodium alum, ammonium alum, potassium alum, ethylenediaminetetraacetic acid, sodium erythorbate, tannic acid, ferulic acid, gallic acid, chitosan, gelatin, arabic gum, maltodextrin, cyclodextrins, polyvinylpyrrolidone, polyethylene glycol, carrageenan, xanthan gum, titanium dioxide, zinc oxide, calcium carbonate, magnesium stearate, lecithin, propylene glycol, polyethylene oxide, bentonite clay, zeolite, phospholipids, lipid nanoparticles, alginate, pectin, shellac, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polymethyl methacrylate, polyvinyl acetate, polyether sulfones, polyurethanes, polyamide resins, acrylate copolymers, ethylene vinyl acetate, styrene maleic anhydride copolymer, polyolefins, polycarbonate esters, polyethyleneimine, polysorbates, cetrimonium chloride, sorbitan monooleate, polyquaternium compounds, copovidone, etc.

[0048]

[0043] BMA produced using different source calcareous organism, mixture of calcareous organism, anatomical parts of the organism, the comminuting method, drying method, and surface-treating will produce BMA that are distinguished from one another by properties, functionalities, and application. The same calcareous organism and calcareousfeedstock may generate multiple types of BMA, for example, type A BMA, type B BMA, and so on. For example in one embodiment, BMA has been produced from strongylocentrotus purpuratus or purple sea urchins. For example, the composition for type A test BMA and type B spine BMA are both composed of calcium carbonate in the form of biocalcite, but exhibit differences in their microstructure, chemical composition, and properties. Processing conditions were tuned to enable preservation of unique microstructure and chemistries of BMA. Resulting Type A BMA derived from the test of the sea urchin, are cellular solids that possess a polycrystalline structure formed by interlocking plates, and distinct foam-like microstructure with intra-particle porosity and complex network of interconnected 3D pore structures, as shown in FIG. 10. In contrast, type B BMA as shown in FIG. 11 that is derived from the spine of the sea urchin show particles containing internal radial symmetry, with angular hooks along its axial plane, with single-crystalline structures, and with higher concentration of spinochrome pigments. Thermogravimetric analysis data shown in FIG. 5, shows a suite of BMA that were produced using different processing methods, yielding distinct differences in organic content providing a range of composition and properties. For example, spine BMA possess an average of 23.8% organic content, and test BMA possess an average of 15.7% organic content. In contrast, geologically derived, quarried calcium carbonate minerals contain average of 0.25% organic content.

[0049] Methods for Making BMA

[0050]

[0044] FIG. l is a flow diagram for a general procedure for manufacturing a surface-treated calcareous biomineral particle in accordance with an embodiment of the present invention. The procedure includes these main steps: receiving calcareous organisms in process 11, drying the received calcareous organisms in process 12, comminuting the dried calcareous organisms in process 13 to create a calcareous biomineral particle, and surfacetreating the biomineral particle in process 14, to generate a surface-treated calcareous biomineral particle as item 15.

[0051]

[0045] FIG. 2 is a flow diagram for a general procedure for manufacturing a calcareous biomineral particle in accordance with an embodiment of the present invention. The procedure includes these main steps: receiving calcareous organisms in process 21, drying the received calcareous organisms in process 22, comminuting the dried calcareous organisms in process 23 to create a calcareous biomineral particle, as item 24.

[0052]

[0046] FIG. 3 is a flow diagram illustrating processes for use in manufacturing of biomineral particles and surface-treated biomineral particles in accordance with embodimentsof the present invention. FIG. 3 illustrates in further detail the steps of FIG. 1 and FIG. 2 and provides an industrial context for the processes. In one embodiment, calcareous sea urchins are received in process 201. Optionally, in process 202 an antimicrobial treatment is applied to prevent biofouling. The treated calcareous organisms are then dried in process 203 to remove moisture. In this embodiment, the calcareous sea urchins are anatomically separated into spines and tests in process 204. In process 205 the separated tests are comminuted, and in process 211, the separated spines are comminuted. Each of these processes 205 and 211 produces a calcareous biomineral particle of a different composition, with process 205 yielding type A particle shown as item 206 and process 211 yielding type B particle shown as item 212. Following the comminuting process, the calcareous biomineral particles of type A and type B are dried in processes 207 and 213. In this embodiment, the dried calcareous biomineral particles of type A and type B are then classified in processes 208 and 214, respectively, according to size. In this embodiment, the size-classified particles of the calcareous biomineral particles of type A and type B are next recombined and mixed in processes 209 and 215 respectively in a precisely tailored manner to produce particle mixtures having desired size distributions for specific biomineral materials and product applications. The resulting calcareous biomineral particle from type A has particular composition, rheology, and functional properties that are distinguished from those of calcareous biomineral particle from type B. In processes 210 and 216 respectively, a surface treatment is then applied separately to the calcareous biomineral particles of type A and type B to produce surface-treated calcareous biomineral particles. The surface-treated calcareous biomineral particles of type A will be distinguished from surface-treated calcareous biomineral particles of type B, as shown in FIG. 3, item 206 and 212.

[0053]

[0047] In an embodiment, biomineral particle (BMA) can be produced from sea urchins to provide a biomineral particle and having a particle size of no larger than 5 millimeters in diameter. In this embodiment, BMA can be dried and having a moisture content below 50%. In an aspect, the mass of the BMA particle is up to 200 milligrams. In this embodiment, fresh sea urchins are harvested by scuba divers or free divers. Once landed, the sea urchins are stored in insulated coolers to maintain temperature below 70 degrees fahrenheit with no water. The sea urchins are transported to a processing facility where they are graded and further processed. Temperatures are maintained to reduce sea urchin fatality and subsequent rapid deterioration and rotting of the sea creatures which produce undesirable compounds and impurities. Sea urchins are dried in large porous containers to maximizesurface area and coelomic fluid drainage in a solar drying convection chamber. Sea urchins are dried until moisture content is below 30%, or up to 720 hours, where the median ambient relative humidity is up to 60%, temperature is above 60 Fahrenheit, and a minimum air velocity of 100 feet per minute. The drained coelomic fluid is collected and further purified to extract pigments and compounds. After initial drying of the calcareous organisms, the LDU or “live dried urchins” are provided and are further processed in a rotary tumbler to separate the anatomical parts from one another. A vibratory sieve is used to sort the parts into test and spine. The test and spine are separately comminuted using a roller mill to provide test BMA and spine BMA, or type A and type B respectively, as shown FIG. 3, item 206 and 212. In an aspect, type A test BMA and type B spine BMA has a moisture content up to 50%, and are used as an additive for solvent casting of biodegradable films for type A, and are used as an efficient intermediate for natural pigment extraction for type B. Optionally, the BMA are dried to reach a moisture content of up to 20%, using a convection dryer for type A test BMA, and using a double cone vacuum dryer for type B spine BMA.

[0054]

[0048] In another embodiment, a biomineral particle (BMA) can be manufactured from a mixture of shellfish farm waste containing calcareous organisms such as oyster and clam, comprising: a) providing a biomineral particle and having a particle size of no larger than 3 millimeter in diameter; b) drying the BMA particle and having moisture content below 50% and organic content above 5%. In an aspect, the mass of the BMA particle is up to 5 milligrams; c) comminuting the BMA particle and having a particle size distribution with a D90 of 2 millimeters, where 90% of the biomineral volume is less than a 2mm, D50 of 500pm , and a D10 of 300pm . The organisms can be received by collection from waste accumulated from shellfish farms. Once received, the calcareous organisms can be dried using a conveyor belt drying chamber until moisture content is below 50%, or up to 720 hours, where the median ambient relative humidity is up to 60%, temperature is above 200 Fahrenheit, and a minimum air velocity of 300 feet per minute. After initial drying of the calcareous organisms, the dried calcareous feedstock are provided and are processed with a vibratory sieve to sort the oyster, and clam parts into type A and type B feedstock. The feedstocks are then separately comminuted using a roller mill to provide oyster BMA and clam BMA, or type A and type B respectively, as shown in FIG. 3, item 206 and 212. In an aspect, type A BMA and type B BMA can have a moisture content up to 50%. Type A has an organic content less than 5%, and Type B can have an organic content above 5%. In an aspect the BMA are used as a filler for engineered stone for type A, and can be used as anintermediate for biomolecule extraction for type B. In an aspect, the particle size distribution of the Type A BMA and Type B BMA have a particle size distribution with a D90 of 2 millimeters, where 90% of the biomineral volume is less than a 2mm, D50 of 500pm , and a DIO of 300pm .

[0055]

[0049] In another embodiment, a surface-treated biomineral particle (BMA) can be produced from sea urchins to provide a biomineral particle particle that is having a particle size of no larger than 2 millimeter in diameter. In this embodiment, BMA particle can be dried and having moisture content below 10%, where the surface is treated to provide a surface-treated BMA with improved binder interfacial adhesion, flowability, dispersion, color stability, brilliance, lightfastness, odor, and anti-microbial properties. In an aspect, the mass of the BMA particle is up to 5 milligrams. In this embodiment, fresh sea urchins are harvested by scuba divers or free divers. Once landed, the sea urchins are rapidly submerged using a strainer, into a solution bath maintained at 140 to 160 degrees fahrenheit, for up to 5 seconds, containing 0.1 wt % solution of quaternary ammonium as an anti-microbial agent, 2 wt % solution of sodium lauryl sulfate as a deodorizing agent, and a 0.1 wt% solution of potassium sorbate as a color stabilizing compound. The solution contains drained coelomic fluid and compounds which are stored and further purified to extract pigments and compounds. The sea urchins are placed onto a vibrating sieve to sort its anatomical parts, providing spine and test. The test and spine are separately comminuted using a ball mill to provide a test BMA slurry and spine BMA slurry. The spine slurry is then dried using a fluidized bed dryer to provide type A test BMA, with moisture content below 10%. The spine slurry is then dried using a spray dryer to provide a surface-treated type B spine BMA, with moisture content below 10%. The particle size distribution (PSD) for surface treated type A test BMA is below 1 millimeter. The PSD for type B spine BMA is below 50pm . Optionally, an additional surface modification is performed separately to type A and type B BMA using a solution coating method (Shi, Xuetao, Roberto Rosa, and Andrea Lazzeri. Langmuir 26.11 (2010): 8474-848). A mixture of stearic acid (octadecanoic acid) and water is heated and incorporated with the BMA slurry after comminuting. The coated particulates are mixed, separated from the mixture using a sieve, and then dried to provide a surface treated BMA with enhanced interfacial adhesion with polymer matrices. In an aspect, the resulting surface treated BMA has increased shelflife and applicability. Type A test BMA is used as a biofiller due to its particle size distribution, morphology, and treated surface characteristics providing packing densities and interfacial adhesion that are suitable for producing biomineral materialswith thermoplastic, thermoset, or gel matrices. Type B spine BMA is used as functional pigments, colorant additives, or pH sensors due to enhanced colorfastness, dispersion properties, and reduced particle settling.

[0056]

[0050] In another embodiment, a surface-treated biomineral particle (BMA) from sea urchins can be produced by: providing a type A biomineral particle and having a particle size of no larger than 1 millimeter in diameter, and type B biomineral particle and having particle size of no larger than 1 pm ; drying the type A and type B BMA particle and having moisture content below 10%; comminuting the type A BMA particle and having a particle size distribution with a D90 of 1 millimeters, where 90% of the biomineral volume is less than a 1mm, D50 of 10pm , and a DIO of 0.01pm , and comminuting the type B BMA particle and having a particle size distribution with a D90 of 1pm , D50 of 0.1pm , and D10 of 0.05pm ; and surface-treating the BMA and providing a surface-treated BMA with improved binder interfacial adhesion, flowability, dispersion, color stability, brilliance, lightfastness, odor, or anti-microbial properties. In an aspect, the mass of the BMA particle is up to 10 milligrams. Fresh sea urchins are harvested by scuba divers or free divers. Once landed, the sea urchins are rapidly submerged using a strainer, into a solution bath maintained at 140 to 160 degrees fahrenheit, for up to 5 seconds, containing a mixture of 0.1-2% sodium hypochlorite, 0.1-5% glycerol carbonate, and 0.1-5% sodium citrate, with water. The solution contains drained coelomic fluid and compounds which are stored and further purified to extract pigments and compounds. The sea urchins are placed onto a vibrating sieve to sort its anatomical parts, providing spine and test. The test and spine are separately comminuted, using a ball mill to provide a test BMA slurry and spine BMA slurry. The spine slurry is then dried using a fluidized bed dryer to provide type A test BMA, with moisture content below 10%. The spine slurry is then dried using a spray dryer to provide a surface-treated type B spine BMA, with moisture content below 10%. In an aspect, the particle size distribution (PSD) for surface treated type A BMA has a D90 of 1 millimeters, D50 of 10pm , and a D10 of 0.01 m , and the particle size distribution (PSD) for surface treated type B has a D90 of 1pm , D50 of 0.1pm , and D10 of 0.05pm . Optionally, an additional surface modification is performed separately to type A and type B BMA using a solution coating method (Eg. Shi, Xuetao, Roberto Rosa, and Andrea Lazzeri. Langmuir 26.11 (2010): 8474-848, which is incorporated by reference in its entirety for all purposes). A mixture of stearic acid and water is heated and incorporated with the BMA slurry after comminuting. The coated particulates are mixed, and then dried to provide a surface treated BMA with enhanced interfacial adhesion with polymermatrices. In an aspect, the surface treated BMA has increased shelflife and applicability. Type A test BMA is used as a biofiller due to its particle size distribution, morphology, treated surface characteristics, increased shelflife, and improved odor, providing packing densities and interfacial adhesion that are suitable for producing biomineral materials with thermoplastic, thermoset, cementitious, or gel matrices. Type B spine BMA is used as functional pigments, pH indicators or sensors, anti-oxidizing agent, or colorant additives, with improved odor, increased shelflife, enhanced colorfastness, dispersion properties, and reduced particle settling.

[0057]

[0051] Organic matter and odor can be removed from the calcareous organisms by any of the following: prior to drying by penetrating the shell and washing the interiors, or in another embodiment post-grinding by washing the ground BMA and filtering the large particle, succeeded by an additional drying phase to lower the moisture content to <10%, or in another embodiment, by submerging into a solution bath at temperatures above 80 degrees fahrenheit, or in another embodiment collecting its coelomic fluid during the drying process for further extraction.

[0058]

[0052] Drying during the making of BMA can use solar irradiation, or a convection oven; or a vacuum oven with up to -30 in Hg gauge pressure, or a flash evaporator, or a continuous microwave process, or a fluidized bed, or a freeze dryer, or a dehydrator, or a spray drying system. A vacuum oven or convection oven can be a rotary drum, conical mixer, or a conventional static chamber. The rotary drum and conical-style operations also facilitate an initial size reduction of the skeleton into particles with sizes on the order of 0.5-2 cm.

[0059]

[0053] The drying operation will be varied based on the moisture target for a given product application’s requirements and the subsequent manufacturing process that follows the production of BMA. Target moisture can be any of the following: 50-80%, 30-50%, 10-30%, 5-10%, or below 5% for uses that do not require, or may even benefit from higher moisture content, for example, solvent cast biomineral materials, pigment extraction, cement or concrete materials, etc. The target moisture can be any of the following: 10-30%, 5-10%, 1-5%, or up to 1% for uses that require lower moisture content, for example, in manufacturing thermoplastic and thermoset biomineral materials such as engineered stone, composite, flooring, vanities, wall covering, artificial marble, molded articles; and thermoplastic biomineral materials such as additive manufacturing 3D printing filaments, extruded sheets, blown films, cast films, extruded films, tubes, rods, molding, etc.

[0054] The drying operation can be controlled to minimize thermal degradation of organic pigments contained within the calcium carbonate phase by minimizing thermal exposure, oxidative stress, maximizing forced air convection, or creating a pressure differential to drive water from the intermediate products.

[0060]

[0055] Dried calcareous organisms can be subjected to comminuting and milling operations to transform the calcareous feedstock into a powder of varying granulometry. The milling is performed via roller mill, or the milling is performed via a ball mill, or via a planetary mill, or via a centrifugal mill, or via hammer mill, or via jet mill, or via a raymond mill, or via a vertical mill, or via a ring roller mill, or via a ball mill. Selection of particle reduction and recapture method is pertinent to processed powder characteristics in morphology, particle size distribution, unit embodied energy, and therefore application, cost, and carbon footprint.

[0061]

[0056] The comminuting process can be controlled to preserve specific properties of the BMA such as particle morphology, size, color quality, porosity, and strength. Applicable comminuting processes include, for example, ball mill, jet mill, ring-roller mill, burr grinder, bead mill, impact mill, hammer mill, roller mill, blade grinder.

[0062]

[0057] Where any embodiment of the milling operation may combine the process with a sieve or particle classification system to be graded according to size, separate out particles less than or equal to a desired size, particles greater than the sieve size are rejected and refluxed back into the mill to be continuously processed in a closed-circulation system.

[0063]

[0058] Natural pigment can be extracted as the milling process enhances the efficiency of extraction techniques. Feedstock for pigment extraction can be harvested by collecting the wash solution during the surface modification process, or using the milled BMA, or collecting the drained coelomic fluid solution during the drying process. Pigment enhancing agents can be incorporated to stabilize the performance of natural pigments contained in the biomineral particle. The granulated BMA is subjected to surface modification to promote flow characteristics, dispersion, color stability, brilliance, lightfastness, anti-microbial properties, and shelflife. Interfacial adhesion and binder compatibility can be promoted between the BMA and polymer matrix, which can be any of thermoplastic, thermoset, and biopolymers that are from natural, synthetic, or hybrid sources. Compatibility can be enhanced by matching hydrophobicity / hydrophilicity, creating physical or chemical bonds with a matrix material, or promoting miscibility within a matrix. Suitable compatibilizing treatments include but are not limited to: maleic anhydride, polyethyleneglycol, decanoic acid, dodecanoic acid, tetradecaonic acid, hexadecanoic acid, octadecanoic acid, stearic acid, icosanoic acid, polysiloxanes, epoxidized vegetable oils, acidic monomers such as benzoic acid, polycarbonates etc.

[0064] Uses for BMA

[0065]

[0059] BMA can be used to make a number of biomineral materials and product applications across a range of industries including, for example, architectural surfaces, building materials for construction, fashion, apparel and accessories, food, personal care, cosmetics, pharmaceuticals, nutraceuticals, supplements and vitamins.

[0066]

[0060] Surface-treating of BMA, provides property enhancements that make them suitable for commercial use across a broad range of applications. BMA can be combined with other materials as an additive, filler, or ingredient to produce biomineral materials and intermediary products. The biomineral materials can be made partially or mostly from BMA, in the manufacture of a product by incorporating BMA with a binder (and optionally with other materials and minerals) to form product applications. Binders can be, for example, thermosetting polymer or resin or plastic, thermoplastic polymer or resin, gel, biopolymer, concrete, or cement, that is produced from natural, synthetic, or hybrid sources. Biomineral materials include, for example, composites, engineered stone, textile, fabric, leather, fiber, plastic, paper, flexible films, packaging, coating, 3d printing filament, solid surface, cast polymer, pigment, sensor, cultured marble, artificial marble, synthetic marble, indicators, inks, paints, rubber, ceramic, glass, cement, fertilizer, adhesive, sealant, fiber, etc.

[0067]

[0061] Biomineral materials can be produced from using BMA in isolation or in combination with other raw materials. For example, some biomineral materials have been made from BMA which include: compounds extracted from BMA derived from sea urchin can provide purple, red, and orange pigments as exhibited in FIG. 6; films as exhibited in FIG. 7; artificial or engineered stone as exhibited in FIG. 8; and 3D printing filament as exhibited in FIG. 9.

[0068]

[0062] In an embodiment, as shown in FIG. 6, extracting compounds from BMA derived from sea urchin have generated spinochrome pigments with absorption spectra of three colors:red, purple, and orange with peaks at 320, 470 nm in the red extract, 280-360 nm in the purple extract, and 330-340, 470-480 nm in the orange extract. In literature, the strongylocentrotus purpuratus has been reported to possess four distinct spinochromes: echinochrome A, spinochrome A, spinochrome B, and spinochrome E with colors red, purple, orange, and orange-yellow (e.g., Thomson, R.H. Comp. Biochem. Physiol. 28.1(1969): 67-80, DOI:10.1016 / 0010-406X(69)91347-4, which is incorporated by reference in its entirety for all purposes). BMA pigment extracts can have or provide a range of properties such as fluorescence, emission at different wavelengths when excited, anti-oxidant, antiinflammatory, anti-microbial, deodorizing, color stability, and / or extended shelf-life. BMA pigment extracts can be manufactured by providing a type of BMA or collecting the postwash solution from the surface modification process; purification and fractionation of the post-wash solution with organic solvents; concentrating the pigment by evaporating the solvents, and providing a pigment extract, and optionally lyophilizing the extract and provide a powder with prolonged shelflife.

[0069]

[0063] In another embodiment, films can be manufactured by: providing a type of BMA; providing a mixture by combining a matrix material such as a biopolymer with BMA, and optionally, other raw materials or crosslinking agents; deposited into a shape or form using methods such as knife over roll method or roll-to-roll manufacturing; and dried to remove solvent to provide a BMA film that can be further formed into functional articles and products. For example, as shown in FIG. 7, films have been made with BMA by formulating with a biopolymeric binder derived from seaweed and crosslinked with an ionic solution to provide films with a diversity of colors and patterns, enhanced moisture resistance, home and / or industrial compostability, biodegradability, with varying levels of optical transmittance and opacity to modulate light diffusion.

[0070]

[0064] In an embodiment, as shown in FIG. 8, biomarble or biocalcite surface engineered stone composites have been made with BMA to provide a diversity of colors and patterns, with a range of properties including fluorescence, high compressive strength, moisture resistance, chemical resistance, and / or temperature resistance. Engineered stone composites can be manufactured by: providing a type of BMA; providing a mixture by incorporating a matrix material with BMA, and optionally other raw materials; degassing the mixture to remove air pockets; shaping the mixture by depositing the mixture into a fixed shape or form. The cured BMA composite can be further cut to desired size, shape, and geometry using, for example, tile cutters, glass cutters, hand saws with carbide or diamond blades, nippers and scoring tools, wet saws, bridge saws, circular saws with diamond blades, angle grinders with diamond blades, jigsaws with carbide or diamond blades, reciprocating saws with carbide-tipped blades, cnc waterjet cutters, cnc routers with diamond tooling, laser cutters, plasma cutters, gang saws, wire saws with diamond wire, slab splitting machines, block cutters, etc. to produce product applications such as bathroom vanity, staircase,monument, memorial, headstone, building facade, column, pillar, exterior paving, art, sculpture, design element, decorative object, bench, lighting fixture, wall cladding, fireplace mantel, trim, molding, wainscot, countertop, tabletop, backsplash, flooring, cabinet, tub, wash basin, storage, wall covering, space divider, mirror, picture frame, tray, signage, furniture, and etc.

[0071]

[0065] In another embodiment, as shown in FIG. 9, 3D printing filament for additive manufacturing has been made with BMA to provide a diversity of colors and designs, and provide a range of properties including improved moisture resistance, stiffness, hardness, rigidity while enhancing surface brightness and gloss. It can improve printing performance by reducing shrinkage, enhancing thermal stability, and enabling sharper surface details. 3D printing filament can be manufactured by: providing a type of BMA; providing a BMA filament by combining a matrix material such as a thermoplastic with BMA during the pelletization, melting or extrusion process; melt and extrude the BMA filament using a 3D printer or other additive manufacturing equipment to form into functional articles and products. The BMA filament can be used with an additive manufacturing tool to generate a variety of shapes and forms to be used for product applications, for example, sculpture, design element, art, decorative object, lighting fixture, picture frame, cutlery, tableware, eyewear, vessel, bowl, planter, tray, signage, furniture, and etc.

[0072]

[0066] Product applications are products that utilize BMA or biominerals materials that use BMA, to fulfill a particular function or set of functions in a use case. A product application can use BMA in isolation or in combination with other raw materials. Product applications can be used for example for, architecture, building, and construction, for example as, bathroom vanity, staircase, monument, memorial, headstone, building facade, cutlery, tableware, column, pillar, exterior paving, art, sculpture, design element, decorative object, bench, lighting fixture, wall cladding, fireplace mantel, trim, molding, wainscot, countertop, tabletop, backsplash, flooring, cabinet, tub, wash basin, storage, wall covering, space divider, mirror, picture frame, vessel, bowl, planter, tray, signage, furniture, and etc; fashion, apparel, and accessories, for example, leather goods, textile, packaging, merchandising decoration, event design element, eyeglass frame, jewelry, handbag, shoe, button, belt, hats, wallets, watch band, glove, and etc; automotive and aerospace, for example, fender, bumper, interior surface, table top, and etc; food, cosmetic, pharmaceuticals, nutriceuticals, personal care, and skincare, for example, fragrance, detergent, candle, foundation, eyeshadow, bronzer, setting powder, highlighter, lipstick, face mask, cleanser,

[0073] 1moisturizer, nail polish, deodorant, shampoo, conditioner, sunscreen, body scrub, eye pencil, toner, toothpaste, bath salt, exfoliator, soap bar, lip balm, body lotion, hair treatment, bath bomb, aftershave, foot scrub, hand creams, face powder, perfume, fragrance, candle, and etc.

[0074] Using BMA with Thermosets

[0075]

[0067] BMA can be used to make a number of products including, for example, three-dimensional patterned composite materials or speckled BMA composite materials or terrazzo composite materials, which are applicable, for example for, architecture, building, and construction, for example as, bathroom vanity, staircase, monument, memorial, headstone, building facade, cutlery, tableware, column, pillar, exterior paving, art, sculpture, design element, decorative object, bench, lighting fixture, wall cladding, fireplace mantel, trim, molding, wainscot, countertop, tabletop, backsplash, flooring, cabinet, tub, wash basin, storage, wall covering, space divider, mirror, picture frame, vessel, bowl, planter, tray, signage, furniture, and etc; fashion, apparel, and accessories, for example, leather goods, textile, packaging, merchandising decoration, event design element, eyeglass frame, jewelry, handbag, shoe, button, belt, hats, wallets, watch band, glove, and etc. Product applications can be for automotive and aerospace, for example, fender, bumper, interior surface, table top, and etc; food, cosmetic, pharmaceuticals, nutriceuticals, personal care, and skincare, for example, fragrance, detergent, candle, foundation, eyeshadow, bronzer, setting powder, highlighter, lipstick, face mask, cleanser, moisturizer, nail polish, deodorant, shampoo, conditioner, sunscreen, body scrub, eye pencil, toner, toothpaste, bath salt, exfoliator, soap bar, lip balm, body lotion, hair treatment, bath bomb, aftershave, foot scrub, hand creams, face powder, perfume, fragrance, candle, and etc.

[0076]

[0068] A thermosetting resin such as, for example, epoxy resins, phenolic resins, polyester resins, vinyl ester resins, polyurethane, melamine formaldehyde, urea formaldehyde, silicone resins, polyimides, cyanate ester resins, bismaleimide resins, benzoxazine resins, alkyd resins, furan resins, acrylic thermosets, biobased epoxy resins, lignin-based phenolic resins, soybean oil-based polyester resins, cashew nutshell liquid resins, tannin-based resins, bio-based polyurethanes, bio-based cyanate esters, starch-derived thermosets, furan resins from biomass, bio-based benzoxazine resins, vegetable oil-based alkyd resins, sugar-derived resins, epoxies, acrylates, polyesters, polyurethanes, gelatin, pectin, alginates, carrageenans, chitosan, chitin derived from natural, biological, synthetic or hybrid origins can be used.

[0069] FIG. 4 is a flow diagram illustrating processes for use of BMA in the manufacturing of biomineral materials and product applications in accordance with embodiments of the present invention. Item 301 represents a general biomineral particle which can be surface-treated, untreated, dried, or not dried. The general BMA, for example, may be a calcareous biomineral particle resulting from a process described in connection with FIG. 1 or FIG. 2.

[0077]

[0070] In an embodiment, in process 310, calcareous biomineral particles shown as item 301 are mixed with thermoset matrix materials as a filler along with curing agents and catalysts. Air pockets are removed from the slurry by vacuum and / or vibration in process 311. In process 312, the slurry is then compression-, transfer-, or cast-molded to achieve a desired geometry and material properties. Once the slurry cures, a biomineral material 313 is produced. Varying the composition of the thermoset matrix and geometry of the mold produces different materials such as cultured marble, solid surface, or engineered stone that is used for product applications like bath vanities, kitchen countertops, wall surrounds, tubs, and furniture. A benefit of artificial marble or cultured marble or engineered stone is its strength and ductility. Commercial engineered marble exhibits tensile strength between 5500 and 7000 psi(e.g., Reichold, reichold.com (2008), which is incorporated by reference in its entirety for all purposes)(e.g., CompositesWorld, compositesworld.com (2013), which is incorporated by reference in its entirety for all purposes). Natural marble varies greatly with its source and sample, given its natural origin and heterogeneous composition.

[0078]

[0071] The composition of the BMA composite mixture can accommodate a wide variety of formulations. BMA composites with BMA loadings from 0.1 - 85 wt%, matrix loadings from 0.1 - 99.9 wt%, performance modifying additives from 0 - 20 wt%, have been prepared to a range of visual and mechanical properties. Combinations of BMA composite mixtures suitable for patterning can be prepared in binary mixtures ranging from 99: 1 to 1:1, or ternary mixtures ranging from 98: 1 : 1 to 1 :98: 1 to 1 : 1 :98, to 1:1:1, and quaternary mixtures and beyond with compositions respective to their binary and ternary counterparts. Optical properties such as translucency and opacity can be tuned to achieve a backlighting effect in the BMA composites by tuning the composite mixture composition and filler content, at ratios where the matrix composition dominates at between 50-95%.

[0079]

[0072] In another embodiment, a thermoset biomineral composite can be produced from sea urchin BMA, for biocalcite engineered stone applications. A biomineral composite can be produced containing at least one particle of calcite with spinochrome compoundpresent in the biomineral composite. An uncured BMA resin mixture is produced by incorporating a thermoset binder with BMA and mixing a hardener or catalyst into the uncured BMA resin mixture. The mixture can then be degassed to remove air pockets and shaped by depositing the uncured BMA mixture into a mold to be cured over a period of time. Optionally, a post-cure heating step can be added to further enhance performance. In an aspect, type A test BMA is combined with a thermoset resin matrix such as an unsaturated polyester to generate a BMA composite mixture. In this embodiment, the BMA may have a moisture content below 5% and a particle size distribution of 30 to 600 pm for D97, 10 to 30 pm for D50, 1 to 2.5 pm for D10. The type A BMA is subsequently added to an epoxy resin such that the mass fraction of BMA in the fully mixed composite will be 70 wt% BMA. Alternatively, a type B is subsequently added to an epoxy resin such that the mass fraction of BMA in the fully mixed composite mixture will be 20 wt% BMA. Either mixture is then stirred at up to 200 RPM to wet the BMA such that all particles are encapsulated by the resin. Optionally, up to 20 wt% titanium dioxide pigment can be added to enhance the color and increase the brightness of the biomineral composite. When added, these particles are stirred into the mixture at up to 200 RPM to wet the TiO? powder. Once all particles have been wetted, the stir speed is then gradually increased to up to 2000 RPM to generate a well dispersed mixture of epoxy resin and BMA while ensuring that loose dry powder does not become airborne and lost to the mixing process. The mixture is then degassed under vacuum for 15 minutes at up to -30 inHg to remove air that becomes entrapped during mixing.

[0080] Optionally, vacuum is applied during the mixing process to increase efficiency of the mixing process and eliminate the need for degassing once mixing is complete. After degassing the mixture, an amine hardener is added to enable the mixture to cure into a solidified biomineral composite. The mixture, now containing all components, is mixed at up to 2000 RPM to combine hardener and epoxy such that the matrix phase can solidify. The curing agent begins reacting slowly at room temperature once combined into the epoxy -BMA mixture.

[0081] Additionally, as heat is applied or generated during further mixing, the reaction rate will increase. Care is taken to avoid excessive heating in this final mixing step. A secondary degassing step is performed to remove the additional air incorporated into the mixture while mixing. This step is once again applied for 15 mins at up to -30 in Hg. Optionally, vacuum is applied during the secondary mixing process to increase efficiency of the mixing process and reduce or eliminate the need for degassing once mixing is complete. The mixed and degassed composite mixture is then spread for type A composite BMA or poured for type B compositeBMA into silicone molds that take the form of the desired composite structure where it is allowed to gel at room temperature over 3 days. The gelled composite is then allowed to fully cure either at room temperature for 7 days or at elevated temperatures up to 60°C for 6 hours. The cured BMA composite is demolded and machined to remove sharp edges to improve handleability.

[0082]

[0073] In another embodiment, a thermoset biomineral composite can be produced from oyster BMA, for biocalcite engineered stone applications. A biomineral composite can be produced containing at least one particle of calcite present, with over 5% organic content, and 30% moisture content in the biomineral composite. An uncured BMA resin mixture is produced by incorporating a thermoset binder with BMA and mixing a hardener or catalyst into the uncured BMA resin mixture. The mixture can then be degassed to remove air pockets and shaped by depositing the uncured BMA mixture into a mold to be cured over a period of time, to provide a biomineral composite. Optionally, a post-cure heating step can be added to further enhance performance. In an aspect, type A test BMA is combined with a thermoset resin matrix such as an unsaturated polyester to generate a BMA composite mixture. In another aspect, BMA is combined with an unsaturated polyester matrix to generate another BMA composite mixture. In this embodiment, the BMA may have a moisture content below 5% and particle size distribution of 35 to 50pm for D97, 15 to 25 pm for D50, and 5 to 10 pm for DIO. The type A BMA is subsequently added to an epoxy resin such that the mass fraction of BMA in the fully mixed composite will be 10 wt% BMA. Alternatively, a type B is subsequently added to an epoxy resin such that the mass fraction of BMA in the fully mixed composite mixture will be 80 wt% BMA. Either mixture is then stirred at up to 200 RPM to wet the BMA such that all particles are encapsulated by the resin. Optionally, up to 1 wt% titanium dioxide pigment can be added to enhance the color and increase the brightness of the biomineral composite. When added, these particles are stirred into the mixture at up to 200 RPM to wet the TiO? powder. Once all particles have been wetted, the stir speed is then gradually increased to up to 2000 RPM to generate a well dispersed mixture of epoxy resin and BMA while ensuring that loose dry powder does not become airborne and lost to the mixing process. The mixture is then degassed under vacuum for 15 minutes at up to -30 inHg to remove air that becomes entrapped during mixing. Optionally, vacuum is applied during the mixing process to increase efficiency of the mixing process and eliminate the need for degassing once mixing is complete. After degassing the mixture, an amine hardener is added to enable the mixture to cure into a solidified biomineral composite. The mixture, nowcontaining all components, is mixed at up to 2000 RPM to combine hardener and epoxy such that the matrix phase can solidify. The curing agent begins reacting slowly at room temperature once combined into the epoxy-BMA mixture. Additionally, as heat is applied or generated during further mixing, the reaction rate will increase. Care is taken to avoid excessive heating in this final mixing step. A secondary degassing step is performed to remove the additional air incorporated into the mixture while mixing. This step is once again applied for 30 mins at up to -30 in Hg. Optionally, vacuum is applied during the secondary mixing process to increase efficiency of the mixing process and reduce or eliminate the need for degassing once mixing is complete. The mixed and degassed composite mixture is then spread for type A composite BMA or poured for type B composite BMA into silicone molds that take the form of the desired composite structure where it is allowed to gel at room temperature over 2 hours. The gelled composite is then allowed to fully cure either at room temperature for 10 days or at elevated temperatures up to 60°C for 6 hours. The cured BMA composite is demolded and machined to remove sharp edges to improve handleability.

[0083]

[0074] The cured BMA composite can be further cut to desired size, shape, and geometry using, for example, tile cutters, glass cutters, hand saws with carbide or diamond blades, nippers and scoring tools, wet saws, bridge saws, circular saws with diamond blades, angle grinders with diamond blades, jigsaws with carbide or diamond blades, reciprocating saws with carbide-tipped blades, cnc waterjet cutters, cnc routers with diamond tooling, laser cutters, plasma cutters, gang saws, wire saws with diamond wire, slab splitting machines, block cutters, etc. to produce product applications such as bathroom vanity, staircase, monument, memorial, headstone, building facade, column, pillar, exterior paving, art, sculpture, design element, decorative object, bench, lighting fixture, wall cladding, fireplace mantel, trim, molding, wainscot, countertop, tabletop, backsplash, flooring, cabinet, tub, wash basin, storage, wall covering, space divider, mirror, picture frame, tray, signage, furniture, and etc.

[0084]

[0075] The cured patterned biomineral composite can be further cut to desired size, shape, and geometry using, for example, tile cutters, glass cutters, hand saws with carbide or diamond blades, nippers and scoring tools, wet saws, bridge saws, circular saws with diamond blades, angle grinders with diamond blades, jigsaws with carbide or diamond blades, reciprocating saws with carbide-tipped blades, cnc waterjet cutters, cnc routers with diamond tooling, laser cutters, plasma cutters, gang saws, wire saws with diamond wire, slab splitting machines, block cutters, etc. to produce product applications such as bathroomvanity, staircase, monument, memorial, headstone, building facade, column, pillar, exterior paving, art, sculpture, design element, decorative object, bench, lighting fixture, wall cladding, fireplace mantel, trim, molding, wainscot, countertop, tabletop, backsplash, flooring, cabinet, tub, wash basin, storage, wall covering, space divider, mirror, picture frame, tray, signage, furniture, and etc.

[0085]

[0076] Bio-based thermoset resins synthesized in part or in whole from biological materials can be combined with BMAs to produce BMA composites with substantially greater bio-content than utilizing resins that are non-biobased common to industry standards, industry. The bulk density of these composites has been tuned between 1 - 3 g / ml.

[0086]

[0077] Fillers can be used with the BMA to make products. Granulated filler materials can be used in the compositions with BMA including, for example, quicklime, calcium silicates, calcium-metal oxides, tricalcium aluminate, calcium carbonate, aluminum oxide, quartz, silica, ground limestone, ground marble, thermoplastic particles, glass microspheres, kaolin, carbon black, bentonite, alumina trihydrate, mica, talc, or other natural or modified or treated minerals. The particle size distribution of the BMA, resin, and filler can facilitate processing of the uncured composite resin with a viscosity between 2000 and 2000000 mPa*s.

[0087]

[0078] Fillers combined with the BMA can have a broad particle size distribution which could enable efficient packing, greater than the Einsteinian limit for hard spheres (Parkinson, C., S. Matsumoto, and P. Sherman. Journal of colloid and interface science 33.1 (1970): 150-160, which is incorporated by reference in its entirety for all purposes).

[0088]

[0079] Pigments or dyes can be used in compositions made with the BMA. Such pigments or dyes include, for example, titanium dioxide, crystal violet, spinochrome, anthocyanins, iron oxide red, iron oxide yellow, iron oxide black, titanium dioxide, carbon black, chromium oxide green, ultramarine blue, cobalt blue, cobalt green, cadmium red, cadmium yellow, bismuth vanadate yellow, zinc oxide, zinc sulfide, nickel titanate yellow, chrome oxide, phthalocyanine blue, phthalocyanine green, quinacridone magenta, quinacridone red, dioxazine violet, indanthrone blue, perylene red, isoindolinone yellow, diarylide yellow, benzimidazolone orange, anthraquinone red, vat orange, indigo, alizarin crimson, carmine, chlorophyll, melanin, sepia, cochineal, turmeric, spirulina, beet pigment, beta-carotene, curcumin, lutein, violacein, tannin-based pigments, lignin-based pigments, cashew nutshell liquid pigments, chitosan-based pigments, furan-based pigments, starch-based pigments, sugar-derived pigments, mica-based pearlescent pigments, aluminumpigments, copper pigments, stainless steel pigments, titanium-coated mica, iron oxide-coated mica, synthetic ultramarine, cerulean blue, prussian blue, manganese violet, cobalt violet, cobalt turquoise, vermilion, realgar, orpiment, natural umber, natural sienna, ochre, green earth, lapis lazuli, charcoal black, graphite powder, soot, bone black, lamp black, hematite, goethite, celadonite, azurite, malachite, madder lake, indigo lake, alizarin lake, beta-naphthol red, azo yellow, monoazo orange, disazo red, pigment blue 15, pigment green 7, pigment red 122, pigment yellow 12, pigment violet 23, pigment orange 36, pigment brown 25, pigment black 7, or other materials, including those that are compatible with the other components of the composition.

[0089]

[0080] The BMA composite mixture can be used with a mold, for example, compression molds, transfer molds, liquid silicone rubber molds, resin casting molds, investment casting molds, lost-wax casting molds, sand casting molds, ceramic molds, silicone molds, multi-cavity molds, overmolding molds, insert molds, hot runner molds, cold runner molds, etc. The desired geometry of the resulting BMA material composite can be based on the geometry of the mold which can be, for example, flat sheets, rectangular blocks, cylindrical shapes, thin-walled sections, ribbed designs, multi-layered structures, tapered sections, domed surfaces, decorative panels, architectural cladding, ornamental moldings, sculpted reliefs, column capitals, balusters, stair treads, terrazzo slabs, decorative wall tiles, ceiling medallions, sculptural furniture bases, stone tabletops, integrated sinks, custom countertops, curved vanity surfaces, decorative cabinet panels, ornate chair legs, lighting fixtures, resin-inlaid furniture, solid surface bathtubs, integrated washbasins, seamless sinks, stone shower trays, decorative backsplash panels, etc. In an embodiment, an uncured BMA composite mixture with a lower viscosity has been placed adjacent in a horizontal or vertical configuration to one or more uncured higher viscosity composite resin mixtures in a mold that will form the composite resin mixture into a desired geometry when cured. The BMA composite mixture can be deposited onto a mold or shaped form manually by hand, semi-automatically, or automatically. BMA composite mixtures can be deposited using, for example, automated metering dispensers, volumetric dispensers, liquid injection molding, resin casting machines, robotic dispensing systems, pressure pot dispensers, pneumatic pumps, peristaltic pumps, centrifugal casting machines, etc.

[0090]

[0081] The air pockets of the composite mixture can be removed by subjecting the mixture to vacuum less than -20 in Hg, or by subjecting the uncured / partially cured molded part to vibration, or by subjecting both the mixture and uncured / partially cured part to bothvacuum and vibration, or subjecting the uncured mixture and part to vibration compression under vacuum, (e.g., US PAT PUBL. 4698010A, US PAT PUBL. 11045973, US PAT PUBL. 10821628, which is incorporated by reference in its entirety for all purposes).

[0091]

[0082] Optionally, a coating or sealant is applied to the surface of the BMA composite at any point in time, for example, before curing or after curing, directly onto the mold / shaped form or on the surface of the composite part.

[0092]

[0083] The cured resin can be demolded and subjected to mechanical post-processing such as sanding, polishing, and surface finishing, or cutting, drilling, and shaping which can be performed manually or via automated processes.

[0093]

[0084] In an aspect, removal of the surface of a cured BMA composite during mechanical processing reveals new sections of the continuously patterned feature. Such a veined structure is apparent regardless of the post-processing method applied.

[0094]

[0085] The amount of moisture that can be absorbed by BMA composites can be tailored as a function of BMA type and loading, between 0.05 - 10 wt% moisture uptake enabling composites to be prepared for a variety of applications that have varying degrees of water exposure.

[0095]

[0086] The cured BMA composite can be further cut to desired size, shape, and geometry using, for example, tile cutters, glass cutters, hand saws with carbide or diamond blades, nippers and scoring tools, wet saws, bridge saws, circular saws with diamond blades, angle grinders with diamond blades, jigsaws with carbide or diamond blades, reciprocating saws with carbide-tipped blades, cnc waterjet cutters, cnc routers with diamond tooling, laser cutters, plasma cutters, gang saws, wire saws with diamond wire, slab splitting machines, block cutters, etc. to produce product applications such as bathroom vanity, staircase, monument, memorial, headstone, building facade, cutlery, tableware, column, pillar, exterior paving, art, sculpture, design element, decorative object, bench, lighting fixture, wall cladding, fireplace mantel, trim, molding, wainscot, countertop, tabletop, backsplash, flooring, cabinet, tub, wash basin, storage, wall covering, space divider, mirror, picture frame, vessel, bowl, planter, tray, signage, furniture, and etc.

[0096]

[0087] Three-dimensional patterned composite materials or speckled BMA composite materials or terrazzo composite materials can be made using BMA and thermoset polymers, or BMA with other binders for example, cement or concrete. In an aspect, BMA can be incorporated with thermoset polymers to provide functional benefits, for example: enhance manufacturing processability such as flow characteristics, interfacial adhesion and matrixcompatibility, working time, pot life; rheological properties such as storage and loss modulus, viscosity, and tan 6, dispersion; extend service life and shelflife such as color stability, lightfastness, UV-re si stance, color brilliance, anti-microbial resistance, chemical resistance; impart new properties and functions such as fluorescence, refractive index, opacity, odor, pH sensing, oxygen sensing, UV sensing, hydrogen peroxide sensing; enhance performance of bulk properties such as impact resistance, fracture toughness, compressive strength, compressive yield strength, hardness, temperature resistance, scratch resistance.

[0097] Using BMA with Thermoplastics

[0098]

[0088] BMA thermoplastic materials and composites can be made using BMA and thermoplastic polymers. BMA can be used to make a number of products including, for example, BMA thermoplastic materials, which are applicable, for example for, architecture, building, and construction, for example as, bathroom vanity, staircase, monument, memorial, headstone, building facade, cutlery, tableware, column, pillar, exterior paving, art, sculpture, design element, decorative object, bench, lighting fixture, wall cladding, fireplace mantel, trim, molding, wainscot, countertop, tabletop, backsplash, flooring, cabinet, tub, wash basin, storage, wall covering, space divider, mirror, picture frame, vessel, bowl, planter, tray, signage, furniture, and etc; fashion, apparel, and accessories, for example, leather goods, textile, packaging, merchandising decoration, event design element, eyeglass frame, jewelry, handbag, shoe, button, belt, hats, wallets, watch band, glove, and etc. Product applications can be for automotive and aerospace, for example, fender, bumper, interior surface, table top, and etc; food, cosmetic, pharmaceuticals, nutriceuticals, personal care, and skincare, for example, fragrance, detergent, candle, foundation, eyeshadow, bronzer, setting powder, highlighter, lipstick, face mask, cleanser, moisturizer, nail polish, deodorant, shampoo, conditioner, sunscreen, body scrub, eye pencil, toner, toothpaste, bath salt, exfoliator, soap bar, lip balm, body lotion, hair treatment, bath bomb, aftershave, foot scrub, hand creams, face powder, perfume, fragrance, candle, and etc.

[0099]

[0089] Thermoplastic matrix material can be, for example, polyethylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polystyrene, acrylonitrile butadiene styrene, polycarbonate, polyamide, polyoxymethylene, polymethyl methacrylate, polyether ether ketone, polyetherimide, polyphenylene oxide, polyphenylene sulfide, thermoplastic polyurethane, thermoplastic elastomers, ethylene vinyl acetate, polyvinylidene fluoride, polyaryletherketone, cyclic olefin copolymer, cyclic olefin polymer, polybutyleneterephthalate, liquid crystal polymer, polylactic acid, polyhydroxyalkanoates, biopolyethylene, bio-polypropylene, bio-polyethylene terephthalate, bio-polyamide, polyhydroxybutyrate, starch-based plastics, cellulose-based plastics, bio-polyurethane, polybutylene adipate terephthalate, polybutylene succinate, polycaprolactone. Thermoplastics can be combined individually or as a co-polymer or as a polymer blend, with BMA.

[0100]

[0090] In an aspect, BMA can be incorporated with thermoplastic polymers to provide functional benefits, for example: enhance manufacturing processability such as flow characteristics, interfacial adhesion and matrix compatibility, working time, pot life; rheological properties such as storage and loss modulus, viscosity, and tan 6, dispersion; extend service life and shelflife such as color stability, lightfastness, UV-resi stance, color brilliance, anti-microbial resistance, chemical resistance; impart new properties and functions such as fluorescence, refractive index, opacity, odor, pH sensing, oxygen sensing, UV sensing, hydrogen peroxide sensing; enhance performance of bulk properties such as impact resistance, fracture toughness, compressive strength, compressive yield strength, hardness, temperature resistance, scratch resistance.

[0101]

[0091] FIG. 4 is a flow diagram illustrating processes for use of biomineral particles and surface-treated biomineral particles in the manufacturing of biomineral materials and product applications in accordance with embodiments of the present invention. Item 301 represents a general biomineral particle which can be surface-treated, untreated, dried, or not dried. The general BMA, for example, may be a calcareous biomineral particle resulting from a process described in connection with FIG. 1 or FIG. 2.

[0102]

[0092] In an embodiment, in FIG. 4 process 306, calcareous biomineral particles 301 can be combined with a thermoplastic matrix material in process 306. BMA loading can be from, for example, 0.01-5% or 5-10% or 20-30% or up to 40% in thermoplastic polymer matrices. The target moisture for BMA can be any of: 10-30%, 5-10%, 1-5%, or up to 1%, depending upon the application. Optical properties such as translucency and opacity can be tuned to achieve a backlighting effect in the BMA composites by tuning the composite mixture composition and filler content, at ratios where the matrix composition dominates at between 50-95%. BMA can be combined by pelletizing together with a thermoplastic to produce a BMA pellet or surface treating the pellet to bind the BMA to its surface to produce a BMA pellet or directly with thermoplastic pellets as a powder during the melting and extrusion process. Thermoplastic and BMA can be pelletized together, as shown in FIG.4 process 307, to produce a BMA thermoplastic pellet. Pelletization process can be conductedthrough, for example, melt extrusion pelletization, wet granulation, dry granulation, spray drying and agglomeration, agglomeration and sintering, roller compaction, die-face pelletizing, underwater pelletizing, strand pelletizing, water-ring pelletizing, fluid bed granulation, pin mixing and extrusion, etc. The pellets can then be used for a variety of processes, for example, injection molding, extrusion, blow molding, thermoforming, 3D printing, or film casting. The BMA pellets are melted, as shown in FIG. 4 process 308, and fed through extrusion-, injection-, blow-, compression-, rotational-, or thermoform- molding to form a biomineral material 309. Altering the particular mold or dye produces different shapes or sizes of biominerals, such as 3D printing filaments, sheets, films, tubes, and rails, just to name a few. In an embodiment, BMA can be used to produce a 3D printing filament made from sea urchin for additive manufacturing applications. In an embodiment, BMA has been combined with polylactic acid (PLA) thermoplastic to produce biomineral materials as shown in FIG. 9. Untreated or surface-treated BMA in an amount of 0.01% to 10% w / w of BMA can be incorporated with PLA pellets. A moisture content of between 20-30%, 10-20%, 5-10%, <5%, or <1% may be used. The shaped BMA thermoplastic material can be further shaped or cut, to desired size, shape, and geometry using to produce product applications such as bathroom vanity, staircase, monument, memorial, headstone, building facade, column, pillar, exterior paving, art, sculpture, design element, decorative object, bench, lighting fixture, wall cladding, fireplace mantel, trim, molding, wainscot, countertop, tabletop, backsplash, flooring, cabinet, tub, wash basin, storage, wall covering, space divider, mirror, picture frame, tray, signage, furniture, and etc.

[0103] Using BMA with Biopolymers

[0104]

[0093] BMA biopolymeric materials and composites can be made using BMA and biopolymer. BMA can be used to make a number of products including, for example, BMA biopolymeric materials, which are applicable, for example for, architecture, building, and construction, for example as, bathroom vanity, staircase, monument, memorial, headstone, building facade, cutlery, tableware, column, pillar, exterior paving, art, sculpture, design element, decorative object, bench, lighting fixture, wall cladding, fireplace mantel, trim, molding, wainscot, countertop, tabletop, backsplash, flooring, cabinet, tub, wash basin, storage, wall covering, space divider, mirror, picture frame, vessel, bowl, planter, tray, signage, furniture, and etc; fashion, apparel, and accessories, for example, leather goods, textile, packaging, merchandising decoration, event design element, eyeglass frame, jewelry, handbag, shoe, button, belt, hats, wallets, watch band, glove, and etc. Product applicationscan be for automotive and aerospace, for example, fender, bumper, interior surface, table top, and etc; food, cosmetic, pharmaceuticals, nutriceuticals, personal care, and skincare, for example, fragrance, detergent, candle, foundation, eyeshadow, bronzer, setting powder, highlighter, lipstick, face mask, cleanser, moisturizer, nail polish, deodorant, shampoo, conditioner, sunscreen, body scrub, eye pencil, toner, toothpaste, bath salt, exfoliator, soap bar, lip balm, body lotion, hair treatment, bath bomb, aftershave, foot scrub, hand creams, face powder, perfume, fragrance, candle, and etc.

[0105]

[0094] FIG. 4 is a flow diagram illustrating processes for use of biomineral particles and surface-treated biomineral particles in the manufacturing of biomineral materials and product applications in accordance with embodiments of the present invention. Item 301 represents a general biomineral particle which can be surface-treated, untreated, dried, or not dried. The general BMA, for example, may be a calcareous biomineral particle resulting from a process described in connection with FIG. 1 or FIG. 2.

[0106]

[0095] In one embodiment, in FIG. 4 process 314, BMA can be incorporated with a biopolymer as an additive, dopant, or crosslinking agent. As shown in FIG. 4, item 301, BMA can be mixed with biopolymer, solvent, and additives under controlled temperature, into a homogenous solution. In an embodiment, a bioplastic film has been produced by using polysaccharides of red and brown algae and BMA made from purple sea urchin as a crosslinker, as exhibited in FIG. 7. A solution of 3% w / v of kappa-carrageenan (KC) with water was prepared by mixing the components in a hot water bath maintained at 158 degrees fahrenheit. In this embodiment, 2% w / v of BMA was incorporated into the biopolymer solution. BMA biopolymer solution was then solvent cast using the knife over roll method, where the solution is poured and drawn down atop a polyvinyl chloride substrate. In some instances, in FIG. 4 process 316, it is then dried under controlled conditions to produce the resulting biomineral material 317. In one embodiment, the film is dried for 24-36 hours under convection, and then released from the substrate. BMA of between 30-50%, 25-30%, 15-25%, 10-15%, 5 - 10%, 3 - 5%, 1-3%, 0.5-1%, or 0.01-0.5%, can be used. BMA moisture content can be between 50-70%, 20-50%, 10-20%, 5-10%, or 1-5%, or <1%. Optionally, 1-3%, or preferably 0.01-1% w / w of glycerin is incorporated into the solution where glycerin is used as an additive or plasticizer. The BMA biopolymer solution can then be electrospun, injection-, extrusion-, or solvent-cast, or cast and molded form any of, for example, fiber, film, coating, block, tube, relief, etc. While a polyvinyl chloride substrate is used in this embodiment, others can also be used for example, polyethylene terephthalate, polyethylene,polypropylene, polylactic acid, polyvinyl alcohol, polycarbonate, polystyrene, thermoplastic polyurethane, cellulose acetate, cellulose films, paper, coated paper, kraft paper, tracing paper, aluminum foil, copper foil, stainless steel foil, textile fabrics, woven fabrics, nonwoven fabrics, mylar, biodegradable films, chitosan films, gelatin films, starch-based films, bacterial cellulose films, synthetic leather, polyurethane-coated fabric, siliconized paper, teflon-coated fabric, flexible glass, polyimide, low density polyethylene, linear low density polyethylene, high density polyethylene, polybutylene succinate, polyhydroxyalkanoates, ethylene vinyl acetate, ethylene methyl acrylate, thermoplastic starch, polyethylene terephthalate glycol, polyamide, polycaprolactone, biodegradable polymer blends, cellulose acetate blends, etc. Drying methods for biopolymeric BMA material can include for example, air drying, oven drying, vacuum drying, freeze drying, infrared drying, microwave drying, convective drying, convection drying, contact drying, spray drying, supercritical drying, tunnel drying, belt drying, solar drying, lyophilization, desiccator drying, hybrid drying, radio frequency drying, hot air drying, drum drying, air impingement drying, infrared-hot air combination drying, ultrasonic-assisted drying, etc. For example, drying can be performed for up to 24, 48, 72, 96, 120, 144, 168, 192, 216, 240, 264, 288, 312, 336, 360, 384, 408, 432, 456, 280, 504, 528, 552, 576, 600, 624, 648, 672, 696, or 720 hours, and / or where the median ambient relative humidity is up to 10%, 20%, 30%, 40%, 50%, or 60%, and / or temperature is above 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 400, 500, or 600 Fahrenheit, and / or a minimum air velocity of 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200 feet per minute.

[0107]

[0096] In an aspect, BMA can be incorporated with a biopolymer as an additive, dopant, or filler for: structural reinforcement, controlled gelation, crosslinking, flame retardancy, biodegradability enhancement, whiteness improvement, opacity enhancement, mechanical strength improvement, stiffness enhancement, barrier property enhancement, pH regulation, slow ion release, texture improvement, controlled degradation, fire resistance, thermal stability, cost reduction, weight reduction, moisture resistance, abrasion resistance, impact resistance, UV resistance, improved printability, enhance structural integrity, binder compatibility, flow characteristics, rheological properties, viscosity, dispersion, odor, color stability, lightfastness, anti-microbial resistance, processability, moisture resistance, chemical resistance, temperature stability, viscosity optimization, impart fluorescence, oxygensensitivity, UV sensitivity, hydrogen peroxide sensitivity, optical properties, refractive index, etc.

[0108]

[0097] Other additives and materials can be incorporated into the mixture to provide functional properties including, for example, plasticizer, pigment, filler, dopant, compatibilizers, crosslinkers, antimicrobial agents, antioxidants, uv stabilizers, thermal stabilizers, colorants, pigments, fillers, reinforcements, coupling agents, nucleating agents, foaming agents, processing aids, flame retardants, anti-block agents, anti-fog agents, antistatic agents, odor absorbers, moisture scavengers, barrier enhancers, lubricants, slip agents, gloss enhancers, tackifiers, surfactants, dispersants, emulsifiers, bioactive compounds, enzymes, essential oils, metal nanoparticles, natural waxes, biochar, starch derivatives, cellulose nanofibers, lignin additives, protein isolates, polyphenols, etc. Additives and materials can include for example, glycerol, sorbitol, polyethylene glycol, triethyl citrate, acetyl tributyl citrate, lactic acid, triacetin, maleic anhydride, citric acid, silane coupling agents, itaconic acid, succinic anhydride, titanate coupling agents, genipin, glutaraldehyde, tannic acid, calcium chloride, sodium tripolyphosphate, boric acid, silver nanoparticles, zinc oxide, chitosan, thymol, eugenol, cinnamaldehyde, triclosan, quaternary ammonium salts, grapefruit seed extract, tocopherol, butylated hydroxytoluene, ascorbic acid, ferulic acid, green tea extract, quercetin, uv-531, titanium dioxide, iron oxide, curcumin, anthocyanins, chlorophyll, carbon black, indigo, cochineal extract, calcium carbonate, talc, kaolin clay, biochar, cellulose nanofibers, lignin, starch, montmorillonite, halloysite nanotubes, ammonium polyphosphate, aluminum hydroxide, magnesium hydroxide, melamine phosphate, beeswax, carnauba wax, stearic acid, shellac, polyglycerol esters, zein, palmitic acid, activated carbon, zeolite, baking soda, cyclodextrin, lecithin, stearoyl lactylate, sodium lauryl sulfate, tween 80, span 60, sorbitan monostearate.

[0109] Using BMA with Cementitious Binders

[0110]

[0098] Cementitious BMA materials and composites can be made by combining BMA with one or more cementitious binders. BMA can be used to make a number of products including, for example, cementitious BMA materials, which are applicable, for example for, architecture, building, and construction, for example as, bathroom vanity, staircase, monument, memorial, headstone, building facade, cutlery, tableware, column, pillar, exterior paving, art, sculpture, design element, decorative object, bench, lighting fixture, wall cladding, fireplace mantel, trim, molding, wainscot, countertop, tabletop,backsplash, flooring, cabinet, tub, wash basin, storage, wall covering, space divider, mirror, picture frame, vessel, bowl, planter, tray, signage, furniture, and etc.

[0111]

[0099] A cementitious binder can be, for example, ordinary Portland cement, Portland-limestone cement, white Portland cement, oil well cement, fly ash, silica fume, slag cement, calcinated clay, volcanic ash, calcium sulfoaluminate cement, calcium aluminate cement, hydrated and hydraulic lime, carbonated calcium silicate, precipitated calcium carbonate-bonded binder, carbon-cured cementitious binder, metakaolin binder, pumicite binder, diatomaceous earth binder, magnesium oxychloride cement, magnesium oxysulfate cement, etc. Cementitious binders can be used individually or combined in hybrid binder systems in use with BMA.

[0112]

[0100] In an aspect, BMA can be combined with cementitious binders to provide functional benefits, for example: enhanced manufacturing processability such as flow characteristics, interfacial adhesion and matrix compatibility, working time; extended service life and shelflife such as color stability, lightfastness, UV-resi stance, color brilliance, antimicrobial resistance, chemical resistance; impart new properties and functions such as fluorescence, refractive index, opacity, odor; enhance performance of bulk properties such as impact resistance, fracture toughness, compressive strength, compressive yield strength, hardness, temperature resistance, scratch resistance.

[0113]

[0101] The target moisture for BMA can be any of: 50-70%, 30-50%, 10-30%, 5-10%, 1-5%, or up to 1%, depending upon the application. The moisture content of BMA can be advantageous in cementitious material applications due to the integral role that moisture plays in curing of the binder.

[0114]

[0102] FIG. 4 is a flow diagram illustrating processes for use of BMA and surface-treated BMA in the manufacturing of biomineral materials and product applications in accordance with embodiments of the present invention. Item 301 represents a general biomineral particle which can be surface-treated, untreated, dried, or not dried. The general BMA, for example, may be a calcareous biomineral particle resulting from a process described in connection with FIG. 4. The biomineral particle has a size range and distribution tuned to the production of the desired final cementitious material.

[0115]

[0103] In an embodiment, in process 310, calcareous biomineral particles shown as item 301 are mixed with cementitious binders along with water. In some embodiments, the moisture content of the BMA particles is high enough to reduce or eliminate the need to add water. Air pockets are removed from the slurry by vacuum and / or vibration in process 311. Inprocess 312, the slurry is then poured into a mold, covered to retain moisture, and cured over the course of 1-10 days. The cured material is then dried, producing a cementitious biomineral material 313.

[0116]

[0104] BMA can be used in combination with traditional cementitious aggregates to make products. BMA can be used with gravel, sand, crushed stone, crushed limestone, crushed granite, crushed basalt, crushed gravel, manufactured sand, recycled concrete, recycled asphalt, crushed masonry, crushed quartzite, shale aggregate, etc. In combination with traditional aggregates, BMA can be used as the fine aggregate, coarse aggregate, or some portion of both in order to achieve the most advantageous combination of processing characteristics and final material properties.

[0117]

[0105] The shaped cementitious BMA material can be further shaped or cut, to desired size, shape, and geometry using to produce product applications such as bathroom vanity, staircase, monument, memorial, headstone, building facade, column, pillar, exterior paving, art, sculpture, design element, decorative object, bench, lighting fixture, wall cladding, fireplace mantel, trim, molding, wainscot, countertop, tabletop, backsplash, flooring, cabinet, tub, wash basin, storage, wall covering, space divider, mirror, picture frame, tray, signage, furniture, and etc.

[0118] Using BMA with Gels & Emulsions

[0119]

[0106] BMA can be incorporated into gels and emulsions to create BMA gels and BMA emulsions. In an aspect, BMA particles can be used in gels and emulsions for skincare and cosmetics product applications. In these applications, BMA can provide functional benefits, for example: sensory and skin feel enhancements such as texture, oil absorption, slip, spreadability; rheology and texture modification such as thickening, thixotropic behavior tuning, suspension stabilization, emulsion stabilization; optical and visual effects such as wrinkle blurring, opacity, glow, color and pigmentation; functional enhancements such as pH buffering, active ingredient delivery, active ingredient stabilization, physical exfoliation, impurity absorption, enhanced barrier properties, etc.

[0120]

[0107] FIG. 4 is a flow diagram illustrating processes for use of BMA and surface-treated BMA in the manufacturing of biomineral materials and product applications in accordance with embodiments of the present invention. Item 301 represents a general biomineral particle which can be surface-treated, untreated, dried, or not dried. The general BMA, for example, may be a calcareous biomineral particle resulting from a process described in connection with FIG. 4.

[0108] In an embodiment, in process 314, calcareous biomineral particles shown as item 301 are mixed with water and at least one emulsifier. The BMA particles may also be mixed with the oil phase if the BMA is surface-treated. After incorporation of the BMA into either phase, the two phases are then mixed into an oil-water emulsion in process 315. In process 316, the mixture is cooled under gentle agitation, resulting in a biomineral emulsion 317.

[0121]

[0109] In some embodiments, BMA can be used as the emulsifying agent itself to form a Pickering emulsion (e.g., de Carvalho-Guimaraes, F.B. Pharmaceuticals. 15 (2022): 1413, DOI:10.3390 / phl5111413, which is incorporated by reference in its entirety for all purposes). In such cases, the BMA is incorporated into the water or oil phase as outlined in paragraph

[0122] , but without the emulsifier. The particle size of the BMA is tuned to stabilize the emulsion of the two phases.

[0122] Extracting BMA Compounds

[0123] [HO] Due to the presence of organic matrix proteins, polysaccharides, and other biomolecules contained in calcareous organisms, the byproducts of the biomineral production process can yield other compounds of interest, or biominerals themselves can be used as efficient intermediates for biomolecule extraction. BMA compounds can be extracted to be used as an additive or ingredient for product applications, or mixed with thermoplastics, thermosets, cementitious binders, or biopolymers as an additive or ingredient to produce biomineral materials and product applications. In an aspect, natural pigment, proteins, polysaccharides, fatty acids, and compounds can be extracted by using any of the various products generated throughout the BMA manufacturing process as feedstock, for example, the comminuted BMA powder, the wash solution during the surface modification process, or the using residual byproduct solutions containing molecules of interest from the cleaning or drying process. For example, calcareous sea urchins contain naphthoquinones that can be extracted directly from mineralized biological calcium carbonates via solvent extraction methods, or utilizing the coelomic fluid byproduct of the solution treatment process from sea urchin biomineral processing.

[0124] [Hl] FIG. 4 is a flow diagram illustrating processes for use of biomineral particles and surface-treated biomineral particles in the manufacturing of biomineral materials and product applications in accordance with embodiments of the present invention. Item 301 represents a general biomineral particle which can be surface-treated, untreated, dried, or not dried. The general BMA, for example, may be a calcareous biomineral particle resulting froma process described in connection with FIG. 1 or FIG. 2. In one embodiment, in process 302 of FIG. 4, a biomineral particle item 301 derived from sea urchin was dissolved and agitated in a solvent solution for up to 48 hours. In process 303, the supernatant solution was separated from the slurry by filtration and centrifugation. Optionally, in process 304 further purification and fractionation with organic solvents yields alternate forms and colors of the compound of interest, for example, spinochrome pigments. In process 305, the addition of an evaporation or lyophilization step was used to dry, concentrate, or powderize the pigment to make a shelf-stable biomineral material.

[0125]

[0112] In another embodiment, spinochrome pigment is extracted by collecting the post-wash solution from the surface modification process. In an embodiment, the post-wash solution from the surface modification process is collected from sea urchin, followed by the purification and fractionation of the post-wash solution with organic solvents. The pigment is then concentrated by evaporating the solvents, and providing an extract containing spinochrome pigment. The extract is then lyophilized to provide a spinochrome pigment powder with prolonged shelflife. Fresh sea urchins are harvested by scuba divers or free divers. Once landed, the sea urchins are rapidly submerged using a strainer, into a solution bath maintained at 160-220, 140-160, or 80-140 degrees fahrenheit, but preferably at 140-160 degrees Fahrenheit. The sea urchins are submerged between 30 minutes to 1 hour, 10 minutes to 30 minutes, 5 minutes to 10 minutes, 1 minute to 5 minutes, 30 seconds to 1 minute, 10 seconds to 20 seconds, or from 5 seconds to 10 seconds, but preferably from 5 seconds to 10 seconds. The solution can contain a mixture of anti-microbial agents, deodorizing agents, and color stabilizing compounds. Impurities and waste products are separated. The sea urchins are removed and used for the production of BMA mineral particles. The post- wash solution contains drained coelomic fluid and compounds which are used for pigment extraction. A 2 molar solution of phosphoric acid is incorporated with the post-wash solution. Optionally, the acidic solution is mixed with 30% v / v of ethyl acetate. A dilute solution between 20-30%, 10-20%, 5-10%, or 1-5% v / v of ethyl acetate can also be used. The acidic solution is fractionated in a separatory funnel, and the pigment solution is collected. The pigment solution is then centrifuged at 5000rpm, for 10 mins @ 23 degrees Celsius. The supernatant is collected, and the pigment extract is concentrated using a vacuum concentrator for 1 to 6 hours.

[0126]

[0113] BMA can be used as additives or ingredients to enhance the properties of biomineral materials or product applications, for example, architecture, building, andconstruction, for example as, bathroom vanity, staircase, monument, memorial, headstone, building facade, cutlery, tableware, column, pillar, exterior paving, art, sculpture, design element, decorative object, bench, lighting fixture, wall cladding, fireplace mantel, trim, molding, wainscot, countertop, tabletop, backsplash, flooring, cabinet, tub, wash basin, storage, wall covering, space divider, mirror, picture frame, vessel, bowl, planter, tray, signage, furniture, and etc; fashion, apparel, and accessories, for example, leather goods, textile, packaging, merchandising decoration, event design element, eyeglass frame, jewelry, handbag, shoe, button, belt, hats, wallets, watch band, glove, and etc; automotive and aerospace, for example, fender, bumper, interior surface, table top, and etc; food, cosmetic, pharmaceuticals, nutriceuticals, personal care, and skincare, for example, fragrance, detergent, candle, foundation, eyeshadow, bronzer, setting powder, highlighter, lipstick, face mask, cleanser, moisturizer, nail polish, deodorant, shampoo, conditioner, sunscreen, body scrub, eye pencil, toner, toothpaste, bath salt, exfoliator, soap bar, lip balm, body lotion, hair treatment, bath bomb, aftershave, foot scrub, hand creams, face powder, perfume, fragrance, candle, and etc.

[0127]

[0114] Compounds present in BMA have a variety of properties such as for example, anti-microbial, anti-oxidant, anti-inflammatory, UV-protective properties, fluorescence, oxygen sensitivity, UV sensitivity, hydrogen peroxide sensitivity, optical properties, refractive index, which can be used with other materials to provide functions such as for example, opacity alteration, color, barrier property enhancement, pH regulation, slow ion release, UV resistance, binder compatibility, rheological properties, viscosity, odor, stability, lightfastness, anti-microbial resistance, processability, chemical resistance, temperature stability, viscosity optimization, chemistry modification, etc.

[0128]

[0115] For example, in sea urchins, species such as diadema antdlarum, echinus esculentus, hemicentrotus pulcherrimus, heliocidaris erythrogramma, mesocentrotus franciscanus, mesocentrotus nudus, strongylocentrotus droebachiensis, strongylocentrotus franciscanus, strongylocentrotus purpuratus, tripneustes gratilla, etc possess compounds such as spinochromes, naphthoquinones, carotenoids, heparin-like sulfated polysaccharides, fucose-containing polysaccharides, echinochrome A, echinocholesterol, desmosterol, sphingolipids, cholesterol, steroid glycosides, antimicrobial peptides, histones, echinochrome a, astaxanthin, beta carotene, lutein, omega-3 fatty acids, phospholipids, zeaxanthin, fucoidans, sulfated polysaccharides, glycosaminoglycans, chitin, trimethylamine, dimethyl sulfide, benzaldehyde, hexanal, nonanal, 2-nonenal, 3 -methylbutanal, methional,phenylacetaldehyde, l-penten-3-one, glutamic acid, glycine, taurine, histidine, aspartic acid, bioactive peptides and proteins, and etc and are present in the skeletal structures, gonad, and coelomic fluid. For example, spinochromes are polyhydroxylated derivatives of juglone or naphthazarin, substituted with various functional groups (e.g., Hou, et al. RSC Adv. 8 (2018): 32637-32650, which is incorporated by reference in its entirety for all purposes). They are slightly soluble in water and acids, and highly soluble in alkalis, alcohol, ether, and acetone solvents (e.g., Tyler, et al. Proc. Natl. Acad. Sci. 25.10 (1939): 523-528, which is incorporated by reference in its entirety for all purpose). Spinochromes, particularly polyhydroxylated 1,4-naphthoquinone have several acid dissociation constants at 5.20, 6.78 and >10, which impact their color (e.g., Lebedev, et al. Arch. Biochem. Biophys. 413 (2003): 191-198, which is incorporated by reference in its entirety for all purposes) and stability (e.g., Zhou, et al. Int. J. Food Sci. Tech. 47 (2012), DOI: 10.1111 / j.1365-2621.2012.02995.x, which is incorporated by reference in its entirety for all purposes) under different pH conditions. In addition to pH, they are also sensitive to oxygen, hydrogen peroxide, sodium sulfite, and oxygen (e.g., Lebedev, et al. Biochemistry 66 (2001): 885-893, which is incorporated by reference in its entirety for all purposes.) These instabilities in natural pigments can be controlled by incorporating anti-oxidants such as ascorbic acid (e.g., Zhou, et al. Int. J. Food Sci. Tec. 47.7 (2012): 1479-1486, DOI: 10.1111 / j.1365-2621.2012.02995.x, which is incorporated by reference in its entirety for all purposes), or exploited by utilizing them as pH sensing biomaterials (e.g., Kan, et al. Proc. CHI Conf. Hum. Factors Comput. Syst. (2017): 989-1000, DOL10.1145 / 3025453.3025952, which is incorporated by reference in its entirety for all purposes). Among pigments in the spinochrome class, echinochrome has been the most widely studied compound for biomedical applications due to its antioxidant, antiviral (e.g., Fedoreyev, et al. Mar. Drugs 16 (2018): 509, which is incorporated by reference in its entirety for all purposes), iron chelation, and free radical scavenging properties (e.g., Lebedev, et al. Life Sci. 76 (2005): 863-875, which is incorporated by reference in its entirety for all purposes). It is an active ingredient in an antioxidant pharmaceutical called Histochrom (e.g., Fedoreyev, et al. Mar. Drugs 16 (2018): 509, which is incorporated by reference in its entirety for all purposes).

[0129]

[0116] Compounds in BMA can be extracted through a variety of methods to provide valuable materials for product applications. Pigments can be extracted by, for example, organic solvent extraction, ultrasound assisted extraction, thin layer chromatography, crystallization, high performance liquid chromatography, etc. Solvents can be used to extractthe pigments, for example, hydrochloric acid, sulfuric acid, ethanol, citric acid, acetic acid, phosphoric acid, formic acid, diethyl ether, petroleum ether, chloroform, ethyl acetate, butanol, alkalis, alcohols, ketones. Lipids and sterols contained in calcareous organisms can be extracted through, for example, soxhlet extraction, chloroform methanol extraction, bligh and dyer method, supercritical fluid extraction, silica gel column chromatography, high performance liquid chromatography, molecular distillation, etc. Proteins and peptides contained in calcareous organisms can be extracted by, for example, salting out using ammonium sulfate precipitation, ultrafiltration and dialysis, enzymatic extraction, ion exchange chromatography, size exclusion chromatography, reverse phase high performance liquid chromatography, etc. Polysaccharides can be extracted by, for example, hot water extraction, enzymatic hydrolysis, acid alkaline extraction, ethanol precipitation, ion exchange chromatography, size exclusion chromatography, etc. Odorants can be extracted by, for example, solid phase microextraction, steam distillation, solvent assisted flavor evaporation, gas chromatography mass spectrometry, high resolution gas chromatography, etc.

[0130]

[0117] Various features and embodiments of the disclosure are illustrated in the following representative examples, which are intended to be illustrative, and not limiting. However, one skilled in the art will readily appreciate that the specific methods and results discussed are merely illustrative of the inventions as described more fully in the claims which follow thereafter. Unless otherwise indicated, the disclosure is not limited to specific procedures, materials, or the like, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0131] Examples

[0132] Example 1. Production of BMA

[0133]

[0118] Disclosed herein is one example process, as exhibited in FIG. 2, for manufacture of a biomineral particle (BMA) from sea urchins, comprising: a) providing a biomineral particle; b) drying the BMA particle and having moisture content below 10%; c) comminuting the BMA and having a particle size of no larger than 150pmin diameter and providing BMA that preserves unique microstructure and organic compounds that can be used for the molecule extraction and production of biomineral materials such as biobased film. In an aspect, the mass of a BMA particle is up to 10 milligrams, and has an organic content of over 20%. In an aspect, the test BMA, or type A BMA, as shown in FIG. 3, item 206, have a particle size distribution where the resulting BMA have a D90 of 20-50pm , aD50 of 10-20pm , and DIO of 0.5-5 pm , and the spine BMA, or type B BMA, as shown in FIG. 3, item 212, have a particle size distribution where the resulting BMA have a D90 of 20-35pm , a D50 of 5-20pm , and DIO of 0.5-5pm .

[0134]

[0119] In one embodiment, as exhibited in greater detail in FIG. 3, fresh sea urchins were harvested by scuba divers. Once landed and received, item 201, the sea urchins were graded based on urchin size distribution and degree of rock or debris contamination, which impact comminution efficiencies. The graded urchin are then placed in a convection oven to be dried, as exhibited in item 203. Sea urchins were dried until moisture content was below 10%, up to 720 hours, where the median relative humidity in the drying chamber was up to 60%, and the temperature was between 60-100 Fahrenheit, with a minimum air velocity of 100 feet per minute. In an aspect, type A test BMA and type B spine BMA have a moisture content of <30%.

[0135]

[0120] After drying of the calcareous organisms, the LDU or dried urchin were provided and further processed with a vibratory sieve using 2400um sieve to sort its anatomical parts following item 204, into type A test feedstock, and type B spine feedstock. The test and spine were separately comminuted using two phases of comminution beginning with a jaw crusher and then hammer mill, as illustrated in item 205 and 211. In an embodiment the type A test BMA was used as an additive for solvent casting to produce biomineral materials of biobased films, as exhibited in FIG. 7, using methods illustrated in FIG. 4, item 314-317, and type B spine BMA were used as an intermediate for biomolecule extraction of spinochrome pigments, as exhibited in FIG. 6, following methods illustrated in FIG. 4, item 302-305. In an embodiment, a biobased film was produced by using polysaccharides of red and brown algae and BMA type A made from purple sea urchin as a crosslinker. A solution of 3% w / v of kappa-carrageenan (KC) with water was prepared by mixing the components in a hot water bath maintained at 158 degrees fahrenheit. In this embodiment, 2% w / v of BMA was incorporated into the biopolymer solution. BMA biopolymer solution was then solvent cast using the knife over roll method, where the solution is poured and drawn down atop a substrate.

[0136]

[0121] In an embodiment, as shown in FIG. 6, extracting compounds BMA type B biominerals from sea urchin have generated spinochrome molecules that are naphthoquinones with absorption spectra of three colors: red, purple, and orange with peaks at 320, 470 nm in the red extract, 280-360 nm in the purple extract, and 330-340, 470-480 nm in the orange extract. In literature, the strongylocentrotus purpuratus has been reported to possess fourdistinct spinochromes: echinochrome A, spinochrome A, spinochrome B, and spinochrome E with colors red, purple, orange, and orange-yellow (e.g., Thomson, R.H. Comp. Biochem. Physiol. 28.1 (1969): 67-80, DOI:10.1016 / 0010-406X(69)91347-4, which is incorporated by reference in its entirety for all purposes).

[0137]

[0122] In an embodiment, BMA pigment extracts were produced by incorporating organic solvents with the type B BMA, and undergoing purification and fractionation, followed by concentrating the pigment by evaporating the solvents, and providing a pigment extract, and lyophilizing the extract and provide a powder with prolonged shelflife. A 2 molar solution of phosphoric acid and 30% v / v of ethyl acetate solution with the type B BMA were incorporated together. The acidic solution was then fractionated in a separatory funnel, and the pigment solution was collected. The pigment solution was then centrifuged at 5000rpm, for 10 mins @ 23 degrees Celsius. The supernatant was collected, and the pigment extract was concentrated using a vacuum concentrator for 1 to 6 hours. A dilute solution between 20-30%, 10-20%, 5-10%, or 1-5% v / v of ethyl acetate can also be used. The spinochrome extracts produced from BMA have demonstrated a range of properties such as fluorescence and emission at different wavelengths when excited, as shown in FIG. 6. These bioactive compounds have a range of properties such as antibacterial antioxidant, inflammatory, and cytotoxic (e.g., Brasseur, L., Hennebert, E., Fievez, L., Caulier, G., Bureau, F., Tafforeau, L., Flammang, P., Gerbaux, P., & Eeckhaut, I. Marine Drugs 15.6 (2017): 179, D01:10.3390 / mdl5060179, which is incorporated by reference in its entirety for all purposes) which can be utilized as additives or active ingredients for the manufacture of product applications such as skincare and cosmetics. For example, skin brightening, hyperpigmentation treatment, melanin synthesis inhibition, tyrosinase inhibition, anti-aging, wrinkle reduction, collagen synthesis promotion, antioxidant and free radical scavenging activity, UV photoprotection, dark spot correction, natural skin and hair colorants, anti-acne treatment, sebum regulation, and antimicrobial preservation (e.g., Papageorgiou VP et al. Angew Chem Int Ed Engl. 1999;38(3):270-301. PMID: 29711637, which is incorporated by reference in its entirety for all purposes), as well as scalp health, hair growth stimulation, wound healing, skin barrier repair, moisturizers, lip, eye, and sun care products, color cosmetics, transdermal and nanoparticle delivery systems, broad-spectrum photoprotective and anti-pollution agents.Example 2. Production of surface-treated BMA

[0138]

[0123] Disclosed herein is one example process, as exhibited in FIG. 1, for the manufacture of a surface-treated biomineral particle (BMA) from sea urchins, comprising: a) providing a surface-treated biomineral particle; b) drying the BMA particle and having moisture content below 8%; c) comminuting the BMA particle and having a particle size of no larger than 380pm in diameter; and d) surface-treating the BMA and providing a surface-treated BMA with enhanced surface hydrophobicity, binder compatibility with polymeric matrices, interfacial adhesion, reduced moisture absorption, enhanced flowability, mechanical and impact properties. In an aspect, the mass of a BMA particle is up to 20 milligrams, and has an organic content below 20%. In an aspect, the particle size distribution (PSD) for surface-treated type A BMA has a D90 of 150 - 300pm , D50 of 20 - 70pm , and a D10 of 0.001 - 10pm , and the particle size distribution (PSD) for surface treated type B has a D90 of 70 - 200pm , D50 of 10 - 80pm , and D10 of 0.001 - 10pm .

[0139]

[0124] In an embodiment, fresh sea urchins were harvested by scuba divers. Once landed, the sea urchins were dewatered until moisture content reached below 25%. The calcareous organisms were then placed onto a vibrating sieve to sort its anatomical parts, providing spine and test feedstocks. The test and spine feedstocks were separately comminuted, using a blade grinder to provide type A test BMA and type B spine BMA respectively, as shown in FIG. 3, item 206 and 212. The BMA were then further dried using a vacuum oven at 113 degrees Fahrenheit for 24 hours, or until moisture content reached below 8%. Surface modification was performed separately to type A and type B BMA by incorporating BMA with 2.5% w / w stearic acid in a heated jacketed blender, as shown in item 209 and 215, at up to 250 degrees Fahrenheit for between 15 - 300 minutes to provide surface-treated type A BMA and surface-treated type B BMA with enhanced surface hydrophobicity, binder compatibility with polymeric matrices, interfacial adhesion, reduced moisture absorption, enhanced flowability, mechanical and impact properties. Surface-treated BMA can be further incorporated with binders to produce biomineral materials and product applications. In an embodiment, as shown in FIG. 8, biomarble, or biocalcite engineered stone composites have been made with BMA by incorporating Type A test BMA and Type B spine BMA separately with a thermoset binder to provide a product application with enhanced packing densities and binder interfacial adhesion, for use as architectural surfaces such as countertops, wall tiles, and flooring, that has a diversity of colors and patterns, with arange of properties including fluorescence, high compressive strength, moisture resistance, chemical resistance, and / or temperature resistance.

[0140]

[0125] All publications, patents, patent applications and other documents cited in this application are hereby incorporated by reference in their entireties for all purposes to the same extent as if each individual publication, patent, patent application or other document were individually indicated to be incorporated by reference for all purposes.

[0141]

[0126] While various specific embodiments have been illustrated and described, it will be appreciated that various changes can be made without departing from the scope of the invention(s) of the disclosure. The foregoing description is intended to be merely exemplary; numerous variations and modifications will be apparent to those skilled in the art. All such variations and modifications are intended to be within the scope of the present invention as defined in any appended claims.

Claims

CLAIMS1. A method for making a biomineral composition, the method comprising:receiving a set of calcareous organisms;drying the set of calcareous organisms;comminuting the set of calcareous organisms to produce a biomineral particle; andmodifying a surface of the biomineral particle to produce a surface-modified biomineral particle.

2. A method for making a biomineral composition, the method comprising:receiving a set of calcareous organisms;drying the set of calcareous organisms; andcomminuting the set of calcareous organisms to produce a biomineral particle.

3. The method according to claim 1 or 2, wherein receiving of calcareous organisms are comprised of sea urchins or oysters.

4. The method according to claim 1 or 2, further comprising, providing an antimicrobial treatment to the set of calcareous organisms.

5. The method according to any one of claims 1-3, further comprising, removing organic matter from the set of calcareous organisms.

6. The method according to any one of claims 1-4, further comprising, separating the calcareous organisms into a plurality of constituents.

7. The method according to any one of claims 1-5, wherein the drying step achieves a moisture target.

8. The method according to any of claims 1-7, further comprising adding a pigment enhancing agent to stabilize performance of a natural pigment contained in the biomineral particle.

9. A composition comprising, a dried comminuted biomineral particle produced according to the method of any one of claims 1-8.

10. The composition of claim 9, further comprising an antimicrobial component.

11. The method according to any one of claims 1-8, further comprising, separating a plurality of particles in the biomineral particle into weight fractions.

12. The method according to claim 11, further comprising making a blend of the weight fractions of the biomineral particle to produce a composition with a desired particle size distribution.

13. The method of claim 12, wherein the blend of weight fractions of the biomineral particle is tailored to optimize for a rheological, a mechanical, or a chemical property.

14. The method according to claims 12 or 13, wherein the blended weight fractions of the biomineral particle are mixed with a matrix material, to produce a biomineral material.

15. A composition comprising a dried comminuted biomineral particle with a controlled particle size distribution made in accordance with any one of claims 11-14.

16. A composition comprising an antimicrobial -treated dried comminuted biomineral particle with a controlled particle size distribution made according to any one of claims 1-8, or 11-14.

17. The method according to any one of claims 1-8 or 11-14, further comprising treating the biomineral particle with compounds that function as antioxidants and UV stabilizers.

18. The method according to any one of claim 1-8, 11-14 or 17, wherein the biomineral particle is subjected to surface treatments to promote compatibility with a material.

19. A composition comprising an antimicrobial -treated dried comminuted surface-modified biomineral particle with a controlled particle size distribution made according to any one of claims 1-8, 11-14, or 17-18.

20. The method according to any one of claims 1-8, 11-14, or 17-19, further comprising adding an antioxidant, a free radical scavenger, or an UV stabilizing mineral to the biomineral particle.

21. A composition comprising a dried comminuted surface-modified biomineral particle made according to any one of claims 1-8, 11-14 or 17-20.

22. The method according to any one of claims 1-8, 11-14 or 17-20, further comprising dissolving the biomineral particle in solvent bath to make a solution, and processing the solution by filtration, fractionation, centrifugation, or distillation to extract compounds and pigments contained within the biomineral particle.

23. The composition of any one of claims 9-10, 15-16, 19 or 21, wherein the particle is combined with a matrix material to form biomineral materials.

24. The composition of any one of claims 9-10, 15-16, 19, 21 or 23, wherein the composition is adapted for use in a product application.

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