Bio-building materials, methods for their manufacture, and articles containing them

Abstract

[0003] Disclosed herein is a transportable biocement comprising: a dehydrated microbial package, the microbial package comprising one or more microorganisms; a first binder, the first binder produced by the microorganisms, the microorganisms protecting themselves with a layer of the first binder; and the transportable biocement lacking water. Also disclosed herein is a method of producing a transportable dry composition, the method comprising blending together a microbial package, nutrients, and a liquid; activating the microbial package to produce the first binder; subjecting the microbial package to dehydration to form a transportable biocement; and blending the transportable biocement with an aggregate, the aggregate comprising a substrate, a second binder, and a liquid to form a bioconcrete.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 407,513, filed September 16, 2022, and U.S. Provisional Patent Application No. 63 / 466,040, filed May 12, 2023, which are incorporated by reference in their entireties.

[0002] Federal Government Support Statement This invention was made with government support under Grant No. HR0011-17-2-0039 awarded by the U.S. Department of Defense. The U.S. Government has certain rights in this invention. [Background technology]

[0003] The present disclosure relates to bio-building materials, methods for their manufacture, and articles comprising same. More specifically, the disclosure relates to biopolymers and biologically active mortars suitable for use in providing building materials with enhanced physical properties. Methods for making and using the disclosed materials are also disclosed.

[0004] Concrete is the most widely used construction material due to its resistance, durability, and low cost compared to other construction materials. Over 10 billion tons of concrete are used globally each year, and experts predict that concrete demand will likely grow to 16 billion tons by 2050. Current technologies used by the construction industry have adverse effects on the global environment and economy. The industrial process involved in producing cement from limestone (the precursor to concrete) consumes 2–3% of global energy demand and generates 0.73–0.99 tonnes of CO₂ per tonne of cement produced, accounting for approximately 8–10% of global anthropogenic CO₂ emissions and 3.4% of total global CO₂ emissions.

[0005] The increase in concrete consumption is a result of the susceptibility of infrastructure to physical, chemical, and biological factors such as temperature fluctuations, exposure to corrosive and radioactive materials, aggressive gases, natural disasters, and microbial activity. These factors cause micro-cracking that affects the mechanical and durability properties of concrete such as compressive strength, flexural strength, and permeability, resulting in a reduced service life of concrete and increased costs of infrastructure maintenance and repair. The global cost of concrete production is $60 / m 3 ~$75 / m 3 range, but the average cost of crack repair is about $130 / m 3 , indicating the high costs associated with maintaining and repairing concrete structures.

[0006] It is therefore desirable to develop new forms of concrete that minimize the amount of carbon dioxide released into the atmosphere. It is also desirable to produce concrete that is cheaper than what is currently produced. Summary of the Invention

[0007] Disclosed herein is a transportable biocement that includes a dehydrated microbial package, the microbial package including one or more microorganisms; a first binder, the first binder being produced by the microorganisms, the microorganisms protecting themselves with a layer of the first binder; and wherein the transportable biocement is devoid of water.

[0008] Also disclosed herein is a bioconcrete comprising: a dehydrated microbial package, the microbial package including one or more microorganisms; a first binder, the first binder being produced by the microorganisms, the microorganisms protecting themselves with a layer of the first binder; a substrate, the substrate serving as a site for bonding with the first binder produced by the microorganisms; and a second binder.

[0009] Also disclosed herein is a method of making a transportable dry composition, the method comprising blending together a microbial package, nutrients, and a liquid; activating the microbial package to produce a first binder; subjecting the microbial package to dehydration to form a transportable biocement; and blending the transportable biocement with aggregate, the aggregate comprising a base material, a second binder, and a liquid, to form a bioconcrete. [Brief explanation of the drawings]

[0010] [Figure 1] 1 illustrates one process for producing a dry composition. [Figure 2] 2 is a depiction of various embodiments of the steps of FIG. 1; [Figure 3] 2 is a depiction of some alternative embodiments of the steps of FIG. 1; [Figure 4] 1 illustrates another method for producing biocement. DETAILED DESCRIPTION OF THE INVENTION

[0011] Disclosed herein is an environmentally friendly dry composition (hereinafter, dry composition) that extracts carbon dioxide from the atmosphere to produce biocement that can be used in a variety of building and construction applications. The dry composition is available as a dry powder and includes a dehydrated microbial package that can be shipped to a manufacturing site where additional ingredients such as a substrate (also referred to as scaffolding), a binder, and a liquid medium (collectively referred to as aggregates) can be added to produce bioconcrete that can be used in construction projects (buildings, bridges, etc.).

[0012] FIG. 1 shows a process 100 for producing the dry composition and its conversion into a biocement that can be molded into a desired shape.

[0013] In process 102, microorganisms are first produced by promoting the growth and reproduction of microorganisms in a vat (or pool) with a first liquid medium and nutrients. The nutrients are consumed by the microorganisms (along with extracting carbon dioxide, nitrogen, and / or sulfur) from the atmosphere, undergo replication, and produce a first binder (which is described in the next process). The nutrients are listed later in this document.

[0014] The next process 104 involves biomineralization, in which the microorganisms produced above in process 102 are provided with a mineral source, such as calcium chloride, to produce a first binder. Note that process 102 (involving microbial replication and growth) can occur simultaneously and / or sequentially with biomineralization process 104. A pH adjusting component (e.g., sodium hydroxide) can be added during the biomineralization process. The pH adjusting agent can be added in an amount effective to promote the formation of a carbonate-based binder, as opposed to a bicarbonate-based binder. During this biomineralization process 104, the microorganisms extract carbon dioxide, nitrogen, and / or sulfur from the atmosphere to produce a first binder.

[0015] The biomineralization reactants are then subjected to a dehydration process 106 (removal of the first liquid medium) and a first granulation process 108 (also called ready mix) to produce a dry biomineralized microbial package (also called biocement) in process 108. During the dehydration process 106, the microorganisms may protect themselves with compounds that promote "dehydration tolerance." An example of a compound produced during the development of dehydration tolerance is trehalose. Trehalose can also be added exogenously to promote dehydration tolerance.

[0016] The biocement can then be packaged and shipped to a manufacturing site 110, where additional materials (collectively referred to as aggregates), such as an external binder (e.g., a (bio)polymer), a substrate (also referred to as a scaffold), and a second liquid medium, can be added to form bioconcrete 112. The bioconcrete can be activated in a process 114 when the second liquid medium contacts it. In a preferred embodiment, the second liquid medium is an aqueous medium. The external binder serves to bind the biomineralizing microbial packages together with the substrate to produce bioconcrete. The activated bioconcrete can then be molded into products that can be used in a variety of ways. Bioconcrete can be used to produce building blocks such as bricks, cinder blocks, and reinforced concrete columns.

[0017] The various processes from Figure 1 and Figures 2 and 3 are detailed below along with the materials used in the particular processes.

[0018] Growing algae102 and biomineralization104 As described above, in process 102 (see FIGS. 1, 2, and 3), microorganisms are allowed to replicate and grow. They do so by consuming nutrients and a first liquid medium to produce a binder. The microorganisms simultaneously extract gases from the atmosphere and use the gases to facilitate a reaction with the nutrients to produce a first binder. The microorganisms facilitate the production of the first binder.

[0019] In one embodiment, the microbial package may include multiple different microorganisms that consume nutrients and extract gases from the atmosphere to produce a first binder that can physically or chemically interact with the final substrate (added on-site as part of the aggregate) to bind the substrate particles together. In one embodiment, the microbial package includes a first microorganism that uses nutrients and extracts carbon dioxide from the atmosphere to produce a first binder. The microbial package may optionally include a second microorganism that uses nutrients and extracts nitrogen from the atmosphere to produce a second binder. The first and second microorganisms are different from each other.

[0020] The microbial package may optionally include a third microorganism that uses nutrients and extracts sulfur from the atmosphere to produce a third binder. Each of the various microorganisms consumes nutrients and extracts gases from the atmosphere to regenerate and promote the formation of the first binder. The formation of the binder is referred to as biomineralization. Regeneration (process 102) and biomineralization (process 104) can occur simultaneously or sequentially. Process 102, in which the microorganisms replicate, can occur in the same or a different location from where biomineralization (process 104) occurs. Biomineralization is a process in which microorganisms are stimulated to produce a binder.

[0021] The amount of replicates prior to biomineralization can be measured by culture density (e.g., grams of biomass per liter of culture, g / L). It is desirable to obtain the culture at as high a density as possible to promote the highest possible yield of biomineral in the subsequent production step. The greater the number of algal cells, the more sites available for CaCO3 nucleation / precipitation.

[0022] In one embodiment, the algae growth process and the biomineralization process are carried out in separate locations. This is done to prevent fouling of the photobioreactor.

[0023] The replication step (102) can be carried out for a period of 1 to 4 weeks, with the duration of replication being determined by the desired culture density, which is ultimately a function of algal growth rate.

[0024] The second step (104), involving biomineralization, can also be carried out over a period of time ranging from 2 hours to 7 days, with the selected period being determined based on yield, product quality, and turnover between batches.

[0025] When two or more microorganisms are present in a microbial package, the various binders produced by the individual (microbial) species can combine to produce a matrix that partially binds the substrates together to form a biocement. The matrix is ​​a combination of biocement and additional binders (e.g., (bio)polymers) added as part of the aggregate. This is discussed in more detail below.

[0026] In one embodiment, the various binders produced by each microorganism may undergo reactions with each other and / or with nutrients and / or with the substrate to produce reaction products (also referred to herein as precipitates) that become part of the final binder.

[0027] The binder (which may be a combination of the first binder, second binder, and reaction product listed above) acts as a partial matrix (together with a later-added external binder) to bind the substrate particles together with an external binder added later after the formation of the biocement, as will be described in more detail below.

[0028] The first microorganism preferably consumes carbon dioxide from the atmosphere to produce carbonate, which serves as the first precipitate in the binder. The microorganism may be a prokaryote or a eukaryote, particularly a bacterium, yeast, or algae, or a combination thereof. Examples of microorganisms include Pseudomonadota, Aquificota, Chlamydiota, Bacteroidota, Chlorobiota, Cyanobacteria, Fibrobacterota, Verrucomicrobiota, Planctomycetota, Spirochaetota, Acidobacteriota, Myxococcaceae, Zymomonas, Escherichia, or a combination thereof.

[0029] Of the above microorganisms, cyanobacteria are preferred. Examples of cyanobacteria that can be used in the dry composition include Chroococcales, Chroococcidiopsidales, Gloeobacterales, Nostocales, Oscillatoriales, Pleurocapsales, Spirulinales, Synechococcales, Incertae sedis, Gunflintia, Ozarkcollenia, Cyanothece, Synechocystis, or combinations thereof.

[0030] Examples of the species of the aforementioned microorganisms that can be used in the dry composition include Gloeobacter violaceus PCC 7421, Nostoc sp. PCC 7120, Prochlorococcus marinus MIT 9312, Prochlorococcus marinus MIT 9313, Prochlorococcus marinus NATL2A, Prochlorococcus marinus marinus CCMP 1375, Prochlorococcus marinus pastoris CCMP 1986, Synechococcus elongatus PCC 6301, Synechococcus elongatus PCC 7942, Prochlorococcus sp. CC9311, Prochlorococcus sp. CC9605, Prochlorococcus sp. CC9902, Synechococcus sp. JA-2-3B’a(2-13), Synechococcus sp. JA-3-3Ab, Prochlorococcus sp. WH8102, Synechocystis sp. PCC 6803, Thermosynechococcus elongatus BP-1, Trichodesmium erythraeum IMS101, Prochlorococcus marinus AS9601, Prochlorococcus marinus MIT 9301, Prochlorococcus marinus MIT 9303, Prochlorococcus marinus MIT 9515, Prochlorococcus marinus NATL1A, Synechococcus sp. RCC 307, Prochlorococcus sp. WH 7803, Prochlorococcus marinus MIT 9215, Acaryochloris marina MBIC11017, Prochlorococcus marinus MIT 9211, Cyanothece sp. BH68, ATCC 51142, Microcystis aeruginosa NIES-843, Synechococcus sp. PCC 7002, Nostoc punctiforme PCC 73102, Cyanothece sp. PCC7424, Cyanothece sp. PCC 7425, Cyanothece sp. PCC 8801, Cyanothece sp. PCC 8802, Cyanobacterium sp. UCYN-A, Anabaena variabilis ATCC 29413, Nostoc azollae 0708, Cyanothece sp. PCC 7822, Arthrospira platensis NIES-39, Synechocystis sp. GT-S, PCC 6803, Mastigocoleus testarum BC008, Crocosphaera watsonii WH 8501, Cyanobacterium stanieri PCC 7202, Geitlerinema sp. PCC 7407, Chroococcidiopsis thermalis PCC 7203, Halothece sp. PCC 7418, Nostoc sp. PCC 7107, Cyanobacterium aponinum PCC 10605, Gloeocapsa sp. PCC 7428, Stanieria cyanosphaera PCC 7437, Leptolyngbya sp. PCC 7376, Oscillatoria nigro-viridis PCC 7112, Calothrix sp. PCC 6303, Anabaena cylindrica PCC 7122, Pseudanabaena sp. PCC 7367, Crinalium epipsammum PCC 9333, Chroococcidiopsis sp. PCC 6712, Calothrix sp. PCC 7507, Planktothrix NIVA-CYA405, Planktothrix NIVA-CYA406, Planktothrix sp. NIVA-CYA407, Microcoleus vaginatus FGP-2, Planktothrix sp. NIVA CYA 15, Planktothrix agardhii NIVA-CYA 34, Planktothrix rubescens NIVA-CYA 98, Anabaena sp. PCC 7108, Spirulina subsalsa PCC 9445, Spirulina major PCC 6313, Synechococcus sp. PCC7336, Pseudanabaena species PCC 6802, Synechococcus species KORDI-49 (Genom pairing determination), Synechococcus species KORDI-52 (Genom pairing determination), Synechococcus species KORDI-100 (Genom pairing determination), Scystonema hofmanni UTEX 2349, Calothrix species PCC 7103, Synechococcus species WH 8016, Cyanothece species BH63E, ATCC 51472, Cyanobium gracile PCC 6307, Synechococcus species PCC 7502, Oscillatoria formosa PCC 6407, Oscillatoria acuminata PCC 6304, Synechococcus species PCC 6312, Microcoleus species PCC 7113, Prochlorothrix hollandica PCC 9006, Oscillatoria species PCC 10802, Dactylococcopsis salina PCC 8305, Pleurocapsa species PCC 7327, Pleurocapsa species PCC 7319, Cylindrospermum stagnale PCC 7417, Nodosilinea nodulosa PCC 7104, Microchaete species PCC 7126, Leptolyngbya boryana PCC 6306, Nostoc species PCC 7524, Leptolyngbya species PCC 7375, Geminocystis herdmanii PCC 6308, Calothrix desertica PCC 7102. Rivularia species PCC 7116, Oscillatoriales species JSC-12, Geitlerinema species PCC 7105, Chamaesiphon minutus PCC 6605, cyanobacterium PCC 7702, Fischerella species PCC 9431, Synechocystis species PCC 6803, PCC-N, Synechocystis species PCC 6803, GT-I, Fischerella species PCC 9605, Fischerella species PCC9339, Synechococcus sp. CC9616, Mastigocladopsis repens PCC 10914, Cyanobacterium sp. ESFC-1, Leptolyngbya sp. PCC 6406, Synechocystis sp. PCC 7509, Synechocystis sp. PCC 6803, PCC-P, Synechocystis sp. PCC 6803, Anabaena species 90, Synechocystis ADH, Zymomonas PDC, Escherichia coli-PAL2-FDC1, Escherichia coli HB101 / pBU11, Escherichia albertii, Escherichia fergusonii, Escherichia hermannii Escherichia marmotae[2], Escherichia vulneris, Pseudomonas D2, Pseudomonas F2, Myxococcus xanthus, Myxococcus xanthus DK 1622, Myxococcus xanthus DZ2, Myxococcus xanthus DZF1, Myxococcus xanthus New Jersey 2, Myxococcus xanthus DSM 16526, T. Bacillus sphaericus, Lysinibacillus sphaericus INQCS 414, and S. pasteurii MTCC 1761, or combinations thereof. Variants, serotypes, and mutations of the foregoing may also be used.

[0031] Green algae can also be used to promote biomineralization. Green algae are a diverse group of photosynthetic, eukaryotic organisms, including species with haplobionic and diplobionic life cycles. They are classified under the kingdom Plantae and are included in the Viridiplantae clade. Green algae include mostly unicellular, colonial flagellates with two flagella per cell, as well as various colonial, globular, and filamentous forms, and macroscopically multicellular marine algae. Approximately 22,000 species of green algae exist. Green algae have chloroplasts containing chlorophyll a and b, giving them their bright green color, and the accessory pigments beta-carotene (red-orange) and xanthophyll (yellow) in stacked thylakoids. Green algae cell walls usually contain cellulose, and they store carbohydrates in the form of starch. All green algae have mitochondria with flattened cristae. When present, paired flagella are used for cell movement. They are anchored by a crisscross system of microtubules and fibrous strands.

[0032] Species of green algae that can be used for biomineralization include members of the Prasinodermophyta, Palmophyllophyceae (prasinophyte clade VI), Prasinodermophyceae, Chlorophytina, Ulvophyceae, Chlorophyceae, Trebouxiophyceae, Chlorodendrophyceae, Pedinophyceae, Prasinophytes clade VIIA, Prasinophytes clade VIIC, Pycnococcaceae, Nephroselmidophyceae, Mamiellophyceae, Pyramimonadales, Streptophyta / Mesostigmatophyceae, Spirotaenia, Chlorokybophyceae, Streptofilum, Klebsormidiophyceae, Phragmoplastophyta, Charophyceae, Coleochaetophyceae, Zygnematophyceae, Mesotaeniaceae ss, or combinations thereof. Calcareous green algae belong to three groups: (1) Codiaceae, (2) Dasycladaceae, and (3) Charophyceae.

[0033] Examples of green algae include Chlorella vulgaris, Ulva lactuca, Caulerpa taxifolia, Nannochloropsis species, Chlamydomonas reinhardtii, Volvox carteri, Dunaliella salina, Chara species, Scenedesmus species, Cladophora species, and Trebouxia species, or combinations thereof.

[0034] The second microorganism that uses the nitrogen to produce the second binder is preferably a urease-producing prokaryotic or eukaryotic cell, in particular a bacterium, yeast, or algae, or a combination thereof.

[0035] Prokaryotic microorganisms can include cells of Sporosarcina pasteurii, Sporosarcina ureae, Proteus vulgaris, Bacillus sphaericus, Myxococcus xanthus, Proteus mirabilis, Helicobacter pylori, or variants, serotypes, mutations, or combinations thereof.

[0036] The first microorganism that produces the first binder using carbon dioxide is about 1 x 10 cells, based on the total weight of the dry composition. 4 ~1×10 12 cells, preferably 1 x 10 cells 6 ~1×10 10 cells, more preferably 1 x 10 cells 7 ~1×10 9 is present in the dry composition in an amount of

[0037] The second microorganism, if present, uses nitrogen to produce a second binder. The second microorganism that uses nitrogen to produce a second binder is present in an amount of 1×10 cells based on the total weight of the dry composition. 4 ~1×10 12 cells, preferably 1 x 10 cells 6 ~1×10 10 cells, more preferably 1 x 10 cells 7 ~1×10 9 is present in the dry composition in an amount of

[0038] The cell ratio of the first microorganism to the second microorganism is 1:6 to 9:1, preferably 1:2 to 8:1 in the environmentally friendly dry composition.

[0039] In one embodiment, the first binder produced by the first microorganism (which consumes carbon dioxide) is calcium carbonate. When initially produced, calcium carbonate can be in one of three crystalline forms: vaterite, aragonite, and calcite. Desirably, calcite forms the majority of the first binder. In one embodiment, calcium carbonate is present in the biocement in an amount of 0.1 to 51 wt. %, based on the total weight of the biocement. The biocement is the product produced after removal of the aqueous medium (i.e., after activation and precipitation).

[0040] The microorganisms produce the same end product, or "binder," which is calcium carbonate. In the first microorganism, the carbonic acid ultimately comes from atmospheric CO, bicarbonate, or carbonate. In the second microorganism, the carbonic acid ultimately comes from urea.

[0041] In one embodiment, the first binder produced by the second microorganism (which consumes urea) is calcium carbonate. When initially produced, calcium carbonate can be in one of three crystalline forms: vaterite, aragonite, and calcite. Desirably, calcite forms the majority of the first binder. In one embodiment, calcium carbonate is present in the biocement in an amount of 0.1 to 51 wt. % based on the total weight of the biocement. The biocement is the product produced after removal of the aqueous medium (i.e., after activation and precipitation). In one embodiment, the microorganism is present in the biocement in an amount of 0.01 to 25 wt. %; the first binder is present in the biocement in an amount of 0.01 to 75 wt. %; and the nutrient is present in the biocement in an amount of 0.01 to 10 wt. % based on the total weight of the biocement.

[0042] Nutrients Nutrients, along with gases from the atmosphere (carbon dioxide, nitrogen, etc.), are consumed by microorganisms to produce the first binder during the biomineralization process. As used herein, the term "nutrient" refers to any chemical compound or composition that provides for the growth or function of microorganisms. For example, in calcium-precipitating bacteria, the source of calcium is a nutrient. In polymer-forming bacteria, glucose may be the nutrient that the bacteria convert into polymeric materials. Cofactors that support bacterial viability (e.g., trace elements) are considered nutrients. The nutrient medium of the present disclosure includes components that provide for microbial growth and the fluidity of the biocement. Microbial growth materials include inorganic salts and a carbon source for microbial metabolism. Some of the nutrients can function as binders, and some of the binders can function as nutrients.

[0043] Suitable nutrients include inorganic salts, especially those containing calcium. The cations from these salts can include hydrogen, lithium, aluminum, barium, calcium, chromium (III), copper (I), copper (II), gold (I), gold (III), iron (II), iron (III), lead (II), lead (IV), magnesium, manganese (II), manganese (III), manganese (IV), potassium, molybdenum, cobalt, nickel, silicon, titanium, zirconium, silver, sodium, strontium, tin (II), tin (IV), zinc, or combinations thereof. Anions include chloride, sulfate, nitrate, nitrite, phosphate, borate, carbonate, bicarbonate, sulfite, bisulfite, boride, iodide, bromide, hydride, oxide, fluoride, sulfide, chloride, nitride, bromide, iodide, oxoanions, arsenate, phosphate, arsenite, hydrogen phosphate, dihydrogen phosphate, sulfate, nitrate, hydrogen sulfate, thiosulfate, sulfite, perchlorate, iodate, chlorate, bromate, chlorite, hypochlorite, hypobromite, carbonate, chromate, hydrogen carbonate or bicarbonate, dichromate, anions from organic acids (e.g., acetate, formate, etc.), cyanide, amide, cyanate, peroxide, thiocyanate, oxalate, hydroxide, permanganate, or combinations thereof.

[0044] Calcium salts are preferred. In one embodiment, the binder precipitated by the microorganisms may react with other nutrients to form reaction products that are present as part of the binder.

[0045] Non-limiting examples of inorganic components that may be used as nutrients include CO2, NaCl, KCl, MgSO4, CaCl2, NaNO3, KH2PO4, H3BO4, ZnCl2, MoO3, MnCF4, CoCl2, ammonia, ammonium, ammonium phosphate, ammonium carbonate, diammonium phosphate, calcium acetate, calcium phosphate, calcium carbonate, sodium carbonate, sodium bicarbonate, calcium lactate, calcium nitrate, or combinations thereof.

[0046] Non-limiting examples of organic components include organic acids (acetic acid) and their salts, tris(hydroxymethyl)aminomethane and its salts, ethylenediaminetetraacetic acid and its salts, glucose, galactose, fructose, and the like.

[0047] The nutrients are added in an amount of 0.0000001 to 10 weight percent based on the weight of the liquid medium, nutrients, and microorganisms based on the total weight of the biomineralizing microorganism package, which is the weight of the package prior to drying (dehydration) of the package.

[0048] liquid medium A liquid medium is added to a plurality of microorganisms along with nutrients to promote growth and reproduction of the microorganisms to form a microbial package. The liquid medium is preferably an aqueous medium. Other non-aqueous liquids may also be used to promote microbial growth. The non-aqueous liquid may or may not be compatible with the aqueous medium.

[0049] In a preferred embodiment, the liquid medium is water. Other organic liquids, such as alcohol, can be added to the mixture of microorganisms and nutrients. Examples of suitable alcohols include ethanol, propanol, butanol, etc., or combinations thereof.

[0050] The liquid medium is added in an amount of 90 to 99.99999 weight percent based on the weight of the liquid medium, nutrients, and microorganisms based on the total weight of the biomineralizing microorganism package, which is the weight of the package prior to drying (dehydration) of the package.

[0051] Dehydration 106, biocement formation 108, and biocement transport 110 The biomineralized microbial package produced in the biomineralization process 104 is then subjected to drying or dehydration 106 to remove the liquid medium (e.g., water and / or alcohol), leaving the microorganisms with the binder (e.g., the binder can include a first binder, a second binder, and / or a third binder). As noted above, during dehydration, the microorganisms can be protected with chemical compounds and are referred to herein as dehydration-resistant. The chemical compounds can be produced endogenously by the microorganisms or can be provided exogenously. The biomineralized microbial package when dried is also referred to as a dried biomineralized microbial package.

[0052] Drying can be done by freeze drying, drum drying, spray drying, or other methods. Drying can be done at elevated temperatures (via spray drying) by spraying the ingredients into an area of ​​elevated temperature. Spray drying is a method of forming a dry powder from a liquid or slurry by generating small droplets in a chamber at elevated temperature. The elevated temperature is low enough and the residence time of the droplets short enough so as not to damage or destroy microorganisms, but high enough to promote evaporation of water. Spray drying equipment can use several types of atomizers or atomizing nozzles that disperse the liquid or slurry into a controlled droplet size spray.

[0053] Drying of the composition can also include lyophilization, where a liquid or slurry is converted to a dry powder via freeze-drying. Freeze-drying, also known as lyophilization or low-temperature dehydration, is a low-temperature dehydration process that involves freezing the product, reducing the pressure, and removing the ice by sublimation.

[0054] The dried biomineralized microorganism package is then subjected to optional grinding 108 to form a powdered biocement. The dried biomineralized microorganisms may be ground prior to or during the blending process to break down any aggregates. Grinding can be performed in a ball mill, Henschel mixer, Waring blender, kneader, or the like, which apply shear and tensile forces to the dry composition. Additionally, the components of the dry composition may be dried to remove any moisture. Thus, the biocement contains microorganisms surrounded by a first binder that has been ground or powdered to a specific size. Biocement is also referred to as a ready mix. Grinding promotes homogeneous distribution during the formation of the bioconcrete.

[0055] The availability of the composition (biocement) as a dry powder is advantageous because it can be sold as a lightweight kit that can be transported to the site of use and activated on-site for use, where one or more of additional microorganisms, additional binders (e.g., synthetic and / or biopolymers capable of nucleating any of the biominerals), substrate (e.g., sand) can be added to the dry composition along with a second liquid medium.

[0056] This allows for lighter materials to be transported to the point of use, reducing costs and resulting in lower fuel consumption. Because the material is activated and used at room temperature without external heating, it also results in energy savings and reduced pollution in the form of reduced emissions of carbon dioxide, which are typically released into the atmosphere when energy (especially in the form of electricity) is generated. Therefore, this process is environmentally friendly in that it facilitates the removal of carbon dioxide from the atmosphere to produce biocement.

[0057] The homogenous biocement can then be packaged and transported to a site for further processing 110. The site (where further operations occur) is generally far away from where the original operations (processes 102-110) occurred.

[0058] Formation of Bioconcrete112 and Activation of Bioconcrete114 Further operations were performed (again with reference to Figures 1, 2, and 3) including mixing the aggregate with biocement to form bioconcrete, which is shown in Figure 1 as process 112. After the bioconcrete is formed, it can be activated and molded into blocks that can be used for construction purposes, among other things.

[0059] The aggregate comprises a base material (also called a scaffold), a binder, an additional binder (e.g., a (bio)polymer), and an additional liquid (which may be a second liquid). The aggregate is mixed with biocement to form bioconcrete. Various materials that may be used for the aggregate are detailed below.

[0060] Base material The substrate (or scaffold) forms the majority of the bioconcrete and is therefore preferably an inexpensive material, and preferably a lightweight material. In one embodiment, the substrate may be inert to the binder. In another embodiment, the substrate may undergo a reaction with the first and / or second binder. The reaction may involve the formation of a covalent or ionic bond between the binder and the substrate. The substrate provides reinforcement to the biocement. Therefore, it is desirable that the substrate be inert to the atmosphere and its contents (e.g., oxygen and moisture). The substrate is preferably uniformly dispersed throughout the binder and may be in the form of particles, fibers, or a combination thereof.

[0061] The binder produced by the microorganisms, along with additional binders (e.g., (bio)polymers) added as part of the aggregate, contacts the substrate and binds the substrates together. The binder forms the matrix of the biocement, even though it is not a major part of the bioconcrete. The substrate can be electrically inert or conductive. Conductive fillers can be added to the biocement in an amount effective to make the biocement conductive. Conductive biocement can be used in buildings where static dissipation and / or electromagnetic shielding are desired.

[0062] Ceramic substrate Suitable particulate substrates include ceramics, metals, polymers, or combinations thereof. Ceramic substrates include metal oxides (e.g., sand, silica, fumed silica, alumina, fumed alumina, titania, zirconia, ceria, metal oxide aerogels, etc., or combinations thereof), metal carbides, metal nitrides, metal borides, metal silicides, metal oxycarbides, metal oxynitrides, metal boron nitrides, metal carbonitrides, metal borocarbides, etc., or combinations thereof. Examples of ceramics that can be used as substrates include silicon dioxide, aluminum oxide, aluminum silicate, calcium hydrate, aluminum hydrate, titanium dioxide, indium tin oxide, antimony tin oxide, cerium oxide, cadmium oxide, titanium nitride, silicon nitride, aluminum nitride, titanium carbide, silicon carbide, titanium niobium carbide, stoichiometric silicon borides (e.g., SiB n , n=14, 15, 40, etc.) (e.g., silicon triboride, SiB3, silicon tetraboride, SiB4, silicon hexaboride, SiB6, etc.), or combinations thereof. A preferred ceramic substrate is sand.

[0063] The ceramic substrate may have a size of 10 nanometers to 5000 micrometers, preferably 100 nanometers to 2000 micrometers, and more preferably 150 nanometers to 1500 micrometers.

[0064] carbon black Carbon black may also be used in the composition. A preferred conductive carbon black also has a viscosity of about 200 square meters per gram (m 2 / g), preferably about 400m 2 / g, and even more preferably about 1000m 2 / g. Preferred conductive carbon blacks have a surface area of ​​about 40 cubic centimeters per 100 grams (cm 3 / 100g), preferably about 100cm 3 / 100g or more, more preferably about 150cm 3The carbon black may have a pore volume (dibutyl phthalate absorption) of greater than 1 / 100 g. Exemplary carbon blacks include those commercially available from Columbian Chemicals under the trade name Conductex®, acetylene black available from Chevron Chemical under the trade names SCF (Super Conductive Furnace) and ECF (Electric Conductive Furnace), carbon black available from Cabot Corp. under the trade names Vulcan XC72 and Black Pearls, and carbon black available from Akzo Co. Ltd. under the trade names Ketjen Black EC300 and EC600. Preferred carbon blacks are those having an average particle size of less than about 100 nm, preferably less than about 70 nm, and more preferably less than about 50 nm. Preferred carbon blacks may be used in an amount of about 0.1 wt. % to about 50 wt. %, preferably 5 to 40 wt. %, based on the total weight of the environmentally friendly dry composition.

[0065] Solid conductive metal fillers may also be optionally used in the composition. Metals such as aluminum, copper, magnesium, chromium, tin, nickel, silver, iron, titanium, and mixtures containing any one of the foregoing metals may be incorporated into the composition as conductive fillers. Physical mixtures and true alloys such as stainless steel and bronze may also function as conductive filler particles. In addition, some intermetallic chemical compounds of these metals, such as borides and carbides (e.g., titanium diboride), may also function as conductive filler particles. Solid non-metallic conductive filler particles, such as tin oxide and indium tin oxide, may also be optionally added to reinforce the composition or to make it conductive.

[0066] In some embodiments, the size (e.g., average size, median size, or minimum size) of the metal fillers along one or two major dimensions can be at least 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 7000 μm, 800 μm, 900 μm, 1,000 μm, or more. For example, in some embodiments, the size (e.g., average size, median size, or minimum size) of the elements can be in the range of 1 μm to 1,000 μm, or any subrange thereof, such as 1 μm to 600 μm.

[0067] In some embodiments, the size of the elements can be relatively uniform, for example, in some embodiments, more than 50%, 60%, 70%, 80%, 90%, 95%, 99%, or more of the elements can have a size along one or two major dimensions that is within 10% of the average size of the elements.

[0068] Functionalizing the particulate substrate generally involves surface treatment. Surface treatment can be carried out by any suitable technique, such as those described herein or known in the art. The functional group applied to the particulate substrate can be selected to promote adhesion between other components of the composition and the substrate. For example, in various embodiments, the functional group can include a carboxyl group, a carbonyl group, an ester group, a hydroxyl group, an amine group, a silane group, a thiol group, a phosphate group, or a combination thereof.

[0069] In some embodiments, the surface treatment of the particulate substrate comprises a thin polymer layer disposed on the substrate that promotes adhesion of the active material to the network. In some such embodiments, the thin polymer layer comprises a self-assembled and / or self-limiting polymer layer. In some embodiments, the thin polymer layer bonds to the components of the composition, for example, via hydrogen bonding.

[0070] Glass beads and crushed glass Glass beads or crushed glass can also be used to reinforce the composition. The glass beads or crushed glass can include SiO2, B2O3, P2O5, GeO2, TeO2, As2O3, Al2O3, TiO2, ZrO2, VO5, or a combination thereof. The average size of the glass beads or crushed glass can range from 1 micrometer to 5 millimeters, preferably 10 micrometers to 2.5 millimeters. The glass beads or crushed glass can also be coated with a polymer to make it compatible with the composition.

[0071] Particulates in the form of carbon black, glass beads, etc. may be added to the composition in an amount of 0.5 to 60% by weight, preferably 1 to 50% by weight, preferably 2 to 40% by weight, more preferably 3 to 20% by weight, based on the weight of the environmentally friendly dry composition.

[0072] Fiber fillers The substrate can also be in the form of fibers. The fibers can include carbon nanotubes, textile fibers, carbon fibers, glass fibers, metal fibers, and the like.

[0073] The fibers can have diameters in the nanometer size range (2 to 100 nanometers) or the micrometer range (101 nanometers to 500 micrometers). Examples of fibers in the nanometer size range include nanotubes (e.g., carbon nanotubes (single-walled carbon nanotubes (SWNTs), double-walled carbon nanotubes (DWNTs), multi-walled carbon nanotubes (MWNTs), vapor-grown carbon fibers, silicon nanotubes, etc.), metal nanorods or nanowires (e.g., silicon, copper, silver, nickel, etc.), and metal oxide nanorods and nanowires (e.g., titanium dioxide nanowires, alumina nanowires, silica nanowires, vananium oxide nanowires, nickel oxide nanowires, iron oxide nanowires, tungsten oxide nanowires, etc.). Combinations of the aforementioned nanowires, nanotubes, and nanorods can also be used in the environmentally friendly dry composition (and in the biocement).

[0074] The fibers may have an average aspect ratio of greater than 3, preferably greater than 5, preferably greater than 10, preferably greater than 100, preferably greater than 1000 up to a value of 100,000. The aspect ratio is the ratio of the major dimension (e.g., length) to the minor dimension (e.g., diameter or width) of the fiber.

[0075] The SWNTs used in the compositions can be produced by laser evaporation of graphite, carbon arc synthesis, or the high-pressure carbon monoxide conversion process (HIPCO). These SWNTs typically have a single wall comprising graphene sheets with an outer diameter of about 0.7 to about 2.4 nanometers (nm). SWNTs with aspect ratios of about 5 or greater, preferably about 100 or greater, and more preferably about 1000 or greater, are typically utilized in the compositions. SWNTs are typically closed structures with hemispherical caps at each end of each tube, although it is contemplated that SWNTs with a single open end or both open ends may also be used. SWNTs are typically hollow but contain a central portion that may be filled with amorphous carbon.

[0076] In an exemplary embodiment, the goal of dispersing SWNTs in an organic polymer is to disentangle the SWNTs to obtain an effective aspect ratio that is as close as possible to that of the SWNTs. The ratio of the effective aspect ratio to the aspect ratio is a measure of the effectiveness of the dispersion. The effective aspect ratio is twice the radius of gyration of a single SWNT divided by the outer diameter of each individual nanotube. It is generally desirable for the average ratio of the effective aspect ratio to the aspect ratio to be greater than or equal to about 0.5, preferably greater than or equal to about 0.75, and more preferably greater than or equal to about 0.90, as measured in electron micrographs at magnifications of about 10,000 or greater.

[0077] In one embodiment, SWNTs can exist in the form of rope-like aggregates. These aggregates, commonly referred to as "ropes," form as a result of van der Waals forces between individual SWNTs. Individual nanotubes in the rope can slide relative to each other and rearrange themselves within the rope to minimize free energy. Typically, the ratio is 10 to 10. 5Ropes having nanotubes can be used in the composition. Within this range, it is generally desirable to have ropes having greater than or equal to about 100 nanotubes, preferably greater than or equal to about 500 nanotubes. Also desirable are ropes having less than or equal to about 10 nanotubes, preferably less than or equal to about 5,000 nanotubes.

[0078] In yet another embodiment, it is desirable for SWNT ropes to connect to each other in the form of branches after dispersion. This results in the ropes sharing between the branches of the SWNT network (or carbon nanotube network), forming a three-dimensional network in the organic polymer matrix. Distances of about 10 nm to about 10 micrometers can separate the branch points in this type of network. SWNTs have an intrinsic thermal conductivity of at least 2000 watts per meter Kelvin (W / mK), while SWNT ropes have an intrinsic thermal conductivity of at least 1000 watts per meter Kelvin (W / mK). 4 It is generally desirable for the SWNTs to have an intrinsic conductivity of at least 80 gigapascals (GPa) and a stiffness of at least about 0.5 talapascals (TPa).

[0079] In another embodiment, the SWNTs can include a mixture of metallic nanotubes and semiconducting nanotubes. Metallic nanotubes exhibit electrical properties similar to metals, while semiconducting nanotubes are electrically semiconducting. Generally, the way graphene sheets are rolled produces nanotubes with various helical structures. Zigzag and armchair nanotubes constitute two possible configurations. To minimize the amount of SWNTs utilized in the composition, it is generally desirable for the composition to contain a high proportion of metallic SWNTs. It is generally desirable for the SWNTs used in the composition to contain metallic nanotubes in an amount of about 1 wt.% or more, preferably about 20 wt.% or more, more preferably about 30 wt.% or more, even more preferably about 50 wt.% or more, and most preferably about 99.9 wt.% or more of the total weight of the SWNTs. In certain circumstances, it is generally desirable for the SWNTs used in the composition to comprise semiconducting nanotubes in an amount of about 1 wt. % or more, preferably about 20 wt. % or more, more preferably about 30 wt. % or more, even more preferably about 50 wt. % or more, and most preferably about 99.9 wt. % or more of the total weight of the SWNTs.

[0080] SWNTs, if desired, are typically used in an amount of about 0.001 to about 80 wt.% of the total weight of the composition. Within this range, SWNTs are typically used in an amount of about 0.25 wt.% or more, preferably about 0.5 wt.% or more, and more preferably about 1 wt.% or more of the total weight of the composition. Furthermore, SWNTs are typically used in an amount of about 30 wt.% or less, preferably about 10 wt.% or less, and more preferably about 5 wt.% or less of the total weight of the environmentally friendly dry composition (and biocement).

[0081] Nano-sized conductive fillers are those having at least one dimension of about 1,000 nm or less. Nano-sized conductive fillers can be one-, two-, or three-dimensional and can exist in the form of powders, drawn wires, strands, fibers, tubes, nanotubes, rods, whiskers, flakes, laminates, platelets, ellipsoids, discs, spheroids, etc., or a combination comprising at least one of the foregoing forms. They can also have fractional dimensions and exist in the form of mass or surface fractals.

[0082] Suitable examples of nano-sized conductive fillers (also referred to herein as high aspect ratio carbon elements) are multi-walled carbon nanotubes (MWNTs), vapor-grown carbon fibers (VGCFs), carbon black, graphite, conductive metal particles, conductive metal oxides, metal-coated fillers, nano-sized conductive organic / metallic fillers, conductive polymers, and the like, as well as combinations comprising at least one of the foregoing nano-sized conductive fillers.

[0083] MWNTs derived from processes not specifically directed to the production of SWNTs, such as laser ablation and carbon arc synthesis, can also be used in the compositions. MWNTs have at least two graphene layers bonded around an internal hollow core. Hemispherical caps typically close both ends of the MWNT, but it may be desirable to use MWNTs with only one hemispherical cap, or MWNTs lacking both caps. MWNTs generally have diameters of about 2 to about 50 nm. Within this range, it is generally desirable to use MWNTs with diameters of about 40 nm or less, preferably about 30 nm or less, and more preferably about 20 nm or less. When MWNTs are used, they preferably have an average aspect ratio of about 5 or greater, preferably about 100 or greater, and more preferably about 1000 or greater.

[0084] MWNTs, if desired, are typically used in an amount of about 0.001 to about 50 wt.% of the total weight of the composition. Within this range, MWNTs are typically used in an amount of about 0.25 wt.% or more, preferably about 0.5 wt.% or more, and more preferably about 1 wt.% or more of the total weight of the composition. Furthermore, MWNTs are typically used in an amount of about 30 wt.% or less, preferably about 10 wt.% or less, and more preferably about 5 wt.% or less of the total weight of the composition.

[0085] Steam-grown carbon fiber Steam-grown carbon fibers or small graphitic or partially graphitic carbon fibers, also known as vapor-grown carbon fibers (VGCFs), can also be used, having diameters of about 3.5 to about 100 nanometers (nm) and aspect ratios of about 5 or greater. These vapor-grown carbon fibers typically contain an amorphous coating on the outer surface of the graphitic carbon fiber. When VGCFs are used, diameters of about 3.5 to about 70 nm are preferred, with diameters of about 3.5 to about 50 nm being more preferred, and diameters of about 3.5 to about 25 nm being most preferred. They also preferably have an average aspect ratio of about 100 or greater, more preferably about 1000 or greater.

[0086] VGCF, if desired, is generally used in an amount of about 0.001 to about 50 wt.% of the total weight of the composition. Within this range, VGCF is generally used in an amount of about 0.25 wt.% or more, preferably about 0.5 wt.% or more, and more preferably about 1 wt.% or more of the total weight of the composition. Furthermore, VGCF is generally used in an amount of about 30 wt.% or less, preferably about 10 wt.% or less, and more preferably about 5 wt.% or less of the total weight of the high aspect ratio conductive element.

[0087] Both SWNTs and other carbon nanotubes (i.e., MWNTs and VGCFs) utilized as high aspect ratio carbon elements can also be derivatized with functional groups to improve compatibility and facilitate mixing with microorganisms and nutrients. SWNTs and other carbon nanotubes can be functionalized either on the graphene sheets that make up the sidewalls, on the hemispherical caps, or on both the sidewalls and the hemispherical end caps. Functionalized SWNTs and other carbon nanotubes can be functionalized with a group having the formula [C n H L ]R m wherein n is an integer, L is a number less than 0.1n, m is a number less than 0.5n, each R is the same, and each R is selected from the group consisting of -SO3H, -NH2, -OH, -C(OH)R', -CHO, -CN, -C(O)Cl, -C(O)SH, -C(O)OR', -SR', -SiR3', -Si(OR') y R′ (3-y), -R", -AlR2', haloid, ethylenically unsaturated functionality, epoxide functionality, etc., where y is an integer less than or equal to 3, R' is hydrogen, alkyl, aryl, cycloalkyl, alkaryl, aralkyl, cycloaryl, poly(alkyl ether), bromo, chloro, iodo, fluoro, amino, hydroxyl, thio, phosphino, alkylthio, cyano, nitro, amido, carboxyl, heterocyclyl, ferrocenyl, heteroaryl, fluoro-substituted alkyl, ester, ketone, carboxylic acid, alcohol, fluoro-substituted carboxylic acid, fluoro-alkyl-triflate, etc., and R" is fluoroalkyl, fluoroaryl, fluorocycloalkyl, fluoroaralkyl, cycloaryl, etc. Carbon atoms, C n is the surface carbon of the carbon nanotube. For both uniformly and non-uniformly substituted SWNTs and other carbon nanotubes, the surface atoms C n reacts.

[0088] Non-uniformly substituted SWNTs and other carbon nanotubes can also be used in the conductive precursor compositions and / or conductive compositions, including compositions of formula (I) above, where n, L, m, R, and SWNT itself are as defined above, except that each R does not contain oxygen or when each R is an oxygen-containing group, COOH is absent.

[0089] Also included are functionalized SWNTs and other carbon nanotubes having the formula: [ka] where n, L, m, R″, and R have the same meaning as above. Most of the carbon atoms in the surface layer of the carbon nanotube are basal plane carbons. Basal plane carbons are relatively inert to chemical attack. For example, at defect sites where the graphitic plane cannot extend completely around the carbon nanotube, carbon atoms similar to the edge carbon atoms of the graphitic planes exist. Edge carbons are reactive and must contain some heteroatoms or groups to satisfy the carbon valence.

[0090] The above-described substituted SWNTs and other carbon nanotubes can be advantageously further functionalized. Such SWNT compositions include those of the formula: [ka] wherein n, L, and m are as defined above; A is selected from -OY, -NHY, -CR'-OY, -C(O)OY, -C(O)NR'Y, -C(O)SY, or -C(O)Y; and Y is a suitable functional group of a protein, peptide, enzyme, antibody, nucleotide, oligonucleotide, antigen, or enzyme substrate, enzyme inhibitor, or transition state analogue of an enzyme substrate; or -R'OH, -R'NH, -R'SH, -R'CHO, -R'CN, -R'X, -R'SiR', -RSi-(OR') y -R′ (3-y) , -R′Si-(O-SiR′2)-OR′, -R′-R″, -R′-NCO, (C2H4O) w Y, -(C3H6O) w H, -(C2H4O) w R′, −(C3H6O) w R', or -(C3H6O) w R′ and R″ are selected from the group consisting of: R′, ...′, R′′′′, R′′′′ and R′′′′′′′”)”)”)”)”)”)”)”)”)”)”)”)”)”)”)”)”)”)”)”)”)”)”. R′ is selected from the group consisting of: R′, R′′, R′′′

[0091] Functionalized SWNTs of the structure shown immediately above and other carbon nanotubes can also be functionalized to produce SWNT compositions having the formula: [ka] wherein n, L, m, R', and A are as defined above.

[0092] The conductive precursor compositions and / or conductive compositions may also include SWNTs and other carbon nanotubes to which certain cyclic compounds are adsorbed. These include SWNT compositions of matter of the formula: [ka] wherein n is an integer, L is a number less than 0.1n, m is less than 0.5n, a is 0 or a number less than 10, X is a polynuclear aromatic or polyheteronuclear aromatic moiety, and R is as defined above. Preferred cyclic compounds are planar macrocycles such as liporphyrins and phthalocyanines.

[0093] The adsorbed cyclic compounds can be functionalized. Such SWNT compositions include compounds of the formula: [ka] where m, n, L, a, X, and A are as defined above, and the carbon is on SWNTs or other nanotubes such as MWNTs, VGCF, etc.

[0094] Without being bound by any particular theory, functionalized SWNTs and other carbon nanotubes are better dispersed in the dry environmentally friendly composition (and biocement) because the modified surface properties may make the carbon nanotubes more compatible with organic polymers, or because the modified functional groups (particularly hydroxyl or amine groups) directly bond to the organic polymer as end groups. In this way, organic polymers such as polycarbonate, polyamide, polyester, polyetherimide, etc., directly bond to the carbon nanotubes, thus facilitating dispersion of the carbon nanotubes due to their improved adhesion to the organic polymer when the organic polymer is dispersed in the dry environmentally friendly composition (and biocement).

[0095] Functional groups can generally be introduced onto the exterior surfaces of SWNTs and other carbon nanotubes by contacting the exterior surfaces of the SWNTs and other carbon nanotubes with a strong oxidizing agent for a period of time sufficient to oxidize the surface, and then further contacting the exterior surfaces with a reactant suitable for attaching functional groups to the oxidized surface. A preferred oxidizing agent comprises a solution of an alkali metal chlorate in a strong acid. A preferred alkali metal chlorate is sodium chlorate or potassium chlorate. A preferred strong acid used is sulfuric acid. A period of time sufficient for oxidation is from about 0.5 hours to about 24 hours.

[0096] Polymer fibers, glass fibers, and carbon fibers Woven fibers, nonwoven fibers, or combinations thereof may be added to the composition. The woven and nonwoven fibers can be mineral fibers, plant fibers, synthetic fibers, or combinations thereof. Exemplary woven and nonwoven fibers include glass fibers, glass wool fibers, mineral wool fibers, slag wool fibers, stone wool fibers, basalt fibers, silica fibers, quartz fibers, alumina fibers, steel fibers, silicon carbide fibers, acrylic fibers, carbon fibers, melamine fibers, cotton fibers, jute fibers, kenaf fibers, bamboo fibers, abaca fibers, hemp fibers, linen fibers, flax fibers, or combinations thereof. Woven and nonwoven fibers can also be made from polymers. A combination of two or more nonwoven fibers can be used. The nonwoven fibers can be carbon fibers. A preferred fiber is abaca fiber.

[0097] The glass fibers can be E, A, C, ECR, R, S, D, or NE glass, etc., or combinations thereof. The glass fibers can be made by standard processes, such as steam or air blowing, flame blowing, and mechanical pulling. An exemplary glass fiber is made by mechanical pulling.

[0098] The glass fibers have a diameter of about 1 to 30 micrometers, preferably 5 to 20 micrometers.

[0099] Carbon fibers are approximately 1 to 30 micrometers in diameter and are composed mostly of carbon atoms. They have several advantages: high stiffness, high tensile strength, high strength-to-weight ratio, high chemical resistance, high temperature resistance, and low thermal expansion. These properties have made them very popular in aerospace, civil engineering, the military, motorsports, and other competitive sports. Depending on the precursor from which the fibers are made, carbon fibers can be turbostratic or graphitic, or they can have a hybrid structure in which both graphitic and turbostratic portions are present. In turbostratic carbon fibers, the sheets of carbon atoms are folded or crumpled together in a disordered manner. Carbon fibers derived from polyacrylonitrile (PAN) are turbostratic, while carbon fibers derived from mesophase pitch are graphitic after heat treatment at temperatures above 2200°C. Turbostratic carbon fibers tend to have high ultimate tensile strength, while carbon fibers derived from heat-treated mesophase pitch have a high Young's modulus (i.e., high stiffness or resistance to elongation under load) and high thermal conductivity.

[0100] The fibers disclosed above can be continuous or chopped. Fibers in the form of chopped strands can have lengths of 0.3 millimeters (mm) to 10 centimeters (cm), or 0.5 mm to 5 cm, or 1.0 mm to 2.5 cm. For example, the fibers can have lengths of 0.2 to 20 mm, or 0.2 to 10 mm, or 0.7 to 7 mm. The fibers can have any cross-section, such as a circular (or annular), flat, or irregular cross-section. For example, the fibers have a circular cross-section. The diameter of the fibers can be 1 to 25 micrometers (μm), or 3 to 20 μm, or 4 to 18 μm, or 5 to 17 μm. For example, the fibers can be short glass fibers having a diameter of 10 μm. Flat glass or bilobed fibers can be used, for example, to provide low-torsion, high-strength articles.

[0101] Woven and / or nonwoven fibers can be treated or coated with a binder containing binder-reactive functional groups to form a reactive fiber system. For example, the reactive fiber system can be a wet-laid mat of nonwoven fibers and binder. The selection of binder is not particularly limited, provided that the binder compound contains binder-reactive functional groups. The binder-reactive functional groups can be hydroxyl, carboxyl, carboxylic acid anhydride, haloformyl, epoxy, silanol, amino, mercapto, vinyl, or combinations thereof. The binder-reactive functional groups and corresponding binder compounds can be selected based on the thermoplastic polymer of the reactive polymer composition and its associated reactivity. Commercially available fiber / binder systems can be used.

[0102] The aforementioned fibrous fillers can be used in the eco-friendly dry composition (and bio-composition) in an amount of 0.5 to 90 wt. %, preferably 1 to 85 wt. %, preferably 5 to 82 wt. %, and more preferably 20 to 80 wt. % based on the weight of the eco-friendly dry composition (and biocement). Solids, as defined herein, exclude any volatile materials that can evaporate from the composition. Particulate substrates can be combined with the fibrous substrate in the eco-friendly dry composition (and biocement).

[0103] It should be noted that the substrate can be added to the environmentally friendly dry composition in several batches. A first batch of substrate can be added to the composition (microorganisms and nutrients) to cause the microorganisms to produce a binder with the first batch of substrate. Then, after the microorganisms have produced the binder, a second batch of substrate can be added to the composition.

[0104] The fibrous substrate may be added to the composition in a second batch after the binder has been produced by the microorganisms. The fibrous substrate may be added to the composition to provide strength and ductility to the composition.

[0105] The substrate may be added to the environmentally friendly dry composition (and biocement) in an amount of 0.5 to 90 wt. %, preferably 20 to 85 wt. %, preferably 40 to 83 wt. %, more preferably 50 to 80 wt. %, based on the total weight of the bioconcrete.

[0106] External Secondary Binder Polymer additives, impact modifiers, gels As described above, in addition to the first binder (e.g., calcium carbonate), an additional externally added binder (external second binder) can be added as part of the aggregate. This second binder is an external binder because it is not produced by the microorganisms in the microbial package. The external second binder, described below, binds the substrate (scaffold) together with the microbial package. The external second binder can interact with the first binder to bind to the substrate.

[0107] The external second binder can be an organic polymer, a gelling agent, a hydrogel, an impact modifier, recycled tires, or a combination thereof.

[0108] The organic polymer can be selected from a wide variety of thermoplastic polymers, blends of thermoplastic polymers, thermosetting polymers, or blends of thermoplastic and thermosetting polymers. The organic polymer can also be a polymer, copolymer, terpolymer, or blend of a combination comprising at least one of the aforementioned organic polymers. The organic polymer can also be an oligomer, homopolymer, copolymer, block copolymer, alternating block copolymer, random polymer, random copolymer, random block copolymer, graft copolymer, star block copolymer, dendrimer, polyelectrolyte (polymer having some repeating groups containing electrolytes), polyampholyte (polyelectrolyte having both cationic and anionic repeating groups), ionomer, etc., or a combination comprising at least one of the aforementioned organic polymers. The organic polymer has a number average molecular weight greater than 10,000 grams per mole, preferably greater than 20,000 g / mol, and more preferably greater than 50,000 g / mol.

[0109] Various polymers are listed below: Polymer additives can be added in the form of particles, films, solutions, and suspensions to impart strength and ductility, resistance to water vapor, etc. to the environmentally friendly dry composition.

[0110] The polymer substrate can be made from a thermosetting or thermoplastic polymer. Thermoplastic polymers that can be used include polyacetal, polyacrylic, polycarbonate, polyalkyd, polystyrene, polyolefin, polyester, polyamide, polyaramid, polyamideimide, polyarylate, polyurethane, epoxy, phenol, silicone, polyarylsulfone, polyethersulfone, polyphenylene sulfide, polysulfone, polyimide, polyetherimide, polytetrafluoroethylene, polyetherketone, polyetheretherketone, polyetherketoneketone, polybenzoxazole, polyoxadiazole, polybenzothiazinophenothiazine, polybenzothiazole, polypyrazinoquinoxaline, polypyromellitimide, polyginoxaline, polybenzimidazole, polyoxindole, poly Examples of the polyisoindoline include dioxoisoindoline, polydioxoisoindoline, polytriazine, polypyridazine, polypiperazine, polypyridine, polypiperidine, polytriazole, polypyrazole, polycarborane, polyoxabicyclononane, polydibenzofuran, polyphthalide, polyacetal, polyanhydride, polyvinyl ether, polyvinyl thioether, polyvinyl alcohol, polyvinyl ketone, polyvinyl halide, polyvinyl nitrile, polyvinyl ester, polysulfonate, polysulfide, polythioester, polysulfone, polysulfonamide, polyurea, polyphosphazene, polysilazane, polypropylene, polyethylene, polyethylene terephthalate, polyvinylidene fluoride, polysiloxane, and the like, or a combination thereof.

[0111] The polymer substrate can also comprise a thermosetting substrate. Examples of thermosetting polymers suitable for use as a host in the light-emitting layer include epoxy polymers, unsaturated polyester polymers, polyimide polymers, bismaleimide polymers, bismaleimide triazine polymers, cyanate ester polymers, vinyl polymers, benzoxazine polymers, benzocyclobutene polymers, acrylics, alkyds, phenol-formaldehyde polymers, novolacs, resoles, melamine-formaldehyde polymers, urea-formaldehyde polymers, hydroxymethylfurans, isocyanates, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, unsaturated polyesterimides, and the like, or combinations thereof.

[0112] In one embodiment, the polymer may be added to the composition in the form of an impact modifier. Impact modifiers may be added to improve the durability and toughness of the composition. Impact modifiers compensate for the inherent brittleness or embrittlement, notch sensitivity, and crack propagation that occurs at temperatures below zero. The mechanism usually involves the introduction of a component that is elastomeric or rubbery in nature, which can absorb or dissipate the energy of the impact. Suitable elastomers for use as impact modifiers in the composition include polybutadiene, polyisoprene, styrene-butadiene rubber, poly(styrene)-block-poly(butadiene), poly(acrylonitrile)-block-poly(styrene)-block-poly(butadiene) (ABS), polychloroprene, epichlorohydrin rubber, polyacrylic rubber, silicone elastomers (polysiloxanes), fluorosilicone elastomers, fluoroelastomers, perfluoroelastomers, polyether block amides (PEBA), chlorosulfonated polyethylene, ethylene propylene diene rubber (EPR), ethylene-vinyl acetate elastomers, and the like, or combinations thereof.

[0113] Impact modifiers and recycled tires In one embodiment, the impact modifier can be added to the composition in the form of recycled tires. Concrete produced by adding impact modifiers in the form of recycled tires is called rubberized concrete. The recycled tires can first be crushed into small particles with a size of 10 micrometers to 10 centimeters, preferably 100 micrometers to 5 centimeters.

[0114] In another embodiment, recycled concrete can be added to the composition. The recycled concrete is first crushed into particles of 10 micrometers to 10 centimeters, preferably 100 micrometers to 5 centimeters.

[0115] Gelling agent In one embodiment, gelling agents may be added to the environmentally friendly dry composition to improve toughness, impact resistance, ductility, and the like.

[0116] Examples of gelling agents include gelatin, alginate, carrageenan, oligosaccharides, polysaccharides, or combinations thereof. Examples of gelling agents added to the composition are hydrocolloids, such as vegetable gums, pectin blends including one or more of konjac, xanthan, pectin, locust bean gum, and / or agar. Examples of other gelling agents that can be used include gelatin, gellan gum, carrageenan, guar gum, psyllium seed gum, yam starch powder, alginate, seaweed powder, zein, lignin, tragacanth gum, hemicellulose, karaya gum, curdlan, soy polysaccharides, alginic acid, carboxymethylcellulose, agar, locust bean gum, gelatin, alginate, arabinoxylan, arrowroot, cassia gum, cellulose, gum arabic, karaya gum, konjac, kudzu, maltodextrin, althea root, pectin, sodium alginate, starch, xanthanzein, gum, β-glucan, or combinations thereof.

[0117] The gelling agent is typically in the form of a dry powder before being mixed with water. The gelling agent is typically added at a pH of 5.0 to 7.5 when dissolved in water.

[0118] Combinations of the aforementioned particulate substrates can also be used in environmentally friendly dry compositions and biocements.

[0119] hydrogel In one embodiment, the composition may include a hydrogel, which may be added separately to the composition or may be produced by microorganisms present in the microbial package.

[0120] Hydrogels are biphasic materials that are mixtures of a porous, permeable solid and at least 10% by weight or volume of interstitial fluid composed entirely or primarily of water. In hydrogels, the porous, permeable solid is a water-insoluble, three-dimensional network of natural or synthetic polymers and fluids that has absorbed a large amount of water or biological fluids.

[0121] The crosslinks that connect the polymers in hydrogels fall into two general categories: physical hydrogels and chemical hydrogels. Chemical hydrogels have covalent crosslinks, while physical hydrogels have non-covalent bonds. Chemical hydrogels result in strong, irreversible gels due to covalent bonds. Chemical crosslinks consist of covalent bonds between polymer chains. Hydrogels produced by this means are sometimes called "permanent" hydrogels.

[0122] Physical hydrogels, on the other hand, are easily reversible by simply changing an external stimulus such as pH, ionic concentration (alginate), or temperature (gelatin). Physical crosslinks are composed of ionic bonds, hydrogen bonds, hydrophobic interactions, and chain entanglements (among others). Hydrogels produced through the use of physical crosslinks are sometimes referred to as "reversible" hydrogels.

[0123] Hydrogels are prepared using a variety of polymeric materials and can be broadly divided into two categories according to their origin: natural polymers and synthetic polymers. Natural polymers for hydrogel preparation include hyaluronic acid, chitosan, heparin, alginate, gelatin, and fibrin. Common synthetic polymers include polyvinyl alcohol, polyethylene glycol, sodium polyacrylate, acrylate polymers, and their copolymers.

[0124] The gelling agents listed above may be included as hydrogels and may be crosslinked in the same manner as hydrogels.

[0125] The hydrogel may be present in the composition in an amount of 2 to 30% by weight, preferably 5 to 15% by weight, more preferably 7 to 12% by weight, based on the total weight of the bioconcrete.

[0126] Gelling agents (listed above) may also be used as nutrients. Gelatin and zein may also be used as nutrients in bioconcrete. In one embodiment, zein is the preferred external secondary binder. The primary binder may be used in an amount of 0.5 to 95% by weight, based on the total weight of binders used in the bioconcrete. The external secondary binder may be used in an amount of 5 to 95% by weight, based on the total weight of binders used in the bioconcrete.

[0127] The external second binder may be used in an amount of 2 to 30% by weight, preferably 5 to 15% by weight, more preferably 7 to 12% by weight, based on the total weight of the bioconcrete.

[0128] The aggregate may also include heat stabilizers, antiozonants, antioxidants, mold release agents, barrier materials, inhibitors, crosslinking agents, initiators, and the like.

[0129] Crosslinking agents may be used to form covalent or ionic bonds in binders. Crosslinking agents may be used to form covalent or ionic bonds in hydrogels, gelling agents, polymeric binders, polymeric additives, impact modifiers, gels, etc. Suitable crosslinking agents include aldehydes, carboxylic and other acids, alcohols, acrylates, isocyanates, or combinations thereof.

[0130] Examples of crosslinking agents include formaldehyde, glutaraldehyde, epichlorohydrin, citric acid, 1,2,3,4-butanetetracarboxylic acid, polymeric dialdehyde starch, 1,2-epoxy-3-chloropropane, dialcohols, acryloyl, or combinations thereof.

[0131] Other crosslinkers can be used to crosslink hydrogels, gelling agents, polymer binders, polymer additives, impact modifiers, gels, etc. Illustrative examples include compounds produced by the condensation of acrylic or methacrylic acid with diepoxides, such as bisphenol-A diglycidyl ether, butanediol diglycidyl ether, or neophenylene glycol dimethacrylate. Specific examples include 1,4-butanediol diglycidyl ether di(meth)acrylate, bisphenol-A diglycidyl ether dimethacrylate, and neopentyl glycol diglycidyl ether di(meth)acrylate. Acryloyl monomers also include the condensation of reactive acrylate or methacrylate compounds with alcohols or amines to produce the resulting multifunctional acrylates or multifunctional acrylamides.Examples include N,N-bis(2-hydroxyethyl)(meth)acrylamide, methylenebis((meth)acrylamide), 1,6-hexamethylenebis((meth)acrylamide), diethylenetriaminetris((meth)acrylamide), bis(gamma-((meth)acrylamido)propoxy)ethane, beta-((meth)acrylamido)ethyl acrylate, ethylene glycol di((meth)acrylate), diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate glycerol di(meth)acrylate, glycerol tri(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, 1,4-benzenediol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,5-pentanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate), 1,3,5-triacryloylhexahydro-1,3,5-triazine, 2, 2-bis(4-(2-(meth)acryloxyethoxy)phenyl)propane, 2,2-bis(4-(2-(meth)acryloxyethoxy)-3,5-dibromophenyl)propane, 2,2-bis((4-(meth)acryloxy)phenyl)propane, 2,2-bis((4-(meth)acryloxy)-3,5-dibromophenyl)propane, and the like, and mixtures comprising at least one of the foregoing acryloyl monomers.

[0132] Other crosslinkers include alkoxylated difunctional monomers such as alkoxylated diacrylate (sold as CD802 by Sartomer Co.), alkoxylated aliphatic diacrylate, alkoxylated cyclohexanedimethanol diacrylate, alkoxylated cyclohexanedimethanol diacrylate, alkoxylated cyclohexanedimethanol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated hexanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, cyclohexanedimethanol diacrylate, cyclohexanedimethanol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, dipropylene glycol diacrylate, and (ethoxylated) bisphenol A diacrylate (the number after the term ethoxylation indicates the average number of ethoxy groups in the ethoxylate chain attached to each oxygen atom of bisphenol A). It will be understood that these terms refer to (ethoxylated) 4 bisphenol A diacrylate, (ethoxylated) 10 bisphenol A diacrylate, (ethoxylated) 30 bisphenol A diacrylate, (ethoxylated) 2 bisphenol A dimethacrylate, (ethoxylated) 4 bisphenol A dimethacrylate, (ethoxylated) 6 bisphenol A diacrylate, (ethoxylated) 8 bisphenol A diacrylate, (ethoxylated) 10 bisphenol A dimethacrylate, (ethoxylated) Alkoxylated trifunctional monomers include 30 bisphenol A dimethacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol (Mn=200-600) di(meth)acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, etc.; and 5 highly (propoxylated) alkoxylated trifunctional monomers.5-glyceryl tri(meth)acrylate, (ethoxylated) 3-trimethylolpropane tri(meth)acrylate, (ethoxylated) 6-trimethylolpropane tri(meth)acrylate, (ethoxylated) 15-trimethylolpropane tri(meth)acrylate, (ethoxylated) 9-trimethylolpropane tri(meth)acrylate, (ethoxylated) 20-trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, (propoxylated) 3-glyceryl tri(meth)acrylate, (propoxylated) 3-trimethylolpropane tri(meth)acrylate, (propoxylated) 6-trimethylolpropane tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate solid, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate liquid, etc.; and tetrafunctional and pentafunctional monomers such as dipentaerythritol penta(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, (ethoxylated) 4-pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate ester, pentaerythritol tetra(meth)acrylate, etc., as well as mixtures containing at least one of the foregoing acryloyl monomers.

[0133] Suitable acryloyl monomers further include trifunctional urethane (meth)acrylates sold by Sartomer Company under the trade names CN 929, CN 945 A60, CN 945 B85, CN 959, CN 962, CN 964, CN 965, CN 968, CN 980, CN 981, CN 983, CN 984, CN 944 B85, CN 953 B70, CN 963 B80, CN 964B85, CN 966 B85, CN 981 B88, CN 982 B88, CN 983 B88, CN 985 B88, CN 961H81, CN 966H90, CN 982 P90, CN 963 A80, CN 964 A85, CN 965 A80, CN Examples of urethane (meth)acrylates include trifunctional urethane (meth)acrylates sold under the trade name CN 966 A80, CN 981 A75, CN 982 A75, CN 980 M50, CN 961 E75, CN 963 E75, CN 963 E80, CN 964 E75, CN 982 E75, CN 963J85, CN 966J75, CN 966 I80, CN 966 R60, and CN 964H90; examples of hexafunctional urethane (meth)acrylates include hexafunctional urethane (meth)acrylates sold under the trade name CN 975 by Sartomer Company; examples of urethane (meth)acrylates include CN 972, CN 2901, CN 2902, CN 978, CN 999, CN 970H75, CN 973H85, CN 970 A60, CN 971 A80, CN 973 A80, CN 977 C70, CN 970 E60, CN 973 J75, and CN 1963, and the like, as well as mixtures comprising at least one of the foregoing acryloyl monomers.

[0134] The acryloyl monomers may also be used to crosslink the first and second binders, hydrogels, gelling agents, polymeric binders, polymeric additives, impact modifiers, gels, or combinations thereof.

[0135] Suitable acryloyl monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropenoate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, ) acrylates, etc.; halogenated (meth)acrylates, such as pentabromobenzyl (meth)acrylate; and acrylamides or methacrylamides, including (meth)acrylamide, diacetone (meth)acrylamide, N(2-hydroxyethyl) (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylamide, etc.; as well as mixtures comprising at least one of the foregoing acryloyl monomers. The suffix (meth)acryl- should be understood to indicate either acryl- or methacryl-.

[0136] Suitable acryloyl monomers also include vinyl-functionalized anhydrides, such as maleic anhydride; and epoxy acrylates sold by Sartomer Company under the tradenames CN 120 AC16 and CN 118, epoxidized soybean oil acrylate CN 111, epoxy acrylate CN 104, epoxy acrylate CN 120, low viscosity epoxy acrylate CN 121, epoxy acrylate CN 124, modified epoxy acrylate CN 136, modified epoxy acrylate CN 115, modified epoxy acrylate CN 116, modified epoxy acrylate CN 117, modified epoxy acrylate CN 119, amine modified epoxy acrylate CN 2100, fatty acid modified epoxy acrylate CN 2101, epoxy acrylate CN 104 B80, epoxy acrylate CN 120 B60, epoxy acrylate CN 120 B80, epoxy acrylate CN 120 M50, epoxy acrylate CN Epoxy acrylates sold under the names CN 104 A80, Epoxy Acrylate CN 120 A60, Epoxy Acrylate CN 120 A75, Epoxy Acrylate CN 120 C60, Epoxy Acrylate CN 120 C80, Epoxy Acrylate CN 120 ESO, Epoxy Acrylate CN 120 D80, Styrene-Added Epoxy Acrylate CN 120 S80, Epoxy Novolac Acrylate CN 112 C60, Epoxy Methacrylate CN 151, and the like may be mentioned.

[0137] Suitable acryloyl monomers further include low viscosity oligomers, such as the low viscosity oligomers sold as polybutadiene dimethacrylate by Sartomer Company under the product numbers CN 130, CN 131, CN 135, and CN 137; polyester acrylate oligomers, such as the polyester acrylate oligomers sold by Sartomer Company under the product names Polyester Acrylate CN 293, CN 292, CN 2200, and Chlorinated Polyester Acrylate CN 2201; adhesion promoting oligomers, such as the adhesion promoting oligomer sold by Sartomer Company under the product number CN 704; polybutadiene dimethacrylates, such as those sold by Sartomer Company under the product numbers CN 301 and CN 303, polybutadiene urethane diacrylate CN 302, and polybutadiene dimethacrylate CN 303; and specialty oligomers, such as those sold by Sartomer Company under the product numbers CN 130, CN 131, CN 135, and CN 137. Specialty oligomers sold by the Company under the trade name SARBOX®, such as aromatic acid methacrylate half esters in EEP Ester Solvents SB 401, SB 404, and SB 405, aromatic acid methacrylate half esters in PM, alcohol / EEP Ester Solvent SB 402, aromatic acid methacrylate half esters in PM, alcohol solvent SB 400, aromatic acid acrylate half esters in SR 339 SB 520 M35, aromatic acid acrylate half esters in SR454 SB 520 E35, aromatic acid methacrylate half esters in SR306 SB 520 A20, aromatic acid methacrylate half esters in SR344 SB 500 K60, aromatic acid methacrylate half esters in SR454 SB 500 E50, and aromatic acid methacrylate half esters in SR454 SB 510 E35;Acrylates include low-viscosity triacrylate oligomer CN 132, low-viscosity triacrylate oligomer CN 133, low-viscosity monoacrylate oligomer CN 152, urethane acrylate CN 959, polyester acrylate CN 293, urethane acrylate CN 968, urethane acrylate CN 2901, urethane acrylate CN 2902, urethane acrylate CN 999, low-viscosity aliphatic monoacrylate CN 135, low-viscosity aliphatic monoacrylate CN 137, amine-modified epoxy acrylate CN 2100, fatty acid-modified epoxy acrylate CN 2101, polyester acrylate CN 2200, chlorinated polyester acrylate CN 2201, acrylated acrylic CN 2800, epoxy acrylate CN 120 ACI 6, polybutadiene urethane diacrylate CN 302, and polybutadiene dimethacrylate CN 303, (meth)acrylate functional monomer P-Cure 300, and (meth)acrylate functional monomer P-Cure 301;Functional acrylic oligomers include those sold by Sartomer Company under the trade name SARCRYL® such as SARCRYL® Functional Acrylic Sarcryl CN816, SARCRYL® Functional Acrylic Sarcryl CN817, SARCRYL® Functional Acrylic Sarcryl CN818, Amine Modified Polyether Acrylate CN 501, Amine Modified Polyether Acrylate CN 502, Amine Modified Polyether Acrylate CN 550, Amine Modified Polyether Acrylate CN 551, trifunctional acrylate esters such as SR 9008 sold by Sartomer Co., metal diacrylate SR9016, and metal diacrylates such as zinc diacrylate, lithium diacrylate, sodium diacrylate, magnesium diacrylate, calcium diacrylate, aluminum diacrylate, monofunctional acid ester CD 9050, trifunctional acid ester CD 9051, and CD 9052. 9052, trifunctional acrylate ester SR 9012, trifunctional methacrylate esters SR 9009 and SR 9011, and mixtures containing at least one of the aforementioned acryloyl monomers.

[0138] Highly preferred acryloyl monomers include trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, isobornyl (meth)acrylate, cyclohexyl methyl (meth)acrylate, dibutyl fumarate, dibutyl maleate, glycidyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, decyl (meth)acrylate, octyl (meth)acrylate, and the like, as well as mixtures comprising at least one of the foregoing acryloyl monomers.

[0139] Other crosslinking agents that can be used include isocyanates that can react with hydroxyl groups in the first and second binders, hydrogels, gelling agents, polymer binders, polymer additives, impact modifiers, gels, or combinations thereof. Suitable isocyanates are di-, tri-, or polyisocyanates that can react with hydroxyl groups in binders, gelling agents, hydrogels, etc. to form polyurethanes. Examples of diisocyanates include, for example, 4,4'-methylenediphenyl diisocyanate, 2,2'-dimethyl-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, methylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, cyclohexane-1,4-diisocyanate, 1,6-hexamethylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, and p-xylylene diisocyanate. , m-xylylene diisocyanate, p-tetramethylxylene diisocyanate (1,4-bis(1-isocyanato-1-methylethyl)benzene), m-tetramethylxylene diisocyanate (1,3-bis(1-isocyanato-1-methylethyl)benzene), isophorone diisocyanate (5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane), bis(4-isocyanatocyclohexyl)methane, naphthalene-1,9-diisocyanate, and combinations thereof. In some embodiments, aliphatic and cycloaliphatic diisocyanates are excluded from the reaction and polyurethane product such that the polyurethane does not contain units derived from aliphatic or cycloaliphatic diisocyanates.

[0140] One means of producing bioconcrete involves blending the biocement, second binder, second liquid, and base material together to form the bioconcrete. A crosslinking agent and / or initiator may optionally be added. The bioconcrete may be molded to form articles of desired shapes. Articles include bricks, cinderblocks, pillars, tiles, etc., and can be produced in a batch or mass production process.

[0141] During the formation of the article, the added second liquid can reactivate the microorganisms and consume some of the binder or nutrients. Upon reactivation, the microorganisms produce a binder (such as calcium carbonate or its reaction products) to bind the base material and reinforcing agent into a moldable solid. The bioconcrete can then be placed or poured into a mold to form bricks, cinderblocks, pillars, tiles, etc.

[0142] In one embodiment, once bioconcrete hardens, the bacteria no longer produce binders. However, the formulator or user can restore the building material's microbiological activity by adding sufficient moisture and / or physical conditions to promote activity. In this way, any surface defects formed during molding of the material into bricks, for example, can be repaired after hardening. This allows the reinforcement of the material to achieve additional strength that the hardened material retains. In this way, any cracks or crevices that form can be filled by existing microorganisms using existing matrix elements and nutrient media.

[0143] Another embodiment of the present disclosure relates to compositions and structures that do not require a form (e.g., frameless manufacturing), where the structure is formed by compressing the dry composition after the addition of water (which acts as an activator). Preferred compression devices include hydraulic presses, with preferred pressures being 100 psi or greater, 250 psi or greater, 500 psi or greater, 1000 psi or greater, 2000 psi or greater, 3000 psi or greater, 4000 psi or greater, or 5000 psi or greater.

[0144] Preferred components of the present disclosure include all of the aforementioned components for forming calcium carbonate structures in the form of a sludge or paste. A compaction device compresses the components into a shape that is maintained under applied pressure and dries without significant change in the resulting shape. The compacted shape can be rapidly generated from a thick slurry or sludge and maintains its shape during calcite formation. Preferably, calcite formation is achieved in a steam chamber (e.g., greater than ambient pressure) involving increased steam pressure or spraying or misting, with the steam, mist, or spray preferably including nutrients or chemical substrates. Preferred shapes include blocks, bricks, thin bricks, artificial or cultured stone, pavers, panels, or any useful structure.

[0145] FIG. 4 shows another method 200 for producing biocement. In this method, in step 202, microorganisms (or a microorganism package) are first mixed with water to activate them. In step 204, other ingredients, such as binders, nutrients, and additives, are blended together. In step 206, the activated microorganism package from step 202 is added to the mixture of ingredients from step 204 to form a first dry composition product (a first-generation product). In steps 206 and 208, a portion of the first dry composition product (a first-generation product) is taken and mixed with several other separate portions of the remaining ingredients from step 204. This results in multiple simultaneous activations of multiple dry compositions, resulting in multiple second-generation products. As shown in step 208, all of the compositions are activated simultaneously to form multiple biocement products. The steps detailed above can be repeated by taking small portions from multiple second-generation biocement products and adding them to another multiple dry compositions to produce a third-generation biocement product. The number of usable products increases with each generation.

[0146] In this manner, small amounts of the activated microbial package can be added sequentially to several different dry compositions to activate them, producing multiple biocement products in a short period of time.

[0147] Biocement and bioconcrete and methods for making bioconcrete are illustrated by the following non-limiting examples.

[0148] Example 1 This example was conducted to demonstrate one exemplary embodiment of a method for making bioconcrete. The biocement is biomineralized algae (up to 1000 grams) present in an amount of 13.5 kg, with the remainder being the first binder (calcium carbonate). The mixing procedure is as follows: The bioconcrete is an 8 inch x 6 inch x 16 inch (H x W x L) block. 1. Add sand to the mixer, then add the appropriate amount of water in the mix design. 2. Blend the sand (substrate) and water until homogeneous and take a sample for moisture analysis. 3. Use a moisture analyzer to determine sand moisture and adjust if necessary depending on mix design. 4. Add the crosslinker solution to the sand and mix until homogeneous (1-2 minutes). 5. Add the second binder / biomineralized algae powder. Continue mixing. 6. Add the fiber. Continue mixing. 7. Add alcohol. Continue mixing. Mixing time begins with the addition of alcohol. 8. Add silica fume. Continue mixing for the appropriate time depending on the mix design. 9. The material is used to form the final product.

[0149] The ingredients are shown in Table 1 below. [Table 1] *The target for this mix design is A:W=60:40 and L:B=1:65. *Calculation: B=735.9g, L=735.9(1.65)=1214.24g, A=1214.24(60%)=728.5g, Water=1214.24(40%)=485.7g. *Total moisture in the mix includes water from the sand, crosslinker solution, and any additions that may be added depending on the mix design.

[0150] Ready-mix formulation evaluation (aggregate sand / rock / 1. Part A: Crosslinker Solution 2. Part B: Second binder, biomineralized algae, and silica fume. 3. Blend the aggregate with the appropriate moisture content for the mix design with Part A. Mix for 1-2 minutes. 4. Add Part B and mix for 1-2 minutes. 5. Add alcohol and mix for the appropriate time according to the mix design. 6. The material is used to form the final product.

[0151] The amounts in cubic yards are shown in Table 2. [Table 2] *Part A is in a separate smaller package with a larger bag for Part A. *All ingredients in Part B are blended together in a large bag.

Claims

1. 1. A transportable biocement comprising: A dehydrated microbial package, the microbial package comprising: a dehydrated microbial package containing one or more microorganisms; A transportable biocement comprising a first binder, the first binder being produced by the microorganism, the microorganism protecting itself with a layer of the first binder, the transportable biocement being devoid of water.

2. 10. The transportable biocement of claim 1, wherein the biocement further comprises nutrients.

3. 10. The transportable biocement of claim 1, wherein the microorganisms are present in the biocement in an amount of 0.01 to 25 weight percent, based on the total weight of the biocement.

4. 10. The transportable biocement of claim 1, wherein the first binder is present in the biocement in an amount of 0.01 to 75 weight percent, based on the total weight of the biocement.

5. 3. The transportable biocement of claim 2, wherein the microorganisms are present in the biocement in an amount of 0.01 to 25 weight percent, the first binder is present in the biocement in an amount of 0.01 to 75 weight percent, and the nutrients are present in the biocement in an amount of 0.01 to 10 weight percent, based on the total weight of the biocement.

6. 10. The transportable dry composition of claim 1, further comprising a reinforcing filler.

7. 7. The transportable dry composition of claim 6, wherein the reinforcing filler comprises fibers, the fibers being carbon fibers, glass fibers, carbon nanotubes, polymer fibers, or combinations thereof.

8. 7. The transportable dry composition of claim 6, wherein the reinforcing filler comprises mineral fibers, plant fibers, synthetic fibers, or combinations thereof.

9. 7. The transportable dry composition of claim 6, wherein the reinforcing filler comprises woven and nonwoven fibers, the woven and nonwoven fibers comprising glass fibers, mineral wool fibers, slag wool fibers, stone wool fibers, basalt fibers, silica fibers, quartz fibers, alumina fibers, steel fibers, silicon carbide fibers, abaca fibers, acrylic fibers, carbon fibers, melamine fibers, cotton fibers, jute fibers, kenaf fibers, bamboo fibers, hemp fibers, linen fibers, flax fibers, or combinations thereof.

10. 10. The transportable dry composition of claim 1, wherein the microbial package comprises microorganisms that extract carbon dioxide from the atmosphere.

11. 10. The transportable dry composition of claim 1, wherein the microorganism package further comprises microorganisms that extract nitrogen from the atmosphere.

12. 10. The transportable dry composition of claim 1, wherein the microorganisms comprise Pseudomonadota, Aquificota, Chlamydiota, Bacteroidota, Chlorobiota, Cyanobacteria, Fibrobacterota, Verrucomicrobiota, Planctomycetota, Spirochaetota, Acidobacteriota, Myxococcaaceae, Zymomonas, Escherichia, or combinations thereof.

13. 10. The transportable dry composition of claim 1, wherein the microorganisms comprise Chroococcales, Chroococcidiopsidales, Gloeobacteriales, Nostocales, Oscillatoryes, Pleurocapsales, Spirulinales, Synechococcales, Incertae sedis, Gunflintia, Ozarkcollenia, Cyanothece, Synechocystis, or combinations thereof.

14. The microorganism is Globacter violaceus PCC 7421, Nostoc sp. PCC 7120, Prochlorococcus marinus MIT 9312, Prochlorococcus marinus MIT 9313, Prochlorococcus marinus NATL2A, Prochlorococcus marinus marinus CCM P 1375, Prochlorococcus marinus pastoris CCM P 1986, Synechococcus elongatus PCC 6301, Synechococcus elongatus PCC 7942, Prochlorococcus sp. CC9311, Prochlorococcus sp. CC9605, Prochlorococcus sp. CC9902, Synechococcus sp. JA-2-3B’a(2-13), Synechococcus sp. JA-3-3Ab, Prochlorococcus sp. WH8102, Synechocystis sp. PCC 6803, Thermosynechococcus elongatus BP-1, Trichodesmium erythraeum IMS101, Prochlorococcus marinus AS960, Prochlorococcus marinus MIT 9301, Prochlorococcus marinus MIT 9303, Prochlorococcus marinus MIT 9515, Prochlorococcus marinus NATL1A, Synechococcus sp. RCC 307, Prochlorococcus sp. WH 7803, Prochlorococcus marinus MIT 9215, Acaryochloris marina MBIC11017, Prochlorococcus marinus MIT 9211, Cyanothece sp. BH68, ATCC 51142, Microcystis aeruginosa NIES-843, Synechococcus sp. PCC 7002, Nostoc punctiforme PCC 73102, Cyanothece sp. PCC 7424, Cyanothece sp. PCC7425, Cyanothece sp. PCC 8801, Cyanothece sp. PCC 8802, Cyanobacterium sp. UCYN-A, Anabaena variabilis ATCC 29413, Nostoc azollae 0708, Cyanothece sp. PCC 7822, Arthrospira platensis NIES-39, Synechocystis sp. GT-S, PCC 6803, Mastigocoleus testarum BC008, Crocosphaera watsonii WH 8501, Cyanobacterium stanieri PCC 7202, Geitlerinema sp. PCC 7407, Chroococcidiopsis thermalis PCC 7203, Halothece sp. PCC 7418, Nostoc sp. PCC 7107, Cyanobacterium aponicum PCC 10605, Gloeocapsa sp. PCC 7428, Stanieria cyanosphaera PCC 7437, Leptolyngbya sp. PCC 7376, Oscillatoria nigro-viridis PCC 7112, Calothrix sp. PCC 6303, Anabaena cylindrica PCC 7122, Pseudanabaena sp. PCC 7367, Crinalium epipsammum PCC 9333, Chroococcidiopsis sp. PCC 6712, Calothrix sp. PCC 7507, Planktothrix NIVA-CYA405, Planktothrix NIVA-CYA406, Planktothrix sp. NIVA-CYA407, Microcoleus vaginatus FGP-2, Planktothrix sp. NIVA CYA 15, Planktothrix agardhii NIVA-CYA 34, Planktothrix rubescens NIVA-CYA 98, Anabaena sp. PCC 7108, Spirulina subsalsa PCC 9445, Spirulina major PCC 6313, Synechococcus sp. PCC 7336, Pseudanabaena sp. PCC6802, Synechococcus sp. KORDI-49 (genome sequencing), Synechococcus sp. KORDI-52 (genome sequencing), Synechococcus sp. KORDI-100 (genome sequencing), Scytonema hoffmanni UTEX 2349, Calothrix sp. PCC 7103, Synechococcus sp. WH 8016, Cyanothece sp. BH63E, ATCC 51472, Cyanobium gracile PCC 6307, Synechococcus sp. PCC 7502, Oscillatoria formosa PCC 6407, Oscillatoria acuminata PCC 6304, Synechococcus sp. PCC 6312, Microcoleus sp. PCC 7113, Prochlorothrix hollandica PCC 9006, Oscillatoria sp. PCC 10802, Dactylococcopsis salina PCC 8305, Pleurocapsa sp. PCC 7327, Pleurocapsa sp. PCC 7319, Cylindrospermum stagnale PCC 7417, Nodosilinea nodulosa PCC 7104, Microchaete sp. PCC 7126, Leptolyngbya boryana PCC 6306, Nostoc sp. PCC 7524, Leptolyngbya sp. PCC 7375, Geminocystis herdmanii PCC 6308, Calothrix desertica PCC 7102, Rivularia sp. PCC 7116, Oscillatoriales sp. JSC-12, Geitlerinema sp. PCC 7105, Chamaesiphon minus PCC 6605, cyanobacterium PCC 7702, Fischerella sp. PCC 9431, Synechocystis sp. PCC 6803, PCC-N, Synechocystis sp. PCC 6803, GT-I, Fischerella sp. PCC 9605, Fischerella sp. PCC 9339, Synechococcus sp. CC9616, Mastigocladopsis repens PCC10914, Cyanobacterium species ESFC-1, Leptolyngbya species PCC 6406, Synechocystis species PCC 7509, Synechocystis species PCC 6803, PCC-P, Synechocystis species PCC 6803, Anabaena species 90, Synechocystis ADH, Zymomonas PDC, Escherichia coli-PAL2-FDC1, Escherichia coli HB101 / pBU11, Escherichia albertii, Escherichia fergusonii, Escherichia hermannii, Escherichia marmotae [2], Escherichia vulneris, Pseudomonas D2, Pseudomonas F2, Myxococcus xanthus, Myxococcus xanthus DK 1622, Myxococcus xanthus DZ2, Myxococcus xanthus DZF1, Myxococcus xanthus NewJersey2, Myxococcus xanthus DSM16526T, Bacillus sphaericus, Lysinibacillus sphaericus INQCS 414, and S. pasteurii MTCC 1761, or a combination thereof, the transportable dry composition according to claim 1.

15. 10. The transportable dry composition of claim 1, wherein the microorganism comprises Sporosarcina pasteurii, Sporosarcina ureae, Proteus vulgaris, Bacillus sphaericus, Myxococcus xanthus, Proteus mirabilis, Helicobacter pylori, or a combination thereof.

16. 2. The transportable dry composition of claim 1, wherein the microorganism comprises green algae, the green algae comprising Chlorella vulgaris, Ulva lactuca, Caulerpa taxifolia, Nannochloropsis species, Chlamydomonas reinhardtii, Volvox carteri, Dunaliella salina, Chara species, Scenedesmus species, Cladophora species, and Trebouxia species, or combinations thereof.

17. 10. The transportable dry composition of claim 1, further comprising a substrate, wherein the substrate comprises a ceramic, a metal, a polymer, or a combination thereof.

18. 20. The transportable dry composition of claim 17, wherein the ceramic substrate comprises at least one of a metal oxide, a metal carbide, a metal nitride, a metal boride, a metal silicide, a metal oxycarbide, a metal oxynitride, a metal boron nitride, a metal carbonitride, a metal borocarbide, or a combination thereof.

19. 20. The transportable dry composition of claim 17, wherein the ceramic substrate comprises at least one of sand, silica, fumed silica, alumina, fumed alumina, titania, zirconia, ceria, metal oxide aerogel, or combinations thereof.

20. 18. The transportable dry composition of claim 17, wherein the ceramic substrate comprises at least one of silicon dioxide, aluminum oxide, aluminum silicate, calcium hydrate, aluminum hydrate, titanium dioxide, zirconium dioxide, indium tin oxide, antimony tin oxide, cerium oxide, cadmium oxide, titanium nitride, silicon nitride, aluminum nitride, titanium carbide, silicon carbide, titanium niobium carbide, stoichiometric silicon boride compounds, or combinations thereof.

21. 20. The transportable dry composition of claim 17, wherein the reinforcing filler comprises glass beads, broken glass, recycled tires, impact modifiers, polymer fibers, carbon black, or combinations thereof.

22. 10. The transportable dry composition of claim 1, further comprising a binder, wherein the binder is at least one of gelatin, alginate, carrageenan, an oligosaccharide, a polysaccharide, or a combination thereof.

23. 10. The transportable dry composition of claim 1, further comprising a binder, wherein the substrate comprises a gelling agent, the gelling agent comprising at least one of a vegetable gum, a pectin blend comprising one or more of konjac, xanthan, pectin, locust bean gum, and / or agar, a pectin blend, gelatin, gellan gum, carrageenan, guar gum, psyllium seed gum, yam starch powder, alginate, seaweed powder, tragacanth gum, karaya gum, curdlan, soy polysaccharides, alginic acid, carboxymethylcellulose, agar, locust bean gum, gelatin, alginate, arabinoxylan, arrowroot, cassia gum, cellulose, gum arabic, karaya gum, konjac, kudzu, maltodextrin, althea root, pectin, sodium alginate, starch, xanthanzein, gum, b-glucan, or a combination thereof.

24. 10. The transportable dry composition of claim 1, wherein the composition is dried by natural evaporation, spray drying, or freeze drying prior to transport.

25. Bioconcrete, A dehydrated microbial package, the microbial package comprising: a dehydrated microbial package containing one or more microorganisms; a first binder, the first binder being produced by the microorganism, the microorganism protecting itself with a layer of the first binder; a substrate, the substrate serving to act as a site for binding the first binding agent produced by the microorganism; a second binder, wherein the second binder is not produced by a microorganism.

26. 26. The biocement of claim 25, wherein the second binder comprises zein.

27. 26. The biocement of claim 25, wherein the second binder comprises calcium carbonate and zein.

28. 1. A method for producing a transportable dry composition, comprising: blending together the microbial package, nutrients, and liquid; activating the microbial package to produce a first binding agent; subjecting the microbial package to dehydration to form a transportable biocement; blending the transportable biocement with an aggregate, the aggregate comprising a base material, a second binder, and a liquid, to form a bioconcrete.

29. 30. The method of claim 28, wherein the transportable biocement is formed at a first site and the bioconcrete is formed at a second site different from the first site.

30. 30. The method of claim 28, wherein the bioconcrete is molded to form an article.

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