US 20140370242A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2014/0370242 A1 Constantz et al. (43) Pub. Date: Dec. 18, 2014

(54) HIGHLY REFLECTIVE Publication Classification MCROCRYSTALLINE/AMORPHOUS MATERIALS, AND METHODS FOR MAKING (51) Int. C. AND USING THE SAME GO2B5/08 (2006.01) E4D 7/00 (2006.01) (71) Applicant: Blue Planet, LTD., Los Gatos, CA (US) (52) U.S. C. CPC ...... G02B5/0808 (2013.01); G02B5/0891 (72) Inventors: Brent R. Constantz, Portola Valley, CA (2013.01); E04D 77005 (2013.01) (US); Chris Camire, Morgan Hill, CA USPC ...... 428/143; 252/582: 252/587; 252/588 (US) (21) Appl. No.: 14/214,130 (57) ABSTRACT Compositions comprising highly reflective microcrystalline/ (22) Filed: Mar 14, 2014 amorphous materials are provided. In some instances, the highly reflective materials are microcrystalline or amorphous Related U.S. Application Data carbonate materials, which may include calcium and/or mag (60) Provisional application No. 61/943,992, filed on Feb. nesium carbonate. In some instances, the materials are CO 24, 2014, provisional application No. 61/866,985, sequestering materials. Also provided are methods of making filed on Aug. 16, 2013, provisional application No. and using the compositions, e.g., to increase the albedo of a 61/793,661, filed on Mar. 15, 2013. Surface, to mitigate urban heat island effects, etc.

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HGHLY REFLECTIVE temperature increases are particularly dangerous and can MCROCRYSTALLINE/AMORPHOUS result in above average rates of mortality. Under certain con MATERIALS, AND METHODS FOR MAKING ditions, excessive heat also can increase the rate of ground AND USING THE SAME level oZone formation, or Smog, presenting an additional threat to health and ecosystems within and downwind of CROSS REFERENCE TO RELATED cities. It is estimated that probability of smog increases by 3% APPLICATIONS for every 0.56°C. (1°F) rise in daily maximum temperature above 21°C. (70°F.). Ozone can be formed when precursor 0001 Under 35 U.S.C. S119(e), this application claims compounds react in the presence of Sunlight and high tem priority to the filing date of U.S. Provisional Patent Applica peratures. Exposure to ambient oZone, even at low levels, may tion Ser. No. 61/943,992, filed on Feb. 24, 2014; U.S. Provi trigger a variety of health problems, especially in Vulnerable sional Patent Application Ser. No. 61/866,985, filed on Aug. populations such as children, the elderly, and those with pre 16, 2013 and U.S. Provisional Patent Application Ser. No. existing respiratory disease. Because wind can carry OZone 61/793,661, filed on Mar. 15, 2013; the disclosures of which and its precursors hundreds of miles, even residents far away applications are incorporated herein by reference from urban centers and sources of pollution can beat risk. The specific health effects associated with oZone exposure INTRODUCTION include irritating lung airways and causing inflammation, 0002. As the development of cities replaces natural lands, possible permanent lung damage by repeated exposure to forests and open grassy fields with pavements, buildings and oZone pollution for several months, as well as resulting in other infrastructures, the relationship between incoming Sun aggravated asthma, reduced lung capacity, and increased Sus radiation and outgoing terrestrial radiation has been changed. ceptibility to respiratory illnesses by even low-level expo The conversion of pervious Surfaces to impervious Surfaces Sure, etc. In addition, oZone pollution can damage vegetation alters local energy balances through changes in (1) the albe and ecosystems within and downwind of cities. For instance, dos of Surfaces; (2) the heat capacities and thermal conduc ground-level ozone interferes with the ability of plants to tivities of surfaces; (3) the ratio of sensible heat to latent heat grow and store food. OZone also damages the foliage of trees flowing from the surface into the atmosphere. Moreover, dis and other vegetation, reducing crop and forest yields, and placing trees and vegetation minimizes the natural cooling tarnishing the visual appeal of ornamental species and urban effects of shading and evaporation of water from soil and green Spaces. leaves (evapotranspiration); and tall buildings and narrow streets can heat air trapped between them and reduce air flow. SUMMARY In addition, waste heat from vehicles, factories, and air con 0005 Compositions comprising highly reflective microc ditioners may add warmth to their surroundings. These rystalline/amorphous materials are provided. In some changes in urban areas lead to urban air and Surface tempera instances, the highly reflective materials are microcrystalline tures are higher than nearby rural areas. This is referred to as or amorphous carbonate materials, which may include cal “heatisland’ effect. Many U.S. cities and suburbs in summer cium and/or magnesium carbonate. In some instances, the time have air temperatures up to 5.6°C. (10 F) warmer than materials are CO sequestering materials. Also provided are the Surrounding natural land cover. In some cities in the world methods of making and using the compositions, e.g., to the air temperatures in summer have up to 10° C. (18 F.) increase the albedo of a Surface, to mitigate urban heat island higher than the rural areas. effects, etc. 0003 Heat islands are of growing concerns. Elevated tem peratures in Summertime can impact communities by increas ing energy demand, air conditioning costs, air pollution lev BRIEF DESCRIPTION OF THE FIGURES els, and heat-related illness and mortality. Summertime heat 0006 FIG. 1 is a schematic view of a roof shingle accord islands may also contribute to global warming by increasing ing to an embodiment of the present invention. demand for air conditioning, which results in additional 0007 FIG. 2A provides picture of a solid block, #11 gran power plant emissions of heat-trapping greenhouse gases. In ules and a faux shingle prepared from formulation BPit 1. FIG. U.S. cities with populations over 100,000, peak utility loads 2B provides picture of a solid block, #11 granules and a faux increase 2.5 to 3.5% for every 1° C. (1.8° F.) increase in shingle prepared from formulation BPH2. Summertime temperature. Higher temperatures in urban heat islands bring with them increased energy use, mostly due to a 0008 FIG. 3A provides graphical results of the observed greater demand for air conditioning. Steadily increasing reflectance of a solid block of BPH1 and BPH2. FIG. 3B downtown temperatures over the last several decades mean provides graphical results of the observed reflectance of a #11 that 3 to 8% of community-wide demand for electricity is granules of BPH1 and BPH2. FIG. 3C provides graphical used to compensate for the heat island effect. On warm after results of the observed reflectance of a faux shingles of BPH1 noons in Los Angeles, for example, the demand for electric and BPH2, as compared to 25 mills WFT brown adhesive. power rises nearly 2% for every 0.56° C. (1°F) of the daily 0009 FIGS. 4A and 4B provide SEM images of two dif maximum temperature rises. In total, it is estimated that about ferent materials produced in the Experimental Section, 1 to 1.5 gigawatts of power are used to compensate for the below. impact of the heat island. (0010 FIG. 5 provides the infrared spectra of sample 96 0004. The heat island effect is one factor among several cured in various liquids, as detailed in the Experimental Sec that can raise Summertime temperatures to levels that pose a tion, below. threat to human health. Extremely hot weather can result in 0011 FIG. 6 provides graphical results of reflectance vs. illness including physiological disruptions and organ damage color for various prepared materials, as detailed in the Experi and even death. Excessive heat events or abrupt and dramatic mental Section, below. US 2014/0370242 A1 Dec. 18, 2014

0012 FIGS. 7 and 8 provide photographs of several dif are cited. The citation of any publication is for its disclosure ferent colored coupons produced in the Experimental Sec prior to the filing date and should not be construed as an tion, below. admission that the present invention is not entitled to antedate 0013 FIG. 9 provides reflectance data of colored precipi such publication by virtue of prior invention. Further, the tates compared to commercial Sakrete pigments, Ferro Pig dates of publication provided may be different from the actual ments and TiO. publication dates which may need to be independently con 0014 FIG. 10 provides a comparison between common firmed. concrete roofing tile and roofing tile including Blue Planet 0022. It is noted that, as used herein and in the appended Pigment, as detailed in the Experimental Section, below. claims, the singular forms “a”, “an', and “the include plural referents unless the context clearly dictates otherwise. It is DETAILED DESCRIPTION further noted that the claims may be drafted to exclude any 0015 Compositions comprising highly reflective microc optional element. As such, this statement is intended to serve rystalline/amorphous materials are provided. In some as antecedent basis for use of Such exclusive terminology as instances, the highly reflective materials are microcrystalline “solely.” “only' and the like in connection with the recitation or amorphous carbonate materials, which may include cal of claim elements, or use of a “negative' limitation. cium and/or magnesium carbonate. In some instances, the 0023. As will be apparent to those of skill in the art upon materials are CO2 sequestering materials. Also provided are reading this disclosure, each of the individual embodiments methods of making and using the compositions, e.g., to described and illustrated herein has discrete components and increase the albedo of a Surface, to mitigate urban heat island features which may be readily separated from or combined effects, etc. with the features of any of the other several embodiments 0016. Before the present invention is described in greater without departing from the scope or spirit of the present detail, it is to be understood that this invention is not limited invention. Any recited method can be carried out in the order to particular embodiments described, as Such may, of course, of events recited or in any other order which is logically vary. It is also to be understood that the terminology used possible. herein is for the purpose of describing particular embodi ments only, and is not intended to be limiting, since the scope Highly Reflective Amorphous/Microcrystalline Materials of the present invention will be limited only by the appended 0024. As summarized above, aspects of the invention claims. include compositions having highly reflective microcrystal 0017. Where a range of values is provided, it is understood line?amorphous materials. The microcrystallinefamorphous that each intervening value, to the tenth of the unit of the lower materials of the invention are those that are highly reflective. limit unless the context clearly dictates otherwise, between As the materials are highly reflective, they have a high total the upper and lower limit of that range and any other stated or surface reflectance (TSR) value. TSR may be determined intervening value in that stated range, is encompassed within using any convenient protocol, such as ASTM E1918 Stan the invention. dard Test Method for Measuring Solar Reflectance of Hori 0018. The upper and lower limits of these smaller ranges Zontal and Low-Sloped Surfaces in the Field (see also R. may independently be included in the Smaller ranges and are Levinson, H. Akbari, P. Berdahl, Measuring solar reflec also encompassed within the invention, Subject to any spe tance Part II: review of practical methods, LBNL 2010). In cifically excluded limit in the stated range. Where the stated Some instances, the materials exhibit a TSR value ranging range includes one or both of the limits, ranges excluding from Rg:0=0.0 to Rg:0.1.0, such as Rg;0, 0.25 to Rg:0.0. either or both of those included limits are also included in the 99, including Rg;0,-0.40 to Rg:0. 0.98, e.g., as measured invention. using the protocol referenced above. 0019 Certain ranges are presented herein with numerical 0025. In some instances, the materials are highly reflective values being preceded by the term “about.” The term “about of near infra-red (NIR) light. By NIR light is meant light is used herein to provide literal support for the exact number having a wavelength ranging from 700 nanometers (nm) to that it precedes, as well as a number that is near to or approxi 2.5 mm. NIR reflectance may be determined using any con mately the number that the term precedes. In determining venient protocol, such as ASTM C1371-04a(2010)el Stan whether a number is near to or approximately a specifically dard Test Method for Determination of Emittance of Materi recited number, the near or approximating un-recited number als Near Room Temperature Using Portable Emissometers may be a number which, in the context in which it is pre (http://www.astm.org/Standards/C1371.htm) or ASTM sented, provides the Substantial equivalent of the specifically G173-03 (2012) Standard Tables for Reference Solar Spectral recited number. Irradiances: Direct Normal and Hemispherical on 37 Tilted 0020. Unless defined otherwise, all technical and scien Surface (http://rredc.nrel.gov/solar/spectra?am 1.5/ tific terms used herein have the same meaning as commonly ASTMG173/ASTMG173.html). In some instances, the understood by one of ordinary skill in the art to which this materials exhibit a NIR reflectance value ranging from invention belongs. Although any methods and materials simi Rg:0=0.0 to Rg:0=1.0, such as Rg:0=0.25 to Rg:0=0.99, lar or equivalent to those described herein can also be used in including Rg;0-0.40 to Rg:0=0.98, e.g., as measured using the practice or testing of the present invention, representative the protocol referenced above. illustrative methods and materials are now described. 0026. In some instances, the materials are highly reflective 0021 All publications and patents cited in this specifica of ultra-violet (UV) light. By UV light is meant light having tion are herein incorporated by reference as if each individual a wavelength ranging from 400 nm and 10 nm. UV reflec publication or patent were specifically and individually indi tance may be determined using any convenient protocol. Such cated to be incorporated by reference and are incorporated as ASTM G173-03 (2012) Standard Tables for Reference herein by reference to disclose and describe the methods Solar Spectral Irradiances: Direct Normal and Hemispherical and/or materials in connection with which the publications on 37'Tilted Surface. In some instances, the materials exhibit US 2014/0370242 A1 Dec. 18, 2014

a UV value ranging from Rg:0=0.0 to Rg:0=1.0, such as ranges, in some embodiments, from 0 to 25%. Such as 1 to Rg:0=0.25 to Rg:0=0.99, including Rg:0=0.4 to Rg:00.98, 15% and including from 2 to 9%. e.g., as measured using the protocol referenced above. 0031. The hardness of the materials may also vary. In some 0027. In some instances, the materials are reflective of instances, the materials exhibit a Mohs hardness of 3 or visible light. By visible light is meant light having a wave greater, such as 5 or greater, including 6 or greater, where the length ranging from 380 nm to 740 nm. Visible light reflec hardness ranges in Some instances from 3 to 8. Such as 4 to 7 tance properties may be determined using any convenient and including 5 to 6 Mohs (e.g., as determined using the protocol, such as ASTMG173-03 (2012) Standard Tables for protocol described in American Federation of Mineralogical Reference Solar Spectral Irradiances: Direct Normal and Societies. “Mohs Scale of Mineral Hardness'). Hardness may Hemispherical on 37 Tilted Surface. In some instances, the also be represented in terms oftensile strength, e.g., as deter materials exhibit a visible light reflectance value ranging mined using the protocol described in ASTMC1167. In some from Rg:0=0.0 to Rg:0=1.0, such as Rg:0=0.25 to Rg:00.99, Such instances, the material may exhibit a compressive including Rg:0=0.4 to Rg;0-0.98, e.g., as measured using the strength of 100 to 3000 N, such as 400 to 2000 N, including protocol referenced above. 500 to 18OON. 0028. The above reflectance properties of the materials 0032. In some instances, the highly reflective material is may be determined using any convenient protocol, including made up of one or more carbonate minerals, such that it is a the specific reflectance determination protocols described carbonate material. By carbonate material is meant a material below. or composition that includes one or more carbonate com 0029. The materials may be amorphous or microcrystal pounds, such as two or more different carbonate compounds, line. In some instances, the materials are microcrystalline. As e.g., three or more different carbonate compounds, five or the materials are microcrystalline, the crystal size, e.g., as more different carbonate compounds, etc., including non determined using the Scherrer equation applied to the FWHM distinct, amorphous carbonate compounds. Carbonate com of X-ray diffraction pattern, is Small, and in some instances is pounds of interest may be compounds having a molecular 1000 microns or less in diameter, such as 100 microns or less formulation X(CO), where X is any element or combina in diameter, and including 10 microns or less in diameter. In tion of elements that can chemically bond with a carbonate Some instances, the crystal size ranges in diameter from 1000 group or its multiple, wherein X is in certain embodiments an um to 0.001 um, such as 10 to 0.001 um, including 1 to 0.001 alkaline earth metal and not an alkali metal; wherein mand in um. In some instances, the crystal size is chosen in view of the are stoichiometric positive integers. These carbonate com wavelength(s) of light that are to be reflected. For example, pounds may have a molecular formula of X(CO).H.O. where light in the visible spectrum is to be reflected, the where there are one or more structural waters in the molecular crystal size range of the materials may be selected to be less formula. The amount of carbonate in the carbonate com than one-half the “to be reflected range, so as to give rise to pounds of the carbonate material, as determined by coulom photonic band gap. For example, where the to be reflected etry using the protocol described as coulometric titration, wavelength range of light is 100 to 1000 nm, the crystal size may be 40% or higher, such as 70% or higher, including 80% of the material may be selected to be 50 nm or less, such as or higher. Carbonate compounds of interest are those having ranging from 1 to 50 nm, e.g., 5 to 25 nm. In some embodi a reflectance value across the visible spectrum of 0.5 or ments, the materials produced by methods of the invention greater, such as 0.6 or greater, 0.7 or greater, 0.8 or greater, 0.9 may include rod-shaped crystals and amorphous solids. The or greater, including 0.95 or greater. rod-shaped crystals may vary in structure, and in certain 0033. The carbonate compounds may include a number of embodiments have length to diameter ratio ranging from 500 different cations, such as but not limited to ionic species of to 1, such as 10 to 1. In certain embodiments, the length of the calcium, magnesium, Sodium, potassium, Sulfur, boron, sili crystals ranges from 0.5 um to 500 um, Such as from 5um to con, strontium, and combinations thereof. Of interest are 100 um. In yet other embodiments, substantially completely carbonate compounds of divalent metal cations, such as cal amorphous Solids are produced. cium and magnesium carbonate compounds. Specific carbon 0030 The density, porosity, and permeability of the highly ate compounds of interest include, but are not limited to: reflective materials may vary according to the application. calcium carbonate minerals, magnesium carbonate minerals With respect to density, while the density of the material may and calcium magnesium carbonate minerals. Calcium car vary, in some instances the density ranges from 5 g/cm to bonate minerals of interest include, but are not limited to: 0.01 g/cm, such as 3 g/cm to 0.3 g/cm and including 2.7 calcite (CaCO), aragonite (CaCO), amorphous Vaterite pre g/cm to 0.4 g/cm. With respect to porosity, as determined by cursor/anhydrous amorphous carbonate (CaCO), Vaterite Gas Surface Adsorption as determined by the BET method (CaCO), ikaite (CaCO.6H2O), and amorphous calcium car (Brown Emmett Teller (e.g., as described at http://en.wikipe bonate (CaCO). Magnesium carbonate minerals of interest dia.org/wiki/BET theory, S. Brunauer, P. H. Emmett and E. include, but are not limited to magnesite (MgCO), barringto Teller, J. Am. Chem. Soc., 1938, 60, 309. doi:10.1021/ nite (MgCO2H2O), nesquehonite (MgCO.3H2O), lanford ja01269a023) the porosity may range in some instances from ite (MgCO.5H2O), hydromagnisite, and amorphous magne 100 m/g to 0.1 m/g, such as 60 m/g to 1 m/g and including sium calcium carbonate (MgCaCO). Calcium magnesium 40 m/g to 1.5 m/g. With respect to permeability, in some carbonate minerals of interest include, but are not limited to instances the permeability of the material may range from 0.1 dolomite (CaMg)(CO)), huntite (Mg,Ca(CO)4) and ser to 100 darcies, such as 1 to 10 darcies, including 1 to 5 darcies geevite (CaMg(CO).H2O). Also of interest are bicar (e.g., as determined using the protocol described in H. Darcy, bonate compounds, e.g., sodium bicarbonate, potassium Les Fontaines Publicques de la VIIIe de Dijon, Dalmont, Paris bicarbonate, etc. The carbonate compounds may include one (1856).). Permeability may also be characterized by evaluat or more waters of hydration, or may be anhydrous. In some ing water absorption of the material. As determined by water instances, the amount by weight of magnesium carbonate absorption protocol, e.g., the water absorption of the material compounds in the precipitate exceeds the amount by weight US 2014/0370242 A1 Dec. 18, 2014

of calcium carbonate compounds in the precipitate. For in some embodiments the carbon atoms in the CO materials example, the amount by weight of magnesium carbonate reflect the relative carbon isotope composition (8'C) of the compounds in the precipitate may exceed the amount by fossil fuel (e.g., coal, oil, natural gas, tarsand) from which the weight calcium carbonate compounds in the precipitate by industrial CO, that was used to make the material was 5% or more, such as 10% or more, 15% or more, 20% or more, derived. In addition to, or alternatively to, carbon isotope 25% or more, 30% or more. In some instances, the weight profiling, other isotopic profiles, such as those of oxygen ratio of magnesium carbonate compounds to calcium carbon (Ö'O) nitrogen (8'N), sulfur (ÖS), and other trace ele ate compounds in the precipitate ranges from 1.5-5 to 1. Such ments may also be used to identify a fossil fuel source that as 2-4 to 1 including 2-3 to 1. was used to produce an industrial CO source from which a 0034. In some instances, the carbonate material may fur CO sequestering material is derived. For example, another ther include hydroxides, such as divalent metal ion hydrox marker of interest is (Ö'O). Isotopic profiles that may be ides, e.g., calcium and/or magnesium hydroxides. The car employed as an identifier of CO sequestering materials of the bonate compounds may include one or more components that invention are further described in U.S. patent application Ser. serve as identifying components, where these one more com No. 14/112,495; the disclosure of which is herein incorpo ponents may identify the Source of the carbonate compounds. rated by reference. For example, identifying components that may be present in 0037. The CO sequestering materials may be fabricated product carbonate compound compositions include, but are using any convenient protocol. In some instances, at least a not limited to: chloride, Sodium, Sulfur, potassium, bromide, portion of the carbonate compounds of the CO sequestering silicon, strontium, magnesium and the like. Any such source materials is obtained using a bicarbonate mediated CO. identifying or “marker' elements are generally present in sequestering protocol. Aspects of such protocols include con Small amounts, e.g., in amounts of 20,000 ppm or less, such as tacting a CO containing gas with an aqueous medium to amounts of 2000 ppm or less. In certain embodiments, the remove CO2 from the CO containing gas. The CO contain “marker” compound is strontium, which may be present in ing gas may be pure CO or be combined with one or more the precipitate incorporated into the aragonite lattice, and other gasses and/or particulate components, depending upon make up 10,000 ppm or less, ranging in certain embodiments the source, e.g., it may be a multi-component gas (i.e., a from 3 to 10,000 ppm, such as from 5 to 5000 ppm, including multi-component gaseous stream). In certain embodiments, 5 to 1000 ppm, e.g., 5 to 500 ppm, including 5 to 100 ppm. CO containing gas is obtained from an industrial plant, e.g., Another “marker” compound of interest is magnesium, where the CO containing gas is a waste feed from an indus which may be present in amounts of up to 20% mole substi trial plant. Industrial plants from which the CO containing tution for calcium in carbonate compounds. The identifying gas may be obtained, e.g., as a waste feed from the industrial component of the compositions may vary depending on the plant, may vary. Industrial plants of interest include, but are particular medium source, e.g., ocean water, lagoon water, not limited to, power plants and industrial product manufac brine, etc. In certain embodiments, the calcium carbonate turing plants, such as but not limited to chemical and content of the carbonate material is 25% w/w or higher, such mechanical processing plants, refineries, cement plants, Steel as 40% w/w or higher, and including 50% w/w or higher, e.g., plants, etc., as well as other industrial plants that produce CO 60% w/w. The carbonate material has, in certain embodi as a byproduct of fuel combustion or other processing step ments, a calcium/magnesium ratio that is influenced by, and (such as calcination by a cement plant). Waste feeds of inter therefore reflects, the water source from which it has been est include gaseous streams that are produced by an industrial precipitated. In certain embodiments, the calcium/magne plant, for example as a secondary or incidental product, of a sium molar ratio ranges from 10/1 to 1/5 Ca/Mg, such as 5/1 process carried out by the industrial plant. to 1/3 Ca/Mg. In certain embodiments, the carbonate material is characterized by having a water source identifying carbon 0038. Of interest in certain embodiments are waste ate to hydroxide compound ratio, where in certain embodi streams produced by industrial plants that combust fossil ments this ratio ranges from 100 to 1, such as 10 to 1 and fuels, e.g., coal, oil, natural gas, as well as man-made fuel including 1 to 1. products of naturally occurring organic fuel deposits, such as but not limited to tar sands, heavy oil, oil shale, etc. In certain embodiments, powerplants are pulverized coal powerplants, CO. Sequestering Highly Reflective Materials Supercritical coal power plants, mass burn coal power plants, 0035) In some instances, the material is a CO, sequester fluidized bed coal power plants, gas or oil-fired boiler and ing. By “CO sequestering is meant that the highly reflective steam turbine power plants, gas or oil-fired boiler simple material has been produced from CO that is derived from a cycle gas turbine power plants, and gas or oil-fired boiler fuel source used by humans. For example, in some embodi combined cycle gas turbine power plants. Of interest in cer ments, a CO2 sequestering material is produced from CO tain embodiments are waste streams produced by power that is obtained from the combustion of a fossil fuel, e.g., in plants that combust syngas, i.e., gas that is produced by the the production of electricity. Examples of sources of such gasification of organic matter, e.g., coal, biomass, etc., where CO include, but are not limited to, power plants, industrial in certain embodiments such plants are integrated gasification manufacturing plants, etc., which combust fossil fuels and combined cycle (IGCC) plants. Of interest in certain embodi produce CO, e.g., in the form of a CO containing gas or ments are waste streams produced by Heat Recovery Steam gases. Examples of fossil fuels include, but are not limited to, Generator (HRSG) plants. Waste streams of interest also oils, coals, natural gasses, tar sands, rubber tires, biomass, include waste streams produced by cement plants. Cement shred, etc. Further details on how to produce a CO seques plants whose waste streams may be employed in methods of tering material are provided below. the invention include both wet process and dry process plants, 0036. The CO sequestering materials may have an isoto which plants may employ shaft kilns or rotary kilns, and may pic profile that identifies the component as being of fossil fuel include pre-calciners. Each of these types of industrial plants origin and therefore as being CO2 sequestering. For example, may burn a single fuel, or may burn two or more fuels sequen US 2014/0370242 A1 Dec. 18, 2014 tially or simultaneously. A waste stream of interest is indus may be made up of a single divalent cation species (such as trial plant exhaust gas, e.g., a flue gas. By "flue gas” is meant Ca") or two or more distinct divalent cation species (e.g., a gas that is obtained from the products of combustion from Ca", Mg", etc.), may vary, and in some instances is 100 ppm burning a fossil or biomass fuel that are then directed to the or greater, such as 200 ppm or greater, including 300 ppm or Smokestack, also known as the flue of an industrial plant. greater, Such as 500 ppm or greater, including 750 ppm or 0039. In producing the CO sequestering material from a greater, such as 1,000 ppm or greater, e.g., 1,500 ppm or CO-containing gas, a CO-containing gas may be contacted greater, including 2,000 ppm or greater. Divalent cations of with an aqueous medium under conditions Sufficient to interest that may be employed, either alone or in combination, remove CO from the CO-containing gas and produce a as the divalent cation source include, but are not limited to: bicarbonate component, which bicarbonate component may Ca", Mg, Be", Ba?", Sr., Pb, Fe, Hg, and the like. then be contacted with a cation source to produce a carbonate Other cations of interest that may or may not be divalent CO sequestering component. The aqueous medium may include, but are not limited to: Na", K", NH", and Li", as well vary, ranging from fresh water to bicarbonate buffered aque as cationic species of Mn, Ni, Cu, Zn, Cu, Ce, La, Al, Y, Nd, ous media. Zr, Gd, Dy, Ti, Th, U, La, Sm, Pr, Co, Cr, Te, Bi, Ge. Ta, As, 0040 Bicarbonate buffered aqueous media employed in Nb, W. Mo, V, etc. Naturally occurring aqueous media which embodiments of the invention include liquid media in which include a cation Source, divalent or otherwise, and therefore a bicarbonate buffer is present. As such, liquid aqueous media may be employed in Such embodiments include, but are not of interest include dissolved CO, water, carbonic acid limited to: aqueous media obtained from seas, oceans, estu (HCO), bicarbonate ions (HCO), protons (H) and car aries, lagoons, brines, alkaline lakes, inland seas, etc. bonate ions (CO). The constituents of the bicarbonate 0044 Contact of the CO containing gas and bicarbonate buffer in the aqueous media are governed by the equation: buffered aqueous medium is carried out under conditions Sufficient to remove CO2 from the CO containing gas (i.e., the CO containing gaseous stream), and increase the bicar The pH of the bicarbonate buffered aqueous media may vary, bonate ion concentration of the buffered aqueous medium to ranging in some instances from 7 to 11, Such as 8 to 11, e.g., produce a bicarbonate rich product. The bicarbonate rich 8 to 10, including 8 to 9. In some instances, the pH ranges product is, in Some instances, a two phase liquid which from 8.2 to 8.7, such as from 8.4 to 8.55. includes droplets of a liquid condensed phase (LCP) in a bulk 0041. The bicarbonate buffered aqueous medium may be a liquid, e.g., bulk solution. By “liquid condensed phase' or naturally occurring or man-made medium, as desired. Natu “LCP is meant a phase of a liquid solution which includes rally occurring bicarbonate buffered aqueous media include, bicarbonate ions wherein the concentration of bicarbonate but are not limited to, waters obtained from seas, oceans, ions is higher in the LCP phase than in the surrounding, bulk lakes, Swamps, estuaries, lagoons, brines, alkaline lakes, liquid. inland seas, etc. Man-made sources of bicarbonate buffered 0045 LCP droplets are characterized by the presence of a aqueous media may also vary, and may include brines pro meta-stable bicarbonate-rich liquid precursor phase in which duced by water desalination plants, and the like. Of interest in bicarbonate ions associate into condensed concentrations Some instances are waters that provide for excess alkalinity, exceeding that of the bulk solution and are present in a non which is defined as alkalinity which is provided by sources crystalline solution state. The LCP contains all of the com other than bicarbonate ion. In these instances, the amount of ponents found in the bulk solution that is outside of the excessalkalinity may vary, so long as it is sufficient to provide interface. However, the concentration of the bicarbonate ions 1.0 or slightly less, e.g., 0.9, equivalents of alkalinity. Waters is higher than in the bulk solution. In those situations where of interest include those that provide excess alkalinity (med/ LCP droplets are present, the LCP and bulk solution may each liter) of 30 or higher, such as 40 or higher, 50 or higher, 60 or contain ion-pairs and pre-nucleation clusters (PNCs). When higher, 70 or higher, 80 or higher, 90 or higher, 100 or higher, present, the ions remain in their respective phases for long etc. Where such waters are employed, no other source of periods of time, as compared to ion-pairs and PNCs in solu alkalinity, e.g., NaOH, is required. tion. 0042. In some instances, the aqueous medium that is con 0046. The bulk phase and LCP are characterized by having tacted with the CO containing gas is one which, in addition different K, different viscosities, and different solubilities to the bicarbonate buffering system (e.g., as described above), between phases. Bicarbonate, carbonate, and divalent ion further includes an amount of divalent cations. Inclusion of constituents of the LCP droplets are those that, under appro divalent cations in the aqueous media can allow the concen priate conditions, may aggregate into a post-critical nucleus, tration of bicarbonate ion in the bicarbonate rich product to be leading to nucleation of a solid phase and continued growth. increased, thereby allowing a much larger amount of CO to While the association of bicarbonate ions with divalent cat become sequestered as bicarbonate ion in the bicarbonate rich ions, e.g., Ca", in the LCP droplets may vary, in some product. In such instances, bicarbonate ion concentrations instances bidentate bicarbonate ion/divalent cation species that exceed 5,000 ppm or greater, such as 10,000 ppm or may be present. For example, in LCPs of interest, Ca"/ greater, including 15,000 ppm or greater may be achieved. bicarbonate ion bidentate species may be present. While the For instance, calcium and magnesium occur in seawater at diameter of the LCP droplets in the bulk phase of the LCP concentrations of 400 and 1200 ppm respectively. Through may vary, in some instances the droplets have a diameter the formation of a bicarbonate rich product using seawater (or ranging from 1 to 500 nm, such as 10 to 100 nm. In the LCP. an analogous water as the aqueous medium), bicarbonate ion the bicarbonate to carbonate ion ratio, (i.e., the HCO/CO concentrations that exceed 10,000 ppm or greater may be ratio) may vary, and in Some instances is 10 or greater to 1, achieved. Such as 20 or greater to 1, including 25 or greater to 1, e.g., 50 0043. In such embodiments, the total amount of divalent or greater to 1. Additional aspects of LCPs of interest are cation source in the medium, which divalent cation Source found in Bewernitz et al., “A metastable liquid precursor US 2014/0370242 A1 Dec. 18, 2014

phase of calcium carbonate and its interactions with polyas bicarbonate component having a bicarbonate content ranging partate.” Faraday Discussions. 7 Jun. 2012. DOI: 10.1039/ from 5 to 40 wt.%, such as 10 to 20 wt.%. The amount of c2fd20080e (2012) 159: 291-312. The presence of LCPs may bicarbonate promoter present in a given bicarbonate compo be determined using any convenient protocol, e.g., the proto nent may vary, where in Some instances the amount ranges cols described in Faatz et al., Advanced Materials, 2004, 16, from 0.000001 wt.% to 40 wt.%, such as 0.0001 to 20 wt.% 996-1000; Wolfetal., Nanoscale, 2011, 3, 1158-1165; Rieger and including 0.001 to 10 wt.%. Such promoters are further et al., Faraday Discussions, 2007, 136,265-277; and Bewer described in U.S. patent application Ser. No. 14/112,495; the nitz et al., Faraday Discussions, 2012, 159, 291-312. disclosure of which is herein incorporated by reference. 0047. Where the bicarbonate rich product has two phases, 0049. As indicated above, in making a CO, sequestering e.g., as described above, the first phase may have a higher material according to certain embodiments of the invention, concentration of bicarbonate ion than a second phase, where the CO containing gas is contacted with an aqueous medium the magnitude of the difference in bicarbonate ion concentra under conditions sufficient to produce the bicarbonate-rich tion may vary, ranging in some instances from 0.1 to 4. Such product. The CO containing gas may be contacted with the as 1 to 2. For example, in some embodiments, a bicarbonate aqueous medium using any convenient protocol. For rich product may include a first phase in which the bicarbon example, contact protocols of interest include, but are not ate ion concentration ranges from 1000 ppm to 5000 ppm, and limited to: direct contacting protocols, e.g., bubbling the gas a second phase where the bicarbonate ion concentration is through a Volume of the aqueous medium, concurrent con higher, e.g., where the concentration ranges from 5000 ppm tacting protocols, i.e., contact between unidirectionally flow to 6000 ppm or greater, e.g., 7000 ppm or greater, 8000 ppm ing gaseous and liquid phase streams, countercurrent proto or greater, 9000 ppm or greater, 10,000 ppm or greater, cols, i.e., contact between oppositely flowing gaseous and 25,000 ppm or greater, 50,000 ppm or greater, 75,000 ppm or liquid phase streams, and the like. Contact may be accom greater, 100,000 ppm, 500,000 or greater. plished through use of infusers, bubblers, fluidic Venturi reac 0048. In addition to the above characteristics, a given tors, spargers, gas filters, sprays, trays, or packed column bicarbonate rich product may include a number of additional reactors, and the like, as may be convenient. markers which serve to identify the source of CO, from it has 0050 Contact occurs underconditions such that a substan been produced. For example, a given bicarbonate component tial portion of the CO present in the CO containing gas goes may include markers which identify the water from which it into Solution to produce bicarbonate ions. In some instances, has been produced. Waters of interest include naturally occur 5% or more, such as 10% or more, including 20% or more of ring waters, e.g., waters obtained from seas, oceans, lakes, all the bicarbonate ions in the initial expanded liquid phase Swamps, estuaries, lagoons, brines, alkaline lakes, inland solution (mother liquor) become sequestered in LCPs. Where seas, as well as man-made waters, e.g., brines produced by desired, the CO containing gas is contacted with the bicar water desalination plants, and the like. In Such instances, bonate buffered aqueous medium in the presence of a catalyst markers that may be present include amounts of one or more (i.e., an absorption catalyst) that mediates the conversion of of the following elements: Ca,Mg, Be, Ba, Sr, Pb, Fe, Hg, Na, CO to bicarbonate. Catalyst of interest are further described K. Li, Mn, Ni, Cu, Zn, Cu, Ce, La, Al, Y, Nd, Zr, Gd, Dy, Ti, in U.S. patent application Ser. No. 14/112,495; the disclosure Th, U, La, Sm, Pr, Co, Cr, Te, Bi, Ge, Ta, As, Nb, W, Mo, V. of which is herein incorporated by reference. etc. Alternatively or in addition to the above markers, a given 0051. Following preparation of the bicarbonate rich prod bicarbonate component may include markers which identify uct (as well as any storage thereof, as desired), the bicarbon the particular CO-containing gas used to produce the bicar ate rich product or component thereof (e.g., LCP) is manipu bonate component. Such markers may include, but are not lated to produce solid phase carbonate compositions, and limited to, one or more of nitrogen, mononitrogen oxides, therefore sequester CO from the initial CO containing gas e.g., NO, NO, and NO, oxygen, Sulfur, monosulfur oxides, into a solid form and produce a CO sequestering material, e.g., SO, SO and SO), Volatile organic compounds, e.g., which may be a highly reflective material of the invention, benzo(a)pyrene COH, benzo(g.h.l)perylene CH e.g., a material having reflective properties, such as described dibenzo(a.h)anthracene CH, etc. Particulate components above. In certain instances of Such embodiments, the bicar that may be present in the CO containing gas from which the bonate rich product or component thereof (e.g., LCP) is com bicarbonate component is produced and therefore which may bined with a cation source (e.g., a source of one or more be present in the bicarbonate component include, but are not alkaline earth metal cations) under conditions sufficient to limited to particles of Solids or liquids suspended in the gas, produce a solid carbonate composition. Cations of different e.g., heavy metals such as strontium, barium, mercury, thal Valances can form solid carbonate compositions (e.g., in the lium, etc. When present, such markers may vary in their form of carbonate minerals). In some instances, monovalent amounts, ranging in Some instances from 0.1 to 10,000. Such cations, such as sodium and potassium cations, may be as 1 to 5,000 ppm. Of interest in certain embodiments are employed. In other instances, divalent cations, such as alka agents (referred to herein as “bicarbonate promoters' or line earth metal cations, e.g., calcium and magnesium cations, “BLCP promoters') that promote the production of high may be employed. When cations are added to the bicarbonate bicarbonate-content bicarbonate additive (which may also be rich product or component thereof (e.g., LCP), precipitation referred to herein as a bicarbonate admixture), e.g., by pro of carbonate Solids, such as amorphous calcium carbonate moting the production and/or stabilization of BLCPs, e.g., when the divalent cations include Ca", may be produced facilitating the formation of a BLCP in a bicarbonate-con with a stoichiometric ratio of one carbonate-species ion per taining solution while preventing precipitation of the solu cation. tion's components to form Solid carbonate-containing mate 0.052 Any convenient cation source may be employed in rials. A high-bicarbonate-content bicarbonate component is Such instances. Cation sources of interest include, but are not one that has a bicarbonate content of 0.1 wt.% or greater, such limited to, the brine from water processing facilities such as as 4 wt.% or greater, including 10 wt.% or greater, such as a sea water desalination plants, brackish water desalination US 2014/0370242 A1 Dec. 18, 2014

plants, groundwater recovery facilities, wastewater facilities, from reaction of carbonate precursors, where carbonate pre and the like, which produce a concentrated stream of solution cursors of interest include, but are not limited to: Calcium high in cation contents. Also of interest as cation Sources are Chloride; Magnesium Chloride; Strontium Chloride; Sodium naturally occurring sources. Such as but not limited to native Sulfate; Sodium Bicarbonate, etc. Reaction conditions for seawater and geological brines, which may have varying cat preparing highly reflective carbonate materials from Such ion concentrations and may also provide a ready source of reagents include those described in the experimental section, cations to trigger the production of carbonate solids from the below. bicarbonate rich product or component thereof (e.g., LCP). 0057. In some instances, the highly reflected materials are The cation source employed in Such solid carbonate produc clay minerals. Clay minerals of interest include hydrous alu tion steps may be the same as or different from the aqueous minium phyllosilicates, where specific examples of clay min media employed in the bicarbonate rich product production erals of interest include, but are not limited to: kaolins, e.g., step, e.g., as described above. For example, the aqueous kaolinite, dickite, halloysite, and nacrite; Smectites, e.g., medium employed to produce a bicarbonate rich product may montmorillonite, nontronite and saponite; illite, chlorites, be native seawater with a calcium cation concentration of etc. In some instances, the materials are combinations of two approximately 400 ppm. A more concentrated cation solu or more of the above different types of materials, e.g., car tion, Such as the brine concentrate from a seawater desalina bonates and clays. tion plant, with over twice the native seawater concentration of calcium cation, may then be employed for the second Modifiers precipitation step. 0053. During the production of solid carbonate composi 0058. The highly reflective materials, e.g., as described tions from the bicarbonate rich product or component thereof above, may include one or more modifiers that modify the (e.g., LCP), one mol of CO may be produced for every 2 mols properties of the reflective materials in some manner. For of bicarbonate ion from the bicarbonate rich product or com example, the highly reflective materials may be produced ponent thereof (e.g., LCP). For example, where solid carbon using a color modifier(s) which modifies the color of the final ate compositions are produced by adding calcium cation to material in some desirable way. Examples of Such modifiers the bicarbonate rich product or component thereof (e.g., include, but are not limited to, ions which substitute into the LCP), the production of Solid carbonate compositions, e.g., carbonate mineral of the carbonate compositions, such as the form of amorphous calcium carbonate minerals, may transition metals, e.g., copper, etc., as may be provided by proceed according to the following reaction: precipitating carbonates from transition metal precursors, such as transition metal chlorides. Examples of such ions include, but are not limited to: Manganese, Iron, Copper, Nichol, Chromium, Cobalt, Zinc, etc. When such modifiers are employed, the highly reflective materials may have a While the above reaction shows the production of 1 mol of visible color that varies, including but not limited to: red, CO, 2 moles of CO2 from the CO containing gas were blue, green, yellow, orange, brown, black, etc. initially converted to bicarbonate. As such, the overall process 0059 Examples of such modifiers also include physical sequesters a net 1 mol of CO and therefore is an effective modifiers. Examples of physical modifier include Si contain CO sequestration process, with a downhill thermodynamic ing compositions, e.g., silicates, colloidal silica, etc. energy profile of -34 kJ mol' for the above reaction. 0060 Modifiers of interest further include crystallinity 0054. In producing the CO sequestering material from a modifiers, e.g., which serve to modify crystallinity or crystal CO-containing gas, a CO-containing gas may be contacted size and composition as desired, e.g., to maintain an amor with an aqueous medium under conditions Sufficient to phous composition. For example phosphate, silica, Sulfate, remove CO from the CO-containing gas and produce the Surfactants, or organics Such as chitin polysaccharides find bicarbonate component, e.g., as described above. While any use to modify grain boundaries or poison/modify crystal convenient protocol may be employed, protocols of interest growth. include, but are not limited to, those described in U.S. patent application Ser. No. 14/112,495; the disclosure of which is Highly Reflective Amorphous/Microcrystalline Material herein incorporated by reference. Compositions 0055 Also of interest as CO sequestering materials are 0061 The highly reflective materials, e.g., as described compounds produced using carbonate mediated sequestra above, may be employed as is following their production, or tion protocols, i.e., alkaline intensive protocols, in which a further manipulated as desired to produce various composi CO containing gas is contacted with an aqueous medium at tions having a variety of forms. Highly reflective amorphous/ pH of about 10 or more. Examples of such protocols include, microcrystalline material compositions may have a variety of but are not limited to, those described in U.S. Pat. Nos. 8,333, different configurations, where configurations of interest 944; 8,177,909; 8,137,455; 8,114,214; 8,062,418; 8,006,446; include, but are not limited to: molded objects in a variety of 7,939,336; 7,931,809; 7,922,809; 7,914,685; 7,906,028; shapes, such as blocks, cylinders, spheres, sheets, etc.; amor 7,887,694; 7.829,053; 7,815,880; 7,771,684; 7,753,618; phous configurations, e.g., aggregates; granular configura 7,749,476; 7,744,761; and 7,735,274; the disclosures of tions, etc. As such, the dimensions of a given highly reflective which are herein incorporated by reference. material of the invention may vary widely, e.g., from nanom Non-CO. Sequestering Highly Reflective Materials eter to meter sized. Compositions that include a highly reflec tive material as described herein may be configured as Solid, 0056. In some instances, the highly reflective materials are semi-solid, or fluid, e.g., liquid or gaseous, compositions, as not CO sequestering, e.g., as described above. For example, desired. As such, in some instances the compositions are solid the highly reflective carbonate materials may be produced compositions, which may be granular compositions, e.g., US 2014/0370242 A1 Dec. 18, 2014

powders, Solid structures, e.g., blocks or other formed mide, cupric carbonate, cupric fluoroborate, and mixtures objects, etc. In some instances the compositions are semi thereof. The Zinc materials can include Zinc oxide, such as Solid compositions, e.g., compositions that have a high vis French process Zinc oxide, Zinc sulfide, Zinc borate, Zinc cosity, ranging in Some instances from 1 to 25,000. Such as Sulfate, Zinc pyrithione, Zinc ricinoleate, Zinc Stearate, Zinc 500 to 2,000 cp. In some instances, the compositions are fluid chromate, and mixtures thereof. Also of interest are eluting compositions, which compositions include liquid composi organic materials. tions as well as gaseous compositions. 0062. In some instances, the materials are present in a 0066. In yet other embodiments, the heterogeneous mate granular configuration, i.e., as a composition made up of rials of interest include combinations of microcrystalline/ Small particles. In certain embodiments, the particles range in amorphous compounds, e.g., carbonates, in combination with size from 0.001 microns to 10,000 microns, e.g., 0.1 to 5,000 pigments, examples of which include PC-9415 Yellow, microns, including 10 to 2,500 microns, e.g., 50 or 100 PC-9416 Yellow, PC-9158 Autumn Gold, PC-9189 Bright microns to 2500 microns, as determined by Scanning electron Golden Yellow, v-9186 Iron-Free Chestnut Brown, V-780 microscopy. In some embodiments, the particle sizes exhibit Black, V0797 IRBlack, V-9248 Blue, PC-9250 Bright Blue, a bimodal or multi-modal distribution. In certain embodi PC-5686 Turquoise, V-13810 Red, V-12600 Camouflage ments, the particles have a high Surface are, e.g., ranging from Green, V12560 IR Green, V-778 IRBlack, and V-799 Black, 0.5 to 100 m/gm, 0.5 to 50 m/gm, such as from 0.5 to 2.0 carbon black, iron oxide, phthalocyanine, umber, chromium m/gm, as determined by Brauner, Emmit, & Teller (BET) oxide, titanium oxide and cobalt blue, etc.). In some Surface Area Analysis. Larger sized objects are also of inter instances, the pigments employed are solar reflective pig est, such as but not limited to objects having a longest dimen ments, e.g., as described in U.S. Pat. Nos. 8.394.498; 8.491, sion ranging from 1 cm to 10 m, Such as 10 cm to 5 m, e.g., 50 985 and 8535,803; the disclosures of which are herein incor cm to 1 m. porated by reference. In some instances, such Solar reflective 0063. In some instances the materials could have varying pigments are selected from the group consisting of Solar crystallinity or crystal size and composition. For example reflective pigments having L* less than 30 and a solar reflec phosphate, silica, Sulfate, Surfactants, or organics Such as tance of at least 20 percent. As used in the present specifica chitin polysaccharides could be used to modify grain bound tion L*, a and b* refer to the parameters of the CIELAB aries or poison/modify crystal growth. color system. “Colored” means having an L* value of 85 or 0064. A given composition may be made up of just the less, such as 55 or less, including 45 or less, when measured highly reflective material, e.g., as described above, or include using a HunterLab Model Labscan XE spectrophotometer one or more additional compositions, such as but not limited using a 0 degree viewing angle, a 45 degree illumination to binders, delivery vehicles, other agents that impart func angle, a 10 degree standard observer, and a D-65 illuminant. tionality to the compositions, UV absorbers, pigments, bio “Colored as so defined is intended to include relatively dark cides, etc., which may vary widely depending on the intended tones. “Dark color” means a color having an L* value of 30 or use of the composition. As such, a given portion or amount of less. “Solar reflective, and “Solar heat-reflective' refer to highly reflective material may be made up of a single com reflectance in the near infrared range (700 to 2500 nm) of the pound, e.g., as described above, Such that it is homogeneous electromagnetic spectrum, and “high Solar reflectance' or pure with respect to that compound, or may be may up of means having an average reflectance of 70 percent or more two or more distinct compounds, such that it is heteroge over the near infrared range (700 to 2500 nm) of the electro neous. In the latter case, the two or more compounds may be magnetic spectrum. combined in a manner Such that they are mixed throughout 0067. In yet other instances, the compositions may include the given amount of the material, where any portion of the a UV absorber, which absorber is present in an amount suf given amount from the interior to the exterior includes each of ficient to absorb at least some of the UV light, e.g., light the component compounds. As such, the interior of the mate having a wavelength ranging from 100 to 400 nm, reflected by rial, e.g., granule, includes two or more compounds dispersed the carbonate compounds of the carbonate material. UV throughout the interior. Heterogeneous materials of interest absorbers of interest include, but are not limited to: benzot include combinations of microcrystalline/amorphous com riazole type ultraviolet light absorbers, such as 2-2-hydroxy pounds, e.g., carbonates, in combination with one or more 3,5-di-(1,1-dimethylbenzyl)-2H-benzotriazole (CASH: additional compounds. A variety of additional compounds 70321-86-7), a blend of C-3-3-(2H-Benotriazol-2-yl)-5-(1, may be included to make up the materials, where such com 1-dimethylethyl)-4-hydroxyphenyl-1-oxopropyl-()-hy pounds include, but are not limited to: pigments, e.g., as droxypoly(oxo-1,2-ethanediyl). CAS #104810-48-2+C.-3- described in greater detail below, biocides (algaecides), fill 3-(2H-Benotriazol-2-yl)-5-(1,1-dimethylethyl)-4- ers, binders, etc. hydroxyphenyl-1-oxopropyl-()-3-3-(2H-benzotriazol-2- 0065 For example, the heterogeneous materials of interest yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl)-1-oxopropoxy include combinations of microcrystalline/amorphous com poly(oxy-12-ethanediyl) CAS #104810-47-1+ pounds, e.g., carbonates, in combination with algae-resis Polyethylene glycol 300 CAS #25322-68-3, 2-(3'-tert-butyl tance compounds (i.e., algaecides), examples of which 2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole (CASii: include copper materials, Zinc materials, and mixtures 3.896-11-5), 2-(2-Hydroxy-3',5'-di-tert-amylphenyl)benzot thereof. For example, cuprous oxide and/or Zinc oxide, or a riazole (CASH: 25973-55-1), 2-(2H-Benzotriazole-2-yl)-4- mixture thereof, can be used. The copper materials that can be methylphenyl (CASH: 2440-22-4), and 2-(2-hydroxy-5-tert used in the present invention include cuprous oxide, cupric octylphenyl)benzotriazole (CASH: 3147-75-9); acetate, cupric chloride, cupric nitrate, cupric oxide, cupric benzophenone UV absorbers, such as 2-Hydroxy-4-n-Oc Sulfate, cupric sulfide, cupric Stearate, cupric cyamide, toxybenzophenone (CASii: 1843-05-6), etc. When present, cuprous cyamide, cuprous stannate, cuprous thiocyanate, the amount of UV absorber in the highly reflective material cupric silicate, cuprous chloride, cupric iodide, cupric bro may range from 0% to 25%, such as 1% to 5%. US 2014/0370242 A1 Dec. 18, 2014

0068. Other components that may be present in the car 5.0 to 7.0. In some instances, the granules exhibit a bulk bonate material include, but are not limited to: fillers, binders, density (crushed) which ranges from 60 to 200, such as 75 to sealants, polymers, other inorganic and organic compounds, 150, e.g., 80 to 115 lb/ft, e.g., as measured by the ARMA etc. method published in Asphalt Roofing Manufacturers Asso ciation (ARMA) Granule Test Procedures Manual. In some Granular Compositions instances, the granules exhibit a specific density which ranges 0069. In some embodiments of the invention, the highly from 1.0 to 5.0, such as 2.0 to 4.0, e.g., 2.5 to 3.0. In some reflective material of interest is a granular composition made instances, the oil absorption of the granular composition is up of highly reflective carbonate granules, where the granules 5% or less, such as 3% or less, including 2% or less. include a carbonate component, which component may be or 0072 The granular composition may exhibit a number of may not be CO2 sequestering, e.g., as described above. In the additional desirable properties. In some instances, the granu granular composition, the size of the granules may vary, rang lar composition exhibits an acid resistance of 5% mass loss or ing in some instances from 50 um to 5 mm, Such as 100 um to less, Such as 3% mass loss or less, including 2% mass loss or 2.5 mm, e.g., 250 um to 2 mm. The size distribution of the less. In some instances, the granular composition is exhibits granules may also vary. In some instances, the weight percent high weatherability as evidenced by substantially little, if any, of granules having a size from 500 um to 1.5 mm ranges from degradation after 10,0000 hours. In some instances, the 50 to 100 wt.%, such as 55 to 95 wt.%, e.g., 60 to 90 wt.%. granular composition satisfies the metal leaching standards as 0070 The mechanical properties of the granules may vary. specified in EPA title 40, section 162.24 for non-hazardous In some instances, the granules have a compressive strength waste. In some instances, the granular composition exhibits ranging of 7,500 psi or greater, such as 10,000 psi or greater, an adhesion to asphalt scrub loss of 5gm or less, such as 2 gm including 12,500 psi or greater, e.g., as measured by ASTM. or less, including 1 gm or less. The granules may, in Some instances, exhibit a freeze-thaw 0073. The above granular compositions may be made resistance of 5% max on mass loss or lower, Such as 3% max using any convenient protocol. In some instances, an initial on mass loss or lower, including 2% max on mass loss or carbonate composition, e.g., as described above, is Subjected lower. The granules may, in Some instances, exhibit a wet-dry to elevated pressure and or combined with a setting liquid in resistance of 3% max on mass loss or lower, Such as 2% max a manner Sufficient to produce a solid product, which result on mass loss or lower, including 1% max on mass loss or ant solid product may then be disrupted as desired to produce lower. The granules may, in Some instances, exhibit a spalling a granular composition. When Subjected to pressure, an initial resistance of 10% max on mass loss or lower, such as 7.5% particulate composition (which may or may not be CO max on mass loss or lower, including 5% max on mass loss or sequestering, such as described above), is Subjected to lower. The granules may, in Some instances, exhibit abrasion elevated pressures for a period of time sufficient to produce a resistance of 1% max or lower, such as 0.5% max or lower, desired solid product. In some instances, the elevated pres including 2% max or lower, e.g., as measured by the ARMA sures range from 1,000 to 100,000 psi, such as 1,500 to test method published in Asphalt Roofing Manufacturers 50,000 psi and including 2,000 to 25,000 psi. The period of Association (ARMA) Granule Test Procedures Manual. The time to which the composition is subjected to elevated pres granules may, in some instances, exhibit a temperature sta Sures may vary, and in Some instances ranges from 1 second bility of 500° C. or greater, such as 600° C. or greater, includ to 24 hours, such as 30 seconds to 30 minutes. ing 700° or greater. The granules may, in Some instances, 0074. In some instances, the initial carbonate composition exhibit a soundness of 2% max on mass loss or lower, such as may be combined with a setting liquid. Setting liquids of 1% max on mass loss or lower, including 0.75% max on mass interest vary, and in some instances are aqueous liquid that loss or lower, e.g., as measured by the ASTM C88. The include one or more solutes, e.g., magnesium, calcium, car granules may, in Some instances, exhibit an abrasion and bonate, bicarbonate, chloride, strontium, Sodium, silicates impact resistance of 15% max or lower, such as 12.5% max or (including but not limited to those described in U.S. Pat. Nos. lower, including 10% max or lower, e.g., as measured by 6,375,935 and 6,719,993, the disclosures of which are herein ASTM C-133. incorporated by reference), etc. When present, these solutes 0071. The physical properties of the granular composi may vary in concentration, ranging in Some instances from 1 tions of these embodiments may also vary. In some instances, to 10 mM, such as 1 to 5 mM. Where desired, the setting the solar reflectance of the granular composition is 60% or liquids may further include a source of silica, e.g., colloidal higher, Such as 70% or higher, including 80% or higher, e.g., silica, etc. When combined with a setting liquid, the liquid to as measured by ASTMC1549. In some instances, the thermal Solid weight ratio may vary, ranging in some instances from emittance of the granular composition is 0.5 or higher, Such as 0.1 to 1.0, such as 0.2 to 0.5. When a setting liquid is 0.7 or higher, including 0.8 or higher, e.g., as measured by employed in combination with elevated pressure, the setting ASTMC1371. In some instances, the water absorption of the liquid may be combined with the initial carbonate composi granular composition is 10% or less, such as 5% or less, tion first and the resultant product, e.g., slurry or paste, may including 4% or less. In some instances, the UV opacity of the be subjected to elevated pressure, e.g., as described above. granular composition is 80% or higher, such as 90% or higher, When pastes or slurries are prepared, where desired such may including 95% or higher, e.g., as measured by the ARMA be subjected to extrusion and/or dewatering. method published in Asphalt Roofing Manufacturers Asso (0075. Where desired, the resultant solid product may be ciation (ARMA) Granule Test Procedures Manual. In some cured for a period of time following production. The curing instances, the moisture content of the granular composition is period of time may vary, ranging in some instances from 15 1.0 wt.% or less, such as 0.5 wt.% or less, including 0.3 wt. minutes to 1 month, such as 1 day to 7 days and including 3 % or less. In some instances, the granules exhibit a hardness days to 7 days. The product may be cured in air at a convenient as measured on the Moh’s mineral scale of 5.0 or greater, such temperature, Such as a temperature ranging from 0 to 100°C., as 6.0 or greater, including 7.0 or greater, e.g., ranging from such as 15 to 60° C. In other instances, the product may be US 2014/0370242 A1 Dec. 18, 2014 cured in a curing liquid. Such as but not limited to, aqueous ing 95% or greater. In some instances, the pigmented com liquids, e.g., water, salt solutions, sea water like Solutions, positions may exhibit visible light reflectivity of 10% or Solutions containing LCP. Solutions containing bicarbonate greater, such as 50% or greater, including 99% or greater. In ion, Solutions containing carbonate ion, Solutions containing Some instances, the pigmented compositions may exhibit strontium, magnesium calcium chloride and the like. NIR reflectivity of 10% or greater, such as 30% or greater, 0076. Where desired, one or more additional components including 99% or greater. may be combined with the carbonate component at Some 0080. The resultant granular compositions, such as point during the production protocol, as desired. Additional described above, find use in a variety of applications, e.g., in components that may be combined with the carbonate com building materials, in roads, etc.. Such as described in greater ponent may vary, where examples include, but are not limited detail below. to, powder consolidation materials, Stearate, antifungal agents, compound eluting agents, pigments (such as Aggregates described in greater detail below); etc. 0077. Following production, the solid product may be dis I0081. Another composition format in which the highly rupted to produce the desired granular composition. The Solid reflective materials may be present is aggregate. The term product may be disrupted using any convenient protocol, e.g., “aggregate' is used herein in its conventional sense to include milling, crushing or granulation using such devices as a jaw, a particulate composition that finds use in concretes, mortars rotor, mortar, crushing, disk, or beater mill, a hammer mill or and other materials, e.g., roadbeds, asphalts, and other struc a screen mill-granulator or reduction device, and the like. tures and is suitable for use in Such structures. Aggregates of 0078. In some instances, the granular composition may the invention are particulate compositions that may in some itself include a pigment, e.g., where the pigment component embodiments be classified as fine or coarse. Fine aggregates may be a distinct component mixed or combined with the according to embodiments of the invention are particulate granular product in a heterogeneous composition, or the pig compositions that almost entirely pass through a Number 4 ment may be integral part of the granules of the granular sieve (ASTM C 125 and ASTM C 33). Fine aggregate com composition. Pigments of interest include, but are not limited positions according to embodiments of the invention have an to: metal based pigments, e.g., Cadmium pigments: cadmium average particle size ranging from 0.001 inch (in) to 0.25 in, yellow, cadmium red, cadmium green, cadmium orange, cad such as 0.05 in to 0.125 in and including 0.01 in to 0.08 in. mium sulfoselenide; Chromium pigments: chrome yellow Coarse aggregates of the invention are compositions that are and chrome green; Cobalt pigments: cobalt violet, cobalt predominantly retained on a Number 4 sieve (ASTM C 125 blue, cerulean blue, aureolin (cobalt yellow); Copper pig and ASTMC 33). Coarse aggregate compositions according ments: AZurite, Han purple, Han blue, Egyptian blue, Mala to embodiments of the invention are compositions that have chite, Paris green, Phthalocyanine Blue BN, Phthalocyanine an average particle size ranging from 0.125 in to 6 in, Such as Green G. Verdigris, viridian; Iron oxide pigments: sanguine, 0.187 in to 3.0 in and including 0.25 in to 1.0 in. As used caput mortuum, oxide red, red ochre, Venetian red, Prussian herein, “aggregate may also in some embodiments encom blue; Lead pigments: lead white, cremnitz, white, Naples yel pass larger sizes, such as 3 in to 12 in or even 3 in to 24 in, or low, red lead; Manganese pigments: manganese violet; Mer larger, Such as 12 in to 48 in, or larger than 48 in, e.g., such as cury pigments: Vermilion; Titanium pigments: titanium yel sizes used in riprap and the like. In some embodiments, such low, titanium beige, titanium white, titanium black and Zinc as producing wave-resistant structures for the ocean, the sizes pigments: Zinc white, Zinc ferrite; inorganic pigments, such as may be even larger, Such as over 48 in, e.g., over 60 in, or over Carbon pigments: carbon black (including vine blac, lamp 72 in. black), ivory black (bone char); Clay earth pigments (iron I0082) Aggregates may be produced from highly reflective oxides): yellow ochre, raw Sienna, burnt Sienna, raw umber, materials in a manner analogous to the process employed to burnt umber, Ultramarine pigments: ultramarine, ultramarine make granules, but with a disruption protocol employed that green shade; biological and organic pigments, e.g., pigments provides for the desired size products, e.g., as described of biological origin: alizarin (synthesized), alizarin crimson above. (synthesized), gamboge, cochineal red, rose madder, indigo, I0083) Aggregates of the invention have a density that may Indian yellow, Tyrian purple, pigments of non-biological vary so long as the aggregate provides the desired properties organic: quinacridone, magenta, phthalo green, phthalo blue, for the use for which it will be employed, e.g., for the building pigment red 170, etc. As indicated above, in some instances material in which it is employed. In certain instances, the the pigment component may be blended with the granular density of the aggregate particles ranges from 1.1 to 5gmfcc. composition to produce the desired colored composition. In Such as 1.3 gm/cc to 3.15gmfcc., and including 1.8 gm/cc to other instances, the pigment may be incorporated into the 2.7 gmfcc. Other particle densities in embodiments of the carbonate granules, e.g., by including the pigment in the invention, e.g., for lightweight aggregates, may range from composition that is subjected to elevated pressure and/or set 1.1 to 2.2 gm/cc, e.g., 1.2 to 2.0 g/cc or 1.4 to 1.8 g/cc. In some ting liquid, such as describe above. Also of interest are pig embodiments the invention provides aggregates that range in ments which substitute into the carbonate mineral of the bulk density (unit weight) from 50 lb/ft to 200 lb/ft, or 75 carbonate compositions, such as transition metals, e.g., cop 1b/ft to 175 lb/ft, or 50 lb/ft to 100 lb/ft, or 75 lb/ft to 125 per, etc., as may be provided by precipitating carbonates from 1b/ft, or 90 lb/ft to 115 lb/ft, or 100 lb/ft to 200 lb/ft, or transition metal precursors, such as transition metal chlo 125 lb/ft to 175 lb/ft, or 140 lb/ft to 160 lb/ft, or 50 lb/ft rides. to 200 lb/ft. Some embodiments of the invention provide 0079. When present, pigmented granular composition still lightweight aggregate, e.g., aggregate that has a bulk density exhibits high reflectivity, such as described above. As such, in (unit weight) of 75 lb/ft to 125 lb/ft. Some embodiments of Some instances pigmented compositions may exhibit UV the invention provide lightweight aggregate, e.g., aggregate reflectivity of 10% or greater, such as 50% or greater, includ that has a bulk density (unit weight) of 90 lb/ft to 115 lb/ft. US 2014/0370242 A1 Dec. 18, 2014

0084. The hardness of the aggregate particles making up position in a variety of different ways depending on the nature the aggregate compositions of the invention may also vary, of the final composition. For example, where the composition and in certain instances the hardness, expressed on the Mohs comprises a Substrate, e.g., metal, glass, fibrous, polymeric, scale, ranges from 1.0 to 9. Such as 1 to 7, including 1 to 6 or etc., the Substrate component may be coated with the material 1 to 5. In some embodiments, the Mohr’s hardness of aggre to produce the composition. In other words, the material may gates of the invention ranges from 2-5, or 2-4. In some be stably associated with a target Surface, e.g., by applying the embodiments, the Mohs hardness ranges from 2-6. Other material to the target Surface. In these instances, the material hardness Scales may also be used to characterize the aggre may be applied to the target Surface using any convenient gate. Such as the Rockwell, Vickers, or Brinell scales, and protocol, e.g., spreading the material on the Surface, spraying equivalent values to those of the Mohs scale may be used to the material onto the Surface, contacting the Surface with the characterize the aggregates of the invention; e.g., a Vickers material, e.g., by at least partially immersing an object having hardness rating of 250 corresponds to a Mohs rating of 3: the surface in the material, etc. Where desired, the composi conversions between the scales are known in the art. tion may include a vehicle, e.g., Solvent, which facilitates 0085. The abrasion resistance of an aggregate may also be application of the material to the surface. Solvents of interest important, e.g., for use in a roadway Surface, where aggre include both aqueous and non-aqueous solvents. For gates of high abrasion resistance are useful to keep Surfaces example, the material may be applied as a liquid to a surface, from polishing. Abrasion resistance is related to hardness but Such as a road surface (e.g., using a mobile liquid spreader, is not the same. Aggregates of the invention include aggre Such as a vehicle having a tank containing the liquid carbon gates that have an abrasion resistance similar to that of natural ate material and a spreader component configured to disperse limestone, or aggregates that have an abrasion resistance the liquid carbonate material on a roadbed), following which Superior to natural limestone, as well as aggregates having an a solvent component of the liquid evaporates leaving a solid abrasion resistance lower than natural limestone, as measured coating of the carbonate material on the road Surface. Alter by art accepted methods, such as ASTM C131-03. In some natively, the material may be incorporated into the object embodiments aggregates of the invention have an abrasion having the surface to be modified, the reflective material may resistance of less than 50%, or less than 40%, or less than be a component with one or more additional components 35%, or less than 30%, or less than 25%, or less than 20%, or (material(s)) of the object during manufacture of the object. less than 15%, or less than 10%, when measured by ASTM C131-03. Methods of Albedo Enhancement 0.086 Aggregates of the invention may also have a poros I0089 Aspects of the invention include methods of enhanc ity within a particular ranges. As will be appreciated by those ing albedo of a surface. Albedo, i.e., reflection coefficient, of skill in the art, in Some cases a highly porous aggregate is refers to the diffuse reflectivity or reflecting power of a sur desired, in others an aggregate of moderate porosity is face. It is defined as the ratio of reflected radiation from the desired, while in other cases aggregates of low porosity, or no Surface to incident radiation upon it. Albedo is a dimension porosity, are desired. Porosities of aggregates of some less fraction, and may be expressed as a ratio or a percentage. embodiments of the invention, as measured by water uptake Albedo is measured on a scale from Zero for no reflecting after oven drying followed by full immersion for 60 minutes, power of a perfectly black surface, to 1 for perfect reflection expressed as % dry weight, can be in the range of 1-40%. Such of a white surface. While albedo depends on the frequency of as 2-20%, or 2-15%, including 2-10% or even 3-9%. the radiation, as used herein Albedo is given without refer Formed Objects ence to a particular wavelength and thus refers to an average across the spectrum of visible light, i.e., from about 380 to 0087 Highly reflective material compositions of the about 740 nm. invention may be configured as formed objects. Formed 0090. As the methods are methods of enhancing albedo of objects according to embodiments of the invention may vary a Surface, the methods in some instances result in a magnitude greatly, which formed objects are made up of materials of increase in albedo (as compared to a suitable control, e.g., shaped (e.g., molded, cast, cut, or otherwise produced) into the albedo of the same surface not subjected to methods of man-made structures with defined physical shape, i.e., con invention) that is 0.05 or greater, such as 0.1 or greater, e.g., figuration. Formed objects are distinct from amorphous 0.2 or greater, 0.3 or greater, 0.4 or greater, 0.5 or greater, 0.6 building materials (e.g., powder, paste, slurry, etc.) that do not or greater, 0.7 or greater, 0.8 or greater, 0.9 or greater, includ have a defined and stable shape, but instead conform to the ing 0.95 or greater, including up to 1.0. As such, aspects of the container in which they are held, e.g., a bag or other container. Subject methods include increasing albedo of a surface to 0.1 Formed objects of the invention are also distinct from irregu or greater, Such as 0.2 or greater, e.g., 0.3 or greater, 0.4 or larly or imprecisely produced objects (e.g., aggregate, bulk greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, 0.8 or forms for disposal, etc.) in that formed objects are produced greater, 0.9 or greater, 0.95 or greater, including 0.975 or according to specifications that allow for use of formed greater and up to approximately 1.0. objects as building materials in, for example, buildings. 0091 Aspects of the methods include associating with a Formed objects of the invention may be prepared in accor Surface of interest an amount of a highly reflective microc dance with traditional manufacturing protocols for Such rystalline or amorphous material composition effective to structures, with the exception that an amount of highly reflec enhance the albedo of the surface by a desired amount, such tive microcrystallinefamorphous material composition of the as the amounts listed above. The material composition may be invention is employed. associated with the target Surface using any convenient pro tocol. As such, the material composition may be associated Composite Structures with the target Surface by incorporating the material into the 0088. In a given composition, the material may be associ material of the object having the surface to be modified. For ated with the other components (when present) of the com example, where the target Surface is the Surface of a building US 2014/0370242 A1 Dec. 18, 2014

material. Such as a roof tile or concrete mixture, the material pigments, UV absorbers, etc. An example of roofing material, composition may be included in the composition of the mate Such as a roof shingle, according to an embodiment of the rial so as to be present on the target Surface of the object. invention is provided in FIG.1. FIG. 1 is a schematic drawing Alternatively, the material composition may be positioned on of a roof shingle 10 according to one embodiment of the at least a portion of the target Surface, e.g., by coating the present invention. The roof shingle 10 includes at least one target surface with the composition. Where the surface is asphalt layer 12, such as a layer of bitumen or modified coated with the material composition, the thickness of the bitumen. Bitumen or modified bitumen can be composed of resultant on the Surface may vary, and in some instances may one or more asphalt layers 14 and one or more layers of a range from 0.1 mm to 25 mm, Such as 2 mm to 20 mm and reinforcing material 16 Such as, for example, polyester or including 5 mm to 10 mm. fiberglass. The upper asphalt layer 12 includes at least one 0092. The albedo of a variety of surfaces may be granular layer 18 including a plurality of carbonate granules enhanced. Surfaces of interest include at least partially facing or particles 20 (e.g., as described above) adhered to or embed skyward Surfaces of both man-made and naturally occurring ded within a top surface of the asphalt layer 12. According to objects. Man-made surfaces of interest include, but are not various embodiments, the carbonate particles have a solar limited to: roads, sidewalks, buildings and components reflectance ranging from 2%% to 99%% such that when thereof, e.g., roofs and components thereof (roof shingles) applied to the reinforced asphalt layer 12 result in a roofing and sides, runways, and other man-made structures, e.g., system having a solar reflectance of 30% or more, Such as walls, dams, monuments, decorative objects, etc. Naturally 45% '% or more. The particles may be white in color or occurring Surfaces of interest include, but are not limited to: pigmented (i.e., hued), and may range in size in some plant Surfaces, e.g., as found in both forested and non-forested instances from 0.01 mm to 5 mm. In one embodiment, the areas, non-vegetated locations, water, e.g., lake, ocean and particles 62 are of substantially the same particle size distri sea surfaces, etc. bution. The roofshingle 10 including the asphalt layer may be 0093 Aspects of the methods may include determining produced using any convenient protocol. Such as by passing a the albedo of a surface following provision of the carbonate reinforcement material 16, Such as fiberglass or polyester, material to the Surface, e.g., following application of the through hot liquid asphalt, which impregnates and coats the carbonate material onto the surface. The albedo of the surface reinforcement material 16. This coated strip is then run under may be determined using any convenient protocol, e.g., with a hopper which dispenses the carbonate particles 20 onto the a pyranometer. Protocols for measuring albedo may also be upper Surface of the hot asphalt coated Strip to Substantially found in: “Residential cooling Loads and the Urban Heat fully cover the surface. This strip is then passed over a roller Island the Effects of Albedo.” Building and Environment, or drum to flatten the particles 20 and press them into the Vol. 23, No. 4, pp. 271-283, 1988; and “Urban climates and asphalt included in the reinforced asphalt layer 12. The roof heat islands: albedo, evapotranspiration, and anthropogenic ing material can be provided in the form of individual heat, “Energy and Buildings 25 (1997) 99-103. shingles or sheets which can then be applied to any commer 0094. The methods and compositions, e.g., as described cial, industrial low or steep slope roofing Surface. above, find use in any application where increasing or 0098. In some embodiments, the highly reflective granules enhancing the albedo of a surface is desired. Applications of used in the roofing materials, e.g., as described above, can interest include, but are not limited to: reducing the tempera include a coating and/or a surface treatment. The granules can ture of urban heatislands, e.g., by 1 °C. or more, such as 2°C. be coated and/or their surfaces treated for any number of or more, including 5° C. or more; reducing lighting needs; reasons including dust control, to enhance and/or increase reducing light absorption by man-made and naturally occur water repellency and to prevent various kinds of staining. ring structures, as well as both new structures and retrofitting Various compounds can be used to coat or treat the Surface the existing structures, etc. granules described above according to the various embodi ments of the present invention. These compounds include, but Utility are not limited to the following: silanes, siloxanes, polysilox anes, organo-siloxanes, silicates, organic silicates, silicone 0095 Highly reflective microcrystalline/amorphous com resins, acrylics, urethanes, polyurethanes, glycol ethers and positions, e.g., as described herein, find use in a variety of mineral oil. Further details regarding Suitable coatings are different applications. Applications are varied, where appli provided in paragraphs 20 to 23 of U.S. Published Patent cations of interest include, but are not limited to: roofing Application No. 20110081537; the disclosure of which para granules; roofing membranes; cool pigments; pavement com graphs is herein incorporated by reference. positions; cements and concretes; formed building materials; paints and primers; photovoltaic devices and systems; etc. Roofing Membranes Roofing Granules 0099. The highly reflective materials, e.g., as described herein, also find use in roofing membranes. The term "roofing 0096. One type of formed building material which may membrane' is employed in its conventional sense to refer to include highly reflective compositions of the invention is single-ply membranes that are flexible sheets of compounded formed roofing materials, such as roof shingles, tiles, sheets, synthetic materials that are configured for use in roofing etc., where incorporation of the materials results may result in applications. Roofing membranes of interest include thermo the material being a "cool roofing material. set, thermoplastic, and modified bitumen roofing membranes. 0097 Roof shingles of interest may include a support Thermoset roofing membranes are made of large, flat pieces component, e.g., made from metal, clay, concrete, wood, of synthetic rubber or similar materials, where the pieces are asphalt, etc., which has on a surface thereof a highly reflective welded together at the seams to form one continuous mem composition, e.g., as described above, where the composition brane. Rubbers of interest include, but are not limited to: may or may include one or more additional components, e.g., ethylene propylene diene monomer (EPDM), neoprene, etc. US 2014/0370242 A1 Dec. 18, 2014

In thermoset roofing membranes, the seams are held together parameters of the CIELAB color system. “Colored' means using Suitable adhesives materials or tapes. Thermoplastic having an L* value of 85 or less, such as 55 or less, including membranes are similar to thermoset membranes, where the 45 or less, when measured using a HunterLab Model Labscan seams are bonded melted or dissolved with heat or solvents, XE spectrophotometer using a 0 degree viewing angle, a 45 and can be as strong as the rest of the membrane. Thermo degree illumination angle, a 10 degree standard observer, and plastic membranes are based on elastomeric polymers that a D-65 illuminant. “Colored as so defined is intended to can be processed as plastics. Thermoplastic polyolefin (TPO) include relatively dark tones. “Dark color” means a color based roofing membranes may be a melt blend or reactor blend of a polyolefin plastic, such as a polypropylene poly having an L* value of 30 or less. “Solar reflective, and “Solar mer, with an olefin copolymer elastomer (OCE), such as an heat-reflective' refer to reflectance in the near infrared range ethylene-3O propylene rubber (EPR) or an ethylene-propy (700 to 2500 nm) of the electromagnetic spectrum, and “high lene-diene rubber (EPDR). TPO-based roofing membranes Solar reflectance' means having an average reflectance of 70 may comprise one or more layers. A TPO membrane may percent or more over the near infrared range (700 to 2500 nm) comprise base-(bottom) and cap-(top) layers with a fiber rein of the electromagnetic spectrum. Cool pigments prepared forcement scrim (middle) sandwiched between the other two from highly reflective materials of the invention may have a layers. The scrim may be a woven, nonwoven, or knitted variety of different colors, including but not limited to: fabric composed of continuous Strands of material used for Whites; e.g., Inorganic Oxide White, Titanium Dioxide reinforcing or strengthening membranes. The scrim is gener White, Titanium White; Blacks/Browns, e.g., Carbon Black, ally the strongest layer in the composite. The fabric can con Ivory Black, Copper Chromite Black, Mars Black, Chrome tribute significantly to the tensile strength of the roofing mem Iron Nickel Black Spinel, Chromium Green-Black Hematite, brane and provide for dimensional stability. In an example, Chromium Green-Black Hematite Modified, Chromium the fabric reinforcement comprises a polyester yarn based Green-Black Hematite Modified, Chromium Green-Black scrim. Modified bitumen membranes are factory-fabricated Hematite Modified, Chromium Iron Oxide, Chromium Iron layers of asphalt, "modified using a rubber or plastic ingre Oxide, Perylene Black, Burnt Sienna, Raw Sienna, Raw dient (e.g., APP (atactic polypropylene) and SBS (styrene Umber. Iron Titanium Brown Spinel, Iron Titanium Brown butadiene styrene) for increased flexibility, and combined Spinel, Iron Titanium Brown Spinel, Manganese Antimony with reinforcement for added strength and stability. While a Titanium Buff Rutile, Zinc Iron Chromite Brown Spinel, Zinc given roofing membrane's thickness may vary, in some Iron Chromite Brown Spinel; Blues/Purples, e.g., Cobalt Alu instances the thickness ranges from 0.75 mm to 1.5 mm. minate Blue Spinel, Cobalt Aluminate Blue Spinel, Cobalt 0100. In roofing membranes of the invention, the highly Aluminate Blue Spinel, Cobalt Aluminum Blue, Cobalt Blue, reflective material of the invention, e.g., as described above, Cerulean Blue, Cobalt Chromite Blue, Cobalt Chromite may be incorporated into the one or more layers of the mem Blue-Green Spinel, Cobalt Chromite Blue-Green Spinel, brane and or provided in a surface coating of the membrane, Prussian Blue, French Ultramarine Blue, Phthalo Blue, e.g., a surface of the membrane (e.g., the skyward Surface of Phthalo Blue, Dioxazine Purple, Greens, e.g., Chrome Green, the membrane which does not face the interior of the building Chromium Oxide Green, Chromium Green-Black Modified, to which the membrane is applied). The highly reflective Cobalt Chromite Blue-Green Spinel, Cobalt Chromite Green material may be incorporated into the roofing membrane in a Spinel, Cobalt Chromite Green Spinel, Cobalt Teal, Cobalt variety of formats, e.g., from particles to granules, e.g., as Titanate Green Spinel, Cobalt Titanate Green Spinel, Phthalo described above. In some instances, the highly reflective Green, Phthalo Green; Reds/Oranges, such as Red Iron material is present as particles, e.g., as ultrafine particles Oxide, Red Iron Oxide, Red Iron Oxide, Red Oxide, Cad having a mean particle size of 165 nm or less, Such as between mium Orange. Acra Burnt Orange, Acra Red, Monastral Red, 125 to 150 nm or between 110 to 165 nm. Naphthol Red Light; Yellows, e.g., Yellow Oxide, Cadmium 0101 Examples of specific roofing membranes and Yellow Light, Chrome Yellow, Chrome Antimony Titanium related compositions into which the highly reflective materi Buff Rutile, Chrome Antimony Titanium Buff Rutile, als of the invention may be incorporated, e.g., in place of or in Chrome Antimony Titanium Buff Rutile, Chrome Titanate addition to the TiO2 component of Such membranes and Yellow, Nickel Antimony Titanium Yellow Rutile, Nickel related compositions, include but are not limited to those Antimony Titanium Yellow Rutile, Nickel Antimony Tita described in United States Published Patent Application Nos. nium Yellow Rutile, Nickel Titanate Yellow, Yellow Medium 20130130581; 20120288678; 20110256378; 20110223385; Azo, Yellow Orange Azo; and Pearlescents, e.g., Bright Gold 2010.0255739; 20100197844; 20100151198; 20100120953; (Pearlescent), Bright White (Pearlescent), Interference Blue, 20080277056; 20070295390; 20070295389; 20070185245; Interference Gold, Interference Green, Interference Orange, 20070054576; 20070054129; 20060280892; 2006019.9453; Interference Red, Interference Violet, Iridescent White, Brass 20060197069; 20060157103; 20050282449; 20050261407; (Pearlescent), Bright Bronze (Pearlescent), Bright Copper 20050257875; 20050250399; 20030207969; the disclosures (Pearlescent), Rich Bronze and Russet (Pearlescent); etc. of the roofing membranes and related compositions of these published applications being incorporated herein by refer 0103) Where desired, the cool pigments may exhibit vary ing reflectance and transmittance values, as desired. For CCC. example, the pigments may be configured to reflect NIR and visible light but transmit UV light. Alternatively, the pig Cool Pigments ments may be configured to reflect visible and UV light but 0102 Highly reflective materials, e.g., as described above, transmit NIR. Alternatively, the pigments may be configured find use as cool pigments. Cool pigments are Solar reflective to reflective NIR and UV light, but transmit visible light. In pigments. In some instances, the pigments have an L* value Some instances, the pigments may be configured to reflect of 85 or less and a solar reflectance of 20 percent or higher. As only one of NIR, UV and visible light, while transmitting the used in the present specification L*, a and b* refer to the wavelengths that are not reflected. US 2014/0370242 A1 Dec. 18, 2014

Pavement Compositions when constantly exposed to wet weather conditions. Hydrau 0104 Highly reflective materials as described herein also lic cements of interest include, but are not limited to Portland find use in pavement compositions, including but not limited cements, modified Portland cements, and blended hydraulic to: asphalt concrete, Seal coats (e.g., chip seals, slurry seals, CementS. microSurfacings, sand seals and cape seals (chip seal fol 0108. In some embodiments, the cement is a Portland lowed by sand seal or slurry seal), etc., where the high reflec cement or a Portland cement blend. Portland cements are tive materials be present as aggregates in combination with hydraulic cement compositions that are produced by grinding one or more components, e.g., asphalt (bitumen), water, or pulverizing clinkers, which are materials consisting essen emulsifiers, other additives, etc. By aggregate is meant both tially of hydraulic calcium silicates and a small amount of one course and fine aggregate. Fine aggregates are materials that or more forms of calcium sulfate as an inter-ground addition. almost entirely pass through a Number 4 sieve (ASTMC125 and ASTM C33). Such as silica sand. Coarse aggregates are Clinkers are made from a sintered material that is produced materials that are predominantly retained on a Number 4 when a raw mixture comprising calcium and silica in prede sieve (ASTMC125 and ASTMC33). The amount and nature termined proportions is sintered, or heated to high tempera of an aggregate that is included in pavement compositions tures. Examples of raw materials used to produce Such a may vary widely. mixture include, but are not limited to, limestone and clay. In addition to Portland cement clinker, a limited amount of calcium sulfate (which controls the set time), and up to 5% Cements and Concretes minor constituents (as allowed by various standards) may 0105. In some instances, the compositions find use in also be included in a Portland cement. As defined by the cementitious compositions that are prepared from a cement. European Standard EN 197.1, “Portland cement clinker is a Embodiments of the compositions may be described as set hydraulic material which shall consist of at least two-thirds by table cementitious compositions, where the cementitious mass of calcium silicates (3CaO.SiO, and 2CaO.SiO), the compositions include an amount of a highly reflective mate remainder consisting of aluminium- and iron-containing clin rial, e.g., carbonate, as described herein, e.g., to enhance the ker phases and other compounds. The ratio of CaO to SiO, albedo of a product produced from the cementitious compo shall not be less than 2.0. The magnesium content (MgO) sition. By “settable cementitious composition' is meant a shall not exceed 5.0% by mass.” In certain embodiments, a flowable composition that is prepared from a cement and a Portland cement is a Portland cement that satisfies the ASTM setting liquid, where the flowable composition sets into a Standards and Specifications of C150 (Types I-VIII) of the Solid product following preparation. Upon production, the American Society for Testing of Materials (ASTM C150 flowable composition may have a variety of consistencies, Standard Specification for Portland Cement). ASTM C150 e.g., paste, putty, etc., where the Viscosity of the flowable covers eight types of Portland cement, each possessing dif composition may vary, ranging in Some instances from 0 to ferent properties, and which are used specifically for those 1000 mPas, such as 2 to 100 mPas. The flowable compo properties. The eight types of Portland cement are: Type 1 sitions set into a Solid product following a period of time from (normal); Type IA (normal, air-entraining). Type II (moderate production of the flowable composition, where this period of Sulfate resistance); Type IIA (moderate Sulfate resistance, time may vary, and in Some instances ranges from 1 minto 24 air-entraining); Type III (high early strength); Type IIIA (high hrs, such as 1 hr to 3 hrs. The compressive strength of the solid early strength, air-entraining); Type IV (low heat of hydra products produced upon setting of the flowable compositions tion); and Type V (high Sulfate resistance). In some embodi may also vary, ranging in some instances from 1 to 20,000 psi, ments, a Portland cement may be a white Portland cement. such as 1000 to 5000 psi, as determined using the ASTM Test White Portland cement is made from selected raw materials No. C 109. Each of the cement and bicarbonate additive com that only contain negligible amounts of iron and magnesium ponents, as well as other optional components, e.g., an addi oxides, which are the chemical compounds that give ordinary tional setting liquid, aggregate, additive, etc., used to produce Portland cement its grey color. White Portland cement is the settable cementitious compositions are now reviewed in typically used for architectural and/or aesthetic purposes in greater detail. Settable cementitious compositions include visible structural walls, panels, terraZZO Surfaces, stucco, cements and concretes, the latter being a cement in combina cement paint, tile grout, and decorative concrete. tion with an aggregate, e.g., a coarse or fine aggregate. 0109. In some embodiments, a cement may be a blended 0106 The term “cement as used herein refers to a par hydraulic cement. The phrase “blended hydraulic cement’ as ticulate composition that sets and hardens after being com used herein refers to a hydraulic cement composition that bined with a setting fluid, e.g., an aqueous solution, such as includes two or more types of cement materials. Materials water oran LCP (e.g., as described in above). The particulate used to form blended hydraulic cements include, but are not composition that makes up a given cement may include par limited to: Portland cement, blast furnace slag, fly ash, silica ticles of various sizes. In some instances, a given cement may fume, calcined clay, poZZolanic materials, hydrated lime, and be made up of particles having a longest cross-sectional combinations thereof. In some embodiments, a cement may length (e.g., diameter in a spherical particle) that ranges from be a masonry or mortar cement. Masonry and mortar cements 1 nm to 100 um, Such as 10 nm to 20 Lum and including 15 nm are cements that are made from a mixture of a Portland to 10 um. cement or blended hydraulic cement and one or more plasti 0107 Cements of interest include hydraulic cements. The cizing materials, such as limestone or hydrated or hydraulic term “hydraulic cement as used herein refers to a cement lime. In certain embodiments, other materials may also be that, when mixed with a setting fluid, hardens due to one or included in a masonry or mortar cement to modulate the more chemical reactions that are independent of the water properties of the cement. Such as the setting time, workability, content of the mixture and are stable in aqueous environ water retention, and durability, e.g., as described in greater ments. As such, hydraulic cements can harden underwater or detail below in the additives section. US 2014/0370242 A1 Dec. 18, 2014

0110. In some embodiments, the cement component may exceeding 337.5x225x112.5 (length}xwidth:xheight). Any be a non-hydraulic cement. By “non-hydraulic cement is unit with dimensions (mm) between 337.5x225x112.5 to meant a cement whose products of hydration (i.e., the com 2000x1000x500 (length}xwidth:Xdepth) is termed a “block.” position that is formed when the cement is mixed with a Structural units with dimensions (mm) exceeding setting fluid) are not resistant to water. Examples of non 2000x1000x500 (lengthxwidth:Xdepth) are termed "slabs.” hydraulic cements include gypsum, plaster and lime cements. Tiles refer to masonry units that possess the same dimensions Non-hydraulic cements may be mixed with other compo as bricks or blocks, but may vary considerably in shape, i.e., nents, such as pozzolanic materials, to render them resistant may not be polygonal (e.g., hacienda-style roof tiles). to water, i.e., to render them hydraulic. The term “pozzolanic materials” as used herein means a material (either a naturally 0114. One type of masonry unit provided by the invention occurring material or a man-made material) containing silica is a brick, which refers to a structural unit of material used in or a mixture of silica and alumina. masonry construction, generally laid using mortar. Bricks of the invention are masonry units with dimensions (mm) not 0111. The highly reflective materials of the invention may exceeding 337.5x225x112.5 (lengthxwidth:xheight). In some be present in the cementitious composition in a variety of embodiments, the bricks may have lengths ranging from 175 formats, e.g., as powders or granules, such as described to 300mm, such as 200 to 250 mm, including 200 to 230 mm: above. The amount of highly reflective material that may be widths ranging from 75 to 150 mm, such as 100 to 120 mm. present in the cement may vary, and in some instances may be including 100 to 110 mm; and heights ranging from 50 to 90 present in amounts ranging from 0.1 to 99, such as 1 to 50 wt mm, such as 50 to 80 mm, including 55 to 75 mm. Bricks of %. the invention may vary in grade, class, color, texture, size, Formed Building Materials weight and can be solid, cellular, perforated, frogged, or hollow. Bricks of the invention may include but are not lim 0112. The highly reflective materials described herein also ited to building brick, facing brick, load bearing brick, engi find use in formed building materials. For example, the com neering brick, thin veneer brick, paving brick, glazed brick, position may be incorporated into formed building materials, firebox brick, chemical resistant brick, sewer and manhole e.g., to enhance the albedo of such materials, etc. Formed brick, industrial floor brick, etc. The bricks may also vary in building materials according to embodiments of the invention frost resistance (i.e., frost resistant, moderately frost resistant may vary greatly, which formed building materials comprise or non-frost resistant), which relates to the durability of bricks materials shaped (e.g., molded, cast, cut, or otherwise pro in conditions where exposure to water may result in different duced) into man-made structures with defined physical levels of freezing and thawing. Frost resistant bricks are shape, i.e., configuration. Formed building materials are dis durable in conditions of constant exposure to water and freez tinct from amorphous building materials (e.g., powder, paste, ing and thawing. Moderately frost resistant bricks are durable slurry, etc.) that do not have a defined and stable shape, but in conditions of sporadic exposure to water and freezing and instead conform to the container in which they are held, e.g., thawing. Non-frost resistant bricks are not durable in condi a bag or other container. Formed building materials of the tions of exposure to water and freezing and thawing. These invention are also distinct from irregularly or imprecisely bricks are suitable only for internal use and are liable to formed materials (e.g., aggregate, bulk forms for disposal. damage by freezing and thawing except when protected by an etc.) in that formed building materials are produced according impermeable cladding during construction. Bricks of the to specifications that allow for use of formed building mate invention may also vary in soluble salt content (i.e., low or rials in, for example, buildings. Formed building materials of normal). Percentage by mass of soluble ions in bricks with a the invention may be prepared in accordance with traditional low soluble salt content does not exceed 0.03% magnesium, manufacturing protocols for such structures, with the excep 0.03% potassium, 0.03% sodium, and 0.5% sulfate. Percent tion that an amount of highly reflective microcrystalline/ age by mass of soluble ions in bricks with a normal salt amorphous material composition of the invention is content does not exceed 0.25% of magnesium, potassium, employed. The portion of components replaced with the and sodium in total and sulfate content does not exceed 1.6%. material composition may vary, and in some instances is 5% The bricks of the invention may vary considerably in physical by weight or more, including 10% by weight or more, 25% by and mechanical properties. The compressive strength of weight or more, 50% by weight or more, 75% by weight or bricks of the invention may range, in certain instances, from more, 90% by weight or more, or even 100% by weight. In 5 to 100 megapascals (MPa), including 20-40 MPa. The flex producing the formed building materials, an amount of the ural strength of bricks of the invention may vary, ranging from highly reflective material composition may be combined 0.5 to 10 MPa, including 2 to 7 MPa, such as 2 to 5 MPa. The additional components. Illustrative formed building materials maximum water absorption of bricks of the invention may according to certain embodiments of the invention are vary, ranging from 5 to 25%, including 10 to 15%. Bricks of reviewed in greater detail below. However, the below review the invention may also undergo moisture movement (expan of formed building materials is not limiting on the invention, sion or contraction) due to the absorption or loss of water to its and is provided solely to further describe various exemplary environment. The dimensional stability (i.e., linear shrinkage embodiments of highly reflective material composition or expansion) due to moisture movement may vary, in certain formed building materials. instances ranging from 0.001 to 0.2%, including 0.05 to 0113 Masonry units are formed building materials used in 0.1%. In some embodiments, the bricks of the invention may the construction of load-bearing and non-load-bearing struc be used for paving a road. Bricks used to pave areas exposed tures that are generally assembled using mortar, grout, and the to heavy traffic (e.g., pedestrian, vehicular, etc.) may have an like. Exemplary masonry units of the invention include abrasion resistance index ranging from 0.1 to 0.5, including bricks, blocks, and tiles. Bricks and blocks of the invention 0.2 to 0.4, such as 0.3. In addition, bricks of the invention may are polygonal structures possessing linear dimensions. Bricks have a volume abrasion loss ranging from 1.0 to 4.0 cm/cm, of the invention are masonry units with dimensions (mm) not including 1.5 to 2.5 cm/cm, such as 2.0 cm/cm. The US 2014/0370242 A1 Dec. 18, 2014 highly reflective material composition of the invention may shape, size, weight, and may be solid, webbed, cellular or be molded, extruded, or sculpted into the desired shape and hollow. Tiles of the invention may vary in dimension, e.g., size to form a brick. The shaped composition is then dried and lengths ranging from 100 to 1000 mm, including 250 to 500 further hardened by hydraulic pressure, autoclave or fired in a mm, such as 250 to 300 mm; widths ranging from 50 to 1000 kiln attemperatures ranging between 900 to 1200°C., such mm, including 100 to 250 mm, such as 125 to 175 mm; and as 900° to 1100° C. and including 1000° C. thickness ranging from 10 to 30 mm, including 15 to 25 mm, 0115. Another type of masonry unit provided by the inven such as 15 to 20 mm. The compressive strengths of tiles of the tion is blocks, (e.g., concrete, cement, foundation, etc.). invention may also vary, in certain instances ranging from 5 to Blocks are distinct from bricks based on their structural 75 MPa, including 15 to 40 MPa, such as 25 MPa. The flexural dimensions. Specifically, blocks exceed the dimensions (mm) strength of tiles of the invention may vary, ranging from 0.5 to of 337.5x225x112.5 (length}xwidth:Xheight). Blocks of the 7.5 MPa, including 2 to 5 MPa, such as 2.5 MPa. The maxi invention may vary in color, texture, size, and weight and can mum water absorption of tiles of the invention may also vary, be solid, cellular, and hollow or employ insulation (e.g., in certain instances ranging from 5 to 15%, including 7 to expanded polystyrene foam) in the block void volume. 12%. Tiles of the invention may also undergo moisture move Blocks of the invention may be load-bearing, non-load-bear ment (expansion or contraction) due to the absorption or loss ing or veneer (i.e., decorative) blocks. In some embodiments, the blocks may have lengths ranging from 300 to 500 mm. of water to its environment. The dimensional stability (i.e., such as 350 to 450 mm, widths ranging from 150 to 250 mm, linear shrinkage or expansion) due to moisture movement such as 180 to 215 mm and heights ranging from 100 to 250 may vary, in certain instances ranging from 0.001 to 0.25%, mm, such as 150 to 200 mm. The blocks of the invention may including 0.025 to 0.075%, such as 0.05%. Tiles used to pave also vary in faceshell thickness. In some instances, the blocks areas exposed to heavy traffic (e.g., pedestrian, vehicular, may have faceshell thicknesses ranging from 15 to 40 mm, etc.) may have an abrasion resistance index that may vary including 20 to 30 mm, such as 25 mm. The blocks may also considerably, ranging from 0.1 to 0.5, including 0.25. In vary in web thickness. In some embodiments, the blocks may addition, tiles may have a Volume abrasion loss ranging from have web thicknesses ranging from 15 to 30mm, including 15 1.0 to 4.0 cm/cm, including 1.5 to 3.0 cm/cm, such as 2.7 to 25 mm, such as 20 mm. The blocks of the invention may cm/cm. Tiles may be polygonal, circular or take on any vary considerably in physical and mechanical properties. The other desired shape. As such, the highly reflective material compressive strength of blocks of the invention may vary, in composition of the invention may be molded or cast into the certain instances ranging from 5 to 100 MPa, including 15 to desired tile shape and size. The shaped composition may be 75 MPa, such as 20 to 40 MPa. The flexural strength of blocks further compacted by roller compaction, hydraulic pressure, of the invention may also vary, ranging from 0.5 to 15 MPa, vibrational compaction, or resonant shock compaction. The including 2 to 10 MPa, such as 4 to 6 MPa. The maximum resultant composition may also be poured out into sheets or a water absorption of the blocks of the invention may vary, roller may be used to form sheets of a desired thickness. The ranging from 7 to 20% by weight including 8 to 15%, such as sheets are then cut to the desired dimensions of the tiles. In 9 to 11%. Blocks of the invention may also undergo moisture Some instances, the resultant composition may also be movement (expansion or contraction) due to the absorption or foamed using mechanically or chemically introduced gases loss of water to its environment. Blocks of the invention may prior to being shaped or while the composition is setting in be Type I moisture-controlled units or Type II non-moisture controlled units. The dimensional stability (i.e., linear shrink order to form a lightweight tile. The shaped composition is age) of the blocks of the invention may vary depending on then allowed to set and further cured in an environment with their intended use and/or geographical location of use, in a controlled temperature and humidity. Tiles may be further certain instances ranging from 0.02 to 0.15%, such as 0.03 to polished, colored, textured, shot blasted, inlaid with decora 0.05%. The highly reflective material composition of the tive components and the like. invention may be molded, extruded, or sculpted into the 0117 Construction panels are formed building materials desired shape and size to form a block. The shaped compo employed in a broad sense to refer to any non-load-bearing sition may be further compacted by roller compaction, structural element that are characterized such that their length hydraulic pressure, vibrational compaction, or resonant and width are substantially greater than their thickness. shock compaction. In some instances, the resultant composi Exemplary construction panels of the invention include tion may also be foamed using mechanically or chemically cement boards, fiber-cement sidings, and drywall. Construc introduced gases prior to being shaped or while the compo tion panels are polygonal structures with dimensions that vary sition is setting in order to form a lightweight concrete block. greatly depending on their intended use. The dimensions of The composition is further cured in an environment with a construction panels may range from 50 to 500 cm in length, controlled temperature and humidity. including 100 to 300 cm, such as 250 cm; width ranging from 0116. Another type of building material provided by the 25 to 200 cm, including 75 to 150 cm, such as 100 cm; invention is a tile. Tiles of the invention refer to non-load thickness ranging from 5 to 25 mm, including 7 to 20 mm, bearing building materials that are commonly employed on including 10 to 15 mm. Cement boards comprise construction roofs and to pave exterior and interior floors of commercial panels conventionally prepared as a combination of cement and residential structures. Some examples where tiles of the and fiberglass and possess additional fiberglass reinforce invention may be employed include, but are not limited to, the ment at both faces of the board. Fiber-cement sidings com roofs of commercial and residential buildings, decorative prise construction panels conventionally prepared as a com patios, bathrooms, saunas, kitchens, building foyer, drive bination of cement, aggregate, interwoven cellulose, and/or ways, pool decks, porches, walkways, Sidewalks, and the like. polymeric fibers and possess a texture and flexibility that Tiles may take on many forms depending on their intended resembles wood. Drywall comprises construction panels con use and/or intended geographical location of use, varying in ventionally prepared from gypsum plaster (i.e., semi-hydrous US 2014/0370242 A1 Dec. 18, 2014

form of calcium Sulfate), fibers (glass or paper) and is sand length, e.g., 250 cm and 50 to 150 cm in width, e.g., 100 cm wiched between two sheets of outer material, e.g., paper or and a thickness ranging from 4 to 20 mm, e.g., 5 to 15 mm, fiberglass mats. including 10 mm. Fiber-cement sidings of the invention may 0118. One type of construction panel provided by the possess physical and mechanical properties that vary. In some invention is cement board. They are formed building materi embodiments, the flexural strength may range between 0.5 to als where in Some embodiments, are used as backerboards for 5 MPa, including 1 to 3 MPa, such as 2 MPa. The compressive ceramics that may be employed behind bathroom tiles, strengths may also vary, in some instances ranging from 2 to kitchen counters, backsplashes, etc. and may have lengths 25 MPa, including 10 to 15 MPa, such as 10 to 12 MPa. In ranging from 100 to 200 cm, such as 125 to 175 cm, e.g., 150 Some embodiments of the invention, fiber-cement sidings to 160 cm; a breadth ranging from 75 to 100 cm, such as 80 to may be employed on buildings that are Subject to varying 100 cm, e.g., 90 to 95 cm, and a thickness ranging from 5 to weather conditions, in Some embodiments ranging from 25 mm, e.g., 5 to 15 mm, including 5 to 10 mm. Cement extremely arid to wet (i.e., low to high levels of humidity). boards of the invention may vary in physical and mechanical Accordingly, the maximum water absorption of the fiber properties. In some embodiments, the flexural strength may cement sidings of the invention may vary, ranging from 10 to vary, ranging between 1 to 7.5 MPa, including 2 to 6 MPa, 25% by mass, including 10 to 20%, such as 12 to 15%. The Such as 5 MPa. The compressive strengths may also vary, dimensional stability (i.e., linear shrinkage or expansion) due ranging from 5 to 50 MPa, including 10 to 30 MPa, such as 15 to moisture movement may vary, in certain instances ranging to 20 MPa. In some embodiments of the invention, cement from 0.05 to 0.1%, including 0.07 to 0.09%. The highly boards may be employed in environments having extensive reflective material composition of the invention may be used exposure to moisture (e.g., commercial saunas). The maxi to produce the desired shape and size to form a fiber-cement mum water absorption of the cement boards of the invention siding. In addition, a variety of further components may be may vary, ranging from 5 to 15% by weight, including 8 to added to the fiber-cement sidings which include but are not 10%, such as 9%. Cement boards of the invention may also limited to: cellulose fibers, plasticizers, foaming agents, undergo moisture movement (expansion or contraction) due accelerators, retarders and air entrainment additives. The CO to the absorption or loss of water to its environment. The sequestering material composition is then poured into sheet dimensional stability (i.e., linear shrinkage or expansion) due molds or a roller is used to form sheets of a desired thickness. to moisture movement may vary, in certain instances ranging The shaped composition may be further compacted by roller from 0.035 to 0.1%, including 0.04 to 0.08%, such as 0.05 to compaction, hydraulic pressure, vibrational compaction, or 0.06%. The highly reflective material composition of the resonant shock compaction. The sheets are then cut to the invention may be used to produce the desired shape and size desired dimensions of the fiber-cement sidings. In some to form a cement board. In addition, a variety of further instances, the resultant composition may also be foamed components may be added to the cement boards which using mechanically or chemically introduced gases prior to include but are not limited to: plasticizers, foaming agents, being shaped or while the composition is setting in order to accelerators, retarders and air entrainment additives. The form a lightweight fiber-cement siding. The shaped compo highly reflective building material composition is then poured sition is then allowed to set and further cured in an environ out into sheet molds or a roller may be used to form sheets of ment with a controlled temperature and humidity. The fiber a desired thickness. The shaped composition may be further cement sidings of the invention may then be covered with a compacted by roller compaction, hydraulic pressure, vibra polymeric film, enamel or paint. Where desired, the fiber tional compaction, or resonant shock compaction. The sheets cement sidings of the current invention may also be prepared are then cut to the desired dimensions of the cement boards. In using chemical admixtures such that they possess increased Some instances, the resultant composition may also be fire, water, and frost resistance as well as resistance to damage foamed using mechanically or chemically introduced gases by bio-degradation and corrosion. prior to being shaped or while the composition is setting in I0120 Another building material provided by the invention order to form a lightweight cement board. The shaped com is a column, which, in a broad sense, refers to a vertical position is then allowed to set and further cured in an envi load-bearing structure that carries loads chiefly through axial ronment with a controlled temperature and humidity. The compression and includes structural elements such as com cement boards of the invention then may be covered in a pression members. Other vertical compression members of fiberglass mat on both faces of the board. Where desired, the the invention may include, but are not limited to pillars, piers, cement boards of the current invention may also be prepared pedestals, or posts. Columns of the invention may be rigid, using chemical admixtures such that they possess increased upright Supports, composed of relatively few pieces. Col fire, water, and frost resistance as well as resistance to damage umns may also be decorative pillars having a cylindrical or by bio-degradation and corrosion. The cement board of the polygonal, Smooth or fluted, tapered or straight shaft with a current invention may also be combined with components capital and usually a base, among other configurations. The Such as dispersed glass fibers, which may impart improved capital and base of the column may have a similar shape as the durability, increased flexural strength, and a smoother Sur column or may be different. Any combination of shapes for face. the capital and base on a column are possible. Polygonal 0119) Another type of construction panel provided by the columns of the invention possess a width that is not more than invention is fiber-cement siding. Fiber-cement sidings of the four times its thickness. Columns of the invention may be invention are formed building materials used to cover the constructed Such that they are solid, hollow (e.g., decorative exterior or roofs of buildings and include, but are not limited columns), reinforcement filled, or any combination thereof. to building sheets, roof panels, ceiling panels, eternits, and the Columns of the invention can be short columns (i.e., columns like. They may also find use as a substitute for timber fascias where strength is governed by construction components and and barge boards in high fire areas. Fiber-cement sidings may the geometry of its cross section) or slender columns (i.e., have dimensions that vary, ranging from 200 to 400 cm in cross-sectional dimensions that are less than 5 times its US 2014/0370242 A1 Dec. 18, 2014

length). The dimensions of the column may vary greatly such as 0.1 to 0.15 m. Formed building materials of the depending on the intended use of the structure, e.g., from invention Such as slabs, and structures made therefrom, may being less than a single story high, to several stories high or be thicker than corresponding structures that lack carbonate/ more, and having a corresponding width. Columns of the bicarbonate components (e.g., highly reflective material com invention may vary in their mechanical and physical proper positions) of the invention. ties. Properties such as compressive and flexural strengths I0122) Another building material provided by the invention may vary depending on the design and intended use of the is an acoustic barrier, which refers to a structure used as a column. For example, unreinforced concrete columns may barrier for the attenuation or absorption of sound. As such, an possess flexural strengths that range from 2 to 20 MPa, acoustic barrier may include, but is not limited to structures including 5 to 15 MPa, such as 7 to 12 MPa and compressive Such as acoustical panels, reflective barriers, absorptive bar strengths that range from 10 to 100 MPa, including 25 to 75 riers, reactive barriers, etc. Acoustic barriers of the invention MPa, such as 50 MPa. Structurally reinforced concrete col may widely vary in size and shape. Acoustic barriers may be umns of the invention may possess considerably larger flex polygonal, circular, or any other shape depending on its ural strengths, ranging from 15 to 50 MPa, including 20 to 40 intended use. Acoustic barrier may be employed in the attenu MPa, such as 25 to 35 MPa and compressive strengths that ation of sound from highways, roadways, bridges, industrial range from 25 to 200 MPa, including 50 to 150 MPa, such as facilities, power plants, loading docks, public transportation 75 to 125 MPa. In some embodiments, columns may be composite, wherein it may act compositely with other struc stations, military facilities, gun ranges, housing complexes, tural units by the introduction of interfacial shear mecha entertainment venues (e.g., stadiums, concert halls) and the nisms. In other embodiments, columns may be non-compos like. Acoustic barriers may also be employed for Sound insu ite, wherein it utilizes the properties of the basic column lation for the interior of homes, music studios, movie theaters, alone. In producing columns of the invention, the highly classrooms, etc. The acoustic barriers of the invention may reflective material compositions may be poured into a column have dimensions that vary greatly depending on its intended form or cast around a correlated Steel reinforcing column use, ranging from 0.5 to 10 m in length or longer, e.g., 5 m and structure (e.g., steel rebar). In some embodiments, the steel 0.1 to 10 m in height/width or wider, e.g., 5 m and a thickness reinforcement is pretensioned prior to casting the composi ranging from 10 to 100 cm, or thicker e.g., 25 to 50 cm, tion around the steel framework. In other embodiments, col including 40 cm. Where desired, the acoustic barrier may be umns of the invention may be cast with a steel reinforcing employed with various coatings or liners (e.g., polymeric), cage that is mechanically anchored to the concrete column. and may be configured for easy joining with each other or The columns of the invention may also employ additional pillars separating additional acoustic barriers to produce long structural Support components such as, but not limited to acoustic barrier structures made up of multiple acoustic bar cables, wires and mesh composed of steel, ductile iron, poly riers of the invention. In some embodiments, acoustic barriers meric fibers, aluminum or plastic. The structural Support of the invention may employ sound absorptive material (e.g., components may be employed parallel, perpendicular, or at wood shavings, textile fibers, glass wool, rock wool, poly some other angle to the carried load. The molded or casted meric foam, Vermiculite, etc.) in addition to a structurally composition may be further compacted by roller compaction, reinforcing framework. In some embodiments, acoustic bar riers of the invention may be used as noise-reduction barriers hydraulic pressure, vibrational compaction, or resonant in an outdoor environment (e.g., along a highway, near an shock compaction. The composition is further allowed to set airport, etc.) and may be employed with structural Support and is cured in an environment with a controlled temperature components (e.g., columns, posts, beams, etc.). In producing and humidity. In addition, the columns of the invention may acoustic barriers of the invention, the highly reflective mate include a variety of additional components, such as but not rial composition is poured into a mold to form the desired limited to: plasticizers, foaming agents, accelerators, retard acoustic barrier shape and size. Also the composition may be ers and air entrainment additives. Where desired, these addi poured out into a sheet mold or a roller may be used to form tional components may include chemical admixtures Such sheets of a desired thickness. The shaped composition may be that the columns of the invention possess increased resistance further compacted by roller compaction, hydraulic pressure, to damage by bio-degradation, frost, water, fire and corrosion. vibrational compaction, or resonant shock compaction. The 0121 Another building material provided by the invention sheets are then cut to the desired dimensions of the acoustic is a concrete slab. Concrete slabs are those building materials barriers. In some instances, the resultant composition may used in the construction of prefabricated foundations, floors also be foamed using mechanically or chemically introduced and wall panels. In some instances, a concrete slab may be gases prior to being shaped or while the composition is setting employed as a floor unit. (e.g., hollow plank unit or double tee in order to form a lightweight acoustic panel structure. The design) In other instances, a precast concrete slab may be a shaped composition is further allowed to set and is cured in an shallow precast plank used as a foundation for in-situ con environment with a controlled temperature and humidity. In crete formwork. Wall panels are, in a broad sense, vertical addition, the acoustic barriers of the invention may include a load-bearing members of a building that are polygonal and variety of further components, such as but not limited to: possess a width that is more than four times its thickness. plasticizers, foaming agents, accelerators, retarders and air Precast concrete foundation, floors and wall panels may vary entrainment additives. Where desired, the further compo considerably in dimension depending on the intended use of nents may include chemical admixtures such that they pos the precast concrete slab (e.g., one or two story building). As sess increased resistance to damage by bio-degradation, frost, Such, precast concrete slabs may have dimensions which water, fire and corrosion. In some embodiments, the acoustic range from 1 to 10 m in length or longer, including 3 to 8 m, barriers of the invention may employ structural Support com such as 5 to 6 m; height that ranges from 1 to 10 m or taller, ponents such as, but not limited to cables, wires and mesh including 4 to 10 m, such as 4 to 5 m; and a thickness that may composed of steel, ductile iron, polymeric fibers, aluminum range from 0.005 to 0.25 m or thicker, including 0.1 to 0.2 m or plastic. US 2014/0370242 A1 Dec. 18, 2014

Paints and Primers bonate compositions. The BP1 and BP2 calcium carbonate 0123. In addition to formed building materials, the highly formulations were prepared from gaseous CO using an LCP reflective material compositions may be incorporated into mediated protocol as described above. The BP1 dry powder liquid compositions, e.g., primers, paints, pavements, other formulation was determined to include three calcium carbon coating materials, etc., for application to a surface of a Sub ate polymorphs in the following amounts: 48.9% aragonite, strate in order to increase the albedo of the Surface, e.g., as 43.2% amorphous Vaterite precursor/anhydrous amorphous described above. As used herein, the term “paint” refers to a carbonate and 8.0% calcite. The BP1 dry powderformulation liquid composition that forms a colored film when applied to also contained less than 5% kaolin. The BP2 formulation a surface. Where the compositions described herein are used contained only reactive carbonate made up of amorphous as a paint, the paint may contain (in addition to the a highly Vaterite precursor/anhydrous amorphous carbonate (50.1%) reflective material, e.g., as described above, one or more of and aragonite (49.9%). binders, pigments; dyes; Solvents; Surface tension modifiers; I0128. The BP1 and BP2 powder formulations were rheology modifiers; stabilizers; binders; antifreeze property blended and hydrated with 10% by weight setting solution modifiers; foaming controllers; skinning controllers; thick and pressed for 15 minutes at 5000 psi. BP1 contained <5% eners; emulsifiers; texture modifiers; adhesion promoters; kaolin, BP2 was only reactive carbonate. antioxidants; UV stabilizers; flatteners (de-glossing agents); I0129 FIG. 2A provides picture of a solid block, #11 gran biocides; and other materials. ules and a faux shingle prepared from formulation BPit 1. FIG. Photovoltaic Devices and Systems 2B provides picture of a solid block, #11 granules and a faux 0.124 Highly reflective materials as described herein also shingle prepared from formulation BPH2. The blocks were find use in photovoltaic devices and systems that include the prepared from a CO2 sequestering cement composition, same. Photovoltaic devices are devices that include one or which composition was prepared as described above. more photovoltaic elements, e.g., cells. Photovoltaic devices further include a component that includes a highly reflective B. Reflectance Testing material, e.g., as described herein. On type of photovoltaic O130 Reflectance was evaluated using the following pro device of interest is a device which includes one or more tocol: albedo Surfaces that are configured to reflect light onto a photovoltaic element, which may or may not be bifacial and 1. Solar Spectral Reflectance/Transmittance: may or may not include an array of photovoltaic cells. The albedo surfaces may be beneath and or to the side of the I0131 Instrument: Perkin-Elmer Lambda 900 Spectropho photovoltaic element, as desired. The albedo surface may be tometer, equipped with a 150-mm diameter Labsphere Spec made up entirely of the highly reflective material describe tralon integrating sphere herein, or be a composite material of the highly reflective 0132 ASTM E903-96 material and one or more additional materials, as desired. An 0.133 measurement spans 300-2500 nm in 5 nm steps example of a photovoltaic device that includes an albedo 0.134 weight spectrometer measurements with Surface which may include a highly reflective material as AM1GH solar spectral irradiance described herein is disclosed in published U.S. Patent Appli cation No. 2007/0017567, the disclosure of which is herein 2. Solar Reflectance incorporated by reference. 0.135 Instrument: Devices and Services, Co. Solar Spec 0.125. Another type of photovoltaic device that may trum Reflectometer, model SSR-ER version 6 include a higher reflective material of the invention is a pho 0.136 ASTM C1549-09 tovoltaic roofing element. An example of such a photovoltaic 0.137 measure AM1 GH solar reflectance (select G1 roofing element is one that includes roofing element which output on device) includes one or more photovoltaic cells, and granules that include a highly reflective material of the invention posi 3. Preparation of Specimens tioned (e.g., as described above) on the active Surface thereof, either directly on the active surface or separated from the a. #11 Granules active Surface of the cell(s) by one or more intervening, e.g., 0.138 1. Crushed the sanded solid blocks with a hammer adhesive, layers. The composition of the granules may be and screened material with a hand sieve configured to reflect only light outside of the active range of 0.139 Reflectance the photovoltaic cell(s) or may be positioned on the active 0140 Poured granules into a Petri dish to create an Surface in Such a manner that not all of the Surface is covered opaque layer (~1 cm thickness) by the granules. Such photovoltaic devices are further 0.141. Measured opaque layer AM1 GH solar reflec described in published U.S. Patent Application No. 2012/ tance with SSR 001 1783, the disclosure of which is herein incorporated by 0.142 Transmittance of ~1 monolayer of #11 granules reference. 0.143 Sandwiched a 1.6 mm layer of #11 granules 0126 The following examples are offered by way of illus between 2 quartz" plates tration and not by way of limitation. 0144. Note that the characteristic diameter of gran EXPERIMENTAL ules is ~1.2 mm, so a 1.6 mm layer represents slightly I. Preparation and Characterization of Reflective more than 1 monolayer of granules CO. Sequestering Compositions 0145 Before measurements, calibrated spectrometer with empty quartz cell in place A. Preparation b. Faux Shingle 0127. Two highly reflective materials (i.e., BP1 and BP2) 1. Applied 25 mills WFT dark brown adhesive (AM1 GH were prepared as follows from highly reactive calcium car SR=0.06) onto a chromated Al panel substrate US 2014/0370242 A1 Dec. 18, 2014 20

2. Pressed ~1 monolayer of granules into adhesive and 3. Scanning Electron Microscopy allowed shingles to cure >1 week 0154 Precipitated Carbonates, Cements and Compacted Carbonate Materials were imaged on a scanning electron C. Results microscope (SEM) (Hitachi S-3400N-II SEM equipped with 0146 FIG. 3A provides graphical results of the observed an INCAE250 EDX System for microanalysis). The SEM is reflectance of a solid block of BPH1 and BPH2. FIG. 3B variable pressure and works with both secondary electrons provides graphical results of the observed reflectance of a #11 (SE) and backscattered electrons (BSE). Samples imaged granules of BPH1 and BPH2. FIG. 3C provides graphical used BSE with gold-coating (15 nm). results of the observed reflectance of a faux shingles of BPH1 and BPH2, as compared to 25 mils WFT brown adhesive. 4. Carbonate Ceramic Testing 0147 The above results are summarized in Table 1 below: (O155 Powders were mixed at 0.12 to 0.16 L:P (liquid to powder) ratio with Solutions and pressed in Carver press model 3850 (12 ton press) using a 1" die. The die used was Blue Planet #1 Blue Planet #2 item SDS25, a 25 mm cylindrical die set purchased from Reflectance of O.76 O.92 Across International Inc. The maximum die pressure for this solid block (opaque) model is 30 metric tons. Reflectance of #11 O.62 O.89 granules (opaque layer) 0156 Materials were weighed and thoroughly homog Reflectance of O.S8 O.74 enized using a Homeland Housewares blender, item MBR faux shingle 1701, and model MB1001B. Powder total weight was chosen Transmittance of O.O2 O.08 between 6 gand 8 g depending on the unconsolidated powder e1 monolayers of volume. Powders were then inserted into the die and placed in #11 granules the press. Materials were compacted to 20,000 lbf. The com pact was held for 5 minutes at pressure. The liquid component The above results demonstrate that the BPH1 and BPH2CO, was added either prior to pressing, and mixed with starting sequestering materials are highly reflective and Suitable for reagents, or after the initial 5 minutes of pressing. In the case use in building applications, such as inclusion in roofing that the liquid component was added, after 5 minutes of shingles. pressing the die was removed, bottom mold components removed, liquid introduced and allowed to absorb into the II. Preparation and Characterization of Highly Reflective sample, and then the die was reassembled and pressed for 2 Compositions minutes at 13,000 lbf, Materials and Methods: 5. Curing 0157. The compacted pellets were further reacted in solu 1. Carbonate Precipitation tions to undergo curing process. Pellets were divided into 0148 Carbonate precipitation reactions were performed pieces and each piece was Submerged into tapwater, seawater, in 16 to 84 L plastic vessels with industrial grade CaCl, 3MMgCl, 1M HCO-containing or 1M NaCO, solutions. MgCl, NaSO and NaHCO. Precipitations were per The Submerged samples were stored in 5-mL plastic vials and formed at ambient temperature and pressure with agitation. kept in 40°C. water bath. The properties were continuously 014.9 The CaCO(s) employed in the following experi monitored using FTIR at regular time intervals. ments may also be produced using the following CO seques tration reaction, which is further described in U.S. application 6. Solar Irradiance Reflectance Measurement Ser. No. 14/112,495; the disclosure of which is herein incor 0158 Solar reflectance measurements were collected porated by reference: using SSR-ER instrument from Devices & Services Com Blue Planet Ltd.-Second Stage/Back End Reaction pany, Dallas Tex. or Lamda 950 from PerkinElmer. Samples were measured for Solar Reflectance and associated color 0150. Front End: rating in accordance with L*, a, b coloration measurement CO(g)+H2O(l)=HCO-(aq)+H" (aq) (1) (CIELab, see e.g. http://en.wikipedia.org/wiki/Lab color space). LAB coloration system is designed to mimic the 0151. Back End: human eye's ability to identify and translate color. Ca" (aq)+2HCO-(aq)=CaCO(s)+CO,(aq)+HO(l) (2) Results: 0152 Precipitations were dewatered using Buchner filters and the resulting slurry was dried at ambient pressure and 1. Precipitation Reactions temperature to produce a powder. 0159 Precipitated Ca-carbonates that were used to form 2. Phase Identification FTIR the densified carbonate samples in this work were synthe sized using a dual decomposition method with four different 0153 Powders, cements and coupons (produced by press chemistries as seen below. Dual decomposition method ing) were tested by hand and graded according to durability involves separate dissolution of CaCl and NaHCO, powders against breaking. All materials were observed by Fourier (indicated by separate parentheses in the reactions below). transform infrared (FTIR) on a Nicolet is 10 unit with a After reagents had fully dissolved, carbonate solutions were germanium crystal ATR attachment. Patterns were observed poured into CaCl, solutions. These chemistries resulted pri and analyzed from 600 cm to 2000 cm wavelength. marily in calcite, amorphous Vaterite precursor/anhydrous US 2014/0370242 A1 Dec. 18, 2014

amorphous carbonate, a low magnesium amorphous calcium 5.29 kg NaHCO was dissolved in a separate container with carbonate (ACC-Mg), and calcium silicate-carbonate co 42 L water. The NaHCO solution was poured into CaCl precipitate. The primary chemistries are as follows: MgCl2 and precipitated for 1 hour with automated stirring. Then the precipitates were Buchner-filtered and the filtered Calcite (1M CaCl2)+(1M NaHCO) 1. slurry initially dried using paper towels and then dried over Amorphous waterite precursor anhydrous amorphous night in ambient condition. carbonate (0.13M CaCl2+0.05M MgCl2)+(0.18M NaHCO+0.05M Na2SO) 2. Precipitate Example 4 Mg-ACC (0.15M CaCl2+0.6MMgCl2)+(0.75M 0.165. To increase the robustness of Ca-carbonate, colloi NaHCO) 3. dal silica was added to precipitate with carbonates to form a Ca-silicate/carbonate coprecipitate (reaction 4). First, 10.95g Ca-silicate/carbonate (0.1M CaCl2)+(0.095M CaCl was dissolved in 500 ml water and another 500 ml NaHCO+0.005M NaCO)+(SiOnH2O) 4. batch was prepared by mixing 0.212 g NaCO, and 3.99g 0160 Reagents used for reactions 1 to 3 are as follows: NaHCO, in 500 ml water. At 100° C., 10 ml of colloidal silica Calcium Chloride Pellets of Fire, Dart Seasonal Products was first added to CaCl Solution with magnetic stirring. Then Inc. (see e.g., the website having address made up of "http:// NaHCO. NaCO solution was added to Ca-silica mixture www.” in front of “dartsp.com'). Magnesium Chloride— and kept stirred for 1 hour at 100° C. to form the Ca-silicate/ MAG Ice Melting Pellets, Dead Sea Works Ltd. (see e.g., the carbonate coprecipitate. The precipitates were Buchner-fil website having address made up of “http://www.” in front of tered and the filtered slurry initially dried using paper towels “iclfertilizers.com'). Strontium Chloride Hexahydrate. The and then dried overnight in ambient condition. Science Company CASH 10025-70-4, Lothi36377. Sodium Sulfate, Dudadiesel Biodiesel supply (see e.g., the website a. Characterization having address made up of “http://www.” in front of “dudadiesel.com'). Sodium Bicarbonate, Arm & Hammer, 0166 Peaks used to identify the materials by way of FTIR Lotfi BSFC-01 170-04. Reagents used for reaction 4 were testing are described in Koutsoukos et al. (J. Chem. Soc., Smaller scale, using ACS grade chemicals: Calcium Chloride Faraday Trans. I, 1989, 85(10), 3165-3172). Calcite is indi Hexahydrate, Aldrich CASH7774-34-7. Loti BCBL2738V. cated by dual peaks at 714 cm and 876 cm and amorphous Sodium Bicarbonate, Arm & Hammer, Loti BSFC-01 170 Vaterite precursor/anhydrous amorphous carbonate is indi 04, Sodium Carbonate Anhydrous, Aqua Solutions cated by a strong band at 745 cm. Amorphous carbonate is CASH497-19-8, Loti 106203, colloidal silica LUDOX identified by a large peak, signifying non-crystallinity, AM-30 (30% suspended in water). between 600 cm and 1000 cm. Selected FTIR results are highlighted below and their associated chemistries are noted. Precipitate Example 1 0.167 FTIR spectra of various precipitates were obtained and analyzed. Without Mg, most stable calcite was precipi 0161 Calcite (reaction 1) was precipitated by dissolving tated (peaks specific to 713 cm and 875 cm), and with 1.75kg of CaClinto 8 kg water and 672g of NaHCO, in 8 kg Small amount of Mg, relatively unstable amorphous Vaterite water. The 8 kg precursor/anhydrous amorphous carbonate phase precipi 0162 NaHCO solution was added to 8 kg CaCl, solution and the mixed solution immediately began to precipitate tated (dark blue spectrum, amorphous Vaterite precursor/an white carbonate precipitates. The precipitation continued for hydrous amorphous carbonate peak shown at 744 cm). With 1 hour with thorough mixing using an automated stirrer. Then higher Mg level, the most unstable amorphous carbonates the precipitates were Buchner-filtered and the filtered slurry (Mg-ACC) appeared (as shown in broadened peaks in the was Squeeze-dried using paper towels and dried overnight in observed spectrum). A strong peak around 1100 cm (red) ambient condition. was indicative of polymerized silica in Ca-silicate precipita tion. Precipitate Example 2 0168 Amorphous precipitates were also imaged on a scanning electron microscope (SEM) and energy dispersive 0163 Amorphous Vaterite precursor/anhydrous amor X-ray (EDX) absorption tests were performed on reaction 3 phous carbonate (reaction 2) was prepared in a similar man (discussed above) and 5 (Sr used instead of Mg in reaction 3) ner to calcite, but in 84 L scale. 2.39 kg CaCl and 0.85 kg which were: MgCl, were dissolved in 56 L water, and 1.27 kg NaHCO and 0.6 kg NaSO were dissolved in 28 L water. After com (0.15M CaCl2+0.6M MgCl)+(0.75M NaHCO) 3. plete dissolution, NaHCO, NaSO mixture was added to CaCl MgCl, mixture and precipitated for 1 hour with auto (0.15M CaCl2+0.6M SrCl)+(0.75M NaHCO) 5. mated stirring. Then the precipitates were Buchner-filtered FIG. 4A provides the image of precipitate 3. The elemental and the filtered slurry was dried using paper towels and dried analysis of this precipitate is provided below: overnight in ambient condition. For amorphous Vaterite pre cursor/anhydrous amorphous carbonate precipitation, sodium sulfate level was kept lower than 0.1 M due to domi Element Weight% Atomic 96 nant precipitation of calcium Sulfate at Sulfate concentration OK 95.99 84.59 higher than 0.1 M. NaK O.31 O.19 Mg K 1.59 O.92 Precipitate Example 3 CK O46 O.18 CaK 40.11 14.11 0164 Mg-ACC (reaction3) was prepared in 84 L-scale, by mixing 2.76 kg CaCl and 10.25 kg. MgCl2 in 42 L water, and US 2014/0370242 A1 Dec. 18, 2014 22

Precipitate 3 appears to be a low magnesium calcite as indi Precipitated Pigment Example 1 cated by Railsbacket al. (LBR 820HMC-LMCSolubilities05 4/95; rev. 10/2006—Railsback Some fundamentals of Min (0173. In reaction 6, 98.59 g CaCl and 6.29 g MnO1 were eralogy and Geochemistry). dissolved in 1 L of water, and 84.01 g NaHCO was separately dissolved in 1L water. The NaHCO solution was poured into 0169 FIG. 4B provides the image of precipitation 5. The CaCl MnCl solution and the mixture was mixed with a elemental analysis of this precipitate is provided below: magnetic stirrer for 1 hour. Then the light red precipitates were Buchner-filtered and the filtered slurry was initially dried using paper towels and then dried overnight under Element Weight% Atomic 96 ambient condition. CK 61.66 51.37 OK 63.39 39.65 Precipitated Pigment Example 2 NaK 2.29 1.00 CK 6.39 18O 0.174 Reaction 7 was precipitated by mixing 62.92 g CaK 4.40 1.10 MnCl into 1 L of water and 84.01 g NaHCO into another Sir K 44.57 S.09 liter of water. Then NaHCO solution was poured into CaCl MnCl solution with magnetic stirring and kept for 1 When strontium was used in the same manner in the calcium hour. The rose red precipitates were Buchner-filtered and the and carbonate system it was apparent by EDX that a high level filtered slurry was initially dried using paper towels and then of Strontium was precipitated in the final carbonate. The dried overnight under ambient condition. material appears to be predominantly amorphous strontium carbonate. Precipitated Pigment Example 3 (0175. In reaction 8,98.59 g CaCl and 6.72g CuCl were b. Carbonate Precipitation from Flue Gas dissolved in 1 L of water, and 84.01 g NaHCO was separately dissolved in 1L water. The NaHCO solution was poured into Precipitate Example 5 CaCl CuCl2 solution and the mixture was mixed with a 0170 In addition to using sodium bicarbonate chemicals, magnetic stirrer for 1 hour. Then the blue precipitates were calcium carbonate precipitate has also been produced by Buchner-filtered and the filtered slurry was initially dried using CO gas. To forman LCP solution, 100 g L-Arginine using paper towels and then dried overnight under ambient and 2 mM/L NaOH were added to 16 L water at 23°C. Then condition. the solution was pressurized to 160 psi with CO. Once CO was dissolved into the liquid phase, the solution was intro Precipitated Pigment Example 4 duced into a reverse osmosis (RO) membrane system which 0176 Reaction 9 was precipitated by dissolving 67.23g allowed the retentate to be captured. Then 2000 mg/L CaCl. CuClinto 1 L of water and 84.01 g NaHCO into another liter 2HO was added to the retentate, which resulted in Ca-car of water. Then NaHCO, solution was poured into CaCl bonate precipitation. The Ca-carbonate was used in forming CuCl2 solution with magnetic stirring and kept for 1 hour. The carbonate cements. In an alternate example, calcium chloride green precipitates were Buchner-filtered and the filtered was added prior to passing the Solution through a membrane. slurry was initially dried using paper towels and then dried overnight under ambient condition. c. Colored Carbonate Precipitation 0177. These resulted in variously colored carbonate pre 0171 Colored carbonate materials were precipitated cipitates. Reaction 6 was light red, and Reaction 7 was rose/ potentially for pigment applications. These materials were red. Reaction 8 produced a blue/green product and Reaction precipitated according to the standard Blue Planet method as 9 produced a green product. outlined above. Transition metal chlorides were used, specifi 2. Manufacture of Albedo Enhancing Materials from Precipi cally MnCl (Sigma-Aldrich Loti MKBG2452V) and CuCl tate (Sigma-Aldrich Loti BCBL2738L) and further reagents a. Ceramic Samples were the same as used in previous reactions. Calcium Chlo 0.178 Precipitated powders were pressed to densify and ride Hexahydrate, Aldrich CASH7774-34-7, observe reactions that may take place during the powder LotfiBCBL2738V and Sodium Bicarbonate, Arm & Ham pressing process. Coupons were composed of 6-11 grams of mer, Lotif BSFC-01 170-04. powders (depending on Volume of respective powders) and 0172. The following reactions were performed in pyrex hydrated with 10 wt.% of a liquid phase to aid and/or promote vessels with magnetic stirring at 400 rpm in the standard dual any potential reaction. The liquid phases introduced into the decomposition method. The reactions were performed at samples (mixing solutions) were 1MMgCl, 3MMgCl, 1M ambient temperature (23°C.) and took place at a lower pH NaCO, 3M NaCO, as well as 10 ppm SrCl and 10,000 than reactions 1-5 (referenced previously). Reactions 6 and 7 ppm SrC1. Samples were compressed in a SD25, 25 mm die occurred at pH 6.1-6.7 and reactions 8 and 9 took place set in a Carver Press at 15,000 lbf. The die was used at between 6.3-7.3. ambient room temperature (23°C.), and at elevated tempera ture 80° C. and 130° C. (0.45M CaCl2+0.05M MnCl)+(1M NaHCO) 6. 0179 Samples were tested for durability qualitatively by hand. The most durable samples were reproduced (S47-S53) (0.5M MnCl2)+(1M NaHCO) 7. (similar to Ceramic Sample Example 3) and sent to measure (0.45M CaCl2+0.05M CuCl2)+(1M NaHCO) 8. reflectance with illumination by a solar irradiance lab tester, model SSR by Devices and Services Company (Data Seen (0.5M CuCl2)+(1M NaHCO) 9. Below Reflectance Data). These samples were not cured US 2014/0370242 A1 Dec. 18, 2014 post compression in a solution. Mechanical testing of various samples 31 and 35, the compressed powders show no reaction coupons as produced is in process. Highlighted below are product after being compressed. various samples that were produced and compared to starting powders to observe any characteristic change in their bond Ceramic Production Example 4 characterization by way of ATR-FTIR. 0183 Sample 19 was a compressed powder coupon com posed of 6 grams of calcite precursor with a significant ACC Ceramic Production Example 1 character. This material was blended with 2 mL of 10 ppm SrC1. Hydrated powder was placed in the die at 130° C. and 0180 Pressed sample 31 was composed of 4.5 grams of compacted for 5 minutes at 15,000 lbf, FTIR analysis magnesium stabilized amorphous calcium carbonate (pre revealed that the no reaction is taking place without a post cipitate section ACC-Mg) as well as 4.5 grams of amorphous curing step.

Sampleti materials Mixing solution Die temp (C.) S11 RXn 2 (amorphous waterite precursor anhydrous 4M MgCl, 2 g 23 amorphous carbonate) 8g S18 RXn 2 (amorphous waterite precursor anhydrous 10 ppm SrCl22g 23 amorphous carbonate) 6g S19 RXn 2 (amorphous waterite precursor anhydrous 10 ppm SrCl 2g 130 amorphous carbonate) 6g S31 RXn 2 (amorphous waterite precursor anhydrous MgCl21 ml 130 amorphous carbonate) + 4.5 g + RXn 3 (Mg-ACC) 4.5g S33 RXn 26 g + RXn 33 g MgCl21 ml 130 S35 RXn 2 (amorphous waterite precursor anhydrous Na2CO. 1 ml 130 amorphous carbonate) 6 g + RXn 33 g S36 RXn 26 g + RXn 33 g + Na2CO. 1g MgCl2, 1 ml 130 S37 RXn 26 g + RXn 33 g + NaHCO. 1g MgCl21 ml 130 S38 RXn 24 g + RXn 33.5g Na2CO. 1 ml 130 S96 RXn 24 g (wetamorphous waterite precursor 23 anhydrous amorphous carbonate) + rXn 1 (calcite) 6g S109 RXn 24 g (dry amorphous waterite precursor DI water 1 ml 23 anhydrous amorphous carbonate) + rXn 16 g S118 RXn 44 g (wet Ca-silicate) and rXn 16 g 65.8 S119 RXn 4 (wet) 4 g and rXn 46 g 1M Na2CO. 1 ml 71.9 S12O RXn 2 (amorphous waterite precursor anhydrous LUDOX colloidal silica 48.4 amorphous carbonate) 4 g + rXn 14 g + AIO 0.5g 1.5 ml S122 RXn 2 (amorphous waterite precursor anhydrous LUDOX colloidal silica 68.9 amorphous carbonate) 4 g + rXn 14 g + silicic acid 1.5 ml

Vaterite precursor/anhydrous amorphous carbonate. The Ceramic Production Example 5 powder was mixed with 1 ml 1M MgCl, solution and com 0.184 Sample E 3 was produced by dewatering reaction pacted to 15,000 lbf for 5 minutes. The die temperature was precipitate #56 during reaction. 100 grams of the wet slurry 130° C. As observed by FTIR, the sample showed no signifi was then placed in an extruder after blending with 120, 100 cant reaction and the pressed coupon indicated a peak pattern and 80 grams of a templating material. These extruded prod indicative of the addition of the curves exhibited by the pow ucts were then exposed to setting and curing conditions. ders. ii. Effects of Preparation Method on Compressed Coupon Samples Ceramic Production Example 2 0185. The compressed sample preparation method can affect the chemistry and hardness of samples. As stated on the 0181 Sample 35 was composed of 6 grams of amorphous table above, sample 18 and 19 were prepared in the exact Vaterite precursor/anhydrous amorphous carbonate and 3 same manner, but sample 19 was heated while pressing, while grams of magnesium stabilized calcium carbonate/low mag sample 18 was pressed at room temperature. As the result, the nesium carbonate, mixed with 1 mL of 1M Na,CO. Powders chemistry of dried sample 18 and 19 was different. Sample 18 were mixed with fluid and placed in the heated die (130°C..) showed mostly ACC with little calcite, while 19 showed then compressed to 15,000 lbf and maintained under pressure calcite and amorphous Vaterite precursor/anhydrous amor for 5 minutes. This sample showed no significant reaction phous carbonate with little aragonite. Also, the compressive after compaction. strength results after curing were significantly different. The unheated sample, 18 was found to be considerably stronger Ceramic Production Example 3 than heated sample 19. 0186 For some samples that contained stable starting 0182 Sample 42 was a mixture of precipitated strontium materials, most transformation occurred mainly during com carbonate (4 g) and amorphous Vaterite precursor/anhydrous pression, and no further reaction occurred during curing. amorphous carbonate (4 g). The powders were blended and Some of our samples contained calcite as the starting material compressed in a die at 130° C. for 5 minutes at 15,000 lbf. No for compression (S96-S122), as calcite can serve as a tem mixing solution was used in this experiment. Similar to plate for continuous calcite growth and eventually develop US 2014/0370242 A1 Dec. 18, 2014 24 strength of the sample (see e.g., Sample 96). As mentioned in were continuously monitored using FTIR, changes in chem the previous table, S96 was made from a mixture of reaction istry occurred according to different reaction conditions. The 2 (amorphous Vaterite precursor/anhydrous amorphous car detailed methodology of cured samples and the results are bonate) and reaction 1 (calcite). Most amorphous Vaterite stated in table below. Different results were obtained by using precursor/anhydrous amorphous carbonates in the sample different curing solutions. transformed into calcite during compression, which was stable enough not to undergo further reactions regardless of Curing Example 1 curing. When S96 was compressed, the coupon came out to 0189 As an example, sample 69, which originally con be very hard, and it maintained its strength even after curing. sisted of ACC, transformed into calcite when cured in 1M The coupons further hardened as all of remaining amorphous Na2CO Solution, while it transformed to aragonite in seawa Vaterite precursor/anhydrous amorphous carbonates trans ter. FTIR spectra comparing the original S69 and S69 cured in formed into calcite. In parallel to curing in tapwater, Na2CO, 1M NaCO, clearly indicated the formation of calcite by seawater, and MgCl, at 40°C., other samples were cured in appearance of representative calcite peak at 713 cm after 4 DI water and 1M NaHCO for 17 days at room temperature. days. All the samples were stable enough to stay as calcite and maintained the very hard strength. The FTIR results are Curing Example 2 shown in FIG. 5. FIG. 5 provides an FTIR of original S96 0190. As a comparison, S69 cured in seawater shows a (top), and S96 cured in water (second from top), in 1M completely different result, as peaks specific to aragonite at NaCO (third from top), in Moss Landing seawater (fourth 853, 713, and 700 cm continues to grow for 7 days. A from top), and in 3MMgCl2 (third from bottom) for 7 days at possible reason for the diverging result is that high pH in 40° C.; FTIR of S96 cured in 1M NaHCO (second from NaCO solution stabilizes the metastable ACC and amor bottom) and DI water (bottom) for 17 days at 23°C. All the phous Vaterite precursor/anhydrous amorphous carbonate to results show the common calcite peak at 877 and 713 cm. calcite, and different kinds of cations and organic compounds 0187 Unlike reaction 4, in which the co-precipitation of induced transformation into aragonite in Seawater as they Ca-silicate and CaCO were prepared before mixing (dis inhibit calcite formation. For instance, past studies show evi cussed more in detail in previous section), other samples were dence that the presence of Mg, Fe", and dissolved organic prepared by adding silicic acid and colloidal silica directly to carbons (DOCs) inhibit calcite formation. The two resulting CaCO powder blends just before pressing (samples 122 and cured samples were intensely hardened, due to formation of 123). The main purpose of adding silicato CaCO blends was calcite and aragonite. to improve the strength and stability of compressed coupons 0191 As mentioned in previous section, amorphous water and cured samples. Unlike sample 118, which the reaction ite precursor/anhydrous amorphous carbonate and ACCs are completed during compression and produced a hard pellet, metastable phases of calcium carbonate that are prone to samples 122 and 123 were still relatively weak after compres transformation into more stable polymorphs as calcite or sion. FTIR results of S122 and S123 coupons indicated pres aragonite depending on reaction conditions. Another ence of ACC, amorphous Vaterite precursor/anhydrous amor example that shows different transformation tendency with phous carbonate, polymerized silica with little calcite. different curing solution was sample 37. However, as the samples were cured, drastic chemistry changes occurred and the samples began to build very high Curing Example 3 strength. 0.192 The coupon was originally composed of amorphous b. Curing of Compressed Samples Vaterite precursor/anhydrous amorphous carbonate, ACC, 0188 After compression, the samples were cured at 40°C. and calcite. Although the original sample contained some to form fully stabilized and hardened materials. Every com calcite, it was transformed into aragonite when cured in water pressed coupon piece was Submerged into 3 ml tapwater, or 3MMgCl, while it transformed to calcite in 1M NaCO, seawater (from Moss Landing), 3M MgCl, or 1M NaCO solution. As the case of S69, the cured sample hardened after Solutions. The Submerged samples were stored in 5-mL plas 4 to 6 days of curing. tic vials and kept in a temperature-adjustable water bath at 40° 0193 The following table provides a summary of a subset C. to maintain the temperature for 1 week. As the samples of the curing samples that were studied.

Curing FTIR before Duration Sampleti solution Cl FTIR after cure hardness (days) tapwater ACC Aragonite Very hard 6 1M Na2CO ACC calcite Very hard 6 tapwater ACC Calcite, soft 6 amorphous waterite precursor? anhydrous amorphous carbonate, ACC 1M Na2CO. Calcite, calcite medium 6 amorphous waterite precursor? anhydrous amorphous carbonate US 2014/0370242 A1 Dec. 18, 2014

-continued

Curing FTIR before Duration Sample# solution Cl FTIR after cure hardness (days) S35-CW tapwater Calcite, Calcite, aragonite medium 7 8OOLS waterite precursor anhydrous 8OOLS carbonate S36-CC 1M Na2CO. Calcite, Calcite medium 8OOLS waterite precursor anhydrous 8OOLS carbonate S37-CC 1M Na2CO. Calcite, Calcite, ACC, Very hard 8OOLS amorphous waterite precursor waterite precursor anhydrous anhydrous 8OOLS amorphous carbonate, ACC carbonate S68-CS Seawater ACC Amorphous Very hard waterite precursor anhydrous amorphous carbonate, aragonite S68-CM 3M MgCl, ACC ACC, calcite, soft amorphous waterite precursor anhydrous amorphous carbonate S68-CC 1M Na2CO ACC ACC, calcite Very hard 7 S96-CS Seawater calcite calcite Very hard

FTIR analysis of original dry S69 coupon and S69 cured in 1 roller mill, hammer mill, media mill and the granules may or M. NaCO, for 4 days was done. The observed peak at 713 may not be treated with a coating process prior to adhering to cm for the cured sample represented calcite. FTIR of origi the shingle. nal dry S69 coupon and S69 cured in seawater for 4 days, and e. Production of Aggregate 7 days was done. The peaks appearing at 853, 713,700 cm 0196. Highly reflective aggregates have been produced by in the spectra of the cured samples represented the generation granulating precipitated powder, then pelletizing or tableting of aragonite. the granulated material. The aggregate could be from 1 mm to 100 mm in diameter and could be angular, fragmented in c. Carbonate Ceramics Containing Colored Industrial Pig shape or round. The materials have been used in concrete, ments & Carbonate Pigments showing good performance data and could be used for high (0194 Samples 87, 88, 89, and 90 (not shown in the table) albedo reflective road Surfacing. Furthermore, the aggregate were prepared in the exact same manner of preparing sample may be produced in a gap graded fashion or reduced from 68, by mixing 4 g of reaction 18 (amorphous Vaterite precur large amounts of extruded materials that have set and cured, Sor/anhydrous amorphous carbonate) and 4 g of reaction 25 as desired. (Mg-stabilized ACC) with 1 ml of 3M NaCO mixing solu f. Reflectance Data tion. However, samples 87, 88, 89, and 90 were added with 0.197 Reflectance Data of carbonate ceramic coupons buff and red Sakrete pigments and, blue, and black Ferro S-47-S-53 can be seen below. Solar reflectance for the non pigments, respectively. The result of curing the samples for 7 pigmented samples ranges from 78-83% reflective and the days indicated that hardness of the samples was not signifi pigmented samples range from 33-57% reflective. Common cantly affected when using these metal oxide dyes. Colored roofing materials are much lower. FIG. 6 provides further coupons were also compressed using MnCl2 or CuCl2 starting results. materials to obtain beige, brown, green, and blue colors, and the samples were cured in Solutions. Color Data Solar Reflectance d. Production of Granules 0.195 Carbonate ceramics were granulated in a jaw Sample ID L* a: b: reading 1 reading 2 Avg. crusher, gap graded on a US Tyler Sieve machine and placed SP-47 95.01 1.09 3.89 0.813 O.831 O.822 on a bitumenbacked shingle tile. # 11 granules were removed SP-48 94.62 1.08 4.52 O.828 O.823 O.826 SP-49 92.95 1.00 3.94 O.764 0.787 0.776 form the sieve stack and used as the granular material coating SP-50 Side1 57.18 18.59 20.21 O.329 O.337 O.333 the shingle. The materials were rolled onto the shingle and SP-50 Side 2 72.71. 15.23 21.57 tested in reflectance. FIGS. 2A & 2B. Solar reflectance was SP-51 61.76 25.73 1948 O.S66 0.579 0.573 measured and resulted in a high solar reflectance FIG. 3C. SP-52 63.28 O.80 -32.21 O.S42 O.S43 O.S43 The reduction process has also been performed on a disk mill, US 2014/0370242 A1 Dec. 18, 2014 26

-continued ganic pigments. Blue Planet cool pigments replace Titanium Dioxide for reflectance purposes and/or are used in conjunc Color Data Solar Reflectance tion with varying amounts of TiO. FIG. 9 is a solar Reflec tance comparison between Blue Planet Pigment, TiO2 and Sample ID L* a: b: reading 1 reading 2 Avg. industrially available pigments from Ferro and Sakrete. Cool SP-53 side 1 58.02 -0.44 -340 O.S.08 OSO4 O.S.06 pigments may also be used as pigment extenders or to extend SP-53 side 2 67.71 -0.69 -3.92 the use of TiO. Blue Planet cool pigments and reflective white materials find use to reduce the required amount of FIG. 7 provides pictures of Samples 47 to 53. Samples were pigment or TiO, required for specific UV absorbtion, Near further sanded with 240 grit then 400 grit sandpaper and the Infra-red reflectance or color additions, where reductions in Solar reflectance increased: requirements of TiO, while maintaining comparable func tionality, e.g., Substantially the same or the same functionality may vary, where reductions in need for TiO, may be 5% or ID 1.5E SR L1 (IR) L2(RED) L3 (Blue) L4 (UV) more, such as 10% or more, including 15%, 20%, 25%, 50%, 75% or more, e.g., ranging in some instances from 5 to 90% SP-47 O.889 O.803 O.927 O.922 O.825 SP-48 O.887 O.805 O921 O921 O.816 reduction, such as 10 to 75% reduction, including 15 to 50% SP-49 0.854 0.752 O.892 O.911 0.793 reduction, where all percentages are by weight. SP-50 O.626 O.654 O.691 O461 O314 c. Roofing Membranes SP-51 O.632 0.75 O.683 O.353 O.317 0200 TPO or other polymer single or multiply roofing SP-52 0.675 0.751 0.658 O606 O.726 membrane process include the use of a cool carbonate pre SP-53 0.558 0.779 O436 O464 0.515 cipitate or a cool pigment to increase the albedo of the roofing product. Blue Planet cool pigments replace Titanium Dioxide Solar reflectance of S156-S164 (The composition of these for reflectance purposes or be used in conjunction with vary materials was similar to ceramic coupon example 1 and 2 ing amounts of TiO. noted above) was measured at Lawrence Berkeley National d. Road Materials Lab (LBNL). These samples were prepared by mixing 4 g of 0201 Pelleted or tableted aggregates are used in applica amorphous Vaterite precursor/anhydrous amorphous carbon tion to road Surfacing by using whole of in granular form. The ate and 4 g. Mg-stabilized ACC blended with 0.5-1 ml aggregates are used with a bitumen glue layer on top of new Na2CO3 mixing solution. Solar reflectance of white samples or existing pavement, in a chip or cape sealing application. range in 85-92%. The reflectance of cured sample (S156.4) Aggregates are also used with tarring applications or asphalt dropped by approximately 7% compared to uncured sample road Surfacing applications that include rubberized asphalt as (S163). Gray, red, orange, and blue-colored samples also well as cold patch and normal asphalt. exhibited relatively high reflectance compared to commercial e. Concrete cool roofing materials. They ranged in 32-59% reflectivity. 0202 Concrete is made using Blue Planet carbonate Results are summarized in the table below: Setting performed aggregates created from pelletizing, granulating and tableted in Humidity Chamber (noted HC at 80 C, 60-99% RH), form. The aggregate is used in precast concrete, brick, block, Curing performed in a solution bath. paver, various weight concrete and other concrete Such as formed masonary units, pumpable concrete and normal Sample Thickness AM1GH solar weight concrete. FIG. 10 provides a comparison between Sample name description (mm) reflectance common concrete roofing tile and roofing tile including Blue Planet Pigment. RXn 10 + sol. Silica (none) 19.2 O.853 S156.4 7 day set HC; 6 day 8.0 O.808 0203 Although the foregoing invention has been cure; 1M Na2CO3 described in some detail by way of illustration and example S157 8 day set HC 6.1 O.919 for purposes of clarity of understanding, it is readily apparent S158 8 day set HC 6.3 O.S91 to those of ordinary skill in the art in light of the teachings of S159 8 day set HC 6.O O.324 S160 8 day set HC 5.3 O.S12 this invention that certain changes and modifications may be S162 8 day set HC 8.5 O438 made thereto without departing from the spirit or scope of the S1634 7 day set HC 6.1 O.876 appended claims. S163.5 7 day set HC 6.O O891 0204 Accordingly, the preceding merely illustrates the S163.6 7 day set HC 6.1 O.896 principles of the invention. It will be appreciated that those skilled in the art will be able to devise various arrangements Pictures of the samples are provided in FIG. 8. which, although not explicitly described or shown herein, C. Products Made from Blue Planet Materials embody the principles of the invention and are included a. Roofing Granules within its spirit and scope. Furthermore, all examples and 0198 Roofing granules will be fed to a continuous process conditional language recited herein are principally intended by a feeder where they may or may not be treated with a liquid to aid the reader in understanding the principles of the inven coating and dried using ambient heat from the bitumen heat tion and the concepts contributed by the inventors to further ing process. The materials will then be passed to and distrib ing the art, and are to be construed as being without limitation uted onto a warmed bitumen surface, adhering to a fiberboard to Such specifically recited examples and conditions. More shingle backing. over, all statements herein reciting principles, aspects, and b. Cool Pigments embodiments of the invention as well as specific examples 0199 Cool pigments are precipitated and used as a thereof, are intended to encompass both structural and func replacement for current pigment technology. Examples are tional equivalents thereof. Additionally, it is intended that Ferro, Shepard, BASF mixed metal oxides, organic and inor Such equivalents include both currently known equivalents US 2014/0370242 A1 Dec. 18, 2014 27 and equivalents developed in the future, i.e., any elements 10. The composition according to claim 9, wherein the developed that perform the same function, regardless of struc bicarbonate rich product comprises droplets of a liquid con ture. The scope of the present invention, therefore, is not densed phase (LCP) in a bulk liquid. intended to be limited to the exemplary embodiments shown 11. The composition according to claim 1, wherein the and described herein. Rather, the scope and spirit of present material has a near infra-red (NIR) reflectance ranging from invention is embodied by the appended claims. 50 to 99%. 1. A light reflective composition, the composition compris 12. The composition according to claim 1, wherein the ing a highly reflective microcrystallinefamorphous material. material has a ultra-violet (UV) reflectance ranging from 50 2. The composition according to claim 1, wherein the mate to 99%. rial comprises a microcrystalline carbonate component. 3. The composition according to claim 2, wherein the 13. The composition according to claim 1, wherein the microcrystalline carbonate component has a crystal size rang material has a visible light reflectance ranging from 50 to ing from 0 or X-ray Amorphous to 100LL. 99%. 4. The composition according to claim 2, wherein the 14. The composition according to claim 1, wherein the microcrystalline carbonate component comprises at least one composition further comprises one or more pigments. of calcium carbonate and magnesium carbonate. 15. The composition according to claim 12, wherein the 5. The composition according to claim 4, wherein the pigments are cool pigments. microcrystalline component comprises both a calcium car 16. The composition according to claim 1, wherein the bonate and a magnesium carbonate. composition is a Solid. 6. The composition according to claim 1, wherein the 17. The composition according to claim 16, wherein the microcrystalline component comprises a clay mineral. microcrystalline material is in a granular form. 7. The composition according to claim 6, wherein the clay 18. The composition according to claim 17, wherein the mineral comprises kaolinite. composition further comprises a solid Support, wherein the 8. The composition according to claim 1, wherein the mate microcrystalline material is present on a Surface of the Solid rial is a CO sequestering material. Support. 9. The composition according to claim 8, wherein the CO 19. The composition according to claim 18, wherein the sequestering material is prepared by: composition is configured as a building material. contacting a CO containing gas with an aqueous medium under conditions sufficient to produce a bicarbonate rich 20. The composition according to claim 19, wherein the product; and building material is roofing material. precipitating a carbonate mineral from the bicarbonate rich 21-48. (canceled) product.