# Patent

## Title
High SRI systems for cementitious applications

## Abstract

High SRI cementitious systems comprising integral concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems are provided. The high-SRI cementitious systems comprise one or more IR reflective pigments and other components to make-up the cementitious system, depending on the application. The high-SRI cementitious systems of the invention may be in the form of mixtures which increase the total solar reflectivity (TSR or albedo) and the Solar Reflectance Index (SRI) of concrete. The high-SRI cementitious systems may be toppings mixed with water for application to existing concrete surfaces, dry-shake hardeners for application to freshly-placed plastic concrete, or the IR reflective pigments may be mixed into integrally colored concrete in various forms, such as conventional cast-in-place concrete, lightweight concrete, pervious concrete and concrete building panels, pavers or masonry units. The topping and dry-shake hardener formulations of the invention may further comprise one or more of cementitious binder(s), graded aggregates, super-plasticizers, one or more pigments selected for improving infrared reflectivity and color composition, and/or optionally other additives, such as dry redispersible polymers or fillers to provide decorative and LEED compliant, highly durable (sustainable) concrete hardscapes and other decorative concrete.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is the U.S. national stage of International Application No. PCT/US09/30615 filed Jan. 9, 2009, which is a continuation-in-part, and claims the benefit of U.S. patent application Ser. No. 12/114,452, filed May 2, 2008, the contents of both of which are incorporated herein by reference in their entirety.


BACKGROUND
For millions of people living in and around cities, the urban heat island effect, i.e., a metropolitan area which is significantly warmer than nearby rural areas, is of growing concern. The elevated temperatures associated with the heat island effect, as well as increasing global temperatures, are impacting communities by increasing peak energy demand, air conditioning costs, air pollution levels, and heat-related illness and mortality. In addition, as energy costs are rising, there is a need to reduce energy consumption. The use of “cool” materials in roads and building construction can be used to mitigate the heat island effect, reduce energy demand and energy consumption. The term “cool” materials is used to describe building materials that have high solar reflectance, or albedo, and which reflect a large portion of the sun's energy. Cool materials may also have a high thermal emittance, releasing a large percentage of absorbed heat.
Keeping building materials cooler in sunlight is historically known. For example, U.S. Pat. No. 21,927 dated Oct. 26, 1858 (Johnson) discloses a new composition for roofing which uses mica as a solar reflector material. Johnson claims: “The mica being transparent and reflective, will act as a reflector of the sun's rays and add greatly to the coolness of the building to which it is applied.” Other historical references also describe the use of building materials to ward off the sun's rays. See, e.g., U.S. Pat. Nos. 35,464; 2,133,988; 3,577,379; 4,289,677; 4,424,292; and 4,624,710. Other references describing pigments used to protect building materials from sun exposure are also known. See, e.g., U.S. Pat. No. 5,006,175. A color restoring (self-cleansing) concrete body based on photo-catalytic TiO2 in anatase form is described in U.S. Pat. No. 3,102,039.
Complex Inorganic Color Pigments (CICPs) that are IR reflective are disclosed in several U.S. Pat. Nos. including 6,174,360, 6,416,868 and 6,541,112. These pigments are generally of spinel, rutile or corundum-hematite basic structure and are manufactured by several companies. Examples of these types of pigment are the Ferro's “GEODE® and EclipseTM Cool ColorsTM”, The Shepherd Color Company's “Arctic® Colors”, BASF's (formerly Engelhard) “Meteor® and Meteor® Plus” and Heubach's “Heucodur®” CICP products. Other references are known which also describe coatings and pigments for use in building materials. See, e.g., U.S. patent application Ser. Nos. 10/680,693 and 10/746,829, which disclose the use of 2-part coatings with infrared reflective pigments primarily for use in coating roofing granules for asphalt roofing, such as shingles; and U.S. patent application Ser. No. 10/989,120, which discloses a thermally insulating reflective coating system which is comprised of infrared reflective pigments, hollow micro-spheres, various fillers and resins where the coating has insulating as well as reflective properties.
During the mid 1970's, the ASTM established a standard for pigments used to integrally color concrete. Under the leadership of chairman David R. Arnold, L. M. Scofield Company, the task group charged with developing this standard completed their work in the early 1980's. The results are summarized in the ASTM Research Report, Pigments for Integrally Colored Concrete, Journal of Cement, Concrete and Aggregates (1980); ASTM C979 Standard, Specification for Pigments for Integrally Colored Concrete, (1982) was adopted following the report publication. More recently, a European Standard EN 12878, Pigments for the colouring of building materials based on cement and/or lime, has been adopted by the European common market standards organization (CEN).
Interest in concrete as a means of improving albedo or SRI of pavement has been studied by Ting, Koomey and Pomerantz as well as by Levinson and Akbari, both groups from the Lawrence Berkeley National Laboratory, and also by Marceau and VanGeem of the Portland Cement Association. These studies have considered gray and white cements as the primary factor in the resulting albedo or solar reflectance of the concrete with Supplementary Cementitious Materials (SCM's), contributing to the overall reflectivity. Marceau and VanGeem found that about 80% of the variation of solar reflectance of concrete was due to the cement reflectance when no SCM was present and 75% when SCM's were included and cement reflection was constant. They report that fine aggregates have a very small effect on the solar reflectance and that coarse aggregates also have been determined to play a very minor role in the resulting concrete's albedo or solar reflectance.
Concrete is a highly versatile and durable structural material that is widely used in nearly all modern construction. There has been a growing trend to make concrete surfaces, structures and other building elements more aesthetically pleasing by making a wide range of colors available and, more recently, to provide sustainable site development with concrete construction.
However, the selection of colors available that provide the desired level of solar reflectivity is limited. Therefore, there is a need to make available decorative concrete, cementitious matrices and other building components manufactured from concrete that have the desired improved solar reflectivity and resulting cooler surfaces.
SUMMARY
The cementitious products of this invention allow significant improvement in infrared (IR) reflectivity of structures made with or covered in the high-SRI cementitious systems of the invention, and also allow for making concrete coloring and texturing possible while providing a new color range of cementitious products. The high-SRI cementitious systems of the invention reduce or mitigate the “heat island effect” as described in publications by the Heat Island Group, Lawrence Berkeley National Laboratory (LBNL), by their improved IR reflectivity. Further, the cementitious application products described herein allow ordinary gray concrete to be cost effectively improved to provide high reflectivity (“albedo”) and high SRI along with a wide range of aesthetically pleasing colors.
The present invention describes high-SRI cementitious systems having infrared reflectivity. The high-SRI cementitious systems include, but are not limited to, integrally colored concrete, dry-shake hardeners, toppings and other cementitious systems, which provide a reduction in the well-documented “urban heat island effect”. The construction and building materials produced according to the invention facilitate and permit environmentally responsible construction practices under current “Green Building” and Leadership in Environmental Engineering and Design (LEED) guidelines as stated in the Ready Mixed Concrete Industry LEED Reference Guide (2006) RMC Research Foundation, to provide improved albedo and SRI performance well beyond what can be achieved with conventional concrete coloring systems currently available with the exception of white concrete.
Using white or even gray portland cement concrete without pigments a fairly high albedo value can be achieved. However, many current colors, in particular darker colors, do not provide adequate albedo and could be referred to as “hot” colors. The present invention permits the designer, or owner of the concrete to improve albedo and SRI values of the concrete while providing an extensive range of colors for concrete construction that can result in a more aesthetically pleasing and varied appearance as compared to conventionally colored architectural concrete. Further, the improved albedo and SRI values of the concrete can be cost effectively produced.
According to one embodiment of the invention, a high-SRI cementitious system comprising an infrared reflective pigment composition having one or more infrared reflective pigments is provided. The high-SRI cementitious system can be a cementitious matrix or a concrete coloring admixture. The infrared reflective pigments are selected from the group consisting of black infrared reflective pigments, red infrared reflective pigments; orange to yellow infrared reflective pigments; beige to brown infrared reflective pigments; green infrared reflective pigments; blue infrared reflective pigments; gray-white infrared reflective pigments; and combinations thereof.
According to the invention, the infrared reflective pigments comprise:
black infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 40%, and preferably are selected from the group consisting of manganese-vanadium oxide spinels, chromium green-black hematites, aluminum- and titanium-doped chromium green-black modified hematites, chromium iron oxides, hematite chromium green-blacks, iron chromite brown spinels including pigment brown 35, chromium iron nickel black spinels including pigment black 30, perylene blacks, and combinations thereof;
red infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 60%, preferably selected from the group consisting of o-chloro-p-nitroaniline coupled β-napthols, m-nitro-p-toluidine coupled with β-napthols, diazotized p-aminobenzamide coupled with BON-o-phentidines, diketo-pyyrolo-pyrrole reds, iron (III) oxide hematites, cerium sesquisulfides, quinacridone magenta B, pigment red 149, perylene reds, and combinations thereof;
orange to yellow infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 65%, preferably selected from the group consisting of benzimidazolone blends, chromium antimony titanate buff rutiles, o-dianisidine coupled with aceto-acetanilides, dinitraniline coupled with beta-naphthols, insoindoline yellows, o-(2-methoxy-4-nitrophenylhydrazono)-α-aceto-2′-methoxyacetanilides, monoarylide yellows, nickel antimony titanates, nickel antimony titanium yellow rutiles, m-nitro-o-anisidine coupled with acetoacet-o-anisidines, potassium cerium sulfides, pyrazolo-quinazolones, quinophthalone yellows, zinc ferrite yellow spinels and combinations thereof;
beige to brown infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 60%, preferably chrome antimony titanium buff rutiles and chrome antimony titanium rutiles, such as pigment brown 24, chromium iron oxide, chromium iron oxide spinels, such as pigment brown 29, chrome niobium buff rutiles, such as pigment yellow 162, chrome tungsten titanium buff rutiles, as pigment yellow 163, iron chromite buff spinels, such as pigment brown 29, iron titanium brown spinels, such as pigment black 12, manganese antimony titanium buff rutiles, such as pigment yellow 164, manganese antimony titanium rutiles, manganese tungsten titanium rutiles, zinc ferrite brown spinels, such as pigment yellow 119, zinc iron chromite brown spinels, such as pigment brown 33, and combinations thereof;
green infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 60%, preferably selected from the group consisting of chlorinated copper phthalocyanine greens, chromium green-black hematites, chromium green-black modified, certain chromium oxides, cobalt chromite blue-green spinels, cobalt chromite green spinels, cobalt titanate green spinels, partially halogenated copper phthalocyanines, and combinations thereof;
blue infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 50%, preferably, selected from the group consisting of cobalt aluminate blue spinels, cobalt chromite blue-green spinels, cobalt chromium zinc aluminate spinels, cobalt lithium titanate green spinels, copper phthalocyanines, indanthrones, and combinations thereof;
gray to white infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 60%, preferably, selected from the group consisting of black to white infrared reflective pigments, chromium green-black hematites, pigmentary anatase, chrome antimony titanium buff rutiles, anatase TiO2 and combinations thereof.
However, as will be understood by those of skill in the art by reference to this disclosure, the high-SRI cementitious system according to the invention can include a combination of infrared reflective pigments to form a range of colored cementitious systems.
According to another embodiment of the invention, the cementitious system is a dry shake color hardener, or a topping. According to another embodiment of the invention, a composition for creating a colored concrete material is provided. The composition comprises a cementitious system and one or more infrared reflective pigments of the invention. The cementitious system may be conventional concrete, lightweight concrete, or pervious concrete. Further, the high-SRI cementitious system may be used in a variety of cementitious applications, such as concrete panels, pavers or masonry units. Further, the integral concrete coloring admixtures may be used in concrete that is cast into manufactured pavers or precast building panels.
Methods for preparing cementitious systems including colored concrete and cementitious mixtures using one or more infrared reflective pigments of the invention are also provided. According to the method, the infrared reflective pigments may be added to the concrete as a coloring admixture or a cementitious mixture in the form of a topping for applying to hardened concrete, or a dry-shake hardener that is broadcast over freshly-placed (plastic) concrete. According to another embodiment, the infrared reflective pigments may be added integrally to concrete in various concrete related applications, such as conventional decorative concrete, lightweight concrete, pervious concrete, pre-cast structural elements and concrete masonry units or pavers.



FIGURES
These and other features, aspects and advantages of the present invention will become better understood from the following description, appended claims, and accompanying figures where:
FIG. 1 is a graph showing direct normal irradiance, ASTM E 891, Air Mass 1.5;
FIG. 2A is a graph of spectral reflectance for conventional black pigmented systems and infrared reflective black pigmented systems according to one embodiment of the invention;
FIG. 2B is a graph of reflected solar energy for conventional black pigmented systems and infrared reflective black pigmented systems according to the embodiment of the invention also shown in FIG. 2A;
FIG. 3A is a graph of spectral reflectance for conventional red pigmented systems and infrared reflective red pigmented systems according to another embodiment of the invention;
FIG. 3B is a graph of reflected solar energy for conventional red pigmented systems and infrared reflective red pigmented systems according to the embodiment of the invention also shown in FIG. 3A;
FIG. 4A is a graph of spectral reflectance for conventional yellow pigmented systems and infrared reflective yellow pigmented systems according to another embodiment of the invention;
FIG. 4B is a graph of reflected solar energy for conventional yellow pigmented systems and infrared reflective yellow pigmented systems according to the embodiment of the invention also shown in FIG. 4A;
FIG. 5A is a graph of spectral reflectance for conventional beige pigmented systems and infrared reflective brown and beige pigmented systems according to another embodiment of the invention;
FIG. 5B is a graph of reflected solar energy for conventional beige pigmented systems and infrared reflective brown and beige pigmented systems according to the embodiment of the invention also shown in FIG. 5A;
FIG. 6A is a graph of spectral reflectance for conventional green pigmented systems and infrared reflective green pigmented systems according to another embodiment of the invention;
FIG. 6B is a graph of reflected solar energy for conventional green pigmented systems and infrared reflective green pigmented systems according to the embodiment of the invention also shown in FIG. 6A;
FIG. 7A is a graph of spectral reflectance for conventional blue pigmented systems and infrared reflective blue pigmented systems according to another embodiment of the invention;
FIG. 7B is a graph of reflected solar energy for conventional blue pigmented systems and infrared reflective blue pigmented systems according to the embodiment of the invention also shown in FIG. 7A;
FIG. 8A is a graph of spectral reflectance for gray portland cement concrete and infrared reflective gray and white pigmented systems according to another embodiment of the invention; and
FIG. 8B is a graph of reflected solar energy for gray portland cement concrete and infrared reflective gray and white pigmented systems according to the embodiment of the invention also shown in FIG. 8A.



DESCRIPTION
According to one embodiment of the present invention, there is provided infrared (IR) reflective pigments for use in high-SRI cementitious systems. The high-SRI cementitious systems of the invention are cementitious applications that incorporate one or more IR reflective pigments into formulations such as, toppings mixed with water for application to existing concrete surfaces, dry-shake hardeners for application to freshly-placed plastic concrete, integral coloring admixtures for concrete of all types including pre-cast and/or even steam-cured concrete structural elements where conventional iron oxide yellow and black pigments would degrade due to temperature, as well as other cementitious systems such as integral colored concrete and stucco. Some of the cementitious topping or dry-shake hardener systems of the invention may include, in addition to one or more IR reflective pigments, one or more of the following: hydraulic cementitious binder(s); graded aggregates; super-plasticizers, water-reducing and/or air-entraining admixtures, pozzolans; one or more pigments selected for improving infrared reflectivity, or a desired color, and/or optionally other additives, such as dry redispersible polymers or fillers, depending on the particular cementitious application, to provide decorative and LEED compliant concrete hardscapes and other decorative concrete surfaces or structures.
The integral concrete coloring admixtures, cementitious toppings, dry-shake hardeners, and other high-SRI cementitious systems of the invention are used to color concrete or as concrete surface treatments and to provide a wide range of “cool” architectural concrete colors, i.e., concrete having high Solar Reflectance Index (SRI), or albedo, and which reflects a large portion of the sun's infrared energy. The integral concrete coloring admixtures, cementitious toppings and dry-shake hardeners according to the invention may be cost effectively used to produce an IR-reflective surface for concrete that is not possible with ordinary gray portland cement concrete with conventional pigments of similar colors. Ordinary gray portland cement concrete can be improved in IR reflectance and colored at the same time by selective use of integral concrete colors made with high IR reflectance pigments and/or additives. Colors included in the IR reflective compositions are: blacks, reds, yellows, oranges, greens, blues, browns, and whites. The IR reflective pigments of the invention may be combined to achieve colors such as beiges, purples, grays, or any intermediate shade thereof.
The color of the infrared reflective pigment described herein refers to the visual property of the pigment derived from the spectrum of light (distribution of light energy versus wavelength) in the corresponding category, e.g., red, orange, yellow, blue, green, etc. The color categories and physical specifications are also associated with the compositions based on their physical properties such as light absorption or reflection spectra. Additionally, the infrared reflective pigments described herein have a composition of reflected light that is detectable as colors by humans (wavelength spectrum from 400 nm to 700 nm, roughly).
In the case of black infrared pigments, the black color is the result of a pigment that absorbs light rather than reflects it back to the eye to “look black”, and a black pigment may be, in fact, a variation of a color, such as a blue-black or a green-black. A black pigment can, however, result from a combination of several pigments that collectively absorb all colors. If appropriate proportions of three primary colors of pigments are mixed, the result reflects so little light as to be called “black”.
In the case of gray-white infrared reflective pigments, the gray-white color refers to white pigments and the range of white to gray shades between near-black and near-white.
The stated colors of the infrared reflective pigments described herein should not be interpreted as absolute. Spectral colors form a continuous spectrum, and the infrared reflective pigments described herein are divided into distinct colors as a matter of convenience as will be understood by those of skill in the art, that the colors of the infrared reflective pigments may be between (or among), 2 or more stated colors, and still fall within the scope of the invention.
As used in this disclosure, the following terms have the following meanings.
“Absorptance” (α, alpha) is the ratio of absorbed radiant flux to incident radiant flux.
“Albedo” is the ratio of reflected sunlight energy to the amount of solar irradiance (energy) falling on a given surface. As used herein, the term refers to the overall spectra reflectance of sunlight from  ̃360 nm to 2500 nm based on calculation from spectral values obtained by ASTM E 903 and solar insolation values from ASTM E 891 using the 50-point or 100-point selected (equal-energy) ordinate method for direct solar irradiance. ASTM E 891 data is at air mass 1.5, turbidity 0.27 and zenith angle of at 48.19° which is a composite value for the contiguous United States. Albedo can be expressed as a percent (29%), or more commonly, as a decimal fraction, such as 0.29. Total Solar Reflectance (TSR) and albedo are used interchangeably. It should be noted that albedo (TSR) includes portions of the UV (up to 400 nm), all of the visible spectra (400-700 nm) and the infrared from (701-2500 nm). Generally dark colored materials have low albedo and light colored materials have high albedo, however IR reflective materials can be fairly dark and still have fairly high albedo values.
“Cementitious application” refers to a building, construction, and/or manufacturing material or process containing a cement, and also includes applications.
“Cementitious matrix” refers to a composition containing cement and optionally one or more other additives, depending on the cementitious application, such as a topping, dry-shake hardener, or other cementitious application, such as concrete.
“Cementitious system” refers to a concrete coloring admixture or cementitious matrix.
“Concrete coloring admixture” refers to a composition containing a pigment and other additives, such as a water reducing agent.
“CICP” is an acronym for “Complex Inorganic Color Pigment”, which is a colored mixed metal oxide.
“High-SRI Cementitious system” refers to a cementitious system having a high-SRI value, generally of at least above about 29 SRI units, more preferably, above about 32 SRI units, and in some colored high-SRI cementitious systems, above about 40 SRI units.
“Infrared (IR) Reflectance” refers to the hemispherical reflectance values measured from ASTM E 903 for wavelengths from 700 to 2500 nm referenced to standards using a diffuse reflectance measurement with a hemispherical integrating sphere.
“LEED” is an acronym for Leadership in Environmental Engineering and Design, a program administered by the U.S. Green Building Council (USGBC), to promote sustainability, energy efficiency and to minimize environmental impact in both new construction (NC) and existing buildings (EB). The LEED requirements referenced herein are related to mitigation of the “Urban Heat Island Effect” under LEED Sustainable Sites Credit 7.1 and possible exemplary and/or innovation credit(s) for high levels of performance, well beyond what is required.
“Kirchoff Relationship” per ASTM E903 defines 3 related properties of light energy as follows:
αs+τs+ρs=1, where αs (alpha sub s) is absorptance, τs (tau sub s) is transmittance and ρs (rho sub s) is reflectance. Transmittance, τs=0 for opaque materials (e.g. concrete). High absorptance is related to the heat build-up and the high reflectance is required to reduce heat build-up.
“Reflectance, ρ (rho)”, is the ratio of the reflected radiant flux to the incident radiant flux.
“Solar Insolation” refers to the solar irradiance that is incident on a surface, considering angle, air mass, global position and other atmospheric conditions.
“Solar Irradiance per unit wavelength” refers to the energy that is available from sunlight under specified conditions, such as air mass=1.5 and 37° tilt, direct, or other variables such as global position and atmospheric chemical composition, turbidity or rural aerosol and unit of wavelength. This information is derived from measured solar irradiance data from SMARTS2 or earlier solar models, such as Fröhlich and Wherli or Neckel and Labs and from ASTM Sunlight Standards E490, E891, E892 and G173.
“Solar Irradiance, Spectral” refers to the solar irradiance (Eλ, or Energy at wavelength) that is available at a given wavelength, λ (lambda), using the units, watts*meter−2*μm−1, where Eλ=dE/dλ.
Solar Reflectance Index (SRI) enables estimation of how hot a surface will become upon exposure to sunlight. It is computed from the TSR or albedo values using the Stefan-Boltzman Constant, 5.67 E-8 watts*m−2*° K−4 and can include a normally assigned emittance (ε, epsilon) value (e.g. ε=0.90 default value for concrete), wind speed, air and sky temperatures as well as reflectances and temperatures of both black and white surfaces.
“Urban Heat Island Effect” is the known increase in the average temperature of cities or urban areas as compared to the temperatures of surrounding non-urban areas. This temperature rise is due to the pavement and buildings with low solar reflectivity as opposed to the trees and vegetation with higher solar reflectivity in the non-urban areas.
As used in this disclosure, the term “comprise” and variations of the term, such as “comprising” and “comprises,” are not intended to exclude other additives, components, integers or steps.
All amounts disclosed herein are given in weight percent of the total weight of the composition.
In one embodiment, the present invention is the use of one or more infrared (IR) reflective pigments in concrete or a cementitious system. The IR reflective pigments of the invention are blacks, reds, yellows, oranges, greens, blues, browns, and whites, and may be combined to achieve colors such as beiges, purples, grays, and other intermediate shades. The IR reflective pigments are formulated in compositions for use in high-SRI cementitious systems, such as integral coloring admixtures, toppings, dry-shake color hardeners, and other cementitious systems. The coloring admixtures for concrete, dry-shake color hardeners, and topping formulations of the invention use pigments that have good IR reflective properties. The IR reflective pigments of the invention may be obtained from commercial sources and are selected based on the criteria described below. The high-SRI cementitious systems according to the invention are designed to maximize the effectiveness of the selected pigments in a system and result in a group of colored products that provide significant improvements in the albedo of the concrete or cementitious system substrate as compared to conventional technology. The concrete coloring admixtures and other cementitious systems according to the invention preferably reduce surface temperature rise with sunlight exposure as compared to analogous conventional products. The use of pigments or cementitious system components including all known toxic or environmentally harmful pigments such as any containing lead, arsenic, cadmium, hexavalent chromium, and aniline-based colors are not preferred materials and are generally eliminated from consideration for use in the invention. All other non-toxic or environmentally-safe systems described in the above compositions are formulated to observe the Twelve Principles of Green Chemistry, (http://www.epa.gov/greenchemistry/pubs/principles.html), wherever applicable.
Most of the IR reflective pigments are pigment types from the category of complex inorganic color pigments (CICPs). CICPs are generally of the rutile, spinel or corundum-hematite crystal structure, as described in Advanced Inorganic Chemistry, Cotton and Wilkinson, 1980, pp. 16-17. These CICPs, formerly referred to as mixed metal oxides (MMOs), have 2 or more metals in the same crystal unit structure. These crystal structures are generally referred to as rutile, spinel or corundum-hematite, based on the composition and crystal lattice structures of the minerals rutile, spinel or corundum-hematite. Corundum structures in α-Al2O3 form may also be referred to as hematites.
Rutiles, as described in Advanced Inorganic Chemistry, Cotton and Wilkinson, 1980, p. 16 are composite metal oxides with a crystal structure corresponding to the rutile form of titanium dioxide TiO2, where each metal ion is in a 6-coordinate system with the oxygen ions. These are generally represented by the formula MO2, where M represents one or more metal ions. Nickel antimony titanate is an example of a rutile structure, with part of the Ti (IV) cations replaced by nickel (II) cations and antimony (V) cations, all occupying the same rutile lattice unit cell structure.
Spinels, as described in Advanced Inorganic Chemistry, Cotton and Wilkinson, 1980, p 17, are composite metal oxide crystal structures generally referring to the formula MgAl2O4. Spinels have a symmetry of ccp (cubic close-packed) of the oxygen ions with one-eighth of the tetrahedral holes filled with Mg+2 ions and one-half of the octahedral holes occupied by Al+3 ions. Many CICPs have this same structure for Ma+2Mb2+3O4 metal oxides, where Ma is a metal ion of valence +2 with one ion per spinel unit structure and Mb2 is a metal of valence +3 with 2 ions per spinel unit structure. Structurally, this is equivalent to Ma[II]O.Mb[III]2O3 metal oxides, for normal spinels, but Ma[IV]O.Mb[II]2O3 or Ma[I]2O.Mb[VI]O3 and other spinel variations can also form.
Corundums, as described in Advanced Inorganic Chemistry, Cotton and Wilkinson, 1980, p 16, are metal oxides crystal structures referring to corundum, α-Al2O3 and hematite Fe2O3 which have a symmetry of hcp (hexagonal close-packed) oxygen ions with two-thirds of the octahedral interstices occupied by metal cations. Examples of these compounds are Cr2O3 or FeCrO3 where the metal cation(s) is/are normally in the +3 valence state.
There are many variations of these unit cell structures as described in Advanced Inorganic Chemistry, Cotton and Wilkinson, 1980, p 17, pp 686-87 and p 753, such as inverse spinels with Fe3O4 (magnetite) as an example of a stoichiometric compound where the Fe+2 and Fe+3 ions occupy the spaces normally occupied by the oxygen ions in the crystal lattice. Disordered spinels which are not stoichiometric, have only a fraction of the tetrahedral sites or the octahedral sites occupied by metal ions. The size (ionic radii) relationships of the metal cations to the size of the oxygen anions and Vegard's Law, along with Crystal Field Stabilization Energy (CFSE) help to determine the resulting crystal lattice structure.
CICP pigments are considerably more costly to produce than conventional iron oxide and chromium oxide based pigments, however, they are very stable chemically and are resistant to high heat and UV exposure as well because they are produced at up to 1000° C. (1800° F.). CICP pigments provide color by electron transitions from one quantum energy level (mostly in d-orbitals) to another (also mostly d-orbital) where part of the white sunlight is absorbed and the remaining complementary color in the visible range (and extending into the NIR) is reflected.
Many organic pigments have fair to good IR reflectivity and are generally more intensely colored than the similar colors are with inorganic pigments. Some of these organic colors extend the available color range to include colors that cannot be achieved with conventional inorganic pigments. Organic pigments provide color by having chromophore groups with conjugated π-electron overlaps that provide resonant structures absorbing energy at certain wavelengths in the visible range and IR spectral range and reflecting energy at other wavelengths. Organic pigments, in many cases, are sensitive to the harsh high (11-12) pH environment of cementitious materials and even though they may work fine in coatings, they may fail rapidly in moist exterior exposed cementitious systems. In some cases the organic pigments also can fail due to UV exposure as noted with BASF (formerly Engelhard) 1270 Diarylide Yellow (below). Additionally, some organic pigments are non-polar and do not disperse well enough in cementitious systems or can cause excessive degradation of physical properties of the cementitious systems such as reduction of compressive strength. Other organic pigments will not remain bound in the cementitious matrix and can wash out or track off over time. Given all of these potential incompatibilities, adequate testing is required to thoroughly evaluate each pigment used in the IR reflective cementitious systems according to the invention.
As described below, pigments used according to the invention may be obtained from commercial sources, where indicated, or are available from a variety of manufactures where indicated. The following abbreviations are used for the following commercial suppliers. BASF having offices in Charlotte, N.C., is referred to as BASF, BASF formerly Engelhard, having offices in Iselin, N.J. is referred to as “BASF-E”; Colorchem International Corp., having offices in Atlanta, Ga. is referred to as “Colorchem” CIBA Specialty Chemicals, having offices in Newport, Del. is referred to as “CIBA”; Ferro Corporation, having offices in Cleveland, Ohio is referred to as “Ferro”; Elementis Pigments, having offices in East St. Louis, Ill. is referred to as “Elementis”; Heucotech, having offices in Fairless Hills, Pa. is referred to as “Heubach”; Ishirara ISK having offices in San Francisco, Calif. is referred to as “ISK”, Lanxess Corporation formerly Bayer, having offices in Pittsburgh, Pa., is referred as “Lanxess”, The Shepherd Color Co., having offices in Cincinnati, Ohio is referred to as “Shepherd”; Sun Chemical, having offices in Cincinnati, Ohio is referred to as “Sun”; TOR Minerals International having offices in Corpus Christi, Tex. is referred to as TOR, and United Color Manufacturing, having offices in Newtown, Pa. is referred to as “United”.
According to one embodiment of the invention, cementitious systems for black concrete integral coloring admixtures, dry-shake hardeners and toppings are provided. These cementitious systems have black IR reflective pigments. Preferably, the black IR reflective pigments have a minimum value of 40% reflectance at 1000 nm. Some black pigments that may not be of high enough SRI on their own but with higher IR reflectance than iron oxide or carbon black, can be used in combinations with higher SRI pigments to meet minimum SRI requirements.
The black IR reflective pigments that provide the desired IR-reflective properties may include one or more of the following pigments:

    
    
        aluminum and titanium doped chromium green-black modified hematites, commercially available as V-780 Cool ColorsTM IR Brown Black (Ferro) and V-799 Cool ColorsTM IR Black (Ferro);
        copper chromium manganese black spinel, commercially available as pigment black 28, such as 7890 Meteor® Black (BASF-E), 9875 Meteor® Plus HS Jet Black, Black 411 (Shepherd);
        copper chromium manganese barium spinel, commercially available as pigment black 28, such as 5875 Meteor® Plus Jet Black, Heucodur® Brown 869 (Heubach) Black, Heucodur® Black 953 (Heubach), Heucodur® Black 963 (Heubach),
        chromium green-black hematites, commercially available as pigment green 17, such as GEODE® V-774 Cool ColorsTM HS Black (Ferro), GEODE® V-775 Cool ColorsTM IR Black (Ferro), V-776 IR Black (Ferro), GEODE® V-778 Cool ColorsTM IR Black (Ferro), GEODE® 10204 IR EclipseTM IR Black (Ferro), O-1775B Ebony (Ferro), Black 10C909 (Shepherd), and Black 30C940 (Shepherd);
        chromium iron nickel black spinels, commercially available as pigment black 30, such as GEODE® 10456 Black (Ferro) and Heucodur® Black 950 (Heubach);
        chromium iron oxide spinels, commercially available as pigment brown 29, such as Black 411 (Shepherd), 9880 Meteor® Plus High IR Jet (blue shade) Black (BASF-E), 9882 Meteor® Plus (blue shade, high strength) Black (BASF-E), 9887 Meteor® Plus (Brown Shade) High IR Black (BASF-E), 9889 Meteor® Plus (brown shade) High IR Black (BASF-E),
        cobalt chromium iron spinel, commercially available as pigment black 27, such as Heucodur® Black 955 (Heubach),
        copper chromium iron spinel, commercially available as pigment black 28, such as Heucodur® Black 9-100 (Heubach)
        hematite chromium green-blacks, commercially available as pigment green 17, such as Heucodur® Black 910 (Heubach);
        iron chromite black spinels, commercially available as pigment brown 35, such as 7895 Meteor® High IR Black (BASF-E), 9891 Black (Blue Shade), MT, High IR Black (BASF-E), 9895 Black, High IR (BASF-E), Heucodur® Black 920 (Heubach), Heucodur® Black 940 (Heubach);
        iron chromium manganese black spinel, commercially available as pigment brown 29, 9880 Meteor® Plus High IR Black; 9882 Meteor® Plus Black (Blue Shade High Strength), 9887 Meteor® Plus High IR Black (Brown Shade), 9889 Meteor®Plus High IR Black (Brown Shade High Strength);
        chromium-free proprietary manganese, bismuth, strontium and/or vanadium oxide spinels, commercially available as GEODE® 10201 EclipseTM Black (Ferro), GEODE® 10202 (new experimental version 0-1786) EclipseTM Black (Ferro), and GEODE® 10203 EclipseTM Black (Ferro); and
        perylene black, commercially available as PaliotolTM L 0086 (BASF).
    
    


In a preferred embodiment, a black high-SRI IR reflective cementitious system is provided. More preferably, the black high-SRI IR reflective composition is a coloring admixture for concrete, topping, dry-shake color hardener, or other cementitious system that utilizes the CICP black pigments, GEODE® V-775 (Ferro), GEODE® V-776 (Ferro) and EclipseTM Black 10202 (Ferro), to achieve the black to gray range of colors with high albedo or SRI. The most preferred black color for integrally colored concrete or cementitious topping or dry-shake color hardener utilizes EclipseTM Black 10202 (new experimental version 0-1786) (Ferro) to achieve the highest possible albedo or SRI values. Bayferrox 303-T (Lanxess), a lower cost CICP manganese ferrite black spinel pigment with moderate IR reflectance (although too low by itself) can be used along with higher IR reflectance pigments to provide required minimum SRI values in more cost effective formulations, where cost constraints must be considered as well as SRI.
As it is known to those in the art, carbon black and black iron oxide absorb strongly across the whole UV, V is and NIR spectrum, have very poor albedo or SRI values, and are generally unsuitable for any application where IR reflectivity is required. Referring now to FIG. 2A, the data covering formulas with these carbon black and black iron oxide pigments are shown to indicate the difference in current knowledge of the art in architectural colored concrete and the cementitious systems, including dry-shake hardener and toppings having black IR reflective pigments of the invention.
As noted, black iron oxide and carbon black are not suitable in systems intended to provide IR reflectivity. In addition, it has also been determined that many CICP pigments in the black range are similarly unsuitable for use in integrally colored concrete, cementitious topping or dry-shake systems intended to provide IR reflectivity. Examples of such low IR reflective systems are with CICP pigments that include a different manganese ferrite black spinel (F-6331-2 (Ferro), Coal Black) and iron cobalt chromite black spinel (pigment black 27, GEODE® 10335 Black (Ferro)), where the latter-named pigment shows the characteristic cobalt trough from 1200-1800 nm. Another system with only weak to moderate IR reflectivity uses chrome iron nickel black spinel, GEODE® 10456 Black (Ferro). It has also been determined that although concrete or cementitious systems can be pigmented with carbazole violet, pigment violet 23 (Sun or Ciba) mixed with phthalocyanine green, (pigment green 7) to provide an intense black with excellent IR reflectivity, this combination of pigments does not remain adequately bound into the concrete or other cementitious matrix and would be expected to wash out over time. The carbazole violet, phthalocyanine green combination was not tested in a dry-shake hardener system due to its failure to remain bound in the topping binder system and also to the possibility of wind-blown organic pigment from dry-shake broadcast application procedures.
According to another embodiment of the invention, high-SRI cementitious systems for red colored dry-shake hardeners and toppings are provided. These high-SRI cementitious systems have red IR reflective pigments. Preferably, the red IR reflective pigments have a minimum value of 50% reflectance at 1000 nm.
The red IR reflective pigments that provide the desired IR-reflective properties may include one or more of the following pigments:

    
    
        o-Chloro-p-nitroaniline coupled β-napthols, such as 1088 Blazing Red (BASF-E);
        m-nitro-p-toluidine coupled with β-napthols, such as 1173 Toluidine Dark Red (BASF-E);
        diazotized p-aminobenzamide coupled with BON-o-phentidines, such as 3169 Red (BASF-E) and 3170 Red (BASF-E);
        diketo-pyyrol-pyrrole (DPP) reds, such as CIBA Irgazin® Red 2030 (CIBA); Monolite® Red 325401 (Heubach),
        iron (III) oxide hematites, such as GEODE® V-13810 High IR Red (Ferro), however, some red iron oxide pigments other than V-13810 may have fair IR reflectance but also may have small amounts of magnetic iron oxide or black iron oxide which can adversely affect their reflective properties across the UV-Vis-NIR spectrum;
        cerium sesquisulfides, such as Rhodia NeolorTM Red S (Colorchem);
        quinacridone magenta B, such as Sunfast® Red 228-1220 (Sun), 228-6725 (Sun); and
        perylene reds, such as United pigment red 149, (United);
    
    


In a preferred embodiment, red IR reflective pigments for cementitious systems including, concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems are provided. More preferably, the IR reflective concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems utilize red IR reflective pigments including iron (III) oxide hematites, such as GEODE® V-13810 High IR Red (Ferro), and cerium sesquisulfides, such as Rhodia NeolorTM Red S to achieve the high albedo and SRI values. The most preferred red IR reflective pigment is Rhodia NeolarTM Red S, used in cementitious systems to provide the best possible albedo and SRI values.
In the selection of pigments in the IR reflective red range it was determined that Casacolor DPP Red 2540, pigment red 254, (Keystone Aniline, Chicago) would not stay in the topping system binder well enough and would be prone to wash out in exterior applications. The performance of the Ciba Irgazin® DPP Red 2030 was satisfactory and it did not have the same wash out tendency, which was likely due to different crystalline structure vs. the Casacolor DPP Red 2540. The conventional iron oxide pigment controls, such as Bayferrox® Red 110 or Red 140, can provide moderate albedo and SRI values when used in both gray and white portland cement systems, however, a gain in albedo and SRI can be achieved by using a system with higher IR reflectivity, for example using GEODE® V-13810 High IR Red (Ferro), Ciba Irgazine® DPP Red (CIBA) or Rhodia NeolorTM Red S (Colorchem) in the integral concrete coloring admixtures, toppings or dry-shake hardeners. A topping test specimen with an orange blend of Casacolor DPP Red 2540 (Keystone) and conventional yellow 2087 pigment also showed loss of red, fading to yellow after 10 months of exterior exposure and was excluded, however the topping with DPP red (CIBA) had satisfactory performance after 1 year of exterior exposure.
According to another embodiment of the invention, high-SRI cementitious systems for yellow and orange colored concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems are provided. These high-SRI cementitious systems have yellow and orange IR reflective pigments. Preferably, the yellow and orange IR reflective pigments have a minimum value of 65% reflectance at 1000 nm.
The yellow and orange IR reflective pigments that provide the desired IR-reflective properties may include one or more of the following pigments:

    
    
        azo complexes, such as Bayfast Y5688 (Lanxess);
        benzimidazolone blends, such as 1207 RightfitTM Yellow 3G (BASF-E);
        chromium antimony titanate buff rutiles, commercially available as pigment brown 24, such as Meteor® 7370 Yellow Buff (BASF-E), Meteor® 7371 Yellow Buff (BASF-E), Meteor® 8380 Yellow Buff Light (BASF-E), Meteor® Plus 9371 Yellow Buff, plastics (BASF-E), Meteor® Plus 9375 Yellow Buff (BASF-E), Meteor® Plus 9377 Buff (BASF-E) Meteor® Plus 9379 FF Yellow Buff, High Strength (BASF-E), Heucodur® Yellow 3R (Heubach), Heucodur® Yellow 251 (Heubach), Heucodur® Yellow 252 (Heubach), Heucodur® Yellow 254 (Heubach), Heucodur® Yellow 256 (Heubach) Heucodur® Yellow 5R (Heubach), Heucodur® Yellow G 9202 (Heubach), Heucodur® Yellow 6R (Heubach), Heucodur® Yellow 259 (Heubach), Heucodur® Yellow 265 (Heubach), GEODE® 10411 Bright Golden Yellow (Ferro); GEODE® 10415 Bright Golden Yellow (Ferro), GEODE® 10657 Bright Golden Yellow (Ferro), GEODE® V-12112 Bright Golden Yellow (Ferro), Yellow 196 (Shepherd), Yellow 10C272 (Shepherd) and Arctic® Yellow 10C272 (Shepherd), Yellow 10P270 (Shepherd), and 30C236 (Shepherd); Tipaque® Yellow TY-100 (Buff), TY-150, TY-200, TY-300 (Buff) and TY-400 (Buff), (ISK);
        chromium tungsten titanium rutile, commercially available as pigment yellow 163, such as 7383 Meteor® Orange (BASF-E), 9384 Meteor® Plus Red-Buff (BASF-E), 9385 Meteor® Plus Golden Buff (BASF-E);
        cobalt niobium titanium buff rutile, commercially available as pigment yellow 221, such as Tipaque Yellow PF-1207 (ISK);
        iron titanium brown spinel, commercially available as pigment black 12, such as Yellow 20P296 (Shepherd);
        o-dianisidine coupled with aceto-acetanilides, such as 2915 Orange (BASF-E);
        dinitraniline coupled with beta-naphthols, such as 2916 Orange (BASF-E);
        insoindoline yellows, such as PaliotolTM Yellow L1820 (BASF-E),
        o-(2-methoxy-4-nitrophenylhydrazono)-α-aceto-2′-methoxyacetanilides, such as 1244 Sunglow Yellow “Hansa yellow” (BASF-E);
        monoarylide yellows, such as Sunfast® 272-6123 (Sun);
        nickel antimony titanates, rutile symmetry crystal structures, such as pigment yellow 53, such as 8320 Meteor® Yellow (BASF-E), 9350 Meteor® Plus Bright Golden Yellow (BASF-E), Heucodur® Yellow HD 152 (Heubach), Heucodur® PLUS Yellow 150 (Heubach) and Heucodur® PLUS Yellow 152 (Heubach), Heucodur® Yellow 156 (Heubach), Heucodur® Yellow 7G (Heubach), Heucodur® Yellow 8G (Heubach), Heucodur® Yellow G 9082 (Heubach), Heucodur® PLUS Yellow 8G (Heubach), GEODE® V-9415 EclipseTM Yellow (Ferro), GEODE® V-9416 Yellow (Ferro), Arctic 10C112 (Shepherd), 10G152 Yellow (Shepherd), Yellow 10P110 Yellow 30C119 (Shepherd), Yellow Tipaque® Yellow TY-50 and TY-70 (ISK)
        nickel antimony chromium titanate, rutile symmetry, commercially available as pigment yellow 53, Heucodur® Yellow G 9116 (Heucotech)
        nickel niobium titanium yellow rutile, commercially available as pigment yellow 161, GEODE® V-9440 Yellow (Ferro),
        nickel niobium buff rutile, commercially available as pigment yellow 162, GEODE® V-12107 Sand Yellow (Ferro);
        nickel tungsten titanate rutile, commercially available as pigment yellow 189, 9304 Meteor® Plus Golden Yellow (BASF-E)
        m-nitro-o-anisidine coupled with acetoacet-o-anisidines, such as 1237 Sunglow Yellow (BASF-E), Sunglow 1244 (BASF-E), and Sunglow 1241 SY (BASF-E);
    
    


Potassium cerium sulfides, such as Rhodia NeolorTM Orange S (Colorchem); pyrazolo-quinazolones, such as PaliotolTM 2930 HD Orange (BASF); and quinophthalone yellows, such as PaliotolTM Yellow L 0962 HD (BASF);
Zinc Ferrite, a temperature stable plastics grade CICP, commercially available as pigment yellow 119, such as Colortherm® 30 or Colortherm® 3950 Yellow or Bayferrox® 950 Yellow (Lanxess);
In a preferred embodiment, a yellow high-SRI cementitious system is provided. More preferably, the yellow concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems utilize a yellow IR reflective pigment including, Ferro V-9416 Yellow, Ferro 10411 Bright Golden Yellow or for toppings only BASF PaliotolTM L0962HD Yellow. The most preferred yellow IR reflective pigment is Ferro GEODE® V-9416 Yellow, used in a concrete coloring admixture, topping, dry-shake hardener, or other cementitious system, to achieve the highest possible albedo and SRI values.
Problems were encountered when evaluating Ciba Yellow 2GTA, a bismuth vanadate pigment. This pigment failed to disperse properly and showed an undue effect on workability of the topping systems and relatively poor tint strength. The compressive strength and other mechanical properties of the topping system were also compromised by the use of this pigment. Another yellow pigment 1270 Diarylide Yellow BASF-E and equivalent diarylide yellows from Sun were excluded because a topping specimen with this pigment bleached after 6 months of exterior exposure to sunlight although the masked area did not bleach, indicating UV failure of the pigment in sunlight exposed area.
According to another embodiment of the invention, a high-SRI cementitious system for beige to brown concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems is provided. These concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems have beige and brown IR reflective pigments. Preferably, the beige and brown IR reflective pigments have a minimum value of 60% reflectance at 1000 nm.
The beige and brown IR reflective pigments that provide the desired IR-reflective properties may include one or more of the following pigments:

    
    
        chrome antimony titanium buff rutiles and chrome antimony titanium rutiles, commercially available as pigment brown 24, 8380 Meteor® Yellow Buff, Light (BASF-E), 9379 Meteor® FF Yellow Buff (BASF-E), GEODE® V-9156 Autumn Gold (Ferro),
        chromium iron oxide spinels, commercially available as pigment brown 29, Black 411 (Shepherd), Heucodur® Brown 855 (Heubach), Heucodur® Brown 869 (Heucotech),
        chrome niobium buff rutiles, commercially available as pigment yellow 162, GEODE® V-12107 Sand Yellow (Ferro);
        manganese chromium antimony titanate rutile, commercially available as pigment brown 40, such as Meteor® 7780 (zinc and iron free) Brown,
        chrome tungsten titanium buff rutiles, commercially available as pigment yellow 163, 7383 Meteor® Orange (BASF-E), 9384 Meteor® Red Buff (BASF-E), 9385 Meteor® Plus Golden Buff (BASF-E), GEODE® V-12110 Deep Burnt Orange (Ferro);
        iron chromite buff spinels, commercially available as pigment brown 29, 9760 Meteor® Plus HS Brown (BASF-E) and 9770 Meteor® Plus HS red Brown (BASF-E);
        iron titanium brown spinels, commercially available as pigment black 12, GEODE® 10358 Yellow Brown (Ferro), Brown 8 (Shepherd), and Brown 20C819 (Shepherd);
        manganese antimony titanium buff rutiles, commercially available as pigment yellow 164, GEODE® 10550 Brown (Ferro), GEODE® 10364 Brown (Ferro), GEODE® V-12100 Iron Free Brown (Ferro), Brown 352 (Shepherd), Brown 10C873 (Shepherd), and Brown 352 (Shepherd), 9749 Meteor® Plus (red shade) Brown (BASF-E) and 9750 Meteor® Plus (blue shade) Brown (BASF-E);
        manganese chromium antimony titanium rutile, commercially available as pigment brown 40, such as 7780 Meteor® Brown (iron and zinc free) (BASF-E);
        manganese tungsten titanium rutiles, commercially available as pigment brown 45, 9730 Meteor® Plus High IR Brown (BASF-E);
        zinc ferrite brown spinels, commercially available as pigment yellow 119, GEODE® V-9115 Buff (Ferro) and GEODE® 10520 Deep Tan (Ferro); and
        zinc iron chromite brown spinels, commercially available as pigment brown 33, GEODE® 10363 Dark Brown (Ferro), Brown 12 (Shepherd) and Brown 157 (Shepherd);
        zinc manganese chromite spinel, commercially available as pigment brown 39, such as 7739 Meteor® Light Brown (iron free) (BASF-E);
        manganese ferrite brown spinel, commercially available as pigment brown 43, such as Bayferrox BF645-T (Lanxess);
        manganese tungsten titanate rutile, commercially available as pigment brown 45, such as 9730 Meteor® Plus High IR Brown;
        buff colored impure rutile titanium dioxide pigment, commercially available as pigment white 6:1, such as HITOX Std, HITOX ULX and HITOX SF (TOR);
        untreated version TIOPREM CW Beige, C Gray, C Brown or C Orange impure rutile;
        titanium dioxide pigment 6:1 with iron oxide blends, commercially available as a blend of anatase pigment white 6:1, and iron oxides TIOPREM (TOR) The commercial TIOPREM versions of these pigments have zinc oxide surface treatment for coating use and this ZnO treatment is undesirable for cementitious systems.
    
    


Bayferrox BF645-T is a dark brown pigment which can be formulated to have a somewhat low but acceptable minimum SRI depending on dosage and using blends with higher SRI pigments.
In addition, beige and brown IR reflective pigments may include all of the red orange and yellow color ranges listed above, as well as pigmentary anatase TiO2 when lighter SRI restoring colors are required for a particular application, and to provide the desired IR-reflective properties.
In a preferred embodiment, brown and beige high-SRI IR reflective concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems are provided. More preferably, the brown and beige concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems utilize manganese antimony titanium buff rutiles, more specifically, GEODE® 10550 Brown (Ferro), and optionally a chrome antimony buff rutile, more specifically, GEODE® 10411 Bright Golden Yellow (Ferro) and anatase to achieve a range of brown to beige colors with high albedo and SRI values.
According to another embodiment of the invention, high-SRI cementitious systems for green concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems are provided. These high-SRI cementitious systems have green IR reflective pigments. Preferably, the green IR reflective pigments have a minimum value of 60% reflectance at 1000 nm.
The green IR reflective pigments that provide the desired IR-reflective properties may include one or more of the following pigments:

    
    
        chlorinated copper phthalocyanine greens, such as pigment green 7, many commercially available sources are known to those in the art;
        chromium green-black hematites, commercially available as pigment green 17, such as GEODE® 10241 EclipseTM IR (Forest) Green (Ferro), 3955 Chrome Oxide Green (BASF-E);
        chromium green-black modified pigments, such as GEODE® V-12650 Cool ColorsTM Green (Ferro);
        chromium oxides, commercially available as pigment green 17, such as G-4099 Chromium oxide green (Elementis), Green 17 (Elementis), 3955 Chromium Green Oxide, (BASF-E);
        cobalt chromite blue-green spinels, commercially available as pigment blue 36, Green 187 B (Shepherd) and Green 201 (Shepherd);
        cobalt chromite green spinels, commercially available as pigment green 26, such as GEODE® V-12600 Camouflage Green (Ferro), V-12604 Camouflage Green (Ferro), and Green 410 (Shepherd);
        cobalt titanate green spinels, commercially available as pigment green 50, such as 9444 Meteor® Plus Bright Green (BASF-E), GEODE® V-11633 Kelly Green (Ferro), Green 10G663 (Shepherd), Green 223 (Shepherd), Green 260 (Shepherd), Heucodur® Green 5G, (Heubach), and 9444 Meteor® Plus Green, (BASF-E) and
        cobalt nickel zinc aluminum titanate, commercially available as pigment green 50, 9444 Meteor® Plus Green, (BASF-E) Heucodur® Green 5G, (Heubach), Heucodur® Green 5600, (Heubach), Heucodur® Green 654, (Heubach),
        partially brominated (or halogenated) copper phthalocyanines, such as pigment green 36, such as Green 36 (BASF) and Monolite Green 860 (Heubach) and many other commercially available sources are known to those in the art.
    
    


In a preferred embodiment, green high SRI IR reflective concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems are provided. More preferably, the green high SRI IR reflective concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems utilize a chromium green-black hematite, such as EclipseTM 10241 Green (Ferro) and optionally a cobalt titanate green spinel, such as V-11633 Kelly Green (Ferro), cobalt chromite green spinels, such as V-12600 Camo Green (Ferro) and V-12604 Camo Green (Ferro), and chromium green-black modified, such as V-12650 Cool ColorsTM Green (Ferro) to achieve a range of green colors with high albedo and SRI values. The most preferred green high SRI IR reflective concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems use light green colors from cobalt chromite green spinels, such as FerroV-12600 Camo Green to achieve the highest possible albedo and SRI values.
According to another embodiment of the invention high-SRI cementitious systems for blue concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems r are provided. These high-SRI concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems utilize blue IR reflective pigments. Preferably, the blue IR reflective pigments have a minimum value of 50% reflectance at 1000 nm.
The blue IR reflective pigments that provide the desired IR-reflective properties in the cementitious systems may include one or more of the following pigments:

    
    
        cobalt aluminate blue spinels, commercially available as pigment blue 28, such as GEODE® V-9236 Blue (Ferro), GEODE® V 9250 Bright Blue (Ferro), GEODE® 10446 Bright Blue (Ferro), 300591 (Shepherd), Blue 300588 (Shepherd), Blue 214 (Shepherd), Blue 385 (Shepherd), Blue 424 (Shepherd), Blue 10K525 (Shepherd), Blue 10G594 (Shepherd), 7540 Meteor® Plus Cobalt Blue (BASF-E), and 9546 Meteor® Plus Cobalt Blue (BASF-E), Heucodur® Blue 550 (Heubach), Heucodur® Blue 552 (Heubach) and Heucodur® Blue 2R (Heubach),
        cobalt chromite blue-green spinels, commercially available as pigment blue 36, such as GEODE® V-9242 Ocean Blue (Ferro), GEODE® V-9248 Ocean Blue (Ferro), GEODE® F-5686 Turquoise (Ferro), Blue 300527 (Shepherd), Blue 211 (Shepherd), Blue 212 (Shepherd), 9538 Meteor® Plus Blue G, (BASF-E) Heucodur® Blue 5-100 (Heubach), Heucodur® Blue 4G (Heubach), and Heucodur® Blue 555 (Heubach), Heucodur® Blue 559 (Heubach),
        cobalt chromium aluminum spinel, commercially available as pigment blue 36, 9538 Meteor® Plus Blue G (BASF-E),
        cobalt chromium zinc aluminate spinels, commercially available as pigment blue 36:1, such as 7590 Meteor® Cerulean Blue (BASF-E),
        cobalt lithium titanate green spinels, commercially available as pigment green 50, such as 9530 Meteor® Plus Teal Blue (BASF-E),
        copper phthalocyanine, commercially available as pigment blue 15:3 and pigment blue 15:1, pigment blue 15:2, pigment blue 15:3 and pigment blue 15:4, several manufacturers, such as BASF and Heubach; and many other commercially available sources are known to those in the art; and
        indanthrones, commercially available as pigment blue 60, such as PaliotolTM Blue L6495 F (BASF), Indanthrone Blue (BASF).
    
    


In a preferred embodiment, blue high-SRI IR reflective concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems are provided. More preferably, the blue IR reflective cementitious systems are concrete coloring admixtures, toppings or dry-shake color hardeners that utilize blue-aqua IR Reflective pigments, including, cobalt chromite blue-green spinels, such as V-9248 Ocean Blue (Ferro), F5686 Turquoise (Ferro) and optionally cobalt aluminum spinels, such as V-9250 Bright Blue (Ferro), Ferro V-9236 Blue (Ferro), and 10446 Bright Blue (Ferro) to achieve a range of blue to aqua colors with high albedo and SRI values. The most preferred blue-aqua IR reflective pigments are cobalt chromite blue-green spinels in blue-green colors, such as V-9248 Ocean Blue or F-5686 Turquoise to achieve the highest possible albedo and SRI values.
According to another embodiment of the invention, high-SRI cementitious systems for dark gray to light gray and pastel shades or white concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems for are provided. These high-SRI dark gray to light gray and pastel shades or white use gray to white IR reflective pigments. Preferably, the gray to white IR reflective pigments have a minimum value of 60% reflectance at 1000 nm.
The range of gray to white concrete coloring admixtures, IR reflective pigments that provide the desired IR-reflective properties may include one or more of any of the above referenced pigments but in generally lower dosage rates and in combination with untreated pigment or photocatalytic grade anatase TiO2 to provide SRI-restoring function upon exposure to UV radiation (from sunlight) and moisture. This SRI-restoring property is important in maintaining the high solar reflectivity (albedo) of the surface. The loss of SRI over time with light colored pavements has been cited as a significant problem. This novel use of anatase TiO2 in pastels or even some dark concrete coloring admixtures or cementitious systems for colored pavements can minimize the loss of SRI over time. Variations of this SRI restoring function would include the use of photocatalytic (ultrafine) TiO2, generally of low tint-strength and/or non-pigmentary particle size anatase TiO2 such Ishihara ST-01 or MC-50, ISK Ishihara, San Francisco, Calif. and Aeroxide® TiO2 P 25, Evonik Degussa Corporation, Alpharetta, Ga. or other microfine nano-sized TiO2 anatase grades.
The loss of reflectivity of white, and even gray to a lesser extent, portland cement concrete over time has been reported, for example in, American Concrete Pavement Association, R & T Report, June 2005, where white portland cement concrete is reported as having an albedo of 0.70-0.80 when new, but dropping to 0.40-0.60 when aged. Ordinary gray portland cement concrete will also drop in reflectance over time.
Additional functional fillers include white metakaolin, such as Burgess Optipozz® (Burgess Pigments, Sandersville, Ga.), BASF Metamax® (BASF-E), Metastar® 450 (Imerys Corporation, Atlanta, Ga.) and various white diatomaceous earth products such as Diafil® 2000 or Celite® for Concrete, C4C, (World Minerals, Lompoc, Calif.). The incorporation of barium sulfate increases the albedo of the surface material while enabling use of darker IR reflective pigments since it has low tint strength. Elotex® ERA 100 (National Starch Corp., Bridgewater, N.J.), an efflorescence reducing admixture, was also found to reduce the effects of white discoloration of dark colored IR reflective systems. Other fillers such as nepheline syenite (Minex, a Unimin product), aluminum trihydroxide or tabular alumina (Almatis), white quartz (Unimin, New Canaan, Conn.), calcium carbonate (Omya or Imerys) and white ceramic microspheres (Zeeospheres®, white grades, 3M Corp, Minneapolis, Minn.), Vitrified Calcium Aluminosilicate, VCAS®, (Vitro Minerals, Atlanta, Ga.) and White Silica Fume (Elkem Materials, Pittsburgh, Pa. or Technical Silica, Atlanta, Ga.) can be used to improve the overall reflectivity of cementitious materials.
In a preferred embodiment, gray, light gray, dark gray and bright white high-SRI IR reflective concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems are provided. More preferably, the gray, light gray, dark gray and bright white high-SRI IR reflective concrete coloring admixtures, toppings, dry-shake hardeners, and other cementitious systems utilize IR reflective pigments in the a dark gray to white color range. Such systems may include pigments and pigment blends such as:
infrared reflective black pigments, a proprietary composition such as GEODE 10202 EclipseTM Black (Ferro);
chromium green-black hematites, commercially available as pigment green 17, such as V-775 Cool ColorsTM IR Brown Black (Ferro);
pigmentary anatase white; and
chrome antimony titanium buff rutiles, commercially available as pigment brown 24, such as 10411 Golden Yellow (Ferro).
Light colors, such as light gray may be made with anatase TiO2 and one or more IR reflective black pigments or pastel colors with anatase TiO2 and other IR reflective pigments normally in white portland cement concretes or mortars. These cementitious systems offer the highest TSR (albedo) and SRI values that can be achieved with the technology described herein. The anatase TiO2 has been determined to provide an SRI restoring characteristic, upon exposure to UV light and moisture, that will help to maintain the high TSR (albedo) and SRI of the surface when exposed to soiling from soot, dirt, plant matter and other staining materials.
White portland cement is preferred for formulating the high-albedo IR reflective cementitious toppings and dry-shake hardeners of the invention. Since these cementitious toppings and dry-shake hardeners only color the top 1⁄8 to 1⁄2 inch of the treated concrete and they are a very cost effective way to use commonly available gray portland cement concrete and still provide very high albedo or SRI and also achieve colors that cannot normally be made in gray concrete such as bright yellow or white.
SecarTM 71 (KerneosTM, Chesapeake, Va.) or Almatis CA25 (Almatis Alumina, Leetsdale, Pa.), white calcium aluminate cements, can be used as well in some formulations.
White portland cement can be used in all of these high albedo and high-SRI topping or high SRI dry-shake hardener formulations as will be understood by those of skill in the art by reference to this disclosure. Ground Granulated Blast Furnace Slag Cement (GGBFS), or simply slag cement, is also light in color and can be blended and used in high-albedo toppings and dry-shake hardeners, however, early strengths may be reduced significantly but ultimate strengths will generally be higher. Alkali activated slag cement can also be used to overcome the low early strength issues.
According to the invention, the infrared reflective pigments are used in high-SRI cementitious systems, such as concrete coloring admixtures, or other compositions containing a cementitious matrix, such as dry-shake hardeners, concrete toppings, or concrete coloring composition.
In one embodiment, the infrared reflective pigments are used in a high-SRI cementitious system comprising a concrete coloring admixture. According to this embodiment, one or more infrared reflective pigments are used as integral pigmenting SRI compliant products and can be either packaged in dry form or in liquid form. Preferably, the concrete coloring admixtures of the invention comprise one or more infrared reflective pigments and a water reducing agent. The concrete coloring admixtures are further used an in integral concrete coloring system, where the concrete coloring admixture is combined with a portland cement concrete. The concrete coloring admixture can be used with gray portland cement concrete but can be also used with white portland cement concrete to provide very high SRI and clean, vibrant colors that are not commercially available by use of the same colors with gray portland cement concrete.
According to another embodiment, the infrared reflective pigments are used in a high-SRI cementitious system comprising a dry-shake hardener. According to this embodiment, one or more infrared reflective pigments are combined with a cementitious matrix to form a high SRI dry-shake color hardener. Preferably, the dry-shake color hardener is formulated from one or more infrared reflective pigments, and other cementitious materials, such as cement, admixtures, and select graded silica aggregates (sands). As is known in the art, dry-shake color hardener products are applied to freshly-placed concrete by broadcasting the material evenly over a wet concrete surface, allowing wet-out, then working the applied material into the surface and then finishing the concrete normally.
According to another embodiment, the infrared reflective pigments are used in a high-SRI cementitious system comprising a cement topping. According to this embodiment, one or more infrared reflective pigments are combined with a cementitious matrix to form a high SRI cementitious topping. The high SRI cementitious toppings can be used as a thin (up to 1⁄2 inch) application to hardened concrete. Preferably, the high SRI toppings are formulated from one or more infrared reflective pigments and other cementitious materials, such as cements, pozzolans, redispersible polymers, fine aggregates, fillers, and admixtures. The high SRI cementitious toppings may be comprised of a base and a color pack which are mixed with water and are typically spread or sprayed onto existing concrete and then troweled, broomed or imprinted to the desired surface texture.
According to another embodiment, the infrared reflective pigments are used in a high-SRI cementitious system comprising a concrete coloring composition. According to this embodiment, one or more infrared reflective pigments are combined with a cementitious matrix to form a high SRI concrete coloring composition. The concrete coloring composition may be prepared in dry form with the final mixing water to be added by the end user. According to this embodiment, other materials of the final product such as aggregate may also be added to the cementitious system by the end user, or may be pre-packaged with the other components of the cementitious system according to the invention. Such coloring compositions include prepackaged dry concrete mixtures for application to poured concrete in a two-course construction method or for other conventional cast-in-place concrete, lightweight concrete, and pervious concrete.
According to another embodiment, the infrared reflective pigments are used to make high-SRI conventional cast-in-place concrete. According to this embodiment, the conventional (i.e., normal) cast-in-place concrete is formulated by others from cementitious materials including one or more: cements, coarse aggregates, fine aggregates, and other cementitious materials such as pozzolans, fillers, fly ash, slag, admixtures, coloring admixtures. The IR reflective pigments according to the invention are added to conventional cast-in-place concrete products by the end user to create a high-SRI conventional cast-in-place concrete. The high-SRI conventional concrete is then placed and consolidated according to known practices in the concrete industry. The high-SRI cast-in-place concrete may then be finished according to standard industry practices, which include but are not limited to a trowel finish or broom finish of the concrete surface, or by imprinting the surface in a multitude of available patterns to provide the desired surface texture.
According to another embodiment, the infrared reflective pigments are used to make high-SRI lightweight concrete, i.e., concrete having an in-place density between about 90 to about 115 lb/ft3, as compared to normal weight concrete which has a density between about 140 to 150 lb/ft3. Structural lightweight concrete can be used to reduce the dead load of a building structure. When the high SRI infrared reflective pigments according to the invention are used in a lightweight concrete, the result of the concrete coloring admixtures provides increased albedo and SRI, resulting in a “cool” concrete, which also is aesthetically pleasing, and is a desirable building material. According to this embodiment, the high-SRI lightweight concrete is formulated by others from cementitious materials including one or more: cements, lightweight or normal weight coarse aggregates, lightweight fine aggregates and/or regular weight fine aggregates, and other cementitious materials such as pozzolans, fillers, fly ash, slag, preformed foam in some cases, admixtures and one or more infrared reflective pigments of this invention. The high-SRI lightweight concrete products may be comprised of a concrete mixture and a high SRI concrete coloring admixture, in either dry or slurry form containing IR reflective pigments according to the invention. The high-SRI lightweight concrete is then placed, consolidated, finished and cured according to known techniques in the concrete industry.
According to another embodiment, the infrared reflective pigments are used to make a high-SRI pervious concrete, i.e., concrete having a typical infiltration rate of water through the concrete normally about 3 gal/ft2/min to about 8 gal/ft2/min, and in extreme cases up to about 17 gal/ft2/min. The use of pervious concrete in sidewalks and paths, which has a high flow rate of water through it, allows rainfall to be captured in the concrete where it can percolate into the ground, reducing storm-water runoff, recharging groundwater, and supporting sustainable construction. When high-SRI pervious concrete is used according to the invention with IR reflective pigments, an aesthetically pleasing solution for construction that is sensitive to environmental concerns is provided. Further, combining high SRI with pervious concrete may also help pavement owners comply with EPA stormwater regulations by addressing rainwater on-site. According to this embodiment, high-SRI pervious concrete may be formulated using the same materials as conventional concrete, with the exception that the fine aggregate is typically greatly reduced or eliminated entirely. The size distribution (grading) of the coarse aggregate is also kept narrow (gap graded), which allows for open channel pervious aggregate packing. Accordingly, the high-SRI pervious concrete materials include one or more: cements, narrow (gap) graded coarse aggregate, a limited fine aggregate component, and other cementitious materials such as pozzolans, fillers, fly ash, slag, admixtures and one or more infrared reflective pigments. The high-SRI pervious concrete after mixing is then placed, consolidated, finished and cured according to known practices in the concrete industry.
According to another embodiment, the infrared reflective pigments can be can be used in cementitious construction materials, such as precast structural concrete panels, beams and tilt-up wall panels to make high-SRI cementitious construction materials. According to this embodiment, the infrared reflective pigments may be added to cementitious building materials as a concrete coloring admixture, or may be integrally contained in a cementitious building material.
According to another embodiment, high-SRI dry-shake hardeners can be applied to the top surface of freshly-placed concrete tilt-up panels and the panels can be erected using a reverse lift procedure to put the high SRI panel face to the exterior of the tilt-up building, thereby reducing heat absorption by the walls of the structure, saving energy and reducing the “heat island effect”, and/or adding an aesthetically pleasing color to the structure.
According to another embodiment, high-SRI cementitious toppings can be used to coat fully cured and hardened building exterior surfaces to achieve the same desirable characteristics as the dry-shake hardeners on freshly placed concrete.
According to another embodiment of the invention, a high-SRI cementitious system can be applied in a two-course construction method, such as adding a second, colored, high-SRI layer to a base concrete that is either in the plastic or hardened state. Concrete masonry units, insulating concrete forms, removable forms (cast-in-place), pre-cast and tilt-up panel systems, pavers, and beams may be colored with a high-SRI cementitious system of the invention, so that the sun exposed surfaces stay cooler than the equivalent colors made with conventionally pigmented similar systems.
The infrared reflective pigments can also be used in high-SRI cementitious systems applied to building surfaces, such as concrete used as a stucco or shotcrete application. According to this embodiment, the high-SRI cementitious system comprises one or more infrared reflective pigments and a cementitious matrix. The high-SRI cementitious system can be applied to wood, steel, polystyrene, or any other surface that concrete can be adhered to. The high-SRI cementitious material may be sprayed or troweled onto the surface, and the surface can be trowelled smooth or texturized while the material is still wet, as will be understood by those of skill in the art by reference to this disclosure.
ASTM C 979 Standard Specification for Pigments for Integrally Colored Concrete is the applicable standard in the architectural concrete industry and is widely cited in specifications and elsewhere. Many conventional iron oxides, cobalt spinels and chromium (III) oxide pigments were tested for C979 and were found to comply, but many of these pigments lack the required IR reflectivity needed to produce high-SRI cementitious systems. Testing for C979 compliance is difficult, time consuming and expensive.
The combinations of materials used to produce test representative test specimens in the laboratory for the high-SRI cementitious systems according to the invention, required extensive testing and produced many failures along with some successful formulations. Evaluation of all of the effects of combining the candidate pigments with other components of the high-SRI concrete coloring admixtures, dry shake-hardeners, toppings, and other high-SRI cementitious systems to maintain a functional product that would produce the desired qualities in an economical manner has been done or will be done to produce the invention described herein. This testing is well beyond that required for ASTM C 979 conformity.
In addition to the extensive testing and screening of pigment candidates noted above, certain materials are included in the invention to provide specific benefits: (1) Anatase TiO2 light to medium colored cementitious systems provides a means to photo-catalytically help to maintain SRI (or albedo), a novel concept in colored concrete, cementitious hardeners, topping systems, concrete integral colorants; (2) High-SRI fillers such as metakaolins can provide increased SRI when incorporated into formulations or when used to replace other less reflective pozzolanic materials such as flyash or dark colored silica fume; and (3) Barium sulfate, a high-SRI, low tint strength white pigment/filler can also be carefully used in darker colored formulated cementitious materials where its effects are controlled.
Further, general knowledge of pigments as related to coatings technology, a field of knowledge familiar to many, did not prove to have any significant relevance to developing the high-SRI cementitious systems and their compatible high SRI pigment components. In general, IR reflective pigments that are made to disperse well in coatings were found to wash out of the high-SRI cementitious systems and risk tracking to adjacent areas, an unacceptable situation in the marketplace. There are many significant differences in a polymer binder systems used in coatings and in the cementitious binder systems described in this disclosure.
The compositions, cementitious systems, and methods according to the invention, including high-SRI integrally colored concrete admixtures, toppings, dry-shake color hardeners, and other high-SRI cementitious systems may include other materials or other modifications as necessary to increase the IR reflectance and to allow higher application rates for dry-shake color-hardeners, and are not limited by the foregoing examples as will be understood by those of skill in the art by reference to this disclosure.
EXAMPLES
General Procedure for Obtaining Spectral Data
Spectral data were obtained using a Shimadzu UV-3101PC UV-Vis-NIR Scanning Spectrophotometer Serial Number A102841000152, equipped with a 150 mm hemispherical (diffuse) reflectance integrating sphere using a D2 light source from 220-360 nm and halogen lamp from 360-2500 nm along with photomultiplier tube (PMT) detection from 220-830 nm and PbS detection from 830-2500 nm.
Example 1
The Solar Insolation Spectrum
FIG. 1 shows the solar insolation spectrum, at air mass 1.5, zenith angle=48.13°, (typical of the contiguous US) curve from E891 data, has direct irradiance values of approximately 3% in the UV (<400 nm) region, approximately 37% in the visible (400-700 nm) region, approximately 58.5% in the near infrared (701-2500 nm) region and approximately 1.5% in the mid infrared (>2500 nm) region. ASTM E903 refers to E 891 50-point selected ordinate method for albedo computations.
These UV, V is, NIR percentages differ from other sources, such as those used by LBNL with E 892 data, 37° tilt, air mass 1.5 and zenith angle 48.13°, which have reported values of approximately 5% in the UV, 43% in the Visible, and 52% in the NIR while omitting the 1.3% in the region above 2500 nm. ASHRAE 2005 reports these percentages as 3% in the ultraviolet, 47% in the visible and 50% in the infrared without stating the wavelength ranges.
Example 2
Black Infrared Reflective Pigments
FIG. 2A is a graph showing conventional black pigments and IR reflective black pigments according to the invention. As shown in FIG. 2A, the reflectance of the black pigments is plotted as % reflectance vs. wavelength from 220 to 2500 nm. The conventional black pigments, iron oxide black and carbon black (Raven H2O, Columbian Chemicals, Marietta, Ga.), both of which are in white portland cement mortar (topping) have very low reflectance across the whole spectrum (220 to 2500 nm) and represent conventional technology. However, as shown in FIG. 2A, the IR reflective pigment system according to the invention using Ferro's GEODE® V-775 and EclipseTM 10202 in white portland cement mortar (topping), although not nearly as high intensity or jetness as the conventional systems, provide near black colors and excellent overall reflectivity in the IR region. As also shown in FIG. 2A, the IR reflective pigment system according to the invention using perylene black is comparable to the conventional system using carbon black in intensity, yet provides fair albedo and SRI values that could be matched with other higher albedo or SRI colors to meet minimum TSR (albedo) or SRI requirements as needed.
FIG. 2B is a graph showing the reflected solar energy of conventional black pigments and IR reflective black pigments according to the invention. As shown in FIG. 2B, the reflected energy is plotted as energy reflected in watts×m−2×um−1 for each wavelength range. The curves with higher reflectivity in the IR range show similar peaks and valleys as the solar irradiance in FIG. 1 but with much lower values. This chart indicates the significant difference in the spectra of the subject systems with conventional iron oxide black (magnetite) and carbon black compared to the IR reflective CICP spinels and perylene black, an organic pigment. It is noted that the carbon black and iron oxide black are of higher tint strength and can produce a higher jetness black, as compared to perylene black. The CICP IR reflective black systems cannot achieve this level of jetness. Colors such as conventional iron oxide black or carbon black have very low visible and NIR region reflectance, typically 5-10%, so most of the visible region and the infrared region is absorbed and converted to temperature rise. The IR reflective black systems are much cooler in sunlight exposure due to their ability to reflect a sizable portion of the solar insolation at wavelengths from 700 to 2500 nm, the near IR range.
Table 2 below provides the reflectance of each of the black systems at 1000 nm and a value of 40% minimum was selected as pass/fail criteria. The E1980 Solar Reflectance Index (SRI) was calculated using the Lawrence Berkeley National Laboratory SRI Calculator Tool by R. Levenson from the TSR calculated from the spectral data and ASTM E 903 and E 891 for each mixture. This SRI assumes that concrete and like cementitious materials have a thermal emittance (ε) of 0.9 (using an average value in the typical range for concrete from 0.85 to 0.95). As a rough comparison the carbon black in white or gray portland cement mortar (PCM) has an SRI of 0 which would have a steady state temperature much higher than that of IR reflective Ferro EclipseTM 10202 Black in WPCM which has an SRI of 45. The CIE L*a*b* color values are also included in this table as well. The L* value represents the lightness or darkness and the carbon black specimen appears to be strongly black with a low L* value. The a* value indicates red (+) or green (−) and the b* value indicates yellow (+) or blue (−). It should be noted that the carbon black in PCM is comparable to fresh asphalt pavement with a typical albedo value of 0.05 per the Ready Mixed Concrete Industry LEED Reference Guide.







TABLE 2







Black Cementitious Systems Data Table










IR Reflective Systems





& Controls
% Reflectance
LBNL
D65 10° CIE


Black Pigment
at 1000 nm
Calc
L*a*b* Color












Description
(40% minimum)
SRI %
L*
a*
b*















Conventional Black
9.35
6
37.38
0.17
−0.27


Iron Oxide WPCM*


Conventional Carbon
4.67
0
25.97
−0.10
1.02


Black WPCM


IR Reflective Ferro
40.95
38
48.39
0.25
−2.53


V-775 Black WPCM


IR Reflective Eclipse
64.08
45
43.61
1.52
0.56


10202 WPCM


IR Reflective
42.55
24
28.38
−0.88
−0.60


(Perylene) Black


WPCM





*WPCM = made with white portland cement mortar






Example 3
Red Infrared Reflective Pigments
FIG. 3A is a graph showing the spectral reflectance of conventional red pigments and infrared reflective red pigments of the invention. As shown in FIG. 3A, the reflectance of the red pigments is plotted as percent reflectance vs. wavelength from 220 to 2500 nm. This chart indicates that improvements in reflectance can be achieved by selection of a red IR reflective pigment in a topping system or in a dry-shake hardener system. There are significantly lower reflectances for the conventional red integrally-colored mortars, the specimen labeled Tile Red made with gray portland cement as well as the Quarry Red gray portland cement mortar both of which would be typical of the prior art technology.
FIG. 3B is a graph showing the reflected solar energy of conventional red pigments and infrared reflective red pigments of the invention. As shown in FIG. 3B, the reflected energy of the red pigments is plotted as reflected solar energy in watts×m−2×um−1 for each wavelength range. This chart indicates significant differences in the reflected solar energy of the Tile Red and the Quarry Red both in gray portland cement compared to the IR reflective systems based on Ferro's V-13810 and Rhodia's NeolarTM Red S in white portland cement mortars.
Table 3 below, as in Table 2 above, shows the data for the red colored systems, and provides the reflectance of each specimen at 1000 nm and a value of 50% minimum was selected as pass/fail criteria. The ASTM E 1980 SRI values are calculated and the L*a*b* color values for the red colored systems are reported. The SRI values of the Tile Red and Quarry Red in gray portland are just over the minimum LEED SRI requirement of 29%. The IR-reflective formulations with Ferro V-13810 and Rhodia NeolorTM Red S allow an increase in SRI of 20-25%, perhaps enough to qualify for an exemplary credit under the LEED system.







TABLE 3







Red Cementitious Systems Data Table










Red Controls and





IR Red Systems
% Reflectance
LBNL
D65 10° CIE


Red Pigment
@ 1000 nm
Calc
L*a*b* Color












Description
(50% Minimum)
SRI
L*
a*
b*















Conventional Tile
39.84
33
46.18
26.68
16.68


Red GPCM**


Conventional Quarry
38.47
31
45.73
27.49
17.59


Red GPCM


IR Reflective Ferro
73.45
58
53.16
31.61
23.08


V-13810 WPCM


IR Reflective Neolor
79.70
66
49.86
34.23
15.99


Red S WPCM





**GPCM = made with gray portland cement mortar






Example 4
Yellow Infrared Reflective Pigments
FIG. 4A is a graph showing the spectral reflectance of conventional yellow pigments and infrared reflective yellow pigments of the invention. As shown in FIG. 4A, the reflectance of the yellow pigments is plotted as percent reflectance vs. wavelength from 220 nm to 2500 nm. The use of conventional iron oxide yellow pigment in a gray portland cement shifts the yellow to a greenish color that is not very reflective. Normally the iron oxide yellow could provide moderate IR reflectivity in a white portland cement mortar, but the use of IR reflective pigments in the subject toppings and dry-shake hardeners will provide significant improvements in albedo and SRI and will also provide a more pleasing, cleaner and brighter range of yellow colors.
FIG. 4B is a graph showing the reflected solar energy of conventional yellow pigments and infrared reflective yellow pigments of the invention. As shown in FIG. 4B, the reflected energy of the yellow pigments is plotted as reflected solar energy in watts per square metre per μm for each wavelength range from 220 nm to 2500 nm. This chart illustrates the improvement that is possible with proper yellow IR reflective pigment selection.
Table 4 below, as in Table 2 above, shows the data for the yellow systems, and provides the reflectance at 1000 nm, with a value of 65% selected as the pass/fail criteria. The computed SRI values and the measured L*a*b* color values for the yellow colored systems are reported. The conventional yellow iron oxide in white portland cement can provide a fairly good albedo and SRI values, however, these values can be increased by 5-15% by selecting a more IR reflective yellow system.







TABLE 4







Yellow Cementitious Systems Data Table










IR Reflective Systems
% Reflectance




& Control
@ 1000 nm
LBNL
D65 10° CIE


Yellow Pigment
(65%
Calc
L*a*b* Color












Description
Minimum)
SRI
L*
a*
b*















Conventional Iron
37.75
42
65.71
2.21
23.64


Oxide Yellow GPCM***


Conventional IronWPCM
61.30
66
81.13
7.46
31.95


Oxide Yellow 


IR Reflective Yellow
76.49
84
84.84
−1.77
26.42


Ferro V-9416 WPCM


IR Reflective Yellow
72.01
73
77.90
6.29
38.62


Ferro 10411 WPCM





***Conventional iron oxide yellow in gray portland cement is a greenish-yellow shade and is not very bright. White portland cement is required to provide a bright yellow.






Example 5
Brown And Beige Infrared Reflective Pigments
FIG. 5A is a graph showing the spectral reflectance of conventional beige pigments and infrared reflective brown and beige pigments of the invention. FIG. 5A shows the reflectance of the conventional beige Desert Sand is in gray portland cement (mortar/topping) because that is the way it is normally done. The IR-reflective Ferro 10550 brown is also a beige color but is in white portland cement. The reflectance curves in IR region demonstrate the value of using the IR reflective pigments in white portland cement systems over conventional pigments in a gray portland cement system.
FIG. 5B is a graph showing the reflected solar energy of conventional beige pigments and infrared reflective brown and beige pigments of the invention. As shown in FIG. 5B, the conventional pigments used to achieve brown or beige colors, such as Desert Sand made with iron oxides and gray portland cement will result in reductions of solar reflectivity as compared to gray portland cement concrete. However, the spectrum of IR reflective CICP pigments, such as Ferro 10550 Brown and the beige colors provide very good solar reflectivity. Further, adding Ferro 10411 Bright Golden Yellow and Anatase to the Ferro 10550 Brown in various ratios, combines to provide a range of clean beige colors with both high albedo and SRI characteristics. Accordingly, infrared pigments of the invention may be combined to produce unique colors, which also have high albedo and SRI.
Table 5 below, as in Table 2 above, shows the data for the Beige (Brown) systems, and provides the reflectance at 1000 nm, with a value of 60% minimum selected as pass/fail criteria. The computed SRI values and the measured L*a*b* color values for the beige (brown) colored systems are reported. This table indicates that the albedo and/or SRI can be more than doubled by using an IR reflective system (dry-shake color hardener or topping).







TABLE 5







Beige (Brown) Cementitious Systems Data Table










IR Reflective
% Reflectance




Systems & Control
@ 1000 nm
LBNL
D65 10° CIE


Brown-Beige
(60%
Calc
L*a*b* Color












Pigment Description
Minimum)
SRI
L*
a*
b*















Conventional Desert
23.80
24
52.00
6.73
10.46


Sand Medium Beige


GPCM


IR Reflective Ferro
68.68
56
56.63
8.74
7.76


10550 Brown WPCM


IR Reflective Dark Beige
73.10
66
65.40
7.03
7.76


Blend WPCM


IR Reflective Medium
74.01
70
70.15
5.84
8.26


Beige Blend WPCM


IR Reflective Light
74.18
78
77.72
3.73
8.82


Beige Blend WPCM









Example 6
Infrared Reflective Green Pigments
FIG. 6A is a graph showing the spectral reflectance of conventional green pigments and infrared reflective green pigments of the invention. As shown in FIG. 6A, conventional green chromium oxide in gray portland cement is fair in reflectivity across the NIR range. However, green IR-reflective pigments in white portland cement provide significant improvements in the NIR range. The spectrum of Ferro V-12600 Camo Green shows the typical cobalt trough absorbing strongly from about 1200 to 1800 nm, but it still provides better overall reflectivity than gray portland cement concrete with conventional chromium oxide pigment.
FIG. 6B is a graph showing the reflected solar energy of conventional green pigments and infrared reflective green pigments of the invention. As shown in FIG. 6B, conventional green chromium oxide in gray portland cement has the lowest solar energy reflected. The effect of the typical cobalt trough in the V-12600 spectra from 1.200 to 1.800 μm does not impact the value very much due to the low solar intensity in this spectral range (FIG. 1).
Table 6 below, as in Table 2 above, shows the data for the green systems, providing the reflectance at 1000 nm, with a value of 60% minimum selected as pass/fail criteria. The computed SRI values and the measured L*a*b* color values are reported. This table indicates that in some cases the albedo (TSR) can almost be doubled and the SRI can be doubled in all cases although the green color is noted to be generally less intense with the IR reflective systems.







TABLE 6







Green Cementitious Systems Data Table










IR Reflective





Systems & Control
% Reflectance
LBNL
D65 10° CIE


Green Pigment
@ 1000 nm
Calc
L*a*b* Color












Description
(60% Minimum)
SRI
L*
a*
b*















Conventional
35.81
31
55.53
−10.23
11.17


Chrome Oxide


Green GPCM


IR Reflective Green
74.34
66
71.09
−13.54
3.17


Ferro Camo


V-12600 WPCM


IR Reflective Green
72.34
62
62.28
−5.60
9.56


Ferro V-12650


WPCM


IR Reflective Ferro
70.28
62
64.93
−10.62
10.77


Green Eclipse


10241 WPCM









Example 7
Infrared Reflective Blue Pigments
FIG. 7A is a graph showing the spectral reflectance of conventional blue pigments and infrared reflective blue pigments of the invention. As shown in FIG. 7A, the conventional blue pigment falls significantly below the IR reflective pigments in the visual and NIR wavelength ranges, indicating that the IR reflective systems can improve the albedo (TSR) and SRI over what can be achieved in like cementitious systems using conventional cobalt blue pigments.
FIG. 7B is a graph showing the reflected solar energy of conventional blue pigments and infrared reflective blue pigments of the invention. As shown in FIG. 7B, the conventional blue pigments used in concrete are cobalt blues, either cobalt chromite or cobalt aluminate spinels. There are some differences in the IR reflectance and visible reflectance of these commercial blue pigments, e.g. Shepherd 10K525, and the IR reflective blue pigments. All of these cobalt blue pigments exhibit the typical cobalt trough, a strong absorbance from about 1,200 to 1,800 μm.
Table 7 below, as in Table 2 above, shows the data for the blue systems, and provides the reflectance at 1000 nm with a value of 50% minimum selected as pass/fail criteria. The computed SRI values and the measured L*a*b* color values for the blue systems are reported. The blue systems chart indicates that the although conventional blue pigment in a white portland cement system can provide fairly good albedo (TSR) and SRI, use of an IR reflective blue or blue-green pigment can provide significantly better albedo (TSR) and SRI values.







TABLE 7







Blue Cementitious Systems Data Table










IR Reflective
% Reflectance




Systems & Controls
@ 1000 nm
LBNL
D65 10° CIE


Blue Pigment
(50%
Calc
L*a*b* Color












Description
Minimum)
SRI
L*
a*
b*















Conventional Blue
21.24
47
50.44
−5.10
−32.35


Shepherd 10K525


WPCM


IR Reflective Bright
51.40
74
72.78
−7.55
−19.75


Blue V-9250


WPCM


IR Reflective Ocean
52.70
67
69.38
−17.46
−16.94


Blue V-9248


WPCM


IR Reflective Blue-
54.20
62
53.68
26.34
−7.07


Green Ferro F-5686


WPCM









Example 8
Gray and White Infrared Reflective Pigments
FIG. 8A is a graph showing the spectral reflectance of gray portland cement concrete and infrared reflective gray and white pigments of the invention. In FIG. 8A, the gray portland cement concrete reflectance spectra is compared to a similar concrete gray color of IR reflective white portland cement mortar, IR Light Gray and IR Dark Gray and Bright White Anatase-pigmented white portland cement mortar. The gray and white infrared reflective pigments of the invention show a greater percent reflectance across the majority of the spectrum.
FIG. 8B is a graph showing the reflected solar energy of gray portland cement concrete and infrared reflective gray and white pigments of the invention. In FIG. 8B, the solar reflected energy of the gray portland cement concrete is compared to a similar IR reflective concrete gray colored WPCM, IR Reflective Light Gray WPCM, IR Reflective Dark Gray WPCM, and IR Reflective Bright White WPCM. The gray and white pigments of the invention show greater reflected solar energy than gray portland cement concrete.
Table 8 below, as in Table 2 above, shows the data for the gray-white systems, and provides the reflectance at 1000 nm, with a value of 60% minimum selected as pass/fail criteria. The computed SRI values and the measured L*a*b* color values for the gray-white systems are reported. This table indicates that an IR-reflective color similar to gray portland cement concrete can provide a measurable improvement in TSR (albedo) and SRI over conventional gray portland cement concrete and that IR Reflective Light and Dark Gray WPCMs can provide improvements in SRI over what is possible with gray portland cement concrete. The IR Reflective Anatase Bright White WPCM is the highest overall TSR (albedo) and SRI of any of the tested systems, although the IR reflective Yellow Ferro V-9416 in FIG. 6A is very close to the anatase values.







TABLE 8







Gray, White Cementitious Systems Data Table










IR Reflective
% Reflectance




Systems & Controls
@ 1000 nm
LBNL
D65 10° CIE


Gray, White or Pigment
(60%
Calc
L*a*b* Color












Description
Minimum)
SRI
L*
a*
b*















Ordinary Gray Portland
33.22
36
61.72
−0.09
4.66


Cement Concrete


No Pigment


IR Reflective Gray
68.30
57
61.72
0.25
7.85


Portland Cement


Colored WPCM


IR Reflective Light Gray
70.84
68
76.80
0.54
1.95


(Anatase + V-775)


WPCM


IR Reflective Dark Gray
68.72
47
57.83
0.07
−2.59


(BaSO4 + V-775)


WPCM


IR Reflective Bright
72.63
86
87.03
1.12
5.58


White Anatase WPCM









Although the present invention has been discussed in considerable detail with reference to certain preferred embodiments, other embodiments are possible. Therefore, the scope of the appended claims should not be limited to the description of preferred embodiments contained herein.

## Claims

1. A method of preparing a high-SRI colored concrete using a high-SRI cementitious system the method comprising:
(a) providing components of a cementitious system comprising a cementitious matrix or concrete coloring admixture;
(b) combining an infrared reflective pigment composition with the cementitious system to form the high-SRI cementitious system, wherein the infrared reflective pigment composition comprises:
one or more infrared reflective pigments selected from the group consisting of: black infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 40%, red infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 60%; orange to yellow infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 65%; beige to brown infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 60%; green infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 60%; blue infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 50%; gray to white infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 60%; and combinations thereof, wherein the percent reflectance at 1000 nm is measured in white portland cement, and wherein the infrared reflective pigments are compliant with ASTM C979; and
(c) applying the high-SRI cementitious system to a concrete to form the high-SRI colored concrete, wherein the high-SRI cementitious system has an SRI value of at least 29 SRI units, and wherein the high-SRI cementitious system is selected from the group consisting of a topping, a dry-shake color hardener, and an integral concrete coloring admixture.

2. The method according to claim 1 wherein the high-SRI cementitious system-comprises a topping for applying to hardened concrete.

3. The method according to claim 1 wherein the high-SRI cementitious system comprises a dry-shake color hardener for applying to freshly placed concrete.

4. The method according to claim 1 wherein the high-SRI cementitious system comprises an integral concrete coloring admixture used in a conventional cast-in-place concrete.

5. The method according to claim 1 wherein the high-SRI cementitious system comprises an integral concrete coloring admixture used in lightweight concrete.

6. The method according to claim 1 wherein the high-SRI cementitious system comprises an integral concrete coloring admixture used in pervious concrete.

7. The method according to claim 1 wherein the high-SRI cementitious system comprises an integral concrete coloring admixture used in concrete cast into manufactured building panels or pavers, and the infrared reflective pigments are added to the concrete during mixing of the wet concrete, and before casting the manufactured building panels or pavers.

8. The method according to claim 1 wherein the high-SRI cementitious system comprises an integral concrete coloring admixture or cementitious matrix, and the pigment composition comprises a blend of brown and black CICP pigments having a % reflectance at 1000 nm of at least 5% and less than 40% with one or more black infrared reflective pigments having a % reflectance at 1000 nm of at least 40% to meet an SRI requirement of 32 or higher.

9. The method according to claim 1 wherein the high-SRI cementitious system has an SRI value of at least 32 SRI units.

10. The method according to claim 1 wherein the high-SRI cementitious system has an SRI value of at least 40 SRI units.

11. The method according to claim 1 wherein the black infrared reflective pigments are selected from the group consisting of:
manganese-vanadium oxide spinels, chromium green-black hematites, aluminum- and titanium-doped chromium green-black modified hematites, chromium iron oxides, hematite chromium green-blacks, iron chromite brown spinels, manganese ferrite spinels, chromium iron nickel black spinels, perylene blacks- and combinations thereof.

12. The method according to claim 1 wherein the black infrared reflective pigment is a complex inorganic colored black pigment (CICP).

13. The method according to claim 1 wherein the red infrared reflective pigments are selected from the group consisting of:
o-chloro-p-nitroaniline coupled β-napthols, m-nitro-p-toluidine coupled with β-napthols, diazotized p-aminobenzamide coupled with BON-o-phentidines, diketo-pyyrolo-pyrrole reds, high IR iron (III) oxide hematites, cerium sesquisulfides, quinacridone magenta B, pigment red 149, perylene reds, and combinations thereof.

14. The method according to claim 13 wherein the red infrared reflective pigments are an iron (III) oxide hematite, a cerium sesquisulfide, or a combination thereof.

15. The method according to claim 1 wherein the orange to yellow infrared reflective pigments are selected from the group consisting of:
benzimidazolone blends, chromium antimony titanate rutiles, o-dianisidine coupled with aceto-acetanilides, dinitraniline coupled with beta-naphthols, insoindoline yellows, o-(2-methoxy-4-nitrophenylhydrazono)-α-aceto-2′-methoxyacetanilides, monoarylide yellows, nickel antimony titanium rutiles, m-nitro-o-anisidine coupled with acetoacet-o-anisidines, potassium cerium sulfides, pyrazolo-quinazolones, quinophthalone yellows, and combinations thereof.

16. The method according to claim 1 wherein the orange to yellow infrared reflective pigments are a nickel antimony titanium rutile, a chrome antimony titanium rutile, an isoindoline yellow, or a combination thereof.

17. The method according to claim 16 wherein at least one of the orange to yellow infrared reflective pigment is a nickel antimony titanium rutile.

18. The method according to claim 1 wherein the beige to brown infrared reflective pigments are selected from the group consisting of:
chrome antimony titanium rutiles, chromium iron oxide spinels, chrome niobium buff rutiles, chrome tungsten titanium rutiles, iron titanium spinels, manganese antimony titanium rutiles, manganese tungsten titanium rutiles, zinc ferrite spinels, zinc iron chromite spinels, manganese ferrite brown spinels, and combinations thereof.

19. The method according to claim 18 wherein at least one of the beige to brown infrared reflective pigment is a manganese antimony titanium rutile.

20. The method according to claim 18 further comprising one or more red, orange, or yellow infrared reflective pigment.

21. The method according to claim 1 wherein the green infrared reflective pigments are selected from the group consisting of:
chlorinated copper phthalocyanines, chromium hematites, chromium modified hematites, chromium oxides, cobalt chromite spinels, cobalt chromite spinels, cobalt titanate spinels, and combinations thereof.

22. The method according to claim 1 wherein the green infrared reflective pigments are a chromium hematite, a cobalt chromite spinel, a chromium modified pigment, and combinations thereof.

23. The method according to claim 22 wherein at least one of the green infrared reflective pigments is a cobalt chromite spinel.

24. The method according to claim 1 wherein the blue infrared reflective pigments are selected from the group consisting of:
cobalt aluminate spinels, cobalt chromite spinels, cobalt chromium zinc aluminate spinels, cobalt lithium titanate spinels, copper phthalocyanines, indanthrones, and combinations thereof.

25. The method according to claim 24 wherein the blue infrared reflective pigments are a cobalt chromite spinel, a cobalt aluminum spinel, or a combination thereof.

26. The method according to claim 1 wherein the infrared reflective pigments are selected to provide a gray, light gray, dark gray or bright white IR reflective cementitious system, and wherein the pigments are selected from the group consisting of: black infrared reflective pigments, chromium hematites, anatase TiO2, chrome antimony titanium rutiles, and combinations thereof.

27. The method according to claim 1 wherein the infrared reflective pigments are:
anatase TiO2 and one or more black infrared reflective pigments; or
anatase TiO2 and one or more infrared reflective pigments to produce a pastel color.

28. The method according to claim 1 wherein the black infrared reflective pigments, red infrared reflective pigments; orange to yellow infrared reflective pigments, beige to brown infrared reflective pigments, green infrared reflective pigments, blue infrared reflective pigments, and gray-white infrared reflective pigments are combined with a concrete coloring admixture in a concrete or a cementitious matrix to form an intermediate colored cementitious system.

29. A method of preparing a high-SRI colored concrete using a high-SRI cementitious system, the method comprising:
(a) providing components of a cementitious system comprising a cementitious matrix or concrete coloring admixture;
(b) combining an infrared reflective pigment composition with the cementitious system to form the high-SRI cementitious system, wherein the infrared reflective pigment composition comprises:
one or more infrared reflective pigments selected from the group consisting of: black infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 40%, red infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 60%; orange to yellow infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 65%; beige to brown infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 60%; green infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 60%; blue infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 50%; gray to white infrared reflective pigments having a percent reflectance at 1000 nanometers of at least 60%; and combinations thereof, wherein the percent reflectance at 1000 nm is measured in white portland cement, and wherein the infrared reflective pigments are compliant with ASTM C979; and
TiO2 comprising anatase TiO2 or rutile TiO2; and
(c) applying the high-SRI cementitious system to a concrete to form the high-SRI colored concrete, wherein the high-SRI cementitious system has an SRI value of at least 29 SRI units, and wherein the high-SRI cementitious system is selected from the group consisting of a topping, a dry-shake color hardener, and an integral concrete coloring admixture.

30. The method according to claim 29 wherein the TiO2 comprises pigment, ultrafine, or photocatalytic grade anatase TiO2, and wherein the TiO2 provides SRI-restoring function upon exposure to UV radiation.

31. The method according to claim 29 wherein the TiO2 comprises low tint strength or non-pigmentary TiO2.

32. The method according to claim 29 wherein the TiO2 comprises low tint strength or non-pigmentary TiO2 and the TiO2 is combined with to improve the overall reflectivity of the cementitious system.