BACKGROUND

1. Field of The Invention

[0001] The invention is in the field of hydraulic cement and cementitious compositions made with hydraulic cement.

2. Technology Review

[0002] Modern Portland cement is a ubiquitous building material that when mixed with water forms a flowable or moldable material and then hardens or cures to form a hardened cementitious binding matrix. Portland cement is typically grey in color owing to the inclusion of iron oxide, typically in the form of the clinker mineral tetracalcium aluminoferrite (C ₄ AF), which can act as a flux to bind the other main clinker minerals together (i.e., tricalcium silicate (C ₃ S), dicalcium silicate (C ₂ S), and tricalcium aluminate (C ₃ A)), which typically melt at higher temperature.

[0003] White Portland cement (or "white cement") is a specialty cement used when the grey color of grey Portland cement is undesirable. The whiteness of white Portland cement powder is measured by its reflectance value ("L value") and qualifies as "white" when the L value exceeds 85%. Often, the whiteness of cement, limestone and other powders is expressed as "brightness". White cement can be used in combination with white or light colored aggregates to produce white or light concrete for prestige construction projects and decorative work. White, light or other decorative concrete can take the form of pre-cast cladding panels, stucco finishes, or glass fiber reinforced concrete (GFRC) since it is generally not economical to use white cement for purely structural elements. An exception is ultrahigh performance concrete (UHPC) which, by nature is very expensive, and which is often made using white cement for both aesthetics and performance.

[0004] White cement has little initial pigmentation and can therefore be used with inorganic pigments to produce colored concretes and mortars or almost any desired color. Grey cement, when used with pigments, produces colors that may be attractive but can also be somewhat dull because of grey background color. With white cement, bright reds, yellows and greens can be readily and more reliably produced. Pigments can be added to the cementitious mixture when mixed. Alternatively, to guarantee repeatable color, some manufacturers supply ready-blended colored cements using white cement as a base. SUMMARY

[0005] Disclosed herein are cementitious compositions comprising dry blends, fresh cementitious mixtures, or hardened cementitious compositions comprised of mixture products of white Portland cement and a light color, relatively high brightness ground granulated blast furnace slag (GGBFS). The cementitious compositions may include other supplementary cementitious materials (SCMs) that are generally white or light colored. The cementitious compositions may also include fibers, admixtures, or other components known in the art of concrete.

[0006] A dry blended cementitious composition comprises white Portland cement and a light color GGBFS, and optionally one or more additional components. The white Portland cement and the light color GGBFS are advantageously ground separately, and without intergrinding with each other, in order to control their respective particle size distribution (PSD).

[0007] A fresh cementitious mixture comprises water, white Portland cement, and a light color GGBFS, and optionally one or more additional components.

[0008] A hardened cementitious composition comprises reaction products of a fresh cementitious mixture comprising water, white Portland cement, and light color GGBFS, and optionally one or more additional components.

DETAILED DESCRIPTION

[0009] In some embodiments, a dry blended cement composition comprises:

a white Portland cement fraction having a Blaine fineness between about 350 m ² /kg and about 650 m ² /kg, a D90 between about 11 μπι and about 50 μπι, and a total combined iron oxide, manganese oxide, and chromium oxide content of less than 1.0% by weight;

a light color ground granulated blast furnace slag fraction having a Blaine fineness greater than the Blaine fineness of the white Portland cement, a D90 less than the D90 of the white Portland cement fraction, and a total combined iron oxide, manganese oxide, and chromium oxide content of less than 2.0% by weight; and

optionally one or more additional components.

[0010] In some embodiments, a fresh cementitious mixture comprises mixture products of:

water;

a white Portland cement fraction having a Blaine fineness between about 350 m ² /kg and about 650 m ² /kg, a D90 between about 11 μπι and about 50 μπι, and a total combined iron oxide, manganese oxide, and chromium oxide content of less than 1.0% by weight;

a light color ground granulated blast furnace slag fraction having a Blaine fineness greater than the Blaine fineness of the white Portland cement, a D90 less than the D90 of the white Portland cement fraction, and a total combined iron oxide, manganese oxide, and chromium oxide content of less than 2.0% by weight; and

optionally one or more additional components.

[0011] In some embodiments, a hardened cementitious composition comprises reaction products of:

water;

a white Portland cement fraction having a Blaine fineness between about 350 m ² /kg and about 650 m ² /kg, a D90 between about 11 μπι and about 50 μπι, and a total combined iron oxide, manganese oxide, and chromium oxide content of less than 1.0% by weight;

a light color ground granulated blast furnace slag fraction (GGBFS) having a Blaine fineness greater than the Blaine fineness of the white Portland cement, a D90 less than the D90 of the white Portland cement fraction, and a total combined iron oxide, manganese oxide, and chromium oxide content of less than 2.0% by weight; and

optionally one or more additional components.

[0012] In some embodiments, the Blaine fineness of white Portland cement in a dry blended cement composition and/or when initially added to a fresh cementitious mixture is between about 375 m ² /kg and about 550 m ² /kg, or between about 400 m ² /kg and about 500 m ² /kg, or between about 425 m ² /kg and about 475 m ² /kg.

[0013] In some embodiments, the D90 of white Portland cement in a dry blended cement composition and/or when initially added to a fresh cementitious mixture is between about 20 μπι and about 46 μπι, or between about 25 μπι and about 42 μπι, or between about 30 μπι and about 38 μπι.

[0014] In some embodiments, the white Portland cement in a dry blended cement composition and/or when initially added to a fresh cementitious mixture has a D10 greater than about 1.0 μπι, or greater than about 1.2 μηι, or greater than about 1.5 μηι, or greater than about 1.8 μηι, or greater than about 2.2 μηι.

[0015] In some embodiments, the Blaine fineness of GGBFS in a dry blended cement composition and/or when initially added to a fresh cementitious mixture is between about 400 m ² /kg and about 750 m ² /kg, or between about 425 m ² /kg and about 700 m ² /kg, or between about 450 m ² /kg and about 650 m ² /kg, or between about 500 m ² /kg and about 600 m ² /kg.

[0016] In some embodiments, the D90 of GGBFS in a dry blended cement composition and/or when initially added to a fresh cementitious mixture is between about 5 μιη and about 45 μιη, or between about 7 μιη and about 40 μιτι, or between about 10 μιη and about 35 μιτι, or between about 12 μιη and about 32 μιτι, or between about 15 μιη and about 27 μιη.

[0017] In some embodiments, the white Portland cement has a total combined transition metal oxide content of less than 1.0% by weight, or less than 0.9% by weight, or less than 0.8%) by weight, or less than 0.7% by weight, or less than 0.6%> by weight, or less than 0.5% by weight, or less than 0.4% by weight.

[0018] In some embodiments, the GGBFS has a total combined transition metal oxide content of less than 2.0% by weight, or less than 1.8% by weight, or less than 1.6% by weight, or less than 1.4% by weight, or less than 1.2% by weight, or less than 1.0% by weight, or less than 0.9% by weight, or less than 0.8% by weight.

[0019] In some embodiments, white Portland cement comprises between about 20% and about 80%), or between about 30% and about 70%, or between about 40% and about 60%, or between about 45% and about 55%, by combined weight of white Portland cement and GGBFS.

[0020] In some embodiments, GGBFS comprises between about 20% and about 80%, or between about 30% and about 70%, or between about 40% and about 60%, or between about

45%) and about 55%, by combined weight of white Portland cement and GGBFS.

[0021] In some embodiments, white Portland cement has a reflectance value ("L value") or

"brightness" of at least 75%, or at least 80%, or at least 85%, or at least 87%, or at least 88%, or at least 89%, or at least 90%.

[0022] In some embodiments, GGBFS has a reflectance value less than the reflectance value of white Portland cement, and that is at least 70%, or at least 72%, or at least 75%, or at least

77%, or at least 80%.

[0023] Because of the reduced quantity of white cement and the inclusion of GGBFS, moldings and other cementitious compositions made using the cementitious composition disclosed herein are expected to have lower efflorescence compared to cementitious compositions in which the cementitious binder is purely white cement. Compared to OPC, white cement can have higher alkali content do to the use of fluxes and other reasons. As a result, while white cement can yield moldings that are initially very beautiful, efflorescence can result in long-term degradation of the beauty and structural integrity of moldings made using white cement as sole cementitious binder. The inclusion of GGBFS can significantly reduce or eliminate the incidence of efflorescence, perhaps because of its pozzolanic activity, which can bind and pacify alkali metal salts.

[0024] Dry blended cement compositions, fresh cementitious mixtures and/or hardened cementitious compositions may further comprise an additional supplementary cementitious material (SCM). In some embodiments, the additional SCM is white or light colored and has a total combined transition metal oxide content of less than 3.0% by weight, or less than 2.5% by weight, or less than 2.2% by weight, or less than 2.0 by weight, or less than 1.8% by weight, or less than 1.6% by weight, or less than 1.4% by weight, or less than 1.2% by weight, or less than 1.0% by weight, or less than 0.9% by weight, or less than 0.8% by weight.

[0025] In some embodiments, the additional SCM is selected from natural pozzolan, ground pumice, metakaolin, ground limestone, ground marble, calcium carbonate, precipitated calcium carbonate (e.g., formed by passing C0 ₂ in flue gas through water comprising calcium ions and alkaline pH), calcined clay, calcine shale, industrial ash, ground glass, and mixtures thereof. In some embodiments, the additional SCM can have a reflectance value ("L value") or brightness of at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 87%, or at least 88%, or at least 89%, or at least 90%.

[0026] In some embodiments, the additional SCM comprises between about 5% and about 70%), or between about 7% and about 60%, or between about 10% and about 50%, or between about 12% and about 40%, by combined weight of white cement, GGBFS, and additional SCM.

[0027] In some embodiments, the additional SCM in a dry blended cement composition and/or when initially added to a fresh cementitious mixture has a Blaine fineness less than the Blaine fineness of the white Portland cement, and a D90 greater than the D90 of the white Portland cement. In some embodiments, the D50 and/or the D10 of the additional SCM is greater than the D50 and/or D10 of the white cement.

[0028] In some embodiments, the Blaine fineness of the additional SCM in a dry blended cement composition and/or when initially added to a fresh cementitious mixture is between about 50 m ² /kg and about 400 m ² /kg, or between about 75 m ² /kg and about 375 m ² /kg, or between about 100 m ² /kg and about 350 m ² /kg, or between about 125 m ² /kg and about 325 m ² /kg.

[0029] In some embodiments, the D90 of the additional SCM in a dry blended cement composition and/or when initially added to a fresh cementitious mixture is between about 40 μηι and about 200 μηι, or between about 45 μιη and about 170 μηι, or between about 50 μιη and about 150 μηι, or between about 55 μιη and about 130 μηι, or between about 60 μιη and about 120 μιη.

[0030] In some embodiments, the D10 of the additional SCM in a dry blended cement composition and/or when initially added to a fresh cementitious mixture is between about 1 μπι and about 100 μπι, or between about 3 μιη and about 90 μπι, or between about 5 μιη and about 80 μπι, or between about 8 μιη and about 70 μπι, or between about 12 μιη and about 60 μπι.

[0031] In order to individually control the particle size distribution (PSD) of each of the various cement, GGBFS and SCM components, they are advantageously produced separately and blended together rather than being interground together. For example, it may be desirable for the GGBFS to have Blaine fineness greater than and/or a D90 less than that of the white cement component. Because GGBFS is typically harder than white cement clinker, intergrinding the two together yields an interground blend in which the white cement component has higher fineness and lower D90 compared to the fineness and D90 of the GGBFS component, respectively. Grinding white cement clinker and granulated blast furnace slag separately and then blending them together permits control over the respective PSDs of the two components, including ensuring that the GGBFS is finer than and/or has a lower D90 than that of the white cement.

[0032] Similarly, SCMs can be softer than white cement and, when interground with white cement clinker, may higher fineness and lower D90 than that of the white cement. For example, where it is desired to include a white limestone powder that is coarser than the white cement, the two materials should be processed separately and then blended together.

[0033] In some embodiments, the cementitious compositions comprise a ternary blend of white cement, GGBFS that is finer than the white cement, and a coarse SCM (e.g., limestone powder) that is coarser than the white cement. The use of coarse SCMs is beneficial in order to increase particle packing density of particles in the cement paste, which increases strength, reduces autogenous, plastic and drying shrinkage, and improve cohesiveness and reduce bleeding and segregate. These qualities are beneficial for concrete in general, including precast concrete, stucco, GFRC, UHPC and SCC.

[0034] In some embodiments, the cementitious composition further comprises at least one additive to improve chemical balance and strength, such as lime (CaO), dolomite lime (CaO MgO), hydrated lime (Ca(OH) ₂ ), hydrated dolomite lime (Ca(OH) ₂ Mg(OH) ₂ ), calcium sulfate hemihydrate (e.g., plaster of Paris), anhydrous calcium sulfate (e.g., anhydrite), and calcium sulfate dihydrate (e.g., gypsum). Calcium oxides and hydroxides can provide an early source of calcium ions to offset premature calcium depletion caused by pozzolanic reactions. Calcium sulfates can adjust sulfate balance to account for sulfate deficiencies caused by GGBFS and/or optional SCMs.

[0035] In some embodiments, the cementitious composition further comprises at least one aggregate selected from fine sand, medium sand, coarse sand, pea gravel, or coarse aggregate. In some embodiments, the at least one aggregate is selected from limestone, marble, dolomite, quartz, quartzite, pumice, shale, and polymers (e.g., post-consumer polystyrene foam beads or fragments).

[0036] In some embodiments, the cementitious composition further comprises fibers. Fibers can be used, for example, in high performance concrete. Glass fiber reinforced concrete (GFRC) can include glass fibers to increase fracture energy. In some cases, GFRC is formed by spraying a cementitious mixture onto a surface and permitting it to harden. In some embodiments, precast decorative concrete may include polymer fibers, such as polypropylene, polyvinyl alcohol or nylon fibers, to increase flexural strength and toughness. Ultra-high performance concrete (UHPC) often uses white cement to maintain higher quality, higher strength, and better aesthetics and can include steel fibers for internal reinforcement and to add ductility.

[0037] Examples of cementitious compositions within the scope of the disclosure are set forth below. The Examples includes mix designs and tables of comparative strength results. In many cases, cementitious compositions in which more than 50% of the white cement was replaced with GGBFS, and optionally coarse powdered limestone, had similar or greater strength than a standard mix comprising white cement as the only cementitious binder. It is believed that the selection of a white cement, GGBFS having a fineness greater than and/or D90 less than that of the white cement, and one or more strengthening components, such as hydrated lime, limestone powder and/or natural pozzolan, synergistically interacted to yield hardened cementitious compositions of high strength even though the amount of white cement was reduced by 50% or more.

[0038] The blended white cement compositions disclosed herein can be used to replace white Portland cement in any desired application and are particularly well-suited for pre-cast concrete, stucco, glass fiber reinforced concrete (GFRC), and ultrahigh performance concrete (UHPC). In some embodiments, the water to cementitious binder ratio (w/cm) is less than 0.45, or less than 0.43, or less than 0.41, or less than 0.39, or less than 0.37, or less than 0.35, or less than 0.33, or less than 0.31, or less than 0.29. The water to cementitious binder ratio is advantageously determined based on the amount of water relative to the hydraulically reactive binder components in the cementitious mixture.

[0039] In order to achieve low w/cm mixes while maintaining flow, it is typically desirable to include superplasticizers, admixtures and other flow aids known in the art of concrete, including pre-cast concrete, GFRC, UHPC, ready mixed concrete, and self-consolidating concrete (SCC). UHPC is itself often designed so as to be self-consolidating. Example admixtures include polycarboxylate ethers known in art, which are preferred over darker colored plasticizers and water reducers, such as lignosulfonates. Latex binders used to bind the cementitious compositions to polymer foam or other non-cementitious structures can sometimes improve the plasticity and flow of cementitious mixtures in addition to their adhesive properties. For example, latex binders based on polyvinyl acetate polymers and copolymers have been found to further improve flow when used in small amounts in combination with a superplasticizer. A viscosity modifying agent (VMA) can be used to provide cohesiveness and moldability and to prevent bleeding and segregation. Examples include cellulosic ethers known in the art (e.g., Methocel).

[0040] Non-reactive components, such as coarse limestone particles coarser than typical cement particles (i.e., particles larger than about 50 μιη), can be excluded from the mass balance of cementitious binder when determining the water to cementitious binder ratio (w/cm). Limestone particles smaller than 50 μιη may, on the other hand, be counted toward the "cement" content for purposes of determining the w/cm. Limestone particles larger than, e.g., 50 μπι are considered to be part of the aggregate content for purposes of determining the w/cm but limestone particles of all sizes may nevertheless be considered to constitute an SCM and form part of the "cement paste" when smaller than about 200 μιη. Limestone and other non-reactive SCM particles can be considered to be "paste aggregates" because they are hardly discernable as ordinary aggregates but are intermixed within the cement paste. In the context of the present invention, they have been shown to increase the strength of the cement paste and overall cementitious composition and therefore contribute to cement paste volume and strength. Adding limestone powder can increase the overall powder content, which also reduces the tendency of the cementitious composition to experience bleeding or segregation, improving workability, cohesiveness, finishability, and overall performance.

[0041] It is postulated that coarse limestone particles increase the strength of the cement paste by filling a niche and effectively extending the continuity of the particle size distribution (PSD) of hydraulic cement and SCM particles from a maximum of 50 μπι, as is typical for Portland cement in general and white Portland cement used in precast, GFRC, UHPC and SCC applications in particular, to a maximum particle size of at least 60 μπι, 70 μπι, 80 μιη, 90 μπι, 100 μιη, 110 μπι, 120 μιη, 130 μπι, 140 μπι, or 150 μιη, and up to 200 μπι. This broadening of the PSD of the cementitious binder particles, including white Portland cement, GGBFS, and coarse SCM particles, substantially increases the particle packing density of particles in the cement paste from a typical packing density of 50% or less to upwards of 57% or greater, such as at least 58%, 60%, 62%, 65%, 70% or 75%. This, in turn, significantly reduces the amount of inter-particle spacing, which is otherwise occupied by water or air in a freshly mixed cementitious composition. Reducing the amount of inter- particle spacing causes the cement and/or GGBFS particles to be statistically closer together at a given w/cm, flow and/or superplasticizer content. This, in turn, yields denser cement pastes of higher strength compared to cement pastes in the absence of coarse filler particles.

Examples

[0042] The following examples are given by way of illustration to demonstrate that reductions of up to 50% or more of Portland white cement are possible while maintaining or increasing the compressive strength of hardened cementitious compositions made from the inventive compositions. The white cement was obtained from Lehigh cement and reportedly had a Blaine of 417.3 m ² /kg, a percent passing at 325 mesh (44 μηι) of 96.5% (for an estimated D90 of about 36-39 μηι), a brightness (L) of 93.1, and an iron oxide (Fe ₂ 03) content of 0.2%. The GGBFS was obtained from Lehigh cement from a source in Japan and reportedly had Blaine of 550 m ² /kg, a percent passing at 21 μπι of 91.7%, a percent passing at 18 μπι of 87.8% (for an estimated D90 of about 20 μηι), an iron oxide (Fe ₂ 0 ₃ ) content of 0.6%), a manganese oxide (MnO) content of 0.1%, and titanium dioxide (Ti0 ₂ ) content of 0.6%). This GGBFS was very light colored, was substantially finer than the white cement, and had a D90 that was nearly half the D90 of the white cement. The whiteness of the GGBFS was estimated by inspection to be between about 70-80 on the brightness scale.

[0043] The "fine limestone powder" used in some of the examples had a PSD of approximately 5 μπι to 50 μπι and was considered to be a "cementitious SCM" and part of the cementitious binder for purposes of determining the w/cm. It had a brightness of about 92%). The "coarse limestone powder" identified in some of the Examples is the same material identified as "fine limestone sand", which reportedly had a brightness of 92% and less than 0.1%) iron oxide (Fe ₂ 0 ₃ ). The fine limestone sand reportedly had 96.7% passing at 212 μηι, 89.6%) passing at 150 μηι, 72.5% passing at 106 μηι, 52.1%> passing at 75 μηι. Based on these numbers, it is estimated that the fine limestone sand had approximately 20-25% passing at 50 μηι. As such, about 20-25%> of the fine limestone sand was deemed to constitute "cementitious SCM particles" for purposes of determining the w/cm of the paste, an estimated 70-75% of the fine limestone sand had particle sizes between 50-150 μπι and therefore constituted "cement paste aggregate", and approximately 10% of the fine limestone sand had particle sizes greater than 150 μπι and was therefore considered to form part of the non-paste aggregate, together with the coarser sand particles.

Examples 1-10 (Decorative Stone Precast)

[0044] Example 1 (control mix) was a standard cementitious mixture used to make precast limestone moldings for commercial sale with a design strength of 8000 psi (55.2 MPa) at 28 days. Examples 2-9 were compositions made according to the present invention and had greatly reduced white Portland cement (clinker) content, with comparable or superior strengths at similar water-to-cementitious binder ratio (w/cm). The amount of sand components in Examples 2-10 was modified to maintain the same volume of cementitious mixture as Example 1. The mix designs and strength results for Examples 1-10 are set forth below in Tables 1 and 2.

[0045] The cementitious mixtures were prepared using a Hobart mixer and made into 2-inch mortar cubes according to ASTM C I 09. After mixing the ingredients together (except for PVA fibers) following the procedure specified in ASTM C I 09, the PVA fibers were mixed at low speed until distributed throughout the cementitious mixture to avoid breaking or fraying the fibers. The flow was estimated to be approximately 100-1 10 (as would be measured using a standard flow table).

[0046] Each cementitious mixture was placed into nine 2-inch mortar cube mold cavities in two stages, with the mold cavities first being filled half-way, followed by tamping using a rubber tool as specified in ASTM C I 09, followed by filling the cavities completely, tamping again using the rubber tool, and then leveling off the cube mold surfaces using a steel trowel. The molds were covered with thin plastic film, and moist towels were placed over the plastic film to completely cover the tops and sides of the molds and the surface around the molds to prevent evaporation of water from the molds during initial setting and curing.

[0047] After 1 day, the hardened cubes were removed from the cube molds and cured in a saturated lime water bath maintained at room temperature. The cubes remained in the saturated lime water bath until tested for compressive strength using a standard hydraulic press for testing mortar cubes and concrete cylinders, including a computerized data gathering processor and numeric readout. Three of the nine cubes were tested at each of 3-, 7- and 28-day intervals as specified by ASTM CI 09. The hydraulic press was located at and operated by CMT Engineering, Inc. in West Valley City, Utah, which tabulated and reported the compressive strengths. The compressive strength of each cementitious mixture was determined to be either (1) the average of compressive strength values of three cubes at each time interval or (2) the average of the top two cube strength values (throwing out the lowest value as being less representative of the true strength of the cementitious composition).

Table 1

VMA - viscosity modifying agent

w/c = water to cement ratio

w/cm = water to cementitious binder ratio

w/p = water to powder ratio

top strength value is average of 3 cubes; bottom value is average of 2 strongest cubes

Note: for Example 1, first cubes tested at 4 days, not 3 days

Table 2

PVA fiber (g) 6.50 6.50 6.50 6.50 6.50

Superplasticizer (ml) 2.7 2.7 2.6 3.0 2.6

VMA (g) 0.1 0.1 0 0.05 0.05 w/c 0.74 0.72 0.73 0.80 0.76 w/cm 0.36 0.36 0.36 0.39 0.38

3 -day (psi / MPa) 6420 / 44.3 5783 / 32.3 3843 / 28.8 5637 / 34.8 7058 / 44.6

6750 / 46.5 5875 / 33.7 3910 / 29.2 5695 / 35.4 7247 / 46.1

7-day (psi / MPa) 7407 / 51.1 8268 / 41.1 6713 / 38.9 8303 / 49.2 8413 / 53.1

7465 / 51.5 8383 / 41.6 6757 / 40.7 8360 / 50.0 8475 / 53.7

28-day (psi / MPa) 8640 / 59.6 8813 / 50.7 9913 / 55.2 9477 / 53.6 9608 / 68.9

8727 / 60.2 8935 / 51.1 10135 / 56.2 9700 / 54.6 9677 / 70.5

VMA - viscosity modifying agent

w/c = water to cement ratio

w/cm = water to cementitious binder ratio

A portion of "fine limestone sand" was allocated to cementitious powder so w/p < w/cm

top strength value is average of 3 cubes; bottom value is average of 2 strongest cubes

[0048] Example 1 contained white cement as the sole binder and had an expected white or off-white coloring. Examples 2-10, when freshly mixed, formed cementitious mixtures that were slightly less white and perceptibly darker than Example 1. After curing and being permitted to surface dry, the color of the hardened cubes were virtually indistinguishable from the hardened cubes of Example 1. This shows that either a "natural" uncolored precast limestone molding can be made using the mixtures of Examples 2-9 or they can be colored using substantially the same amount(s) of pigment(s) as would be added to mixture of Example 1 to yield a precast limestone molding of desired color. Because of the reduced quantity of white cement and the inclusion of GGBFS, and optionally recycled glass or hydrated lime, moldings made using the mixtures of Examples 2-10 would be expected to have lower efflorescence compared to Example 1.

Examples 1 1-15 (GFRC)

[0049] Example 1 1 (control mix) was a standard cementitious mixture used to make glass fiber reinforced concrete (GFRC) for commercial sale with a design strength of 8000 psi (55.2 MPa) at 28 days. Examples 12-15 were compositions made according to the present invention and had greatly reduced white Portland cement (clinker) content, with superior strengths at similar water-to-cementitious binder ratio (w/cm). The coarse limestone powder was apportioned between "sand" and "cementitious powder." The amount of sand components in Examples 12-15 was modified to maintain the same volume of cementitious mixture as Example 1 1. The mix designs and strength results for Examples 1 1-15 are set forth below in Table 3. [0050] The cementitious mixtures were prepared using a Hobart mixer and made into 2-inch mortar cubes according to ASTM C I 09. After mixing the ingredients together (except for PVA fibers) following the procedure specified in ASTM C I 09, the glass fibers were mixed at low speed until distributed throughout the cementitious mixture to avoid breaking or fraying the fibers. The flow was estimated to be approximately 100-1 10 (as would be measured using a standard flow table).

[0051] Each cementitious mixture was placed into nine 2-inch mortar cube mold cavities in two stages, with the mold cavities first being filled half-way, followed by tamping using a rubber tool as specified in ASTM C I 09, followed by filling the cavities completely, tamping again using the rubber tool, and then leveling off the cube mold surfaces using a steel trowel. The molds were covered with thin plastic film, and moist towels were placed over the plastic film to completely cover the tops and sides of the molds and the surface around the molds to prevent evaporation of water from the molds during initial setting and curing.

[0052] After 1 day, the hardened cubes were removed from the cube molds and cured in a saturated lime water bath maintained at room temperature. The cubes remained in the saturated lime water bath until tested for compressive strength using a standard hydraulic press for testing mortar cubes and concrete cylinders, including a computerized data gathering processor and numeric readout. Three of the nine cubes were tested at each of 3-, 7- and 28-day intervals as specified by ASTM CI 09. The hydraulic press was located at and operated by CMT Engineering, Inc. in West Valley City, Utah, which tabulated and reported the compressive strengths. The compressive strength of each cementitious mixture was determined to be either (1) the average of compressive strength values of three cubes at each time interval or (2) the average of the top two cube strength values (throwing out the lowest value as being less representative of the true strength of the cementitious composition).

Table 3

Medium-fine silica sand (g) 623.10 654.25 654.25 654.25 654.25

Glass fiber (g) 98.38 98.38 98.38 98.38 98.38

Superplasticizer (ml) 23 23 23 23 23

VMA (g) 1.05 1.05 1.05 1.05 1.05 w/c 0.27 0.55 0.61 0.61 0.61 w/cm 0.27 0.27 0.27 0.29 0.27 w/p 0.25 0.25 0.25 0.25 0.25

3 -day (psi / MPa) 7253 / 50.0 7337 / 50.6 8403 / 57.9 6662 / 45.9 6125 / 42.2

7385 / 50.9 7338 / 50.6 8540 / 58.9 6937 / 47.8 6285 / 43.3

7-day (psi / MPa) 8180 / 56.4 9342 / 64.4 11377 / 78.4 11170 / 77.0 8017 / 55.3

8235 / 56.8 9665 / 66.6 11565 / 79.7 11230 / 78.1 8225 / 56.7

28-day (psi / MPa) 9563 / 65.9 11607 / 80.0 12167 / 83.4 12635 / 87.1 10790 / 74.4

9705 / 66.9 11755 / 81.0 12250 / 84.5 12862 / 88.7 10960 / 75.6

VMA - viscosity modifying agent

ultrafine pumice has D50 = 3-4 μιη

interground volcanic ash-limestone has D90 = 56 μιη

UFFA has D90 = 10 m.

w/c = water to cement ratio

w/cm = water to cementitious binder ratio

w/p = water to powder ratio (half of coarse limestone powder allocated to cement; half to sand) top strength value is average of 3 cubes; bottom value is average of 2 strongest cubes [0053] Example 1 1 contained white cement as the sole binder and had an expected white or off-white coloring. Examples 12-15, when freshly mixed, formed cementitious mixtures that were slightly less white and perceptibly darker than Example 1 1. After curing and being permitted to surface dry, the color of the hardened cubes were virtually indistinguishable from the hardened cubes of Example 1 1. This shows that either a "natural" uncolored GFRC material can be made using the mixtures of Examples 12-15 or they can be colored using substantially the same amount(s) of pigment(s) as would be added to mixture of Example 1 1 to yield a GFRC material of desired color. Because of the reduced quantity of white cement and the inclusion of GGBFS, and optionally pumice, interground volcanic ash-limestone, ultrafine fly ash, or hydrated lime, GFRC made using the mixtures of Examples 12-15 would be expected to have lower efflorescence compared to Example 1 1.

Examples 16-32 (Decorative Stone Precast)

[0054] Example 16 (control mix) was derived from the cementitious mixture of Example 1, except that Example 16 used a single type of medium silica sand instead of the coarse and medium limestone sands used in Example 1. Example 16 has a presumed design strength of 8000 psi (55.2 MPa) at 28 days. Examples 17-32 were compositions made according to the present invention and had greatly reduced white Portland cement (clinker) content, with comparable or superior strengths at similar water-to-cementitious binder ratio (w/cm). The amount of sand in Examples 17-32 was modified to maintain the same volume of cementitious mixture as Example 16. The mix designs and strength results for Examples 16- 32 are set forth below in Tables 4-7.

[0055] The cementitious mixtures were prepared using a Hobart mixer and made into 2-inch mortar cubes according to ASTM CI 09. The flow for Example 16 was estimated to be approximately 140 (as would be measured using a standard flow table). The flow of Examples 17-32 was comparable.

[0056] Each cementitious mixture was placed into nine 2-inch mortar cube mold cavities in two stages, with the mold cavities first being filled half-way, followed by tamping using a rubber tool as specified in ASTM CI 09, followed by filling the cavities completely, tamping again using the rubber tool, and then leveling off the cube mold surfaces using a steel trowel. The molds were covered with thin plastic film, and moist towels were placed over the plastic film to completely cover the tops and sides of the molds and the surface around the molds to prevent evaporation of water from the molds during initial setting and curing.

[0057] After 1 day, the hardened cubes were removed from the cube molds and cured in a saturated lime water bath maintained at room temperature. The cubes remained in the saturated lime water bath until tested for compressive strength using a standard hydraulic press for testing mortar cubes and concrete cylinders, including a computerized data gathering processor and numeric readout. Three of the nine cubes were tested at each of 3-, 7- and 28-day intervals as specified by ASTM CI 09. The hydraulic press was located at and operated by CMT Engineering, Inc. in West Valley City, Utah, which tabulated and reported the compressive strengths. The compressive strength of each cementitious mixture was determined to be either (1) the average of compressive strength values of three cubes at each time interval or (2) the average of the top two cube strength values (throwing out the lowest value as being less representative of the true strength of the cementitious composition).

Table 4

w/c 0.36 0.90 1.03 1.03 0.80 w/cm 0.36 0.44 0.44 0.44 0.44 w/p 0.36 0.36 0.36 0.36 0.36

3 -day (psi / MPa) 5737/39.6 4887/33.7 4688/32.3 3520/24.3 4613/31.8

5900/40.7 5260/36.3 4762/32.8 3545 /24.4 4755 /32.8

7-day (psi / MPa) 6847/47.2 7233 /49.9 6208/42.8 6461 /44.6 5991 /41.3

7010/48.3 7375 /50.8 6625/45.7 6692/46.1 6147/42.4

28-day (psi / MPa) 8313 /57.3 9282 / 64.0 8325 /57.4 9047 / 62.4 7792/53.7

8380/57.8 9400 / 64.8 8463 /58.4 9105 /62.8 7830/54.0

VMA - viscosity modifying agent

w/c = water to cement ratio

w/cm = water to cementitious binder ratio

w/p = water to powder ratio

top strength value is average of 3 cubes; bottom value is average of 2 strongest cubes

Table 5

VMA - viscosity modifying agent

w/c = water to cement ratio

w/cm = water to cementitious binder ratio

w/p = water to powder ratio

top strength value is average of 3 cubes; bottom value is average of 2 strongest cubes

Table 6

Hydrated lime (g) 23.60 23.60 23.60 11.80 11.80

Water (g) 424.06 347.73 347.73 424.06 424.06

Medium silica sand (g) 1320 1250 1320 1304 1300

Superplasticizer (ml) 2.02 6.0 4.0 2.2 1.5

VMA (g) 0.4 0.6 0.4 0.2 0.1 w/c 0.72 0.82 0.72 0.90 0.90 w/cm 0.45 0.41 0.36 0.36 0.40 w/p 0.36 0.33 0.24 0.30 0.33

3 -day (psi / MPa) 6670/46.0 3837/26.5 5053 /34.8 5028 /34.7 4820/33.2

6770/46.7 3955 /27.3 5165 /35.6 5133 /35.4 4960/34.2

7-day (psi / MPa) 8743/60.3 7330/50.5 7023/48.4 5778 /39.9 5240/36.1

8775 /60.5 7670/52.9 7140/49.2 5903 /40.7 5345 /36.9

28-day (psi / MPa) 9667/66.7 8910/61.4 8502/58.6 7493 /51.7 7123/49.1

9735 /67.1 9025 / 62.2 8585 /59.2 7520/51.8 7293/50.3

VMA - viscosity modifying agent

interground volcanic ash-limestone has D90 = 56 μιη

coarse fly ash had D10 =20 μιη

w/c = water to cement ratio

w/cm = water to cementitious binder ratio

w/p = water to powder ratio

top strength value is average of 3 cubes; bottom value is average of 2 strongest cubes

Table 7

VMA - viscosity modifying agent

interground volcanic ash-limestone has D90 = 56 μιη

w/c = water to cement ratio

w/cm = water to cementitious binder ratio

w/p = water to powder ratio

top strength value is average of 3 cubes; bottom value is average of 2 strongest cubes [0058] Example 16 contained white cement as the sole binder and had an expected white or off-white coloring. Examples 17-32, when freshly mixed, formed cementitious mixtures that were slightly less white and perceptibly darker than Example 16. After curing and being permitted to surface dry, the color of the hardened cubes were virtually indistinguishable from the hardened cubes of Example 16. This shows that either "natural" uncolored molded objects can be made using the mixtures of Examples 17-32 or they can be colored using substantially the same amount(s) of pigment(s) as would be added to mixture of Example 16 to yield molded objects of desired color. Because of the reduced quantity of white cement and the inclusion of GGBFS, and optionally interground volcanic ash-limestone, fly ash, or hydrated lime, molded objects made using the mixtures of Examples 17-32 would be expected to have lower efflorescence compared to Example 16.