Abstract:
The present invention relates to pre-blend cement for general-purpose concrete construction containing Class-F fly ash, Class-C fly ash or slag, and less than about 5 percent (w/w) of sodium thiocyanate (NaSCN) and/or calcium nitrate (Ca(NO 3 ) 2 ), as a substantial replacement for cement. The sodium thiocyanate and/or calcium nitrate are additives for improved high early strength and accelerated setting times, thereby allowing the concrete structure to be put into service sooner, reducing labor cost, and allowing precast concrete and concrete masonry manufacturers to achieve rapid form and mold turnover.

Description:
FIELD OF THE INVENTION 
     The present invention relates to pre-blend compositions for general purpose concrete mixes, and more particularly to pre-blend compositions containing additives for shortened setting times that meet ASTM C595 specification for pre-blend cements. 
     BACKGROUND OF THE INVENTION 
     The present invention is concerned with the utilization of non-chloride additives, namely sodium thiocyanate (NASCN) and/or calcium nitrate (Ca(NO 3 ) 2 ), for shortening the setting times of concrete ready-mixes. Further, the invention is also concerned with the utilization of three industrial by-products; namely, Class-F fly ash, Class-C fly ash, and blast furnace slag in general purpose concrete-making compositions. 
     When finely divided or pulverized coal is combusted at high temperatures, for example, in boilers for the steam generation of electricity, the ash, consisting of the incombustible residue plus a small amount of residual combustible matter, is made up of two fractions, a bottom ash recovered from the furnace or boiler in the form of a slag-like material and a fly ash which remains suspended in the flue gases from the combustion until separated therefrom by known separation techniques, such as electrostatic precipitation. This fly ash is an extremely finely divided material generally in the form of spherical bead-like particles, with at least 70% by weight passing a 200 mesh sieve, and has a generally glassy state resulting from fusion or sintering during combustion. As recognized in the American Society of Testing Materials (ASTM) specification designations C618-00 entitled “Fly Ash and Raw or Calcined Natural Pozzolan for Use as a Mineral Admixture in Portland Cement Concrete” and D5370-96 entitled “Standard Specification for Pozzolanic Blended Materials in Construction Application,” fly ash is subdivided into two distinct classifications; namely, Class-F and Class-C. The definitions of these two classes given in the aforementioned ASTM specifications are as follows: 
     “Class-F—Fly ash normally produced from burning anthracite or bituminous coal that meets the applicable requirements for this class as given herein. This class fly ash has pozzolanic properties. 
     Class-C—Fly ash normally produced from lignite or subbituminous coal that meets the applicable requirements for this class as given herein. This class of fly ash, in addition to having pozzolanic properties, also has some cementitious properties. Some Class-C fly ashes may contain lime contents higher than 10%.” 
     The latter reference to “pozzolanic properties” refers to the capability of certain mixtures that are not in themselves cementitious, but are capable of undergoing a cementitious reaction when mixed with calcium hydroxide in the presence of water. Class-C fly ash possesses direct cementitious properties as well as pozzolanic properties. ASTM C618-00 is also applicable to natural pozzolanic materials that are separately classified as Class N but are not pertinent here. 
     As the above quotation from the ASTM specification indicates, the type of coal combusted generally determines which class fly ash results, and the type of coal in turn is often dependent upon its geographic origin. Thus, Class-C fly ash frequently results from the combustion of coals mined in the Midwest United States; whereas Class-F fly ash often comes from combustion of coals mined in the Appalachian region of the United States. The ASTM specification imposes certain chemical and physical requirements upon the respective fly ash classifications which are set forth in U.S. Pat. No. 5,520,730, the disclosure of which is incorporated herein by reference. 
     Blast furnace slag is a by-product of the production of iron in a blast furnace; silicon, calcium, aluminum, magnesium and oxygen are the major elemental components of slag. Blast furnace slags include air-cooled slag resulting from solidification of molten blast furnace slag under atmospheric conditions; granulated blast furnace slag, a glassy granular material formed when molten blast furnace slag is rapidly chilled as by immersion in water; and pelletized blast furnace slag produced by passing molten slag over a vibrating feed plate where it is expanded and cooled by water sprays, whence it passes onto a rotating drum from which it is dispatched into the air where it rapidly solidifies to spherical pellets. In general the glass content of the slag determines the cementitious character. Rapidly cooled slags have a higher glass content and are cementitious; slowly cooled slags are non-glassy and crystalline and, thus do not have significant cementitious properties. 
     The quantities of these by-product materials that are produced annually are enormous and are likely only to increase in the future. As petroleum oil as the fuel for the generation of electricity is reduced because of conservation efforts and unfavorable economics, and as political considerations increasingly preclude the construction of new nuclear power electrical generating facilities, or even the operation or continued operation of already completed units of this type, greater reliance will necessarily fall on coal as the fuel for generating electricity. As of 1979, the volume of Class-F fly ash that was available then was estimated to be about five times what could be readily utilized. The estimated annual total production of coal ash in the U.S. is about 66.8 million tons, while the annual total coal ash sales in the U.S. is only about 14.5 million tons. Further, in Canada, the recovery of copper, nickel, lead and zinc from their ores produces over twelve million tons of slag per year, which is usually accumulated near the smelters with no significant use. Obviously, there is an urgent and growing need to find effective ways of employing these unavoidable industrial by-products since they will otherwise collect at a staggering rate and create crucial concerns regarding their adverse environmental effects. 
     Various proposals have already been made for utilizing both types of fly ash. According to Lea (1971),  The Chemistry of Cement and Concrete , Chemical Publishing Company, Inc., page 421 et seq., fly ash, i.e., Class-F type, from boilers was first reported to be potentially useful as a partial replacement for Portland cement in concrete construction about 50 years ago, and its utilization for that purpose has since become increasingly widespread. It is generally accepted that the proportion of Portland cement replaced by the usual fly ash should not exceed about 20% to avoid significant reduction in the compressive strength of the resultant concrete, although some more cautious jurisdictions may impose lower limits, e.g., the 15% maximum authorized by the Virginia Department of Highways and Transportation (VDHT). As described in Lea on page 437, the substitution of fly ash tends to retard the early rate of hardening of the concrete so that the concrete exhibits up to a 30% lower strength after seven days testing and up to a 25% lower strength after 28 days of testing, but in time the strength levels normalize at replacement levels up to 20%. Increasing the substitution quantity up to 30% gives more drastic reduction in the early compression values as well as an ultimate strength reduction of at least about 15% after one year. 
     The limited substitution of fly ash for Portland cement in concrete formulations has other effects beyond compressive strength changes, both positive and negative. The fly ash tends to increase the workability of the cement mix and is recognized as desirably reducing the reactivity of the Portland cement with so-called reactive aggregates. On the other hand, fly ash contains a minor content of uncombusted carbon that acts to absorb air entrained in the concrete. Because entrained air desirably increases the resistance of the hardened concrete to freezing, such reduction in entrained air is undesirable, but can be compensated for by the inclusion as an additive of so-called air-entraining agents. 
     Dodson, et al. in U.S. Pat. No. 4,210,457, while recognizing the accepted limit of 20% replacement with fly ash of the Portland cement in concrete mixes, proposes the substitution of larger amounts, preferably 50% or more, of the Portland cement with particular selected fly ashes having a combined content of silica, alumina and ferric oxide content, less than 80% by weight, and a calcium oxide content exceeding 10%, based on five samples of such ashes, varying from about 58-72% combined with a calcium oxide range of about 18-30%. Six other fly ash samples that are not suitable at the high replacement levels of 50% or more were shown to vary in the combined oxide content from about 87-92% and in calcium oxide content from about 4% to about 8%. Evaluating these values against the ASTM C618-00, one observes that the acceptable fly ashes come under the Class-C specifications, while the unacceptable ashes fell within the Class-F specification. Thus, Dodson, et al. in effect establish that Class-C fly ashes are suitable for substantially higher levels of replacement for Portland cement in concrete mixes than are Class-F fly ashes, and this capacity is now generally recognized, with Class-C fly ashes being generally permitted up to about a 50% replacement level while maintaining the desirable physical properties of the concrete, especially compressive strength. 
     In U.S. Pat. No. 4,240,952, Hulbert, et al. while also acknowledging the generally recognized permissible limit of Class-F fly ash replacement for Portland cement of 20%, propose replacement of at least 50% and up to 80%, provided the mix contains as special additives about 2% of gypsum and about 3% of calcium chloride by weight of the fly ash. The fly ash described for this purpose, however, was a Class-C fly ash analyzing about 28% calcium oxide and combined silica, alumina and ferric oxide content of about 63%. With up to 80% of this fly ash and the specified additives, compressive strengths comparable to straight Portland cement were said to be generally achievable. In one example using 140 pounds Portland cement and 560 pounds of fly ash (20:80 ratio) with conventional amounts of coarse and fine aggregate, and water and including the requisite additives, compressive strengths tested at 3180 psi for 7 days, 4200 psi for 14 days and about 5000 psi at 28 days. 
     In U.S. Pat. Nos. 4,018,617 and 4,101,332, Nicholson proposed the use of mixtures of fly ash (apparently Class-F in type), cement kiln dust and aggregate for creating a stabilized base supporting surface replacing conventional gravel or asphalt aggregate stabilized bases in road construction wherein the useful ranges were fly ash 6-24%, CKD (cement kiln dust) 4-16% and aggregate 60-90%, with 8% CKD, 12% fly ash and 80% aggregate preferred. Compressive strength values for such measures as revealed in the examples varied rather erratically and generally exhibited only small increases in compressive strength over the 7 to 28 day test period. Among the better results were for the preferred mixture wherein the values increased from about 1100 psi at 7 days to 1400 psi at 28 days. The addition of a small amount of calcium chloride improved those values by about 200 psi. On the other hand, the addition of 3% of lime stack dust recovered from a lime kiln significantly reduced the results to about 700 psi at 7 days to 900-1300 psi at 28 days. Elimination of the aggregate reduced the strength to a fraction of the values otherwise obtained, a mixture of 12% CKD and 88% fly ash alone showing strength values of only about 190-260 psi over the 28-day test period. Similarly, the choice of a finely divided aggregate such as fill sand resulted in about the same fractional level of strength values in the range of about 140-230 psi. A combination of finely divided and coarse aggregate in approximately equal amounts reduced the compressive strength values by about 50% with virtually no change over the test period, giving values ranging from 650-750 psi, except where 1% of Type 1 Portland cement was included which restored the strength values to about their original level, except at the initial 7 days period where the strength values were about 800-900 psi, increasing at 28 days to about 1200-1600 psi. Curiously, the best strength results were attained when 11.6% fly ash was combined with 3.4% lime with the balance crushed aggregate, the CKD being omitted entirely, for which the strength values while starting at a lower level of about 850-950 at 7 days increased to about 1700 psi at 28 days. 
     The combination of fly ash and lime stack dust incidentally mentioned in the later patent was explored further by Nicholson in U.S. Pat. No. 4,038,095 which concerns mixtures of about 10-14% fly ash, about 5-15% lime stack dust with the balance aggregate in the range of 71-85%. Somewhat inexplicably, the compressive results reported here for such mixtures do not reach the high level specified in the first two aforementioned Nicholson patents, the strength values specified being only about 1000 psi with the more general levels well below that depending on particular proportions. 
     In U.S. Pat. No. 4,268,316, Wills, Jr. discloses the use of mixtures of kiln dust and fly ash as a replacement for ground limestone and gypsum for forming a mortar or masonry cement, using proportions of about 25-55% Portland cement, about 25-65% CKD and 10-25% fly ash. When these mortar formulations were mixed with damp sand in the proportions of about one part cement mixture to 2.5-3 parts sand, compression strengths comparable to those of standard masonry cement composed of 55% cement clinkers, 40% limestone and 5% gypsum were shown for mixtures containing 50% cement, 24-40% CKD and 15-25% fly ash. Inexplicably, in one example, when the cement content was increased to 55% with 35% CKD and 10-% fly ash, the compressive strengths dropped by about 30-40% at both the 7 day and 28 day ages to levels inferior to the standard material. As the cement content was decreased, with corresponding increases in the CKD, the compressive strength values dropped drastically. On the other hand, in another similar example, mixtures containing 55% cement, 35% CKD and 10% fly ash proved superior in compressive strength, particularly at the 28 day age, to mixtures containing 50% cement, 35% fly ash and 15% CKD, as well as other standard masonry cements containing 50% cement, 47% limestone and 3% gypsum. Indeed, strength values dropped about 40% for the mixtures having a 5% reduction in cement and a corresponding 5% increase in the fly ash to values definitely inferior to the standard cements. Similar variations were shown under laboratory test conditions for comparable 50/35/15 mixtures dependent on the source of the fly ash while under actual construction conditions for the same mixtures, compressive strength values were reduced by about 50% for both the conventional masonry cement containing 55% Portland cement and comparable mixtures within the patented concept. The fly ash here was preferably Class-F with Class-C materials being less desirable. 
     In U.S. Pat. No. 4,407,677, Wills, Jr. went on to teach that in the manufacture of concrete products such as blocks or bricks, the fly ash usually employed in combination with Portland cement therein could be replaced in its entirety by CKD with modest improvement in early compressive strength values for such products. Thus, at one-day and two-day tests compressive strength values of about 500-800 psi were shown, but were said to increase to about 1200 psi after 28 days. The mixes disclosed in Wills, Jr. &#39;677 contained 0.4-0.9 parts cement, about 0.1-0.6 parts CKD and 10-12 parts aggregate combining both fine and coarse materials, such as expanded shale and natural sand in a weight ratio of 80/20. Masonry cements generally develop at least about 95% of their strength properties at 28 days age so that additional aging of the patented products would not be expected to result in any significant increase in their compressive strength values. 
     U.S. Pat. Nos. 5,520,730 and 5,266,111 of the present inventor, disclose a general-purpose concrete composition comprising Portland cement, Class-F fly ash, and CKD. The patents also disclose a “synthetic Class-C fly ash blend” comprising Class-F fly ash and CKD. These patents disclose the advantages of early strength of concrete; however, utilization of sodium thiocyanate and/or calcium nitrate as a cement additives are not disclosed. 
     U.S. Pat. No. 6,008,275 to Moreau et al. discloses a cement composition comprising greater than about 10% by weight of a pozzolanic cement replacement based on the weight of said hydraulic cement and cement replacement, and a polycarboxylate polymer. The composition can also contain an accelerator such as calcium nitrate and sodium thiocyanate. The pozzolanic replacement material can be fly ash, class C and/or class F; blast furnace slag; calcine clay; and natural pozzolan materials. The amounts of calcium nitrate and sodium thiocyanate used by Moreau et al. are impractical and do not meet ASTM specifications for pre-blend cement. Further, the compositions of Moreau et al. are not pre-blend cements and are wet concrete mixtures. 
     U.S. Pat. No. 4,606,770 to Gerber discloses a cement mix including hydraulic cement, aggregate, sufficient water to affect hydraulic setting of the cement, and an additive comprising an N-methylol amide, specifically, tri- or tetramethylolglycoluril alone or in combination with other accelerators, such as calcium nitrate and sodium thiocyanate. The additive is present in an amount sufficient to decrease the time necessary for the hardening of the concrete mix. The compositions of Gerber are not pre-blend cements and are wet concrete mixtures. 
     U.S. Pat. No. 5,531,825 to Gartner et al. discloses a cement set-accelerating admixture and compositions containing such admixtures. The admixture compositions comprise one or more nitroalcohols present in an amount effective to increase the set acceleration of a hydraulic cement composition. The invention further comprises one or more conventional accelerators, including calcium nitrate and sodium thiocyanate. Gartner et al. disclose only pastes, mortars and concrete compositions, but fail to mention a pre-blend composition. 
     None of the above patents disclose pre-blend cement compositions for fast settling times, meeting ASTM Designations C 595 specifications for pre-blend cements; therefore, there remains a need for pre-blend cement mixes with fast setting times, because the addition of fly ash or slag to concrete often results in slow setting. There are many advantages for fast setting times, such as allowing the concrete structure to be put into service sooner, thereby reducing labor cost, and allowing pre-cast concrete and concrete masonry manufacturers to achieve rapid form and mold turnover. 
     SUMMARY OF THE INVENTION 
     Applicant has discovered an optimal range of non-chloride accelerators, namely sodium thiocyanate and/or calcium nitrate, for use with pre-blend cement (also referred to as blended cement) compositions. The optimal range of sodium thiocyanate and/or calcium nitrate is less than about 5 percent by weight, preferably from about 0.2 percent to about 4 percent by weight, in a pre-blend composition. Above about 5 percent of sodium thiocyanate, the accelerator advantage is no longer effective; and above about 5 percent of calcium nitrate, the cement composition does not meet ASTM C595 specification. Further, because sodium thiocyanate and calcium nitrate are hygroscopic, using greater than about 5 percent in a pre-blend cement yields an undesirable mix because of water absorption problems. Therefore, it is critical that the concentration of sodium thiocyanate and/or calcium nitrate in the pre-blend composition is maintained at less than about 5 percent by weight. Within this range, however, the amount of non-chloride accelerators can be varied to achieve desired set times. For example, the pre-blend cement can be adjusted to accommodate seasonal uses. In the summer, the pre-blend should contain a lower amount of non-chloride accelerator(s) because the cement naturally sets faster in the summer heat. Alternatively, in the winter, the pre-blend should contain a higher amount of non-chloride accelerator(s) because the cold naturally retards the cement setting rate. 
     An objective of the present invention is to provide a pre-blend cement composition for improved early strength containing cement and sodium thiocyanate and/or calcium nitrate. In a preferred embodiment, cement is present in an amount greater than about 50% by weight; sodium thiocyanate and/or calcium nitrate are present in an amount of less than about 5 percent by weight (w/w). 
     A further objective of the present invention is to provide a pre-blend cement composition for improved early strength containing cement, Class-F fly ash, and sodium thiocyanate and/or calcium nitrate. In a preferred embodiment; cement is present in an amount greater than about 50% by weight; Class-F fly ash is present in an amount of about 20 percent to about 30 percent by weight; and sodium thiocyanate and/or calcium nitrate is present in an amount of less than about 5 percent by weight. 
     A further objective of the present invention is to provide a pre-blend cement composition for improved early strength containing cement, Class-C fly ash, and sodium thiocyanate and/or calcium nitrate. In a preferred embodiment; cement is present in an amount greater than about 50% by weight; Class-C fly ash is present in an amount of about 20 percent to about 30 percent by weight; and sodium thiocyanate and/or calcium nitrate is present in an amount of less than about 5 percent by weight. 
     A further objective of the present invention is to provide a pre-blend cement composition for improved early strength comprising cement, Class-C fly ash, Class-F fly ash, and sodium thiocyanate and/or calcium nitrate. In a preferred embodiment, cement is present in an amount greater than about 50% by weight; Class-C fly ash is present in an amount of about 10 percent to about 20 percent by weight; Class-F fly ash is present in an amount of about 10 percent to about 20 percent by weight; and the sodium thiocyanate and/or calcium nitrate is present in an amount of less than about 5 percent by weight. 
     A further objective of the present invention is to provide a pre-blend cement composition for improved early strength comprising cement, slag, and sodium thiocyanate and/or calcium nitrate. In a preferred embodiment, cement is present in an amount greater than about 50% by weight; slag is present in an amount of about 20 percent to about 30 percent by weight; and the sodium thiocyanate and/or calcium nitrate is present in an amount of less than about 5 percent by weight. 
     A further objective of the present invention is to provide a pre-blend cement composition for improved early strength comprising cement, Class-C fly ash, slag, and sodium thiocyanate and/or calcium nitrate. In a preferred embodiment, cement is present in an amount greater than about 50% by weight; Class-C fly ash is present in an amount of about 10 percent to about 30 percent by weight; slag is present in an amount of about 10 percent to about 20 percent by weight; and sodium thiocyanate and/or calcium nitrate is present in an amount of less than about 5 percent by weight. 
     A further objective of the present invention is to provide a pre-blend cement composition for improved early strength comprising cement, Class-F fly ash, slag, and sodium thiocyanate and/or calcium nitrate. In a preferred embodiment, cement is present in an amount greater than about 50% by weight; Class-F fly ash is present in an amount of about 10 percent to about 30 percent by weight; slag is present in an amount of about 10 percent to about 20 percent by weight; and sodium thiocyanate and/or calcium nitrate is present in an amount of less than about 5 percent by weight. 
     A further objective of the present invention is to provide a pre-blend cement composition for improved early strength comprising cement, Class-C fly ash, Class-F fly ash, slag, and sodium thiocyanate and/or calcium nitrate. In a preferred embodiment, cement is present in an amount greater than about 50% by weight; Class-C fly ash is present in an amount of about 10 percent to about 20 percent by weight; Class-F fly ash is present in an amount of about 10 percent to about 20 percent by weight; slag is present in an amount of about 10 percent to about 20 percent by weight; and sodium thiocyanate and/or calcium nitrate is present in an amount of less than about 5 percent by weight. 
     Silica fume can also be included in any of the pre-blend cements of the present invention. 
     Methods of making concrete from the above compositions are also disclosed. 
     Pre-blend as used herein refers to settable compositions mixed prior to the addition of water and/or aggregated materials, i.e., a dry mix. Pre-blend cements (also referred to as blended cements) are mixed without the addition of water, sand, and/or gravel, and are sold, in bags and/or in tanker loads, for concrete making. The standard for pre-blend cement is specified in ASTM Designation C 595. A major advantage of pre-blend include the ability for concrete producer to custom blend a cement for his own application, e.g., higher strength for multistory building; higher durability for bridges, highways, and parking structures; lower pozzolan content for economic effect, such as maximum pozzolan content for plants with single silos. The pre-blend cement of the present invention is particularly for making pre-blend cement and should not be confused with ready-mix processes for making concrete. The ready-mix processes involve adding water, sand, stone, admixtures, etc. to cement to form concrete, while the pre-blend cement is a dry powder. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Several different types of Portland cement are available and all are useful with the present invention. Type I is the general-purpose variety and is most commonly employed; Type II Portland cement is used where precaution against moderate sulfate attack is important; Type III is a high-early strength Portland cement; Type IV is a low heat of hydration cement for use where the rate and amount of heat generated must be minimized; Type V is a sulfate-resisting cement used only in concrete exposed to severe sulfate action. Although most types of cement are useful with the present invention, Type III is preferable for the early strength application. Commercial blended cements, such as Type I-P, wherein 20% Class-F fly ash is blended with 80% by weight Portland cement clinker during pulverization should be avoided, because Type I-P cements do not meet ASTM C595 specification. 
     Any standard or common Class-F fly ash obtained from boilers and like furnaces used for the combustion of pulverized coal, particularly of a bituminous or anthracite type, and especially from coal-fired, steam-generating plants of electrical utilities, is suitable for use as the Class-F fly ash component of this invention. Such fly ash should have a combined silica, alumina and ferric oxide content of at least about 70% and preferably 80% or higher by weight and a lime (CaO) content below about 10%, usually about 6% by weight or less. 
     Any standard or common Class-C fly ash obtained from the burning of lignite or subbituminous coal is suitable for use as the Class-C fly ash component of this invention. Such Class-C fly ash generally contains more calcium and less iron than Class-F fly ash and has a lime content in the range of 15% to 30%. 
     In certain embodiments, CF fly ash is used. This is a mixture of Class-C and Class-F fly ashes, which can be manufactured by adding Class-C fly ash and Class-F fly ash together or by the combustion of a mixture of western and eastern coal. An all-western coal produces Class-C fly ash; and an all-eastern coal produces Class-F fly ash. Because of emissions and environmental concerns, some power plants may burn a mixture of eastern and western coals. The percentages of eastern and western coals may vary according to the needs of the individual power plant, thus, resulting in different ratios of Class-C fly ash to Class-F fly ash. 
     Likewise, any blast furnace slag is appropriate for the present invention. Slag is a non-metallic co-product produced in the production of iron in a blast furnace. It consists primarily of silicates, aluminosilicates and calcium-alumina-silicates. The molten slag usually comprises about twenty percent by mass of iron production. Different forms of slag products are produced depending on the method used to cool the molten slag. These products include air-cooled blast furnace slag, expanded or foamed slag, pelletized slag, and granulated blast furnace slag. Granulated blast furnace slag satisfying ASTM 989 specification is preferred. 
     Any sodium thiocyanate is appropriate for the present invention. Sodium thiocyanate is a salt generally available as colorless or white crystals. Sodium thiocyanate is sold in several different grades and forms, depending on the intended end use. Main uses for sodium thiocyanate are in sectors of industrial chemicals, pharmaceuticals, pesticides, photography, etc. Although any sodium thiocyanate is appropriate for the present invention, cost is a major consideration because sodium thiocyanate is available in many grades. Therefore, the least expensive form of sodium thiocyanate that is effective for the present invention is most preferred. 
     Any calcium nitrate is appropriate for the present invention. Calcium nitrate is a salt generally available as colorless to white, usually hydrated, granules, crystals, or powder. Calcium nitrate is sold in several different grades and forms, depending on the intended end use. Main uses for calcium nitrate are in sectors of explosive, pesticides, industrial chemicals, etc. Although any calcium nitrate is appropriate for the present invention, cost is a major consideration because calcium nitrate is available in many grades. Therefore, the least expensive form of calcium nitrate that is effective for the present invention is most preferred. 
     As will be established hereinafter, within the above limits for the compositions of the invention, the concretes produced therefrom exhibit substantially comparable or superior properties for use in general purpose cement construction, especially early setting time. 
     Final concrete mixes using the pre-blend cement of the present invention may further contain aggregate materials. The choice of aggregate material for concrete mixes using the present blends will pose no problem to the person skilled in the design of such mixes. The coarse aggregate should have a minimum size of about ⅜ inch and can vary in size from that minimum up to one inch or larger, preferably in gradations between these limits. Crushed limestone, gravel and the like are desirable coarse aggregates, and the material selected in any case should exhibit a considerable hardness and durability inasmuch as crumbly, friable aggregates tend to significantly reduce the strength of the ultimate concrete. The finely divided aggregate is smaller than ⅜ inch in size and again is preferably graduated in much finer sizes down to 200-sieve size or so. Ground limestone, sand and the like are common useful fine aggregates. 
     In accordance with the present invention, silica fume can also be added to the cement mixture to achieve high strength and chloride protection for the concrete. Silica fume is preferably used from 5-15 percent by weight. 
     Other additives can also be used in making concrete using the pre-blend cement of the present invention, including, but is not limited to, water reducers, accelerators, air entrainment agents, as well as other additives that are commonly used in the concrete industry. 
     The pre-blend mixes of the invention are prepared by homogeneously and uniformly mixing all of the mix ingredients including cement, Class-F fly ash, Class-C fly ash, slag, and sodium thiocyanate and/or calcium nitrate prior to addition of water and/or aggregate material, such as sand and/or gravel. Mixing can be accomplished with mixing techniques commonly employed in the concrete mix industry. The ultimate compositions are no more susceptible to undergoing separation during handling and storage than are ordinary concrete mixes. They can be transported and stored in the same manner as the ordinary mixes, as can the individual ingredients. The storage containers should, of course, be closed to protect the contents thereof from weather. 
     The following examples are given to illustrate the present invention. It should be understood that the invention is not limited to the specific conditions or details described in these examples. 
     The results in the following examples were actually obtained by pre-blending, in each case, Class-F fly ash, Class-C fly ash, slag, and/or silica fume with sodium thiocyanate and/or calcium nitrate together to form a pre-blend composition and then combining the blend with the other mix ingredients. The pre-blend components are added prior to the addition of water. However, the results would be expected to be identical if the same proportionate amount for each of the component was added separately to the remaining dry mix ingredients. The proportionate amounts of the Class-F fly ash, Class-C fly ash, slag, silica fume, sodium thiocyanate and calcium nitrate have been expressed in each case in terms of their relative weight percentages of the pre-blend composition. 
     EXAMPLE 1 
     
       
         
               
               
             
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Composition in weight percent 
                   
               
             
          
           
               
                   
                 Silica 
                   
                 Set time 
               
             
          
           
               
                 Cement 
                 Class-F 
                 Class-C 
                 Slag 
                 Fume 
                 M* 
                 NaSCN 
                 Ca(NO 3 ) 2   
                 Initial 
                 Final 
               
               
                   
               
             
          
           
               
                 60 
                 10 
                 10 
                 15 
                 5 
                 0 
                 0 
                 0 
                 135 
                 495 
               
               
                 60 
                 10 
                 10 
                 15 
                 5 
                 0 
                 0 
                 0.6 
                 145 
                 410 
               
               
                 50 
                 10 
                 15 
                 20 
                 0 
                 5 
                 0 
                 0 
                 210 
                 395 
               
               
                 50 
                 10 
                 15 
                 20 
                 0 
                 5 
                 0 
                 1 
                 120 
                 285 
               
               
                 60 
                 10 
                 10 
                 0 
                 0 
                 20 
                 0 
                 0 
                 60 
                 230 
               
               
                 60 
                 10 
                 10 
                 0 
                 0 
                 20 
                 0 
                 0.6 
                 60 
                 200 
               
               
                 50 
                 0 
                 30 
                 0 
                 0 
                 20 
                 0 
                 0 
                 35 
                 240 
               
               
                 50 
                 0 
                 30 
                 0 
                 0 
                 20 
                 0 
                 1.2 
                 25 
                 220 
               
               
                 50 
                 0 
                 0 
                 40 
                 0 
                 10 
                 0 
                 0 
                 100 
                 280 
               
               
                 50 
                 0 
                 0 
                 40 
                 0 
                 10 
                 0 
                 0.2 
                 115 
                 265 
               
               
                 90 
                 10 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0.2 
                 210 
                 305 
               
               
                 69 
                 0 
                 29 
                 0 
                 0 
                 0 
                 0 
                 2 
                 130 
                 200 
               
               
                 70 
                 0 
                 0 
                 30 
                 0 
                 0 
                 0 
                 0.2 
                 210 
                 350 
               
               
                 40 
                 0 
                 0 
                 60 
                 0 
                 0 
                 0 
                 0.2 
                 190 
                 355 
               
               
                 65 
                 0 
                 0 
                 30 
                 5 
                 0 
                 0 
                 0.2 
                 175 
                 255 
               
               
                 60 
                 10 
                 0 
                 30 
                 0 
                 0 
                 0 
                 0.2 
                 205 
                 300 
               
               
                 50 
                 0 
                 20 
                 30 
                 0 
                 0 
                 0 
                 0.4 
                 210 
                 375 
               
               
                 90 
                 0 
                 0 
                 0 
                 0 
                 10 
                 0 
                 0.2 
                 150 
                 250 
               
               
                 60 
                 0 
                 0 
                 30 
                 0 
                 10 
                 0 
                 0.2 
                 140 
                 265 
               
             
          
           
               
                 ASTM 595 Specification 
                 45 min. 
                 420 max. 
               
               
                   
               
               
                 *Calcined Metakaolin 
               
             
          
         
       
     
     Compositions from Table 1 shows that calcium nitrate, in amounts up to 1.2 percent (w/w) reduces setting times for cement compositions to comply with ASTM Designation C595. Applicant has also found that the optimal amounts for calcium nitrate are between about 0.1-5 percent (w/w). Above this amount, the setting times are too fast to meet the ASTM specification. It must be noted that, throughout the examples, because the numbers are approximate, the components of some compositions do not add up to exactly 100%; however, they are all within the error range of 100±1%. 
     EXAMPLE 2 
     
       
         
               
               
             
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Composition in weight percent 
                   
               
             
          
           
               
                   
                 Silica 
                   
                 Set time 
               
             
          
           
               
                 Cement 
                 Class-F 
                 Class-C 
                 Slag 
                 Fume 
                 M* 
                 NaSCN 
                 Ca(NO 3 ) 2   
                 Initial 
                 Final 
               
               
                   
               
             
          
           
               
                 60 
                 5 
                 5 
                 20 
                 5 
                 5 
                 0 
                 0 
                 140 
                 435 
               
               
                 60 
                 5 
                 5 
                 20 
                 5 
                 5 
                 0 
                 0.2 
                 420 
                 345 
               
               
                 60 
                 5 
                 5 
                 20 
                 5 
                 5 
                 0.2 
                 0 
                 155 
                 340 
               
               
                 50 
                 10 
                 15 
                 20 
                 0 
                 5 
                 0 
                 0 
                 210 
                 395 
               
               
                 50 
                 10 
                 15 
                 20 
                 0 
                 5 
                 0 
                 1 
                 120 
                 285 
               
               
                 50 
                 10 
                 15 
                 20 
                 0 
                 5 
                 1 
                 0 
                 140 
                 400 
               
               
                 50 
                 10 
                 15 
                 20 
                 0 
                 5 
                 0.5 
                 0.5 
                 170 
                 395 
               
               
                 70 
                 20 
                 0 
                 0 
                 0 
                 10 
                 0 
                 0 
                 120 
                 300 
               
               
                 70 
                 20 
                 0 
                 0 
                 0 
                 10 
                 0 
                 0.2 
                 130 
                 275 
               
               
                 70 
                 20 
                 0 
                 0 
                 0 
                 10 
                 0.2 
                 0 
                 95 
                 310 
               
               
                 70 
                 20 
                 0 
                 0 
                 0 
                 10 
                 0.1 
                 0.1 
                 120 
                 300 
               
               
                 50 
                 0 
                 0 
                 40 
                 0 
                 10 
                 0 
                 0 
                 100 
                 280 
               
               
                 50 
                 0 
                 0 
                 40 
                 0 
                 10 
                 0 
                 0.2 
                 115 
                 265 
               
               
                 50 
                 0 
                 0 
                 40 
                 0 
                 10 
                 0.2 
                 0 
                 95 
                 270 
               
               
                 50 
                 0 
                 0 
                 40 
                 0 
                 10 
                 0.1 
                 0.1 
                 105 
                 250 
               
               
                 45 
                 0 
                 0 
                 36 
                 0 
                 9 
                 0 
                 10 
                 3 
                 10 
               
               
                 45 
                 0 
                 0 
                 36 
                 0 
                 9 
                 5 
                 5 
                 3 
                 80 
               
             
          
           
               
                 ASTM C595 Specification 
                 45 min. 
                 420 max. 
               
               
                   
               
               
                 *Calcined Metakaolin 
               
             
          
         
       
     
     The trend from Table 2 shows that the higher the calcium nitrate and/or sodium thiocyanate the faster the set time. However, up to a maximum amount of calcium nitrate, the mix hardens too quickly to meet ASTM C 595 specification. Interpolation of the data shows that the amount of non-chloride accelerators (calcium nitrate and sodium thiocyanate) used should not exceed about 5 percent. 
     EXAMPLE 3 
     
       
         
               
               
             
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Composition in weight percent 
                   
               
             
          
           
               
                   
                 Silica 
                   
                 Set time 
               
             
          
           
               
                 Cement 
                 Class-F 
                 Class-C 
                 Slag 
                 Fume 
                 M* 
                 NaSCN 
                 Ca(NO 3 ) 2   
                 Initial 
                 Final 
               
               
                   
               
             
          
           
               
                 Control 
                   
                   
                   
                   
                   
                   
                   
                 220 
                 315 
               
               
                 63 
                 0 
                 0 
                 27 
                 0 
                 0 
                 0 
                 10 
                 6 
                 12 
               
               
                 63 
                 0 
                 0 
                 27 
                 0 
                 0 
                 5 
                 5 
                 10 
                 45 
               
               
                 45 
                 0 
                 0 
                 45 
                 0 
                 0 
                 0 
                 10 
                 7 
                 15 
               
               
                 45 
                 0 
                 0 
                 45 
                 0 
                 0 
                 5 
                 5 
                 11 
                 50 
               
             
          
           
               
                 ASTM C595 Specification 
                 45 min. 
                 420 max. 
               
               
                   
               
               
                 *Calcined Metakaolin 
               
             
          
         
       
     
     Table 2 shows accelerator concentration (sodium thiocyanate and/or calcium nitrate) of 10 percent (w/w) allows the mixes to set up too fast and does not meet the ASTM C595 specification. 
     EXAMPLE 4 
     
       
         
               
               
             
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 Composition in weight percent 
                   
               
             
          
           
               
                   
                 Silica 
                   
                 Set time 
               
             
          
           
               
                 Cement 
                 Class-F 
                 Class-C 
                 Slag 
                 Fume 
                 M* 
                 NaSCN 
                 Ca(NO 3 ) 2   
                 Initial 
                 Final 
               
               
                   
               
             
          
           
               
                 57 
                 9 
                 0 
                 29 
                 0 
                 0 
                 5 
                 0 
                 310 
                 &gt;420 
               
               
                 50 
                 0 
                 20 
                 30 
                 0 
                 0 
                 1 
                 0 
                 160 
                 315 
               
               
                 48 
                 0 
                 19 
                 29 
                 0 
                 0 
                 5 
                 0 
                 195 
                 &gt;420 
               
               
                 85 
                 15 
                 0 
                 0 
                 0 
                 0 
                 0.2 
                 0 
                 190 
                 285 
               
               
                 81 
                 14 
                 0 
                 0 
                 0 
                 0 
                 5 
                 0 
                 340 
                 &gt;420 
               
               
                 69 
                 0 
                 29 
                 0 
                 0 
                 0 
                 2 
                 0 
                 200 
                 405 
               
               
                 67 
                 0 
                 29 
                 0 
                 0 
                 0 
                 5 
                 0 
                 120 
                 &gt;420 
               
               
                 70 
                 15 
                 15 
                 0 
                 0 
                 0 
                 1 
                 0 
                 240 
                 335 
               
               
                 67 
                 14 
                 14 
                 0 
                 0 
                 0 
                 5 
                 0 
                 400 
                 &gt;420 
               
               
                 50 
                 0 
                 0 
                 50 
                 0 
                 0 
                 0.2 
                 0 
                 160 
                 245 
               
               
                 48 
                 0 
                 0 
                 48 
                 0 
                 0 
                 5 
                 0 
                 275 
                 &gt;420 
               
               
                 60 
                 10 
                 0 
                 30 
                 0 
                 0 
                 0.2 
                 0 
                 150 
                 250 
               
               
                 57 
                 9 
                 0 
                 29 
                 0 
                 0 
                 5 
                 0 
                 310 
                 &gt;420 
               
               
                 50 
                 0 
                 20 
                 30 
                 0 
                 0 
                 1 
                 0 
                 160 
                 315 
               
               
                 48 
                 0 
                 19 
                 29 
                 0 
                 0 
                 5 
                 0 
                 195 
                 &gt;420 
               
             
          
           
               
                 ASTM C595 Specification 
                 45 min. 
                 420 max. 
               
               
                   
               
               
                 *Calcined Metakaolin 
               
             
          
         
       
     
     Table 4 shows that the accelerating effect of sodium thiocyanate only occurs at concentrations less than 5 percent (w/w). At about 5 percent (w/w) sodium thiocyanate actually retards the setting time of the mixes. From Table 4, the retarding effect is sufficient to produce a mix that does not comply with ASTM Designation C595. This discovery is unexpected and not previously known in the art. 
     The above examples clearly show faster setting times of cement mixes by the addition of less than about 5 percent sodium thiocyanate and/or calcium nitrate. Importantly, the setting times also meets ASTM specifications. The improvement is effective not only for cement, but also for mixes comprising industrial by-products such as Class-F fly ash, Class-C fly ash, blast furnace slag, silica fume and combinations thereof. The invention, however, is not limited to the conditions illustrated in the examples. 
     Although certain presently preferred embodiments of the invention have been specifically described herein, it will be apparent to those skilled in the art to which the invention pertains that variations and modifications of the various embodiments shown and described herein may be made without departing from the spirit and scope of the invention. Accordingly, it is intended that the invention be limited only to the extent required by the appended claims and the applicable rules of law.