Abstract:
A method and composition for cementing a well by combining water, blast furnace slag and sodium tripolyphosphate to form a cement slurry, displacing the cement slurry into a well and allowing the cement slurry to set.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention pertains to the optimization of methods and formulations for zonal isolation for vertical, deviated, and horizontal oil and gas wells using blast furnace slag cement. 
     2. Description of Prior Art 
     The general procedure of drilling an oil or gas well includes drilling a borehole using a drilling fluid. Subsequent to drilling the borehole, casing is run into the well and a cement slurry is placed in the annulus between the outside of the casing and the borehole wall. Typically, the cement slurry is placed in the annulus using a successive fluid displacement technique. In this technique, the cement is first pumped into the casing. Another fluid, often drilling fluid or water, is pumped behind the cement to space it out the bottom of the casing and up into the annulus between the casing and the borehole wall. The cement slurry is usually raised to a point above the uppermost section of the formations to be isolated and may be raised into the annulus between the casing string being cemented and a previously cemented casing. 
     Once placed, the purpose of the cement slurry is to harden in the annulus and provide an effective seal between the casing and the borehole. The hardened cement sheath prevents or inhibits communication of fluids between the various formations penetrated by the wellbore. Conditions providing zonal isolation of the cement is in contact with the casing and provides mechanical support and resistance to axial movement through the shear bond developed between the interfaces of cement and pipe and cement and formation. 
     Applicant&#39;s U.S. Pat. No. 5,058,679 dealt with an improvement in the bonding of the cement to the casing and borehole surfaces. This improvement was realized through the use of a cement comprising drilling fluid and blast furnace slag. This has proven to be an effective cementing technique and is rapidly gaining commercial acceptance. However, the formulation and design methodology for blast furnace slag cement and drilling fluid-blast furnace slag cements are presently not well defined. Requirements for slurry and hardened material properties are generally the same as Portland cement for a specific set of well conditions. The most effective way to formulate blast furnace slag cements or drilling fluid-blast furnace slag slurries and to obtain the desired properties is not completely understood by the art. Accordingly, the present invention is directed toward overcoming these and other problems in the art. 
     SUMMARY OF THE INVENTION 
     It is a primary purpose of the present invention to provide compositions and methods for optimizing the use of blast furnace slag cement and drilling fluid-blast furnace slag cements for cementing oil and gas wells. 
     A preferred embodiment of the invention comprises a composition and method for cementing a well by combining constituents comprising water and blast furnace slag having a particle size within the range of 2,000 cm 2  /g to 15,000 cm 2  /g, and an activator comprising sodium tripolyphosphate to form a cement slurry; displacing the cement slurry into the well; and allowing the cement slurry to set. 
     Other purposes, distinctions over the art, advantages and features of the invention will be apparent to one skilled in the art upon review of the following. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 shows the total impact of activator on set time of slag formulations, rate of early compressive strength development immediately after set time, and final or total compressive strength of the formulations. 
     FIG. 2 shows sodium carbonate as the preferred carbonate when the basic formulation is blast furnace slag plus 50% distilled water by weight of slag. 
     FIGS. 3-5 show the effects of the ratios of different components in the total activator on compressive strength, early compressive strength development rate and set time. 
     FIG. 6 shows data suggesting that sodium hydroxide has greater impact on set time of the formulation while sodium carbonate has greater impact on the compressive strength of the formulation. 
     FIG. 7 shows ratios of components controlling set time, compressive strength and early compressive strength development rate. 
     FIG. 8 shows similarity of benefits from sodium oxalate and sodium citrate. 
     FIGS. 9-10 are comparisons of the combination of citrate with phosphate and citrate, phosphate and sodium hydroxide. 
     FIGS. 11-12 show the effect of component ratios when other activators were used. 
    
    
     DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
     The following preferred embodiments of the invention, together with the following Examples, explain the principles of the invention. 
     The present invention provides unique methods and formulations which are devised to provide optimum zonal isolation for vertical, deviated, and horizontal wells. The invention centers around the optimized solidification of oil or water-based muds in combination with blast furnace slag to compressive strengths well in excess of that required for casing support, zonal isolation, and borehole stability. 
     Water-based drilling fluids typically include water and several other additives such as viscosifiers, thinners, dissolved salts, solids from the drilled formations, solid weighting agents to increase the fluid density, formation stabilizers to inhibit deleterious interaction between the drilling fluid and geologic formations, and additives to improve the lubricity of the drilling fluid. The term &#34;water-based&#34; means that water is the continuous phase of the drilling fluid. The water for water-based drilling fluids can be fresh water, brackish water, brine, seawater or other water containing fluids. 
     Oil-based drilling fluids typically include oil, water, organophilic clay, primary and secondary emulsifiers and wetting agents. Oil may be diesel, mineral oil, vegetable oil, fish oil, synthetic oils (polyalphaolefins), and esters thereof. 
     Many different additives and dispersants have been utilized that provide the desired properties in drilling fluids. Exemplary of those additives are barium sulfate (barite), bentonite, low and medium yield clays, salt water clay, iron oxide, calcium carbonate, starch, carboxymethylcellulose, acrylonitrile, natural gum, molecularly dehydrated phosphate, tannin compounds, quebracho, mined lignins, lignosulfonate, mica, sugar cane fibers, and granular materials. Bentonite is an especially common additive which gives the drilling fluid a thixotropic or a gel structure. Bentonite is also a common additive which is added to the drilling fluids to control fluid loss; phosphate and lignosulfonate additives which deflocculate colloidal solids and thin the drilling fluids are also common. 
     Solidification of drilling fluid is accomplished by the addition of blast furnace slag along with additives for the control of setting time and rheological properties of the slag-treated fluid. The term &#34;blast furnace slag&#34; refers to the refuse from the melting of metals or reduction of ores in a furnace. Most notably, blast furnace slag is a by-product of the manufacture of steel in a blast furnace. In steel making, the blast furnace slag is discharged from the service as a molten stream at a temperature typically between 1400° C. and 1600° C. Rapid quenching of the slag results in its conversion into a material which has hydraulic properties. The rapid quenching of the slag converts it into a glassy state and it is generally recognized that the hydraulic quality of the slag depends upon the effectiveness of the process used to rapidly cool the slag and freeze it into the granulated, glassy state. The preferred blast furnace slag of the invention is a high glass content slag produced by quickly quenching the molten slag through intimate contact with large volumes of cool water. Slags produced by air quenching may be used in the invention provided they are determined to have cementitious properties. However, these are less desirable. The finest of the slag particles should be between about  2,000 cm 2  /g and 15,000 cm 2  /g, more preferably between 3,000 cm 2  /g and 9,000 cm 2  /g, most preferably between 4,000 cm 2  /g and 6,500 cm 2  /g. A commercially available blast furnace slag which fulfills the requirements of the invention is marketed under the trade name &#34;NEWCEM&#34; by the Blue Circle Atlantic Company. This slag is obtained from the Bethlehem Steel Corporation blast furnace at Sparrow&#39;s Point, Md. 
     Rheological properties of the slag treated drilling fluid can be modified through the use of many conventional chemical dispersants for water-based or oil-based drilling fluids. Examples of such compounds include lignosulfonates, naphthalene sulfonates, phenol sulfonates, phosphates, phosphonates, sulfonated styrene maleic anhydride, sulfonated toluene maleic anhydride, sulfonated styrene maleimide, polyacrylates, polymethacrylates, blends of polyacrylates and polymethacrylates, acrylamide-acrylic acid copolymers, or blends of any of these classes of materials provided they are chemically compatible to allow their mixing while retaining the ability to disperse particles in the drilling fluid. 
     SELECTING GENERAL TYPES OF ACTIVATORS 
     Blast furnace slag is a latent hydraulic material. It must be activated to set in order to form a useful cement. Activation can be either thermal energy (heat) or chemical energy (chemical activation). If there is sufficient thermal energy (high temperature) no chemical activators may be required. However, at low temperatures, chemical activators are almost certainly required to optimize set time and compressive strength. In most cases, it is common and often desirable to use a combination of thermal and chemical activation to optimize the properties of the slag-containing cementitious mixture. 
     Alkali or bases, compounds which increase the pH of the liquid portion of a blast furnace slag/drilling fluid mixture or blast furnace slag cement slurry, are used as chemical activators. However, since thermal energy contributes to the total activation energy, the type of chemical activators and their amount can vary. Strong alkali are required at low temperatures where weak alkali can be used when the temperature is higher. 
     Components of the activator can be a mixture of alkali or alkali in combination of chelating, complexing or sequestering agents. It is desirable in cases where temperatures are low to use strong alkali-containing hydroxyl groups such as alkali earth metal hydroxides. These oxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, as examples. The more soluble alkali earth metal hydroxides are, in general, better activators at low temperature. It is believed that their higher solubility in water at low temperatures is the primary reason they are better low temperature activators. The most commonly applied alkali earth metal hydroxides at low temperature are sodium hydroxide, potassium hydroxide, lithium hydroxide and barium hydroxide. These alkali earth metal hydroxides have a greater effect on the set time of the slag-containing cementitious mixture. Concentrations range between 0.01 to 20% wt of slag, more preferably 0.1 to 16% wt of slag, even more preferably between 0.25 to 14% wt of slag, and most preferably 0.5 to 10% wt of slag. 
     It is also common to use a weaker alkali as part of the activator component, in particular, weaker alkali containing a carbonate or phosphate group. The carbonate ion in particular has a beneficial effect on the compressive strength development and overall compressive strength of the slag-containing mixture. Few anion species can replace carbonate as a part of the activator which significantly affects compressive strength. Alkali earth metal carbonates which are most commonly applied as a component in the total activator include lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, sodium potassium carbonate, etc., as examples. Again, as with the alkali-containing hydroxyl groups, greater solubility provides greater effects. The most commonly applied carbonate-containing compounds used include sodium carbonate, potassium carbonate and sodium potassium carbonate. Typical concentrations are 0.25 to 25% wt of slag, more preferably 0.5 to 20% wt of slag, even more preferably 1.0 to 15% wt of slag, and most preferably 2 to 12% wt of slag. 
     The phosphate anion is an anionic chemical species which can contribute to compressive strength like the carbonate ion. However, the phosphate ion-containing compounds tend to retard the slag hydration much more than the carbonate. Basic phosphates such as sodium tripolyphosphate, sodium hexametaphosphate, tetrasodium polyphosphate, etc., have application in formulations to control set time and contribute to compressive strength development. Of these, sodium tripolyphosphate has shown the greatest potential. Typical concentrations are 0.001 to 15% wt of slag, more preferably 0.01 to 10% wt of slag, even more preferably 0.1 to 8% wt of slag, and most preferably 0.25 to 6% wt of slag. 
     The citrate ion also can contribute to compressive strength. Alkali earth metal salts of citric acid such as sodium citrate, calcium citrate, potassium citrate, etc., are examples. Of these, sodium or potassium citrate are most preferred. 
     Compounds containing phosphate and citrate have an advantage over carbonate or hydroxyl-containing compounds in rheological properties of the slurry. Phosphate or citrate-containing compounds are effective dispersants for slag and clays in drilling fluid formulations. Thus, less dilution may be required for drilling fluid-blast furnace slurries or better rheological properties may be obtained. 
     Other components of the activator include a chelating, complexing or sequestering agent. These types of compounds include the phosphate and citrate ion-containing compound previously described. Other compounds such as ethylenediamine tetraacetic acid and its salts, phosphonic acids and their salts, glutamic acid and its salts, gluconic acid and its salts, some amines, phosphinic acids and their salts, aminophosphinic acids and their salts, lactic acid and its salts, aspartic acid and its salts, tartaric acid and its salts, etc. It is most desirable to use salts since the acid forms counteract the alkali added for chemical activation. Highly soluble salts are preferred. Sodium and potassium salts are usually quite soluble. Many other types of chelating, complexing or sequestering agents are known and many are listed in the book Organic Sequestering Agents by Stanley Chaberek and Arthur E. Martell, published by John Wiley &amp; Sons, New York. Concentrations typically range between 0.001 to 10% wt of slag, more preferably 0.01 to 8% wt of slag and most preferably 0.05 to 5% wt of slag. 
     Chemical compounds which are chelating, complexing, or sequestering agents for alkali earth metals and transition metals through iron in the Periodic Table of Elements have been found most suitable as components in the chemical activator mixture. Concentrations typically range between 0.001 to 10% wt of slag, more preferably 0.01 to 8% wt of slag and most preferably 0.05 to 5% wt of slag. Chelating, complexing or sequestering compounds with log (base 10) values for the equilibrium stability constants for complexed calcium between 2 and 5 have been most effective in improving strength and dispersing the slag with lowest effect on set time. A broad range for these log values is 0.5 to 11. The lower values tend to be stronger retarders while the higher values (above about 6) have less retarding effect but do not show an improvement in compressive strength development. In general, small amounts of these materials are used. Concentrations typically range from 0.001 to 8% wt of slag, preferably 0.01 to 6% wt of slag, and most preferably 0.05 to 5% wt of slag. 
     SELECTING TOTAL ACTIVATOR CONCENTRATION 
     There is an optimum amount of activator which provides the maximum compressive strength for a given concentration of slag. The optimum total activator concentration is based upon the weight of slag used in the formulation. Therefore, the optimum weight ratio of total activator to slag is selected. This weight ratio varies with temperature because thermal energy (heat or temperature which is a measure of heat) is an activator for slag. The optimum weight ratio of total activator to slag decreases with temperature. For example, the optimum ratio is about 6 percent or 0.06 percent (activator weight/slag weight) at 125° F. The optimum may be about 8 percent (0.08) at 100° F., 12 percent (0.12) at 80° F., 2.5 percent (0.025) at 175° F. These optimum ratios also may vary with the compounds used as the activators. The ratios cited above are exemplary of mixtures of sodium hydroxide and sodium carbonate. Ranges for total activator concentrations are: 0.01 to 20% wt of slag, preferably 0.1 to 18% wt of slag, even more preferably 0.25 to 14% wt of slag, and most preferably 0.5 to 10% wt of slag. 
     SELECTING THE RATIO OF COMPONENTS IN THE TOTAL ACTIVATOR 
     Within the total activator concentration, there is a ratio of the individual components which provide optimum set time or optimum compressive strength or optimum early compressive strength development rate or optimum rheological properties for the cementing operation. There is also a combination of activators which will produce optimum properties for all these variables for a specific cementing operation. 
     The total activator concentration may be made up of different concentrations of different chemical components. 
     SELECTING THE RETARDER 
     Once the total amount of activator and ratio of activator components has been selected which will optimize compressive strength and compressive strength development, a retarder is usually required to provide adequate fluidity time (sufficiently long set time) in order to place the cement in the well. Retarders are often added in a concentration of 0.001% to 12% by weight of slag, preferably 0.01 to 8%, and more preferably 0.05% to 5% wt of slag. 
     Retarders are of two types: complexing agents and salts of transition metals with atomic numbers above iron or nickel in the periodic chart. In particular, copper, zinc and aluminum salts can be effective retarders for slag hydration. 
     Complexing agents such as lignosulfonates and sulfonated lignins, and sulfonated Kraft lignins, lignin amines, etc., can be effective retarders. These are common retarders for Portland cements. 
     The most desirable retarders are low molecular weight complexing agents because they also contribute to improved compressive strength and early compressive strength development rate. Sodium glucoheptonate, sodium gluconate, sodium citrate, etc. can improve strength in combination with the activators in the formulation. 
     There is a ratio of activator to retarder which provides the greatest early compressive strength development and final strength for a given slag concentration. This ratio depends upon the strength of the retarders and activators used. In general, a combination of activators and retarders which will produce a set time less than about 10 hours, more preferably less than about 8 hours, and most preferably between 3 and 6 hours at the static temperature of the well will provide a high rate of early compressive strength development after setting and high final strength for the selected slag concentration. 
     DISPERSION 
     Given two formulations with optimized ratios of slag and activators, activator components and activator-retarder ratio, the formulation which is more dispersed will generally have better compressive strength development after setting. Many of the complexing, sequestering or chelating agents mentioned earlier in this text are good dispersants for slag and drilling fluids containing clays. 
     CONTROL OF SULFIDE ODORS 
     Blast furnace slags contain some sulfur as residue from the iron or steel making process. This sulfur may be in forms which can produce sulfide species. Hydrogen sulfide may form although this is not expected at the alkaline pH of most activated slag cements. 
     However, sulfide scavenging compounds may be included as part of the activator or retarder on the slag-containing cementitious material. Additives such as zinc oxide, zinc carbonate are known scavengers for sulfide. Inclusion of one or more of these scavengers may prevent formation of hydrogen sulfide if a set slag-containing cement is drilled out or otherwise comes into contact with a low pH fluid which would favor formation of hydrogen sulfide. 
     EXAMPLES 
     The data presented in FIG. 1 is based on the following: Test Temperature: 125° F. (52° C.); Base Formulation: &#34;NEWCEM&#34; blast furnace slag+50% distilled water (by wt of slag)-(a) total activator concentration is percent by weight of slag; (b) the weight ratio of sodium hydroxide to sodium carbonate is 1:3 for all total activator concentrations; hence, 1% total activator=0.25% sodium hydroxide+0.75% sodium carbonate (by wt of slag); 2% total activator=0.5% sodium hydroxide+1.5% sodium carbonate (by wt of slag); 4% total activator=1% sodium hydroxide+3% sodium carbonate (by wt of slag). 
     FIG. 1 shows the impact of total activator on the: 
     a) set time of slag formulations, 
     b) rate of early compressive strength development immediately after set time, and 
     c) final or total compressive strength of the formulations. 
     A decrease in set time is seen along the X-axis as the lines showing compressive strength begin to move upward off of the O compressive strength line which is represented as the horizontal line of the X-axis. No activator produced a set time of about 2.5 hours. Increasing the activator concentration to 4% or 6% by weight of slag reduced the set time to less than 1 hour. 
     The rate of early compressive strength development is directly impacted by the activator concentration. The slope of the line from the set time until the strength reaches a plateau, wherein the rate of strength change with time has decreased to a near steady-state rate, is affected by the activator concentration. The slope is gradual without activator and becomes near vertical at 4% to 6% total activator at this temperature. It is desirable to have rapid early compressive strength development in many cementing operations. Slopes as compared in Table 1 labeled Example A-2. 
     The final compressive strength of each formulation increases with the total activator concentration. It is important to remember that the only thing changed is the total activator concentration. The amount of slag in each formulation is constant. 
     Also, there is an upper limit to the total activator concentration. This limit is the dilution effect limit and solubility limit of the activators. 
     Base Formulation: &#34;NEWCEM&#34; Blast Furnace Slag+50% Distilled Water (by weight of slag) Test temperature: 125° F. (52° C.) 
     a) Total Activator concentration is percent by weight of Slag. 
     b) The weight ratio of sodium hydroxide to sodium carbonate is 1:3 for all total activator concentrations, hence: 
     1% total activator=0.25% sodium hydroxide+0.75% sodium carbonate (by weight of slag) 
     2% total activator=0.5% sodium hydroxide+1.5% sodium carbonate (by weight of slag) 
     4% total activator=1% sodium hydroxide+3% sodium carbonate (by weight of slag). 
     
                                           TABLE 1__________________________________________________________________________Set Time and Compressive Strength Data                  Equation for                             Compressive   Total        Text      Line Between                             Strength                                    FinalAdditives and   Activator        Duration             Set Time                  50 psi and 500 psi                             14 hrs after                                    StrengthConcentration   % bwos        Hours             Hours                  Slope                       Intercept                             Set Time                                    psi__________________________________________________________________________None    0    18   2.72  78.44                       -128.72                              723    740None    1    18   1.68 507.51                       -844.57                             1039   1068None    2    18   1.4  741.96                       -1046.07                             1611   1677None    4    18   0.6  1024.55                       -647.00                             2836   2966None    6    18   0.5  794.33                       -417.14                             3824   3924__________________________________________________________________________ Base Formulation: &#34;NEWCEM&#34; Blast Furnace Slag + 50% Distilled Water (by w of slag) Test Temperature: 125° F. (52° C.) 
    
     FIG. 2 shows sodium carbonate as the preferred carbonate. The basic formulation is: &#34;NEWCEM&#34; blast furnace slag+50% distilled water (by weight of slag)+4% total activator (by weight of slag). Test temperature: 125° F. (52° C). 
     FIGS. 3-6 and Tables 2 and 3 show the effects of the ratios of different components in the total activator on: 
     1) 24 hour compressive strength (FIG. 3) 
     2) early compressive strength development rate (FIG. 4) 
     3) set time (FIG. 5) 
     Each formulation contained 4% total activator. This total activator could be composed entirely of sodium hydroxide or entirely sodium carbonate or any weight ratio in between of these two components. The X-axis of these plots shows the amount of sodium carbonate present in the total activator. Hence, at 0 on the X-axis there is no sodium carbonate in the total activator; the total activator is 4% sodium hydroxide. At 4 on the X-axis only sodium carbonate is used as the total component of the activator; no sodium hydroxide is present in the total activator. At 2 on the X-axis, the total activator concentration of 4% (by weight of slag) is made up of 2% sodium hydroxide and 2% sodium carbonate. 
     The data in FIG. 3 is based on the following: Base Formulation: &#34;NEWCEM&#34; blast furnace slag+50% distilled water (by wt of slag)+4% total activator (by wt of slag). 
     This data (FIG. 3) shows that higher compressive strengths are obtained (slag concentration is constant for all tests) when the sodium carbonate concentration is slightly in excess of the sodium hydroxide concentration in the total amount of activator. 
     A small amount of sodium carbonate (FIG. 4) in the total activator concentration is beneficial for improving the early compressive strength development rate. 
     A small amount of sodium hydroxide (FIG. 5) in the total activator concentration is beneficial for reducing the set time of the slag cement mixture. 
     This data suggests that sodium hydroxide has greater impact on the set time of the formulation while sodium carbonate has greater impact on the compressive strength of the formulation. This is more clear in FIG. 6. 
     
                                           TABLE 2__________________________________________________________________________Effects of Ratios of Different Components in Total Activatoron Compressive Strength Development Rate and Set Time       Weight             Molar         Elapsed       Ratio of             Ratio of      Time in       Sodium             Sodium                   Elapsed Time                           MinutesSodium Sodium       Hydroxide             Hydroxide                   in Minutes.sup.1                           Between                                 Compressive Strength, psi, after                                 indicatedHydroxide Carbonate       to Sodium             to Sodium                   to Reach                           50 psi and                                 elapsed time% bwos* % bwos*       Carbonate             Carbonate                   50 psi                       500 psi                           500 psi.sup.2                                 2 hrs                                     4 hrs                                         8 hrs                                             12 hrs                                                 24__________________________________________________________________________                                                 hrs4     0       4 to 0    13  118 105.sup. 5                                  516                                      907                                         1272                                             1379                                                 15363.27  0.73  4.5 to 1             11.87 to 1                   17  52  35     885                                     1068                                         1236                                             1339                                                 15293.2   0.8     4 to 1             10.6 to 1                   19  51  32     882                                     1038                                         1204                                             1306                                                 15143.12  0.88  3.5 to 1              9.4 to 1                   17  52  35      856                                      994                                         1136                                             1247                                                 14453     1       3 to 1             7.95 to 1                   17  48  32     823                                      919                                         1038                                             1126                                                 13242.85  1.15  2.5 to 1             6.57 to 1                   18  50  32     961                                     1128                                         1271                                             1376                                                 15942.66  1.34    2 to 1             5.26 to 1                   18  49  31     966                                     1148                                         1310                                             1419                                                 16422.4   1.6   1.5 to 1             3.97 to 1                   17  46  29     967                                     1136                                         1298                                             1407                                                 16092     2       1 to 1             2.65 to 1                   16  42  26    1082                                     1269                                         1469                                             1592                                                 18202     2       1 to 1    15  36  21     997                                     1138                                         1315                                             1424                                                 16261.6   2.4   0.67 to 1             1.77 to 1                   20  49  29    .sup. 1374.sup.4                                     .sup. 1657.sup.4                                         .sup. 1921.sup.4                                             .sup. 2084.sup.4                                                 .sup. 2356.sup.41.34  2.66  0.5 to 1             1.33 to 1                   25  56  31    1645                                     2011                                         2366                                             2534                                                 28301.15  2.85  0.4 to 1             1.07 to 1                   37  75  38    1341                                     1792                                         2132                                             2344                                                 26511     3     .33 to 1             0.88 to 1                   42  74  32    1466                                     1861                                         2216                                             2438                                                 27580.88  3.12  .28 to 1             0.75 to 1                   43  64  21    1534                                     1870                                         2195                                             2381                                                 26560.8   3.2   .25 to 1             0.66 to 1                   .sup. 79.sup.3                       102 23    1121                                     1806                                         2180                                             2399                                                 27520.73  3.27  .22 to 1             0.59 to 1                   .sup. 83.sup.3                       107 24     995                                     1830                                         2241                                             2465                                                 27970     4       0 to 4             0.00  134.sup.3                       170 36     33 1566                                         2011                                             2237                                                 2631__________________________________________________________________________ *By weight of slag Total Activator concentration was 4% by weight of slag for all tests. Sample Formulation: &#34;NEWCEM&#34; Blast Furnace Slag + 50% fresh water (bwos) 4% Total Activator (bwos) Test Temperature: 125° F. .sup.1 This is set time. .sup.2 Early compressive strength development rate .sup.3 Sodium hydroxide in small quantity helped reduce this set time .sup.4 Higher strength when carbonate in excess of hydroxide .sup.5 Early compressive strength development rate increased due to carbonate 
    
     
                                           TABLE 3__________________________________________________________________________Effects of Ratios of Different Components in Total Activatoron Compressive Strength       Weight             Molar         Elapsed       Ratio of             Ratio of      Time in       Sodium             Sodium                   Elapsed Time                           MinutesSodium Sodium       Hydroxide             Hydroxide                   in Minutes.sup.1                           Between                                 Compressive Strength, psi, after                                 indicatedHydroxide Carbonate       to Sodium             to Sodium                   to Reach                           50 psi and                                 elapsed time% bwos* % bwos*       Carbonate             Carbonate                   50 psi                       500 psi                           500 psi.sup.2                                 2 hrs                                     4 hrs                                         8 hrs                                             12 hrs                                                 24__________________________________________________________________________                                                 hrs4     0       4 to 0    12  51  39     998                                     1097                                         1190                                             1255                                                 13793.27  0.73  4.5 to 1             11.87 to 1                   12  30  18    1027                                     1178                                         1348                                             1463                                                 16993.2     0.8   4 to 1             10.6 to 1                    9  27  18     991                                     1122                                         1287                                             1397                                                 16233.12  0.88  3.5 to 1              9.4 to 1                   10  28  18     846                                      955                                         1092                                             1200                                                 13893     1       3 to 1             7.95 to 1                   12  32  20     911                                     1027                                         1174                                             1288                                                 15112.85  1.15  2.5 to 1             6.57 to 1                   11  29  18    1049                                     1152                                         1317                                             1427                                                 16762.66  1.34    2 to 1             5.26 to 1                   10  25  15    1067                                     1173                                         1342                                             1454                                                 17332.4   1.6   1.5 to 1             3.97 to 1                    9  25  16    1042                                     1130                                         11275                                             1382                                                 16032     2       1 to 1             2.65 to 1                   10  22  12    1078                                     1182                                         1331                                             1422                                                 16451.6   2.4   0.67 to 1             1.77 to 1                   12  25  13    .sup. 1657.sup.4                                     .sup. 1870.sup.4                                         .sup. 2055.sup.4                                             .sup. 2200.sup.4                                                 .sup. 2455.sup.41.34  2.66  0.5 to 1             1.33 to 1                   16  32  16    1953                                     2237                                         2495                                             2637                                                 29071.15  2.85  0.4 to 1             1.07 to 1                   19  34  15    1993                                     2280                                         2543                                             2686                                                 29201     3     .33 to 1             0.88 to 1                   21  32  11    1864                                     2131                                         2343                                             2441                                                 26500.88  3.12  .28 to 1             0.75 to 1                   21  28   9    1937                                     2186                                         2405                                             2505                                                 26830.8   3.2   .25 to 1             0.66 to 1                   .sup. 26.sup.3                       35   9    2065                                     2399                                         2641                                             2792                                                 29510.73  3.27  .22 to 1             0.59 to 1                   .sup. 31.sup.3                       40   9    1980                                     2298                                         2565                                             2673                                                 29070     4       0 to 4             0.00  .sup. 44.sup.3                       58  14    1593                                     1888                                         2127                                             2274                                                 2465__________________________________________________________________________ *by weight of slag Total Activator concentration was 4% by weight of slag for all tests. Sample Formulation: &#34;NEWCEM&#34; Blast Furnace Slag + 50% fresh water (bwos) 4% Total Activator (bwos) Test Temperature: 175° F. 
    
     FIG. 7 and Table 4 show sodium citrate as a viable replacement for sodium hydroxide. Combinations of sodium citrate, sodium carbonate and sodium hydroxide can be made with improved properties. The data in FIG. 7 is based on the following: Base Formulation: &#34;NEWCEM&#34; blast furnace slag+50% distilled water (by wt of slag)+4% total activator (by wt of slag). 
     FIG. 7 shows ratios of components are still important to controlling set time, compressive strength and early compressive strength development rate. 
     Replacing sodium hydroxide with sodium citrate improved total compressive strength while maintaining a high early compressive strength development rate. 
     Table 4 shows incorporation of sodium hydroxide to change the set time and early compressive strength development rate. 
     
                       TABLE 4______________________________________Incorporation of Sodium Hydroxide to ChangeSet Time and Early Compressive Strength Development Rate            0.5% Sodium                       0.5% Sodium                                1% sodium            Hydroxide  Hydroxide                                Hydroxide  1% Sodium 0.5% Sodium                       1% Sodium                                1% Sodium  Citrate   Citrate    Citrate  CitrateTime   3% Sodium 3% Sodium  2.5% Sodium                                2% SodiumHours  Carbonate Carbonate  Carbonate                                Carbonate______________________________________0        0         0          0        00.8     18        18         15        90.sup.41.07    18        18         17        263.sup.41.33    16        28          46.sup.3                                  502.sup.41.6     18         92.sup.2   206.sup.3                                 7182.04     50.sup.1              620.sup.2                        791      9882.4      188.sup.1            1116       1170     11723.2     934      1584       1621     14664      1468      1782       1849     16964.8    1762      1930       2003     18365.6    1933      2035       2113     19376.4    2038      2146       2199     20177.2    2149      2234       2290     21008      2207      2326       2353     215812     2526      2628       2660     237216     2704      2816       2811     250520     2857      2935       2970     264724     2978      3059       3054     2721______________________________________ .sup.1,2,3 Show fast early compressive strength development .sup.4 Shows slower early compressive strength development. 
    
     
                                           TABLE 5__________________________________________________________________________Evaluation of Phosphates to Replace Sodium Hydroxide in Total Activator1% Sodium      1% Calcium             1% Trisodium                     1% Sodium                              1% Sodium                                       1% Sodium 1% TetrasodiumHydroxide      Phosphate             Phosphate                     Pyrophosphate                              Tripolyphosphate                                       Hexametaphosphate                                                 PyrrophosphateTime 3% Sodium      3% Sodium             3% Sodium                     3% Sodium                              3% Sodium                                       3% Sodium 3% SodiumHoursCarbonate.sup.1)      Carbonate.sup.2)             Carbonate.sup.3)                     Carbonate.sup.4)                              Carbonate.sup.5)                                       Carbonate.sup.7)                                                 Carbonate.sup.8)__________________________________________________________________________0      0     0      0      0        0        0         00.5333333 13    22     20     22       18       11        181.066667 355   25     23     20       20       13        161.6  1207   25     23     22       20       15        162.1333331488   60     25     22       18       17        162.6666671633   440     0     22       16       17        153.2  1721  1024     0     22       18       19        163.7333331815  1288     0     22       18       19        154.2666671889  1409    25     22       18       21        154.8  1940  1502    531    22       18       21        156.4  2103  1644   1577    26       18       21        168    2219  1754   1906    26       20       23        169.6  2311  1848   2069    26       20       23        1611.2 2408  1922   2216    30       20       25        1612.8 2474  1999   2341    172      18       25        1314.4 2508  2053   2407    786      16       23        1116   2578  2107   2544    1373     34       21        5817.6 2613  2136   2616    1626     155      31        35919.2 2650  2194   2690    1806     506      103       96820.8 2686  2222   2690    1955     931      393       130324   2761  2283   2805    2176     1563     1368      171432   2880         3010             2234     2418      229540   2960         3141             .sup.6) 2593                                       2849      259348   3044         3233    .sup.1 &#34;Control&#34;                              .sup.2 Lower compres-                                       .sup.3 Set time                                                 .sup.4 Set time                                                 delayed.                              sive strength than                                       Slightly higher                                                 Lower comp.                              &#34;Control&#34;                                       comp. strength                                                 strength than                                       than &#34;Control&#34;.                                                 &#34;control&#34; at                                                 24 hrs.56   3088         3325    .sup. 5 Set time delayed.                              .sup.6 Strength                                       .sup.7 Set time                                                 .sup.8 Set time                                                 delayed.                     Lower comp.                              increasing,                                       Lower comp.                                                 Lower comp.                     strength than                              approaching                                       strength than                                                 strength than                     &#34;control&#34; at                              &#34;control&#34;                                       &#34;control&#34; at                                                 &#34;control&#34; at                     24 hrs            24 hrs    24 hrs64   3131         3374__________________________________________________________________________ 
    
     
                                           TABLE 6__________________________________________________________________________Evaluation of Phosphates to Replace Sodium Carbonate in Total Activator                             1% Sodium    1% Sodium     1% Sodium            1% Sodium                    1% Sodium                             Hydroxide                                   1% Sodium   1% Sodium    Hydroxide     Hydroxide            Hydroxide                    Hydroxide                             3% Sodium                                   Hydroxide   HydroxideTime    3% Sodium     3% Calcium            3% Trisodium                    3% Sodium                             Tripoly-                                   3% Sodium   3% TetrasodiumHours    Carbonate.sup.1)     Phosphate.sup.2)            Phosphate.sup.3)                    Pyrrophosphate.sup.4)                             phosphate.sup.5)                                   Hexametaphosphate.sup.6)                                               Pyrrophosphate.sup.7)__________________________________________________________________________0     0    0       0       0        0    0            00.5  13    40      9      19       13   14           171.07355  208     11      21       19   12           1111.6 1207  330     16      42       24   17           4672.13    1488  407     17      323      30   26           6812.67    1633  463     67      551      38   33           8663.2 1721  499     113     751      42   37          10203.73    1815  538     452     943      46   41          11434.27    1889  566     921    1097      49   43          12024.8 1940  587    1331    1199      51   45          12656.4 2103  617    1899    1344      263  51          13828   2219  673    2128    1451     1450  53          14739.6 2311  716    2297    1527     1934  55          153011.2    2408  742    2419    1608     2180  59          159012.8    2474  780    2516    1650     2362  64          165314.4    2508  809    2616    1715     2493  117         169616  2578  829    2721    1760     2632  574         174117.6    2613  849    2794    1806     2705  1303        176319.2    2650  870    2869    1830     2820  1823        180920.8    2686  892    2832    1878     2858  2079        183324  2761  925    2947    1928     3021  2375        190632  2880         3152    2059     3239  2792        200840  2960         3239    2170     3378  .sup.6 3076 .sup.                                               211648  3044         3375    2258     3526  .sup.1 &#34;Control&#34;                                               217356  3088         3420    2319     3626  .sup.2 Lower comp.                                               .sup.4 Lower comp.                                   than &#34;control&#34;                                               strength than                                               control64  3131         3467    2382     3733  .sup.3 Higher comp.                                               .sup.5,6,7 Longer set                                               time,                                   than control, but                                               higher comp.                                               strength                                   set time.   .sup.8 Higher                                               strength than                                               control @ 40__________________________________________________________________________                                               hrs 
    
     
                                           TABLE 7__________________________________________________________________________Combination of Phosphate (Sodium Tripolyphosphate),Sodium Carbonate and Sodium Hydroxide to Vary Set Time and Strength(Total and Early Compressive Strength Development Rate    0.5% Sodium        1% Sodium    Tripolyphosphate        Tripolyphosphate    0.5% Sodium        1% Sodium                 3% Sodium                          1% Sodium                                   1% Sodium    Hydroxide        Hydroxide                 Tripolyphosphate                          Tripolyphosphate                                   HydroxideTime    3% Sodium        2% Sodium                 1% Sodium                          3% Sodium                                   3% SodiumHours    Carbonate        Carbonate                 Hydroxide                          Carbonate                                   Carbonate__________________________________________________________________________0    0        0        0        0         00.53    18       16       13       18        131.07    19       20       19       20        3551.6 19       22       24       20       12072.13    19       24       30       18       14882.67    21       24       38       16       16333.2 21       26       42       18       17213.73    21       26       46       18       18154.27    21       28       49       18       18894.8 21       28       51       18       19406.4 23       30       263      18       21038   23       65       1450     20       22199.6 23       884      1934     20       231111.2    23       1465     2180     20       240812.8    61       1830     2362     18       247414.4    352      2035     2493     16       250816  875      2204     2632     34       257824  1984     2701     3021     1563     2761__________________________________________________________________________ 
    
     
                                           TABLE 8__________________________________________________________________________Effect of Cation of Sulfate Salts on Set Time and Compressive Strength ofBlast Furnace Slag CementBase Formulation: NEWCEM Blast Furnace Slag mixed with 50% DistilledWater(by weight of the slag) plus indicated activator mixturesTest Temperature: 125 F. (52 C.)Curing Pressure: 3000 psiCompressive Strength, psi, of Formulations Containing the IndicatedActivators__________________________________________________________________________1% Sodium      1% Sodium            1% Sodium                    1% Sodium                           1% Sodium                                  1% Sodium                                        1% SodiumElapsedHydroxide      Hydroxide            Hydroxide                    Hydroxide                           Hydroxide                                  Hydroxide                                        HydroxideTime 3% Sodium      3% Sodium            3% Magnesium                    3% Calcium                           3% Ferrous                                  3% Ferric                                        3% CobaltHoursCarbonate      Sulfate            Sulfate Sulfate                           Sulfate                                  Sulfate                                        Sulfate__________________________________________________________________________0      0    0      0       0      0      0     01.07  281  150    20      34     13     13    302.13 1505  374    28      109    193    11    3324.09 1886  576    275     4578    2216  703    948    1002    742    419   69612.1 2438  770   1294    105316   2575  821   1506    1093    968   1510   87217.6 2610  843   1564    1093    980   1589   89419.2 2647  854   1604    1106   1018   1695   92820.8 2683  876   1667    1120   1044   1762   95222.4 2721  888   1710    1134   1071   1832   97624   2758  899   1744    1134   1084   1880   96425.6       911   1800           1098   1930  100127.2       935   1823           1127   1981  102628.8       947   1871           1141   2034  103930.4       959   1895           1155   2061  105232         959   1920           1170   2088  106633.6       972   1945           1185   2144  107935.2       984   1971           1200   2172  109236.8       997   1996           1215   2202  110638.4       1010  2022           1231   2202  110640         1010  2022           1247   2230  112041.6       1023  2049           1247   2260  113543.2                            1263   2291  114944.8                            1278   2291  114946.4                            1278   2321  116348                              1295   2352  117856                              1345   2416  120864                              1380   2482  125572                                           128680                                           131988                                           1353__________________________________________________________________________            1% Sodium                  1% Sodium                        1% Sodium                              1% Sodium                                      1% Sodium       Elapsed            Hydroxide                  Hydroxide                        Hydroxide                              Hydroxide                                      Hydroxide       Time 3% Nickel                  3% Cupric                        3% Zinc                              3% Aluminum                                      3% Ammonium       Hours            Sulfate                  Sulfate                        Sulfate                              Sulfate Sulfate__________________________________________________________________________       0      0   0      0     0        0       1.07  121  12     19   17       13       2.13  473  10     17   16       13       4.09       8     899  10     17   19       95       12.1       16   1100  9      13   17      1141       17.6 1129  9      11   17      1261       19.2 1157  9      11   17      1342       20.8 1187  8      11   17      1430       22.4 1217  8      14   17      1504       24   1202  8      20   17      1562       25.6 1233  8      29   17      1602       27.2 1249  8      40   17      1665       28.8 1265  8      54   17      1708       30.4 1265  8      67   17      1730       32   1280  8      82   17      1775       33.6 1297  8      99   17      1821       35.2 1313  8     114   17      1845       36.8 1330  8     129   17      1869       38.4 1347  8     141   17      1893       40   1347  8     152   17      1918       41.6 1364  8     163   17      1943       43.2 1364  8     171   17      1969       44.8 1382  8     177   17      1994       46.4 1382  9     186   17      1994       48   1400  10    189   17      2020       56   1435  323   207   17      2101       64   1473  1084  217   17      2157       72   1511  1541        29       80   1530  1820        16       88   1570  1993        16__________________________________________________________________________ Calcium Sulfate = CaSo.sub.4.2H.sub.2 O Ferrous Sulfate = FeSo4.7H.sub.20 - Ferric Sulfate = Fe.sub.2 (So.sub.4).sub.3.H.sub.2 O Cobalt Sulfate = CoSo.sub.4.7H.sub.2 O Nickel Sulfate = NiSo.sub.4.6H.sub.2 O Zinc Sulfate = ZnSo.sub.4.7H.sub.2 O Aluminum Sulfate = Al.sub.2 (So.sub.4).sub.3.16H.sub.2 O 
    
     
                                           TABLE 9__________________________________________________________________________Set Time and Compressive Strength DataComparisons of Activator:Retarder Ratio with Different Retarder Types andStrengths         Total              Test       Equation for Line Between                                       Compressive Strength         Activator              Duration                   Set Time                         50 psi and 500 psi                                       14 hours after                                                  Final StrengthAdditives and Concentration         % bwos              hours                   hours Slope Intercept                                       Set Time   psi__________________________________________________________________________None          0    18   2.72   78.44                                -128.72                                        723        740None          1    18   1.68  507.51                                -844.57                                       1039       1068None          2    18   1.4   741.96                               -1046.07                                       1611       1677None          4    18   0.6   1024.55                                -647.00                                       2836       2966None          6    18   0.5   794.33                                -417.14                                       3824       39240.1% &#34;REAX&#34; 100M         0    18   3.78  113.04                                -470.89                                        867        8690.1% &#34;REAX&#34; 100M         1    18   1.93  574.26                               -1109.86                                       1153       11630.1% &#34;REAX&#34; 100M         2    18   1.48  877.10                               -1311.57                                       1707       17780.1% &#34;REAX&#34; 100M         4    18   0.65  1316.57                                -931.80                                       2941       30830.1% &#34;REAX&#34; 100M.sup.1)         6    18   .sup.3) 60:1  0.52                         976.74                                -519.82                                       3498       35480,2% &#34;REAX&#34; 100M         0      22.5                   6.15  130.57                                -768.22                                        996       10600.33% &#34;REAX&#34; 100M         0    18   14.63 135.26                               -1971.55                                        795        5680.33% &#34;REAX&#34; 100M         1    18   2.97  527.32                               -1561.04                                       1278       12940.33% &#34;REAX&#34; 100M         2    18   2.12  732.72                               -1558.23                                       1655       17140.33% &#34;REAX&#34; 100M         4    18   .sup.3) 12.1  0.75                         1652.63                               -1304.50                                       3032       31130.33% &#34;REAX&#34; 100M         6    18   .sup.3) 18.2  0.6                         1455.75                                -768.60                                       3504       35540.1% &#34;SEQLENE 540&#34;         0    66   34.2  78.68 -1674.31                                        939       13650.1% &#34;SEQLENE 540&#34;         1    66   5.78  434.89                               -2502.49                                       1248       16440.1% &#34;SEQLENE 540&#34;         2    66   3.62  862.37                               -3138.26                                       1849       24820.1% &#34;SEQLENE 540&#34;         4    66   1.4   1680.75                               -2407.00                                       3166       39900.1% &#34;SEQLENE 540&#34;.sup.2)         6    68   .sup.3) 60:1  0.77                         1708.88                               -1369.30                                       3670       45220.1% Sodium Gluconate         0    90   57.72  55.19                               -3173.07                                        808       14780.1% Sodium Gluconate         1    90   6.88  460.20                               -3172.23                                       1435       20080.1% Sodium Gluconate         2    90   3.77  792.32                               -3018.93                                       1873       26550.1% Sodium Gluconate         4    90   1.95  1239.75                               -2429.60                                       2993       39360.1% Sodium Gluconate         6    90   .sup.3) 60:1  1.23                         1618.88                               -2000.70                                       3607       45650.33% Sodium Gluconate         0    43   --    --    --      --         --0.33% Sodium Gluconate         1    43   24.5  147.93                               -3633.58                                       2540       28050.33% Sodium Gluconate         2    43   17.23 197.88                               -3398.37                                       2919       34830.33% Sodium Gluconate         4    43   .sup.3) 12.1  8.9                         344.25                               -3079.35                                       3858       45470.33% Sodium Gluconate         6    43   .sup.3) 18.2  6.05                         633.48                               -3844.71                                       4050       47100.33% Sodium Gluconate         8    43   .sup.3) 24.2  3.73                         1468.02                               -5457.53                                       3412       4148__________________________________________________________________________ .sup.1) &#34;REAX&#34; is sulfonated Kraft lignin .sup.2) &#34;SEQLENE 540&#34; is sodium glucohepatonate .sup.3) Activator:Retarder ratio 
    
     FIG. 8 shows sodium oxalate as giving similar benefits as sodium citrate. 
     FIGS. 9 and 10 show comparison of the combination of citrate with phosphate and citrate, phosphate and sodium hydroxide. (Sodium hydroxide can reduce set time.) 
     Other activators were tried and the effect of component ratios is clearly distinguishable in FIGS. 11 and 12. 
     Tables 9 through 12 show that ratio for set time, early compressive strength development rate and final strength varies with retarder strength, temperature and activator strength. 
     
                                           TABLE 10__________________________________________________________________________Base Slurry: &#34;NEWCEM&#34; Blast Furnace Slag +0.1% Sodium Gluconate (bwos*) + 50% Distilled Water (bwos)Test Temperature: 125° F.__________________________________________________________________________ No   0.10%           0.20%                0.40%                     0.80%                          1%   1.20%                                    1.40%                                         1.60%                                              1.80% Activator      Activator           Activator                Activator                     Activator                          Activator                               Activator                                    Activator                                         Activator                                              Activator__________________________________________________________________________Time to              33.93                     18.1 16   12   11.55                                         9.72 73750 psiTime to              43.97                      20.63                          17.9 13.55                                    12.93                                         10.9 8.43500 psiTime from            10.04                      2.53                          1.9  1.55  1.38                                         1.18 1.0650 psi to500 psiActivator:           4:1  8:1  10:1 12:1 14:1 16:1 18:1RetarderRatio__________________________________________________________________________ 2%   2.20%           2.40%                2.60%                     2.80%                          3%   4%   5%   6%   7% Activator      Activator           Activator                Activator                     Activator                          Activator                               Activator                                    Activator                                         Activator                                              Activator__________________________________________________________________________Time to 6.08 5.38 5.27 5.2  5.17 4.43 3.1  0.93 1.78 1.1550 psiTime to 6.82 6.03 5.97 5.87 5.8  5    3.58 1.28 2.1  1.4500 psiTime from 0.74 0.65 0.7  0.67 0.63 0.57 0.48 0.35 0.32 0.2550 psi to500 psiActivator: 20:1 22:1 24:1 26:1 28:1 30:1 40:1 50:1 60:1 70:1RetarderRatio__________________________________________________________________________ *bwos = by weight of slag 
    
     
                                           TABLE 11__________________________________________________________________________Base Slurry: &#34;NEWCEM&#34; Blast Furnace Slag + 0.1% Sodium Gluconate + 50%Distilled Water (bwos)Test Temperature: 150° F.__________________________________________________________________________ No   0.10%           0.20%                0.40%                     0.80%                          1%   1.20%                                    1.40%                                         1.60%                                              1.80% Activator      Activator           Activator                Activator                     Activator                          Activator                               Activator                                    Activator                                         Activator                                              Activator__________________________________________________________________________Time to 43.15      22.52           15.7 9.68 4.98 4.53 4.2  4    2.95 2.2750 psiTime to 53.37      28.9  20.35                12.62                     6    5.58 5.28 4.83 3.57 2.63500 psiTime from 10.22       6.38            4.65                2.94 1.02 1.05 1.08 0.83 0.62 0.3650 psi to500 psiActivator: 0    1:1  2:1  4:1  8:1  10:1 12:1 14:1 16:1 18:1RetarderRatio__________________________________________________________________________ 2%   2.20%           2.40%                2.60%                     2.80%                          3%   4%   5%   6%   7% Activator      Activator           Activator                Activator                     Activator                          Activator                               Activator                                    Activator                                         Activator                                              Activator__________________________________________________________________________Time to 2.23 2    2.1  1.82 1.43 1.5  1.2  1.02 1    0.9750 psiTime to 2.68 2.38 2.45 2.2  1.62 1.75 1.45 1.15 1.15 1.12500 psiTime from 0.45 0.38 0.35 0.38 0.19 0.25 0.25 0.13 0.15 0.1550 psi to500 psiActivator: 20:1 22:1 24:1 26:1 28:1 30:1 40:1 50:1 60:1 70:1RetarderRatio__________________________________________________________________________ *bwos = by weight of slag 
    
     
                                           TABLE 12__________________________________________________________________________Base Slurry: &#34;NEWCEM&#34; Blast Furnace Slag + 0.1% Sodium Gluconate + 50%Distilled Water (bwos)Test Temperature: 175° F.__________________________________________________________________________ No   0.10%           0.20%                0.40%                     0.80%                          1%   1.20%                                    1.40%                                         1.60%                                              1.80% Activator      Activator           Activator                Activator                     Activator                          Activator                               Activator                                    Activator                                         Activator                                              Activator__________________________________________________________________________Time to 17.95      10.3 7.37 4.17 2.58 2.1  1.87 1.38 1.48 1.450 psiTime to 22.27      15.12           9.57 5.68 3.45 2.72 2.38 1.68 1.78 1.73500 psiTime from  4.32       4.82           2.2  1.51 0.87 0.62 0.51 0.3  0.3  0.3350 psi to500 psiActivator: 0    1:1  2:1  4:1  8:1  10:1 12:1 14:1 16:1 18:1RetarderRatio__________________________________________________________________________ 2%   2.20%           2.40%                2.60%                     2.80%                          3%   4%   5%   6%   7% Activator      Activator           Activator                Activator                     Activator                          Activator                               Activator                                    Activator                                         Activator                                              Activator__________________________________________________________________________Time to 1.05 1.17 1.03 1.15 1.22 0.73 0.6  0.62 0.62 0.7250 psiTime to 1.22 1.37 1.27 1.33 1.4  0.83 0.73 0.75 0.7  0.83500 psiTime from 0.17 0.2  0.24 0.18 0.18 0.1  0.13 0.13 0.08 0.1150 psi to500 psiActivator: 20:1 22:1 24:1 26:1 28:1 30:1 40:1 50:1 60:1 70:1RetarderRatio__________________________________________________________________________ *bwos = by weight of slag