CA1128076A - Cement composition - Google Patents

Abstract

ABSTRACT

A cement composition comprising cement, a pozzolan material, fine aggregate, air, water, at least one alkali metal constituent selected from the group consisting of so-dium, potassium, and lithium ions, and at least one anoinic constituent which is capable of forming complexes with ferric ions, is soluble in water, and forms a calcium salt which is also water soluble, wherein the alkali metal con-stituent is present in an amount up to approximately 4.0 percent by weight, in terms of the equivalent weight of so-dium ions, of the pozzolan material; the anoinic constituent 13 present in an amount up to approximately 6.0 percent by weight, in terms of the equivalent weight of chloride ions, of the pozzolan material; and the cement composition is fur-ther characterized by: (a) having a solid volume ratio of cement to the pozzolan material within the range of approxi-mately 0.05 to 2.0; (b) having a ratio of the volume of paste (fly ash, cement, air, and water) to the solid volume of sand within the range of approximately 0.75 to 2.5; and (c) having a ratio of the solid volume of cement to the volume of mortar less than about 0.19. The cement composi-tion of the present invention is substantially less expen-sive than cement compositions presently employed in the in-dustry having equivalent compressive strengths.

Description

~ ~76 The present invention relates to cement compositions utilizing a pozzolan material, preferably fly ssh. One of the princlpal advantages of the present invention is that it provides cement compositions which are slgnificantly cheaper per unit volume than conventional cement compositions having essentially the same structural propertles. This result is achleved through proper proportioning of the various ingre-dients in the cement composition and the substitution of re-latively lsrge amounts of inexpenslve pozzolan material for the more expensive cementltious lngredients normally utiliz-ed.
It has been known for many years that various ~inely dividedJ siliclous materials react wlth llme ln the presence of molsture to produce cementltious material whlch may be mixed wlth sand and stone to form a product simllar to mo-i dern concrete. These sillcious materlals, which are common-ly referred to as pozzolans, occur naturally or are by-products of various manufacturing processes. ExAmples of pozzolan materials include blast furnace slag, volcanic a8h, calcined shale, trass, pumice, diatomaceous earth, sillclous clays, and fly ash, whlch is the fine, solid by-product contalned ln the gases from the combustlon o~ pul-verized coal. With the advent of increasing public envlron-mental concerns and the resultlng limitatlons lmpo6ed on gaseous and partlculate emlssions from such combustion reactlons, increasingly large amounts of fly ash are being , ~ . ~

recovered from the stack gases of commercial coal burning facilities, particularly high efficiency electric power generating plants. Desplte the resultlng availability of considerable quantities of fly ash, at present there ls no ma~or commercial use for fly ash.
Fly ashJ as well as other pozzolan materials, have been utilized to replace a portion of the more expensive cementitious ingredients conventionally utilized in various cement compositions, but full utilization of fly ash has not been achieved. The primary obstacle to the use of larger proportions of fly ash in these cement compositions is that the reaction of pozzolan materials, ~ncluding fly ash, with lime is slow compared to the normal cement reaction. Thus, pozzolan containing cement compositions have an early com-presslve strength (typically measured at seven or twenty-eight days) which i8 signlficantly less than slmilar cement compositions based on conventional cementitious materlals, such as Portland cement. If pozzolan ls substituted for too large a proportion of the cement, the resulting cement com-position will have a poor initial strength and wlll requlreadditional time prior to imposition of the servlce load. It may be necessary to provide external support for the cement composltion untll the pozzolanlc reaction has proceeded sufficiently so that the cement composition is self-support-ing.
The slow curing time of cement composltions havinga high proportion of pozzolan material ls unacceptable or undeslrable for most commercial applications, Attempts have been made to solve this problem by utllizing heat to accelerate the curing rate and by adding large amounts of excess llme and/or various chemicals. These techniques have produced various speclalized products, but they have not accelerated the pozzolanlc reactlon sufficlently to be useful in preparlng cement compo~itlons suitable for a broad range o~ structural applicatlons, The present invention concerns cement composltions which reallze the economic beneflts of using larger amounts of pozzolan material. This result is achieved by properly proportioning the ingredients in the cement composition and by including certain alkali metal in the composition ions and, in addition, anionic constituents capable of forming complexes with ferric ions, i.e., iron complexing agents.
~y utilizing the appropriate amounts of cement, pozzolan, water, and fine aggregate, it is possible to minimize the void content of the cement composition and to insure maxi-mum compressive strength. The addition of relatively large amounts of sodium, potassium, and/or lithium ions apparently accelerates the pozzolanic reaction and makes it possible to add the larger amounts of pozzolan material, in the proper proportion to the other ingredients of the cement composition, without incurring a concomitant loss in early compressive strength. The iron complexing agents assist in promoting lS early compressive strength by chemically tying up ferric ions which under normal circumstances would engage in chemical reactions inhibiting the cementitious reactions necessary to the development of compressive strength.
Because these benefits can be achieved when the requisite alkali metal ions and iron complexing anions are provided in the form of sodium chloride, the present inven-tion has the further significant advantage that the cement compositions can be prepared from sea water or other brack-ish waters. Prior to the present invention it was generally believed that the incorporation of sea water in cement com-positions would be deleterious to the product. The present invention now makes it possible to prepare relatively inex-pensive cement compositions with sea water, an advantage which is particularly useful in localities where sea water is more readily available than fresh water.
The present invention relates to a cement composi-tion which maximizes the substitution of relatively inex-pensive pozzolan material for Portland cement.
In particular, the present invention provides a cement composition comprising: a cementitious material, such as Portland cement, natural cement or cement systems having bonding mechanisms similar thereto, a pozzolan ma-terial, fine aggregate, air, water, a metal constituent se--- 4 --lected from either calcium chloride or an alkali metal of sodium, potassium or lithium ions, and an anionic constit-uent; the alkali metal constituent being present in an a-mount up to approximately 4.0 percent by weight in terms of the equivalent weight of sodium ions of the pozzolan mater-ial; the anionic constituent being an iron complexing anio-nic constituent which is capable for forming complexes with ferric ions, is soluble in water, and forms a calcium salt which is also water soluble, the iron complexing anionic constituent being present in an amount up to approximately 6.0 percent by weight in terms of the equivalent weight of chloride ions of the pozzolan material; said composition having a solid volume ratio of cement to the pozzolan mat-erial within the range of approximately 0.05 to 2.0; the ratio of the solid volume of cement to the volume of mortar (cement, pozzolan material, water and fine aggregate) being less than about 0.19, and the ratio of the volume of paste (pozzolan material, cement, air and water) to the solid volume of fine aggregate being within the range of approx-20 imately 0.75 to 2.5.
It is an object of this invention to provide a ce-ment composition which maximizes the substitution of rela-tively inexpensive pozzolan material, such as fly ash, for more expensive cement, without reducing the early compres-sive strength of the cement composition.
It is a further object of the invention to provide a cement composition which is significantly less expensive than an equal volume of a conventional cement co~position having equivalent structural properties.
It is another ob~ect of this invention to provide an economical cement composition which can be prepared from brackish or sea water.
Finally, it is another object of the invention to provide a cement composition which is highly resistant to attack by acids.
Further objects of the present invention will be apparent from the detailed description of the invention ~:128~76 which f~llows.
Figure 1 is a graph depicting the 28-day compressive strength ~ersus the cement content of various cement compo-sitions, including commercially available cement compositlons without pozzolan material (IA), cement compositions containing pozzolan material ~n amounts commercially utilized at the pre-sent time (IB), and cement compositions containing a large proportion of pozzolan material ln accordance with the present invention (ID).
The present inventlon relates to cement compositions of all types ln which Portland cement or ~imilar cementitious material reacts w$th water to bind together various inert ingredients, such as sand, stone, crushed rock, etc. As used herein the term "cement composition" refers to all such cemen-tltious mixtures including, fo~ example, those generally designated in the art as mortar, grout, and concrete. The present invention is applicable, but not limited, to the following types of cement compositions: ready mixed concrete compositions~ prefabricated concrete structural elements prepared by autoclaving or steam curing cement compositions, concrete compositions utilized in large mass structures,such as gravlty dams, and concrete compositions employed as high-way bases and surfaces. These cement compositions may be employed with additional reinforcing elements conventionally utilized in the art to supplement their structural properties.
Despite the inherent economic advantages associated with the substitutlon of pozzolan materials, such as fly ash, typical pozzolan cement compositions, such as concrete, presently used in commerclal practlce contain enough pozzo-lan material to replace only about 20 to 30 percent by weightof the cement normally present. (If M y ash i8 substituted for 30 percent of the cement, the cement:fly ash ratio, as hereina~ter defined, is approximately 2.24). The primary obstacle to the utiliz`ation of larger proportions of fly ash is the slow reaction rate of pozzolan material compared with the normal reaction of cementitious materials such as Port-land cement. Attempts to substitute larger amounts of pozzo-lan material for cement have resulted in cement compositions ~ 12 having an undesirably slow setting time and unacceptably poor early strength characteristics. As a result costly delays are encountered before the cement composition can bear a service load. Prior to the present invention at-tempts to reallze the economic advantages assoclated withthe utilization of large amounts of pozzolan materlal in cement compositions have been unsuccessful largely because of the undesirable properties of the resulting products.
The present invention i8 applicable to cement com-positions containing pozzolan and cement, in relative pro-portions such that the cement:pozzolan ratio is within the range of approximately 0.05 to 2Ø PreferablyJ the cement:
pozzolan ratio is within the range of approximately 0.1 to 2Ø For present purposes the "cement:pozzolan ratio" means the ratio of the solid volume of dry cement to the solid volume of dry pozzolan material contQined in the cement com-position. As used herein the term "solid volume" (parti-cularly as applied to the proportions of cement, pozzolan material, and fine aggregate or sand) means the volume of the solid constituent exclusive of its voids and is deter-mined by dividing the weight of the materlal by its specific gravity.
The cement compositions of the present invention include cement, pozzolan, fine aggregate or sand, water, and entrained and entrapped air, which enters the cement composition during mixing of these ingredients. The cement constituents which may be utilized lnclude any of the typi-cal Portland cementæ known in the art, such as those meeting the description o~ ASTM Standard C 150-74, Types I~ II, and III. However, the proportion of cement contained in the present cement compositions is considerably less than that normall~y utllized in conventional cement compositions having comparable structural properties.
The pozzolan materlals which may be utilized include any of the materials ralling within the definltlon of Class N, F, or S set forth in ASTM Standard C 618-72. Suitable pozzolan materials include trass, volcanic ash, pumice, slag, diatomaceous earth, silicious clays, calcined shale, and fly ash. Fly ash is the preferred pozzolan material, because it is readily available, inexpensive, and has cer-tain desirable physical properties. The shape and size distribution of fly ash particles lmprove the workability of cement compositions, and acceptable workabillty of such compositions containing fly ash can generally be achieved with less water than with other pozzolan materlals. This reductlon in the water requirement alds ln minlmizing the void content of the cement composition and increases the compresslve strength of the cement product.
The cement compositions also comprise fine aggregate or sand which may be any clean durable sand conventionally used in the art for preparing mortar or concrete. Suitable sands include those which are deficient in material passing through a No~ 50 mesh screen. The amount of sand incorpora-ted in the cement composition is determined by the volume of the cement composltion and the strength properties which are desired, taking into account that the paste:sand ratio, as defined herein, must be kept within the defined range.
The cement composition also includes su~ficient water to comply with ASTM and ACI standards for workability.
Within these parameters it is desirable to minimize the quan-tity of water added to maximize the strength of the cement composition.
The cement compositions of the present invention may also include any of the chemical ingredients commonly known to those skilled in the art as "chemical admixes." The baslc types of chemical admixes presently utllized are set ~orth in ASTM Standard C 4~4-71 and are generally classified ac-3o cording to their function, i.e., whether they are utilized to retard or accelerate the cementltious chemlcal reactlons, to reduce the water requirement, or for a combination of these reasons. The chemical admixes which are used commonly today include derivatives of lignosulfonic acld and its salts, hydroxylated carboxylic acids and their salts, and polymer derivatives of sugar. More recently certain chemi-cal admixes Icnown as "super plasticiæers" or "super water reducers" have been employed which consist primarily of - 1128~76 salts of organic sulfonates of the type RS03Na where ~
is a complex organic group, frequently of high molecular weight, e.g. melamine, naphthalene, or lignin. One or more of these chemical admixes may be incorporated in the present cement compositions in the amounts conventionally utilized in the art.
The foregoing cement composition constituents may be combined in any manner conventionally utilized in the art and are generally mixed in accordance with the proce-dures set forth in ASTM Standard C-94.
During the curing and hardening o~ the cement com-position air and water leave voids which cause weakness in the cured product. To maximize the early compressive strength properties of the present cement compositions, it is desirable to minimize the voids in the cement composi-tion, since an inverse relationship exists between the volume of such voids and the compressive strength of the cement composition. It has now been found that these voids are minimized, if enough pozzolan material is added to a mixture comprising cement, sand, water, and air so that the volume ratio of paste (cement, pozzolan, water, and air) to sand (fine aggregate) is in the range of approximately 0.75 to 2.5 and, preferably, ln the range of approximately 1.0 to 2Ø For present purposes, the "paste:sand ratio"
means the ratlo o~ the volume Or the paste constituents (cement, pozzolan, water, and air) to the solld volume of dry sand (fine aggregate). Although the optimum paste:
sand ratio for any speciflc cement composition depends on the type of sand and cementitious ingredients utilized, 3 the optimum amount will fall wlthin the foregoing range.
The early compressive strength ls also lncreased by acceleratlng the pozzolanic reaction, i.e., the reaction between calcium hydroxide, which is formed during hydration of the normal cementitious components, with the silicates present in the pozzolan material to form additional calcium silicate. The rate of this reactlon ls dependent on three mechanisms. First, the rate of hydration of the cement controls the rate of formatlon of additional caIcium hy-~Z~76 g droxide needed in the pozzolanic reaction. Chemicalswhich increase the hydration of cement itself will, therefore, increase the pozzolanic reaction concurrently taking place. Secondly, the rate of dissolution of sllica from the pozzolanic material into the reaction medium wlll govern the availability of the other reactant silica. Thus, materials which stimulate the dissolution of silica will also increase the rate of the pozzolanic reaction by in-creasing the availability of silica for reaction with the calcium hydroxide. Finally, the rate of the pozzolanic reaction is influenced negatively by the formation of ferric hydroxide gel which retards the reaction of cslcium hydrox-ide and silica. Iron and ferrous or ferric ions are compo-nents normally present in most pozzolanic materials, par-ticularly fly ash, and are also present in most cements.However, the eventual controlled release of ferrous and ferric ions is beneficial and eliminates excess hydroxide lons, formed during the hydration or available from other chemical reducing or accelerating agents, which would tend to drlve the reaction of calcium hydroxide with silica in the reverse direction. Thus, the pozzolanic reactlon is accelerated by materials which initially form ferric lon complexes, such materials being generally referred to herein as iron complexing agents.
It has now been found that two of these factors determining the rate of the pozzolanic reaction can be posltively lnfluenced by the addltlon of one or more anlonic confitituents, meeting the Pollowlng crlterla:
(a) the anion forms ferric ion complexes;
(b) the anion is soluble ln water; and (c) the calcium salt of the anlon is also soluble in water.
While the flrst crlteria is important to the pozzolanic reaction for the reason set forth in the previous paragraph, the second two criteria assure that the anion will be avall-sble in the aqueous environment of the hardening cement com-positions and that its calcium salt wlll not precipltate out of that environment or otherwlse physically impede the .
:.

`` ~LlZ~3~76 cementitious and pozzolanic reactions taking pl~ce.
For purposes of the present invention an anion and lts calcium salt are considered water soluble if they have a solubility approximately equal to the water solubility of calcium hydroxide and preferably in excess thereof.
Examples of anions which meet these three require-ments and are useful in the present invention are chloride~
bromide, nitrite, thiocyanate, cyanide, and lactate ions.
One or more of the anions in this group may be employed in the cement compositions of the present invention. It has been noted that any measurable amount of these anions will have some identifiable effect on the pozzolanic reaction rate and the early compressive strength of the cement com-position. The cement compositions may contain sufficient chloride ions to constitute up to approximately 6.o percent by weight of the pozzolan materlal present and, preferably, from approximately 0.1 to 2.4 percent by weight of the pozzo-lan material. In cement composltions employing bromide, nitrite, thiocyanate, cyanide or lactate ions these ions should be present in an amount corresponding to equal quan-tities of chloride ions within the general and preferred ranges set out above. In cement compositions employing combinations of the anions the total amount of these ions should be maintalned withln the same general and preferred ranges.
A portlon of the chloride, bromlde, lactate, nitrite, thiocyanateJ or cyanide ions may be replaced and supplemented by one or more ions selected from the group consistlng of sulfate, thiosulfate, nitrate, 9ul flte, or sillcylate ions.
These ions do not fully meet the three criteria set forth prevlously. Sulfate, nitrate, sulfite, or sallcylate ions are much weaker iron complexing agents ln the alkaline en-vlronment of concrete than the ions ldentlfied ln the pre-vious paragraph, and the sulfate and sulflte ions are much less soluble in water. Thiosulfate is only a weak ion com-plexing agent in the alkallne envlronment of cement compo-sitions and partially decomposes into sulfate which forms insufficiently soluble calcium sulfate in these compositions.

` `" 1128~76 Thus, although these ions are partially effective in com-plexing ferric ions in pozzolan cement compositions, they cannot be used to totally replace the chloride, bromide, nitrite, thiocyanate, cyanide, and/or lactate lons in the pozzolan cement compositions of thls invention. Preferably the pozzolan cement compositions should always contain suf-ficient anions fully meeting the criteria previously set forth, such as those selected from the group consisting of chloride, bromide, nitrlte, thiocyanate, cyanide, and/or 1~ lactate ions to constitute at le~st approximately 0.1 per-cent by weight, in terms of the equivalent weight of chlor-ide ions, of the pozzolan material. In addition, one or more of the ions in the group consisting of thiosulfate, nitrate, sulfate, sulflte, or salicylate ions may be used ln an amount such that the total amount of anions present from both groups, i.e., chloride, bromide, nitrite, thio-cyanate, cyanide, lactate, thiosulfate, nitrate, sulfate, sulfite, and salicylate, is present in an amount up to approximately 6.o percent by weight, in terms of the equl-valent weight of chloride ions, Or the pozzolan material.
It has been found that the pozzolanic reactlon canbe accelerated further by adding sufficlent quantities of at least one alkali metal ion selected from the group con-sisting of sodium, potassium, and lithium ions. These ions apparently accelerate the pozzolanic reaction by the third means, i.e., by increasing the water solubility of the siliclous constituents in the pozzolan material, thereby permitting the silica in solution to react with excess lime liberated by the hydratlon of the cement.
Any measurable amounts of sodium, potassium and/or lithium ions will have some identifiable effect in catalyz-ing the pozzolanic reaction and offsetting the reduction in early compressive strength usually assoclated with high pozzolan content cement compositions. If sodium ions are utilized, the cement composition should contain sodium ions in an amount comprising up to approxlmstely 4.0 percent by weight of the pozæolan material present in the cement com-position, and preferably, sufficient sodium ions should be present to constitute from approxlmately 0.2 to 1.6 percent by weight of the pozzolan material. In cement compositions employing potassium or lithlum ions as the alkali ion con-stituent, the potasslum or llthium ions may be present ln amounts correspondlng to equal quantities of 60dium ions within the general and preferred ranges set out above. It is also possible to utilize mixtures of sodium, potassium, and/or lithium ions, with the total quantity of potassium and/or lithium ions again being translated into the equi-valent molecular weight of sodlum ions. When alkali metalions are added in amounts in excess of 4.0 percent by weight, in terms of the equivalent weight of sodium lons, of the pozzolan material, the beneficial effects are diminished, and after the water has evaporated from its surface, the ex-terior of such a cement composition 18 notlceably discoloredby a powdery white residue.
Compositions of the present invention are highly resistant to attack by acids, particularly sulfuric acid and its related acids found in sewer environments. Thus, cement compositions of the present inventlon are particularly use~ul in those areas where cement compositions would nor-mally be subject to acid attack and would deteriorate rapid-ly, such as sewer pipe and conduits and other exposed con-crete surfaces. The maxlmum acid resistance is present when the ratio o~ the weight of water to the weight of cement is greater than o.8. This is achieved by minimizing the amount of cement and maxlmizing the amount of water consistant wlth the strength requirements of the final hardened product.
Since ~ome pozzolan materials or types of fly ~sh contain calcium compounds or unusual ferric ion contents, which af~ect acid resistance, these factors may alter the limiting ratio of water to cement for the maximum acld reslstance to be achieved.
The following are examples of pozzolan cement com-positions within the present invention:Composition l:
188 grams Type I cement 500 grams fly ash 1250 grams of a 50/50 mix~ure of sands from Ottawa, ., ~ .~ . .

Z8~76 224 milliliters of water 20 grams NaCl (1.57 percent sodium ions and 2.43 percent chloride lons per weight of fly ash) 0.29 cement:poæzolan ratio 1.09 paste:sand ratLo o.o6 volu~e of cement:volume of mortar Composition 2:
188 grams Type I cement 500 grams fly ash 1250 grams of a 50/50 mixture of sands from Ottawa Illinois) 217 milliliters of water.
1.5 grams NaSCN
8.4 grams NaN03 9.6 grams Na2S203 (1.10 percent sodium ions and the equivalent of 1.27 percent chloride lons per weight of fly ash) 0.29 cement:pozzolan ratio 1.07 paste:sand ratio o.o6 volume of cement:volume of mortar Composition 3:
188 grams Type I cement 500 grams fly ash 1250 grams of a 50/50 mixture of sand~ from Ottawa, Illlnois 215 milliliters of water

2.5 grams NaSCN
10.0 grams NaN03 1.0 grams Na2S04 (o.8 percent sodium ions and the equivalent of 1,16 percent chloride ions per weight of the fly ash) 0.29 cement:pozzolan ratlo 1,07 paste:sand ratio o.o6 volume of cement:volume of water comPosition 4:
188 grams Type I cement 500 grams fly ash 1250 grams of a 50/50 mixture of sands from Ottawa, Tl l ~ n~

" ~2l~3~76 207 milliliters of water 1.0 grams sodium salicylate 5.0 grams NaSCN
10.0 grams NaN03

3.18 grams Na2S203 (1.04 percent sodium ions and the equivalent of 1.46 percent ch~oride lons per weight o~
the fly ash) 0.29 cement:poæzolan ratio 1.09 paste:sand ratio o.o6 volume of cement:volume of mortar One of the preferred additives is sodium chloride which may be incorporated into the cement composition in the form of sea water. Sea water is particularly useful, because lt contains appreciable amounts of potassium and sulfate ions in addltion to sodium chloride. The following is a ty-pical chemical analysis of the lonic constituents of sea water:
Ion (ppm) Sodium 10,000 Potassium 700 Calcium 440 Magnesium 1,316 Sulfate 2,515 Chloride 20,750 The beneficial effect of sea water is particularly surprising, since heretofore lt has been generally accepted that sea water i9 deleterious to cement composltions. The present invention now provldes cement composition utilizlng sea water, thereby maklng cement compositlons more readily available in areas where sea water ls plentiful and fresh water relatlvely scarce.
In another speclflc embodlment lt has been found that the benefits of the present lnventlon can be achieved without adding an alkali metal constltuent if chloride ion is added in the form of calcium chloride in an amount suf-ficient to comprise approximately 0.5 to 4.0 and preferably from approximately 0.5 to 3.0 percent by weight of the poz-.; .

. ..
.
:: . .

. .

" 1~28~76 zolan material present and the other ingredients of the cement compos ition are added in accordance ~ith the propor-tions described herein. These cement compositlons may con-tain alkali metal ions, iron complexing lons and other anions 5 in the amounts previously set forth. However, cement compo-sitions in which chloride ion is added with an alkali metal constituent demonstrate larger early compressive strengths than analagous cement compositions in which the chloride ion is added as calcium chloride.
Another advantage of the present lnvention is that the benefits of using relatively large amounts of fly ash can be achieved without adding extraneous lime, i.e , lime other than that produced in situ by hydration of the cement.
The cement compositions of the present invention, may tolerate extraneous lime in amounts up to approximately 4.0 percent by weight of the fly ash, although the setting time of the product i8 reduced. When additional lime i9 added in amounts exceeding about 4.0 percent by weight of the pozzolan material, the early strength of the cement composi-tion i9 diminished. Accordingly, the present cement compo-sitions may contain additlonal extraneous lime in amounts less than approximately 4.0 percent by weight of the pozzo-lan material.
EXAMPLES

This example demonstrates the procedure for deter-mining the requisite amount of fly ash to maximize the com-pressive strength of a cement composition. A number of different compositions were prepared employing various amounts of cement, and the amount of fly ash for each cement composition was varied. The 28-day compre3sive strength of each cement composition was measured and is reported ln Table I.
The cement utlllzed in each of the tests consisted of a blend of equal portions by weight of three Type I Port-land cements, as defined in ASTM Standard C 150-,4, which were obtained from three different mills. This cement was utilized throughout the examples hereln except as otherwlse . . .

noted.
Unless otherwise noted, the sand utilized in each of the tests in this example and the other examples herein, conslsted of a mixture of equal proportions of a relatively ~ine (No. 109) and a relatively coarse (No. l90)sand from Ottawa, Illinois. In tests G-l pond screenlngs pa~sing through a No. 200 mesh screen were utilized in addition to the Ottawa sand. In tests I-l through I-5 the sand con-sisted of equal amounts of a commercially available sand known as Waugh sand from Montgomery, Alabama, and a com-mercially available sand typlcal of those ln Atlanta, Geor-gia.
Unless otherwise noted, the pozzolan material utilized in each o~ the tests in this example and the other examples herein consisted of Bowen fly ash recovered from the combustion of pulverized bituminous coal at the Bowen Plant of the Georgia Power Company. In tests H-l through H-3 and K-l through K-3 a di~ferent pozzolan material was utilized comprising fly ash collected from the McDonough Plant of the same power company.
The mixing procedure utillzed in each test was the basic procedure described in ASTM Standard C 109 with a few modifications. First the cement, fly ash, and water were added to the mixer descrlbed in the standard test procedure.
The amount of cement utilized remained constant for a given series o~ tests, but the amount of water utilized in each test was ad~usted to obtain relatively equal slumps (a mea-sure of workabllity) for all tests within a given series of tests, e.~., tests A-l through A-4. The cement, fly ash, and water were then~ mixed at the slow speed ~or 30 seconds, after which the sand or other fine aggregate was added to the mixer during a 30 second period while mixing at the slow speed. These ingredients were then mixed at the medium speed ~or an additional 30 seconds. The amount of sand added was ad~usted to provide relatively equal volumes for all samples prepared.
The mixer was then turned off for 90 seconds, and during the first 15 seconds, the sides of the mixer were scraped down. The cement composition was then mixed at .

~12~Q76 the medium speed for an additional 60 seconds.
During the flrst 90 seconds after the final mlxing, the bowl was removed from the mixer. One-half of the mortar was removed and measured for slump, the test taking approxi-mately 30 to 45 seconds to perform. Ir the slump variedfrom the slump of the other test samples within a given series of tests, the cement composltion was reformulated to achieve approximately equivalent workability of all test compositions within the series of tests. The remaining half of the test sample was then tested by the procedure defined herein to determine the void content. Following completion of these tests, both fractions were returned to the mixing bowl and were mixed for fifteen seconds at the medium speed. The ce-ment composition was compacted into six standard 2-inch cubes for measurement of compresslve strength. The cubes were cured using llme water under ASTM Standard C lO9 condi-tions. All tests were conducted under standard conditions of temperature and humidity specified in the same ASTM stan-dard.
The slump was measured utilizing a measuring cone as described in paragraph 2.3 of ASTM Standard C 128-73.
Initially one-half o~ the cone was filled with the test sam-ple and rodded 25 times with a rounded tip rod having a dia-meter of l/4". The remainder of the metallic cone was then filled and rodded 25 times with the rod passing through the top layer and barely into the second to consolid~te the two layers. Followlng the second rodding, excess material was ~truck from the top of the cone utilizlng the edge of a trowel, and the cone was slowly removed during a ten second interval. The cone was placed beside the conical mass of the te~t sample material, and the difference between the height of the standard cone (the orlginal height of the sample) and the helght of the sample after removal of the cone was then measured as the slump.
The volume of potential volds (water and entrained and entrapped air) was determined utillzing the following experimental procedure. A metallic cylinder, closed at one end and having a ~nown volume and weieht, was utillzed to ::

~1~8 determine the density of each cement compositlon prepared.
The cylinder wa~ filled in three equal parts with subsequent rodding after each addit~on of the test sample as ln the slump test. Following the rodding of the third layer, the excess test sample mater~al was struck from the top and the density determined by dividin~ the volume of the cylinder by the dlfference in weight between the filled and unfilled cylinder. By knowing the total weight of the test sample msterial produced in a given test and the density, the total volume of the sample prepared could be computed. The dif-ference between the total volume of the test sample and the total volume of the individual solid constituents in the test sample represents the void content of the sample.
The composition of the various test samples and the results of these tests are reported in Table I. These re-sults lndicate that for a given cement composltion there is an optimum amount of pozzolan material which can be added to maximize the compresslve strength of that composition.
This maximum is reached when sufficient pozzolan material is added that the cement:pozzolan ratlo is in the range of approximately 0.1 to 2Ø When more than the maximum amount of pozzolan material is added to the cement composition there i9 a commensurate decrease in the 28-day strength.
The test results indicate that the 28-day strength of such pozzolan containing cement composltions is maxlmized when the void content of the composition is minlmized as indica-ted by a pa~te:sand ratlo between approxlmately 1.0 and 2Ø

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~Z~76 Example 2:
A series of tests were conducted illustrating the effect of including various ions in a pozzolan containing cement composition. The base composition or control utilized in these tests was as follows:
188 grams cement 500 grams fly ash 1250 grams sand 235 milliliters water The cement:pozzolan ratio in this cement composition is 0.29, representing the optimum amount of fly ash for this composi-tion as determined in examples A-l through A-4 and B-l through ~-4 in Example 1.
The cement compositions ln this example were prepared and tested as in Example 1. The water content of each test sample waæ ad~usted in an attempt to prepare samples with equivalent workability within a given series of tests. The slump of each test sample was measured in sixteenths of an inch, and the compressive strength of the 2-inch cubes pre-pared from the various cement composltions was measured atthe end of 7 and 28 days.
As noted in Table II various ionic materials in the amounts indicated were added in aqueous solution to the ce-ment and pozzolan material at the beginning of the mixing procedure. The results of these tests are reported in Table II. Where tests with various ionlc constituents were pre-pared on different days the results are compared to those of the base composltion wlthout ions prepared on the same day.
The column at the extreme right in Table II indicates the ratio of the 28-day strength of the test sample to the 28-day strength of the control.

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~, : ~Z8~76 The results of these tests demonstrate that the use of the ions indicated improve both the 7-day and 28-day strengths of high pozzolan content cement compositions. How-ever, over longer periods of time the advantages of using sodium sulfate by itself are doubtful. Test AD-2 al~o lndi-cates that the early strength of high pozzolan cement compo-sitions can be improved when calcium chloride is employed in the cement composition in the absence of an alkali metal ion.

Tests were conducted with cement composition~ contain-ing various amounts of sodium chloride. In tests BA-l through BA-4, the base cement composition or control conslsted of the following ingredients:
188 grams cement 250 grams fly ash 1475 grams sand 250 milliliters water The cement:pozzolan ratio of this cement composition is o.58.
In tests BB-l through BB-4, the base cement composi-tion con9isted of the following lngredlents:
188 grams cement 550 grams ash 1222 grams sand 250 milllliters water The cement:pozzolan ratio of thls cement composltlon is 0.27.
The remaining lngredlents in the varlous test samplesare set forth in Table III. These test samples were prepared and tested in accordance wlth the procedure set forth ln Example 2, and the results are reported in Table III. These results indicate that the sodlum and chlorlde lons lncrease the early compressive strength of high pozzolan content cement compositions.

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1~28~:3i76 Example 4:
A series of tests were conducted to demonstrate that the advantages of the present invention can be achieved utiliz-ing different sands and dif~erent pozzolan materials.
In tests CA-l and CA-2 the base cement compositlon or control consisted of the following ingredients:
188 grams cement 400 grams of Bowen fly ash 1260 grams o~ a 50/50 blend of commercially available sands comprlsing Waugh sand from Montgomery, Alabama and a commer-cially available sand typical of Atlanta~ Georgia 276 milliliters water The cement:pozzolan ratio of this cement composition is o.36.
The base cement compositlon or control utilized in test samples CB-l through CB-3 consisted of the following constituents:
188 grams cement 390 grams of a New York fly ash 1260 grams o~ a 50/50 blend of sands from Ottawa, Illinois 262 milliters water The cement:pozzolan ratio for thls cement composition is 0.32.
Finally, tests CC-l through CC-3 utilized the ~ollow-lng control cement composition:
188 grams cement 444 grams of a Class N (natural)pozzolan obtalned from the Oregon P.C. Co., Lime, Oregon 1290 gram~ of a 50/50 blend of sands from Ottawa, Illinois 253 milliliters water The cement:pozzolan ratlo for thls cement composition ls o.36.

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1~2~ )76 ` 36 The remalning ingredients in each of the test samples are set forth in Table IV. The test samples were prepared and tested in accordance with the procedure descrlbed in Example 2, and the results are reported ln Table IV. These results lndl-cate that the present lnvention is applicable to cement compo-sitions containlng various types of fly ash or other pozzolan material and fine aggregate.
Example 5:
To demonstrate the effect of varying the cement-pozzo-lan ratio and the proportion of ionic constituents included w~thin the cement composition the following series of tests were performed.
In tests DA-l through DA-5 the control cement compo-sition consisted of the followlng ingredients:
376 grams cement 330 grams fly ash 1240 grams sand 250 milliliters water The cement:pozzolan ratlo for this composition is o.88.
20The base cement composition utilized in samples DB-l through DB-6 consisted of the following:
376 grams cement 125 grams fly ash 1450 grams sand 254 mLlliliters water The cement:pozzolan ratio of this sample composition i5 2, 33.
The following compositlon was utilized as the control cement composition in te~t samples DC-l through DC-4:
564 grams cement 50 grams fly ash 1343 grams sand 260 milliliters water The cement:pozzolan ratlo for this sample is 8.74.
Finally, test samples DD-l through DD-4 were prepared 35 based on the following control composition:
564 grams cement 250 grams fly ash 1115 grams sand 270 milliliters water :

1~L28Q76 This composition has a cement:pozzolan ratio of 1.75.
A~ain the test samples were prepared and tested accord-ing to the procedure described ln Example 2. The results and the remaining constituents in each test sample are reported in Table V.
The results indicate that the advantages of the present invention were achieved in the DA series of tests whereln the ingredients were proportioned in accordance with the present invention. For the DB and DC series of tests signi~icant in-creases in the early compressive strength were not realized,because of the relatively low proportion of fly ash in these tests as indicated by the cement:pozzolan ratios of 2.33 and 8.74 respectively for each series. In test series DD signi-ficant improvement in the compressive strength of the cement compositlon was not achieved because of the large amount of cement already ln the cement composition. It has been found that the benefits o~ the present invention are achieved if the ratio of the solid volume of cement to the volume of mor-tar (cement, pozzolan, water, air, ionic constituents and sand) is less than about 0.19.

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~lZ8~76 Example 6:
To demonstrate that the advantages of the present invention are achieved because of the interaction of the pozzo-lan material and the ionic constituents, cement compositions were prepared in wh~ch the pozzolan material was replaced by granite dust, an inert material with a fine particle size.
The control cement composltion utilized in these test samples (EA-l through E~-5)comprised the following:
376 grams cement 250 grams of granite dust passing through a 200 mesh screen 1240 grams sand 270 milliliters water The ratio of cement to fine granite dust on a dry volume basis is 1.22.
The procedure described in Example 2 was followed in the preparation and testlng of the test samples. The remain-ing constituents ln each test sample and the results of the tests are reported in Table VI. These test results indlcate that the presence of lonlc constituents whlch are effective ln increasing the early strength of high pozzolan cement com-posltlons are ineffective for the same purpose in cement compositlons including a hlgh content of fine inert material.
Example 7:
A series of tests were conducted to demonstrate that the present inventlon is applicable to cement compositions containing different types Or Portland cement.
In test samples FA-l through FA-3 the control cement composition contained the rollowing ingredlents:

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-`- ` 1128~)76 188 grams of a Type II Portland cement 500 grams fly ash 1250 grams sand 253 mllliliters o~ water In test FB-l through FB-3 the same control compositlon was utilized except that the cement utilized was a Type III
Portland cement~ The cement:pozzolan ratio in each of the control samples for the FA snd FB Serie-s of tests is 0.29.
Again the test samples were prepared and tested according to the procedure described in Example 2. The remaining constituents ln each test sample and the results of the tests are reported in Table VII. The tests demon-strate that excellent results are achieved with the cement compositions of the present invention regardless of the type of cement which is utilized.
~xample 8;
The purpose of this series of tests was to demonstrate that the present invention is applicable to cement composi-tions, such as those employed in manufacturing prefabricated structural elements, which are sub~ected to thermal treatment or autoclaving to accelerate the curlng rate. The composi-tions of the test samples are indicated in Table VIII. Un-less otherwise indicated the samples utilized a blend o~ three Type I Portland cements, Bowen fly ash, and a 50/50 blend o~
fine and coarse sands from Ottawa, Illinois as the maJor con-stituents as previously described in Example 1. The test procedure described in Example 2 was followed, except that the cubes formed from the various test samples were maintained in the laboratory ~or 24 hours at atmospheric condltions and then cured for 17 hours at a minimum temperature o~ 167 degrees Fahrenheit in water. The compressive strength of the cubes was then measured and the results are repnrted in Table VIII.
The test results indicate that the present invention can be applied to cement composltions which are sub~ected to accelerated curing by heating. Again the presence of the ionic constituents imprnved the early compressive strength charac-teristics o~ these cement compositions.

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1~28t~76 ~xample ~:
Tests were performed to demonstrate that the advan-tages of the present invention are achieved when the ion~
are supplied in the form of sea water. The composition of the test samples is recorded in Table IX. Unless otherwise noted all samples utilized a blend of three Type I Portland cements, Bo~en fly ash, and a 50/50 blend of fine and coarse sands from Ottawa, Illinois. The test samples were prepared and tested according to the procedure outlined in Example 2.
The test results are reported in Table IX.
The test results indicate that the use of sea water in a high pozzolan content cement composition significantly increases the early strength of the product.

To demonstrate the economic advantages of the present invention a series of tests were performed comparing the relative cost of typical commercially available cement compo-sitions not containing pozzolan material (tests IA-l through IA-5), cement compositlons containing pozzolan materlal as presently used in the industry (test samples IB-l through I~-4), cement compositions containing a large proportion of pozzolan (test samples IC-l through IC-4), and cement co~po-sitions containing a large proportion of pozzolan and sodium chloride in an amount equal to 6.65 wt percent of the pozzo-lan materlal (test samples ID-l through ID-8). The test compositions employed cement comprising a blend of three Type I Portland cements, Bowen fly ash, and a 50/50 mixture of fine and coarse sands from Ottawa, Illinois.
The composition of these test samples is reported in Table X. Test samples were prepared and tested ln accordance with the procedure set forth in Example 2, and the results of those tests are also reported in Table X. The cost of the cementitious material per yard of concrete was based on a cement cost of $1. 80 per 100 pounds and a pozzolan cost oY
35 $o. 50 per 100 pounds.
Figure 1 is a graph of these test results for the IA, IB, and ID series of tests, indicating the relationship be-tween the amount of cement in a cement c~mposition versus the 28-day strength of that composition. The graph indi-cates that for a given amount of cement the strength can be improved by addlng pozzolan up to the normal amount used in co~mercially available cement compositions. However, as indicated by the IC series of tests, the early strength of the cement composition decreases if additional pozzolan is added without utilizing ionic constituents as employed in the present invention. Thus, any economic advantage asso-ciated with the use of pozzolan material in excess of the normal amount is offset by a decrease in structural proper-tles.
As lndicated by Flgure 1, significant economic ad-vantages are achieved when excess pozzolan material is util-Lzed in conjunction with the proper amounts of ions which accelerate the pozzolanic reactlon. Cement compositions prepared in accordance with the present invention are signi-ficantly less expensive per unit volume than commercially available cement compositions having equivalent compressive strengths.
The line representing cement compositions of the present invention intersects the line corresponding to normal pozzolan cement compositions at the point where the ratio of the solid volume of cement to the volume of mortar is about 0.19.

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7~i Example 11:
Tests were performed to demonstrate the e~ficacy of utilizing potassium bromide as the source of the ionic con-stituents in cement compositions o~ the present invention.
The control cement compositlon utilized in each of the tests JA-l through JA-3 is as follows:
188 grams Type I cement 550 grams fly ash 1170 grams Waugh sand 247 milllliters water Each of the samples utilized in this series of tests has a cement:pozzolan ratio of 0.26 and a p~ste:sand ratio of 1.26.
As indicated in Table XI, sample JA-l contained 22.0 grams of sodium chloride or approximately 4 percent by weight of the fly ash. Otherwise stated, sample JA-l contained 1.6 percent sodium ions and 2.4 percent chlorine ions by weight of the fly ash present. In sample JA-2 and JA-3 sufficlent amounts of potassium bromide and potassium iodide were added respectively to supply ions in an equivalent weight of the sodium and chloride ions present ln sample JA-l.
The test procedures previQusly identlfied were fol-lowed with respect to samples JA-l through JA-3 with the ex-ception that the compressive strength was measured at the end of 33 rather than 28 days. The results are reported in Table XI. These results indicate that cement compositions of the present invention employing potassium bromide demon-strate strength characterlstics at least as good as, lf not better than, those employlng sodlum chlorlde. However, the same degree of strength improvement was not achleved when potassium iodide was utllized.

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~28 Tests were performed to dem~nstrate the efficacy of utilizing various lons in cement compositions of the present inventionO The base cement composition utilized in each of the test series KA, KB, KC, KE, and KF is as follows:
188 grams Type I cement 500 grams Bowen fly ash 1250 grams of a 50/50 blend of sands from ottawa, Illinois 247 milliliters water Each of the samples utilized in these series of tests has a cement:pozzolan ratio of 0.29 and a paste:sand ratio ~n the amount indicated in Table XII.
The base cement compositlon utilized in each of the test series KD and KG is as follows:
188 grams Type I cement 450 grams Bowen fly ash 1260 grams Shorter, a commercially available sand from Shorter, Alabama 247 milliliters water Each of these samples had a cement:pozzolan ratio of 0.32 and a paste:sand ratio as indicated in Table XII. Each of the samples contained ionic constituents of the type ~nd amount lndicated in Table XII.
The test procedures previously identified in Example 2 were followed with respect to samples KA through KG. In QdditionJ ldentical samples were prepared and subJected to accelerated curing conditions as described in Example 8.
The test results are reported in Table XII.

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Example 13:
Tests were performed to demonstrate the efficacy of utilizing various combinations of anions in cement composi-tions of the present invention. The base cement compositions utilized in each of the test series LA and L~ is as follows:
188 grams Type I cement 500 grams Bowen fly ash 1250 grams of a 50/50 mixture of sands from Ottawa, Illinois 247 millilLters water Each of the samples utilized in these series of tests had a cement:pozzolan ratio of 0.29 and a paste:sand ratio as indi-cated in Table XIII.
The base cement composition utilized in the LC series of tests is as follows:
213 grams Type I cement 500 grams Bowen fly ash 1230 grams of a 50/50 mixture of sands from Ottawa, IlllnoLs 247 milliliters water Each of the samples utilized in the LC series of tests had a cement:pozzolan ratio of 0.33 and a paste:sand ratio as indicated in Table XIII. Each of the samples contained ionic constituents of the type and amount indicated in Table XIII.
The test procedures previously ldentified in Example ` 2 were followed with respect to test samples-LA through LC.
In addition identical samples were prepared and sub~ected to accelerated curing condltlons as described in Example 8.
The test results are reported in Table XIII. These results indicate that various combinations of ions may be used in the cement compositions of the present invention.

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_ 80 -Example 14:
Tests were performed to demonstrate the efficacy of the cement compositions of the present invention in reslsting attack and deterioration bv aclds. The following cement com-positions were utllized:
COMPOSITION
Ingredient A B C D
Cement (grams--Type I Portland) 55 295 255 215 Fly Ash (Marshall Plant of Duke Power Company~
North Carolina) ~ 376 436 476 Sand (grams--Broad River, South Carolina) 1578 1350 1350 1350 Water (grams--CLty of Atlanta, Georgia) 217 199 199 199 NaCl (grams) - 2.6 2.6 2.6 Sodium thiosulrate (5 hydrate) (grams) _ 15.0 15.0 15.0 Wt. Water/
Wt. Cement 0.40 o.67 0.78 -93 Paste:Sand (ratio) _ o.g8 o.98 1.01 These composition~ were prepared in accordance wlth the procedure set forth in Example 2. Standard 2-lnch square cubes of these composltions were prepared and cured for 28 days with the compressive strength being measured at the end of 7 and 28 days. The cured cubes were then weighed and im-mersed ln aqueous solution containlng 10 percent by volume of 98% sulfuric acid. After 24 hours the cubes were withdrawn ~ 28076 from solution and scrubbed lightly to remove loose matter onthe surface of each cube. The cubes were then reimmersed in the acid for 24 hours, scrubbed again and weighed. The weight loss as a percentage of the initial weight of the cubes indi-cates the degree to which the cement compositions have beenattacked by the acid. The following table contains the re-sults:
COMPOSITION
A B C D
7-Day strength (psi)7750 6100 5150 4450 28-Day strength (psi)10,690 9300 8280 7500 Weight Loss (1%) 14.1 8.6 4.6 1.7 :

Claims (13)

The embodiments in which an exclusive property or privilege is claimed are defined as follows:

1. A cement composition comprising: a cementitious material such as Portland cement, natural cement or cement sys-tems having bonding mechanisms similar thereto, a pozzolan ma-terial, fine aggregate, air, water, a metal constituent select-ed from either calcium chloride or an alkali metal of sodium, potassium or lithium ions, and an anionic constituent; the alkali metal constituent being present in an amount up to approx-imately 4.0 percent by weight in terms of the equivalent weight of sodium ions of the pozzolan material; the anionic constituent being an iron complexing anionic constituent which is capable of forming complexes with ferric ions, is soluble in water, and forms a calcium salt which is also water soluble, the iron complexing anionic constituent being present in an amount up to approximately 6.0 percent by weight in terms of the equiva-lent weight of chloride ions of the pozzolan material; said composition having a solid volume ratio of cement to the poz-zolan material within the range of approximately 0.05 to 2.0;
the ratio of the solid volume of cement to the volume of mor-tar (cement, pozzolan material, water and fine aggregate) be-ing less than about 0.19 and the ratio of the volume of paste (pozzolan material, cement, air, and water) to the solid vol-ume of fine aggregate being within the range of approximately 0.75 to 2.5.

2. The cement composition of claim 1, wherein the anionic constituent includes at least one additional anion selected from thiosulfate, sulfate, sulfite, nitrate, and sali-cylate anions, and wherein the total amount of such additional ions and said iron complexing anionic constituent constitute up to approximately 6.0 percent by weight, in terms of the e-quivalent weight of chloride ions, of the pozzolan material.

3. The cement composition of claim 1, wherein the ratio of the volume of paste to the solid volume of sand is within the range of approximately 1.0 to 2Ø

4. The cement composition of claim 1, wherein the total iron complexing anionic constituent and any additional anion are present in an amount within the range of approxi-mately 0.1 to 2.4 percent by weight, in terms of the equivalent weight of chloride ions, of the pozzolan material.

5. The cement composition of claim 1, wherein the anionic constituent is selected from chloride, bromide, nitrite, thiocyanate, cyanide, and lactate ions.

6. The cement composition according to claim 1, wherein the pozzolan material comprises fly ash.

7. The cement composition according to any of claim 1, wherein the ratio of the weight of water to the weight of cement is greater than 0.8.

8. The cement composition of claim 1, wherein the metal constituent is calcium chloride present in an amount up to approximately 4.0 percent by weight in terms of the equiva-lent weight of the pozzolan material.

9. The cement composition of claim 8, wherein the metal constituent also includes at least one alkali metal ion selected from sodium, potassium, and lithium ions.

10. The cement composition of claim 9, wherein there is present at least one additional anion selected from bromide, nitrite, thiocyanate, cyanide, lactate, thiosulfate, sulfate, nitrate, and salicylate anions; and the total amount of such ions and chloride ions comprises up to approximately 6.0 percent by weight in terms of the equivalent weight of chloride ions, of the pozzolan material.

11. The cement composition of claim 10, wherein the chloride ions and any anionic constituent are present in an amount within the range of approximately 0.1 to 2.4 percent by weight in terms of the equivalent weight of chloride ions of the pozzolan material.

12. The cement composition according to claim 8, wherein the pozzolan material comprises fly ash.

13. The cement composition according to claim 8, wherein the ratio of the weight of water to the weight of cement is greater than 0.8.