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UNIVERSITY OF GAZI ANTEP CIVIL ENGINEERING DEPARTMENT

CE 444 PROPERTIES OF FRESH AND HARDENED CONCRETE CHEMICAL ADMIXTURES

Submitted by: Abdulkadir Egemen Azaz Submitted to: Assoc. Prof. Dr. Mustafa ahmaran Submission Date: Oct, 22, 2011

FALL 2011

CHEMICAL ADMIXTURES CONTENTS I. II. Introduction Main Admixtures A. Air Entraining Admixtures B. Water-Reducing / Set Controlling Admixtures Injection Procedure Conclusion ASTM Standards for Chemical Admixtures References

III. IV. V. VI.

Introduction During previous lectures, weve learned that concrete gains its properties from the behavior of cement, its components, aggregates and/or water content it consists of. Until some point, again blended cements are frequently used. Yet, for some reason, those versatilities are not to be considered as enough. Through many decades, people looked for newer, more advanced but more economical ways to compensate their requirements during many processes including the production/usage of concrete. But what could have been the best alternatives for these needs? The answer of this question is hidden in additional products we call as chemical and mineral admixtures In this report, Ill share the basic knowledge about CHEMICAL ADMIXTURES known among many people in civil engineering as useful and essential. During this presentation, Ive made some classifications under certain headlines. In first chapter, Ill tell you about the functions of admixtures In second chapter, Ill make some classifications about the functions of admixtures and explain in details. In third chapter, i will give info about injection of admixtures. And in final chapter, ill make a conclusion and finish this part of the presentation. Before any further information, its fair to define the possible main objectives choosing one or more admixtures. The properties defining those objectives commonly modified are the heat of hydration, accelerate or retard setting time, workability, water reduction, dispersion and air-entrainment, impermeability and durability factors. In the light of those properties, our main objectives in using admixtures are; Increase workability without increasing water content or decrease the water content at the same workability Retard or accelerate time of initial setting; Reduce or prevent shrinkage or create slight expansion; Modify the rate or capacity for bleeding; - Plasticizer or Superplasticizer (reducing w/c ratio)

Reduce segregation; Plasticizer or Superplasticizer Improve pumpability; Reduce rate of slump loss; Retard or reduce heat evolution during early hardening; Control expansion caused by the reaction of alkalies with potentially reactive aggregate constituents; Inhibit corrosion of embedded metal All of those needed properties will be discussed in further pages. Chapter II Main Admixtures Main chemical admixtures are; Air-Entraining Agents Water-Reducers Retarders Accelerators High Range Water Reducers Despite the limited types, those serve in many functions weve talked about so far when used properly in true proportions. Pre-job testing should be conducted to ensure compatibility of the admixture system. Especially in-situ tests are more vital in case of concreting under special environmental conditions to make more realistic and precise anticipation. (e.g: Cold weather concreting) Test placements on-site are recommended to verify proper workability, finishability, and setting time of the proposed mixture. Chapter II-A Air Entraining Admixtures The primary use of air-entraining concrete is for freeze-thaw resistance. Freeze-thaw is a result of a change in the volume of water particles and tendency to expansion. The air voids provide pressure relief sites during a freeze event, allowing the water inside the concrete to freeze without inducing large internal stresses.

Air-entraining admixtures are liquid chemical admixtures added during batching concrete to produce microscopic air bubbles, called entrained air, when concrete is mixed. When water freezes, it expands about 9%. As the water in moist concrete freezes, it produces pressure in the pores of the concrete. If the pressure developed exceeds the tensile strength of the concrete, the cavity will dilate and rupture. The accumulative effect of successive freeze-thaw cycles and disruption of paste and aggregate can eventually cause expansion and cracking, scaling, and crumbling of the concrete. Air Entraining Admixtures are not so essential for most interior structures whereas highly crucial for exterior structures where especially the surface is directly exposed to contrast weather conditions which causes thermal effects resulting freeze-thaw.

Advantages of using Air-entraining admixture are; Freezing and thawing cycles Improve workability (larger air voids to keep water inside) Reduce tendency for segregation and bleeding Disadvantages are; Loss in strength (for each 1% of air causes 5% loss in strength) Increase permeability In case of overdoses, they cause delay in setting and hardening Chapter II-B Water Reducing / Set Controlling Admixtures Water-reducing, set-controlling admixtures are added to concrete during mixing to increase workability, improve durability, provide easier placement, control the setting time, and produce easier finishing with less segregation of the ingredients. This is accomplished while allowing a reduction of the total water content and providing the ability to control the time of setting to meet changing jobsite and climatic conditions.

The strength improvement resulting from water-reducing admixtures is primarily a result of reducing the water/cement ratio and increasing cement efficiency. For a given air content, concrete strength is inversely proportional to the water-cementitious materials ratio and, therefore, the reduction in water needed to achieve the desired slump and workability when a water-reducing agent is used will effect an increase in strength. The result of water-reducing admixtures in improving strength, however, often exceeds the results of simply reducing the water content.

The admixture manufacturer should be able to provide information covering typical dosage rates, times of setting, and strength gain for local materials and conditions. The evaluation and application of the admixture should be made with specific job materials using the construction procedures under anticipated ambient conditions. Laboratory tests conducted on concrete with water-reducing admixtures should indicate the effect on pertinent properties necessary for the construction project, including: water requirement, air content, slump, rate of slump loss, bleeding, time of setting, compressive strength, flexural strength, and resistance to freezing and thawing. Following the laboratory tests, field test should be conducted to fully comprehend how the admixtures will work in actual field conditions. ASTM C 494, Standard Specification for Chemical Admixtures for Concrete, classifies admixtures into seven types as follows: Type A - Water-reducing admixtures; Type B - Retarding admixtures; Type C - Accelerating admixtures; Type D - Water-reducing and retarding admixture; Type E - Water-reducing and accelerating admixtures; Type F - Water-reducing, high-range, admixtures; and Type G - Water-reducing, high-range, and retarding admixtures. Type S Special Performance Admixtures Water Reducing Admixtures (Plasticizers) Water-reducing admixtures are used to Reduce the water requirement of the mixture for a given slump, Produce concrete of higher strength, Obtain specified strength at lower cement content Or increase the slump of a given mixture without an increase in water content.

Typically, the use of Type A water-reducers will decrease mixing water content by 5 to 12%, depending on the admixture, dosage, and other materials and proportions. Dosage rates of water-reducing admixtures depend on the type and amount of active ingredients in the admixture. Typically the dosage rate of Type A water-reducers range from 130 to 390 mL per 100 kg of cementitious materials. Usually, the primary ingredients of all water-reducing admixtures are organic, which tend to retard the time of setting of the concrete. This retardation may be offset by small additions of chloride or nonchloride acceler-ating admixtures at the batch plant. Typically, Type A admixtures already contain some accelerators that offset this natural retardation. The use of WRA may accelerate or retard the initial setting time of concrete. The WRA that retards the initial setting time more than three hours later is classified as WRA with retarding effect (Type D), the controverse is WRA with accelerating effect Type C. Commonly used WRA is lignosulfonates and hydrocarboxylic (HC) acids. The use of HC acids as WRA requires higher water content compared to the lignosulfonates. Rapid bleeding is a problem for concrete treated with HC acids. Increase of slump is different according to its type and dosage. Typical dosage rate is based upon the cementitious material content (milliliters per hundred of kilograms). The figure below illustrates the influence of dosage of Lignosulfonates and HC acid on slump. It is shown in the figure that HC acids give a higher slump compared to lignosulfonates with the same dosage.

Retarding Admixtures (Type B and Type D) The use of this admixture is defined in ASTM C494. There are two kinds of retarders, defined as Type B (Retarding Admixtures) and Type D (Water Reducing and Retarding Admixtures). The main difference between these two is the water-reducing characteristic in Type D that gives higher compressive strengths by lowering w/c ratio.

Retarding admixtures are used to slow the rate of setting of concrete. By slowing the initial setting time, the concrete mixture can stay in its fresh mix state longer before it gets to its hardened form. Use of retarders is beneficial for: Complex concrete placement or grouting Special architectural surface finish Compensating the accelerating effect of high temperature towards the initial set Preventing cold joint formation in successive lifts. Retarder can be formed by organic and inorganic material. Commonly used retarders are lignosulfonates acids and hydroxylated carboxylic (HC) acids, which act as Type D (Water Reducing and Retarding Admixtures). The use of lignosulfonates acids and hydroxylated carboxylic acids retard the initial setting time for at least an hour and no more than three hours when used at 65 to 100 oF. There has been some tests conducted to analyze the effect of temperature on retarding process. The table below describes the effect of air temperature on retardation of setting time:

Type D D D B

Description Hydroxylic acid Lignin Lignosulfonates Phosphate-based

Retardation of initial setting time (h:min) at 30oC 40oC 50oC 4:57 1:15 1:10 2:20 0:42 0:53 3:37 1:07 1:25 --3:20 2:30

Accelerating Admixtures (Type C and E) Accelerating admixtures are added to concrete to shorten the setting time and accelerate the early strength develop-ment of concrete. Some widely used and effective chemicals that accelerate the rate of hardening of concrete mixtures, including calcium chloride, other chlorides, triethanolamine, silicates, fluo-rides, alkali hydroxide, nitrites, nitrates, formates, bromides, and thiocyanates. The earlier setting time and increased early strength gain of concrete brought about by an accelerating admixture will result in a number of benefits, including reduced bleeding, earlier finishing, improved protection against early exposure to freezing and thawing, earlier use of structure, and reduction of protection time to achieve a given quality. Although calcium chloride is the most effective and economical accelerator for concrete, its potential to cause corro-sion of reinforcing steel limits its use. 1. Prestressed concrete0.06% by mass of cementitious material; and

2. Reinforced concrete0.15% by mass of cementitious material. 1. It should not be used in prestressed concrete because of its potential for causing corrosion; 2. The presence of chloride ion has been associated with corrosion of galvanized steel such as when this material is used as permanent forms for roof decks; 3. Where sulfate-resisting concrete is required, calcium chloride should not be used; 4. Calcium chloride should be avoided in reinforced con-crete in a moist condition. In nonreinforced concrete, the level of calcium chloride used should not exceed 2% by weight of cementitious material; 5. Calcium chloride should be dissolved in a portion of mixing water before batching because undissolved lumps may later disfigure concrete surfaces; 6. Calcium chloride precipitates most air-entraining agents so it must be dispensed separately into the mixture; and 7. Field experience and laboratory tests have demonstrated that the use of uncoated aluminum conduit in reinforced con-crete containing 1% or more of calcium chloride may lead to sufficient corrosion of the aluminum to collapse the conduit or crack the concrete. Superplasticizers The primary difference between these admixtures and conventional water-reducing admixtures is that high-range water-reducing (HRWR) admixtures, often referred to as superplasticizers, may reduce the water requirement by more than 30%, without the side effect of excessive retardation. By varying the dosage rate and the amount of mixing water, an HRWR admixture can be used to produce: 1. Concrete of normal workability at a lower w/c ratio; 2. Highly flowable, nearly self-leveling concrete at the same or lower w/cm as concrete of normal workability; and 3. A combination of the two; that is, concrete of moderately increased workability with a reduction in the w/cm. HRWR admixtures should meet the requirements of ASTM C 494 for classification as Type F, High-Range Water-Reducing, or Type G, High-Range Water-Reducing and Retarding, admixtures. HRWR admixtures act in a manner similar to conventional water-reducing admixtures, except that they are more efficient at dispersing fine-grained materials such as cement, fly ash, ground granulated blast-furnace slag, and silica fume. Potential Advantages of HRWR

Significant water reduction Reduced cement contents; Increased workability; Reduced effort required for placement; More effective use of cement; More rapid rate of early strength development; Increased long-term strength Reduced permeability.

Potential Disadvantages of HRWR Additional admixture cost (the concrete in-place cost may be reduced); Slump loss greater than conventional concrete; Modification of air-entraining admixture dosage; Less responsive with some cement; Mild discoloration of light-colored concrete; and Air-void and color blemishes on exposed and formed finishes. Other typically used admixtures can be classified as; Corrosion Inhibiting Admixtures: To protect the concrete against corrosion attacks especially by chlorides. Shrinkage Reducing Admixtures: Alkali-Silica Reaction Controlling Admixtures: Especially lithium-based admixtures are used to react with silicates in aggregates, forming nonabsorptive gel. The loss of moisture from the concrete as it dries results in a volume contraction termed drying shrinkage. Internal or external restraints may occur which cause cracking. Drying shrinkage can be reduced significantly by using shrinkage-reducing admixtures. These are organic-based formulations that reduce the surface tension of water in the capillary pores of concrete, thereby reducing the tension forces within the concrete matrix that lead to drying shrinkage. Also underwater admixtures are used which has water binding properties despite the challenging medium of underwater.

Chapter III Injection Procedure The basic rules of application and injection are that the admixtures should not be mixed together. This problem is handled in several ways: 1. Injecting admixtures into the waterline at separate points at least 3 ft apart and only when the water is running; 2. Placing the air-entraining admixture on the fine aggre-gate and injecting the waterreducer into the stationary or truck mixer along with water; and

Admixtures Air-entraining admixture Plasticizers Accelerators Superplasticizers

Injection Sequence With early water or on sand Follow air entraining solution With water, dont mix with air entraining admixtures Immediately before discharge for placement or with the last portion of the water at the batch plant Polycarboxylate With early water or with the last portion of the water at Superplasticizers the batch plant 3. Sequentially discharging the admixtures. The air-entraining admixture is discharged first; and the water-reducer, or combi-nation of water-reducers, is discharged later. Recommended injection sequences for various admixtures are as follows:

Generally, it is not necessary to distribute the admixtures throughout the entire water batch to get good dispersion in the mixture. There is evidence that the timing of injection of waterreducing retarders has important effects on the length of retardation and, to a lesser extent, the slump and air content. A delay of 1 to 5 min between the water addition and dispers-ing of the retarder may result in a three-fold increase in set retardation time with lignin and polymer retarding admixtures, a one and one-half to two-fold increase in entrained air, and lesser increases in slump. Chapter IV Conclusion According to the behaviors and properties of the admixtures weve learned so far, we can answer the requirements and comment the behaviors given in introduction. Increase workability without increasing water content or decrease the water content at the same workability Plasticizer Retard or accelerate time of initial setting; - Accelerator/Retarder w/ or w/o Plasticizer/Superplasticizer Reduce or prevent shrinkage or create slight expansion; - Shrinkage reducing admixtures, Modify the rate or capacity for bleeding; - Plasticizer or Superplasticizer (reducing w/c ratio) Reduce segregation; Plasticizer or Superplasticizer (reducing w/c ratio) Improve pumpability; Retarder, plasticizer Reduce rate of slump loss; Retarder. Retard or reduce heat evolution during early hardening; Retarder Control expansion caused by the reaction of alkalies with potentially reactive aggregate constituents; ASR Controlling Admixtures Inhibit corrosion of embedded metal Plasticizer/Corrosion reducing Admixtures As seen, the admixtures do not only serve a simple purpose. Even, while they are used for multi-purpose, they have potential behaviors in certain cases like interaction with eachother or environmental effects. Finally, an engineer needs to choose true admixtures in true proportions to maximize the benefit for a defined budget.

Chapter V- ASTM Standards For Chemical Admixtures Air-Entraining Admixtures ASTM C 260 Standard Specification for Air-Entraining Admixtures for Concrete AASHTO M 154 Standard Specification for Air-Entraining Admixtures for Concrete CRD-C 13 Chemical Admixtures ASTM C 494 Standard Specification for Chemical Admixtures for Concrete AASHTO M 194 Standard Specification for Chemical Admixtures for Concrete CRD-C 87 Calcium Chloride ASTM D 98 Standard Specification for Calcium Chloride AASHTO M 144 Foaming Agents ASTM C 869 Admixtures for Shotcrete ASTM C 1141 Admixtures for Use in Producing Flowing Concrete ASTM C 1017 Grout Fluidifier For Preplaced Aggregate Concrete ASTM C 937 Pigments For Integrally Colored Concrete ASTM C 979

References 1. NRMCA.ORG Concrete in Practice http://www.nrmca.org/aboutconcrete/cips/15p.pdf 2. CEMENT.ORG Air-entrained concrete http://www.cement.org/tech/cct_con_design_finishing_aec.asp 3. ASTM.ORG Admixture Classifications http://www.astm.org/Standards/C494.htm 4. ABOUT CIVIL Admixtures - http://www.aboutcivil.com/concretetechnology-admixtures.html 5. BERKELEY.EDU Chemical Admixtures http://www.ce.berkeley.edu/~paulmont/241/chemical_admixture.pdf 6. ACI Education Bulletin Chemical Admixtures http://www.concrete.org/general/fE4-03.pdf

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