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Chap. 7 (2010).qxd:EB001 (2010) 1/27/11 2:35 PM Page 117 CHAPTER7 Chemical Admixtures for Concrete Chemicaladmixturesarethoseingredientsinconcrete Themajorreasonsforusingchemicaladmixturesin other than hydraulic cement, supplementarycementitious concrete mixtures are: materials (SCMs), water, aggregates, and fiber reinforce- 1. Toachievecertainpropertiesinconcretemoreeffec- mentthatareaddedtothemixtureimmediatelybeforeor tively than by other means; duringmixing(Figure7-1).Thereareavarietyofchemical 2. Tomaintainthequalityofconcreteduringthestages admixturesavailableforuseinconcretemixturestomod- of mixing, transporting, placing, finishing, and ify fresh and hardened concrete properties. Chemical ad- curing(especially in adverse weather conditions or mixturescanbeclassifiedbyfunctionasfollows: intricate placements); 1. Air-entraining 3. Toovercomecertainemergenciesduringconcreting 2. Normal,Mid-range,andHigh-rangewater-reducing operations; and 4. Set accelerating 4. Economy. 5. Set retarding Despitetheseconsiderations,noadmixtureofanytypeor 6. Hydration-control amountisasubstituteforgoodconcretingpractice. 7. Rheologymodifying 8. Corrosioninhibitors Theeffectivenessofanadmixturedependsuponfactors suchasitscomposition,additionrate,timeofaddition; 9. Shrinkagereducers type, brand, and amountofcementingmaterials;water 10. Permeabilityreducingadmixtures content; aggregate shape, gradation, and proportions; 11. Alkali-silica reactivity inhibitors mixingtime;slump;andtemperatureoftheconcrete. 12. Coloringadmixtures Chemicaladmixturesconsideredforuseinconcrete 13. Miscellaneousadmixturessuchasworkability, shouldmeetapplicablespecificationsaspresentedin bonding,grouting,gas-forming,anti-washout, Table7-1. Trial mixtures should be made with the admix- foaming,andpumpingadmixtures ture and the other concrete ingredients at the temperature andrelativehumidityanticipatedduringplacement.Then, observationscanbemadeonthecompatibilityofthe admixturewithotheringredients,aswellasitseffectson the properties of the fresh and hardened concrete. The amountofadmixturerecommendedbythemanufacturer shouldbeused,ortheoptimumdosageshouldbeverified bylaboratorytesting.Formoreinformationonchemical admixturesforuseinconcreteseeACICommittee212 (2004 and2010),ThomasandWilson(2002),Hewlett (1998), and Ramachandran(1995). Figure 7-1. Liquid admixtures, from far left to right: antiwashout admixture, shrinkage reducer, water reducer, foaming agent, corro- sion inhibitor, and air-entraining admixture. 117 Chap. 7 (2010).qxd:EB001 (2010) 1/27/11 2:35 PM Page 118 Design and Control of Concrete Mixtures ◆ EB001 Table 7-1. Concrete Admixtures by Classification Type of admixture Desired effect Material Accelerators Accelerate setting and early-strength Calcium chloride (ASTM D98 and AASHTO M 144) (ASTMC494and development Triethanolamine, sodium thiocyanate, calcium formate, calcium AASHTOM194,TypeC) nitrite, calcium nitrate Air detrainers Decrease air content Tributyl phosphate, dibutyl phthalate, octyl alcohol, water- insoluble esters of carbonic and boric acid, silicones Air-entraining admixtures Improve durability in freeze-thaw, deicer, Salts of wood resins (Vinsol resin), some synthetic detergents, (ASTMC260and sulfate, and alkali-reactive environments salts of sulfonated lignin, salts of petroleum acids, salts of AASHTOM154) Improve workability proteinaceous material, fatty and resinous acids and their salts, alkylbenzene sulfonates, salts of sulfonated hydrocarbons Alkali-aggregate reactivity Reduce alkali-aggregate reactivity Barium salts, lithium nitrate, lithium carbonate, lithium inhibitors expansion hydroxide Antiwashout admixtures Cohesive concrete for underwater Cellulose, acrylic polymer placements Bonding admixtures Increase bond strength Polyvinyl chloride, polyvinyl acetate, acrylics, butadiene-styrene copolymers Coloring admixtures Colored concrete Modified carbon black, iron oxide, phthalocyanine, umber, (ASTMC979) chromium oxide, titanium oxide, cobalt blue Corrosion inhibitors Reduce steel corrosion activity in a Amine carboxylates aminoester organic emulsion, calcium nitrite, (ASTMC1582) chloride-laden environment organic alkyidicarboxylic, chromates, phosphates, hypophosphites, alkalis, and fluorides Dampproofing admixtures Retard moisture penetration into dry Soaps of calcium or ammonium stearate or oleate concrete Butyl stearate, Petroleum products Foaming agents Produce lightweight, foamed concrete Cationic and anionic surfactants with low density Hydrolized protein Fungicides, germicides, Inhibit or control bacterial and fungal Polyhalogenated phenols and insecticides growth Dieldrin emulsions, Copper compounds Gas formers Cause expansion before setting Aluminum powder Grouting admixtures Adjust grout properties for specific See Air-entraining admixtures, Accelerators, Retarders, and applications Water reducers Hydration control Suspend and reactivate cement Carboxylic acids admixtures hydration with stabilizer and activator Phosphorus-containing organic acid salts Permeability-reducing Water-repellent surface, reduced water Long-chain fatty acid derivatives (stearic oleic, caprylic capric), admixture: non-hydrostatic absorption soaps and oils, (tallows, soya-based), petroleum derivatives conditions (PRAN) (mineral oil, paraffin, bitumen emulsions), and fine particle fillers (silicates, bentonite, talc) Permeability reducing Reduced permeability, increased resis- Crystalline hydrophilic polymers (latex, water-soluble, or liquid admixture: hydrostatic tance to water penetration under polymer) conditions (PRAH) pressure Pumping aids Improve pumpability Organic and synthetic polymers Organic flocculents Organic emulsions of paraffin, coal tar, asphalt, acrylics Bentonite and pyrogenic silicas Hydrated lime (ASTM C141) Retarding admixtures Retard setting time Lignin, Borax (ASTMC494and Sugars, Tartaric acid and salts AASHTOM194,TypeB) Shrinkage reducers Reduce drying shrinkage Polyoxyalkylene alkyl ether Propylene glycol Superplasticizers* Increase flowability of concrete Sulfonated melamine formaldehyde condensates (ASTMC1017,Type1) Reduce water-cement ratio Sulfonated naphthalene formaldehyde condensates Lignosulfonates, Polycarboxylates 118 Chap. 7 (2010).qxd:EB001 (2010) 1/27/11 2:35 PM Page 119 Chapter 7 ◆ Chemical Admixtures for Concrete Table 7-1. Concrete Admixtures by Classification (Continued) Type of admixture Desired effect Material Superplasticizer* and Increase flowability with retarded set See superplasticizers and also water reducers retarder (ASTM C1017, Reduce water–cement ratio Type 2) Water reducer Reduce water content at least 5% Lignosulfonates (ASTM C494 and Hydroxylated carboxylic acids AASHTOM194,TypeA) Carbohydrates (Also tend to retard set so accelerator is often added) Water reducer and Reduce water content (minimum 5%) See water reducer, Type A (accelerator is added) accelerator (ASTM C494 and accelerate set and AASHTO M 194, Type E) Water reducer and Reduce water content (minimum 5%) See water reducer, Type A (retarder is added) retarder (ASTM C494 and and retard set AASHTOM194,TypeD) Water reducer—high Reduce water content (minimum 12%) See superplasticizers range (ASTM C494 and AASHTOM194,TypeF) Water reducer—high Reduce water content (minimum 12%) See superplasticizers and also water reducers range—and retarder and retard set (ASTM C494 and AASHTOM194,TypeG) Water reducer—mid Reduce water content (between 6 and Lignosulfonates range 12%)without retarding Polycarboxylates * Superplasticizers are also referred to as high-range water reducers or plasticizers. These admixtures often meet both ASTM C494 (AASHTOM194)andASTMC1017specifications. . Applicable requirements Air-Entraining Admixtures Air-Entraining Hydraulic Cement for air-entraining cements are given inASTM C150, Stan- Oneofthegreatestadvancesinconcretetechnologywas dard Specification for Portland Cement andAASHTOM85. the developmentofair-entrainedconcreteinthemid- SeeChapter11,Klieger(1966),andWhitingandNagi 1930s.Air-entrainmentdramaticallyimprovesthedur- (1998) for more information. ability of concrete exposed to cycles of freezing and Air-Entraining Materials thawinganddeicerchemicals(seeChapter11).Thereare also other important benefits of entrained air in both Theprimaryingredientsusedinair-entrainingadmix- freshly mixedandhardenedconcrete(seeChapter9). tures are listed in Table 7-1. Numerous commercial air- entraining admixtures, manufacturedfromavarietyof Air-entraining concrete is produced by using either an air- materials, are available. Most air-entraining admixtures entraining cementorbyaddinganair-entrainingadmix- consist of one or more of the following materials: wood tureduringbatching,oracombinationoftheseapproaches. resin (Vinsol resin), sulfonated hydrocarbons, fatty and Air-entraining cement is a portland cement with an air- resinous acids, and synthetic materials. Chemical descrip- entraining addition interground with the clinker during tions and performancecharacteristics of commonair- manufacture(seeChapter3).Anair-entrainingadmixture, entraining agents are shown in Table 7-2.Air-entraining ontheotherhand,isaddeddirectlytotheconcretemate- admixturesareusuallyliquidsandshouldnotbeallowed rials either before or during mixing. Regardless of the ap- to freeze.Admixturesaddedatthemixershouldconform proachused,adequatecontrolandmonitoringisrequired toASTMC260(AASHTOM154). to ensure the proper air content at all times. Air-entraining cements complywithASTMC150and Specifications and methods of testing air-entraining C595(AASHTOM85andM240).Toproducesuch admixturesaregiveninASTMC260,StandardSpecification cements,air-entraining additions conforming toASTM for Air-Entraining Admixtures for Concrete, and C233, Stan- C226areintergroundwiththecementclinkerduring dard Test Method for Air-Entraining Admixtures for Concrete manufacture.Air-entrainingcementsgenerallyprovidean (AASHTOM154andT157).Air-entrainingadditionsfor adequateamountofentrainedairtomeetmostjobcondi- useinthemanufactureofair-entrainingcementsmust tions; however, a specified air content may not necessarily beobtainedintheconcrete.Ifaninsufficientvolumeof meetrequirementsofASTMC226,StandardSpecification air is entrained, it may also be necessary to add an air- for Air-Entraining Additions for Use in the Manufacture of entraining admixtureatthemixer. 119 Chap. 7 (2010).qxd:EB001 (2010) 1/27/11 2:35 PM Page 120 Design and Control of Concrete Mixtures ◆ EB001 Table 7-2. Classification and Performance Characteristics of Common Air-Entraining Admixtures Classification Chemical description Notes and performance characteristics Wood derived acid salts Alkali or alkanolamine salt of: ® Vinsol resin Amixture of tricyclic acids, phenolics, Quick air generation. Minor air gain with initial mixing. and terpenes. Air loss with prolonged mixing. Mid-sized air bubbles formed. Compatible with most other admixtures. Wood rosin Tricyclic acids-major component. Sameasabove. Tricyclic acids-minor component. Tall oil Fatty acids-major component. Slower air generation. Air may increase with prolonged Tricyclic acids-minor component. mixing. Smallest air bubbles of all agents. Compatible with most other admixtures. Vegetable oil acids Coconut fatty acids, alkanolamine salt. Slower air generation than wood rosins. Moderate air loss with mixing. Coarser air bubbles relative to wood rosins. Compatible with most other admixtures. Synthetic detergents Alkyl-aryl sulfonates and sulfates (e.g., Quick air generation. Minor air loss with mixing. Coarser sodium dodecylbenzenesulfonate). bubbles. May be incompatible with some HRWR. Also applicable to cellular concretes. Synthetic workability aids Alkyl-aryl ethoxylates. Primarily used in masonry mortars. Miscellaneous Alkali-alkanolamine acid salts of ligno- All these are rarely used as concrete air-entraining agents sulfonate. in current practice. Oxygenated petroleum residues. Proteinaceous materials. Animal tallows. Mechanism of Air Entrainment coalescenceofbubbles(C&D).Thesurfacechargecauses Air-entraining admixtures are surfactants (surface-active theairbubbletobeadheredtothechargedsurfacesof agents) whichconcentrateattheair-waterinterfaceand cementandaggregateparticles.Thefineaggregateparti- reducethesurfacetensionencouragingtheformationof cles also act as a three-dimensional grid to help hold the microscopicbubblesduringthemixingprocess.Theair- bubblesinthemixture(E).Thisimprovesthecohesionof entraining admixturestabilizes those bubbles, enhances themixtureandfurtherstabilizestheairbubbles(F). the incorporation of bubbles of various sizes, impedes Entrainedairbubblesarenotlikeentrappedairvoids, bubblecoalescence,andanchorsbubblestocementand whichoccurinallconcretesasaresultofmixing,handling, aggregateparticles. andplacing.Entrappedairvoidsarelargelyafunction Theair-entrainingadmixtureactsattheair-waterinterface. of aggregate characteristics. Intentionally entrained air Air-entrainingadmixturestypicallyhaveanegatively bubblesareextremelysmallinsize,between10to1000µm chargedheadwhichishydrophilicandattractswater,and in diameter, while entrappedvoidsareusually1000µm ahydrophobictailwhichrepelswater.Asillustratedin (1 mm)orlarger.Themajorityoftheentrainedairvoidsin Figure7-2;thehydrophobicendisattractedtotheair normalconcretearebetween10µmand100µmindiam- withinbubblesgeneratedduringthemixingprocess.The eter. As showninFigure7-3,thebubblesarenotintercon- polarend,whichishydrophilic,orientsitselftowards nected. Theyarewelldispersedandrandomlydistributed. water(A).Theair-entrainingadmixtureformsatough, Non-air-entrainedconcretewitha25-mm(1-in.)maximum- water-repellingfilm, similar to a soap film, with sufficient size aggregate has an air content of approximately 1.5%. strengthandelasticitytocontainandstabilizetheair Thissamemixtureairentrainedforseverefrostexposure bubbles.Thehydrophobicfilmalsokeepswateroutofthe wouldrequireatotalaircontentofabout6%,madeupof bubbles(B).Thestirringandkneadingactionofmechan- bothcoarseentrappedairvoidsandfineentrainedair ical mixing disperses the air bubbles. The charge around voids. However,itisthefinelyentrainedairsystemthatis eachbubbleleadstorepulsiveforces,thatpreventthe mosteffectiveatprovidingfrostresistance. 120
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