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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 ...

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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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...Chap qxd eb pm page chapter chemical admixtures for concrete chemicaladmixturesarethoseingredientsinconcrete themajorreasonsforusingchemicaladmixturesin other than hydraulic cement supplementarycementitious mixtures are materials scms water aggregates and fiber reinforce toachievecertainpropertiesinconcretemoreeffec mentthatareaddedtothemixtureimmediatelybeforeor tively by means duringmixing figure thereareavarietyofchemical tomaintainthequalityofconcreteduringthestages admixturesavailableforuseinconcretemixturestomod of mixing transporting placing finishing ify fresh hardened properties ad curing especially in adverse weather conditions or mixturescanbeclassifiedbyfunctionasfollows intricate placements air entraining toovercomecertainemergenciesduringconcreting normal mid range andhigh rangewater reducing operations set accelerating economy retarding despitetheseconsiderations noadmixtureofanytypeor hydration control amountisasubstituteforgoodconcretingpractice rheologymodifying corro...

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