Modern-Concrete-Admixture-Technology--现代混凝土外加剂技术

ModernConcreteAdmixtureTechnologyJiangsuBote,NanjingApril22,2012Prof.Dr.JohannPlankChairforConstructionChemicalsTechnischeUniversitätMünchen©Prof.Plank2013Content…....…..Foamcontrolinready-mixconcrete预拌混凝土的消泡…..HighearlystrengthforCEMII/IIICEMII/III的高早强…..Ultra-highstrengthconcrete(UHPC)超高强度混凝土…..Machinerygrouts机械灌浆…..Additivesforsprayedconcrete喷射混凝土添加剂…..Self-healingconcrete自修复混凝土…..Conclusions结论Allylether–basedPCE烯丙基醚PCEMn=22,800DaMw=63,100DaPDI~2.8nEO=34©Prof.Plank2013FoamingProblemofPCEPCE的引气问题•after2hoursinready-mixtruck,upto18vol.%offoamcanbeobserved•2小时后，预拌混凝土会产生18%的气泡FoamingproblemofPCEPCE的引气问题PCEpreparedinaqueoussolutionat70°Cusing(NH4)2S2O8采用水溶液聚合法，反应温度：70°，过硫酸铵为始发剂GPCspectraofPCEasis未经提纯的PCE的GPC图谱GPCspectraofpurifiedPCE经提纯的PCE的GPC图谱PCEcontainslargeamountsofallylethermonomer此时,PCE中含有大量烯丙基醚单体PCEisfreeofresidualmonomer此时,PCE中无残留单体,strongfoaming引气严重nofoaming没有气泡产生©Prof.Plank2013ResidualMonomer:残留单体PCEPolymer:PCE聚合物•PurifiedPCEpolymerdoesnotfoam•Pureallylethermonomerdoesnotfoambut…•combinationofPCEpolymerandmonomerfoamsThesameresultwasobtainedwithMPEG-MAPCEsSolutiontothefoamingproblem:•residualmonomercontentmustbe5%•carefullyreactallmonomeror或者•usedefoamerse.g.diphenyloxidesulfonates•reactdefoamerwithPCEtoobtainachemicalbondbetweenPCEanddefoamerFoamingproblemofPCEPCE的引气问题©Prof.Plank2013解决引气问题的途径•残留单体必须小于5%•仔细控制各单体之间的反应或者•使用消泡剂•经提纯的PCE聚合物无引气现象•仅烯丙基醚单体也无引气现象•若将PCE聚合物和烯丙基醚单体混合则产生引气现象而MPEG型PCE，也有相同发现SolutionForFoamingProblem引气问题的解决方法©Prof.Plank2013Mechanism:thedefoamermustbreakuptheassociatesbetweenPCEandMPEG/macromonomer机理:消泡剂应当将PCE和MPEG/大单体之间的缔合物予以去除Forready-mixconcrete:defoamerpackage(1)Short-termdefoamereffective0–30min.(2)Long-termdefoamereffective30–120min对于预拌混凝土而言,消泡剂的使用（1）短效消泡剂的有效时间为0-30分钟（2）长效消泡剂的有效时间为30-120分钟ResultsWithDifferentDefoamers不同去消泡剂所产生的不同效果©Prof.Plank2013ResultsWithDifferentDefoamers不同消泡剂所产生的不同效果©Prof.Plank2013SpecificdefoamersalsoenhancedispersionpowerofPCEhigherconcreteflow某些消泡剂增强了PCE的分散力即提高了混凝土的流动性Content目录…....…..Foamcontrolinready-mixconcrete预拌混凝土的消泡…..HighearlystrengthforCEMII/IIICEMII/III的高早强…..Ultra-highstrengthconcrete(UHPC)超高强度混凝土…..Machinerygrouts机械灌浆…..Additivesforsprayedconcrete喷射混凝土用添加剂…..Self-healingconcrete自修复混凝土…..Conclusions结论Nano–C-S-H(X-Seed®)asActivator作为催化剂的纳米C-S-HNano–sizedC-S-Hcrystals,preparedinpresenceofPCEasnanodispersionPCE作为纳米分散剂掺入时，制备出纳米C-S-H晶体actasseedcrystalsforhydrationofC3S,C2S作为C3S,C2S发生水化反应的耔晶providehigherearlystrength(e.g.CEMII/IIIcements)提供高早强©Prof.Plank2013SEMImageofnanoC-S-H©Prof.Plank2013PreparationofNanoC-S-HUsingPCE利用PCE制备纳米C-S-HBASFPatentWO10/026155(2010)BASF专利,专利号为WO10/026155(2010)Na2SiO3+HNO3SiO2·nH2OsilicasolSiO2·nH2O+Ca(NO3)2C-S-HΔT,H2OPCEfineneedles,dispersedbyPCE©Prof.Plank2013TestResultsWithX-Seed®测试结果Increasedstrengthdevelopmentinfirstdays前期强度增加的变化曲线©Prof.Plank2013CaCO3-PCENanoCompositesMicrostructureofnacre(aragonitepolymorphsofCaCO3)©Prof.Plank2013TemplatingEffectofPCEonCalciumCarbonateMechanismofnucleation©Prof.Plank2013TemplatingEffectofPCEonCalciumCarbonateMesocrystalsofCaCO3–PCEcomposite©Prof.Plank2013Contentofpolymer[wt.%]PCEContentinCaCO3-PCENanoComposite©Prof.Plank2013TestswithcementpastesCaCO3-PCECompositesasAdmixtureforOPCw/c=0.67w/c=0.53CementA+2wt.%CaCO3+2wt.%CaCO3-23PC7CementB+2wt.%CaCO3+2wt.%CaCO3-23PC7Time[h]Time[h]Compressivestrength[N/mm2]©Prof.Plank2013ParticlesofcompositematerialsCaCO3-PCECompositesasAdmixtureforOPCContent目录…....…..Foamcontrolinready-mixconcrete预拌混凝土的消泡…..HighearlystrengthforCEMII/IIICEMII/III的高早强…..Ultra-highstrengthconcrete(UHPC)超高强度混凝土…..Machinerygrouts机械灌浆…..Additivesforsprayedconcrete喷射混凝土用添加剂…..Self-healingconcrete自修复混凝土…..Conclusions结论UltraHighPerformanceConcrete(UHPC)超高强度混凝土•Compressivestrength150Mpa•Water/cementratio0.25•Denseparticlepacking©Prof.Plank2013•抗压强度150MPa•水灰比0.25•颗粒紧密堆积Ultra-HighStrengthConcreteFormulation超高强度混凝土制备L/m³158water-0.19w/cementw/(cement+microsilica)kg/m³194steelfibres(2.5vol.-%)kg/m³325quartzd50=15µmkg/m³354quartzsand0.125/0.50mmkg/m³177Microsilicakg/m³650CEMI52.5RHS/NAunitkg/m³597basalt2/8mmkg/m³30,4superplasticizerkg/m³131quartzd50=60µm©Prof.Plank20130.22SilicaFumeSamplesSF1andSF2硅粉样品:SF1和SF2SF1SF2PropertySF1SF2Cementspecificsurfacearea,BET[m2/g]16241.3d50[nm]237846.750©Prof.Plank2013nSO3NaCOONaOOCH3OCH3CH3CH3abc=45a:b:c=12:1:3•MethacrylateesterPCE•Wormpolymer•Mn=12.000g/mol•Anionicchargeamount1200µeq/gincementporesolutionabcPCE11ChemistryofMA-PCESamplePCE11MPEG型PCE样品；PCE11©Prof.Plank2013•甲基丙烯酸/烯酸甲酯PCE•蠕虫型聚合物•分子量:12.000g/mol•阴离子电荷量:1200µeq/g(在水泥孔隙溶液中)•AllyletherPCE•Starpolymer•Mn=8.000g/mol•Anionicchargeamount65µeq/gincementporesolutionnCOONaCOONaOOCH3aba:b=1:1=34abPCE21ChemistryofAE-PCESamplePCE21APEG型PCE样品：PCE21©Prof.Plank2013•烯丙基醚PCE•星型聚合物•分子量:8.000g/mol•阴离子电荷量:65µeq/g(在水泥孔隙溶液中)EffectivenessofPCEsinUHPCPastePCE在超高强度混凝土Methacrylate-basedPCEisveryeffectivewithcement甲基丙烯酸/烯酸甲酯PCE对水泥的分散性较好Allyether-basedPCEismoreeffectivewithmicrosilica烯丙基醚PCE对微硅粉分散性较好PCEdosageforpasteflow26cm00,20,40,60,811,2PCE11PCE21Dosage[wt.-%bwoc]CementCement+MS1Cement+MS2©P