US «i» United States « Farrington et al. (5) ACCELERATING ADMIXTURE FOR CONCRETE (73) Inventors: Stephen A. Farrington, Univesity Heights, OH (US); Bruce J Christensen, Soloa, OH (US) Correspondence Address: JOSEPH G CURATOLO, ESQ. RENNER KENNER GREIVE BOBAK TAYLOR & WEBER 24500 CENTER RIDGE ROAD, SUITE 280 WESTLAKE, OH 44148 (US) (73) Assignoe: MBI Holding AG, Zurich (CH) (21) Appl. Nos 108388,585 22) Filed: Feb. §, 2003 NOMOL491 74% Patent Application Publication co Pub. No.: US 2004/0149174 AL 43) Pub, Date: Aug. 5, 2004 (1) Incl? Co4B 7/00; COB 16,00; Coats 24/00; COsB 24/10 (2) US. 106/802; 1067808; 10682: 52455 on ABSTRACT Accold-weather admixture composition that aeelerates the selling time and streagth development of cementitious com- positions i provided whieh comprises the components of a Soluble inorganic salt having freezing point depressing prop- enties, an inowganic early set and stength aoocleatoe, a polycarboxylate high range water reducing dispersant, and An organic et accelerator, With lower dosages of dispersant than those disclosed in the prior art the admixture compo- sition provides to concrete inteased dispersant erforman and acceleration of seting time and strength development.US 2004/0149174 AI ACCELERATING ADMIXTURE FOR CONCRETE, BACKGROUND [0001] The placement of concrete under cold-weather ‘conditions eals fr special considerations to ensure proper hardening and strength development. Committee 306 of the American Concrete Insitute defines cold-weather condi- tions as three consecutive days where two eondtions must ‘occur-—ibe average daily air temperature is less than 5° C, And the airtemperature doesnot exceed 10" C. for more than twelve hours in any 24-hour period. Under cold-weather ‘conditions, the concrete as tobe protected to avoid damage ‘due to freezing at early ages, ensure that adequate strength ‘will be realized for removal of formwork, avoid thermal ‘racking, ancl ensure that the structure will meet its service life requirements, Protective measures include 1) heating of the concrete materials, 2) use of Type IIT cement, 3) use of adsitional cement, 4) use of chemical aclmixtures that accel- ‘erate seting and srength development, 3) use of provective insulation, and 6) enclasing and heating the area in which the eonerete will be placed [0002] Over the past ten years, developments in the field ‘of chemical admixtures for use in placement of concrete under sub-freezing conditions have been reported. Many of these studies have focused on a group of chemicals that bot lower the freezing point of the pore water of conerete and accelerate the hydration of cement, while ether studies have focused on materials that provide acceleration without freez- jing point reduction. Inthe majority ofthe studies presented the literature, the concrete was batched at 20° C-and then ‘cured af subficezing temperatures, and strength develop- ‘ment was compared to concrete Ihat was cured at 20° C. Under these testing conditions, the results may be mislead- ing, as setting and strength development are governed by ‘concrete temperature, and the effect of the ambient condi tions on the lowering ofthe concrete temperature is depen- ‘dent on the conerete mass and specimen geometry. In one sludy, the concrete was hatched wit frozen materials, and ‘strength development in the conecete with the antifreeze admistures developed poorly. [0003] Dispersants are substances that improve the flow ‘characteristics ofthe cement paste by breaking up cement sgalomerates and freeing the Water, ths providing a paste of| lower viscosity and allowing desirable flow coneitions to be ‘obtained. Superplasticiers such as sulfonated melamine formaldehyde condensate (SMF) and naphthalene sul- fonated formaldehyde condensate (BNS) are commonly used as dispersants. However, these compounds are not as ‘efficient as polycarboxylate dispersant that have been into ‘duced to the concrete industry more recenly. The standard rule in the industry that is used 10 compare dispersant performance of palycarhoxylates versis sulfonated naphths Tene formaldehyde condensates is thatthe polyearboxylates are thre times more ecient om an equivalent sacs basis. [0004] 1s important that dispersant are used in conerete Jn situations where strength and durability ae involved, as “dispersants are 4 necessary component ia high stength ind high durability coneretes. Due to the use of low water amounts in the high performance concretes, high dispersant mounts are sometimes necessary to achieve workable con- ‘retes. High BNS levels can lead to undesirable retardation ‘of stand may not provide the required workability retention ‘overtime, Aug. 5, 2004 [0005] 11 is desirable to provide an admixture with a polyearboxylate high range water reducing dispersant that is a least several times more elicent as a cement or concrete isporsant than the tational materials like BNS and SMF. Improving ellicieney reduces the amount of material required to achieve a desired level of eonerete workability oF ‘water reduction, With respect o the presently used dispers- nls, BNS and SMF, it is also desirable to improve the siting time ofthe conerete (accelerating) while maintaining the desired siregth development [0006] US, Pat. No. 5,176,753 discloses a chloride-tree admixture for use a8 a cold weather concrete set accelerator Which comprises a soluble inorganic salt having freezing point depressant properties, a naphthalene sulphonate Form: aldeiyde condensate or sulphonated melamine formalde- hyde condensate, inorganic ealy set and stength aceelers- tor, and optionally an organic set accelerator. [0007] USS. Pat. No, 5,840,114 discloses 4 high early strength admixture for precast hydraulic cement which com- prises a calcium salt and a copolymer having a carbon containing backbone to whieh are atacied cement-anchor- ng members, suc as carboxyl groups an to which are also hed oxyalkylene pendant groups by linkages selected from the group consisting of amide and imide members. ‘SUMMARY, [0008] An admixture composition dhat accelerates the set ting time and stength development of cementitious com- positions under cold weather conditions is proved which ‘comprises the components of soluble inorganic salt having Ireezing point depressing properties, inorganic early set and stwngil acevlerator, polyearboxylate high range water reducing dispersant, and organic set accelerator, [0009] A cementitious composition is provided that com- prises hydraulic cement and a cold weather admixture ccompositio, wherein the admixture composition comprises soluble inorganic sat having freezing point depressing prop- eis, inowganie early set and strength accelerator, polyear- boxylate high range water reducing dispersant, and organic sot aocelerator [0010] _A method of making a cementitious composition is provided which comprises forming a mixture of water, bnydraulic cement aod a cold weather admixture composition ‘wherein the admisture compesition comprises soluble inor ganic salt having freezing point depressing properties, inot ganic early set and steenglh accelerator, polyearboxylate high range water reducing dispersant, and organic set accel- [0011] _A cold weather admixture composition for cemen- ‘ious compositions & provided which comprises soluble inorganic salt having freezing point depressing properties, ‘inorganic early set and strength accelerator, a polyearbo le high range water reducing dispersant; wherein the polyearboxylate high range water reducing dispersant bas the general structure shown below:US 2004/0149174 AI 7 [0012] wherein in Fosrmula (I): [0013] D=a component selected from the group con- sisting of the structure dl, the structure d2, and mixtures thereof; [0014] XH, CH, C. to C, Alkyl, Phenyl, p-Metby Phenyl, or Sulfonated Phenyl; [0015] Y-11 or —cooM; [0016] Re or CH, [0017] ZH, —SO.M, —P0,M, —cooM, O(CH),OR, where 22 W 6, [0018] —COOR,, or {CH),OR, where n=0 10 6 [0019] — contin, —coniic(ci): CH.SO,M, —COO(CHR), OH where n=? 106, o¢ O(CH),OR, wherein =? 65 {oo20] Ry, Roy Rov Re are cach imlependenly —(CURCH_G},R, random copolymer of oxvetbye ne unitsandoxypiopylene unis where m=10 to 500 nd wherein the amount of oxyethyene inthe rn- ddom enpolymer from about 6% to TOF ad the mount of oxypropslene inthe random copmymer from Of wo about 0%; {0021} RyrHl, Methyl, C. about C, Allyl or about Coto about Co ar [0022] MoH, Alkali Metal, Alkaline Earth Metal, “Ammonium, Amine, trthanol amine, Methyl, oF Cs twahout Alby: {0023} a0 0 about 08: {0028} besbout 02 to sot 1.0, [0025] C=0 1 about 05; {0026] 0 about 05; and {0027} wherein a,b, and d represent the mote fraction of each unit athe sum of 3, ,e, and dis 10; an an onganic et accelerator [0028] A cementitious composition is provided which ‘comprises hydraulic cement and a cold weather admixture ‘composition, said mixture composition comprising! soluble inoeganie salt having freezing point depressing prop- certes, inorganic early set and strength accelerator, a poly Aug. 5, 2004 carboxylate high range water reducing dispersant; where the high range water reducing dispersant is « polyearboxy- late high range water reducing dispersant and bas the general siruetuse shown below: eats [0029] wherein in Formula (I: [0030] =a component selected from the group con- sisting of the structure di, the structure 43, and mixtures thereof; [0081] _X=H, CH,, C. tC, Alkyl, Phenyl, p-Metby Phenyl, or Sulfonated Phenyl, [0032] Y-11 or —cooM; [0033] RH o¢ CH: [0034] Z-H, —SO.M, —PO.M, —cooM, —O(CH),OR, where 22 6, [002s] —coor,, or (CH [0036] —conniR,, —CONHC(CH,)- CH,SO,M, —COO(CHR,), 011 where n=2 10'6, or —O(CH,OR, wherein he? to 6; [0037]. R,, Ray Ray Ry are each independently —(CHRCHO),.R, random copolymer of oxyethyl- ‘ene units and oxypropylene units where m=10 to 500 tnd wherein the amount of oxyethylene in the an ‘dom copolymer is from about 60% to 100% and the amount of oxypropylene in the random copolymer is from 0% 40 about 405%; [0038] R,-H, Methy!, C, to about C, Alkyl or about Gq 0 about Cio acyl [0039] MeH, Alkali Metal Alkaline Earth Metal, ‘Ammonium, Amine, rethanol amine, Methyl, or tw about C, Alkyl; [0040] a0 to about 08; [0041 [0082] c=0 10 about 05; [0043] dO to about 05; and [0044] wherein a, b, ©, and d represent the mole fraction of exch unit snd the sum of a,b,c, and d is 110; and an organic set accelerator. ),OR, where n= 10