US010336652B2 (12 ) United States Patent (10 ) Patent No. : US 10 , 336 ,652 B2 Berodier et al. (45 ) Date of Patent: Jul. 2 , 2019 ( 54 ) ENHANCING CALCINED CLAY USE WITH 8 ,435 , 930 B2 * 5/ 2013 Woytowich .. C04B 28/ 02 106 /681 INORGANIC BINDERS 8 , 906 , 155 B2 12 /2014 Gasafi et al . ( 71 ) Applicant: GCP Applied Technologies Inc ., 9 ,212 ,092 B2 12 / 2015 Herfort et al. Cambridge , MA (US ) FOREIGN PATENT DOCUMENTS ( 72 ) Inventors : Elise Berodier , Lausanne (CH ) ; CN 103613303 A * 3 /2014 Josephine H . Cheung , Lexington , MA EP 3109216 6 /2015 (US ) ; Nathan A . Tregger , KR 101219673 B1 * 1 / 2013 Northborough , MA (US ) WO 2016206780 6 / 2016 ( 73 ) Assignee : GCP Applied Technologies Inc ., OTHER PUBLICATIONS Cambridge , MA (US ) Sabir, B . B ., Wild , S . , & Bai, J ., Metakaolin and calcined clays as pozzolans for concrete: a review . Cement and Concrete Composites , ( * ) Notice : Subject to any disclaimer , the term of this 23 ( 6 ) , 441- 454 , 2001 . patent is extended or adjusted under 35 Siddique , R . , & Klaus , J . , Influence of metakaolin on the properties of mortar and concrete : A review . Applied Clay Science , 43 ( 3 ) , U . S . C . 154 ( b ) by 0 days. 392 -400 , 2009 . T . Chappex , K . L . Scrivener , The effect of aluminum in solution on (21 ) Appl . No. : 15 / 809, 530 the dissolution of amorphous silica and its relation to cementitious systems, J . Am . Ceram . Soc . 96 ( 2013 ) 592 - 597 . doi : 10 . 1111/ jace . (22 ) Filed : Nov . 10 , 2017 12098 . L . Nicoleau , E . Schreiner , A . Nonat , Ion - specific effects influencing Prior Publication Data the dissolution of tricalcium silicate , Cem . Concr . Res . 59 (2014 ) (65 ) 118 - 138 . doi: 10 . 1016 / j. cemconres .2014 .02 . 006 . US 2019 /0144334 A1 May 16 , 2019 Snellings, R ., Solution - controlled dissolution of supplementary cementitious material glasses at pH 13 : The Effect of Solution (51 ) Int. Ci. Composition on Glass Dissolution Rates . Journal of the American Ceramic Society , 96 ( 8 ) , 2467 - 2475 , 2013. C04B 14 / 10 ( 2006 .01 ) Kyle Riding, Denise A . Silva , Karen Scrivener, Early Age Strength C04B 24 / 12 ( 2006 .01 ) Enhancement of Blended Cement Systemsby CaCl2 and Diethanol C04B 24 / 28 ( 2006 .01 ) isopropanolamine; Cement and Concrete Research 40 ( 2010 ) 935 C04B 28 / 04 ( 2006 . 01 ) 946 , 2010 . C04B 103 / 32 ( 2006 .01 ) ( 52 ) U . S . CI. * cited by examiner CPC . .. .. C04B 14 / 10 ( 2013 .01 ) ; C04B 24 / 122 Primary Examiner — Anthony J Green ( 2013 .01 ) ; C04B 24 / 283 (2013 .01 ) ; C04B 28 / 04 ( 2013. 01 ) ; C04B 2103/ 32 ( 2013 .01 ) ( 74 ) Attorney , Agent, or Firm — Craig K . Leon (58 ) Field of Classification Search (57 ) ABSTRACT CPC . .. .. C04B 14 / 10 ; C04B 28 / 04 ; C04B 24 / 383 ; The present invention discloses cementitious compositions C04B 24 / 122 ; C04B 2103 / 32 which contain hydratable cement, limestone , or mixture See application file for complete search history . thereof, having improved strength properties due to the presence of calcined clay and certain higher alkanolamines , (56 ) References Cited wherein the calcined clay has an Fe20 , content of greater than one percent ( 1 % ) . Also disclosed are exemplary addi U . S . PATENT DOCUMENTS tives and methods for enhancing strength of cement and /or 4 ,642 , 137 A 2 / 1987 Heitzmann et al . limestone compositions. 5 ,626 , 665 A 5 / 1997 Barger et al . 6 , 048 ,393 A 4 / 2000 Cheung et al . 17 Claims, 6 Drawing Sheets atent Jul. 2 , 2019 Sheet 1 of 6 US 10 ,336 ,652 B2 2500 . 0 2000 . 0 YYYYYYYYYYYYYYYYYY Alconcentration(umol/gclay) 1500 . 0 1000 . 0 500 . 0 20 30 40 Time (hours ) Key A : Calcined Clay 3 B : Calcined Clay 3 with DEIPA FIG . 1A atent Jul. 2 , 2019 Sheet 2 of 6 US 10 ,336 ,652 B2 2000 . 0 1800 . 0 1600 . 0 1400 . 0 1200 . 0 Siconcentrationumol(/gclay) 1000 . 0 10203040 Time ( hours ) Key A : Calcined Clay 3 B : Calcined Clay 3 with DEIPA Fig . 1B atent Jul. 2 , 2019 Sheet 3 of 6 US 10 ,336 ,652 B2 50 .0 45. 0 40 . 0 35 . 0 30 . 0 Feconcentration(umol/gclay) 25. 0 20. 0 15. 0 10 . 0 5 . 10203040 Time ( hours ) Key A : Calcined Clay 3 B ; Calcined Clay 3 with DEIPA Fig . 1C U. S . Patent atent Jul. 2 , 2019 Sheet 4 of 6 US 10 ,336 ,652 B2 HeatFlow(mW/gofcement) w * B www. c . D 10 15 20 Time (hours ) Key A : Blank sample with Calcined Clay 1 B : DEIPA sample with Calcined Clay 1 C : TEA sample with Calcined Clay 1 D : TIPA sample with Calcined Clay 1 Fig . 2 atent Jul. 2 , 2019 Sheet 5 of 6 US 10 ,336 ,652 B2 HeatFlow(mW/gofcement) Time ( hours ) ??? A : Blank sample with Calcined Clay 2 B : DEIPA sample with Calcined Clay 2 Fig . 3 U. S . Patent atent JulJul .. 2, , 2019 2019 Sheet 6 of 6 US 10 ,336 ,652 B2 www : : : : : : : : : : : : : : Compressivestrength(MPa) ??????? tedeti TiXX ** ** * * * * ** * ** * * * * * HUU ??????????????????????????????????????????????????????????????????????????????????????? -W Time (days ) Key A : OPC B : Limestone Calcined Clay 1 Cement C ; Limestone Calcined Clay 1 Cement and DEIPA D : Limestone Calcined Clay 1 Cement and TIPA E : Limestone Calcined Clay 1 Cement and TEA Fig. 4 US 10 , 336 ,652 B2 ENHANCING CALCINED CLAY USE WITH have improved strength properties at both early ages ( e . g ., 1 , INORGANIC BINDERS 3 , and 7 days ) and later ages ( e . g . , 28 day ) . The positive effect that the use of a higher alkanolamine such as diethanolisopropanolamine ( otherwise known as FIELD OF THE INVENTION 5 N , N -bis ( 2 - hydroxyethyl ) - 2 -hydroxypropylamine , or The invention relates to the field of construction materi “ DEIPA ” ) was found by the present inventors to have on the pozzolanic reactivity of calcined clay would not have been als , and more particularly to methods and systems for predicted in view , for example , of a study entitled “ Early age enhancing the use of calcined clay in hydratable cementi strength enhancement of blended cement systems by CaCl, tious compositions. 10 and diethanolisopropanolamine , ” by Riding et al . in Cement and Concrete Research , 2010 , which demonstrates that the BACKGROUND OF THE INVENTION impact of DEIPA on the pozzolanic reaction is not signifi cant at early ages . This shows that the SCMs are basically It is known to use calcined clay as a clinker substitute for inert at this early age . making cement or otherwise combining with cement, which 15 The present inventors discovered that calcined clay did is the binder that holds together aggregates in concrete and not need to be used with calcium chloride or other salt in mortar compositions. The following patents provide order for its pozzolanic activity , in combination with cement examples . and / or limestone , to be enhanced , but that surprisingly it was U . S . Pat. No . 4 ,642 , 137 of Heitzmann et al . taught a required that the calcined clay have at least one percent ( 1 % ) binder composition that included portland cement in com - 20 content of iron oxide in the form of Fe ,Oz . Indeed , this was bination with metakaolin and at least one material selected surprising , given that iron , which imparts a reddish color to from fly ash , calcined shale , and calcined clay, among other clays, usually is considered to reduce the reactivity of clays. components . For example , the detection of red color will limit the use of U . S . Pat. No . 5 ,626 ,665 of Barger et al. taught cementi - a clay in the ceramics and cement industries due to its lower tious systems comprising gypsum , calcined clay , and clinker 25 reactivity . consisting essentially of hydratable calcium silicates . The The main components of calcined clay are alumina and systems of this invention were described as having a water silica . It has been previously demonstrated that the presence demand of less than about 33 % nc (normal consistency ) ; of alumina decreases the dissolution rate of silica (See e . g . , one - day strengths of at least about 1000 psi ; and low alkali “ Solution - controlled dissolution of supplementary cementi functionality . By increasing the amount of calcined clay , the 30 tious material glasses at pH 13 : The effect of solution resulting cementitious system was believed sequentially to composition on glass dissolution rates ,” by Snellings, Jour gain alkali non -reactiveness , alkali resistance, and low chlo - nal of the American Ceramic Society, 2013 ; See also " Ion ride permeability . specific effects influencing the dissolution of tricalcium U . S . Pat . No . 8 , 906 , 155 of Gasafi et al . taught a method silicate , " Nicoleau et al. , Cement and Concrete Research , for producing a clinker substitute which included pre - drying 35 2014 ; See also “ The Effect of Aluminum in Solution on the clay with an iron content greater than 1 . 5 wt- % to a moisture Dissolution of Amorphous Silica and its Relation to Cemen level of less than 10 wt- % , comminuting the clay to a grain titious Systems, ” Chappex et al ., Journal of the American size of less than 2 mm , calcining it in a furnace at 600 - 1000º Ceramics Society, 2013 ) . It was thus believed that the C . , and then cooling the resultant material. pozzolanic reaction in cementitious materials is limited due U . S . Pat . No. 9 , 212 , 092 of Herfort et al. taught a cemen - 40 to the decreased dissolution rate of silica . titious composition having portland clinker cement and However, the present inventors surprisingly discovered supplementary cementitious material which comprised heat that the dissolution rate of silica is maintained and even treated clay and optionally heat treated carbonate material. increased in the presence of a higher alkanolamine , such as The clay became substantially dehydroxylated while the diethanolisopropanolamine (otherwise known as N , N -bis ( 2 optionally heat - treated carbonate material remained substan - 45 hydroxyethyl) - 2 -hydroxypropylamine , or “ DEIPA ” ) , even tially carbonated ; this could be accomplished by premixing with the increase of the alumina concentration .