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CALCUM SULFOALUMNATE CEMENT HYDRATON N THE PRESENCE OF FLY ASH

Marta Garca-Mat*, Isabel Santacruz*, ngeles G. De la Torre, Miguel A.G. Aranda Departamento de Qumica Inorgnica, Cristalografa y Mineraloga, Facultad de Ciencias, Campus de Teatinos s/n, University of Malaga, 29071 Malaga, Spain *e-mails: martagmate@uma.es, isantacruz@uma.es
Introduccin
Calcium sulfoaluminate (CSA) cements are receiving increasing attention since their manufacture produces less CO2 than ordinary Portland cement (OPC) [1]. These binders may have quite variable compositions, but all of them contain Yeelimite phase, also called Kleins salt or tetracalcium trialuminate sulfate (C4A3S) as the main phase [2]. They may also have minor amount of phases such as C2S, CA, C4AF, CS, CSH2 [3], where C=CaO, S=SiO2, A=Al2O3, F=Fe2O3, S=SO3, M=MgO, T=TiO2 and H=H2O. The mortar and concretes derived from these cements show high strength developments at early-ages [4] and could also be used for radioactive element encapsulation [5]. Another environmental strategy for reducing the negative impact of the cement industry is related with the reduction of the clinker content in concretes [6]. This is possible by the partial substitution of cement by supplementary cementitious materials (SCMs) mainly from power stations or metal industry (fly ash, slag or silica fume). The environmental benefits of the use of waste materials are two folds: the clinker reduction will produce lower CO2 emissions; and the valorization of an useless product. Furthermore, fly ash improves some properties of OPC mortars and concretes due to the pozzolanic reaction and its role as a micro-filler. Objetive This work deals with the study of the potential pozzolanic effect of fly ash (FA) on CSA cement pastes and mortars. This will allow the fabrication of environmentally friendly cements (by the use of CSA clinker and its partial substitution with by-products), and mortars with improved mechanical properties at long ages.

Pastes and mortars preparation


Quartz Mullite Quartz Magnesium ferrite Hematites Mullite Lime Mullite Quartz Mullite Mullite Quartz Periclase C4A3S Gypsum

Hydration studies (pastes) qualitative approach


AFt Gibbsite C4A3S CSH2

Hydration studies (pastes) quantitative approach


0 wt% FA, w/b=0.65
Minor initial phases: CT + M + C2MS2 +C4AF
Minor Initial phases CSH2 C4A3S Amorphous ? -C2S FW

DTA-TGA
0 wt% FA, w/b=0.50
28 days

X10E 3 3 .0

0 wt% FA, w/b=0.65

Gypsum

Gypsum

Mullite

Quartz

Mullite

Gypsum

C4A3S

Mullite

Mullite

2 .0

C4A3S

C4A3S

28d
wt%

Gibbsite

CO2

C o u n ts

0 .0

1 .0

20.0 2-Theta, deg

30.0

40.0

7d
Gibbsite

AFt

(BELITH S.P.R.L., Belgium)

CSA Clinker

Gypsum 25 wt%

Fly Ash

(Lada, Spain)

0 wt% 15 wt% 30 wt%

3d
10 20

Vaterite

AFt

days

30

40

0.50 Water/binder 0.65 (without FA) (w/b) Sand Hydration time: Mortar 3, 7, 28 days To be 6 months, 1 year

AFt Gibbsite C4A3S CSH2

0 wt% FA, w/b=0.50

0 wt% FA, w/b=0.50


Minor initial phases: CT + M + C2MS2 +C4AF

15 wt% FA, w/b=0.50


28 days

28d

CSH2 C4A3S

Minor initial phases

-C2S FW

CO2 Gibbsite

wt%

Cement Pastes

7d

Amorphous

Rietveld methodology Compressive Strength LXRD Amorphous quantification (G-factor) Calorimetry TDA-TGA Porosimetry

measured

AFt

3d
10 20

Gibbsite Vaterite
30 40

AFt

days

Calorimetry (pastes) 7 days


1.0x10-2
Normalized Heat Flow (W/g)

AFt Gibbsite C4A3S CSH2

15 wt% FA, w/b=0.50

15 wt% FA, w/b=0.50


Minor initial phases: CT + M + C2MS2 +C4AF SCM crystalline phases: Mullite + Quartz
SCM Phases CSH2 C4A3S Minor initial phases -C2S FW
AFt

Rietveld
15 wt% FA, w/b=0.50
3 days

1.0x10-2

8.0x10

-3

300
0 wt% FA, w/b=0.50 15 wt% FA, w/b=0.50 30 wt% FA, w/b=0.50

28d

Normalized Heat Flow (W/g)

6.0x10

-3

4.0x10-3 2.0x10-3 0.0 0.0

200 150 100


0.5 1.0
time (days)

2.0x10-3 0.0 0 2

0 wt% FA, w/b=0.50 15 wt% FA, w/b=0.50 30 wt% FA, w/b=0.50

1.5

2.0

AFt

50 0

10

12

14

10

12

14

time (days)

time (days)

3d
10 20

Vaterite

Gibbsite

days

Porosimetry (pastes)
Compressive Strength (MPa)
Open Porosit y* (vol %) 20.3 14.7 17.4 18.8

Compressive Strength - Mortars


0 wt% FA, w/b=0.65 0 wt% FA, w/b=0.50 15 wt% FA, w/b=0.50 30 wt% FA, w/b=0.50

30

40

AFt Gibbsite C4A3S CSH2

30 wt% FA, w/b=0.50

30 wt% FA, w/b=0.50


Minor initial phases: CT + M + C2MS2 +C4AF SCM crystalline phases: Mullite + Quartz
SCM Phases CSH2 C4A3S
AF t Gypsum AFt

15 wt% FA, w/b=0.50


28 days

PASTE 0 wt% FA, w/b=0.65 0 wt% FA, w/b=0.50 15 wt% FA, w/b=0.50 30 wt% FA, w/b=0.50

80 60 40 20 0

AFt

28d
wt%

Minor initial phases

-C2S FW

AFt

AFt

4.0x10-3

0 wt% FA, w/b=0.50 15 wt% FA, w/b=0.50 30 wt% FA, w/b=0.50

AFt

7d

Amorphous

AFt Gibbsite AFt Gibbsite Gypsum AFt AFt C A 4 3S AFt AFt Vaterite AFt Quartz Vaterite AFt

AFt

7d

Amorphous

AFt

AFt Gibbsite

3d
1 3

Vaterite

days
10 20

* Mercury Intrusion Porosimetry

days

3d3

2 7

3 28

30

40

- Pastes ( 28 days). By Increasing FA content: Normal heat flow decreases (due to the lower hydraulic active matter) Amorphous/non-diffractive matter content increases. Weight loss decreases (for the same w/b) according to TGA. Open porosity increases. - Mortars ( 28 days). By Increasing FA content: Compressive strength values decrease. However, it may be expected a different behaviour at longer hydration times (6 months).

Conclusions

References
[1] Gartner E., Cem. Concr. Res. 2004, 34, 1489. [2] lvarez-Pinazo G., Cuesta A., Garca-Mat M., Santacruz I., Losilla E.R., De la Torre A.G., Len-Reina L., Aranda M.A.G., Cem. Concr. Res., 2012, 42, 960. [3] Sahu S., Majling J., Cem. Concr. Res., 1993, 23, 1331. [4] Glasser F.P., Zhang L., Cem. Concr. Res., 2001, 31, 1881. [5] Zhou Q., Milestone N.B., Hayes M., J. Hazard. Mater., 2006, 136, 120. [6] Bensted J., Barnes P., Structure and performance of cements. 2002, 2nd ed. New York: Spon Press.

Acknowledgements
This work has been supported by Spanish Ministry of Science and Innovation through MAT2010-16213 research grant, which is cofunded by FEDER, and Ramn y Cajal Fellowship (RYC-2008-03523).

AFt

Gypsum

Gypsum

AFt Gibbsite AFt Gibbsite Gypsum AFt AFt C4A3S AFt AFt Vaterite AFt Quartz Vaterite AFt Gypsum AFt Gypsum

wt%

AFt Gypsum AFt

AF t

8.0x10-3

6.0x10-3

250