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Silva 01 Cement-Summit-Retarders3 PDF
Silva 01 Cement-Summit-Retarders3 PDF
Portland Cement
Denise Silva
Overview
1. Introduction
Examples of performance
4. Knowledge Gaps
July 29th, 2009 International Summit on Cement Hydration Kinetics, Quebec, 27-29 July 2009 2
1. Introduction
Point of view of a formulator
Development of products for cement plants: dosage constraints (~0.03 - 0.3%) and
specific technical targets
Benefits of having a model
In depth understanding of cement and SCMs hydration mechanisms and in depth
understanding of interactions mechanisms of cement x admixtures (molecular level)
Ability to design molecules for specific responses
A model would allow reduction of testing (different cements/SCMs respond differently to a
given chemical admixture) Utopia?
However
Mechanisms of accelerators and retarders are not well understood
Possible mechanisms are:
Adsorption on the surface of particles
Chelation of metal ions
Poisoning of nucleation and growth
Precipitation of insoluble salts
Change in microstructure of hydrated phases
Several variables involved:
Chemical admixture composition; chemical admixture dosage.
chemical composition, PSD, mineralogy of cement; impurities/inclusions and crystal structure
of individual anhydrous phases; presence of SCM; alkali and sulfate contents; etc.
July 29th, 2009 International Summit on Cement Hydration Kinetics, Quebec, 27-29 July 2009 3
1. Introduction
Retarders
Water soluble salts: sodium metaborate, sodium tetraborate, stannous sulfate, lead
acetate, monobasic calcium phosphate.
Salts of lignosulfonic acid (Ca, Na, NH4)
Salts of hydroxylated carboxylic acids (Na, NH4)
Carbohydrates
Accelerators
Soluble inorganic salts (chlorides, bromides, fluorides, carbonates, thiocyanates, nitrites, nitrates,
thiosulfates, silicates, aluminates, alkali hydroxides).
Soluble organic compounds (TEA, Ca formate, Ca acetate, Ca propionate, Ca butyrate)
Admixtures for shotcrete (Na silicate, Na aluminate, Al chloride, Na fluoride, strong alkalis)
July 29th, 2009 International Summit on Cement Hydration Kinetics, Quebec, 27-29 July 2009 4
2. Mechanisms of Acceleration with Calcium Chloride
Kinetic Parameters: QENS work by Peterson & Juenger (2006) with 2% CaCl2 (C3S wt)
Juenger et al, 1995: Ability of CaCl2 to flocculate hydrophilic colloids, resulting in a more
permeable C-S-H surface layer, through which water and ions can diffuse faster (higher
hydration rate during first stages of diffusion-controlled period)
July 29th, 2009 International Summit on Cement Hydration Kinetics, Quebec, 27-29 July 2009 6
2. Mechanisms of Acceleration with Calcium Chloride (cntd)
Interaction with aluminate phases:
July 29th, 2009 International Summit on Cement Hydration Kinetics, Quebec, 27-29 July 2009 7
Source: Dodson, 1990
2. Mechanisms of Acceleration with Calcium Chloride (cntd)
CaCl2 dosage effect
Limit for
reinforced
concrete
July 29th, 2009 International Summit on Cement Hydration Kinetics, Quebec, 27-29 July 2009 8
2. Mechanisms of Acceleration with Calcium Chloride (cntd)
70% slag cement
Impact of chlorides on blended cements 0.42%NaCl 0.40%CaCl2
0.02% Na-Gluconate
NaCl x CaCl2
SCN x Cl
Blank
4.00E+00
2.00E+00
Amine
1.50E+00
0.00E+00
1 3 5 7 9 11 13 15 17
July 29th, 2009 International Summit on Cement Hydration Kinetics, Quebec, 27-29 July 2009 9
Times [Hours]
2. Mechanisms of Acceleration with Calcium Chloride (cntd)
OPC High alkali cement
SCMs, alkalis, sulfates,
additives
30% C ash
30% slag
Light colors: 600ppm
CaCl2 (0.06%)
30% slag
July 29th, 2009 International Summit on Cement Hydration Kinetics, Quebec, 27-29 July 2009 10
3. Mechanisms of Retardation with Sucrose
frutose
a-glucose
July 29th, 2009 International Summit on Cement Hydration Kinetics, Quebec, 27-29 July 2009 11
3. Mechanisms of Retardation with Lignosulfonate
Lignosulfonates may contain up to 30% sugars/sugar acids
July 29th, 2009 International Summit on Cement Hydration Kinetics, Quebec, 27-29 July 2009 12
3. Mechanisms of Retardation with Na-gluconate
Impact of delayed addition (3 minutes) of Na-gluconate in two different cements
30% C ash
July 29th, 2009 International Summit on Cement Hydration Kinetics, Quebec, 27-29 July 2009 13
4. Knowledge gaps
Controversies
Different starting materials (C3A, C3S) with different reactivity
Full analysis of sulfate source not provided
Different mixing conditions
Different contents of water
Structure for complexes formed between organic molecules and cement ions not
agreed upon
July 29th, 2009 International Summit on Cement Hydration Kinetics, Quebec, 27-29 July 2009 14
4. Knowledge gaps
Impact of crystal structure
of anhydrous phases
ORTHOROMBIC C3A
CUBIC C3A
July 29th, 2009 International Summit on Cement Hydration Kinetics, Quebec, 27-29 July 2009 15
Bibliography
J.F. Young. A review of the mechanism of set-retardation in portland cement pastes containing organic
admixtures. Cem. Conc. Res. 1972, 2, 415-433.
N. Tenoutasse. The hydration mechanism of C3A and C3S in the presence of calcium chloride and calcium
sulphate. 7th ICCC, Paris, 1980. Supplementary paper II-118.
W.L. De Keyser, N. Tenoutasse. The hydration of the ferrite phase of cements. 7 th ICCC, Paris, 1980.
Supplementary paper II-120.
N.B. Singh, P.N. Ojha. Effect of CaCl2 on the hydration of tricalcium silicate. J. Mater. Sci. 1981, 16, 2675-
2681.
N.L. Thomas, J.D. Birchall. The retarding action of sugars on cement hydration. Cem. Conc. Res. 1983, 13,
830-842.
V. Dodson. Concrete Admixtures. New York: Van Nostrand Reinhold, 1990.
V.S. Ramachandran (Ed.). Concrete admixtures handbook, Noyes Publications, New Jersey, 1995.
M.R. Rixom, N.P. Mailvaganam. Chemical admixtures for concrete, E&FN Spon Ltd, London, UK, 1999.
M.C.G. Juenger, H.M. Jennings. New insights into the effects of sugar on the hydration and microstructure of
cement pastes. Cem. Conc. Res. 2002, 32, 393-399.
M.C.G. Juenger, P.J.M. Monteiro, E.M.Gartner, G.P. Denbeaux. A soft X-ray microscope investigation into the
effects of calcium chloride on tricalcium silicate hydration. Cem. Conc. Res. 2005, 35, 19-25.
V.K. Peterson, M.C.G. Juenger. Hydration of tricalcium silicate: effects of CaCl2 and sucrose on reaction
kinetics and product formation. Chem. Mater. 2006, 18, 5798-5804.
V.K. Peterson, M.C.G. Juenger. Time-resolved quasielastic neutron scattering study of the hydration of
tricalcium silicate: Effects of CaCl2 and sucrose. Phys.B, 2006, 385-386, 222-224.
M. Bishop, A.R. Barron. Cement hydration inhibition with sucrose, tartaric acid, and lignosulfonate: analytical
and spectroscopic study. Ind. Eng. Chem, Res. 2006, 45, 7042-7049.
A.J. Allen, J.J. Thomas. Analysis of C-S-H gel and cement paste by small-angle neutron scattering. Cem.
Conc. Res. 2007, 37, 319-324.
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