Impact of Accelerators and Retarders on the Hydration of

Portland Cement

Denise Silva
Overview
1. Introduction

2. Mechanisms of Acceleration with Calcium Chloride

Latest theories about the mechanisms

Examples of performance

3. Mechanisms of Retardation with Sucrose and Lignosulfonate

Latest theories about the mechanisms

Examples of performance with retarders

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)

Goal for this presentation

Present a brief glance on the complexity of hydration of cement in the presence of admixtures
Highlight some knowledge gaps preventing modeling

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)

V.K. Peterson, M.C.G. Juenger. Chem. Mater. 2006, 18, 5798-5804

Length of induction Rate of formation of Length of nucleation Degree of hydration at Diffusion

period hydrated phases (BWI) and growth period early ages coefficient

More permeable (higher SSA) hydrates

July 29th, 2009 International Summit on Cement Hydration Kinetics, Quebec, 27-29 July 2009 5
 2. Mechanisms of Acceleration with Calcium Chloride (cntd)
More permeable C-S-H with CaCl2:

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)

M.C.G. Juenger et al. Cem. Conc. Res. 2005, 35, 19-25

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:

Chlorides participate of aluminates reactions, forming chloroaluminate phases mostly when

sulfate available is not enough to react with C3A. Ettringite will not convert to monosulfate if
free chlorides are available (Tenoutasse, 1980).

Uptake of CaCl2 by C3A (no sulfates

present)

V. Dodson. Concrete Admixtures, 1990.

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

Non linear dose x

performance for vast
majority of systems

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

50% slag cement Amine:NaCl

3.50E+00

Amine:CaCl2 600ppm Cl-

Amine:NaSCN
3.00E+00

700ppm SCN- Blank

2.50E+00
Power [mW/g]

2.00E+00
Amine

1.50E+00

1.00E+00 Same impact on

mortar strength
5.00E-01
regardless the type
of salt

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%)

SCM content and 30% F ash

characteristics play key
role in the interaction with
chemicals

Fly ash presents a huge

challenge on its own
Particle to particle Low alkali cement
variation OPC

Presence of contaminants 30% F ash 30% C ash

(e.g. carbon particles)

30% slag

July 29th, 2009 International Summit on Cement Hydration Kinetics, Quebec, 27-29 July 2009 10
 3. Mechanisms of Retardation with Sucrose

Impact on kinetics Mechanisms of interaction with Mechanisms of

C3S interaction with C3A
QENS of C3S with 0.01 and 0.05% sucrose: Chelation of Ca2+ & adsorption onto C-S- Accelerates ettringite
Longer induction period; increased rate of H and CH nuclei (growth poisoning). formation due to
formation of hydrated phases; longer More nuclei form. Heterogeneous growth consumption of Ca2+ from
nucleation and growth period, resulting in after sucrose depletion: delayed gypsum.
higher degree of hydration after this period. accelerator.
Formation of interlayer
Higher diffusion coefficient.
complexes with hydrated
aluminate phases.

frutose
a-glucose

M.C.G. Juenger, H.M. Jennings, Cem. Conc.

V.K. Peterson, M.C.G. Juenger. Chem. Mater. 2006, Res. 2002, 32, 393-399.
18, 5798-5804

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

Mechanisms of Strong retardation of C3S

interaction with hydration.
C3S Adsorption of sulfonate and OH
groups onto C-S-H and CH,
possibly incorporating into the C-
S-H gel layer. Possible formation
of a more impermeable hydrated
Adsorption of LS on
layer on cement grains (diffusion
OPC
barrier to hydration)
Chelation of Ca2+ by the
polymer.
M.R. Rixom, N.P. Mailvaganam, 1999
Bishop and Barron, 2006

Mechanisms of Strongly adsorbs on AFt and

interaction with AFm phases (C3A is said to be a
sink for LS). Molecules can
C3A
enter the layers of aluminate
hydrates (intercalation).
Delayed addition of LS reduces
adsorption onto aluminate
phases: more LS to retard C3S

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

Mechanisms of hydration with very high dosages of admixtures

Non-linearity in dose x performance

Structure for complexes formed between organic molecules and cement ions not
agreed upon

Timing factor: delayed addition of chemicals

More than one admixture in the same system: synergistic effects?

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

V.K. Peterson, M.C.G. Juenger. Chem. Mater. 2006, 18, 5798-5804

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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