(How) Can C-S-H Growth Behavior Be Predicted?: Questions From A Modeling Perspective

(How) Can C-S-H Growth Behavior Be Predicted?
Questions from a Modeling Perspective

Jeff Bullard Materials and Construction Research Division National Institute of Standards and Technology Gaithersburg, Maryland USA
VCCTL Consortium
Objectives of Modeling
Primary purposes of modeling are to: Gain Insight: Distill real system into one with simpler physics/chemistry that you think are relevant. Analyze behavior of model to better understand qualitative behavior of the real system. Represents a research tool. Predict: Use basic mathematical equations, perhaps with some physical basis, having tting parameters that can be calibrated to experiment. Use to interpolate predictions on similar systems... an empirical approach. Both: Build as much realistic physics/chemistry back into the research tool to gain better quantitative predictions. Represents a design tool.
A Sampling of Cement Hydration Models

HYMOSTRUC (TU Delft):
multi-parameter semi-empirical equation for kinetics, based on

PSD, w/c ratio, and clinker composition
C-S-H assumed as a continuous layer around spherical particles

IC (EPFL):
modeling platform for representing microstructure user-dened kinetic equations (Avrami-type, multi-parameter
semi-empirical, etc.)
user species growth rules for C-S-H and CH

CEMHYD3D (NIST):
discretized, heterogeneous particles probabilistic rules for dissolution, nucleation, growth rules calibrated to simulate OPC hydration
Materials Science Microstructure Models

Cellular Automaton Models:
Used to simulate dendrite growth and morphology during

solidication, recrystallization, grain growth, etc.
Crystallographic orientation dependence

Phase Field Models:
Based on localized reduction in free energy using TDGL Captures phase separation, solidication, coarsening, sintering Parameters directly linked to local composition and phase
volume fraction
Localized Kinetic Description

Let be a material parameter that can be distributed heterogeneously in a system (like a microstructure representation) In any volume element small enough that and all other parameters are approximately homogeneously distributed, then Rate of change of = (Kinetic factor) (Thermodynamic driving force)
Examples:
Dc c= kT
2
Single component diffusion
= k+ {A}{B} 1 K [C] Keq
Rate of elementary reaction A+BC
Why is a Localized Description Important?

1. Cement paste has heterogeneous phase distribution and composition 2. Dissolution, nucleation, and growth are mediated by pore solution. 3. Driving force, e.g. saturation index, for each phase is generally different from point to point 4. Location and morphology of precipitated phases is inherently localized 5. The parameters describing the process are actual physical/chemical properties of the materials comprising the system, instead of model-dependent empirical parameters 6. Any change to the system that affects local driving force or kinetics can be accommodated naturally w/c, particle size distribution, temperature, chemical additives.
Why is a Localized Description Important?

1 m 1 m
M.G. Juenger et al, J. Mater. Sci. Lett. 22 (2003) 1335
P.E. Stutzman, Ch. 14 in FHWA Petrographic Manual, FHWA-HRT-04-150 (2006)
IP OP
Morphology of C-S-H varies signicantly over small distances. Therefore, morphology appears to be governed by some differences in local growth conditions: (solution chemistry, connement ... ?)
I.G. Richardson, Cem. Concr. Res. 34 (2004) 1733
What are the Effects of Length Scale?
A. Allen J. Thomas, H. Jennings , Nature Mater. 6 (2007) 311
I.G. Richardson, Cem. Concr. Res. 34 (2004) 1733
If C-S-H is built from 5-nm bricks, then 1. What determines how the bricks assemble together at greater length scales? 2. How can bricks collectively know whether to grow as foils, bers, etc., and what determines the ber width and length?
What are the Effects of Solution Chemistry?

Several studies have indicated a composition range for C-S-H gel
C-S-H(I) has Ca/Si ~ 1.2 and forms in
solutions with low Ca/Si ratios. Reported to form a dense layer on C3S surfaces with high Ca/Si ratios. Reported to be less dense, less protective on C3S
C-S-H(II) has Ca/Si ~ 2 and forms in solutions

S. Garrault-Gaufnet and A. Nonat, J. Crystal Growth 200 (1999) 565 S. Garrault-Gaufnet and A. Nonat, Langmuir 17 (2001) 8131
Pore solution chemistry also inuences the kinetics of hydration dramatically Nonat and coworkers also argue that solution chemistry affects the growth anisotropy of C-S-H nuclei on C3S surfaces
HydratiCA: Operating Principles
...
Site n Site 0 Site 1 Site n Site 0
Each lattice site has a set of occupation numbers, {N} of cells of each type of substance. <N> = C Cells at a given node can, with dened probability
Diffuse, with specic mobility, to a neighboring node React with other cells at that node according to values of {N}
and a given rate constant for the reaction
C3S Hydration Simulation
25 m
Real-shape particles obtained by FIB (R. Flatt and L. Holzer) w/c = 1.4
C3S Simulations
= 1.0 m/site, with C-S-H(m)
0.30 0.25
11 mmol/L experiment 22 mmol/L experiment
log Ksp(C3S) = 0.48 log Ksp(C-S-H(m)) = -17.1 Open points are experimental data from Garrault and Nonat
11 mmol/L experiment 22 mmol/L experiment [Ca ] = 11 mmol/L
2+
Degree of Hydration
0.20 0.15
[Ca ] = 11 mmol/L
2+
[Ca ] = 22 mmol/L
2+
0.10 0.05 0.00 0

[H2SiO4 ] (mol/L)
10
Unconstrained
100 200 300 400 500 600
10
2-
10
[Ca ] = 22 mmol/L
2+
time (min)
10
Experimental data from S. Garrault and A. Nonat, Langmuir, 17 8131-8138 (2001)
10
15
20
25
time (min)
Example: Inuence of Calcium Salts

0.20
Tricalcium Silicate, w/s = 0.75 2 375 m /kg
0.080
Degree of Hydration
0.15
C-S-H Volume Fraction
22 mM Ca(OH)2 fixed
0.060
20 mM CaCl2
0.040
Con
trol
0.10
20 mM CaCl2
Con
trol
20 mM Ca(OH)2
0.020
0.05
20 mM Ca(OH)2
0.00 0
0.015
200
400
600
800
t (min)
0.000 0
200
400
600
800
t (min)
Ca(OH)2 Volume Fraction
0.010
Ca(OH)2 is predicted to delay hydration of C3S, extending the induction period and reducing hydration rates everywhere.
trol
20 mM CaCl2
Con
0.005
CaCl2 is predicted to have no effect on the induction period, but to accelerate hydration through more rapid growth of hydration products.
400
20 mM Ca(OH)2
0.000 0 100 200 300
t (min)
Ongoing Questions
1. These simulations assume that reaction order is equal to the molecularity. Can we obtain experimental measurements of reaction order, i.e. rate law, for growth of C-S-H and other complex minerals like ettringite? 2. These simulations assume that C-S-H nucleates heterogeneously on C3S surfaces, but there are reports that C-S-H may rapidly ll capillary pore space at very early ages and then densify with time. What mechanism could explain this rapid growth? 3. How do other solution components, especially aluminates and other anions (Cl-, SO42-) affect C-S-H in terms of its growth rate constant, its composition, its morphology, and its density? 4. Can we characterize C3S surfaces to better understand how its dissolution rate varies with time (see talk by Patrick Julliand) ? 5. HydratiCA simulations indicate that induction period can be modeled well by assuming either (a) low-solubility C3S surface or (b) high-solubility C3S surface protected by a metastable layer of a calcium silicate hydrate (Stein & Stevels). Can experiments be devised to distinguish between these two mechanisms?
Outlook
Many questions persist about the nature of C-S-H growth kinetics and morphology A model framework that uses a localized description of microstructure evolution can
provide much-needed links between solution chemistry, temperature, and material properties that are not provided by other kinds of cement hydration models. HydratiCA is one example.
This modeling approach requires knowledge about fundamental properties or
materials and their interactions with water: Keq, growth and dissolution rate constants, density, activation energies, adsorption isotherms for impurities, nucleation barriers. emergence of various C-S-H morphologies. We can build this detail into the model if we understand the mechanism. modeling approach and make the model increasingly powerful
Also requires more research into the link between nanoscale C-S-H structure and the
As more fundamental information becomes available, it can be incorporated into this This will require a sustained collaboration between experimentalists and modelers

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(How) Can C-S-H Growth Behavior Be Predicted?

Questions from a Modeling Perspective

A Sampling of Cement Hydration Models

multi-parameter semi-empirical equation for kinetics, based on

C-S-H assumed as a continuous layer around spherical particles

user species growth rules for C-S-H and CH

Materials Science Microstructure Models

Used to simulate dendrite growth and morphology during

Crystallographic orientation dependence

Localized Kinetic Description

Single component diffusion

= k+ {A}{B} 1 K [C] Keq

Rate of elementary reaction A+BC

Why is a Localized Description Important?

Why is a Localized Description Important?

M.G. Juenger et al, J. Mater. Sci. Lett. 22 (2003) 1335

P.E. Stutzman, Ch. 14 in FHWA Petrographic Manual, FHWA-HRT-04-150 (2006)

I.G. Richardson, Cem. Concr. Res. 34 (2004) 1733

What are the Effects of Length Scale?

A. Allen J. Thomas, H. Jennings , Nature Mater. 6 (2007) 311

I.G. Richardson, Cem. Concr. Res. 34 (2004) 1733

What are the Effects of Solution Chemistry?

C-S-H(I) has Ca/Si ~ 1.2 and forms in

C-S-H(II) has Ca/Si ~ 2 and forms in solutions

HydratiCA: Operating Principles

C3S Hydration Simulation

11 mmol/L experiment 22 mmol/L experiment

0.10 0.05 0.00 0

Experimental data from S. Garrault and A. Nonat, Langmuir, 17 8131-8138 (2001)

Example: Inuence of Calcium Salts

Tricalcium Silicate, w/s = 0.75 2 375 m /kg

Tricalcium Silicate, w/s = 0.75 2 375 m /kg

C-S-H Volume Fraction

Ca(OH)2 Volume Fraction

This modeling approach requires knowledge about fundamental properties or

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