A Surface energy-based expansion mechanism

associated with delayed ettringite formation

Beaudoin, J.J.; Marchand, J.

NRCC-45995

A version of this document is published in / Une version de ce document se trouve dans :

RILEM Workshop on Internal Sulfate Attack, Villars, Switzerland, Sept. 4-6, 2002, pp. 1-7

www.nrc.ca/irc/ircpubs

A SURFACE ENERGY-BASED EXPANSION MECHANISM

ASSOCIATED WITH DELAYED ETTRINGITE FORMATION
J.J. Beaudoin * and J. Marchand+
*

Institute for Research in Construction, National Research Council

Ottawa, ON, Canada, K1A 0R6
+
Universit Laval, Ste. Foy, Qubec, Canada, G1K 7P4

ABSTRACT
A surface energy-based mechanism for expansion in cement systems
susceptible to Delayed Ettringite Formation (DEF) is proposed. The volume
change behavior of nanoporous materials filled with impregnants and exposed to
water vapor (considered analogous to the DEF situation) is described. The
relevance of expansion due to Bangham swelling and dissolution phenomena is
explained. The role of microcracking in expansion due to DEF is discussed. It is
suggested that it is not necessary to invoke classical crystal growth theory to
explain expansion due to DEF. It appears that both AFt precipitation and surface
effects are occurring concurrently and influencing the volume stability of the
material.

Introduction
The deleterious effects of delayed ettringite formation (DEF) in concrete that has
experienced temperatures above about 70C have been documented by
numerous investigators [1]. Taylor et.al. have described an expansion
mechanism that suggests that substantial pressures from crystal growth are most
likely to be generated in confined spaces at high saturation [2]. In their
description, monosulfate is intimately mixed with C-S-H at the end of the heat
treatment. The ettringite subsequently formed under conditions giving rise to
expansion is also closely intermixed with C-S-H. Although the descriptor
intimately mixed is not a precise definition of the state of the monosulfate or
ettringite it is apparent that these compounds would be finely divided (with a high
surface area) and occupy nanospace. It is argued by them that this would satisfy
the requirement that a substantial pressure can arise at a pore wall only if the
pore radius is below ~100 nm. Arguments based on surface energy
considerations will be presented in this note that suggest it is not necessary to
invoke a crystal growth mechanism to explain the source of expansion due to
DEF. It will be further argued that surface energy considerations for explaining
DEF expansion are consistent with the generation of significant levels of stress at
microcrack tips.
Surface Energy-Length Change Phenomena in Porous Materials
The charged nature of the calcium silicate hydrate (C-S-H) surface and its
characteristics as a highly divided solid favors effects related to the adsorption of
ions or molecules. It is apparent that the surface energy of C-S-H surfaces can
be modified by various phenomena: gas or molecular adsorption; ionic
adsorption; chemical reactions including dissolution phenomena. The C-S-H
compounds present in hydrated Portland cement compounds are generally illcrystalline. At the molecular scale, their nanostructure is analogous to that of the
natural clay tobermorite [3]. Their primary structural unit is organized in layers
composed of chains of silica tetrahedra bound to CaO polyhedral sheets. The
silicate chains are negatively charged [3,4]. Zetametry studies indicate that the
surface charge of C-S-H is strongly influenced by their Ca/Si ratio [5,6]. The
specific adsorption of positively charged calcium ions modifies the charge of the
surface (as the Ca/Si ratio increases). The net charge ultimately becomes
positive.
The pure C-S-H phases investigated by the authors had nitrogen surface areas
ranging from 30.7 to 111.9 m2/g [7]. The C/S ratios varied from 0.68 to 1.49.
These surface areas are of similar magnitude to those obtained for porous silica
glass. Length change due to surface energy changes of these relatively high
surface area materials can be appreciable [7].

The Bangham equation provides a basis for testing Gibbs equation on solids
L
= k1
L

(1)

L
is the length change of an adsorbent during the reversible adsorption
L
process, is the change in surface free energy.

where

Several authors are of the opinion that Bangham effects are at the origin of
volume instability of hydrated cement systems, especially at low values of
relative humidity [8,9]. The mass and length change sorption isotherm for
hydrated Portland cement exhibits large primary and secondary hysteresis [10].
The secondary hysteresis is associated with both intercalation effects and
surface adsorption phenomena. These effects have been separated by
constructing (through appropriate use of scanning loops) reversible and
irreversible sorption isotherms [10]. The reversible expansion due to adsorption
is about 20% of the total expansion along the isotherm and amounts to a
significant value of about 0.1%. This represents a substantial volume change
and results from surface energy changes due to sorption of water.
Length Change Due to Dissolution
The dissolution of porous solids in various solvents has been shown to be
expansive [11-13]. Examples are: the dissolution of porous silica glass in NaOH
solutions (0.1M - 3.2M); the dissolution of Ca(OH)2 in distilled water and various
salt solutions; the dissolution of hydrated cement paste in 1.0N aqueous HCl; the
dissolution of ettringite in various salt solutions. These results indicate that
changes occurring on the surface whether due to sorption of inert ions or
dissolution of a constituent or a portion of the entire solid produce significant
expansion. This can be attributed to a change in the surface free energy of the
solid.
It would appear that there may be an apparent contradiction between the two
following observations : expansion resulting in the dissolution of silica glass (or
AFt or Ca(OH)2) and shrinkage that results from the decalcification of C-S-H
[14,15]. This can be explained as follows. During the initial leaching of the paste
in distilled water there is expansion. Accompanying the expansion there is
dissolution of both the C-S-H and CH phases. Both are occurring simultaneously
and both are expansive. The key is the time scale. Expansion occurs for pure
C-S-H in distilled water during the first few hours. The subsequent contraction
observed by Feldman and attributed to C-S-H was observed after several days.
This is likely due to the eventual collapse of structure on removal of structural
lime. The result is not incompatible with our observations.
It is also noted that ionic adsorption can also accentuate the volume instability of
the solid. This is demonstrated by the length change behavior of C 3S paste

immersed in distilled water and sodium chloride solutions [16]. Samples

immersed in sodium chloride solutions (20-180 g/L) expand up to about 0.04%
within 24h and continue to expand slowly over a period of several days. The
expansion at all concentrations exceeds that for the C 3S paste immersed in
distilled water. The fact that no new chloride bearing compounds were detected
indicates that the adsorption of ions could account for the additional expansion.
This argument goes against the assumption that the desorption of sulfate ions
from the C-S-H surface could eventually lead to swelling.
Nanoporous Materials Impregnated with a Second Phase
Nanoporous materials with high surface area e.g. porous silica glass and
hydrated Portland cement paste, are useful models for demonstrating the
potential deleterious effects of surface energy phenomena due to wetting. Vycor
glass impregnated with elemental sulfur, polymethylmethacrylate (PMMA) or
calcium hydroxide undergoes significant expansion (>1%) when exposed to
water vapor [17,18]. In order to fill the small pores the impregnant has to be in a
very finely divided state. The impregnant in porous glass can have a surface
area in the range of of 300-500 m2/g. If this surface can be reached by water
vapor molecules and the interaction energies are of the normal adsorptive type,
then the swelling forces created by the decrease in surface free energy could be
very high. Depending on the irregularity of the interfacial boundary and the
extent of interfacial bonding, high local stresses acting at specific sites along the
interface may develop causing ultimate destruction of the matrix. The driving
force possibly emanates from differences in surface energy release (a net
Bangham effect). Adsorption occurs on both the glass and sulfur (or calcium
hydroxide) surfaces. Large expansion of both solids due to the Bangham effect
should result. One possibility is that the sulfur (or calcium hydroxide) expands
more than the glass due to differences in the free energy changes with respect to
each solid. It is unlikely that there is any chemical interaction especially in the
glass-sulfur system. This explains why sulfur and calcium hydroxide are expelled
or extruded from some of the pores (Figure 1). Similar length change results are
observed for the PMMA cement paste composite although no disintegration of
the specimen is observed. The adhesion or interfacial bond between the
polymer and the hydrated Portland cement may be responsible for maintaining
the integrity of the high surface area matrix. The process is diffusion controlled
and dependent on the thickness of the test specimen.
A Surface Energy-Based Expansion Mechanism for DEF
The concept of an intimate mixture of sulfate phases (e.g. monosulfate and
ettringite) with C-S-H suggests that the sulfate phases are either microcrystalline
or mixtures of microcrystalline and amorphous material. These phases can be
considered to be finely divided with a high surface area. The surface area of the
mixture is specially high as the interfacial zone bounds both the surface of the
matrix (C-S-H) and the surface of the sulfate phase. Exposure to water vapor

can potentially result in large decreases in surface free energy. The principal
requirements of the DEF mechanism include a pre-heating treatment = 70C and
subsequent moist curing. The transformation of AF m to AFt involves the
consumption of an additional 20 moles of water. The heat treatment is also likely
to drive moisture out of a specimen. Therefore subsequent exposure to water
vapor is likely to involve readsorption. Expansion due to DEF does not occur in
absence of moist conditions. Mass transfer of water into fully impregnated
porous bodies occurs more effectively in the vapor phase. For example sulfur
impregnated porous glass, fully immersed in liquid water does not undergo the
same deleterious behavior, at least within a similar time frame. It is suggested
that intimately mixed C-S-H and AF m/AFt phases (at the nanoscale) can be
modelled as a mixture of finely divided solids at the nanoscale. Mass transfer of
water to interfacial sites in such mixtures is more likely to occur (in a manner
analogous to behavior of the porous glass/sulfur system) in the vapor phase. It
should also be noted that in industrial environments heat treatment is often
carried out under non-ideal conditions. The resultant Bangham swelling or
dissolution can result in deleterious volume changes analogous to those that
occur when impregnant-filled porous silica glass is exposed to water vapor. It is
therefore not necessary to invoke a crystal-growth theory to explain the
expansive behavior of DEF.
As stated previously adsorption of sodium ions appears to be associated with
expansion. An association of the desorption of sulfate ions with expansion would
require a decrease in surface free energy on desorption. Desorption is usually
accompanied by an increase in surface free energy. Desorption of sulfate ions
from the C-S-H surface as an explanation for expansion would not appear to be
tenable.
Concluding Remarks
It is suggested that changes in surface free energy due to sorption or dissolution
phenomena can account for expansion due to DEF. The sulfate phases
(monosulfate and ettringite) when intimately mixed with C-S-H can be
characterized as finely divided with high surface area and are essentially
nanoparticulates. Water vapor can likely permeate into the interfacial zones
generating the expansive forces related to surface free energy. It is therefore not
necessary to invoke a crystal-growth mechanism to account for expansion due
to DEF. Similar length change phenomena can occur due to the presence of
microcrystalline or mixtures of microcrystalline and amorphous phases in the
vicinity of microcrack tips. The population of microcracks may be sufficient to
generate damage via the mechanism suggested. The response of the C-S-Hsulfate phase to water vapor ingress is likely to occur in coincidence with
expansive processes occuring in the vicinity of crack tips.

References
1. B. Erlin (Ed), Ettringite The Sometimes Host of Destruction, SP177, Am.
Concr. Inst. Intl., Farmington Hills, MI, USA, 1999, pp265.
2. H.F.W. Taylor, C. Famy and K.L. Scrivener, Delayed Ettringite Formation,
Cem. Concr. Res. 31, 683-693 (2001).
3. H.F.W. Taylor, Cement Chemistry, London, Academic Press, (1990) pp. 475.
4. R.J. Kirkpatrick, J.L. Yarger, P.F. McMillan, P. Yu, and X. Cong, Raman
Spectroscopy of C-S-H, Tobermorite and Jennite, Advn. Cem. Bas. Mat. 5,
93-99 (1997).
5. L. Nachbaur, P.C. Nkinamubanzi, A. Nonat and J.C. Mutin, Electrokinetic
Properties which Control the Coagulation of Silicate Cement Suspensions
during Early Age Hydration, Journal of Colloid and Interface Science 202,
261-268 (1998).
6. H. Viallis-Terrisse, Ph.D. thesis, Universit de Bourgogne,Interaction des
Silicates de Calcium Hydrates,principaux constituants du ciment avec les
chlorures dalcalins.Analogie avec les argiles ,Oct.2000,pp.257..
7. J.J Beaudoin, R.F. Feldman, J. Baron and M. Conjeaud, Dependence of
Degree of Silica Polymerization and Intrinsic Mechanical Properties of C-S-H
on C/S Ratio, Proc. 8 th Int. Cong. Chem. Cem., Rio de Janeiro, Brazil, 1-6
(1986).
8. R. Kondo and M. Daimon, Phase Composition of Hardened Cement Paste, in
Proc. VI Int. Conf. Chem. Cement, Moscow, 1974.
9. R.A. Helmuth, Dimensional Changes and Water Adsorption of Hydrated
Portland Cement and Tricalcium Silicate, M.S. Thesis, Illinois Inst. Tech.,
1965, pp 64.
10. R.F. Feldman, Sorption and Length-Change Isotherms of Methanol and
Water on Hydrated Portland Cement, Proc. 5 th Intl. Symp. Chem. Cem.,
Tokyo, Japan, Vol. 3, 53-56 (1970).
11. G.G. Litvan, Volume Instability of Porous Solids Part 2. Dissolution of Porous
Silica Glass in Sodium Hydroxide, J. Matls. Sci., 19, 2473 (1984).
12. G.G. Litvan, Volume Instability of Porous Solids Part 1. Proc. 7 th Int. Congr.
Chem. Cem., Paris, Vol III, Paper VII-46 Vll-50 (1980).
13. J.J Beaudoin, S. Catinaud and J. Marchand, Volume Stability of Calcium
Hydroxide in Aggressive Solutions, Cem. Concr. Res., 31, 149-151 (2001).
14. R.F. Feldman, V.S. Ramachandran, Length Change in Calcium Hydroxide
Depleted Portland Cement Pastes, II Cemento, 86 (2), 87-96 (1989).
15. R.F. Feldman, P.J. Sereda, V.S. Ramachandran, A Study of Length Changes
of Compacts of Portland Cements on Exposure to H2 O, High. Res. Rec. No.
62, 106-118 (1965).
16. S. Catinaud, Ph.D. Thesis, Universit Laval, Durabilit a Long Terme de
Matriaux Cimentaires Avec ou Sans Fillers Calcaires en Contact avec de
Solutions Salines, Dec. 2000, Chapter 7, pp 202-361.
17. R.F. Feldman and J.J Beaudoin, Some Factors Affecting the Durability of
Sulfur-Impregnated Porous Bodies, Cem. Concr. Res., 8, 273-281 (1978).

18. V.S. Ramachandran, R.F. Feldman and J.J Beaudoin, Concrete Science,
Heyden & Son Ltd., London, 1981, p 264.

(a
)

(a
)

Figure 1. Impregnated porous glass exposed to 100% RH

(a) the porous glass sulfur system showing extruded sulfur rods
(b) the porous glass calcium hydroxide system showing nodules of calcium hydroxide extruded from the pores