Nature of C-S-H in cements with CRMs

The partial replacement of Portland cement with

slag, fly ash, silica fume or metakaolin results a
MM9819(CIVE5026M/5926M) reduction in the quantity of calcium hydroxide i.e.
CH is consumed during the reaction of the CRM.

Effect of CRMs on C-S-H It also results in a marked change in the C-S-H.

The nature of the change depends on the type of

CRM, and the percentage replacement.
Prof. I.G. Richardson
In this part of the lecture, I shall outline and illustrate
the most important changes.

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The pozzolanic reaction & C-S-H The pozzolanic reaction & C-S-H
The CRMs are glassy or poorly crystalline. However, the alkali-silica gel Original boundary of PFA particle
The SiO2 or SiO2–Al2O3 part of the CRM structure is is not stable in the presence
attacked by the OH− ions of the cement pore solution (which of Ca2+ ions. Outer products
is very alkaline).
There is an abundant supply
The OH− ions attach to silicon or aluminium atoms, breaking
of Ca2+ ions from the reaction PFA
bonds between them and oxygen atoms:
of the alite (i.e. impure C3S). Inner
ºSi–O–Siº + OH− ® ºSi–OH×××HO–Siº products
The alkali-silica gel reacts
quickly with the Ca2+ ions
The ºSi–OH (called silanol) groups react with more OH−
and transforms into C-S-H. PFA
ions, which leaves negatively charged oxygens:
The picture on the right is a
ºSi–OH + OH− ® ºSi–O− + H2O TEM micrograph that shows
a partially reacted PFA
Since the pore solution of the cement is essentially alkali particle surrounded by C-S-H
hydroxides, the negative charge on the terminal oxygen in a hydrated cement paste.
atoms is likely to be balanced by Na+ or K+ ions.

3 4

1
 Composition of C-S-H in cements Composition of C-S-H in cements
Si/Ca = 0.400 + 2.71(Al/Ca)
0.2 0 0.2 0 0.2 0
25, 55 & 85 °C The individual points on this

M
0.1 8 0.1 8 0.1 8
graph represent the average

f CR
0.1 6 0.1 6 0.1 6 composition of the C-S-H that

ti o n o
0.1 4 0.1 4 0.1 4 is present in cements that had
Al/Ca Atom Ratio

Al/Ca Atom Ratio

Al/Ca Atom Ratio

Portland cement replaced by

re a c
0.1 2 0.1 2 0.1 2
GGBS (10-100%), PFA (30%),
0.1 0 0.1 0 0.1 0
or MK (20%).

d%
0.0 8 0.0 8 0.0 8 Ages range between 1 month

M an
0.0 6 0.0 6 0.0 6 and 20 years & temperature of

% CR
0.0 4 0.0 4 0.0 4
hydration between 20-85 °C.

0.0 2 0.0 2 0.0 2

In fact, all CRMs that contain
Al produce C-S-H with this
0.0 0 0.0 0 0.0 0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
linear relationship between
GGBS Si/Ca Atom Ratio
PFA Si/Ca Atom Ratio Si/Ca Atom Ratio Al/Ca and Si/Ca ratios.
5 6

Composition of C-S-H in cements Op morphology

Si/Ca = 0.400 + 2.71(Al/Ca) Si/Ca = 0.400 + 2.71(Al/Ca)
0.2 0 0.2 0
M

M
0.1 8 0.1 8
f CR

f CR
0.1 6 0.1 6
on o

ti o n o
0.1 4 The morphology of Op C-S-H 0.1 4
Al/Ca Atom Ratio

Al/Ca Atom Ratio

a c ti

changes with composition,

re a c
0.1 2 0.1 2
% re

from fibrillar to foil-like.

0.1 0 0.1 0

d%
d

0.0 8 0.0 8
M an

M an
0.0 6 0.0 6
% CR

% CR
0.0 4 0.0 4
In fact, all CRMs that contain
0.0 2 0.0 2
Al produce C-S-H with this
0.0 0
linear relationship between 0.0 0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 Foil-like morphology
Si/Ca Atom Ratio Al/Ca and Si/Ca ratios. Si/Ca Atom Ratio

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2
 Op morphology Op morphology
Si/Ca = 0.400 + 2.71(Al/Ca) Si/Ca = 0.400 + 2.71(Al/Ca)
0.2 0 0.2 0

M
0.1 8 0.1 8

f CR

f CR
0.1 6 0.1 6

on o

ti o n o
0.1 4 0.1 4
Al/Ca Atom Ratio

Al/Ca Atom Ratio

a c ti

re a c
0.1 2 0.1 2

0.1 0 % re 0.1 0

d%
d
0.0 8 0.0 8
M an

M an
0.0 6 0.0 6
% CR

% CR
0.0 4 0.0 4

0.0 2 0.0 2

0.0 0 0.0 0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 Foil-like & fibrillar 0.0 0.2 0.4 0.6 0.8 1.0 1.2 Fibrillar Op morphology
Si/Ca Atom Ratio morphology Si/Ca Atom Ratio

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So, reaction of the CRMs results in a different Is that important? Yes

morphology for Op C-S-H. In the structure of C-S-H, the aluminium substitutes for silicon
in the so-called ‘bridging’ tetrahedra only, and the average
Is this important? length of the aluminosilicate chains can get very long.
Yes, the foil-like morphology of Op C-S-H fills space
with a finely distributed, poorly-interconnected The substitution of Al3+
porosity that accounts for the reduced chloride ions for Si4+ ions results
diffusion rates found in cements with CRMs, and so in an extra negative
contributes to enhanced durability (but the CRM charge that must be
balanced: this can be
needs to be allowed to react – curing is important!). met by alkali ions (Na+
Reaction of the CRMs that contain Al also results in or K+).
substitution of Si by Al in C-S-H. This is relevant to the
(It’s actually often called C-A-S-H!) problem of alkali-
reactive aggregates.
Is that important?

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3
 In Summary:
Concretes that are made using cements that include CRMs
can have properties that are desirable for particular purposes,
such as slower and decreased total heat evolution in large
structures, improved durability or, especially with silica fume,
strengths above the normal range.
CRMs modify significantly the hydration of Portland cement.
The way that the hydration reactions and products are
modified depends on many factors, which include:
the chemical composition and physical characteristics
(including particle size) of both the CRM and Portland
cement;
the CRM : Portland cement ratio;
the compositional heterogeneity of the CRM;
the temperature of hydration;
and the water:solids ratio.
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In Summary cont'd
The partial replacement of Portland cement results in:
1. Reduced content of CH because it is consumed by the reaction
of the CRM.
2. Significant change in the chemical composition of the C-S-H i.e.
the main binding phase.
3. The Al/Ca and Si/Ca ratios of the C-S-H both increase with
increases in the % CRM and % reaction of the CRM.
4. The change in composition is accompanied by a change in
nanostructure of the C-S-H.
5. In particular Al substitutes for Si in the 'bridging' tetrahedra and
the alumino-silicate chains can get very long.
6. The change in nanostructure results in a change in morphology
of the Op C-S-H.
7. The change in morphology results in reduced connectivity of the
capillary pores.
8. The reduced connectivity results in reduced permeability and
lower chloride diffusion rates, which contributes to enhanced
durability.
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