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29/03/2016

Cement, Concrete,
and Sustainability

Ellis Gartner and Vanderley John

USP, March 2016

5 – Alkali-activated binders

(including geopolymers)

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Terminology of alkali-activated binders


• In Portland based binders, reactive alumina-silicate SCMs (e.g.
pozzolanic materials) are “lime-activated,” i.e. they react with the
Ca(OH)2 produced by reaction of PC clinker with water.

• In simple geopolymers, the same types of reactive alumina-


silicate can be made to act as binders simply by reaction with
concentrated solutions of alkali metal hydroxides or silicates not
involving calcium compounds.

• The term “alkali-activated binder” is more general than


“geopolymer” because it allows for the fact that alkali metal
compounds can also catalyse the conventional lime-activation
(pozzolanic) reaction when calcium compounds are present.

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Comparison of “geopolymerization” with


the pozzolanic reaction: NASH vs. CASH!
The “geopolymerization” reaction needs water to dissolve
the activator but consumes very little of it (δ is small):
ASx + NSy + nH  NAS(x+y)Hδ + (n-δ)H
The solid product is a porous “N-A-S-H” gel.

The pozzolanic reaction consumes a lot of water (z+m)>> δ


ASx + zCH + mH  C-A-S-H + C4AH13 (etc.)
The solid products are a mix of C-A-S-H and AFm phases.
This is a true hydration reaction, unlike geopolymerization.

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Some relevant chemical formulae


Kaolinite = Al2Si2O5(OH)4 = AS2H2
Metakaolin = Al2Si2O7 = AS2
Simplified zeolite formation chemistry:
Al2Si2O7 + Na2SiO3 + 2H2O → Na2Al2Si3O10•2H2O
(S/N = 1) (natrolite)
Al2Si2O7 + Na2Si2O5 + 2H2O → Na2Al2Si4O12•2H2O
(S/N = 2) (analcime)
or Na2Al2Si4O12•6H2O
(chabazite)
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Physical properties of N-A-S-(H) type geopolymers made from


metakaolin plus NSx activators (Duxson et al, Colloids and
Surfaces A: Physicochem. Eng. Aspects 269 (2005) 47–58)

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Young’s moduli and ultimate compressive strengths of metakaolin-based


geopolymers. Error bars indicate the average deviation from the mean over
the six samples measured. (Duxson et al, 2005)

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SEM micrographs of Na-geopolymers made from metakaolin with


Si/Al ratios of (a) 1.15, (b) 1.40, (c) 1.65, (d) 1.90 and (e) 2.15

(Duxson et al, Colloids and


Surfaces A: Physicochem. Eng.
Aspects 269 (2005) 47–58)

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Pore size distribution of sodium geopolymers made from


metakaolin (by N2 adsorption). (Duxson et al, 2005)

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Making geopolymers from PFA is far more complex!

• PFAs cover an enormous range of compositions,


mineralogies & particle (size, type) distributions.
• Ideally, the most reactive component should
probably be an A-S glass with a high A/S ratio.
This can dissolve steadily in the activator soln.
• However, C-A-S glasses also occur, and behave
more like BF slags, promoting C-S-(A)-H
formation and causing rheological/setting
problems. Even worse are CaO & C3A!

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Pseudo-ternary plot relating fly ash oxide composition to the compressive


strength of alkali-activated binders obtained from that ash (RILEM AAM STAR),

SiO2

High strength FA
Medium strength FA
Low strength FA
BFS

½Al2O3 2 M2+O + ½ M+2 O


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One good thing about fly ash geopolymers!

cost
strength

Increasing liquid demand of fly ash


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What are the main effects of Ca in geopolymer systems?

• Ca2+ ions released into solution precipitate quickly, e.g.:


1. Ca2+ + H2SiO4= + ≈2H2O → C-S-H ↓
2. 4Ca2+ + 2H4AlO4- + 6 OH- + 6H2O → C4AH13 ↓
3. Ca2+ + CO3= → CaCO3↓
4. Ca2+ + =
SO4 + 2H2O → CaSO4.2H2O ↓
• These precipitates can produce rapid gelation which
manifests itself as setting or high viscosity.
• H igh dosages of strong retarders (especially calcium
chelators like citrates) may be needed to combat this.
• At later ages, main hydration products are C-S-(A)-H plus
AFm phases plus some N-A-S-(H) gels if total Ca is low.

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What are “alkali activators”?


• The simplest activator is a solution of an alkali hydroxide (e.g. NaOH)
• Sodium hydroxide is produced industrially by the “Chlor-Alkali” process, in
which a concentrated salt solution is electrolyzed:
2NaCl(aq) + H2O + electric power  2NaOH(aq) + H2(g) + Cl2(g)
• There are two other valuable products: hydrogen gas and chlorine gas.
Thus, sodium hydroxide prices tend to fluctuate strongly, especially with
Cl2 or HCl demand. In addition, the process is energy- and CO2-intensive.

• The other main class of activator is alkali metal silicates (‘water glass’).
Water glass is so-called because it is a glass which is soluble in water. It is
manufactured with a range of “silica modulus” (S/N) values, typically >1.5.
But lower values (≈1.0-1.5) are often considered better for alkali-activator
solutions. These can be made easily by mixing NaOH and water glass.

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A typical flowsheet for a chlor-alkali plant

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Production of water glass


Sodium silicate is commonly manufactured two different
processes: Aqueous process or Melt process. Both
processes use quartz sand as the silica source.
Aqueous process
• A mixture of caustic soda, quartz sand, and water is prepared in a mixing
tank, then fed into a reactor, where steam is introduced. The reaction is:
n SiO2 + 2NaOH → Na2O•nSiO2 + H2O

Melt process (thermal process)


• Sodium carbonate (and sodium sulfate) melt at temperatures far below that
of silica. (<900°C vs >1600°C) They are melted together with sand, which
dissolves in the molten material and reacts to form sodium silicates:

Na2CO3 + xSiO2 → Na2O•xSiO2 + CO2


2Na2SO4 + C + 2SiO2 → 2Na2SiO3 + 2SO2 + CO2
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The Aqueous (Hydrothermal) Process

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The Melt Process

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A glass-making furnace

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Typical commercial sodium silicate solutions


(“water glasses”) (data from PQ corp.)

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Water glass
solution
viscosity as a
function of N:S
mass ratio and
concentration
at 20°C

(data from PQ)

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Viscosities of
sodium
silicate
solutions at
20°C as a
function of
N:S mass ratio
at constant
solids content.

(data from PQ)

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Viscosities of
selected
sodium
silicate
solutions as a
function of
temperature

(data from
PQ Corp.)

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pH of water glass solutions of differing S/N ratios at 20°C

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Qualitative
interpretation
of Silicate
Anion Structure
Equilibria
Source:
G. Engelhardt,
et al., "Z.Anorg,
Allg, Chem.,"
4188, 17-28
(1975)

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Water glasses are also available in solid form

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Typical commercial sodium metasilicates


(Na2SiO3; N/S = 1) (data from PQ corp.)

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More about alkali activators!


• Potassium hydroxide or silicates can also be used but are usually
more expensive than the sodium equivalents.
• The optimal requirements for activator composition [concentration
and silica modulus (y)] are not very well-defined. Use of a high
silica modulus increases safety, as pH decreases with increasing (y).
But the viscosity also increases, so the mixes become “sticky.”
• High initial alkali concentrations are needed for rapid strength gain,
but the total liquid volume depends on the “alkali activator solution
demand” of the solids. It is thus very advantageous to use mixes
that give good fluidity at low liquid contents. Dilution with water is
usually very detrimental to strength development, and adding more
activator is always very expensive.
• If basic calcium compounds (e.g. slags, lime, or clinker) are present,
the alkaline activator can be created in-situ by reaction of an alkali
sulfate or carbonate. This is relatively safe and cheap, but it can be
very difficult to control the rheology and setting rates of such mixes.

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Advantages of geopolymer binders


compared to PC-based pozzolanic cements.
• Very high pozzolan contents (>80% of dry mass) can be used, which can result
in very low carbon footprints if the pozzolan itself is low-CO2.
• Low-calcium fly ashes and other pozzolans that are not very reactive in lime- or
PC-activated binders can often be used effectively.
• High strengths can be obtained quickly if the binders are cured at >60°C,
making these systems particularly suitable for precast items.
• Sealed or humid curing conditions are not usually required.
• Most of the alkali hydroxide is combined into the product in an insoluble form.
• The binder has good chemical resistance, especially to acids.
• The binder adheres very well to steel.
• The binder paste is less dense than PC pastes of similar strength.
• Light-coloured products are easy to make.

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Disadvantages of geopolymer binders


compared to PC-activated pozzolanic cements.
• General mix design rules for making geopolymer concretes of any specific properties from
any given reactive aluminoslicate raw materials are not yet publicly available.
• The “quality” of the binder is mainly dependent on the “quality” of the aluminosilicate,
especially its “water demand” (which should preferably be low).
• If industrial by-products are used, variations in quality are a big risk.
• “Pure” geopolymer binders do not harden quickly enough at 0-40°C to be usable in most
site-mixed or ready-mixed applications.
• Although the activator is a small fraction of the binder it is much more expensive than
OPC, and subject to large price swings. The activators are produced by chemical
companies and global production capacity is very limited compared to cement.
• Durability: Considering the wide range of possible formulations, there are not yet
sufficient data on durability except for a few very specific cases.
• Safety risk: the activator is often a very corrosive alkaline liquid, so special safety
precautions may be needed when the fresh concrete is being mixed and cast.
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Conceptual model for the


synthesis of an alkali-
activated binder by
hydroxide activation of an
aluminosilicate source,
including multi-step gel
evolution reactions.

From: Duxson, P., Fernández-


Jiménez, A., Provis, J.L., Lukey,
G.C., Palomo, A. and van
Deventer, J.S.J.: Geopolymer
technology: The current state of
the art. J. Mater. Sci. 42(9),
2917-2933 (2007)
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What is missing from the current model?


• No clear formulation of a “nucleation and
growth” mechanism for N-A-S-(H) gels
• Limited understanding of long-term reaction
mechanisms (after initial gelation)
• Limited ability to estimate degree of reaction
and degree of space filling by products.
• Limited understanding of long-term
compatibility of N-A-S-(H) and C-S-(A)-H gels
• No well-accepted mix design procedures (hence
the problem of N° of PhD’s/m3 !)
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