Geopolymer Concretes

Geopolymer Concretes

www.liv.ac.uk/concrete
The aims of this project
NW Construction Knowledge Hub

All collaborating institutions have a role in disseminating knowledge to the 
All collaborating institutions have a role in disseminating knowledge to the
construction industries, but only Liverpool are involved in active research into 
low‐carbon construction materials.
Environmental considerations of OPC usage: CO2 emissions

Global usage of OPC 2.6 billion tonnes globally 
Global usage of OPC 2 6 billion tonnes globally
(2009 figures).

0.82 tonnes of CO2 for every tonne of OPC.

5‐8% of all human‐generated atmospheric CO2.
Geopolymer Concretes
Geopolymers refer to alkali‐activated binders 
(AAB’s).

Geopolymers studied for the last 40+ years.

Applications in replacing Portland cement‐based 
concrete materials.

Geopolymers are a cement‐free concrete.

Performance often exceeds that of Portland cement 
concretes.  

Increased
• durability,
• resistance to chemical attack,
• fire protection.
fire protection
Geopolymer Concretes

Produced from natural and synthetic pozzolanic solids, 
activated with alkaline solutions
activated with alkaline solutions.

Originally metakaolinite with siliceous solutions.

Use of other synthetic reactive aluminosilicate pozzolans 
and alkaline activators possible.

Waste‐stream
Waste stream or by‐product pozzolans
or by product pozzolans readily available , 
readily available
e.g. PFA, GGBS, etc.

Using PFA‐based geopolymers will have an impact on 
national and international targets on CO2 reduction.
Environmental Considerations of PFA: Landfill

Waste‐stream pozzolans such as PFA not recycled to 

their full capacity, and excesses are stockpiled or 
“l dfill d”
“landfilled”.

Commercialisation of PFA in geopolymers will help 
g p y p
to reduce landfill.

F t
Future demand may help to utilise existing stocks.
d d h l t tili i ti t k
Geopolymer Concretes

Three basic steps  to reaction:

1. Dissolution of pozzolan with in alkaline solution,

2. Gel formation of aluminosilicate chains,

3. Polycondensation of chains to form interlocking 
network.
Our starting work on geopolymers

At Liverpool: Investigated mortars using PFA.

Effect of different lab‐grade alkali activators and 
curing temperatures on strength development.

Alkalis tested include:

• Sodium hydroxide, NaOH,
• Potassium hydroxide, KOH,
• Sodium silicate
The effect of curing temperature on strength

Example:

PFA activated
ti t d with
ith
Na-silicate SG 1.2

Increased curing temperature increases the strength of 
Increased curing temperature increases the strength of
geopolymer by increasing reaction between PFA and alkali.
Effect of too high curing temperature!

Curing at 90oC:
Curing at 90 C
• development of a “muffin‐top” at 
the free surface.

Due to the expansive action of gases 
and vapours/steam developing in the 
paste.

Curing at <70oC:
• eliminates swelling, 
• maintains good strength 
development.
The effect of activator concentration on strength
Example:
PFA activated with
sodium silicate of 3
different concentrations:

1. SG 1.5
2. SG 1.33
3. SG 1.2

The mass of activator

solution added to mix
was kept constant
through these
experiments

Using sodium silicate activator, increasing the concentration gives 
increase in strength.

Further experiments for hydroxide activation expected to be similar.
The effect of the activator on strength
Example:
BS EN 771 PFA activated with:
Class B
Engineering brick • sodium silicate SG1.5,
• KOH 10M,
10M
• NaOH 10M,

and for comparison:

• 2:1 sodium silicate and

KOH mix.

Curing temperature
70oC.
Concrete masonry
blocks Alkali added to each mix
to give a constant
workability.

Type of activator, hydroxide or silicate, has an effect of the strength.

Alkali cation, K or Na, also has an effect.
What alkaline activators are in the waste-stream?

Current work uses lab‐grade alkaline activators.

Undertaking market research to identify:
• What alkalis are currently in the waste‐stream in 
the UK?
• Quantity?
Q tit ?
• Quality?
• Consistency through time?

Any further information that you can provide us with 
will be well received.
Porosity development

Geopolymer mixes continue to be affected by 
high porosity.  

Porosity on a sub‐micron to mm scale, due to:
b l d

1. Porosity developed during mixing that 
cannot escape due to high viscosity of mixes.
cannot escape due to high viscosity of mixes.

2. Porosity inherent to dissolution of hollow 
PFA cenospheres.  Porosity cannot escape 
d
due to viscous
i gelling and polycondensing
lli d l d i
paste at elevated temperature.
Problems and benefits of porosity

P
Porosity is
i i closed‐cell, hence permeability is
l d ll h bili i low.
l

Potential problems:
• Percolation
e co at o oof atmospheric acid solutions and 
at osp e c ac d so ut o s a d
sulphates.  Effects on paste not yet fully 
investigated.  Deterioration of re‐bar expected.

Benefits of porosity:  
B fit f it
• Resilience to freeze‐thaw weathering.
• Thermal insulation.

Ways to manage porosity:
• Use more suitable surfactants/ defoamers/ 
wetting agents/ superplasticisers.
Microstructural & microchemical characterisation

Important to understand why different materials have 

different strengths
different strengths.

What does the material look like?

Is the material homogenous or heterogeneous?

Can initial ingredients be altered or processed to make 
a better product?
a better product?

How does the reaction proceed in space and time?

Answers will help gain a fuller understanding of the 
products and help feed‐back into fine‐tuning the 
process.
Microstructural Characterisation
with Scanning Electron Microscopy
CamScan X500 FEG‐SEM.
Philips XL30 W‐SEM.
Department of Earth & Ocean Science has 
p
a state‐of‐the‐art electron optics facility.
Combining electron optic imaging 
capabilities with in situ chemical analysis 
with EDS allows full microstructural 
characterisation of materials.
Microstructural Characterisation

Reacted geopolymer matrix

PFA spherules

Fe nodules

Backscatter imaging can assess the 
microstructural characteristics:
Qtz Sand
Qtz Sand •quality and nature of fractions
•quality and nature of fractions,
•porosity, 
•connectivity of structural 
Porosity
elements/load bearing framework
elements/load bearing framework, 
•relationship between unreacted or 
Backscatter image of PFA – Na‐silicate geopolymer. partially reacted components,
nature of interfaces between particles 
•nature of interfaces between particles
and paste.
Microstructural Characterisation

Qtz Sand Backscatter image of PFA – Na‐silicate geopolymer.

Reacted geopolymer matrix

Fe nodules Si Al

PFA spherules
Porosity Fe Mg

Chemical mapping provides means of assessing the 
distribution of elements in samples thus
distribution of elements in samples, thus 
identifying constituent mineral components,  
impurities, and spatial distribution of phases.
Ca K
Microstructural Characterisation

Graphite

Secondary electron imaging and chemical 
analysis of PFA provides:

• grain size distribution,
• non‐aluminosilicate content,
• micro‐chemistry.
Microstructural Characterisation

Qtz Sand Unreacted PFA Porosity

Secondary electron imaging and 
chemical analysis of PFA geopolymer 
identifies:

• nature of interface between 
aggregate particles and paste,
• unreacted PFA,
• porosity,
• desiccation cracks as lines of 
weakness and permeability
weakness and permeability.
Intensity (counts)
Other analytical techniques
Quartz

8000

X‐ray diffraction spectroscopy 
6000 Mullite
Assess the fraction of reactive amorphous material 
Mullite in PFA
in PFA.
4000
Quartz
Mullite X‐ray fluorescence spectroscopy
2000

Significant
g non-crystaline
y component
p
Analysis of bulk chemistry of PFA or geopolymers.

0
5 10 15 20 25 30 35 40 45 50 55 60 65
2Theta (°)
Coulter laser diffraction granulometry
Grain size distribution of PFA.  Can compare this to 
the grain size distribution in geopolymer. Gives
the grain size distribution in geopolymer.  Gives 
insight into grain‐size dependence of the reaction.

Environmental scanning electron microscopy
Lower vacuum.  Observe real‐time curing and 
b l d
associated change in chemistry and elemental 
distribution.

Isothermal calorimeter
Determined rate and amount of reaction.
Future work

• Investigate effects of different alkali activators 
with a more detailed matrix of mixes.
• The type of alkali
9Aluminates
9Hydroxides
9Silicates
• Alkali concentration
• Curing temperature

• Investigate other pozzolanic solids, 
particularly GGBS, Class C PFA.

• Study and refine geopolymer properties, e.g. 
management of porosity with admixtures.
Future thoughts and considerations: from the lab to the marketplace

Current limiting factor in commercialising PFA‐geopolymers is 
alkali activators.

To find widespread appeal, geopolymers need to be more user‐
friendly:
• Dry ready‐mixes,
Dry ready mixes
• Minimising the corrosivity and irritation hazards.  This means 
using silicate activators preferentially to caustic ones (use of 
admixtures to manage rheology and porosity is necessary).  

Estimated usage of geopolymers in 2015 is 1000 million tonnes 
globally.  For geopolymers made from 100% recycled materials, 
work needs to be done now in order to establish, maintain and 
work needs to be done now in order to establish maintain and
secure the industry and infrastructure.

UK’s northwest industries have the opportunity to be innovative, 
pivotal and market‐leading.