Durability of Geopolymer Concrete Related to Carbonation

Summary
Abstract
Geopolymer concretes are slowly seeiming more widespread use due to their environmental implications
Theyre a number of issues in regards to their durability, one such issue is carbonation
At high pH environments, a protective oxide layer forms on the surface of the reinforcement steel, which
prevents corrosion
Overtime, carbon dioxide seeps into the concrete, forming acidic compounds, chloride, sulphate and carbonic
acid. These react with basic compounds in the concrete which will lower the pH, which will in turn inhibit the
formation of this oxide, causing corrosion and causing the strength of the geopolymer concrete to falter
Method
Produce concrete mixes at varying compositions
Leave to saturate in carbon dioxide environments
o Ambient
o 1%
o 3%
Derive pH curve along depth of specimen
o By grinding
o By pore solution extraction
Perform xray diffraction on paste specimen to check for carbonation products, sodium carbonate and sodium
bicarbonate
Also perform compressive strength tests
Geopolymerisation
The geopolymer structure merely acts as the binder, where the silicon and aluminium react with hydroxide in an
alkali activation reaction.
Concrete Composition
Binder reaction is dependent on the presence of silicon calcium ratio. The alkaline activator reacts with these to
form the water glass binder (sodium metasilicate).
o As fly ash composition increased, binder generation fell
Fly Ash Based Composition
Compressive strength develops much earlier, within first 24 hours
Optimal curing temperature sits at 80oC, lower temperatures are less efficient due to reduced hyrdration
Alkali to fly ash ratio?
o Optimal ratio is 2.5
Slag Based Concrete
Greater degree of Carbonate precipitation in Portland concrete, these calcium carbonate precipitates prevent
further precipitation of carbon dioxide.
Binder reaction increases porosity increased, for water glass activator; when sodium hydroxide activator is used,
carbonate precipitation reduced porosity.
Air Carbonation Environment Test
o 10-20% CO2 70% Humidity for 4 months
o Current tests were insufficient and with not enough specimens to draw conclusive results
Student places great deal of emphasis on lack of direct correlation between carbonation and compressive
strength of concrete

o Strength of concrete is largely dependent on the binder

In an experiment where the sample was exposed to K2CO3, the paste specimens saw failed matrices.
o Ratio of fly ash to OPC controlled the durability when the concrete was immersed in monoethanomaline
or K2CO3
o Pure fly ash samples showed resistance, possibly due to low silicon oxide and aluminium oxide ratios
o By increasing the sodium oxide, silcon dioxide rations, alkalinity increased. Higher alkalinity further
reduced porosity.
Increasing this increases water though, increasing porosity.
o Ground furnace slag or alkali activated slag
o Using Sodium Hydroxide activator increased compressive strength by producing N-A-S-H geopolymer gel
Metakaolin as alumino-silicate source and GBFS as calcium precursor
Carbonation caused these samples to see significant reduction in compressive strength and
increased pore size and carbonation depth relationships remained linear.
Linear in regards to increasing metakaolin
Accelerated Carbon
Fresh concrete cubes cast and cured for 28 days until weight change is less than 0.2%
Store for 14 days
Then left in storage chamber with CO2 at 1% by volume at 21+/-2oC at 60+/-10% humidity
Also soak concrete in solution abundant in carbonate ion
o This experiment is much more extreme than natural carbonation, and so doesnt accurately reflect reality
Monitoring pH
Indicator: shows depth of carbonation
Concrete specimens are exposed after 28 days
o Concrete specimens are sliced at 7, 14 and 28 days respectively
Grinding
o Drill into speciement, and extract powder for every 2.5mm up to 30mm
o Powder was then mixed with distilled water with ratio 1:20
Pore Solution Extraction
o Extract solution by compression and test
o Method is feasible after curing due to presence of water
Fluorescent Optical Sensor
o Allows for constant pH monitoring
Procedure
Produce mixture proportion
Mix on pan
Cast in moulds
Cure at 75oC for 18 hours
Dry condition to set humidity
o Cut speciemen from standard cylinder, cut off top and bottom carbonate layers before accelerated
carbon test
Natural carbonation
o Specimens kept in fog room with the same humidity and temperature of dry conditioning
o Speciemens tested on week 2,4,6
Compared against 18month old concrete specimen
o two 50mm specimens for grinding and testing were cut from the top and bottom respectively

Accelerated Carbonation
o Carbonation levels are between 1-3%
o 23oC at 58% humidity
o Side surface was covered while top and bottom were exposed
Grinding
o Grinded 1mm at a time, producing 5g of concrete powder
o Powder was dissolved in water of the same weight
o pH meter then measured pH
Measuring Carbonation Depth
o Cylinder spit through centre of cross section, and rainbow indicator srayed over surface
o Also use phenolphthalein
Pore Solution Extraction
o Use machine to extract solution
o Match peaks in data from grinding data to develop ph distribution
o Geopolymer paste is batched as specimen for girding but without aggregates
Paste specimen is compressed to extract solution
o Paste samples stored in bags and sprayed with distilled water twice every week to keep moisture inside
the concrete and avoid carbonation
o After two months storage, sufficient liquid can be extracted from the paste specimen.
X-Ray Diffraction
o Study crystalline phases of hydration products produced in geopolymer concrete
o Paste speciemens were exposed to accelerated conditions, 1 and 3% for two weeks
o Analysis was conducted on surface and centre to compared the chemical composition at different depths
of the cubes
Compressive Strength and Modulus of Elasticity
o Test total of 6 cylinders, 3 for compressive strength and 3 for elasticity
o Test conducted 28 days after dry conditioning

Results Summary
6 weeks is not sufficient for natural carbonation
Indicator has a number of issues
Pore extraction is key to calibration
XRD Analysis
o Sodium carbonate does not appear until 3% accelerated carbonation
Key Things to Note
When cutting samples from the primary cylinder, due to distribution of aggregate, group top, middle and bottom
of concrete cylinders together for greater control of variables
Thickness of exposed layer should be enlarged to greater than 25mm

Geopolymers Article
Geopolymers are chains or networks of mineral molecules linked with co -valent bonds. They
have following basic characteristics:
a) Nature of the hardened material:

X-ray amorphous at ambient and medium temperatures

X-ray crystalline at temperatures >500C

b) Synthesis Routes:

alkaline medium (Na, K, Ca) hydroxides and alkali-silicates yielding poly(silicates)

poly(siloxo) type or poly(silico-aluminates) poly(sialate) type

acidic medium (Phosphoric acid) yielding poly(phospho-siloxo) and poly(aluminophospho) types

As an example, one of the geopolymeric precursors, MK-750 (metakaolin) with its alumoxyl
group Si-O-Al=O, reacts in both systems, alkaline and acidic. Same for siloxo-based and
organo-siloxo-based geopolymeric species that also react in both alkaline and acidic medium.

Geopolymer Terminology

In the late 1970s, Joseph Davidovits, the inventor and developer of geopolymerization,
coined the term geopolymer to classify the newly discovered geosynthesis that produces
inorganic polymeric materials now used for a number of industrial applications. He also set a
logical scientific terminology based on different chemical units, essentially for silicate and
aluminosilicate materials, classified according to the Si:Al atomic ratio:
Si:Al = 0, siloxo
Si:Al = 1, sialate (acronym for silicon-oxo-aluminate of Na, K, Ca, Li)
Si:Al = 2, sialate-siloxo
Si:Al = 3, sialate-disiloxo
Si:Al > 3, sialate link.

This terminology was presented to the scientific community at a IUPAC conference in 1976.
See for details in the Library the paper Milestone Paper IUPAC-76
In the introduction of his book on alkali-geopolymer cement, the alkali-cement scientist John
Provis, challenged the use of the word sialate arguing that the term sialate was already
in use (since the 1950s) to describe any of the salts of organic sialic acid He simply forgot
to mention that long before 1950 geology has been using extensively the term sialic, for
example in sialic metamorphic rocks, or the oceanic crust is mostly basaltic and the
continental crust is mostly sialic, meaning the rocks, such as granite, con tain high amounts of
aluminum and silica. Not to forget the fact that fly ashes were and still are commonly
classified into three entities: calcic-, ferric- and sialic-groups; the sialic component results
from the %weight of (Si02 + Al203 + TiO2). There exists another example, namely the well
known term SIALON, a specialist class of high temperature refractory materials, acronym of
silicon-aluminum-oxo-nitride, i.e. a scientific logical terminology. The geopolymeric sialate
term proceeds from the same scientific logic (it is the acronym of silicon-oxo-aluminate), in
contrast with the organic molecule sialic acid that was derived from an ancient Greek word
meaning saliva, with no scientific association. In fact, for our geopolymer molecules we write
poly(sialate) / polysialate or poly(sialate-siloxo), a terminology never used in biochemistry.
We shall therefore keep our terminology, use it and promote it without any restriction.
Geopolymers comprise following molecular units (or chemical groups):
-Si-O-Si-O- siloxo, poly(siloxo)
-Si-O-Al-O- sialate, poly(sialate)
-Si-O-Al-O-Si-O- sialate-siloxo, poly(sialate-siloxo)
-Si-O-Al-O-Si-O-Si-O- sialate-disiloxo, poly(sialate-disiloxo)
-P-O-P-O- phosphate, poly(phosphate)
-P-O-Si-O-P-O- phospho-siloxo, poly(phospho-siloxo)
-P-O-Si-O-Al-O-P-O- phospho-sialate, poly(phospho-sialate)
-(R)-Si-O-Si-O-(R) organo-siloxo, poly-silicone
-Al-O-P-O- alumino-phospho, poly(alumino-phospho)
-Fe-O-Si-O-Al-O-Si-O- ferro-sialate, poly(ferro-sialate)
Geopolymers are presently developed and applied in 10 main classes of materials:

Waterglass-based geopolymer, poly(siloxonate), soluble silicate, Si:Al=1:0

Kaolinite / Hydrosodalite-based geopolymer, poly(sialate) Si:Al=1:1

Metakaolin MK-750-based geopolymer, poly(sialate-siloxo) Si:Al=2:1

Calcium-based geopolymer, (Ca, K, Na)-sialate, Si:Al=1, 2, 3

Rock-based geopolymer, poly(sialate-multisiloxo) 1< Si:Al<5

Silica-based geopolymer, sialate link and siloxo link in poly(siloxonate) Si:Al>5

Fly ash-based geopolymer

Ferro-sialate-based geopolymer

Phosphate-based geopolymer, AlPO4-based geopolymer

Organic-mineral geopolymer