Review of Related Literature For Geopolymer Cobcrete

CHAPTER III: REVIEW OF RELATED LITERATURE
What to do? Compose it narratively.

1. Background:
- Discoveries: What is the current level of knowledge on the chosen subject?
What is known in this research?
- Inventions: Identify Groundbreaking Researches
- Explanations
2. Critique and evaluate other research work (Strengths and Weaknesses)
3. Justification for the research undertaken
- Why is conducting research on alkali-activated wood ash-mussel concrete
reasonable?
- Identify opposing views, if any
4. Shortcomings in the existing knowledge base on the subject
5. Ano mga dapat ituloy based sa mga past researches?
6. Mention other scientists working in the same field
7. How is the research project related to the works already done by others?
8. Identify Methodologies and research techniques used
9. Discuss the relationship between new findings and previous findings.
WOOD ASH
MUSSEL SHELL
GEOPOLYMER
PREPARATION
BINDING PROPERTIES OF ALKALI METAL COMPOUNDS
Retrospective Regarding Research in the Field of Alkali-Activated Geopolymer Materials
Geopolymers and geopolymerization – chemical characteristics

Most of the time, the rules of standards in force do not apply in producing new materials.
So, it is necessary to understand its chemical occurrences and its formation to a new
alternative and innovative material. This step towards developing the existing knowledge
about Geopolymer Concrete has a promising potential in practice to promote green
production. Geopolymer is a cementitious aluminum-silicate, amorphous material. In the
process of geopolymerisation, a polycondensation reaction between a geopolymer material
(fly ash) and alkali polysilicates takes place. It is where several aluminum-silicate materials
become geopolymers or inorganic polymers.
Simply put, geopolymers are a combination of different materials by alkaline activation
of materials rich in SiO2 and Al2O3. The entire process is still subject to a lack of data
consistency. The context of the mechanisms of the geopolymerisation shall cause the
dissolution of Al in an alkaline medium, transportation (orientation) of the solute, forming a
3D aluminum-silicate network structure.
With the abundance of Si-Al compounds sharing more than 65% in the Earth's crust, it is
essential to understand further how these new materials can contribute to developing new
types of concrete with good mechanical properties.
In 1999, Palomo proposed that pozzolanic materials like blast furnace slag and fly ash
can be activated "using alkaline liquids, to form a binder and completely replace the use of
Portland cement in the production of concrete." Still, only in 2001, research on geopolymer
concrete began to take shape. Publications specializing in this topic are a few. However, little
research exists; it's not enough to produce this material, considering that there are no full-
scale studies conducted with limited literature to understand what is known.
Mehta suggested in 2002 that by using fewer natural resources, using less energy, and
minimizing carbon dioxide emissions over long periods to produce new green concrete. He
positively correlated the reduction in calcined material, cement in concrete, and the number
of buildings made with conventional cement, to carbon dioxide emissions. For alkali-
activated geopolymer concrete to compete with Portland cement, it has to consider the
following: availability, cost, type of process used, and specific requests from users.
The empirical formula for the entire geopolymerisation process is:
M n {-(SiO2)z-AlO2}n, wH2O
Where:
 M = alkaline element, which can be: K (Potassium); Na (Sodium); Ca (Calcium)
 - = indicates the presence of bonding between elements
 n = degree of polymerization
 z = Si/Al ratio, ranging from 1 to 32
The reaction between the reactive solid and the alkaline activator will form an aluminum-
silicate network that is hard and water-resistant. The geopolymerisation reaction is shown
according to Figure 1.1.
Figure 1.1. Geopolymerization reaction.
In the case of alkali-activated fly ash-based geopolymer materials, the dissolution process
(geopolymerisation reaction) of Si and Al occurs when the fly ash comes into contact with the
alkaline solution. Then the large molecules will condense and form a gel that, under the alkaline
attack occurring on the surface of the particles, will lead to an expansion of the formed gel
covering the remaining voids to form a matrix. This alkaline attack occurs both from the outside
and from the inside of the molecules. As a result, the reaction product is generated inside and
outside the spheres until the ash particles are completely dissolved (Figure 1.2).
Figure 1.2. Descriptive model of alkali-activation of fly ash.

The materials exposed to a highly alkaline solution will break the Si-O-Si bond structure,
forming aluminum-silicate gels. This process is “synthesis via solution” with the introduction of
Al atoms as the catalyst. C-S-H (Calcium silicate hydrate) and C-A-H (Calcium aluminate
hydrate) phases depend on the chemical composition of the materials used and the reaction
conditions. Also, the concentration of solid matter plays a vital role in the alkaline activation
process.
The chemical reactions that produce alkali-activated fly ask-based geopolymers are
shown below showing the thermodynamic properties (enthalpy and entropy) of the fly ash.
Hydrating process SiO2 + 2OH- < > SiO3- + H2O
for vitreous silica,
with pH > 12 is:
And Al2O3 is Al2O3 + 2OH- < > 2AlO2- + H2O

hydrated
according to:
And CaO and CaO + H2O < > Ca2+ + 2OH-

MgO react as:
With Na2O and Na2O + H2O < > 2Na+ + 2OH-

K2O reacting:
Fe2O3 reacts Fe2O3 + 3H2O < > 2Fe3+ + 6OH-

according to:
And TiO2 TiO2 + OH- < > HTiO3

hydrates:
The chemical
reaction of fly ash
is:
It can be seen that silicon (Si), aluminum oxide (Al2O3), and titanium dioxide (TiO2)
consume hydroxides (OH-), and the earth alkalis, calcium oxide (CaO) and magnesium oxide
(MgO), and the alkaline substances sodium oxide (Na2O), potassium oxide (K2O) and iron oxides
(Fe2O3) produce hydroxides (OH-). Fly ash is rich in aluminum and amorphous silicon, which
make sit usable to produce geopolymers. The only important factor in the geopolymerisation
process is the type and concentration of the alkaline activator, which can affect the dissolution of
the fly ash.
Utilization of non-thermally activated clays in the production of geopolymers
explored the structural effects of the thermal pre-treatment of clays, as required in the
conventional synthesis of aluminosilicate geopolymers from metakaolin.
Joseph Davidovits (1991) was the first to produce aluminosilicate geopolymers. He
started by initiating a reaction in dehydroxylated kaolinite with a solution known for increasing
the intermolecular forces between particles; under high pH levels.
In his original literature, kaolinite must be treated at 800 degrees Celsius to achieve
complete dehydroxylation. This process helps geopolymer materials attain their energy-saving
property to set at ambient temperatures. The benefit was reducing the energy expenses required
to pre-process the primary solid reactant without compromising the product’s properties.
Earlier to this experiment was the works of Berg et al. (1970), where they produced
hydroxysodalite from blended raw kaolinite with NaOH solution and sand. This hydroxysodalite
requires 2 hours to form under 140-170 degrees Celsius of heat. It had a solid binding effect on
quartz sand and brick wastes, producing a building material that is highly resistant to abrasion
and frost.
On the other hand, Verdolotti et al. (2008) did not use controlled heat as pre-treatment in
their solid material. Instead, they used pozzolanic soils by reaction with an alkaline solution,
N AlO or a highly concentrated NaOH solution. The result was a strong material with similar
a 2,
XRD (X-ray diffraction) and NMR (Nuclear magnetic resonance) characteristics of a

conventional geopolymer. After all, it was found that the pozzolanic soil had contact with heat
from volcanic actions. With this, exposure to the high temperature of solid raw materials remains
essential in synthesizing and achieving geopolymer’s strong properties.
With the evidence that the products mentioned above have similarities with Davidovits’
geopolymers, Skvara (2007) shed light on the relationship between geopolymers and other
alkali-activated materials. He claimed that geopolymers are formed when reaction mixtures
contain a high proportion of the solid phase. In contrast, other reaction conditions of raw
materials can produce different zeolitic cementing compounds or gels, considering the effects of
reaction conditions such as alkali type, concentration, water content, reaction temperature, etc.
Two years later, Professor Kenneth Mackenzie came to explore the effect range of
thermal pre-treatment to the original atomic structure and composition of aluminosilicate clay
minerals. He also questions why the minerals' increased reactivity to alkali after thermal pre-
treatment makes it usable to form geopolymers similar to Davidovit’s (Mackenzie, 2009). His
doctorate in solid-state chemistry and significant contributions to materials chemistry took his
research to explore more methods that form other geopolymer precursors. Mackenzie (2009)
considered alternative pre-treatment methods for producing similar results on clays to synthesize
lower-energy geopolymers. The alternative pre-treatments include mechanochemical processing
(energetic grinding) of the raw clay and treatment with acid or alkali. He discussed how the
chemical reaction of solid starting materials could reorganize the materials’ simple atomic
structure into something more complex yet essential for easier production. In this way, producing
uncommon yet soft geopolymers is possible without using any aluminosilicate materials.
Mackenzie explored the dehydroxylation of a 1:1 layer-lattice aluminosilicate minerals,

kaolinite, and halloysite. Kaolinite is the starting material used in the synthesis phase of the
Davidovits-type of geopolymer. Its structure is composed of sheets of silicon-oxygen tetrahedra
(silica) and a series of aluminum-oxygen octahedra (alumina). Since each molecular geometry
has hydroxyl groups in its common layers, aluminum atoms are mostly affected during
hydroxylation. If energy absorption occurs wherein kaolinite is exposed to 500 to 600 degrees
Celsius, it will remove the hydroxyl water forming a kaolinite dehydroxylate (or metakaolin)
with 14% mass loss. This process is called dehydroxylation. When observed under x-ray
analysis, the atomic structure of metakaolin is highly distorted. The result enforced the disorder
in the solid-state MAS NMR spectroscopy. The findings explained that the distortion caused by
thermal dehydroxylation increased the reactivity of the metakaolinite during geopolymerisation.
This is also why there are different behaviors of the 2:1 layer lattice aluminosilicate mineral.
Halloysite is another geopolymer precursor with a similar chemical composition to kaolinite but
is different in form and structure. This mineral comes in kaolinite plate tubes with added water
inside. After two endothermic events at 150 and 550 degrees Celsius, there was a 2.6% loss of
internal hydration water, and normal hydroxylation was achieved, respectively. Mackenzie et al.
(2007) mentioned that halloysite dehydroxylate is preferred in some studies to metakaolin
because of their difference in availability in a highly pure form.
Figure 1.3 Structures of the layer-lattice aluminosilicate minerals, showing the octahedral Al-O
and tetrahedral Si-O sheets and how these are stacked in (A) 1:1 layer lattice aluminosilicate
(e.g., kaolinite) and (B) 2:1 layer lattice aluminosilicate (e.g., pyrophyllite).

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CHAPTER III: REVIEW OF RELATED LITERATURE

What to do? Compose it narratively.

Geopolymers and geopolymerization – chemical characteristics

Figure 1.2. Descriptive model of alkali-activation of fly ash.

And Al2O3 is Al2O3 + 2OH- < > 2AlO2- + H2O

And CaO and CaO + H2O < > Ca2+ + 2OH-

With Na2O and Na2O + H2O < > 2Na+ + 2OH-

Fe2O3 reacts Fe2O3 + 3H2O < > 2Fe3+ + 6OH-

And TiO2 TiO2 + OH- < > HTiO3

Utilization of non-thermally activated clays in the production of geopolymers

XRD (X-ray diffraction) and NMR (Nuclear magnetic resonance) characteristics of a

Mackenzie explored the dehydroxylation of a 1:1 layer-lattice aluminosilicate minerals,

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