Geopolymer Concrete

GEOPOLYMER CONCRETE Abstract
Limestone and clay are the prime raw materials used in the manufacturing of Portland cement and quarrying of them is becoming the source of environmental degradation. Past few researches showed that in coming years limestone will be hardly available for cement production. Besides that, carbon footprints due to cement production are causing global warming. In addition to this, waste disposal is also becoming a global issue because of scarcity and expensiveness of landfills Polymeric concrete utilizes waste materials such as Fly Ash (FA) and Rice Husk Ash (RHA) together with alkaline solution (NaOH & NaSiO 2), which results in a green binder to replace cement. This study focuses on complete elimination of Portland cement for production of concrete. This study incorporates Fly Ash as base source material in polymeric concrete. Polymeric concrete gives higher compressive strength and tensile strength values for external exposure curing as well as better development of microstructure for the same, compare to ordinary concrete

1. Introduction
Concrete usage around the world is second only to water. Ordinary Portland cement (OPC) is conventionally used as the primary binder to produce concrete. The environmental issues associated with the production of OPC are well known. The amount of the carbon dioxide released during the manufacture of OPC due to the calcination of limestone and combustion of fossil fuel is in the order of one ton for every ton of OPC produced. In addition, the extent of energy required to produce OPC is only next to steel and aluminium. On the other hand, the abundant availability of fly ash worldwide creates opportunity to utilize this by-product of burning coal, as a substitute for OPC to manufacture concrete. When used as a partial replacement of OPC, in the presence of water and in ambient temperature, fly ash reacts with the calcium hydroxide during the hydration process of OPC to form the calcium silicate hydrate (C-S-H) gel. The development and application of high volume fly ash concrete, which enabled the replacement of OPC up to 60% by mass is a significant development. (Malhotra 2002; Malhotra and Mehta 2002), In 1978, Davidovits (1999) proposed that binders could be produced by a polymeric reaction of alkaline liquids with the silicon and the aluminium in source materials of geological origin or by-product materials such as fly ash and rice husk ash. He termed these binders as geopolymers.

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Geopolymer Concrete

2. Materials in Geopolymer Concrete 2.1 Fly Ash
A waste material from power stations, fly ash has been used as a mineral admixture component of Portland-pozzolans blended cement for nearly 60 years. This, the largest use of fly ash, consumes about 10 percent of fly ash produced throughout the world. Another 10-15 percent is used for construction, building materials and beneficiation applications. Remaining 75-80 percent is disposed of as waste. According to the American Concrete Institute (ACI) Committee, fly ash is defined as ‘The finely divided residue that results from the combustion of ground or powdered coal and that is transported by flue gasses from the combustion zone to the particle removal system’ (ACI Committee 232 2004) ’ . Fly ash is removed from the combustion gases by the dust collection system, either mechanically or by using electrostatic precipitators, before they are discharged to the atmosphere. Fly ash particles are typically spherical, finer than Portland cement and lime, ranging in diameter from less than 1 µm to no more than 150 µm. The chemical composition is mainly composed of the oxides of silicon ( SiO2), aluminium (Al2O3), iron (Fe2O3), and calcium (CaO), whereas magnesium, potassium, sodium, titanium, and sulphur are also present in a lesser amount. The major influence on the fly ash chemical composition comes from the type of coal (Malhotra and Ramezanianpour 1994).
Table 1. Chemical composition ash weight% fly ash SiO2 53.79 Al2O3 32.97 Fe2O3 5.51 CaO 1.84 MgO 0.92 SO3 0.46 K2O 1.76 Na2O 0.37 TiO2 2.1 P2O5 0.15

U s e o f Fl y A sh in Co n cre te One of the efforts to produce more environmentally friendly concrete is to reduce the use of OPC by partially replacing the amount of cement in concrete with by-products materials such as fly ash. As a cement replacement, fly ash plays the role of an artificial pozzolan, where its silicon dioxide content reacts with the calcium hydroxide from the cement hydration process to form the calcium silicate hydrate (C- S-H) gel. The spherical shape of fly ash often helps to improve the workability of the fresh concrete, while its small particle size also plays as filler of voids in the concrete, hence to produce dense and durable concrete. An important achievement in the use of fly ash in concrete is the development of high volume fly ash (HVFA) concrete that successfully replaces the use of OPC in concrete up to 60% and yet possesses excellent mechanical properties with enhanced durability performance. HVFA concrete has been proved to be more durable and resource-efficient than the OPC concrete.The HVFA technology has been put into practice, for example the construction of roads in India, which implemented 50% OPC replacement by the fly ash (Malhotra 2002). Page 2

Geopolymer Concrete

2.2 Alkaline Solutions
A combination of sodium silicate solution and sodium hydroxide solution was used to react with the aluminium and the silica in the fly ash. The sodium silicate solution comprised Na2O=14.7%, SiO2=29.4%, and water=55.9% by mass. Sodium hydroxide (commercial grade with 97% purity) pellets were dissolved in water to make the solution. .

3. GEOPOLYMER CONCRETE
In this work, fly ash-based geopolymer is used as the binder, instead of Portland or other hydraulic cement paste, to produce concrete. The fly ash-based geopolymer paste binds the loose coarse aggregates, fine aggregates and other un-reacted materials together to form the geopolymer concrete, with or without the presence of admixtures. The manufacture of geopolymer concrete is carried out using the usual concrete technology methods. As in the case of OPC concrete, the aggregates occupy about 75-80 % by mass, in geopolymer concrete. The silicon and the aluminium in the fly ash react with an alkaline liquid that is a combination of sodium silicate and sodium hydroxide solutions to form the geopolymer paste that binds the aggregates and other un-reacted materials. Geopolymers are members of the family of inorganic polymers. The chemical composition of the geopolymer material is similar to natural zeolitic materials, but the microstructure is amorphous instead of crystalline. The polymerisation process involves a substantially fast chemical reaction under alkaline condition on Si-Al minerals that result in a three- dimensional polymeric chain and ring structure consisting of Si-O-Al-O bonds, as follows (Davidovits 1999): M n [ -(SiO2) z –AlO2] n. wH 2 O (2-1) Where: M = the alkaline element or cation such as potassium, sodium or calcium; the symbol – indicates the presence of a bond, n is the degree of polycondensation or polymerization; z is1,2,3, or higher, up to 32. Geopolymerization involves the chemical reaction of alumino-silicate oxides (Si2O5, Al2O2) with alkali polysilicates yielding polymeric Si – O – Al bonds. Polysilicates are generally sodium or potassium silicate supplied by chemical industry or manufactured fine silica powder as a by-product of ferro-silicon metallurgy. Equation 2-2 shows an example of polycondensation by alkali into poly. The schematic formation of geopolymer material can be shown as described by Equations (2-2) and (2-3) (van Jaarsveld et al. 1997; Davidovits 1999):

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Geopolymer Concrete

(Si2O5, Al2O2)n + nSiO2 + nH2O

NaOH, KOH

n(OH)3 -Si-O-Al-O-Si-(OH)3 (OH)2

(-)

n(OH)3 -Si-O-Al-O-Si-(OH)3 (OH)2

(-)

NaOH, KOH

(Na,K)(+) –(-Si-O-Al-O-Si-O-) + nH2O O O O (2-2)

(-)

Unlike ordinary Portland/pozzolanic cements, geopolymers do not form calciumsilicate-hydrates (CSHs) for matrix formation and strength, but utilise the polycondensation of silica and alumina precursors and a high alkali content to attain structural strength. Therefore, geopolymers are sometimes referred to as alkali- activated alumino silicate binders. The last term of Equation 2-2 indicates that water is released during the chemical reaction that occurs in the formation of geopolymers. This water is expelled from the mixture during the curing process.

3.1 Fresh Geopolymers and Manufacturing Process
Only limited information on the behaviour of the fresh geopolymers has been reported. Using metakaolin as the source material, Teixeira-Pinto et al (2002) found that the fresh geopolymer mortar became very stiff and dry while mixing, and exhibited high viscosity and cohesive nature. They suggested that the forced mixer type should be used in mixing the geopolymer materials, instead of the gravity type mixer. An increase in the mixing time increased the temperature of the fresh geopolymers, and hence reduced the workability. To improve the workability, they suggested the use of admixtures to reduce the viscosity and cohesion. While Teixeira-Pinto et al (2002) concluded that Vicat needle apparatus is not appropriate to measure the setting time of fresh geopolymer concrete, Chen and Chiu (2003) reported the only information available to date on the quantitative measure of the setting time of geopolymer material using the Vicat needle. For the fresh geopolymer paste based on metakaolin and ground blast furnace slag, they measured the setting time of the geopolymer material both at room and elevated temperature. In the elevated temperature, the measurement was done in the oven. They found that the initial setting time was very short for geopolymers cured at 60oC, in the range of 15 to 45 minutes. Barbosa et al (1999) measured the viscosity of fresh metakaolin-based geopolymer paste, and reported that the viscosity of the geopolymer paste increased with time.

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Geopolymer Concrete

Most of the manufacturing process of making geopolymer paste involved dry mixing of the source materials, followed by adding the alkaline solution and then further mixing for another specified period of time.

3.2 Reaction Mechanism
The chemical reaction may comprise the following steps • Dissolution of Si and Al atoms from the source material through the action of hydroxide ions. • Transportation or orientation or condensation of precursor ions into monomers. • Setting or polycondensation/polymerization of monomers into polymeric structures. However, these three steps can overlap with each other and occur almost simultaneously, thus making it difficult to isolate and examine each of them separately

3.3 Mixing
It was found that the fresh fly ash-based geopolymer concrete was dark in colour (due to the dark colour of the fly ash), and was cohesive. The amount of water in the mixture played an important role on the behaviour of fresh concrete. When the mixing time was long, mixtures with high water content bled and segregation of aggregates and the paste occurred. This phenomenon was usually followed by low compressive strength of hardened concrete. Davidovits suggested that it is preferable to mix the sodium silicate solution and the sodium hydroxide solution together at least one day before adding the liquid to the solid constituents. He also suggested that the sodium silicate solution obtained from the market usually is in the form of a dimer or a trimer, instead of a monomer, and mixing it together with the sodium hydroxide solution assists the polymerization process. When this suggestion was followed, it was found that the occurrence of bleeding and segregation ceased. From the preliminary work, it was decided to observe the following standard process of mixing in all further studies. • • Mix sodium hydroxide solution and sodium silicate solution together at least one day prior to adding the liquid to the dry materials. Mix all dry materials in the pan mixer for about three minutes. Add the liquid component of the mixture at the end of dry mixing, and continue the wet mixing for another four minutes.

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Geopolymer Concrete

3.4 Curing
Geopolymer concrete specimens should be wrapped during curing at elevated temperatures in a dry environment (in the oven) to prevent excessive evaporation. Unlike the small geopolymer paste specimens, which can easily be wrapped by placing a lid on the mould, a suitable method was needed for large size geopolymer concrete specimens. Extensive trials revealed wrapping of concrete specimens by using vacuum bagging film is effective for temperatures up to 100oC for several days of curing. Preliminary tests also revealed that fly ash-based geopolymer concrete did not harden immediately at room temperature. When the room temperature was less than 30oC, the hardening did not occur at least for 24 hours. Also, the handling time is a more appropriate parameter (rather than setting time used in the case of OPC concrete) for fly ash-based geopolymer concrete.

4.Rheological Properties. 4.1 Strength Development
The strength values of pastes, mortars and concretes prepared on the basis of fly ash geopolymers obtained at periods of 2 – 360 days show a rising trend. Depending on the conditions of preparation and composition, the values of compressive strength for pastes, mortars and concretes range between 15-70 MPa after 28 days. The highest strength values obtained were for geopolymers based on fly ash and blast-furnace slag ranging between 100-160 MPa of compressive strength at 28 days after preparation. Fig 1 illustrates the strength development of geopolymer concrete.

60

Compressive strength (MPa )

50 40 30 20 10 0 40 30 20 10

28 d 14 d 7d Fly ash content in concrete (m ass%)

Figure 1. Time pattern of geopoplymer concrete's strength development
(Courtesy : Frantisek ŠKVÁRA and all, Thailand)

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Geopolymer Concrete

4.2 Chemical Composition
1088 466 117 2

564 780 468 563

799 103 9 117 2

Fly ash

780 799

geopolyme r

380

580

780

980

1180

1380

Waven umbers (cm

-1

)

Figure 2. IR spectra of fly ash and geopolymer
(Courtesy : Frantisek ŠKVÁRA and all, Thailand)

The FTIR spectra (Fig.2) reflect the differences caused by different conditions of alkaline activation. The strip corresponding to Si-O and Al-O vibrations for original fly ash is 1080-1090 cm-1, while for geopolymer it is shifted to lower values. This shift is interpreted as the result of Al penetration into the original structure of the Si-O-Si skeleton, analogically to what was detected in zeolites. The more dramatic the shift, the higher the penetration degree of Al from glasslike fly ash components into [SiO4]4- the network probably is. In Si NMR MAS spectra, the majority signal identified for original fly ash is the signal attributed to tetrahedric [SiO4]4- (Si(0Al), which belongs to the presence of silica. In this spectrum, the coordination Si(2-3Al) was further found, which probably belongs to the mullitic phase. The situation detected for the geopolymer was different. Here, the Si(0Al) coordination was less represented, while the Si(2-3Al) coordination was more represented, which again proves the penetration of Al into the [SiO4]4- network. This interpretation of NMR spectra is supported by other reference publications.

Table 2. Spectrum measurements FTIR and NMR MAS Fly ash geopolymer (paste = 0,27) strength 70 MPa Al NMR Si NMR -89.5 ppm 56 % Si(3Al) 50.4 ppm 90 % AlQ4(ASi) -97.6 ppm 31 % Si(1Al) -4.3 ppm 10 % AlQ2-3(2-3Si) -107.6 ppm 13 % Si(0-1Al)

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Geopolymer Concrete

Figure .3. Detailed nature of geopolymer (paste w=0.27, fracture surface, 28 days after preparation)
(Courtesy : Frantisek ŠKVÁRA and all, Thailand)

The geopolymerization process (alkaline activation of fly ashes in a water environment at pH 12) during which material hardening occurs differs from the hydration processes of inorganic binders, e.g. Portland cement. This process seems to follow mostly a mechanism "through a solution" where in a highly alkaline environment fly ash particles are first dissolved, and a new geopolymer structure is formed from the solution, see Fig. 3. A 2D-3D inorganic hydrated polymer (geopolymer) arises with a general formula M n [ -(SiO2) z –AlO2] n. wH 2 O A prominent share in this process, apart from preparation conditions, is also that given by the presence of Ca atoms, which enter the Si-O-Al-O skeleton compensating the charge on Al atoms. These charges are usually compensated by Na+ ions. Ca2+ ions, however, can probably interconnect individual Si-O-Al-O chains thus forming a more solid structure with higher strengths during alkaline activation of fly ashes with the presence of Ca- containing substances. The prominent role of Ca atoms in the geopolymer skeleton is also testified by the results of reference publications.

4.3 Porosity of Geopolymer
The mass of fly ash-based geopolymer shows the presence of residues of original fly ash particles on which the effect of gradual dissolution is evident . In these geopolymers, relatively high porosity (up to 50%) was determined regardless of the type of conditions of their preparation. Closed spherical pores are present here, which were formed by the dissolution of the original fly ash particles or by air entrainment during preparation. The effect of preparation conditions, i.e. the content of Na2O or the SiO2/Na2O ratio respectively, is manifested not only by the strength values of the geopolymers reached, but also by the pore size distribution. The porosity of geopolymers is also significantly affected by the water/cement (H2O /fly ash) ratio, see Fig.4.

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Geopolymer Concrete

Figure 4. Porous nature of geopolymer (paste w=0.27, fracture surface, 28 days after preparation
(Courtesy: Frantisek ŠKVÁRA and all, Thailand)

0.4

AAFa

0.1

0.32

0.3

0.30

0.08

dV/dlog(r) (cm 3/g)

dV/dlog(r) (cm 3 /g)

0.06

0.2

0.27

0,25

0.23
0.1

0,23

0.02

Fly ash+slag
0 10
0

0 10
1

10

2

r (nm)

10

3

10

4

10

5

1

10

100

r (nm)

Figure 5. Effect of water/cement ratio on pore size in geopolymer, paste with w/c ratio Figure 8. Pore size distribution in distribution (Hg pore-volume analysis)

Figure 6. Pore size distribution in Geopolymers (BET)

geopolymers

geopolymers (BET)
(Courtesy : Frantisek ŠKVÁRA and all, Thailand)

The effect of adding Ca-containing substances is manifested not only by increased strength, but also by lowered porosity. The considerably lower porosity is obtained in the geopolymers prepared from fly ash and slag mixes, where total porosity amounted to 2-10%, and a shift Page 9

Geopolymer Concrete towards lower pore dimensions was recorded. For these substances, the compressive strength reached was 100-160 MPa. The high-pressure Hg pore-volume analysis, however, provides only limited information on the nature of pores in the nanometric domain. Additional information is obtained through BET isotherm measurement. Fig. 6 displays pore size distribution in geopolymers prepared under different conditions. The results clearly point out the fact that in the nanometric domain geopolymers are of a relatively similar nature, which does not much depends upon conditions of preparation.

4.4 Durability of Geopolymer Concrete
The mass of the sample bodies did not change practically during the freezing and defrosting cycles taking place in the aqueous environment The compressive strength of the sample bodies after the freezing cycles were lower as compared with those obtained for the samples after 28 days without any frost resistance tests. No visible defects or deformation could be observed after 150 cycles. After 150 freezing cycles, the strength values dropped to about 70% of the strength measured in the same period of time. It is obvious from the results obtained that the geopolymers materials on the basis of the fly ash possess an excellent frost resistance. Geopolymer mortars and concretes kept in the NaCl solution for long periods of time resist to corrosion without showing any signs of sample damage. The exposure of the geopolymers materials to the NaCl solution resulted in the consistent increase in the compressive strength during the whole period of measurement (720 days) and the values were as high as 70 MPa. The mass of the samples kept in the NaCl solution grew during the 1st year (by about 3% relative) to become stable afterwards. The penetration of chloride ions into the body of the geopolymers materials (point analyses, the measurement was carried out in the direction perpendicular to the surface in contact with the NaCl solution) shows a decreasing trend and the chloride concentration in the body is low. Almost no corrosion products could be found on the surface of the geopolymer materials while they were kept in the NaCl solution. The exposure of geopolymers materials to the solutions of sulfates and NaCl did not result in the formation of new crystalline phases. The RTG diffraction analysis only confirmed the occurrence of original crystalline phases present in the fly ash. The absence of expansive products as, for instance, the ettringite or Friedel salt in the samples after the two-year exposure to the salt solution is an important finding. The resistance of geopolymer concretes to the action of salt solutions is better than that of the cement-based concrete in which the crystalline ettringite or the Friedel salt are formed; eventually, the body disintegrates in result of the crystallization stress. The effect of high temperatures on the properties of geopolymer mortars was investigated in the temperature range of 150 to 1100oC. A geopolymer material exposed to the action of high temperatures loses a substantial part of its strength that drops to 40 % of its original value. The strength already starts dropping at a temperature of 250 oC and it remains practically the same at higher firing temperatures. The lowest values of the residual strength were observed in the temperature range of 600 to 700oC; they were due to the presence of the melt started forming. The values of the residual strength after the firing were rather higher than those characterizing the materials on the basis of Portland cement. Page 10

Geopolymer Concrete The test aimed at determining the resistance of the concrete on the basis of fly ash to the action of higher temperatures was carried out by the 3-point loading of the bodies while the tensile strength under bending was determined. Of course, the selection of the aggregate plays an important role in this case

4.5 Geopolymer – aggregate interface
There is a transition layer between the aggregate grain and hardened cement in the ordinary concrete on the basis of the standard Portland cement. The thickness of the layer ranges from 20 to 100 µm; the layer microstructure and composition differ from that of hardened cement. The contents of Ca (OH) 2 and ettringite are higher. There are often Ca (OH) 2 particles oriented along the aggregate particles. The porosity of the transition layer is larger than that of the hardened cement and a porosity gradient with the decreasing character in the direction away from the aggregate particles could be observed. The character of the geopolymer – aggregate boundary is quite different. No transition zone could be detected either morphologically or by a direct measurement of the geopolymer compositions in the proximity of the aggregate itself (Fig. 7, 8) in contrast to the concrete made of Portland cement

Fig. 7. Geopolymer concrete (polished section, optical microscope).
(Courtesy : Frantisek ŠKVÁRA and all, Thailand)

Fig. 8. Boundary between the aggregate (reinforcement) and the geopolymer in the concrete (polished section, BSE representation).
(Courtesy : Frantisek ŠKVÁRA and all, Thailand)

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5. Parameters Influencing Compressive Strength Of Concrete
The following parameters have effect on compressive strength of geo-polymer concrete:

Fluid-to-fly ash ratio Concentration of NaOH solution

• Sodium silicate (Na2SiO3) to sodium hydroxide (NaOH) ratio (by weight) • Curing type (microwave oven and hot air oven), curing temperature • Curing time • Molarity of sodium hydroxide (NaOH) solution • Water-to-fly ash ratio, • Water-to-geopolymer solids ratio, • Rest period

Effect of Salient Parameters
5.1 Fluid-To-Fly Ash Ratio

30

Compressive Strength (MPa)

24 18 12 6 0 10 20 30 Age Of Concrete ( Days ) Fluid/Fly Ash=0.31 Fluid/Fly Ash=0.35 Fluid/Fly Ash=0.41

Graph 1. Variation Of Compressive Strength With Fluid/Fly Ash Ratio

5.2 Concentration Of Sodium Hydroxide (NaOH) Solution

50 40 30 20 10 0 8C6 10C1 12C1 mix no.
Graph 2. Variation Of Compressive Strength Of Geopolymer Concrete With Molarity Of NaOH solution ( For Fluid-to-Fly Ash Ratio = 0.35 )

3 days 7 days 28 days

16C1

20C1

5.3 Curing Conditions Hot Air Oven
Curing Temperature
Compressive Strength (MPa)
30 25 20 15 10 5 0 0 20 40 60 80 100 Curing Temperature In Degree Centrigrade 3 Days 7 Days 28 Days

Graph 3. Effect Of Curing Temperature On Strength Of Geopolymer Concrete

Duration of Curing
Compressive Strength (MPa)
45 40 35 30 0 5 10 15 20 Time Of Testing In Days 25 30 60 hours 72 hours 48 hours

Graph 4. Effect Of Duration Of Curing (hrs) On Compressive Strength

Conclusions

1. A concrete can be prepared by using the geopolymer binder. No shrinkage due to hydration (typical for the cement-based concretes) takes place in the concrete. The ratio of the compressive strength to the tensile strength under bending varies in the range of 10.0: 5.5 . The strength values of the geopolymer concrete increase in the long run. 2. Rheological properties of concretes differ from those of Portland cement. 3. The geopolymer concrete is resistant to the corrosive environments. 4. No transition phase with a different composition as this is typical for a concrete on the basis of Portland cement was found between the geopolymers and the aggregate.

COURTESY
• Frantisek ŠKVÁRA , Pavel SVOBODA : Concrete Based on Fly Ash as Geopolymer. The Tenth East Asia-Pacific Conference on Str.Engg And Construction

• H.W. Nugteren,V.C.L. Butselaar-Orthlieb produced from coal combustion fly ash

M. Izquierdo : High Strength Geopolymers

• The Student Projects, Jadavpur University, Kolkata: Study on Strength of Fly Ash Based Geopolymer Concrete • Mark Drechsler, Adelaide, South Australia: Geopolymers- A new tech. for sustainability in mining, construction and hazardous wastes in industries • M.F.Nuruddin, Sobia Qazi, N.Shafiq, Kusbiantoro: Polymeric Concrete: Complete Elimination of Cement For Sustainable Futures. ICSBI 2010 KL Conference • D. Hardjito and B. V. Rangan , Development And Properties Of Low Calcium Fly Ash Based Geopolymer Concrete