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.

0. .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). 5‐8% of all human‐generated atmospheric CO2.82 tonnes of CO2 for every tonne of OPC.

   Increased • durability.Geopolymer Concretes Geopolymers refer to alkali‐activated binders  (AAB’s). • fire protection fire protection. . Performance often exceeds that of Portland cement  concretes. Applications in replacing Portland cement‐based  concrete materials. Geopolymers are a cement‐free concrete. • resistance to chemical attack. Geopolymers studied for the last 40+ years.

.g. Use of other synthetic reactive aluminosilicate pozzolans  and alkaline activators possible. activated with alkaline solutions Originally metakaolinite with siliceous solutions. etc. Using PFA‐based geopolymers will have an impact on  national and international targets on CO2 reduction.Geopolymer Concretes Produced from natural and synthetic pozzolanic solids. PFA. GGBS.  Waste stream or by product pozzolans readily available e. Waste‐stream or by‐product pozzolans readily available .  activated with alkaline solutions.

 and excesses are stockpiled or  “landfilled”. “l dfill d” Commercialisation of PFA in geopolymers will help  g p y p to reduce landfill. F t d d h l t tili i ti t k . Future demand may help to utilise existing stocks.Environmental Considerations of PFA: Landfill Waste‐stream pozzolans such as PFA not recycled to  their full capacity.

3. . Dissolution of pozzolan with in alkaline solution. Gel formation of aluminosilicate chains. Polycondensation of chains to form interlocking  network.Geopolymer Concretes Three basic steps  to reaction: 1. 2.

Alkalis tested include: • Sodium hydroxide. KOH. • Potassium hydroxide.Our starting work on geopolymers At Liverpool: Investigated mortars using PFA. NaOH. • Sodium silicate . Effect of different lab‐grade alkali activators and  curing temperatures on strength development.

.The effect of curing temperature on strength Example: PFA activated with ti t d 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 90 C: Curing at 90oC • 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.

.33 3.2 The mass of activator solution added to mix was kept constant through these experiments Using sodium silicate activator. Further experiments for hydroxide activation expected to be similar. SG 1. increasing the concentration gives  increase in strength.5 2. SG 1.The effect of activator concentration on strength Example: PFA activated with sodium silicate of 3 different concentrations: 1. SG 1.

 also has an effect. Concrete masonry blocks Type of activator.The effect of the activator on strength BS EN 771 Class B Engineering brick Example: PFA activated with: • sodium silicate SG1. Curing temperature 70oC. . 10M • NaOH 10M. hydroxide or silicate. • KOH 10M. Alkali cation. and for comparison: • 2:1 sodium silicate and KOH mix.5. Alkali added to each mix to give a constant workability. K or Na. has an effect of the strength.

. Undertaking market research to identify: • What alkalis are currently in the waste‐stream in  the UK? • Q Quantity? tit ? • Quality? • Consistency through time? Any further information that you can provide us with  will be well received.What alkaline activators are in the waste-stream? Current work uses lab‐grade alkaline activators.

Porosity developed during mixing that  cannot escape due to high viscosity of mixes. cannot escape due to high viscosity of mixes. due to: b l d 1. 2.  Porosity cannot escape  due to viscous gelling and polycondensing d i lli d l d i paste at elevated temperature. Porosity inherent to dissolution of hollow  PFA cenospheres.   Porosity on a sub‐micron to mm scale.Porosity development Geopolymer mixes continue to be affected by  high porosity. .

  Effects on paste not yet fully  investigated. Potential problems: • Percolation of atmospheric acid solutions and  e co at o o at osp e c ac d so ut o s a d sulphates. • Thermal insulation.Problems and benefits of porosity Porosity is closed‐cell. Ways to manage porosity: • Use more suitable surfactants/ defoamers/  wetting agents/ superplasticisers. Benefits of porosity:   B fit f it • Resilience to freeze‐thaw weathering. . hence permeability is l P i i l d ll h bili i low.  Deterioration of re‐bar expected.

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 & microchemical characterisation Important to understand why different materials have  different strengths. .

.Microstructural Characterisation with Scanning Electron Microscopy CamScan X500 FEG‐SEM. Combining electron optic imaging  capabilities with in situ chemical analysis  with EDS allows full microstructural  characterisation of materials. Philips XL30 W‐SEM. Department of Earth & Ocean Science has  p a state‐of‐the‐art electron optics facility.

•quality and nature of fractions •porosity. •nature of interfaces between particles nature of interfaces between particles  and paste. Backscatter imaging can assess the  microstructural characteristics: •quality and nature of fractions.  elements/load bearing framework •relationship between unreacted or  partially reacted components.  •connectivity of structural  elements/load bearing framework.Microstructural Characterisation Reacted geopolymer matrix PFA spherules Fe nodules Qtz Sand Qtz Sand Porosity 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.   impurities. and spatial distribution of phases. Ca K . thus  distribution of elements in samples thus identifying constituent mineral components.Microstructural Characterisation Qtz Sand Backscatter image of PFA – Na‐silicate geopolymer.

• micro‐chemistry.Microstructural Characterisation Graphite Secondary electron imaging and chemical  analysis of PFA provides: • grain size distribution. . • non‐aluminosilicate content.

• porosity. weakness and permeability . • unreacted PFA.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. • desiccation cracks as lines of  weakness and permeability.

Isothermal calorimeter Determined rate and amount of reaction.Other analytical techniques Intensity (counts) Quartz 8000 6000 Mullite Mullite X‐ray diffraction spectroscopy  Assess the fraction of reactive amorphous material  in PFA. in PFA X‐ray fluorescence spectroscopy Analysis of bulk chemistry of PFA or geopolymers. 45 50 55 60 65 2Theta (°) 4000 Quartz Mullite 2000 Significant non-crystaline component g y p 0 5 10 15 20 25 30 35 40 Coulter laser diffraction granulometry Grain size distribution of PFA. Gives insight into grain‐size dependence of the reaction.  Observe real‐time curing and  b l d associated change in chemistry and elemental  distribution. . Environmental scanning electron microscopy Lower vacuum.  Can compare this to  the grain size distribution in geopolymer.  Gives  the grain size distribution in geopolymer.

Future work • Investigate effects of different alkali activators  with a more detailed matrix of mixes.  management of porosity with admixtures.g. • The type of alkali Aluminates Hydroxides Silicates • Alkali concentration • Curing temperature Investigate other pozzolanic solids. • • . Study and refine geopolymer properties. Class C PFA.  particularly GGBS. e.

. To find widespread appeal.  This means  using silicate activators preferentially to caustic ones (use of  admixtures to manage rheology and porosity is necessary).  work needs to be done now in order to establish.  pivotal and market‐leading. • Minimising the corrosivity and irritation hazards.  For geopolymers made from 100% recycled materials. maintain and  work needs to be done now in order to establish maintain and secure the industry and infrastructure.   Estimated usage of geopolymers in 2015 is 1000 million tonnes  globally. geopolymers need to be more user‐ friendly: • Dry ready mixes Dry ready‐mixes.Future thoughts and considerations: from the lab to the marketplace Current limiting factor in commercialising PFA‐geopolymers is  alkali activators. UK’s northwest industries have the opportunity to be innovative.

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