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    2 16 rue Galilée INSTITUT F-02100 Saint-Quentin, France ws) c. > Tel.: +33/ (0)323 676 988 @~% GEOPOLYMERE Fax: 433/(0)959 977 711 copoly-info@ geopalymer.org wreb: www geopolymer rg GEOPOLYMER CEMENT a review by Professor Joseph Davidovits January 2013 Content 1. Introduction 2. Portland cement chemistry vs Geopolymer cement chemistry 2.1 Alkali-activated materials vs Geopolymer cements. 2.2 User-friendly alkaline-reagents 3. Geopolymer cement categories 3.1 Slag-based geopolymer cement 3.2 Rock-based geopolymer cement 3.3 Fly ash-based geopolymer cements 3.4 Ferro-sialate-based geopolymer cement 4. CO; emissions during manufacture 4.1 CO; emission during manufacture of Portland cement clinker 4,2 Geopolymer Cements Energy Needs and CO, emissions 4.2.1 Rock-based Geopolymer cement manufacture involves: 4.2.1.1 Energy needs 4.2.1.2 CO; emissions during manufacture 4.2.2 Fly ash-based cements Class F fly ashes 5. Properties for Rock-based geopolymer cement (Ca,K)-poly(sialate-disiloxo) 6. The need for standards References Geopolymer Cement, a review; J. Davidovits 2 1. Introduction From a terminological point of view, geopolymer cement [1] is a binding system that hardens at room temperature, like regular Portland cement. if a geopolymer compound requires heat setting it may not be called geopolymer cement but rather geopolymer binder. Geopolymer cement is an innovative material and a real alternative to conventional Portland cement for use in transportation infrastructure, construction and offshore applications. It relies on minimally processed natural materials or industrial byproducts to significantly reduce its carbon footprint, while also being very resistant to many of the durability issues that can plague conventional concretes ‘Alumino-silicates Creating geopolymer cement requires an Cucoot care alumina silicate material, a user-friendly take alkaline reagent [2] (sodium or potassium ‘geo soluble silicates with a molar ratio MR fee een SiOzM,0>1,65, M being Na or K) and teres water (See the definition for "user-friendly" reagent below). Room temperature hardening relies on the addition of calcium cations, essentially iron blast furnace slag. Geopolymer cements cure more rapidly =a than Portland-based cements. They gain = geopolymer cements most of their strength within 24 hours. However, they set slowly enough that they can be mixed at a batch plant and delivered in a concrete mixer. Geopolymer cement also has the ability to form a strong chemical bond with all kind of rock-based aggregates. On March 2010, the US Department of Transportation Federal Highway Administration released a TechBrief titled Geopolymer Concrete that states [3]: The production of versatile, cost-effective geopolymer cements that can be mixed and hardened essentially like Portland cement represents a game changing advancement, revolutionizing the construction of transportation infrastructure and the building industry. Geopolymer concrete There is often confusion between the meanings of the two terms ‘geopolymer cement’ and ‘geopolymer concrete’. A cement is a binder whereas concrete is the composite material resulting from the addition of cement to stone aggregates. In other words, to produce concrete one purchases cement (generally Portland cement or Geopolymer cement) and adds it to the concrete batch. Geopolymer chemistry was from the start aimed at manufacturing binders and cements for various types of applications. For example the British company banah UK (www.banahuk.co.uk) sells its banah-Cem™ as geopolymer cement, whereas the Australian company Zeobond (www.zeobond.com) markets its E-crete™ as geopolymer concrete. Geopolymer Cement, a review; J Davidovits 3 2. Portland cement chemistry vs Geopolymer cement chemistry Left: hardening of Portland cement (P.C.) through simple hydration of Calcium Silicate into Calcium Di-Silicate hydrate (CSH) and lime Ca(OH)2. Right: hardening (setting) of Geopolymer cement (GP) through poly- condensation of Potassium — Oligo- (sialate-siloxo) into. Potassium Poly(sialate-siloxo) cross __linked network. 2.1 Alkali-activated materials vs Geopolymer cements. Geopolymerization chemistry requires appropriate terminologies and notions that are evidently different from those in use by Portland cement experts. Numerous publications on Geopolymer summarize how geopolymer cements belong to the category of Inorganic polymer. On this matter, the Australian Geopolymer Alliance [4] outlines on his web site the following statement: " Joseph Davidovits developed the notion of a geopolymer (a Si/Al inorganic polymer) to better explain these chemical processes and the resultant material properties. To do so required a major shift in perspective, away from the classical crystalline hydration chemistry of conventional cement chemistry. To date this shift has not been well accepted by practitioners in the field of alkali activated cements who stil tend to explain such reaction chemistry in Portland cement terminology. Indeed, geopolymer cement is sometimes mixed up with alkali-activated cement and concrete, developed more than 50 years ago by G.V. Glukhovsky in Ukraine, the former Soviet Union [5]. They were originally known under the names "soil silicate concretes" and “soil cements". Because Portland cement concretes can be affected by the deleterious Alkali-aggregate reaction, coined AAR or Alkali-silica reaction coined ASR (see for example the RILEM Committee 219-ACS Aggregate Reaction in Concrete Structures [6]), the wording alkali-activation has a negative impact on civil engineers. Nevertheless, several cement scientists continue to promote the idea of alkali-activated materials or alkali-activated geopolymers. These cements coined ‘AAM encompass the specific fields of alkali-activated slags, alkali-activatedcoal fly ashes, blended cements (see RILEM Technical committee DTA) [7]. However, it is interesting to mention the fact that geopolymer cements do not generate any of these deleterious reactions (see below in Properties), 2.2 User-friendly alkaline-reagents Although geopolymerization does not rely on toxic organic solvents but only on water, it needs chemical ingredients that may be dangerous and therefore requires some safety procedures. Material Safety rules classify the alkaline products in two Geopolymer Cement, a review; J. Davidovits 4 categories: corrosive products (named here: hostile) and irritant products (named here: friendly). The two classes are recognizable through their respective logos : The table lists some alkaline chemicals and teat fondly & their corresponding safety label [8]. The corrosive products must be handled with CaO (quick lime) Ca(OH)z gloves, glasses and masks. They are User- NaOH, Portland cement, hostile and cannot be implemented in mass Kon tron slag applications without the appropriate safety Sodium metasilicate Sly soluble procedures. In the second category one Se ee aoe finds Portland cement or hydrated lime, typical mass products. Geopolymeric alkaline reagents belonging to this class Anysolublesiicate | Any soluble siicate may also be termed as User-friendly. SiOzNaz0<1.60 S102 NazO >1.60 1.25

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