Geopolymers are materials which are used for fire- and heat-resistant coatings and adhesives, medicinal applications, high-temperature ceramics, new binders for fire-resistant fiber composites, toxic and radioactive waste encapsulation and as cementing components to make concrete. The properties and uses of geopolymers are being explored in many scientific and industrial disciplines: modern inorganic chemistry, physical chemistry, colloid chemistry, mineralogy, geology, and in other types of engineering process technologies. Raw materials used in the synthesis of silicon-based polymers are mainly rock-forming minerals of geological origin, hence the name: geopolymer. Joseph Davidovits coined the term in 1978 and created the non profit French scientific institution (Association Loi 1901) Institut Géopolymère (Geopolymer Institute).
According to T.F. Yen geopolymers can be classified into two major groups: pure inorganic geopolymers and organic containing geopolymers, synthetic analogues of naturally occurring macromolecules. In the following presentation, a geopolymer is essentially a mineral chemical compound or mixture of compounds consisting of repeating units, for example silico-oxide (-Si-O-Si-O-), silico-aluminate (-Si-O-Al-O-), ferro-silico-aluminate (-Fe-O-Si-O-Al-O-) or alumino-phosphate (-Al-O-P-O-), created through a process of geopolymerization. This mineral synthesis (geosynthesis) was first presented at an IUPAC symposium in 1976.
The microstructure of geopolymers is essentially temperature dependent:
- It is X-rays amorphous at room temperature,
- But evolved into a crystalline matrix at temperatures above 500 °C.
One can distinguish between two synthesis routes:
- In alkaline medium (Na+, K+, Li+, Ca++, Cs+ and the like);
- 1 What is a geopolymer?
- 2 Geopolymer synthesis
- 3 Commercial applications
- 4 Geopolymer resins and binders
- 5 Geopolymer cements
- 6 Geopolymer applications to arts and archaeology
- 7 References
- 8 Bibliography
- 9 External links
What is a geopolymer?
In the 1950s, Viktor Glukovsky, of Kiev, Ukraine, developed concrete materials originally known under the names "soil silicate concretes" and "soil cements", but since the introduction of the geopolymer concept by Joseph Davidovits, the terminology and definitions of 'geopolymer' have become more diverse and often conflicting. The examples below were taken from 2011 scientific publications, written by scientists with different backgrounds.
Definitions of the term geopolymer
- '...Geopolymers consist of a polymeric Si–O–Al framework, similar to zeolites. The main difference to zeolite is geopolymers are amorphous instead of crystalline. The microstructure of geopolymers on a nanometer scale observed by TEM comprises small aluminosilicate clusters with pores dispersed within a highly porous network. The clusters sizes are between 5 and 10 nanometers.'
For geopolymer material chemists
- '...The reaction produces SiO4 and AlO4, tetrahedral frameworks linked by shared oxygens as poly(sialates) or poly(sialate–siloxo) or poly(sialate–disiloxo) depending on the SiO2/Al2O3 ratio in the system. The connection of the tetrahedral frameworks is occurred via long-range covalent bonds. Thus, geopolymer structure is perceived as dense amorphous phase consisting of semi-crystalline 3-D alumino-silicate microstructure.'
For alkali-cement scientists
- '... Geopolymers are framework structures produced by condensation of tetrahedral aluminosilicate units, with alkali metal ions balancing the charge associated with tetrahedral Al. Conventionally, geopolymers are synthesized from a two-part mix, consisting of an alkaline solution (often soluble silicate) and solid aluminosilicate materials. Geopolymerization occurs at ambient or slightly elevated temperature, where the leaching of solid aluminosilicate raw materials in alkaline solutions leads to the transfer of leached species from the solid surfaces into a growing gel phase, followed by nucleation and condensation of the gel phase to form a solid binder.'
For ceramic scientists
- '...Geopolymers are a class of totally inorganic, alumino-silicate based ceramics that are charge balanced by group I oxides. They are rigid gels, which are made under relatively ambient conditions of temperature and pressure into near-net dimension bodies, and which can subsequently be converted to crystalline or glass-ceramic materials.'
Ionic coordination or covalent bonding ?
In 1937, W. L. Bragg published a method for classifying all kinds of silicates and their crystal structures based on the concept of the ionic theory by L. Pauling. The fundamental unit is a tetrahedral complex consisting of a small cation such as Si4+, or Al3+ in tetrahedral coordination with four oxygens (Pauling’s first rule). Many textbooks explain the geometry of the SiO4− tetrahedron and other mineral structures as determined by the relative sizes of the different ions. This ionic coordination representation is no longer adapted to the requirements of geopolymer chemistry that is governed by covalent bonding mechanisms. The double tetrahedron structure (coordination) is sharing one oxygen anion O2−, whereas in the Si-O-Si- molecular structure, the covalent bond is achieved through Si and O co-sharing only one electron. This results in stronger bond within the latter structure. The American mineralogist and geochemist G. V. Gibbs and his team studied the polymeric bond Si-O-Si-O and stated in 1982-2000: The successful modeling of the properties and structures of silica ... lends credence to the statement that a silica polymorph like quartz can be viewed as a giant molecule bound together by essentially the same forces that bind the atoms of the Si-O-Si skeleton into a small siloxane molecule. The term giant molecule used by G.V. Gibbs is equivalent to the definition of geopolymer and the wording small siloxane molecule describes the actual oligomers of organo-silicon compounds well known as silicone polymer. These siloxane oligomers have the same structure as the silico-aluminate oligomers described below in this article.
Geopolymerization starts with oligomers
Geopolymerization is the process of combining many small molecules known as oligomers into a covalently bonded network. The geo-chemical syntheses are carried out through oligomers (dimer, trimer, tetramer, pentamer) which are believed to contribute to the formation of the actual structure of the three-dimensional macromolecular framework, either through direct incorporation or through rearrangement via monomeric species. In 2000, T.W. Swaddle and his team proved the existence of soluble isolated alumino-silicate molecules in solution in relatively high concentrations and high pH, at very low temperatures, as low as −9 °C. Indeed, it was discovered that the polymerization at room temperature of oligo-sialates was taking place on a time scale of around 100 milliseconds, i.e. 100 to 1000 times faster than the polymerization of ortho-silicate, oligo-siloxo units. At room temperature or higher, the reaction is so fast that it cannot be detected with conventional analytical equipment.
The image shows 5 soluble oligomers of the K-poly(sialate) / poly(sialate-siloxo) species, which are the actual starting units of potassium-based alumino-silicate geopolymerization.
Example of (-Si-O-Al-O-) geopolymerization with metakaolin MK-750 in alkaline medium
It involves four main phases comprising seven chemical reaction steps:
- Alkaline depolymerization of the poly(siloxo) layer of kaolinite;
- Formation of the ortho-sialate (OH)3-Si-O-Al-(OH)3 molecule (#1 in the figure);
- In the presence of waterglass (soluble K-polysiloxonate) one gets the creation of ortho-sialate-disiloxo cyclic structure (#5 in the figure), whereby the alkali KOH is liberated and reacts again;
- Geopolymerization (polycondensation) into higher oligomers and polymeric 3D-networks.
The geopolymerization kinetics for Na-poly(sialate-siloxo) and K-poly(sialate-siloxo) are slightly different respectively. This is probably due to the different dimensions of the Na+ and K+ cations, K+ being bigger than Na+.
Example of zeolitic (Si-O-Al-O-) geopolymerization with fly ash in alkaline medium
It involves 5 main phases
- Nucleation stage in which the aluminosilicates from the fly ash particle dissolve in the alkaline medium (Na+), releasing aluminates and silicates, probably as monomers.
- These monomers inter-react to form dimers, which in turn react with other monomers to form trimers, tetramers and so on.
- When the solution reaches saturation, an aluminum-rich gel (denominated Gel 1) precipitates.
- As the reaction progresses, more Si-O groups in the initial solid source dissolve, increasing the silicon concentration in the medium and gradually raising the proportion of silicon in the zeolite precursor gel (Gel 2).
- Polycondensation into zeolite-like 3D-frameworks.
Geopolymerization forms aluminosilicate frameworks that are similar to those of rock-forming minerals. Yet, there are major differences. In 1994, Davidovits presented a theoretical structure for K-poly(sialate-siloxo) (K)-(Si-O-Al-O-Si-O) that was consistent with the NMR spectra. It does not show the presence of water in the structure because he only focused on the relationship between Si, Al, Na, K, atoms. Water is present only at temperatures below 150 °C – 200 °C, whereas numerous geopolymer industrial and commercial applications work at temperatures above 200 °C, up to 1400 °C, i.e. at temperatures above dehydroxylation. Nevertheless, scientists working on low temperature applications, such as cements and waste management, tried to pinpoint cation hydration and water molecules. This model shows an incompletely reacted geopolymer (left in the figure), which involves free Si-OH groups that will later with time or with temperature polycondense with opposed Al-O-K, into Si-O-Al-O sialate bonds. The water released by this reaction either remains in the pores, is associated with the framework similarly to zeolitic water, or can be released and removed. Several 3D-frameworks are described in the book 'Geopolymer Chemistry and Applications'. After dehydroxylation (and dehydration), generally above 250 °C, geopolymers become more and more crystalline (right in the picture) and above 500-1000 °C (depending on the nature of the alkali cation present) crystallise and have X-ray diffraction patterns and framework structures identical to their geological analogues.
There exist a wide variety of potential and existing applications. Some of the geopolymer applications are still in development whereas others are already industrialized and commercialized. See the incomplete list provided by the Geopolymer Institute. They are listed in three major categories:
Geopolymer resins and binders
- Fire-resistant materials, thermal insulation, foams;
- Low-energy ceramic tiles, refractory items, thermal shock refractories;
- High-tech resin systems, paints, binders and grouts;
- Bio-technologies (materials for medicinal applications);
- Foundry industry (resins), tooling for the manufacture of organic fiber composites;
- Composites for infrastructures repair and strengthening, fire-resistant and heat-resistant high-tech carbon-fiber composites for aircraft interior and automobile;
- Radioactive and toxic waste containment;
Geopolymer cements and concretes
- Low-tech building materials (clay bricks),
- Low-CO2 cements and concretes;
Arts and archaeology
- Decorative stone artifacts, arts and decoration;
- Cultural heritage, archaeology and history of sciences.
Geopolymer resins and binders
The class of geopolymer materials is described by Davidovits to comprise:
- Metakaolin MK-750-based geopolymer binder
- chemical formula (Na,K)-(Si-O-Al-O-Si-O-), ratio Si:Al=2 (range 1.5 to 2.5)
- Silica-based geopolymer binder
- chemical formula (Na,K)-n(Si-O-)-(Si-O-Al-), ratio Si:Al>20 (range 15 to 40).
- Sol-gel-based geopolymer binder (synthetic MK-750)
- chemical formula (Na,K)-(Si-O-Al-O-Si-O-), ratio Si:Al=2
The first geopolymer resin was described in a French patent application filed by J. Davidovits in 1979. The American patent, US 4,349,386, was granted on Sept. 14, 1982 with the title Mineral Polymers and methods of making them. It essentially involved the geopolymerization of alkaline soluble silicate [waterglass or (Na,K)-polysiloxonate] with calcined kaolinitic clay (later coined metakaolin MK-750 to highlight the importance of the temperature of calcination, namely 750 °C in this case). In 1985, Kenneth MacKenzie and his team from New-Zealand, discovered the Al(V) coordination of calcined kaolinite (MK-750). This had a great input towards a better understanding of its geopolymeric reactivity.[disputed ]
Potential utilization for geopolymer composites materials
Metakaolin MK-750-based and Silica-based geopolymer resins are used to impregnate fibers and fabrics to obtain geopolymer matrix-based fiber composites. These products are fire-resistant; they release no smoke and no toxic fumes. They were tested and recommended by major international institutions such as the American Federal Aviation Administration FAA. FAA selected the carbon-geopolymer composite as the best candidate for the fire-resistant cabin program (1994-1997).
Flashover is a phenomenon unique to compartment fires where incomplete combustion products accumulate at the ceiling and ignite causing total involvement of the compartment materials and signaling the end to human survivability. Consequently, in a compartment fire the time to flashover is the time available for escape and this is the single most important factor in determining the fire hazard of a material or set of materials in a compartment fire. The Federal Aviation Administration has used the time-to-flashover of materials in aircraft cabin tests as the basis for a heat release and heat release rate acceptance criteria for cabin materials for commercial aircraft. The figure shows how the best organic-matrix made of engineering thermoplastics reaches flashover after the 20 minute ignition period and generates appreciable smoke, while the geopolymer-matrix composite will never ignite, reach flashover, or generate any smoke in a compartment fire.
Carbon-geopolymer composite is applied on racing cars around exhaust parts. This technology could be transferred and applied for the mass production of regular automobile parts (corrosion-resistant exhaust pipes and the like) as well as heat shields. A well-known motorcar manufacturer already developed a geopolymer-composite exhaust pipe system.
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.
There is ongoing debate regarding the distinction between geopolymer cement and alkali-activated cement and concrete. Despite more than 50 years of application in Eastern Europe after the development by V.D. Glukhovsky, alkali-activated materials are not in general sold to third parties as commercial cement. They are instead marketed as 'alkali-activated concretes'. Conversely, geopolymer chemistry was from the start aimed at manufacturing binders and cements for various types of applications. For example the Northern Ireland-based company banah UK (http://www.banahuk.co.uk) sells its banah-Cem™ as geopolymer cement, whereas the Australian company Zeobond (http://www.zeobond.com) markets its E-crete™ as geopolymer concrete (not cement).
Portland cement chemistry vs geopolymer chemistry
Left: hardening of portland cement (P.C.) through hydration of calcium silicate into calcium silicate hydrate and lime Ca(OH)2.
Right: hardening (setting) of geopolymer resin (GP) through poly-condensation of potassium oligo-(sialate-siloxo) into potassium poly(sialate-siloxo) cross linked network.
CO2 emission during manufacture
- 5CaCO3 + 2SiO2 → (3CaO,SiO2)(2CaO,SiO2) + 5CO2
The production of 1 tonne of Portland clinker directly generates 0.45-0.55 tonnes of chemical CO2 and requires the combustion of carbon fuel, which to yield an additional 0.30-0.40 tonnes of carbon dioxide.
- To simplify: 1 t of portland cement = 0.75-0.95 t of carbon dioxide
On the other hand, geopolymer cements do not rely on calcium carbonate and generate much less CO2 during manufacture, i.e. a reduction in the range of 40% to 80-90%. For detailed calculation go to the article Geopolymer cement.
Geopolymer cement categories
- Slag-based geopolymer cement.
- Rock-based geopolymer cement.
- Fly ash-based geopolymer cement
- Ferro-sialate-based geopolymer cement.
Slag-based geopolymer cement
The first geopolymer cement developed in the 1980s was of the type (K,Na,Ca)-poly(sialate) (or slag-based geopolymer cement) and resulted from the research developments carried out by Joseph Davidovits and J.L. Sawyer at Lone Star Industries, USA and yielded to the invention of the well known Pyrament® cement. The American patent application was filed in 1984 and the patent US 4,509,985 was granted on April 9, 1985 with the title 'Early high-strength mineral polymer'. The combination of alkali sources with blast furnace slag to produce cementing binders was known since the pioneering work of J. Whiting (U.S. Patent 544,706, 1895), H. Kuhl (U.S. Patent 900,939), and others including A.O. Purdon, who marketed such a material as 'Purdociment' in the 1950s in Belgium, and these materials later began to be described by some researchers using geopolymer nomenclature.
Fly ash-based geopolymer cement
In the 1990s, building on the works conducted on slag-based and clay-based geopolymeric cements, on the long-term success of fly ash as a pozzolanic additive to concrete, and on the synthesis of zeolites from fly ashes, workers including Wastiels et al., Silverstrim et al., and van Jaarsveld and van Deventer developed geopolymeric fly ash-based cements.
Geopolymer applications to arts and archaeology
Because geopolymer artifacts look like natural stone, several artists started to cast in silicone rubber molds replications of their sculptures. For example, in the 1980s, the French artist Georges Grimal worked on several geopolymer castable stone formulations.
Egyptian Pyramid stones
With respects to archaeological applications, in the mid-1980s, Joseph Davidovits presented his first analytical results carried out on genuine pyramid stones. He claimed that the ancient Egyptians knew how to generate a geopolymeric reaction in the making of a re-agglomerated limestone blocks. The Ukrainian scientist G.V. Glukhovsky endorsed Davidovits' research in his keynote paper to the First Intern. Conf. on Alkaline Cements and Concretes, Kiev, Ukraine, 1994. Later on, several materials scientists and physicists took over these archaeological studies and are publishing their results, essentially on pyramid stones.
From the digging of ancient Roman ruins, one knows that approximately 95% of the concretes and mortars constituting the Roman buildings consist of a very simple lime cement, which hardened slowly through the precipitating action of carbon dioxide CO2, from the atmosphere and formation of calcium silicate hydrate (CSH). This is a very weak to medium good material that was used essentially in the making of foundations and in buildings for the populace.
But for the building of their "ouvrages d’art", especially works related to water storage (cisterns, aqueducts), the Roman architects did not hesitate to use more sophisticated and expensive ingredients. These outstanding Roman cements are based on the calcic activation of ceramic aggregates (in Latin testa, analogue to our modern metakaolin MK-750) and alkali rich volcanic tuffs (cretoni, zeolitic pozzolan), respectively with lime. MAS-NMR Spectroscopy investigations were carried out on these high-tech Roman cements dating to the 2nd century AD. They show their geopolymeric make-up.
- An article published by the Commission of the European Communities in 1982, outlines the reasons why the generic term geopolymer was chosen for this new chemistry. See: J. Davidovits, The Need to Create a New Technical Language For the Transfer of Basic Scientific Information, in Transfer and Exploitation of Scientific and Technical Information, Proceedings of the symposium, Luxemburg, 10–12 June 1981, pp. 316-320. It is available as a pdf-file and may be downloaded from the European Parliament Bookshop. Go to < http://bookshop.europa.eu/en/transfer-and-exploitation-of-scientific-and-technical-information-pbCD3381271/> and click on 'download'.
- Kim, D.; Lai, H.T.; Chilingar, G.V.; Yen T.F. (2006), Geopolymer formation and its unique properties, Environ. Geol, 51, 103–111.
- See at http://www.geopolymer.org/science/introduction
- Pdf-file #20 Milestone paper IUPAC 76 at http://www.geopolymer.org/category/library/technical-papers
- Zoulgami, M; Lucas-Girot, A.; Michaud, V.; Briard, P.; Gaudé, J. and Oudadesse, H. (2002); Synthesis and physico-chemical characterization of a polysialate-hydroxyapatite composite for potential biomedical application, Eur. Phys. J. AP, 19, 173-179. See also: Kriven, W.M.; Bell, J.; Gordon, M. (2003), Microstructure and Microchemistry of Fully-Reacted Geopolymers and Geopolymer Matrix Composites, Ceramic Transactions, 153, 227–250; Perera, D.S. and Trautman R.L. (2005), Geopolymers with the Potential for Use as Refractory Castables, Advances in Technology of Materials and Materials Processing, 7, 187–190.
- Wagh, A.S. (2004), Chemically Bonded Phosphate Ceramics – A Novel Class of Geopolymers, Proceedings of the 106th Ann. Mtg. of the American Ceramic Society, Indianapolis. See also, Chapter 13, Phosphate-based Geopolymers, in J. Davidovits' book Geopolymer Chemistry and Applications.
- Perera, D.S., Hanna, J.V., Davis, J., Blackford, M.G., Latella ,B.A., Sasaki ,Y. and Vance E.R. (2008), Relative strengths of phosphoric acid-reacted and alkali-reacted metakaolin materials, J. Mater. Sci., 43, 6562–6566. See also, Cao, D.; Su, D.; Lu, B. and Yang Y. (2005), Synthesis and structure characterization of geopolymeric material based on metakaolinite and phosphoric acid, Journal Chinese Ceramic Society, 33, 1385–89.
- Gluchovskij V.D.:"Gruntosilikaty" Gosstrojizdat Kiev 1959, Patent USSR 245 627 (1967), Patent USSR 449894 (Patent appl. 1958, granted 1974).
- See, Discussion at the Geopolymer Camp 2012, video Geopolymer definition in Wikipedia at http://www.geopolymer.org/camp/gp-camp-2012.
- Huang, Yi and Han, Minfang (2011) (China University of Mining and Technology, Beijing), The influence of α-Al2O3 addition on microstructure, mechanical and formaldehyde adsorption properties of fly ash-based geopolymer products, Journal of Hazardous Materials, 193, 90–94
- Pimraksaa, K.; Chindaprasirt, P.; Rungchet, A.; Sagoe-Crentsil, K. and Sato, T. (2011) (Department of Industrial Chemistry, Chiang Mai University, Thailand; CSIRO, Melbourne, Australia; Tohoku University, Sendai, Japan), Lightweight geopolymer made of highly porous siliceous materials with various Na2O/Al2O3 and SiO2/Al2O3 ratios, Materials Science and Engineering A, 528, 6616–6623.
- Feng, Dingwu; Provis, John L. and van Deventer, Jannie S. J. (2012) (University of Melbourne, Australia), Thermal Activation of Albite for the Synthesis of One-Part Mix Geopolymers, J. Am. Ceram. Soc., 95  565–572.
- Bell, Jonathan L.; Driemeyer, Patrick E. and Kriven, Waltraud M. (2009) (University of Illinois, USA), Formation of Ceramics from Metakaolin-Based Geopolymers. Part II: K-Based Geopolymer, J. Am. Ceram. Soc., 92 , 607-615.
- See the figure at http://www.geopolymer.org/science/about-geopolymerization
- Gibbs, G.V.; Hill, F.C.; Boisen Jr, M.B. and Downs R.T., (2000), Molecules as a Basis for Modeling the Force Field of Silica, Chapter 6 in Structure and Imperfections in Amorphous and Crystalline Silicon Dioxide, Edited by R. A. B. Devine, J.-P. Duraud and E. Dooryhee, John Wiley & Sons Ltd
- North, M.R. and Swaddle, T.W. (2000). Kinetics of Silicate Exchange in Alkaline Aluminosilicate Solutions, Inorg. Chem., 39, 2661–2665.
- see at http://www.geopolymer.org/science/about-geopolymerization
- Duxson, P.; Fernández-Jiménez, A.; Provis, J.l.; Lukey, G.C; Palomo, A. and Van Deventer, J.S.J., (2007), Geopolymer technology: the current state of the art, J. Mat. Sci., 42 (9) 2917–2933.
- Davidovits, J., (1994), Geopolymers: Man-Made Rock Geosynthesis and the Resulting Development of Very Early High Strength Cement, J. Materials Education, 16 (2&3), 91–139.
- Barbosa, V.F.F; MacKenzie, K.J.D. and Thaumaturgo, C., (2000), Synthesis and characterization of materials based on inorganic polymers of alumina and silica: sodium polysialate polymers, Intern. Journal of Inorganic Materials, 2, pp. 309–317.
- Rowles, M.R. (2004), The Structural Nature of Aluminosilicate Inorganic Polymers: a Macro to Nanoscale Study, PhD Thesis, Curtin University of Technology, Perth, Australia.
- See: Structural frameworks and chemical mechanisms, in Davidovits' book Geopolymer Chemistry and Applications, Sections 8.6-8.7.
- see at http://www.geopolymer.org/about/business-fellows
- see the Chapters 8, 11, 20 in J. Davidovits' book Geopolymer Chemistry and Applications.
- MacKenzie, K.J.D.; Brown, I.W.M; Meinhold, R.H. and Bowden, M.E. (1985), Outstanding Problems in the Kaolinite-Mullite Reaction; Sequence Investigated by 29Si and 27Al Solid-State Nuclear Magnetic Resonance: I, Metakaolinite, J. Am. Ceram. Soc., 68 , 293–297.
- see the updates in the Keynotes State of Geopolymer R&D, 2009, 2010, 2011, and 2012 at http://www.geopolymer.org/camp)
- The FAA research project, 1994-1997 involved the collaboration between the research teams of: – FAA Fire Department, Atlantic City, USA ; – Rutgers University of New Jersey, USA; – Cordi-Géopolymère laboratory, Saint-Quentin, France. A picture of geopolymer composite testing by FAA (Oil Burner Test of Fireproof composite) can be downloaded at http://www.fire.tc.faa.gov/research/targtare.stm
- Lyon, R.E.; Foden, A.J.; Balaguru, P.N.; Davidovits, J. and Davidovics, M. (1997), Properties of Geopolymer Matrix-Carbon Fiber Composites, Fire and Materials, 21, 67–73.
- Davidovics, M.; Bruno, M. and Davidovits, J. (1999), Past and Present Experience on the Use of Carbon-Géopolymère Composite in Formula One and CART Racing Cars, Geopolymer ’99 Proceedings, 141–142.
- Davidovits, J. (2002), 30 Years of Successes and Failures in Geopolymer Applications, Market Trends and Potential Breakthroughs, Geopolymer 2002 Conference, Oct. 28-29, Melbourne, Australia. Download the pdf-file #15 at http://www.geopolymer.org/category/library/technical-papers.
- See the PCT patent application publication WO 2004/106705 filed by Porsche AG, 2004.
- Davidovits, J. (1993), Carbon-Dioxide Greenhouse-Warming: What Future for Portland Cement, Emerging Technologies Symposium on Cements and Concretes in the Global Environment, organized by the Portland Cement Association, Chicago, Illinois, March 1993. See also the paper: Davidovits, J. (1993), Geopolymer Cements to minimize Carbon-Dioxide Greenhouse Warming, Ceramic Transactions, 37, Cement-Based Materials: Present, Future and Environmental Aspects, pp. 165–182.
- Davidovits, J. and Sawyer, J.L., (1985), Early high-strength mineral polymer, US Patent 4,509,985, 1985, filed February 22, 1984. The first commercial geopolymer cement was coined Pyrament 2000™ designed for repair and patching operations.
- Gimeno, D.; Davidovits, J.; Marini, C.; Rocher, P.; Tocco, S.; Cara, S.; Diaz, N.; Segura, C. and Sistu, G. (2003), Development of silicate-based cement from glassy alkaline volcanic rocks: interpretation of preliminary data related to chemical- mineralogical composition of geologic raw materials. Paper in Spanish, Bol. Soc. Esp. Cerám. Vidrio, 42, 69–78. [Results from the European Research Project GEOCISTEM (1997), Cost Effective Geopolymeric Cements For Innocuous Stabilisation of Toxic Elements, Final Technical Report, April 30, 1997, Brussels, Project funded by the European Commission, Brite-Euram BE-7355-93, Jan. 1, 1994 to Feb. 28, 1997].
- Palomo, A.; Grutzeck, M.W. and Blanco, M.T. (1999), Alkali-activated fly ashes: a cement for the future, Cement Concrete Res, 29, 1323–1329.
- GEOASH (2004–2007), The GEOASH project was carried out with a financial grant from the Research Fund for Coal and Steel of the European Community. The GEOASH project is known under the contract number RFC-CR-04005. It involves: Antenucci D., ISSeP, Liège, Belgium; Nugteren H.and Butselaar-Orthlieb V., Delft University of Technology, Delft, The Netherlands; Davidovits J., Cordi-Géopolymère Sarl, Saint-Quentin, France; Fernández-Pereira C. and Luna Y., University of Seville, School of Industrial Engineering, Sevilla, Spain; Izquierdo and M., Querol X., CSIC, Institute of Earth Sciences Jaume Almera, Barcelona, Spain. See: Izquierdo M., Querol X., Davidovits J., Antenucci D., Nugteren H. and Fernández-Pereira C., (2009), Coal fly ash-based geopolymers: microstructure and metal leaching, Journal of Hazardous Materials, 166, 561–566. See also: Chapter 12 in J. Davidovits' book Geopolymer Chemistry and Applications.
- Davidovits, J. et al., Geopolymer cement of the Calcium-Ferroaluminium silicate polymer type and production process, PCT patent publication WO 2012/056125.
- Buchwald, A.; Vanooteghem, M.; Gruyaert, E.; Hilbig, H.; de Belie, N. "Purdocement: application of alkali-activated slag cement in Belgium in the 1950s", Materials and Structures 48(2015):501-511
- Purdon, A.O., "The action of alkalis on blast-furnace slag", Journal of the Society of Chemical Industry 59(1940):191-202
- Wastiels, J.; Wu, X.; Faignet, S.; Patfoort, G. (1993) "Mineral polymer based on fly ash", Proceedings of the 9th International Conference on Solid Waste Management, Philadelphia, PA, Widener University, 8pp.
- Silverstrim, T.; Rostami, H.; Larralde, J.C and Samadi-Maybodi, A. (1997), Fly ash cementitious material and method of making a product, US Patent 5,601,643.
- Van Jaarsveld, J.G.S., van Deventer, J.S.J. and Lorenzen L. (1997), The potential use of geopolymeric materials to immobilize toxic metals: Part I. Theory and Applications, Minerals Engineering, 10 (7), 659–669.
- See Potential utilizations in art and decoration, at http://www.geopolymer.org/applications/potential-utilizations-in-art-and-decoration ; a pdf article #19 Dramatized sculptures with geopolymers at http://www.geopolymer.org/category/library/technical-papers/
- Davidovits, J. (1986), X-Rays Analysis and X-Rays Diffraction of Casing Stones from the Pyramids of Egypt, and the Limestone of the Associated Quarries; pp. 511–20 in Science in Egyptology Symposia, Edited by R. A. David, Manchester University Press, Manchester, U.K. (Pdf-file #A in the Geopolymer Institute Library, Archaeological Papers); see also: Davidovits J., (1987), Ancient and modern concretes: what is the real difference? Concrete International: Des. Constr, 9 , 23–29. See also: Davidovits, J. and Morris, M., (1988), The Pyramids: An Enigma Solved. Hippocrene Books, New York, 1988.
- G.V Glukhovsky passed away before the conference. His keynote paper titled: Ancient, Modern and Future Concretes, is included in the Proceedings of the First Intern. Conf. on Alkaline Cements and Concretes, pp. 1-9, Kiev, Ukraine, 1994.
- Demortier ,G. (2004), PIXE, PIGE and NMR study of the masonry of the pyramid of Cheops at Giza, Nuclear Instruments and Methods, Physics Research B, 226, 98–109.
- Barsoum, M.W.; Ganguly, A. and Hug, G. (2006), Microstructural Evidence of Reconstituted Limestone Blocks in the Great Pyramids of Egypt, J. Am. Ceram. Soc. 89, 3788–3796.
- MacKenzie, Kenneth J.D.; Smith, Mark E.; Wong, Alan; Hanna, John V.; Barry, Bernard and Barsoum, Michel W. (2011), Were the casing stones of Senefru's Bent Pyramid in Dahshour cast or carved? Multinuclear NMR evidence, Materials Letters 65, 350–352.
- Túnyi, I. and El-hemaly, I. A. (2012), Paleomagnetic investigation of the great egyptian pyramids, Europhysics News 43/6, 28-31.
- As part of the European research project GEOCISTEM , Davidovits J. and Davidovits F. sampled archaeological mortars and concretes dating back to the 2nd century AD and later, in Rome and Ostia, Italy. They selected two series of artifacts: Opus Signinum in Rome, Opus Caementicum / Testacaeum: mortars and concretes (carbunculus), in Ostia. Partly published in Geopolymer ’99 Proceedings, 283-295 and in Davidovits' book, Geopolymer Chemistry and Applications, Section 17.4. See also the NMR spectra at: http://www.geopolymer.org/applications/archaeological-analogues-roman-cements
- Geopolymer Chemistry and Applications, Joseph Davidovits, Institut Géopolymère, Saint-Quentin, France, 2008, ISBN 9782951482050 (3rd ed., 2011). In Chinese: National Defense Industry Press, Beijing, ISBN 9787118074215, 2012.
- Geopolymers Structure, processing, properties and industrial applications, John L. Provis and Jannie S. J. van Deventer, Woodhead Publishing, 2009, ISBN 9781845694494.