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Chapter 1

The discovery of a new class of inorganic materials, geopolymer resins, binders, cements and concretes, resulted in wide scientific interest and kaleidoscopic development of applications. From the first industrial research efforts in 1972 at the Cordi-Géopolymère private research laboratory, Saint-Quentin, France, until the end of 2006, hundreds of papers and patents were published dealing with geopolymer science and technology. On August 31. 2005, the Geopolymer Institute (a non-profit scientific organization founded in 1979) was proud to announce in its News on line (www.geopolymer.org): "Since 1997, 80000 papers have been downloaded by 15000 scientists around the world at the geopolymer.org website". The extent of international scientific and commercial interest in geopolymers was evidenced by several large conferences. In France, the First European Conference on Soft Mineralurgy, organized by the Geopolymer Institute and sponsored by the European Economic Commission, was held at the University of Technology of Compiègne in June 1988 (Geopolymer ’88 ). Eleven years later in June-July 1999, the Geopolymer Institute organized the Second International Conference Geopolymere ’99, held in Saint-Quentin; the published proceedings included 32 papers presented to the 100 scientists from over 12 countries. The Third International Conference, Geopolymer 2002 was held in Australia in October 2002. Organized by the University of Melbourne and chaired by J.S.J. van Deventer, it focused on the ways needed to "Turn Potential into Profit". Since 2003, several national and international scientific institutions have organized "geopolymer sessions", "geopolymer seminars" 3

waste encapsulation and new cement for concrete. 2005. low-tech building materials. They are new materials for coatings and adhesives. thermal insulation. the University of Alabama. and in all types of engineering process technologies. mineralogy. They cover a wide scope of topics ranging from geopolymer chemistry. geology. Perth. geopolymer concretes (including fly ash-based geopolymers). The properties and uses of geopolymers are being explored in many scientific and industrial disciplines: modern inorganic chemistry. new binders for fiber composites. USA. geopolymer cements. radioactive 4 . organized by Curtin University of Technology. Green Chemistry and Sustainable Development Solutions. France. the International Workshop on Geopolymer Cements and Concrete in Perth. refractory items. and applications in archaeology. high-tech composites for aircraft interior and automobile. composites for infrastructures repair and strengthening. high-tech resin systems.1 Geopolymer technology How should we consider geopolymers? Are they a new material. colloid chemistry. organized by the Geopolymer Institute. cements and concretes. matrix for fire/heat resistant composites. More than 200 scientists attended the congress and 85 international public and private research institutions presented a total of 75 papers. chaired by V. physical chemistry. September 2005. Rangan. Davidovits. applications in high-tech materials. The main topic of the world congress was Geopolymer-chemistry and sustainable Development. The conference and workshop covered the science and application of geopolymers. June-July. 1.1. Introduction and "geopolymer conferences". and sponsored by the National Science Foundation. Australia.J. USA. The published proceedings (Geopolymer 2005 ) includes 60 selected papers and is titled: Geopolymer. applications in construction materials. low energy ceramic tiles. foundry applications. The wide variety of potential applications includes: fire resistant materials. The Geopolymer 2005 World Congress was a tribute to the 26th anniversary of the creation of the Geopolymer Institute by J. industrial wastes and raw materials. a new binder or a new cement for concrete? Geopolymers are all of these. thermal shock refractories. decorative stone artifacts. It gathered two major events in two different locations: the Fourth International Conference in Saint-Quentin.

which involved common organic plastic. Figure 1. On the other hand. arts and decoration. I was struck by the fact that the same simple hydrothermal conditions governed the synthesis of some organic plastics in alkali medium. as well as mineral feldspathoids and zeolites. In my pursuit to develop new inorganic polymer materials. one of the oldest man-made plastic (Figure 1. the aluminosilicate kaolinite reacts with NaOH at 100–150°C and polycondenses into hydrated sodalite (a tectoaluminosilicate. I founded the private research company Cordi SA. In 1972. phenol and formaldehyde polycondense into the famous Bakelite invented by Bakeland at the beginning of the 20th Century. My chemistry background had focused on organic polymer chemistry and in the aftermath of various catastrophic fires in France between 1970–72. I proceeded therefore to develop amorphous to semi-crystalline three-dimensional silico-aluminate materials.Geopolymer technology and toxic waste containment. which I call in French "géopolymères". research on nonflammable and noncombustible plastic materials became my objective. a feldspathoid). later called Cordi-Géopolymère. From the study of the scientific and patent literature covering the synthesis of zeolites and molecular sieves — essentially in the form of powders — it became clear that this geochemistry had so far not been investigated for producing mineral binders and mineral polymers. geopolymers (mineral polymers resulting from geo5 . archaeology and history of sciences.1: Phenoplast polycondensation between phenol and formaldehyde. in alkali medium. cultural heritage.1).2). or hydroxysodalite (Figure 1. Thus.

2: Polycondensation of kaolinite Si2 O5 . the Chairman of Lone Star Industries Inc. produce. 6 . 1976). coined Geopolymite™. The commercial product. was a good fire resistant alternative to organic resin. the hardening of organic material (wood chips and organic resin based on urea-formaldehyde aminoplast) occurred simultaneously with the setting of the mineral silicoaluminate (Na–poly(sialate)/quartz nanocomposite). An unusual feature was observed to characterize the manufacturing process: for the first time. The title of the patent. architectural. Neuschäffer (1983) at the licensed German Company Dynamit Nobel (later Hüls Troisdorf AG) discovered the high reactivity of silica and alumina fumes.Al2 (OH)4 in alkali medium. at this time the leading cement manufacturer on the American continent. Introduction Figure 1. However. was self evident (Davidovits. 1979). by-products of the manufacture of high-tech ceramics. Lone Star Industries and Shell Oil Company had just announced the formation of a corporation to develop.. when applying the same thermosetting parameters as for organic resin: 150–180°C temperature (Davidovits. the real breakthrough took place when. in which the entire panel was manufactured in a one-step process (Davidovits. and market a new class of materials that were expected to have a wide-ranging impact on construction. The first applications were building products developed in 1973– 1976. Mineral polymer. 1973). such as fire-resistant chip-board panels. Then. was traveling in Europe and learned about our new geopolymeric binders. comprised of a wooden core faced with two geopolymer nanocomposite coatings.1. in 1978–1980. It was the first mineral resin ever manufactured. and engineering applications. chemistry or geosynthesis). In early 1983. we developed at the CORDI laboratory a metakaolin-based geopolymeric liquid binder comprising soluble alkali silicate.

filed in 1985. and highway roads. which was exclusively dedicated to the implementation of this new class of cement. The first Davidovits and Sawyer (1985) patent was filed in Feb. The corresponding European Patent. A few months later. is titled "Early High-Strength Concrete Composition" and these patents disclose our preliminary finding from the research carried out in August-September of 1983. Their purpose was to take advantage of the good properties of geopolymeric cement along with the low manufacturing cost of Portland cement. it was an "organic polymer concrete". In other words. It comprised 80 % ordinary Portland cement and 20 % of geopolymeric raw materials (Heitzmann et al. PYRAMENT PBC was recognized in the construction industry for its ability to gain very high early strength quite rapidly (US Army Corps of Engineers. and titled "Early HighStrength Mineral Polymer" (US Patent). while Lone Star supplied the mineral aggregates. I started to develop early high-strength geopolymeric binders and cements based on both geopolymeric and hydraulic cement chemistries. 22. At Lone Star. Richard Heitzmann and James Sawyer likewise blended Portland cement with geopolymer. accelerates the setting time and significantly improves compressive and flexural strength. It was discovered that the addition of ground blast furnace slag. 1985). 1984. to the poly(sialate) type of geopolymer. industrial pavements. PYRAMENT. which is a latent hydraulic cementitious product. Geopolymer cements are acid-resistant cementitious materials with zeolitic properties that can be applied to the long-term containment of hazardous and toxic wastes. It was the ideal material for repairing runways made of concrete. Lone Star took the opportunity to challenge Shell Oil’s chemical expertise. The resulting PYRAMENT®Blended Cement (PBC) was very close to alkali. 7 . with James Sawyer as Head of Lone Star’s research laboratory in Houston. By enlisting our new inorganic geopolymers.activated pozzolanic cement. Lone Star separated from the Shell Oil deal. Lone Star Industries Inc. Within one month. in 1984. a 4–6 hours hardening is enough to allow the landing of an Airbus or a Boeing. whereas plain concrete gets to this strength after several days. In August 1983. Shell Oil supplied the chemical expertise in organic polymers. The geopolymeric cement reaches a compression strength of 20 MPa after 4 hours. Texas.Geopolymer technology These materials were made from mineral aggregates combined with organic polymers and monomers. In the case of a runway. As of fall 1993.. formed the development company. 1989).

Both fields of application are strongly dependent on politically driven decisions. 1991).1. funded by the European Union. In 1994 the American Federal Aviation Administration (FAA) with R. Introduction PYRAMENT concrete was listed for over 50 industrial facilities and 57 military installations in the USA.Ca)–poly(sialate-siloxo) / (K. Lyon. 1990) has used geopolymer molds and tooling in the development of French Airforce fighters (Davidovits et al. initiated a cooperative research program to develop environmentally friendly. 1999).Ca)–poly(sialatedisiloxo) cements. The safe containment of uranium mine tailings and radioactive sludge started in 1994 within the European research project GEOCISTEM.. On the other hand. In the field of so-called high-tech applications. In industrialized countries (Western countries) emphasis is put on toxic waste (heavy metals) and radioactive waste safe containment. Ontario Research Foundation. with the financial support of CANMET Ottawa. essentially geopolymeric cements with very low CO2 emission. in emerging countries. Germany.Ca)– poly(sialate-siloxo) is a prime candidate to cost-efficiently fill the gap between conventional concrete technology and vitrification methods (Hermann et al. Environmentally-driven geopolymer applications are based on the implementation of (K. It was experimented on two important uranium-mining locations of WISMUT. More than a hundred tooling and other items have been delivered for aeronautic applications and SPF Aluminum processing. since 1982. and Comrie Consulting (Davidovits and Comrie. 1997). Major efforts were dedicated to greenhouse CO2 mitigation with 8 . with the collaboration of BPS Engineering. The Geopolymer composites were selected by FAA as the best candidate for this program (Lyon. and 7 in other countries. in Canada. The GEOCISTEM project was aimed at manufacturing cost-effectively new geopolymeric cements (Geocistem. Heavy metal waste encapsulation with geopolymer started in 1987. 1997). the French aeronautic company Dassault Aviation (Vautey. In 1994 the US Army Corps of Engineers released a well-documented study on the properties of PYRAMENT Blended Cements based concretes. and for nonmilitary airports. 1988). Toronto. which are performing better than had ever been expected for high-quality concretes. former East Germany. Our results clearly show that solidification with geopolymeric cement (K. fire resistant matrix materials for aircraft composites and cabin interior applications. the applications relate to sustainable development.

Belgian scientist Purdon (1940) discovered that the alkali addition produced a new. characterization.e. 1. alkalis. 1993). i. chemistry applications are included. such as sodium and potassium hydroxide. My research on this very important geopolymer application started in 1990 at PennState University. and a reference for additional information. It is this void that we hope to fill with this book. Each chapter is followed by a bibliography of the relevant published literature including patents. for students. In the course of studying the testing systems for slag.2 The scope of the book Although review articles and conference proceedings cover various aspects of the science and application of geopolymers. There are two main purposes in preparing this book: it is an introduction to the subject of geopolymers for the newcomer to the field.3 Early observations In the 1930s. were originally used to test iron blast furnace ground slag to determine if the slag would set when added to Portland cement. USA. from combustion carbon-fuel.The scope of the book the development of low CO2 geopolymer cements. There are many examples in geopolymer science where an issued patent is either a primary reference or the only source of essential technical information. Background details on structure. The industrial applications of geopolymers with engineering procedures and design of processes is also covered in this book.180 tonnes of CO2 . rapid-hardening 9 . for the same emission of green house gas CO2 (Davidovits. synthesis. properties. This simply means that. Fly ash basedgeopolymeric cement emits even less CO2 . Excerpts from the more important patents are included in some chapters. six to nine times more cement for infrastructure and building applications might be manufactured. up to nine times less than Portland cement. The production of 1 tonne of kaolin based-geopolymeric cement generates 0. in newly industrializing countries. a researcher or engineer is still at a loss to readily obtain specific information about geopolymers and their use. Materials Research Laboratory. six times less. 1. compared with 1 tonne of CO2 for Portland cement.

1974). In fact. at 100°C. without firing. the ceramicist team Jean Paul Latapie and Michel Davidovics confirmed that water-resistant ceramic tiles could be fabricated at temperatures lower than 450°C. preventing the formation of hydrosodalite. Flint & al (1946). In 1972. Paris. but without any successful industrial implementation. In 1969. In 1972. He also noted that rocks and clay minerals react during alkali treatment to form sodium alumino-silicate hydrates (zeolites). (Besson et al. One intermediary step of the extraction process involved the precipitation of a sodalite-like compound. a Russian team. 1969). Besson. (1970). 1953). the industrial application of this kaolinite reaction with alkali began in the ceramic industry with Niels Olsen (1934) and was later on reinvented in 1964 by Berg & al. reacted with caustic soda at 150°C. Howell (1963) obtained a Zeolite A type. at CORDI laboratory in Saint-Quentin.5 % NaOH to 97 % ground slag mix (U. which has been disclosed in various patents issued on the applications of the so-called "SILIFACEProcess" (Davidovits and Legrand. Glukhovsky called the concretes produced with this technology "soil silicate concretes" (1959) and the binders "soil cements" (1967). Alkali-activated slag cements (called Trief cements) were used in large-scale construction as early as the 1950s. carried out the synthesis of hydrosodalite from various phyllosilicates (kaolinite.5 % NaCl and 1. Victor Glukhovsky. confirming earlier work carried out on clay reactivity (see below). at the National Bureau of Standards were developing various processes for the extraction of alumina starting from clays and high-silica bauxites. Borchert and Keidel (1949) prepared hydrosodalite (Na–PS) by reacting kaolinite in a concentrated NaOH solution. Army Engineer Waterways Experiment Station. One component of clay. montmorillonite. halloysite) at 100°C in concentrated NaOH solution.S. kaolinite. Introduction binder (see Table 1.1. Caillère and Hénin at the French Museum of Natural History.e. In 1957.1). and calcium and sodium alumino-silicate hydrates (zeolites) as solidification products. To a natural kaolinite/quartz 10 . i. The usual activation called for adding 1. using calcined kaolin (metakaolin) instead of kaolinite. we developed a technology based on this geosynthesis. Earlier. a scientist working in the Ukraine at the KICE (Kiev Institute of Civil Engineering in the USSR) investigated the problem of alkali-activated slag binders and in the 1960s and 1970s made major contribution in identifying both calcium silicate hydrates..

notably apatite. however. but phosphate geopolymers are fabricated by acid-base reactions. which was then hot-pressed (thermosetting process) in a mold equipped with a porous layer for water evaporation. i. – Time: one minute per millimeter thickness at 150°C or 10 minutes for a 10 millimeters thick plate. oil well cements. They represent another variety of mineral geopolymer.5 g water for 1 g NaOH). – Applied hydraulic pressure: higher than the saturated vapor pressure of water. and water (1–1. is their syntheses. and hazardous and radioactive waste stabilization.e. Virtually any divalent or trivalent oxide that is sparingly soluble may be used to form these phosphate geopolymers. the polycondensation into hydrosodalite occurs very rapidly in a time as short as 15–20 seconds per millimeter thickness. They contain naturally occurring mineral phases. The thermosetting parameters were: – Temperature: 130°C to 180°C. at 180°C and 40 kg/cm2 hydraulic pressure. The main difference between the silicate based geopolymers and phosphate geopolymers. They are formed by an acid-base reaction between a metal oxide and an acid phosphate. 1.4 Phosphate-based geopolymer Phosphate ceramics are synthesized at room temperature and they set rapidly like conventional polymers. They have found a wide range of applications such as dental cements. it is recommended to wait until the item has cooled down to room temperature before opening the press. where Si is totally or partially replaced by P. The setting time is relatively short. Yet. Poly(sialate) geopolymers and their derivates are synthesized in alkaline environment. 11 . 65 to 75 % of the total time is devoted to degassing water. In the absence of any pervious device. when degassing is not working.e. construction materials. Otherwise. The resulting granules were cold-pressed at 15 MPa into a green body. i. for the selected temperature. 10 to 30 bars. the press must be equipped with safety devices (see for more details in Chapter 7). due to the high internal pressure of water and the danger of explosion.Phosphate-based geopolymer blend (50/50 weight ratio) was added and mixed solid NaOH in the proportion of 2 moles or less of NaOH for 1 mole Al2 O3 of the contained kaolinite.

2004) 2CaO + Ca(H2 PO4 )2 + H2 O ⇒ CaO + 2CaHPO4 ·H2 O ⇒ Ca3 (PO4 )2 + 2H2 O MgO + KH2 PO4 + 5 H2 O ⇒ MgKPO4 ·6H2 O (Ceramicrete™). Introduction Table 1. By controlling the rate of reaction. ceramics can be formed. Wagh. The reaction product is generally a poly(hydrophosphate) or an anhydrous poly(phosphate) that consolidates into a ceramic. With trivalent oxides. The following are the most common examples (Wagh and Yeong.4. 2003.1. sim12 . (1) (2) These reactions occur at room temperature. (France) 1972 : Davidovits (France) Siliface Process 1976 : Davidovits (IUPAC terminology) 1979 : Davidovits (France) Geopolymer 1. Keidel (Germany) Geopolymer 1950 1960 1970 1963 : Howell (USA) 1964 : Berg & al. White (UK) 1956 : Milton (USA) 1940 : Purdon (Belgium) 1953: Trief Cement (USA) 1957: Glukovsky (Ukraine) soil-silicate concrete Alkali-activation (slag) Hydrosodalite (kaolin) 1934 : Olsen (Netherland) 1945 : US Bureau of Standard (USA) 1949 : Borchert. (USSR) 1969 : Besson & al.1 Phosphate geopolymers A very wide range of phosphate geopolymers may be synthesized by acid-base reaction between an inorganic oxide (preferably that of divalent and trivalent metals) and an acid phosphate. Zeolite molecular sieve 1930 1940 1945 : Barrer (UK) 1953 : Barrer.1: Milestones in alumino-silicate chemistry.

Information about this technology is scarce and restricted to the patent literature (see in Chapter 13).5 1. As observed by Noll (1968) it is possible to pass from the polymeric silicate to the polymeric covalent molecules of an organosiloxane by replacing the bridging oxide ions of the silicate anions with methyl groups.5. chains. The reaction may be described by the following equation: X2 O3 + X + 3H3 PO4 + nH2 O ⇒ 3XHPO4 ·(n+3)H2 O where X is Fe or Mn. rings. Almennigen et al.Organic-mineral geopolymers ilar ceramics can be formed at a slightly elevated temperature. for example in quartz. and networks of silicon and oxygen found in silica and the silicate minerals.2 Silico-phosphate geopolymers Another system involves the reaction between phosphoric acid and wollastonite. The structures that result from this replacement closely resemble the silicate and aluminosilicate molecules: monomers. Chapter 2 and Chapter 14 focus on silicone poly(organo-siloxane). dimers. sheets and frameworks of corner-sharing silicate [SiO4 ] groups. (1963) reported the correspondence in a study of disiloxane H6 Si2 O. rings.1 Organic-mineral geopolymers Silicone The similarity of the siloxane (Si-O-Si) structure in organo-silicones to the chains. which is formed by the reaction between alumina and phosphoric acid: Al2 O3 + 2H3 PO4 ⇒ 2AlPO4 + 3H2 O (3) It was also demonstrated that phosphate geopolymers of trivalent oxides such as Fe2 O3 and Mn2 O3 might be produced by reduction of the oxide and then acid-base reaction of the reduced oxide with phosphoric acid.. trimers. A good example is berlinite (AlPO4 ). (4) 1.4. has been pointed out many times. When the organic radical is methylene the structures of the oligomeric 13 . 1. etc.

The small content of organics is a key parameter governing the strength and durability of material in a large volume of inorganics. Some geopolymeric materials can last for a long time due to their unique geopolymeric structure. (Kim et al. Kerogen-geopolymer is the most stable material and the final alternating product in the Earth. synthetic analogue of naturally occurring macromolecules (Kim et al. Humic materials represent an inorganic-organic structure.. Organic compounds can be incorporated into refractory macromolecules such as lignin and melanodin or humic materials (Henrichs 1992). 1.3: Evolution of organic matter to kerogen-geopolymer 14 . working on the transformation of geomolecules through geochemical processes during diagenesis.1. 2006). 2004. Yen and his team. Geopolymers can be classified into two major groups: pure inorganic geopolymers and organic containing geopolymers.5.2 Humic-acid based: kerogen geopolymer T.K. Introduction poly-methyl-siloxanes are identical with those of poly(siloxonate) (SiO-Si-O) and poly(sialate) (Si-O-Al-O-Si) geopolymers. Figure 1. so-called three-dimensional crosslink. 2006) have drawn attention to the concept of geopolymer in association with kerogen and petroleum. 2004..

References Almennigen. New Polymers of high stability. Topic III. Davidovits J. It is. about 1000 times more abundant than coal. Ewing. typical inorganic-organic composites that show extreme durability and mechanical strength. 1. 9.427 filed Jan... filed Jan.204. D269. Kerogen is a geopolymer that contains a high content of organics. Davidovits J. by partial destruction and rearrangement of the main organic building blocks (Figure 1..470. Caillère S.. filed Jan. Procédé de fabrication de panneaux agglomérés et panneaux resultant de l’application de ce procédé. and Henin S. Besson H. 1975. 17.246.Organic-mineral geopolymers Diagenesis of organic matter leads from biopolymers synthesized by organisms through "humin" to Kerogen. 22. Min.. which will result in a geopolymeric structure.. 1974 .S. (1979). (1949). filed Dec. u. Davidovits J.J. O.. IUPAC International Symposium on Macromolecules Stockholm. 1976. evident that both inorganics and organics are required in a mix at a certain ratio.C. (1963).950. Stroitel’nye Materialy (USSR). 11.324. V. Solid phase synthesis of a mineral blockpolymer by low temperature polycondensation of aluminosilicate polymers. and Legrand J. 1974. K. and Nisamov N. 10.A. (1970).. C. (1972). A. Heidelb. Davidovits J. German Patent DE 25 00 151 (1979). however. French Patent Application FR 15 .I.382). z. Sci. US Patent 3. Scand. 31. The mechanism of geomacromolecule formation involves the crosslink reaction between the inorganic and organic materials. M. Bastiansen.. see also US Patent 4. which forms primarily from terrigenous remains of higher plants. (1976)..479 (1977). 1367. French Patent Application FR 72. Rend.3).454 (1977). (1969). Kerogen is considered to be the major starting material for most oil and gas generation as sediments are subjected to geothermal heating in the subsurface.999) and FR 73. Reminikova V.481. Kerogen geopolymers generally occur in numerous forms: some have more organics and less inorganics. and Keidel J.028.. Conditions de préparation de l’hydrosodalite à basse température. It is the most abundant form of organic carbon on Earth. Process for the fabrication of sintered panels and panels resulting from the application of this process.35979 (FR 2. Polymère Minéral. 3. Berg L. Sept. Beitr. (1974) French Patent FR 2. while others have the opposite.. United Kingdom Patent UK 1. Borchert W. Hedberg. 2. Demidenko B.38746 (FR 2.. a geopolymer. This geopolymeric structure exhibits a similar organization to human bone and teeth... Acad. and Traetteberg. 1975. Acta Chem. 2455–2460. Petr.

1. Society for the Advancement of Material and Process Engineering.349. Geopolymer ’88 Proceedings. 1984. 1988. Geopolymer: Ultra-High Temperature Tooling Material for the Manufacture of Advanced Composites". Kunze C. Ukraine (former USSR).Na. Al.. California. Flint E.. Civil Engineering Institute. Marini and S. France. Geocistem (1997). Italy. Belgium. Stand.386. Gabelica at that time in Namur University. Covina. Extended Abstracts. 16 . and Sawyer. and Davidovics M.. Heitzmann R. Shartsis L.M. (1991). Early high-strength mineral polymer. US Patent 4..509. University of Barcelona. Newman E. 211–228. J. Portland Cement Association. Toronto. Davidovits J. 2. Bur.114. 63. Solidification of various radioactive residues by Geopolymere with special emphasis on long-term stability.. Gravitt. 1989. American Chemical Society.22041 (FR 2. MAS-NMR spectroscopy was performed by Z.. France. Technology and Manufacturing and Fields of Application. – D. July 1997. Vitrification at temperatures ranging from 1200°C to 1350°C and mineral binder formulations were performed by J.L. Kiev. pp. Early diagenesis of organic matter in marine sediments: progress and perplexity..P. Glukhovsky V. 36. Tocco. Vol. Res. 1985. and Davidovits J... See also: Long Term Durability of Hazardous Toxic and Nuclear Waste Disposals. The selection of European geological materials was carried out by – P. and Sawyer J. (1963). US Patent 4. (1999). (1993). Saint-Quentin. Bishop D. Soil silicates. – C. Cement Composition Curable at Low Temperature. Davidovits J. Doct Tech Sc. March 1993.F.18970 (FR 2. Davidovits in the laboratory of Cordi-Géopolymère SA. Davidovits J.Fe2+ . Carbon-Dioxide Greenhouse-Warming: What Future for Portland Cement. US Patent 3.. US Patent 4. Mineral polymer. BRITE-EURAM European research project BE-735593. Nat.K)2 [(Mg.649. (1946).842. Geology Dept. Orléans. 1939–1949. Chicago. The primary objective of the Geocistem research project was the fabrication of alkalimelilitic glass (Ca. 237–240. (1988). Synthesis Report and Final Technical Report.. Henrichs S. Gatzweiler R. Chem.. University of Cagliari. 39.L. Archaeological long-term durability of hazardous waste disposal: preliminary results with geopolymer technologies. (1965). USA. J. filed February 22. B. Kiessig G.Si)3 O7 ]. SAMPE Symposium.A. Degree thesis. Their Properties. 119–149.. Geopolymer ’99 Proceedings.S.B.F. (1985). Illinois. Emerging Technologies Symposium on Cement and Concrees in the Global Environment.. 125–134..464.603.D. GEOCISTEM. Introduction 79.36. Division of Environmental Chemistry. BRGM Bureau de Recherches Géologiques et minières. 21p. Rocher. Howell P. Hermann E. and Comrie D.227) and FR 80. (1992). Spain..S. Mar.489.290). Gimeno. Clarke W. Proceedings.985.. GEOCISTEM is the acronym for "cost effective GEOpolymeric Cements fo Innocuous Stabilisation of Toxic EleMents". and Wells L. Davidovits J.

Belgium. Foden A. (1940).F. 1960. (1985). Noll W. 59.J.. (1934). Randal C. Wagh. V. and Davidovics M. Carbohyd Polym. Vautey P.. edited by Joseph Davidovits and Joseph Orlinski... Wakeley.A. (1994).Y.H. Lai H. Chemically Bonded Phosphate Ceramics – A Novel Class of Geopolymers. and Jeong S. US Army Corps of Engineers.. Chapter 6. A.. June 1988.-T. Engels US Patent 4. 56. Balaguru P. Vicksburg. Yen T. G. June 12–14.org) Geopolymer ’88. Fire and Materials.3 (pp.S. Purdon A. Soc. Engels H.. Mtg. 287 -317) on the "Siloxane Bonds in Molecules of Siloxanes and Anions of Silicates. (1986). Petrisor I. Final Report CPAR-SL-94-2.. 103–111... 67–73.. (First published in the German language under the title "Chemie und Technologie der Silicone".. 17 . Publications of the Geopolymer Institute (www. Indianapolis. Performance of Concretes Proportioned with Pyrament Blended Cement. Wagh A. in particular.. and Kirkpatrik T. Proceedings of the 106th Ann. (2003). Ceram.522. D. 1–22. S. of the American Ceramic Society..795 (1986). 51[1]. Geopolymer formation and its unique properties. Olsen N. Thermoplastic and Thermosetting Composites for Structural Applications. 1990 pp.W.E. Journal de la Société des Industries Chimiques. Germany). (Journal of the Society of Chemical Industry). see also K. Neuschäffer."). N. France. Report WES/MP/GL-85-15.Organic-mineral geopolymers Kim D.geopolymer. 21. Spielau.H. Engels and G. (1990). 213–217.608. F. Philip. Environ Geol. Malone. (2006). by Tony B.O. Bruxelles. US Patent 4. 191–202. Potential for Use of Alkali-Activated Silico-Aluminate Binders in Military Applications. German Patent 600. Corps of Engineers. Spielau. Verlag Chemie. and Zoche G. Husbands. 86 [11] 1838–1844. Compiègne.W.. P.G. P. (1968). Chemically Bonded Phosphate Ceramics: I. Zoche and H.G.W.. US Army Corps of Engineers.. April 1994.393 (1985). Y. Yen T. H. Proceedings of the First European Conference on Soft Mineralulgy. Malone P. Lilian D.. US Army Corps of Engineers.W. Washington.. Geo-polymerization of biopolymers: a preliminary inquiry. G.H. Zoche US Patent 4.C. Neuschäffer. (2004). Properties of Geopolymer Matrix-Carbon Fiber Composites. (2004).652 . J. Lyon R.. Davidovits J. K. Neuschäffer K. L’action des alcalis sur le laitier de haut-founeau (The action of alkalis on blast furnace slag). Chemistry and Technology of Silicone. Comparison of Mechanical Properties.. Chilingar G. Academic Press. French Aerospace ’90 Aeronautical Conference. Gebert H... Kim D. (1997).327. Mississipi.J. A Dissolution Model of Formation. Laube R.533.

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