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Geopolymer Book Chapter1

Geopolymer Book Chapter1

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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

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

2). as well as mineral feldspathoids and zeolites. In my pursuit to develop new inorganic polymer materials. or hydroxysodalite (Figure 1. a feldspathoid). In 1972. one of the oldest man-made plastic (Figure 1. later called Cordi-Géopolymère. in alkali medium. research on nonflammable and noncombustible plastic materials became my objective.Geopolymer technology and toxic waste containment. which I call in French "géopolymères".1). 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. On the other hand. cultural heritage. which involved common organic plastic. geopolymers (mineral polymers resulting from geo5 . Thus. I proceeded therefore to develop amorphous to semi-crystalline three-dimensional silico-aluminate materials. archaeology and history of sciences. I founded the private research company Cordi SA. the aluminosilicate kaolinite reacts with NaOH at 100–150°C and polycondenses into hydrated sodalite (a tectoaluminosilicate. My chemistry background had focused on organic polymer chemistry and in the aftermath of various catastrophic fires in France between 1970–72.1: Phenoplast polycondensation between phenol and formaldehyde. arts and decoration. Figure 1. I was struck by the fact that the same simple hydrothermal conditions governed the synthesis of some organic plastics in alkali medium. phenol and formaldehyde polycondense into the famous Bakelite invented by Bakeland at the beginning of the 20th Century.

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

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

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

Each chapter is followed by a bibliography of the relevant published literature including patents. for the same emission of green house gas CO2 (Davidovits. Materials Research Laboratory. characterization. in newly industrializing countries. six times less.e.The scope of the book the development of low CO2 geopolymer cements. rapid-hardening 9 . The production of 1 tonne of kaolin based-geopolymeric cement generates 0.3 Early observations In the 1930s. six to nine times more cement for infrastructure and building applications might be manufactured. This simply means that. for students. from combustion carbon-fuel. It is this void that we hope to fill with this book. Background details on structure. Excerpts from the more important patents are included in some chapters.2 The scope of the book Although review articles and conference proceedings cover various aspects of the science and application of geopolymers. Belgian scientist Purdon (1940) discovered that the alkali addition produced a new. My research on this very important geopolymer application started in 1990 at PennState University. chemistry applications are included. 1993). Fly ash basedgeopolymeric cement emits even less CO2 . The industrial applications of geopolymers with engineering procedures and design of processes is also covered in this book. USA. such as sodium and potassium hydroxide. 1.180 tonnes of CO2 . compared with 1 tonne of CO2 for Portland cement. i. There are two main purposes in preparing this book: it is an introduction to the subject of geopolymers for the newcomer to the field. alkalis. were originally used to test iron blast furnace ground slag to determine if the slag would set when added to Portland cement. and a reference for additional information. a researcher or engineer is still at a loss to readily obtain specific information about geopolymers and their use. up to nine times less than Portland cement. 1. There are many examples in geopolymer science where an issued patent is either a primary reference or the only source of essential technical information. In the course of studying the testing systems for slag. properties. synthesis.

(1970). at the National Bureau of Standards were developing various processes for the extraction of alumina starting from clays and high-silica bauxites. 1953). at 100°C.e. He also noted that rocks and clay minerals react during alkali treatment to form sodium alumino-silicate hydrates (zeolites). without firing. montmorillonite. In 1972. In 1972.1. Glukhovsky called the concretes produced with this technology "soil silicate concretes" (1959) and the binders "soil cements" (1967). In 1957. (Besson et al. 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.1). but without any successful industrial implementation. we developed a technology based on this geosynthesis. Paris. carried out the synthesis of hydrosodalite from various phyllosilicates (kaolinite. the ceramicist team Jean Paul Latapie and Michel Davidovics confirmed that water-resistant ceramic tiles could be fabricated at temperatures lower than 450°C. Earlier. i.5 % NaCl and 1. which has been disclosed in various patents issued on the applications of the so-called "SILIFACEProcess" (Davidovits and Legrand. kaolinite.5 % NaOH to 97 % ground slag mix (U.. Borchert and Keidel (1949) prepared hydrosodalite (Na–PS) by reacting kaolinite in a concentrated NaOH solution. using calcined kaolin (metakaolin) instead of kaolinite. and calcium and sodium alumino-silicate hydrates (zeolites) as solidification products. Introduction binder (see Table 1. Flint & al (1946). 1969). One component of clay. One intermediary step of the extraction process involved the precipitation of a sodalite-like compound. Howell (1963) obtained a Zeolite A type. The usual activation called for adding 1. a Russian team. Besson. Victor Glukhovsky. confirming earlier work carried out on clay reactivity (see below). In fact. at CORDI laboratory in Saint-Quentin. halloysite) at 100°C in concentrated NaOH solution. 1974).S. Caillère and Hénin at the French Museum of Natural History. To a natural kaolinite/quartz 10 . In 1969. 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. Alkali-activated slag cements (called Trief cements) were used in large-scale construction as early as the 1950s. Army Engineer Waterways Experiment Station. reacted with caustic soda at 150°C. preventing the formation of hydrosodalite.

the polycondensation into hydrosodalite occurs very rapidly in a time as short as 15–20 seconds per millimeter thickness. In the absence of any pervious device. for the selected temperature. at 180°C and 40 kg/cm2 hydraulic pressure. due to the high internal pressure of water and the danger of explosion. and hazardous and radioactive waste stabilization. The thermosetting parameters were: – Temperature: 130°C to 180°C. it is recommended to wait until the item has cooled down to room temperature before opening the press. i. The resulting granules were cold-pressed at 15 MPa into a green body. oil well cements. Yet. when degassing is not working. which was then hot-pressed (thermosetting process) in a mold equipped with a porous layer for water evaporation. construction materials. Otherwise. but phosphate geopolymers are fabricated by acid-base reactions. The main difference between the silicate based geopolymers and phosphate geopolymers. The setting time is relatively short. 11 . Poly(sialate) geopolymers and their derivates are synthesized in alkaline environment. 65 to 75 % of the total time is devoted to degassing water. notably apatite. Virtually any divalent or trivalent oxide that is sparingly soluble may be used to form these phosphate geopolymers. They contain naturally occurring mineral phases.e. 10 to 30 bars.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.4 Phosphate-based geopolymer Phosphate ceramics are synthesized at room temperature and they set rapidly like conventional polymers.5 g water for 1 g NaOH). They are formed by an acid-base reaction between a metal oxide and an acid phosphate. however. – Applied hydraulic pressure: higher than the saturated vapor pressure of water. 1. and water (1–1. the press must be equipped with safety devices (see for more details in Chapter 7). is their syntheses. – Time: one minute per millimeter thickness at 150°C or 10 minutes for a 10 millimeters thick plate. i.e. They represent another variety of mineral geopolymer. They have found a wide range of applications such as dental cements. where Si is totally or partially replaced by P.

4. Zeolite molecular sieve 1930 1940 1945 : Barrer (UK) 1953 : Barrer. The reaction product is generally a poly(hydrophosphate) or an anhydrous poly(phosphate) that consolidates into a ceramic. 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. ceramics can be formed. Introduction Table 1. The following are the most common examples (Wagh and Yeong. By controlling the rate of reaction. (France) 1972 : Davidovits (France) Siliface Process 1976 : Davidovits (IUPAC terminology) 1979 : Davidovits (France) Geopolymer 1.1. Wagh. sim12 . 2003.1: Milestones in alumino-silicate chemistry. With trivalent oxides. 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™). (USSR) 1969 : Besson & al. (1) (2) These reactions occur at room temperature. Keidel (Germany) Geopolymer 1950 1960 1970 1963 : Howell (USA) 1964 : Berg & 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.

1. trimers. sheets and frameworks of corner-sharing silicate [SiO4 ] groups.2 Silico-phosphate geopolymers Another system involves the reaction between phosphoric acid and wollastonite. (4) 1. chains.5.Organic-mineral geopolymers ilar ceramics can be formed at a slightly elevated temperature. (1963) reported the correspondence in a study of disiloxane H6 Si2 O. Chapter 2 and Chapter 14 focus on silicone poly(organo-siloxane).4. The structures that result from this replacement closely resemble the silicate and aluminosilicate molecules: monomers. Information about this technology is scarce and restricted to the patent literature (see in Chapter 13). When the organic radical is methylene the structures of the oligomeric 13 .. has been pointed out many times. and networks of silicon and oxygen found in silica and the silicate minerals.1 Organic-mineral geopolymers Silicone The similarity of the siloxane (Si-O-Si) structure in organo-silicones to the chains. rings. for example in quartz. rings. 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. A good example is berlinite (AlPO4 ). dimers. Almennigen et al.5 1. etc. 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. 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.

The small content of organics is a key parameter governing the strength and durability of material in a large volume of inorganics..3: Evolution of organic matter to kerogen-geopolymer 14 . Yen and his team. Some geopolymeric materials can last for a long time due to their unique geopolymeric structure. 2006). Organic compounds can be incorporated into refractory macromolecules such as lignin and melanodin or humic materials (Henrichs 1992). Kerogen-geopolymer is the most stable material and the final alternating product in the Earth.2 Humic-acid based: kerogen geopolymer T.1. working on the transformation of geomolecules through geochemical processes during diagenesis. 2004.. Humic materials represent an inorganic-organic structure. so-called three-dimensional crosslink. Figure 1. Introduction poly-methyl-siloxanes are identical with those of poly(siloxonate) (SiO-Si-O) and poly(sialate) (Si-O-Al-O-Si) geopolymers.K. (Kim et al.5. 1. synthetic analogue of naturally occurring macromolecules (Kim et al. 2004. Geopolymers can be classified into two major groups: pure inorganic geopolymers and organic containing geopolymers. 2006) have drawn attention to the concept of geopolymer in association with kerogen and petroleum.

It is.454 (1977). 3. (1969). 11. 1976. (1976). Demidenko B. Ewing.A. US Patent 3.Organic-mineral geopolymers Diagenesis of organic matter leads from biopolymers synthesized by organisms through "humin" to Kerogen. Topic III. Rend. Polymère Minéral. Besson H. German Patent DE 25 00 151 (1979). 10.470.J. United Kingdom Patent UK 1. V. u. K. 22. The mechanism of geomacromolecule formation involves the crosslink reaction between the inorganic and organic materials. M. Reminikova V. Petr.. Kerogen is a geopolymer that contains a high content of organics. C. French Patent Application FR 72. see also US Patent 4. D269. Conditions de préparation de l’hydrosodalite à basse température. 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. 1.204. and Nisamov N..028.38746 (FR 2. Process for the fabrication of sintered panels and panels resulting from the application of this process. a geopolymer. 9.. 1974. Davidovits J. filed Dec.. References Almennigen. and Traetteberg. filed Jan.3). which will result in a geopolymeric structure.. Sept. z. about 1000 times more abundant than coal. 1975. Kerogen geopolymers generally occur in numerous forms: some have more organics and less inorganics.479 (1977). Hedberg.. (1949). 31. Davidovits J. (1970).. Sci. Min. however. typical inorganic-organic composites that show extreme durability and mechanical strength. (1979). Heidelb. which forms primarily from terrigenous remains of higher plants. Beitr.999) and FR 73.. (1974) French Patent FR 2. 2455–2460.S. Davidovits J. A. (1963). Berg L. 1975..35979 (FR 2.. Scand. Acta Chem. Solid phase synthesis of a mineral blockpolymer by low temperature polycondensation of aluminosilicate polymers. (1972).. Borchert W. while others have the opposite. evident that both inorganics and organics are required in a mix at a certain ratio. and Legrand J. Acad. by partial destruction and rearrangement of the main organic building blocks (Figure 1. It is the most abundant form of organic carbon on Earth. Davidovits J. 1367.. Caillère S.950. 1974 . and Keidel J.C.I. O. Stroitel’nye Materialy (USSR). Bastiansen..427 filed Jan.481. French Patent Application FR 15 .. IUPAC International Symposium on Macromolecules Stockholm. filed Jan.382). 2.. Procédé de fabrication de panneaux agglomérés et panneaux resultant de l’application de ce procédé.246. This geopolymeric structure exhibits a similar organization to human bone and teeth. New Polymers of high stability. 17. and Henin S.324.

1..S. Gabelica at that time in Namur University.. See also: Long Term Durability of Hazardous Toxic and Nuclear Waste Disposals...985. France. Emerging Technologies Symposium on Cement and Concrees in the Global Environment. Tocco. University of Cagliari. B. Proceedings. Geocistem (1997). Soil silicates. California. Al. US Patent 3. Mar. and Sawyer. Davidovits J. US Patent 4. 1939–1949. Belgium. 1989.F. Newman E. American Chemical Society. Davidovits J. Technology and Manufacturing and Fields of Application. Gatzweiler R.D. Davidovits in the laboratory of Cordi-Géopolymère SA. BRITE-EURAM European research project BE-735593. Archaeological long-term durability of hazardous waste disposal: preliminary results with geopolymer technologies. 1985. and Davidovits J. University of Barcelona.22041 (FR 2. 125–134. The primary objective of the Geocistem research project was the fabrication of alkalimelilitic glass (Ca. US Patent 4.P. SAMPE Symposium. Vol. Davidovits J.Si)3 O7 ]. Mineral polymer. Ukraine (former USSR). BRGM Bureau de Recherches Géologiques et minières. (1988). Toronto. 16 . Glukhovsky V. and Davidovics M. (1985).649. Spain. Civil Engineering Institute. Early high-strength mineral polymer. Heitzmann R. Introduction 79. Kunze C. Society for the Advancement of Material and Process Engineering. Marini and S. Kiev. USA. Cement Composition Curable at Low Temperature. Extended Abstracts. (1963). Orléans.842.Fe2+ . (1991). J. Shartsis L. – C. Geopolymer ’99 Proceedings.386. Rocher. GEOCISTEM. 1984. Degree thesis. filed February 22. Illinois. Geopolymer ’88 Proceedings. Portland Cement Association. Bur.K)2 [(Mg. Solidification of various radioactive residues by Geopolymere with special emphasis on long-term stability..M.L. and Comrie D. Saint-Quentin.227) and FR 80. July 1997. 2. Geology Dept. US Patent 4. Their Properties. 63. (1965). Early diagenesis of organic matter in marine sediments: progress and perplexity. and Sawyer J.. 39.Na. (1946). Covina. March 1993.290). GEOCISTEM is the acronym for "cost effective GEOpolymeric Cements fo Innocuous Stabilisation of Toxic EleMents". 36. Hermann E. Flint E.. Nat..464..349.18970 (FR 2. Italy. Henrichs S. Vitrification at temperatures ranging from 1200°C to 1350°C and mineral binder formulations were performed by J.B. Geopolymer: Ultra-High Temperature Tooling Material for the Manufacture of Advanced Composites". Chicago.L. 211–228.F. Stand.. and Wells L. – D.. Gimeno. Carbon-Dioxide Greenhouse-Warming: What Future for Portland Cement. The selection of European geological materials was carried out by – P. 21p. Res. 119–149.36. Howell P. Kiessig G.509.. 237–240.. J. (1993). Davidovits J. France. Clarke W.S. Division of Environmental Chemistry. MAS-NMR spectroscopy was performed by Z.A. 1988.114. Doct Tech Sc. Chem.. (1999). pp. Bishop D.. Synthesis Report and Final Technical Report.603.489. (1992).. Gravitt..

.A.Organic-mineral geopolymers Kim D. 287 -317) on the "Siloxane Bonds in Molecules of Siloxanes and Anions of Silicates. Kim D.. France. Ceram. by Tony B. Malone P. (2006).E. in particular. Comparison of Mechanical Properties. Engels US Patent 4. 67–73. April 1994. of the American Ceramic Society...652 . P. US Army Corps of Engineers. Gebert H.W.O... (1985).. Germany). US Patent 4. 86 [11] 1838–1844. Final Report CPAR-SL-94-2. D. Balaguru P. (2004). Randal C.G. Wagh. Thermoplastic and Thermosetting Composites for Structural Applications. see also K. 59. Chemically Bonded Phosphate Ceramics: I.3 (pp. Malone. F.. Geopolymer formation and its unique properties. S. Proceedings of the 106th Ann. Carbohyd Polym.J. (1986). Engels H. US Army Corps of Engineers. Spielau. US Army Corps of Engineers. French Aerospace ’90 Aeronautical Conference. Bruxelles. June 12–14. K. Davidovits J. Report WES/MP/GL-85-15. Petrisor I. and Jeong S.Y.H.. Yen T. 21.. Foden A. Chemistry and Technology of Silicone. H.. Neuschäffer K. (1940). Lai H. (1934).H.W. (2004). Verlag Chemie. Washington.G.522. June 1988. (2003). (1997). 1–22. Wakeley.608. 1960.. 103–111. 56. Olsen N. Yen T. (1994). Chapter 6. Fire and Materials.. Compiègne.H. Philip. (1968).J..W. Noll W. G. Chemically Bonded Phosphate Ceramics – A Novel Class of Geopolymers. Vautey P.327. A Dissolution Model of Formation.. German Patent 600. L’action des alcalis sur le laitier de haut-founeau (The action of alkalis on blast furnace slag). and Davidovics M. edited by Joseph Davidovits and Joseph Orlinski.. Chilingar G.. Spielau. V.W. 191–202. N. and Kirkpatrik T. Zoche US Patent 4. Potential for Use of Alkali-Activated Silico-Aluminate Binders in Military Applications. Vicksburg.C. Laube R. Neuschäffer.393 (1985). Neuschäffer. Corps of Engineers. J. Engels and G.. Properties of Geopolymer Matrix-Carbon Fiber Composites. Husbands. A. Geo-polymerization of biopolymers: a preliminary inquiry. Purdon A.").. and Zoche G. 213–217. Mtg. Y..S.F. P. Lyon R. Academic Press.-T. Journal de la Société des Industries Chimiques. Soc. Belgium. 51[1]. Mississipi. Performance of Concretes Proportioned with Pyrament Blended Cement. 17 .org) Geopolymer ’88. Publications of the Geopolymer Institute (www. Lilian D.. Environ Geol. Indianapolis. (1990). Proceedings of the First European Conference on Soft Mineralulgy. (First published in the German language under the title "Chemie und Technologie der Silicone". Wagh A. Zoche and H.geopolymer.. 1990 pp. (Journal of the Society of Chemical Industry).. G.795 (1986).533.

Geopolymer Workshop. edited by Joseph Davidovits. June 30-July 2. Geopolymer 2005. France. 2005. France. Australia. July 2005. 18 . Saint-Quentin. Proceedings of the Second International Conference Géopolymère ’99. Ralph Davidovits and Claude James. Green Chemistry and Sustainable Development Solutions. Proceedings of the World Congress Geopolymer 2005. Introduction Geopolymere ’99.1. 4th International Geopolymer Conference. Sept. edited by Joseph Davidovits. Perth. Saint-Quentin. 1999. Geopolymer.

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