Geopolymer chemistry and sustainable Development

Geopolymer chem istry and sustain able Dev elopment. The Poly(s ialate) term inolog y : a v ery useful and simp le model for th e p rom otion and understanding of green-chemistr y. La chimie du géopolymmère et le développement durable. La terminologie Poly(sialate): un modèle très simple et utile à la promotion et la compréhension de la chimie verte.

Joseph Davidovits Geopolymer Institute, 02100 Saint-Quentin, France

Abstract: Geopolymer Resins and Geopolymer Cements are new advanced mineral binders. In both cases, resins/binders and cements, the same green chemistry is used: geopolymerization. In industrialized countries, for geopolymer applications, emphasis was put on fire and heat resistance, and also in radioactive and toxic-waste management, yielding sophisticated geopolymer resins and binders: K-poly(sialatesiloxo), K-poly(sialate-disiloxo) systems, as well as K-nano-polysialate matrices. In emerging countries, the driving elements for sustainable development are Green-House and Global Warming concerns. The geopolymer green-chemistry generates new types of low-CO2 cements for building and infrastructure applications, based on geological as well as industrial waste-materials (coal fly-ashes, coal-mining waste, etc.). As a consequence, Geopolymer Concrete possesses physico-chemical properties entirely different from those of regular Portland-Cement-based concrete. Les résines et ciments géopolymères sont des nouveaux liants minéraux à haute performance. Dans les deux cas, résines et ciments, on utilise la même chimie verte: la géopolymérisation. Dans les pays industrialisés elle fut utilisée pour obtenir des résistances au feu et à la chaleur et aussi pour traiter les déchets toxiques et radioactifs, utilisant des résines et des liants très spéciaux de type: Kpoly(sialate-siloxo), K-poly(sialate-disiloxo), ainsi que des matrices K-nano-polysialate. Dans les pays émergents, le développement durable résulte des effets du réchauffement climatique, effet de serre. La chimie verte géopolymèrique permet d'obtenir des nouveaux ciments à basse émission de CO2 réalisés à partir de déchets industriels (cendres volantes, stériles de charbon, etc.) et de matériaux géologiques. Les bétons géopolymères possèdent des propriétés physico-chimiques totalement différentes de celles du béton normal fait de ciment Portland.

Introduction Thirty three years ago, I showed how naturally occurring alumino-silicates, such as kaolinite, were transformed at low-temperature, in an astonishingly short time, into tridimensional tecto-aluminosilicates. The geosynthesis is based on the ability of the aluminum ion (6-fold or 4-fold coordination) to induce crystallographical and chemical changes in a silica backbone. The thermosetting method invented in the manufacture of various items, was very similar to that used for the polycondensation of organic resins. The process yields nanocomposites that are actually man-made rocks. This geosynthesis is also manifest in nature itself in great abundance. At least 55% of the volume of the Earth's crust is composed of siloxo-sialates and sialates, with pure silica or quartz at only 12%. One basic innovation, the low-temperature transformation from kaolinite into hydrosodalite, demonstrated the tremendous latent potential of this new mineral reaction. This potential was neglected by the mainstream ceramic and cement industries, by virtue of the infamous NIH principle (not invented here). It also failed to have any impact on other branches of industry because it was classified as an inexpensive clay product and listed under the heading of cheap construction materials. As such, it did not have the «cachet» of developments in the «advanced» or so-called high-tech industries.

To define the importance of this chemistry, in 1976 I established a new terminology that served to properly classify mineral polymers.

Terminology In 1979, I went further by creating and applying the term «geopolymer». I also put it in the public domain for general usage. In the mean time, it has been adopted as a generic term for advanced inorganic polymer compounds by numerous scientific institutions around the world. Since 2002, several national and international scientific and technological institutions are organizing “geopolymer sessions” ,“geopolymer seminars”, "geopolymer conferences". Yet, especially for cement and concrete applications, we are witnessing an increase in various names. This abundance of names and acronyms describing the very same system is misleading, and creates a lot of confusion in people's mind.

The ambiguous and preju dicial terminology based on al kali-activation Below are some examples of ambiguous terminology: applications dealing with high-tech: - ABC, alkali-bounded-ceramic. This is a reminder of the defunct Chemically Bounded Ceramic, CBC of the 1980's in USA. - hydroceramic, also a reminder of 1980' US research on radioactive waste containment. 9

Applications on geopolymer cement and geopolymer concrete: - AAC: alkali-activated-cement - AAFA, alkali-activated-fly ash, for application involving fly- ashes. These can be confused with - AAR: alkali-aggregate-reaction, a harmful property well-known in concrete, or - AAC (Autoclaved Aerated Concrete) a well known foamed Portland cement like Hebel and Ytong. In all cases, resins/binders and cements, the same green chemistry is used: geopolymerization. Yet, especially for these cement and concrete applications, these various names involve essentially alkali-activation. Yet, for every concrete civil-engineer alkali means danger like the harmful alkali-aggregate-reaction. This creates a lot of confusion in people's mind, generating false granted ideas, about the properties of Geopolymer-Concrete, for example: a) the pH of the geopolymer cement will induce steel bar corrosion! As a consequence of the above mentioned misinterpretation between alkali-activation and geopolymer cement, concrete engineers believe that the pH of geopolymer cement is very high, between 12 and 14. This is wrong. The pH is in the range of 11.5 to 12.5, depending on the formulations. Concrete engineers should not forget that the pH of regular concrete with Portland cement ranges between 12-13. It is this high pH which protects the steel bars against corrosion. As for geopolymer concrete, if the pH is higher than 12,5, this means that something is wrong with the geopolymerization and the formulation must be adapted in order to get values ranging between 11.5 and 12.5 maximum. Why would this pH be deleterious for geopolymer concrete, and safe for Portland concrete? b) Carbonation activities in the vicinity of steel will deteriorate the reinforcement! The matrices of Portland cement contains free hydroxyl ions that could be involved in carbonation of Ca(OH)2 into CaCO3. Carbonation of Portland cement reacts with these hydroxyl ions and lowers the pH, opening the route for corrosion. Yet, the carbonation of geopolymer concrete is different. It does not significantly affect the pH. In the case of Portland cement, the carbonation yields calcium carbonate, with a pH of 7-8. On the opposite, carbonation of geopolymer concrete yields to potassium carbonate or sodium carbonate, with a minimum pH of 10-10.5, involving steady chemical protection against corrosion. c) The alkali will cause the deleterious Alkali-AggregateReaction! Portland cement customers commonly require from the cement manufacturers the supply of low-alkali cements. Figure 1 displays the results of the tests carried out in 1990 according to ASTM C227 bar expansion on Poly(sialate-siloxo) geopolymeric cement and Portland cement. Geopolymer cements, even with alkali contents as high as 9.2%, do not generate any dangerous alkaliaggregate reaction.

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Figure 1: Alkali-aggregate reaction; ASTM C227 bar expansion for (KCa)-poly(sialate-siloxo) cement and ordinary Portland cement.

d) There is danger for high corrosion with chloride ions! This is a field where we have little experience. However, we know that chloride ions have no deleterious activity on the geopolymer matrix itself. We can use salted sea water to make a geopolymer concrete. Several studies have shown that the chloride anions are becoming trapped within the geopolymeric network and therefore cannot move and migrate within the matrix. Like for the well known AAR Alkali-Aggregate-Reaction, dangerous for Portland cement, but totally harmless for geopolymer concrete, all pre-granted false ideas must be settled with an appropriate teaching and terminology. This is why the geopolymer terminology is important in showing that the chemistry is different.

The geop olymer t erminolog y Alumino-silicate binders are called inorganic geopolymeric compounds, since the geopolymeric cement obtained is the result of an inorganic polycondensation reaction, a so-called geopolymerisation. Such reactions yield three-dimensional tecto-aluminosilicate frameworks with the general empirical formula Mn[-(SiO2)z-AlO2]n.wH2O wherein M is a cation (K, Na, Ca) and n is the degree of polycondensation and z is 1, 2, 3 or >>3. Such frameworks are called polysialates, where sialate stands for the siliconoxo-aluminate building unit. The sialate network consists of SiO4 and AlO4 tetrahedras linked by sharing all oxygen atoms. Positive ions (Na+, K +, Ca2+, etc) must be present to balance the negative charge of Al in 4-fold coordination. Chains and rings may be formed and cross-linked together, always through a sialate Si-O-Al bridge. For the chemical designation of geopolymers based on silico-aluminates, poly(sialate) was suggested. Sialate is an abbreviation for silicon-oxo-aluminate. Polysialates are chain and ring polymers with Si4+ and Al3+ in IV-fold coordination with oxygen and range from amorphous to semi-crystalline. The amorphous to semi-crystalline three dimensional silico-aluminate structures were christened «geopolymers» of the types (Figure 2):

Geopolymer: green chemistry and sustainable development solutions

Figure 3: silica fume nanopheres

Figure 2: the geopolymer terminology.

The new terminology was the key to the successful development of new materials. For the high-tech user, geopolymers are polymers and, therefore, by analogy with the organic polymers derived from oil, they are transformed, undergo polycondensation, and set rapidly at low temperature, within few minutes. But they are, in addition, GEO-polymers, i.e. inorganic, hard, stable at temperature up to 1250°C and non-inflammable. This gave a tremendous boost to creativity and innovation.

The second polymeric phase is entirely amorphous under the microscope. It corresponds to a poly(silanol) (Figure 4), a poly(siloxo) (Figure 5) or a poly(sialate) (Figure 6), in which the chains of linear poly(silanol) are more or less cross-linked by a a siloxo bridge (-Si-O-Si-O) or a sialate bridge (-Si-O-Al-O-).

Common silicate minerals according to the terminology used above are strictly spoken polycondensated sialates. In that sense the majority of the Earth’s crust is composed of siloxo-sialates and sialates. It can easily be checked that according to this terminology the common feldspar series albite-anorthite (NaAlSi3O8 – CaAl2Si2O8) can be described as poly(sialate-disiloxo) for albite to poly(disialate) for anorthite.

Green-chemistry and sustainable develo pment In industrialized countries emphasis was put on fire and heat resistance, and also in radioactive and toxic-waste management, yielding sophisticated geopolymer resins and binders based on K-poly(sialate-siloxo) and Kpoly(silate-disiloxo) systems, as well as K-nanopolysialate matrices.

Nano-composite geop olymer m atrices: K-nano-poly(siloxo) for bio-mat erial, Knano-poly(sialate) for fir e-heat resistance Nanocomposite geopolymers are materials containing two components, of which at least one is visible under a microscope, and has a dimension of the order of tens or hundreds of manometers. Nanocomposite geopolymers contain two phases with a) a primary nodular silica fume phase composed of nanospheres of diameter less than 1 micron, and preferably less than 500 nm (Figure 3). b) a polymeric phase, composed essentially of alkaline poly(silanol), crosslinked with at least one, or several sialate bridges (-Si-O-Al-O-), or siloxo bridges (-Si-O-SiO).

Figure 4: K-nano-poly(silanol) and 29Si NMR.

K-nano-poly(siloxo) matrix for bio-materials K-poly(silanol) (Figure 4) polycondenses above 200°C into K-poly(siloxo) –Si-O-Si- cross-link with the formation of H2O (Figure 5). The matrix expands owing to the release of this polycondensation water. The degree of expansion is obviously a function of the cross-linking density in the polymeric phase, i.e. the presence or not of sialate bridges (-Si-O-Al-O-) linking together the poly(silanol) chains and the surfaces of the siliceous nanosphères. Preliminary research involving the addition of Hydroapatite (HP) has shown the potential as biomaterial for bone replacement and implant (se the corresponding paper by Oudadesse & al. in this book).

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Ceramic Transactions Volume 37, Cement-Based Materials: Present, Future, and Environmental Aspects. The calculated CO2 emission for the production of 1 tonne of geopolymeric cement is 0.184 tonnes including the calcination of minerals and the grinding and mixing energies.

Figure 5: K-nano-poly(siloxo), (Si-O-Si-O) cross-link, and 29Si NMR.

K-nano-poly(sialate) matrix and binders The addition of Al-networking compounds to the poly(silicate) reaction mixture provides strong crosslinked heat stable matrices, with no expansion or shrinkage. The matrix is of the poly(sialate) type (Figure 6).

The geopolymer green-chemistry generates new types of cements for building and infrastructure applications, based on geological as well as industrial waste-materials (coal fly-ashes, coal-mining waste, etc.). The chemistry mechanism no longer involves dissolution of all reactive ingredients, but the creation of a new matrix that interreact with the surface of reactive alumino-silicate fillers. The chemical make-up of these cementitious matrices is more complicated that the one of pure geopolymer resins. However, the composition of these geopolymer cement matrices can be determined. The Electron-micro-beam analysis provides the chemical composition and the average value of these measurements gives the following atomic ratios (between brackets, the lowest and the highest values): Si:Al 2.854 (2.047 to 5.57) K:Al 0.556 (0.306 to 0.756) Si:K 6.13 (3.096 to 9.681) Ca:Al 0.286 (0.107 to 0.401) Si:Ca 15.02 (4.882 to 41.267)

Figure 6: K-nano-poly(sialate), (Si-O-Al-O-) cross-link, and 29Si NMR.

To simplify, the geopolymer matrix is of the Poly(sialatedisiloxo) type, Si:Al =3, with the approximate formula K, Ca)(-Si-O-Al-O-Si-O-Si-O). In fact if we look at geological analogues we could compare it to materials like plagioclase, Na[AlSi3O8]-Ca[Al2Si2O8], a solid solution of albite-anortite. In our present potassium based geopolymer, albite would be replaced by orthoclase K[AlSi3O8]. The geopolymer matrix would involve an amorphous, vitreous solid solution of: - Ca-poly-di-(sialate) (Ca)(Si-O-Al-O-)2 , Si:Al=1 (anortite CaSi2Al2O8), - K-poly(sialate-disiloxo), (K)(Si-O-Al-O-Si-O-Si-O), Si:Al=3 , orthoclase K[AlSi3O8] and an additional phase - K-silicate cross-linked with a sialate link, Si:Al>3, (low MgO amphibole/pyroxene)

The K-nano-poly(sialate) resin has a high potential for fire-heat resistant coatings as well as corrosion resistant paint for steel. With tailored ceramic fillers one obtains heat stable materials with remarkable heat resistance.

It is interesting to compare the energy needs as well as the greenhouse gas CO2 emissions of traditional Portland cements vis a vis this new type of geopolymeric cement:

Low CO 2 cement In emerging countries, the driving elements for sustainable development are Green-House and Global Warming concerns. Since 1993, I have been strongly involved in the development of low CO2 cements. My first paper on the subject was titled: Carbon-Dioxide Greenhouse-Warming: What Future for Portland Cement. It was presented at the Emerging Technologies Symposium on Cements and Concretes in the Global Environment, organized by the Portland Cement Association, Chicago, Illinois, March 1993. A more detailed study was presented at the Cement Division meeting of the 95th Annual Meeting of the American Ceramic Society held in Cincinnati, OH, April 18, 1993, with the title: Geopolymer Cements to minimize CarbonDioxide Greenhouse-Warming. It was published in 12

Energy needs, MJ/tonne

Type

calcination

crushing

total

Portland cement

3200

430

3430

geopolymeric

600

390

990

Greenhouse gas Emission, CO 2 in tonne/tonne

Portland cement

1.00

geopolymeric cement

0.15-0.20

Geopolymer compound of the Poly(sialate-disiloxo) type, or (K, Ca)-PSDS, requires 3.5 times less energy than that of Portland cement; in addition, it emits 5 to 6 times less of the greenhouse gas CO2. Moreover, my optimistic view states that by applying our new fly ash based geopolymer


technologies described below, that reduces the CO2 emissions for cement production by 80-90%, the future for coal combustion can as well be secured. Electricity utilities can then produce energy and low-CO2 cement in the same plant. I foresee that by the year 2015 the required 3500 million tonnes of world cement could be produced in this way.

European Community. The GEOASH project is known under the contract number RFC-CR-04005. It involves : Delft University of Technology, Delft, The Netherlands ; Cordi-Géopolymère Sarl, Saint-Quentin, France ; ISSeP, Liège, Belgium ; University of Seville, School of Industrial Engineering, Sevilla, Spain ; CSIC, Institute of Earth Sciences ‘Jaume Almera’, Barcelona, Spain

Fly ash based co ncrete: the GEOASH project

The milestones of geopolym er chem istry are taken from the li st available at:

Since November 2004 the author is involved in a EU sponsored project ‘Understanding and mastering coal fired ashes geopolymerization process in order to turn potential into profit’, known under the acronym ‘GEOASH’. Although it is a bit early to come now with a scientific sound paper on this activity, I have found it appropriate to outline the preliminary results of this GEOASH project performed in our laboratory at CordiGéopolymère (www.cordi-geopolymere.com). A preliminary paper was also presented by the consortium at WOCA (World of Coal Ash) 2005 [Geopolymerization of Fly Ashes, Henk Nugteren, Joseph Davidovits, Diano Antenucci, Constantino Fernández Pereira and Xavier Querol].

www.geopolymer.org/davidovits/milestones_geopolymer.html

Normally, the curing of fly ash based geopolymeric matrices, like those described in other papers in this book, is done at temperatures between 60 and 90°C. In this project, since the idea is to use the geopolymers as a cement, the curing is taking place at room temperature like for regular Portland cement.

1972: first patent on polycondensation of kaolinite with NaOH TI : Sintered composite panels AU : Davidovits J AF : Coordination et Developpement de l’lnnovation S. A. SO : FR72138746 721102 ; US Patent 3,950,470; US 4,028,454 KW : building panel manuf; kaolin building panel; sand building panel; resin building panel 1975: first patent on hydrosodalite Na-PS shaped articles TI : Agglomerating compressible mineral materials in the form of powder, particles, or fibers AU : Davidovits J AF : Coordination et Developpement de l’lnnovation S. A.; Cordi SA Fr. SO : Patent DE2621815- 761209;Ger.Offen.; 10pp.; FR75/17337-75O603 GB Patent 1,481,479 KW : hydrosodalite shaped article 1976: terminology of the sialate chemistry TI : SOLID PHASE SYNTHESIS OF MINERAL BLOCKPOLYMER BY LOW TEMPERATURE POLYCONDENSATION OF ALUMINO-SILICATE POLYMERS. AU : DAVIDOVITS J AF : CORDI S.A., SAINT-QUENTIN, FR. SO : IN: LONG-TERM PROP. POLYM. POLYM. MATER. INT. UNION PURE APPL. CHEM. MACROMOL. SYMP.; STOCKHOLM; 1976; S.L.; DA. S.D.; PP. (3P.) KW : INORGANIC COPOLYMER; BLOCK COPOLYMER; CROSSLINKING; PREPARATION

Figure 7: room temperature 28 day compressive strength

Fifteen samples of (co-)combustion European fly ashes have so far been tested on their suitability for geopolymeric cements. The ashes, 60-80% by weight of the mix, were mixed with the various required chemical components used in (K,Ca)-poly(sialate-siloxo) cement and cured at room temperature. The results of compressive strength tests after 28 days are shown in Figure 7. There is a large variation in behavior of the different fly ashes, ranging from unworkable situations in which the paste hardens during mixing (flash-set) to remarkable and excellent strength of 90 and 95 MPa after 28 days. The GEOASH project is carried out with a financial grant from the Research Fund for Coal and Steel of the

1979: first patent on geopolymeric resin TI : Inorganic polymer AU : Davidovits J AF : Cordi S. A.; Fr. SO : Patent FR2454227 – 810306; Fr Demande; 11 pp.; FR79.22041- 790904; US patent 4,349,386; US patent 4,472,199 KW : zeolite hard nonporous 1979: first papers on archaeology applications: TI : La fabrication des vases de pierres au V et IV Millenaires. AU : Davidovits J. SO : 2nd International Congress of Egyptology, 1979, Grenoble; Abstracts KW : stone vases; prodynastic period; fabrication without carving. 13

TI : Les offrandes de natron et le symbole de l’incarnation divine dans la pierre. AU : Davidovits J. SO : 2nd international Congress of Egyptology, 1979, Grenoble; Abstracts KW : natron salt; sodium carbonate; petrification; ceramics; objects in stone; pyramids construction with agglomerated stone. 1980: first patent on low cost building material TI : Structural components using ferruginous, lateritic and ferrallitic soils AU : Davidovits J AF : Coordination et Developpement de l’Innovation S. A.; Fr. (FR) SO : Patent FR2490626 A1, 820328; Fr. Demaride; 7 pp.; FR80l20388, 800923 KW : ferruginous soil building material; lateritic soil building material; ferrallitic soil building material 1981: first patent on geopolymeric foam TI : Expanded minerals based on potassium poly(sialates) and/or sodium, potassium poly(sialate-siloxo) types AU : Davidovits J; Legrand J J AF : Societe Anon. Coordination et Developpement de l’lnnovation (CORDI); SO : Patent FR2512805A1, 830318; Fr. Demande; 11 pp.; FR81117543, 810917 KW : potassium alumnosilicate foam polycondensation 1984: first patent on geopolymeric cement TI : Early high-strength mineral polymer AU : Davidovits J; Sawyer J L AF : Pyrament, Inc.; USA (US) SO : Patent US 4,509,985 A 850409; U.S.; 7 pp.; European Patent EP 0 153 097 KW : aluminosilicate polymer slag concrete; sialate polymer slag concrete 1987: first patent on fiber/geopolymer composite TI : Ceramic-ceramic composite materials and their manufacture AU : Davidovits N; Davidovics M; Davidovits J SO : Patent WO 88/02741 A1880421; PCT Int. Appi.; 21 pp.; US patent 4,888,311. KW : silicon carbide fiber reinforced aluminosilicate; sodium sulfite silicon carbide aluminosilicate; alkali metal silicon carbide; aluminosilicate 1987: first patent on geopolymeric waste containment TI : Method for stabilizing, solidifying and storing waste material AU : Davidovits J. SO : Patent WO 89/02766; International Patent Application published April 08, 1989 Priority US 104,190, filed october 02, 1987; US patent 4,859,367. KW : waste stabilization, solidification, storage with geopolymer matrix. long term durability. 1987: first paper on ancient concretes TI : Ancient and modern concretes: what is the real difference? AU : Davidovits J AF : Barry Univ.; lnst. AppI. Archaeol. Sci.; Miami Shores; FL; USA 14

SO : Concrete International: Des. (ClDCD2,01624075); 87; Vol.9(12); pp.23-9

Constr,

1988 : first hieroglyphic text deciphered on pyramid construction TI : Pyramid Man-Made Stone, Myths or Facts,( III) : The Famine Stela provides the hieroglyphic names of chemicals and minerals involved in the construction. AU : Davidovits J AF : Barry Univ.; lnst. AppI. Archaeol. Sci.; Miami Shores; FL; USA (uS) SO : Fifth Internationl Congress of Egyptology, Cairo 1998, Abstracts of papers, pp. 57-58 1990 TI : Geopolymeric concretes for environmental protection AU : Davidovits J; Comrie D C; Paterson J H; Ritcey D J AF : Barry Univ.; Inst. Appl. Archaeol. Sci.; Miami Shores; FL; USA (US) SO : Concrete International. (CIDCD2,01624075); 90; VOL.12 (7); PP.30-40 1991 TI : Geopolymer: ultrahigh-temperature tooling material for the manufacture of advanced composites AU : Davidovits J; Davidovics M AF : Cordi-Geopolym. S. A.; Geopolym. Inst.; Saint Quentin; F-02100; Fr. (FR) SO : INT. SAMPE SYMP. (ISSEEG,08910138); 91; VOL.36 (2); PP.1939-49 TI : Geopolymers: inorganic polymeric new materials AU : Davidovits J AF : Cordi-Geopolymere S. A.; Geopolym. Inst.; Saint Quentin; 02100; Fr. (FR) SO : J. THERM. ANAL. (JTHEA9,03684466); 91; VOL.37 (8); PP.1633-56SC : S57-000/1992

1993 : First paper on Global-Warming CO2 mitigation TI : Geopolymer Cements to minimize Carbon-dioxide greenhouse-warming AU : Davidovits, J. AF : Géopolymère, Saint-Quentin, France SO : CERAMIC TRANSACTIONS, VOL. 37 (1993), CEMENT-BASED MATERIALS: PRESENT, FURURE, AND ENVIRONMENTAL ASPECTS, M. MOUKWA & AL. EDS., PP. 165-182; AMERICAN CERAMIC SOCIETY. 1994 TI : Recent Progresses in Concretes for Nuclear Waste and Uranium Waste ContainmentAU : Davidovits, J AF : Géopolymère, Saint-Quentin, France SO : CONCRETE INTERNATIONAL, Vol. 16, N°12, PP. 53-58 (1994) TI : Geopolymers: Man-Made Rock Geosynthesis and the Resulting Development of Very Early High Strength Cement AU : Davidovits, J AF : Géopolymère, Saint-Quentin, France SO : JOURNAL OF MATERIALS EDUCATION, PP. 91137, Vol. 16, N°2&3 (1994)


TI : High Alkali Cements for 21st Century Concretes AU : Davidovits, J. AF : Géopolymère, Saint-Quentin, France SO : CONCRETE TECHNOLOGY, PAST, PRESENT, AND FUTURE, P.K. MEHTA ED., PP. 383-397, AMERICAN CONCRETE INSTITUTE, DETROIT, SP144 (1994). TI : Global Warming Impact on the Cement and Aggregates Industries AU : Davidovits, J. AF : Géopolymère, Saint-Quentin, France SO : WORLD RESOURCE REVIEW, PP.263-276, Vol. 6, N°2 (1994). 1994-1997: European reseach project GEOCISTEM; first MAS-NMR study of ancient Roman cement. TI: Archaological analologues and long-term stability of geopolymeric materials. Results from the European research project GEOCISTEM. AU: Davidovits Joseph and Davidovits Frédéric. AF: Institut Géopolymère, Saint-Quentin, CERLA, Universié de Caen, France SO: GEOPOLYMER ‘99 Proceedings 2nd Int. Conf. on Geopolymers, Saint-Quentin, 1999, pp. 283-295. 1997: First paper on CARBON/GEOPOLYMER composite and F.A.A. testing TI : Fire-resistant Aluminosilicate Composites AU : Lyon, R., Foden, A., Balaguru, P.N., Davidovics, M. and Davidovits, J., AF : Federal Aviation Administration Technical Center, USA, Rutgers The State University New Jersey, USA, Géopolymère, Saint-Quentin, France SO : Journal FIRE AND MATERIALS, Vol. 21, PP. 6773 (1997)

2.490.626 – 2.512.805 2.523.118 – 2.528.818 2.621.260 – 2.657.867 2.659.963 – 2.666.253 2.709.258 – 2.712.584 – patents pending.

– 2.512.806 – 2.512.808 – – 2.528.822 – 2.604.994 – – 2.671.344 – 2.659.320 – – 2.666.328 – 2.669.918 – 2.756.840 – 2.758.323 – ; other

Granted and i ssued US pat ents 3,950,470 – 4,028,454 – 4,349,386 – 4,472,199 – 4,509,985 – 4,859,367 – 4,888,311 – 5,288,321 – 5,342,595 – 5,352,427 – 5,349,118 – 5,539,140 – 5,798,307 – 5,925,449 ; other patents pending.

PCT patent publicat ions EP 0 026 687 – WO 82/00816 – WO 88/02741 – 89/02766 – WO 91/13830 – WO 91/13840 – 91/11405 – WO 92/04298 – WO 95/13995 – 98/31644 – WO 03/040054 – WO 03/087008 – 03/099738; other patents pending.

WO WO WO WO

General Litt erature See on the Internet, www.geopolymer.org, the Geopolymer Institute Library page for the list of other publications. GÉOPOLYMÈRE ‘88 , Proceedings 1rst European Conference on Soft Mineralurgy, 1988, edited by J. Davidovits and J. Orlinski, Université de Technologie, Compiègne, France (1989). GÉOPOLYMÈRE ‘99 , Proceedings of the Second Conference on Geopolymer, 1999, edited by J. Davidovits, R. Davidovits and C. James, Geopolymer Institute and I.N.S.S.E.T., Saint-Quentin, France (1999)

1998-1999: first prototype experimentation on radioactive waste containment at WISMUT, Germany. TI: Solidification of various radioactive residues by Geopolymere with special emphasis on long-term stability. AU: Hermann E., Kunze C., Gatzweiler R., Kiessig G. and Davidovits J., AF: BPS Engineering, Zwickau, Germany, WISMUT GmbH, Chemnitz, Germany, Cordi-Géopolymère SA, Saint-Quentin, France. SO: GEOPOLYMER ‘99 Proceedings 2nd Int. Conf. on Geopolymers, Saint-Quentin, 1999, pp. 211-228. 2002: the making of 15 metric tones of agglomerated limestone (pyramid stone), in Saint-Quentin. TI: La nouvelle théorie, des blocs en aggloméré? AU: Davidovits J., AF: Institut Géopolymère, Saint-Quentin, France. SO: Revue Historia, Paris, nr. 674, feb. 2003, pp. 70-77. See also on the Internet the English and French video See also the book: La nouvelle histoire des pyramides d’Égypte, édition Jean-Cyrille Godefroy, Paris, ISBN 286553-175-9.

Granted and issu ed French pat ents 2.204.999 – 2.246.382 – 2.324.427 – 2.346.121 – 2.259.056 – 2.366.233 – 2.314.158 – 2.341.522 – 2.358.371 – 2.464.227 – 2.489.290 – 2.489.291 – 15

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