Joseph Davidovits_ Geopolymers

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Geopolymers

Wikipedia: Joseph Davidovits/Geopolymers

Biography

www.geopolymer.org: Introduction

www.geopolymer.org: Formula

Charles Bremner/The Times Online (December 01, 2006): Pyramids were built with concrete rather than rocks, scientists

claim

Davidovits' US Patents --- List

J. Davidovits: US Patent # 4,349,386 -- Mineral polymers and methods of making them

J. Davidovits: US Patent # 4,472,199 --- Synthetic mineral polymer compound of the silicoaluminates family and preparation

process

J. Davidovits: US Patent # 4,509,985 --- Early high-strength mineral polymer

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www.wikipedia.org

Joseph Davidovits

Sodium Phenoxy Acetate

Used in the synthesis of the ester

derivativeswww.niacet.com

Einstein's Method

A Fresh Approach to Relativity &

Q.M. - A scholarly inquiry...www.einsteinsmethod.com

SteamTab

Spreadsheet Add-in for Properties

of Water and Steamwww.chemicalogic.com

Joseph Davidovits: Geopolymers --Biography, 3 patents, &c http://www.rexresearch.com/davidovits/davidovits.htm

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Joseph Davidovits (born 1935) is a French materials scientist who has posited that the blocks of the Great Pyramid are not carvedstone, but mostly a form of limestone concrete. He holds the Ordre National du Mérite, is the author and co-author of more than 130scientifical papers and conferences reports, and holds more than fifty patents.

Theory

Davidovits was not convinced that the ancient Egyptians possessed the tools or technology to carve and haul the huge (2.5 to 15 ton)limestone blocks that made up the Great Pyarmid. Davidovits suggested that the blocks were molded in place by using a form oflimestone concrete. According to his theory, a soft limestone with a high kaolinite content was quarried in the wadi on the south of theGiza plateau. It was then dissolved in large, Nile-fed pools until it became a watery slurry. Lime (found in the ash of ancient cookingfires) and natron (also used by the Egyptians in mummification) was mixed in. The pools were then left to evaporate, leaving behind amoist, clay-like mixture. This wet "concrete" would be carried to the construction site where it would be packed into reusable woodenmolds. In the next few days the mixture would undergo a chemical hydration reaction similar to the setting of cement.

Using Davidovits theory, no large gangs would be needed to haul blocks and no huge and unwieldy ramps would be needed totransport the blocks up the side of the pyramid. No chiseling or carving with soft bronze tools would be required to dress their surfacesand new blocks could be cast in place, on top of and pressed against the old blocks. This would account for the unerring precision ofthe joints of the casing stones (the blocks of the core show tools marks and were cut with much lower tolerances). Proof-of-conceptexperiments using similar compounds were carried out at Davidovit's geopolymer institute in northern France. It was found that a crewof ten, working with simple hand tools, could build a structure of fourteen, 1.3 to 4.5 ton blocks in a couple of days. According toDavidovits the architects possessed at least two concrete formulas: one for the large structural blocks and another for the white casingstones. He argues earlier pyramids, brick structures, and stone vases were built using similar techniques.

His ideas are not accepted by mainstream Egyptologists.


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Summary of evidence

Davidovits cites primarily evidence related to his profession as a materials scientist, re-interpreting the observations of conventionalEgyptology within this light. Briefly, his points include:

The thin layer of 'mortar' found at the top of casing blocks is actually the the result of settling and water percolating to the top of theblock while drying; the layer found would be too weak to bind the massive blocks together

The humidity inside the pyramids is much higher than would be expected in a desert environment; this is caused by the moisturereleased into the halls and galleries while the blocks cure

The arrangement of fossils within the blocks is jumbled, rather than stratified, pointing to the blocks being crushed, then poured whilecasting rather deposited in layers as would conventional sedimentary rock

Certain blocks have elongated air pockets, caused by the cement hardening while air bubbles were in the process of rising to the topAncient descriptions of the pyramids being built featured the use of short blocks of wood, conventionally seen as levers or cranes;Davidovits suggests their use as frames to mold the blocks

Books

Davidovits, Joseph, Margie Morris (1988). The Pyramids: An Enigma Solved. New York: Dorset Press.Davidovits, Joseph (1983). Alchemy and the Pyramids. Saint Quentin, France: Geopolymer Institute.Davidovits, Joseph (2002). Ils ont Bâti les Pyramides: Les Prouesses Technologiques des Anciens Egyptiens. Paris: J.-C. Godefroy.Davidovits, Joseph (2005). La Bible avait raison, Tome 1: L’archéologie révèle l’existence des Hébreux en Égypte. Paris: J.-C.Godefroy.Davidovits, Joseph (2006). La Bible avait raison, Tome 2: sur les traces de Moïse et de l’Exode. Paris: J.-C. Godefroy.Davidovits, Joseph (2006). La nouvelle histoire des pyramides. Paris: J.-C. Godefroy.

http://www.davidovits.info/

Biography

Background of Joseph Davidovits

International renown French Scientist, born in 1935, working in France, Europe, USA, Australia and China.Honored with one of France’s two highest honors, the grade of ” Chevalier de l’Ordre National du Mérite ” (Nov. 1998).Discoverer and inventor of the geopolymer chemistry and its technical applications.


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Author and co-author of more than 130 scientifical papers and conferences, and more than 50 patents.

Archaeology

Joseph Davidovits has also presented different papers and studies in ceramics, ancient cement and roman concrete in severalcongresses in archaeology and archaeometry.He is mainly well-known by the general public for its theory on the method of building the pyramids of Egypt with re-agglomeratedstones, say a natural limestone manufactured like a concrete.Member of the International Association of Egyptologists, he presented several conferences on ceramics, blue faience, cements,pigments, and the analysis of pyramids stones at several International Congresses of Egyptology in 1979 (Grenoble, France), 1982(Toronto, Canada), 1988 (Cairo, Egypt), 2004 (Grenoble, France).Authors of several books:

1988, The Pyramids: An Enigma Solved.2002, Ils ont bâti les pyramides édition Jean-Cyrille Godefroy, Paris, ISBN 2-86553-157-0.2004, La nouvelle histoire des pyramides d’Egypte édition Jean-Cyrille Godefroy, Paris, ISBN 2-86553-175-9.2005, La Bible avait raison t.1, l’archéologie révèle l’existence des Hébreux en Égypte édition Jean-Cyrille Godefroy, Paris, ISBN2-86553-182-1.2006, La Bible avait raison t.2, sur les traces de Moïse et de l’Exode édition Jean-Cyrille Godefroy, Paris, ISBN 2-86553-190-2.

Education

French Degree in Chemical Engineering.German Doctor Degree in Chemistry (PhD).Professor and founder of the Institute for Applied Archaeological Sciences, IAPAS, Barry University, Miami ,Florida, (1983-1989).Visiting Professor, Penn State University, Pennsylvania (1989-1991).Honorary Professor, Xian Universtity of Architecture and Technology, China (1999).1979 to present: Professor and Director of the Geopolymer Institute , Saint-Quentin, France.2001 to present: Research Director at CORDI-Géopolymère .

Professional expertise

World expert in Modern and Ancient Cements.World expert in Geosynthesis and man-made rocks.Consultant (expert) to the European Union Commission.Inventor of Geopolymers and the chemistry of Geopolymerization.Polyglot: English, French, German, Spanish, Latin, Ancient Greek, Hieroglyphs

Member of the following societies


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International Association of EgyptologistsNew York Academy of SciencesAmerican Concrete Institute (former member)American Chemical Society (former member)American Ceramic Society (former member)

International Scientific Awards

NASTS Gold Ribbon, awarded at the National Press Club, Washington DC, Sept. 26, 1994, by the National Academy of Engineering,The Federation of Materials Societies and the National Association for Science, Technology and Society.Honorary Membership awarded by the National Noise Observatory of the Czech Republic (Narodni Hlukova Observator CR), Prague(Czech Republic), 04 Nov. 2005

http://www.geopolymer.org/category/archaeology/pyramids/

What is a geopolymer? Introduction

The remarkable achievements made through geosynthesis and geopolymerisation include mineral polymers (geopolymers), flexibleceramics which transform like plastics at low temperatures, ceramic composite made at room temperature or thermoset in a simpleautoclave, concrete which after 4 hours has higher strength and durability than the best currently-used concrete. Resulting from thisare industrial applications which, while using ceramics as the basic material, no longer need heavy equipment and high temperatures.Geopolymers enable product designers to envisage the use of ceramic type materials with the same facility as some plastics andorganic polymers.

The Geopolymer Institute not only coordinates the fundamental research in mineral polymer chemistry, but also promotes appliedresearch made with industrial companies ( see the Proceedings of Géoplymère 2005 ). Because the range of applications is too vast, weonly show the most interesting and innovative products. This insight will reveal how geopolymers can improve and change our dailylife.

Joseph Davidovits , the inventor and developer of geopolymerization, coined the term “geopolymer” in 1978 to classify the newlydiscovered geosynthesis that produces inorganic polymeric materials now used for a number of industrial applications. If you wantmore information go to the Geopolymer Library and download the papers #12 J. Thermal Analysis and #3 NASTS award for scientificinformation, and #10 From ancient concretes to Geopolymers for general information.

You can also buy online samples of geopolymers to test these products in your laboratory.


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http://www.geopolymer.org/category/archaeology/pyramids/

Pyramids (3) The formula, the invention of stone

Why do geologists see nothing?

This is due to the geological glue, which, though artificial, is seen by the geologists either as an impurity, and therefore useless to study,or as a natural binder. At best, the analysis tools and the working methods of geologists consider the glue as a perfectly natural“micritic binder”. A geologist not informed of geopolymer chemistry will assert with good faith that the stones are natural.The chemical formula:

People think that because we use chemicals, it is very easy to find these ingredients in the final product. This is wrong. Thanks to thegeopolymer chemistry, the chemical reaction generates natural elements, minerals that can be analysed as natural if scientists are notaware of their artificial nature.

During geosynthesis kaolinite clay (naturally included in the Giza limestone) first reacts with caustic soda (see chemical formula 2). Tomanufacture this caustic soda, one uses Egyptian natron (sodium carbonate) and lime (coming from plant ashes) (see chemical formula1). The so obtained soda will react with clay.

The most interesting point is that this chemical reaction creates also pure limestone (calcite) as well as hydrosodalite (a mineral of thefeldspathoids or zeolites family).

But, the mixture is still quite caustic. In order to neutralize it, one adds a special salt called carnallite (magnesium chloride) easilyfound in evaporites, in saline deposits like natron but not at the same place (see chemical formula 3 and 4).

The re-agglomerated stone binder is the result of this geosynthesis (a geopolymer) that creates several natural minerals: limestone(calcite), hydrated feldspars (feldspathoid, mica-chlorite), magnesite and halite. We understand why geologists can easily be misled.


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http://www.timesonline.co.uk/article/0,,13509-2480751,00.html

The Times (December 01, 2006)

Pyramids were built with concrete rather than rocks, scientists claim

Charles Bremner

How the Egyptians really built a Pyramid

The Ancient Egyptians built their great Pyramids by pouring concrete into blocks high on the site rather than hauling up giant stones,according to a new Franco-American study.

The research, by materials scientists from national institutions, adds fuel to a theory that the pharaohs’ craftsmen had enough skill andmaterials at hand to cast the two-tonne limestone blocks that dress the Cheops and other Pyramids.

Despite mounting support from scientists, Egyptologists have rejected the concrete claim, first made in the late 1970s by JosephDavidovits, a French chemist.

The stones, say the historians and archeologists, were all carved from nearby quarries, heaved up huge ramps and set in place byarmies of workers. Some dissenters say that levers or pulleys were used, even though the wheel had not been invented at that time.

Until recently it was hard for geologists to distinguish between natural limestone and the kind that would have been made byreconstituting liquefied lime.

But according to Professor Gilles Hug, of the French National Aerospace Research Agency (Onera), and Professor Michel Barsoum,of Drexel University in Philadelphia, the covering of the great Pyramids at Giza consists of two types of stone: one from the quarriesand one man-made.

“There’s no way around it. The chemistry is well and truly different,” Professor Hug told Science et Vie magazine. Their study is beingpublished this month in the Journal of the American Ceramic Society.

The pair used X-rays, a plasma torch and electron microscopes to compare small fragments from pyramids with stone from the Touraand Maadi quarries.

They found “traces of a rapid chemical reaction which did not allow natural crystalisation . . . The reaction would be inexplicable if thestones were quarried, but perfectly comprehensible if one accepts that they were cast like concrete.”

The pair believe that the concrete method was used only for the stones on the higher levels of the Pyramids. There are some 2.5million stone blocks on the Cheops Pyramid. The 10-tonne granite blocks at their heart were also natural, they say. The professorsagree with the “Davidovits theory” that soft limestone was quarried on the damp south side of the Giza Plateau. This was then


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dissolved in large, Nile-fed pools until it became a watery slurry.

Lime from fireplace ash and salt were mixed in with it. The water evaporated, leaving a moist, clay-like mixture. This wet “concrete”would have been carried to the site and packed into wooden moulds where it would set hard in a few days. Mr Davidovits and his teamat the Geopolymer Institute at Saint-Quentin tested the method recently, producing a large block of concrete limestone in ten days.

New support for their case came from Guy Demortier, a materials scientist at Namur University in Belgium. Originally a sceptic, hetold the French magazine that a decade of study had made him a convert: “The three majestic Pyramids of Cheops, Khephren andMykerinos are well and truly made from concrete stones.”

The concrete theorists also point out differences in density of the pyramid stones, which have a higher mass near the bottom andbubbles near the top, like old-style cement blocks.

Opponents of the theory dispute the scientific evidence. They also say that the diverse shapes of the stones show that moulds were notused. They add that a huge amount of limestone chalk and burnt wood would have been needed to make the concrete, while theEgyptians had the manpower to hoist all the natural stone they wanted.

The concrete theorists say that they will be unable to prove their theory conclusively until the Egyptian authorities give them access tosubstantial samples.

http://www.amazon.com/Pyramids-Enigma-Solved-Joseph-Davidovits/dp/0880295554

The Pyramids: An Enigma Solved

by

Joseph Davidovits, Margie Morris


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Joseph DAVIDOVITS' US Patents

5,925,449 --- Method for bonding fiber reinforcement on concrete and steel structures and resultant products5,798,307 --- Alkaline alumino-silicate geopolymeric matrix for composite materials with fiber reinforcement and method forobtaining same5,539,140 --- Method for obtaining a geopolymeric binder allowing to stabilize, solidify and consolidate toxic or waste materials5,352,427 --- Geopolymeric fluoro-alumino-silicate binder and process for obtaining it5,349,118 --- Method for obtaining a geopolymeric binder allowing to stabilize, solidify and consolidate toxic or waste materials5,342,595 --- Process for obtaining a geopolymeric alumino-silicate and products thus obtained5,288,321 --- Method for eliminating the alkali-aggregate reaction in concretes and cement thereby obtained4,888,311 --- Ceramic-ceramic composite material and production method4,859,367 --- Waste solidification and disposal method4,509,985 --- Early high-strength mineral polymer4,472,199 --- Synthetic mineral polymer compound of the silicoaluminates family and preparation process4,349,386 --- Mineral polymers and methods of making them4,028,454 --- Process for agglomerating compressible mineral substances under the form of powder, particles or fibres4,000,027 --- Process of manufacturing panels composed of units in, for example, ceramic, assembled by a thermoplastic material3,985,925 --- Composite floor coverings3,950,470 --- Process for the fabrication of sintered panels and panels resulting from the application of this process

US Patent # 4,349,386


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Mineral polymers and methods of making them

September 14, 1982

Joseph Davidovits

Abstract --- New mineral polymers called polysialates have the empiral formula M.sub.n [--(Si--O.sub.2 --).sub.z --Al--O.sub.2--].sub.n,wH.sub.2 O where z is 1, 2 or 3, M is sodium, or sodium plus potassium, n is the degree of polycondensation, and w has avalue up to about 7. The method for making these polymers includes heating an aqueous alkali silico-aluminate mixture having anoxide-mole ratio within certain specific ranges for a time sufficient to form the polymer.

Current U.S. Class: 106/813 ; 106/286.2; 106/286.5; 106/626; 106/638; 264/319; 264/333; 423/328.2; 501/153Current International Class: C04B 28/00 (20060101); B22C 1/18 (20060101); B22C 1/16 (20060101); C04B 35/63 (20060101)Field of Search: 423/327-330,118 252/455Z 106/288B,39.5,4R,73.4,85,86,286.2,286.5,74,84 264/299,319,333U.S. Patent Documents: 3030181 // 3054657 // 3248170 // 3374058 // 3594121

Other References

Barrer et al. "J. Chemical Society", 1959, pp. 195-208, 1956, pp. 2882-2891. .Barrer "Trans. Brit. Ceramic Soc." 56, 1957, pp. 155-173..

Description

This invention relates to a mineral polyconcondensation process for making cast or molded products at temperatures generally up toabout 120.degree. C. This process is related to processes for making zeolites or molecular sieves. The products of this process,however, have characteristic three-dimensional frameworks which are successions of tetrahedrons TO.sub.4 where T is silicon,aluminum, gallium, phosphorous or the like. These products form channels or voids of regular dimensions when cast or molded. Thevoids are molecular in size. Accordingly, the polymers can be used to separate organic molecules of different molecular sizes. Thesestructures also exhibit ion exchange properties. Moreover, the products catalyze several different organic polymerization systems.

Numerous patents and other references describe methods for making these synthetic minerals, zeolites and molecular sieves. D. W.Breck's book entitled "Zeolite Molecular Sieves," published by Interscience in 1974, is a good reference. Generally, these methods arehydrothermal synthesis of silico-aluminate gels in strong, highly concentrated aqueous alkali. The reactant mixture, containing a largeexcess of water, is sealed in a container at constant pressure and temperature. Preferably, the pressure is atmospheric, and thetemperature is in the range of about 25.degree. C., to about 120.degree. C. The reaction continues until crystallization of the productoccurs. The chemical formula for the resulting synthetic zeolites and molecular sieves may be written as follows:

wherein M is a cation with the valence "n." Many crystalline products have been made in such hydrothermal syntheses. However,these products are very porous, and have poor mechanical properties, even when agglomerated with a binder.


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An object of this invention is to provide synthetic mineral products with such properties as hard surfaces (4-6 on the Mohs scale),thermal stability, and high surface smoothness and precision. Such products are useful for tooling, and for molding art objects,ceramics and the like.

Another object is to provide novel three-dimensional mineral polymers.

Another object is to provide a method of making such new three-dimensional polymers.

Other objects such as use of these polymers as binders are apparent from this specification and claims.

The names for these novel three-dimensional polymers are set forth in the following publications: IUPAC International Symposium onMacromolecules, Stockholm in 1976, Topic III; and PACTEC IV, 1979, Society of Plastic Engineers, U.S.A., preprint page 151. Thesemineral polymers are called polysialates, and have this empiracal formula:

wherein z is 1, 2 or 3; M is a monovalent cation such as potassium or sodium, and n is the degree of polycondensation. Where z is 2,the polysialate has the formula: ##STR1## and is called polysialatesiloxo or PSS for short.

Our new polymers are of the PSS type where M is sodium or a mixture of sodium and potassium. In the latter case, the polymer iscalled (sodium, potassium) polysialatesiloxo or NaKPSS. The chemical formula of NaKPSS may be written as: ##STR2##

A suitable method for distinguishing our new polymers from known polymers is through their x-ray powder diffraction patterns.NaKPSS has the characteristic x-ray powder diffraction pattern given in Table A below. To obtain this data, we used the Debye-Scherrer method. The radiation used was the K-alpha doublet of copper.

TABLE A ______________________________________ Diffraction Pattern for (Na,K)PSS Interplanar Spacing Relative Intensity (inAngstroms) of the Lines ______________________________________ 11.20 Broad amd blurred 4.30 Middle strong 3.43 Strong 3.29Strong 3.08 Middle strong 2.97 Middle strong 2.71 Weak 2.46 Weak 2.30 Middle Strong 2.11 Weak 1.92 Very strong 1.81 Middlestrong ______________________________________

The x-ray pattern of (Na,K)PSS is related to, but distinctly different from that of natural Gmellinite. Gmellinite is a zeolite with thischemical formula:

Gmellinite is called zeolite "S" in U.S. Pat. No. 3,054,657. The x-ray pattern of zeolite S shows middle strong lines at the interplanarspacings 7.16, 5.03, 4.50, and 4.12 Angstroms. Zeolite S plainly differs greatly from NaKPSS.

As Table B shows, the oxide-mole ratios of the reactant mixtures for these two polymers are completely different:

TABLE B ______________________________________ Oxide-Mole Ratios of the Reactant Mixtures Zeolite S (Na,K)PSS______________________________________ Na.sub.2 O/SiO.sub.2 0.3 to 0.6 (Na.sub.2 O,K.sub.2 O)/SiO.sub.2 0.25 to 0.28SiO.sub.2 /Al.sub.2 O.sub.3 6 to 25 SiO.sub.2 /Al.sub.2 O.sub.3 4.0 H.sub.2 O/Na.sub.2 O 18 to 100 H.sub.2 O/(Na.sub.2 O,K.sub.2


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O) 16 to 17.5 Na.sub.2 O/Al.sub.2 O 1.80 to 15 (Na.sub.2 O/K.sub.2 O)/Al.sub.2 O.sub.3 1.0 to 1.14______________________________________

The method for making NaKPSS comprises preparing a sodium silico-aluminate/potassium silico-aluminate water mixture where thecomposition of the reactant mixture, in terms of oxide-mole ratios, falls within the ranges shown in table C below.

TABLE C ______________________________________ Oxide-Mole Ratios of the Reactant Mixture (Na.sub.2 O,K.sub.2O)/SiO.sub.2 0.20 to 0.28 SiO.sub.2 /Al.sub.2 O.sub.3 3.5 to 4.5 H.sub.2 O/(Na.sub.2 O,K.sub.2 O) 15 to 17.5 (Na.sub.2 O,K.sub.2O)/Al.sub.2 O.sub.3 0.8 to 1.20 ______________________________________

The usual method for preparing this mixture comprises dissolving in water an alumino-silicate oxide, alkali, and a colloidal silica sol oralkali polysilicate. The alumino-silicate oxide (Si.sub.2 O.sub.5,Al.sub.2 O.sub.2).sub.n may be prepared from a polyhydroxy-alumino-silicate having the formula (Si.sub.2 O.sub.5,Al.sub.2 (OH).sub.4).sub.n, where the aluminum cation is in the octahedral state and is insix-fold coordination. The polyhydroxy-alumino-silicate is calcined and dehydroxylated at, say, 550.degree. C. The resulting alumino-silicate oxide has the aluminum cation in four-fold coordination and in a tetrahedral position.

Various polyhydroxy-alumino-silicates may be used as the starting material for the preparation of alumino-silicate oxide, includingminerals having basal spacings of about seven Angstroms and having at least one aluminum cation located in the octahedral layers.Examples are alushite, carnat, china clay, lithomarge, neokaolin, parakaolinite, pholenite, endellite, glossecolite, halloysite, milanite,berthierine, fraignotite, grovenite, amesite, and chamoisite.

The quantities of the reactants, namely colloidal silica sol and/or polysilicate, and strong alkalis such as sodium hydroxide andpotassium hydroxide, fall in the ranges shown in Table C. Preferably, the ratio (Na.sub.2 O,K.sub.2 O)/Al.sub.2 O.sub.3 is about 1.0and the ratio SiO.sub.2 /Al.sub.2 O.sub.3 is about 4.0. Higher ratios induce a free alkalinity in the solidified polymer and cause alkalisilicate migration which can disturb the physical and mechanical properties of the resulting mineral products. However, if the ratio ofsodium oxide and potassium oxide combined to aluminum trioxide is lower than 0.8, and the ratio of silicon oxide to aluminum trioxideis lower than 3.5, the alumino-silicate oxide in excess may not polycondense and will remain as a white powder within the hardenedNaKPSS product. Preferably, the oxide-mole ratios should be close to stoichiometric values. The NaKPSS will have a compositionexpressed in terms of oxides as follows:

where, in the fully hydrated form, w is in the range of about 5 to about 7, x is a value in the range of about 3.5 to about 4.5, y and zhave values up to 1, and the sum of y and z is 1.

By contrast, stoichoimetric conditions are not used to make synthetic crystalline zeolites and molecular sieves. The oxide-mole ratiosof reactant mixtures for such products are always much higher than stoichoimetric values, as Table B shows.

In the reactant mixture, the quantity of water present equals the sum of solvent water plus the bound water in the reactants. Thereactant mixture is viscous, but is not a gel. Rather, the mixture becomes a mineral resin with unique rheological properties afterreacting for at least about one hour at ambient temperature, say 25.degree. C.


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After aging, the mineral resin may be used alone, or may be mixed with inorganic or organic additives or fillers. The resin may be usedas a binder or a mineral cement for organic or mineral particles or fibers. The resin is cast, poured or squeezed into a mold and heatedto a temperature up to about 120.degree. C., but preferably to a temperature in the range of about 60.degree. C., to about 95.degree. C.When polycondensation is complete, the solids are separated from the mold and dried at a temperature in the range of about 60.degree.C., to about 100.degree. C.

Polycondensation and heating times are a function of the temperature and the heating process used. At an ambient temperature such as25.degree. C., polycondensation requires more than 15 hours. At 50.degree. C., polycondensation requires about four hours; at85.degree. C., about 1.5 hours, and at 95.degree. C., about 0.5 hours. These times may differ and are often shorter when other heatingtechniques are used. Such other techniques include high frequency, microwave, Joule effect, or electrical wires within the reactantmixture itself. Because the reactant mixtures are polyelectrolytes, these heating techniques effect polycondensation and drying veryrapidly. For example, using a microwave heater, the polycondensation described in Example 1 is complete in only 30 seconds, insteadof the 1.5 hours required there.

The shelf life of the mineral resin can be as long as two to four hours at ambient temperature depending on the sequence of mixing thereactants. Longer pot life is attained if the strong alkali is not mixed directly with the reactive alumino-silicate oxide. In fact, if thealkalis are added directly to the alumino-silicate oxide solution, the resulting product differs from the polymers of this invention. Directaddition gives a strongly exothermic reaction, and produces a product similar to zeolite A or hydroxysodalite.

Our method of preparing our new polymers comprises making either the alumino-silicate oxide or the sodium and potassiumhydroxides. Making of the sodium and potassium hydroxides can be effected by mixing the alkalis in water with polysilicate, and thenadding this solution to the alumino-silicate oxide. Preferably, we mix the alumino-silicate oxide with aqueous polysilicate, to theexclusion of alkali, and add this solution to a strong aqueous solution. These two reactant mixtures are stable and retain their reactivityeven after long storage periods. Moreover, these mixtures are easy to handle and store.

Polycondensation is best effected in a closed mold under hydrothermal conditions and in the presence of water. Evaporation of waterfrom the mixture during polycondensation is undesirable. To prevent water evaporation at the surface of a reactant mixture placed inan open mold, the surface can be covered with a thin plastic film or thin layer of a hydrophobic liquid. After heating the mixture in themold, the polycondensed solid is separated from the mold and dried. The molded object has good physical and mechanical properties,including a surface hardness in the range of 3 to 6 Mohs, depending on the nature of the mineral fillers added to the resin. Theprecision of the molded product's surface compares favorably with the quality obtained with such organic resins as epoxies andpolyurethanes.

The following examples illustrate the methods of making the new polymers, and some of the properties of these polymers as well.

EXAMPLE I

We prepared 317 grams of a reactant mixture containing 8.1 moles water, 0.47 moles sodium oxide, 1.65 moles of silicon dioxide, and0.41 moles of aluminum trioxide. The source of aluminum trioxide is the alumino-silicate oxide prepared by dehydroxylating a natural


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polyhydoxy-alumino-silicate (Si.sub.2 O.sub.5,Al.sub.2 (OH).sub.4).sub.n. The source of silicon dioxide is this alumino-silicate oxideand an alkali silicate. The source of sodium oxide is sodium hydroxide. The oxide molar ratios in the reactant mixture are shown inTable D.

TABLE D ______________________________________ Na.sub.2 O/SiO.sub.2 0.28 SiO.sub.2 /Al.sub.2 O.sub.3 4.02 H.sub.2O/Na.sub.2 O 17.20 Na.sub.2 O/Al.sub.2 O.sub.3 1.14 ______________________________________

The reactant mixture, which had the viscosity of a resin, was aged for a period of one hour at ambient temperature, then placed undervacuum to eliminate air and gas bubbles. The outgassed resin was poured into a urethane mold to reproduce the relief of a medal.

The surface of the resin in contact with the atmosphere was covered with a thin polyethylene film to prevent water evaporation duringcuring, which was effected at 85.degree. C., in an oven over a period of 1.5 hours.

The hardened mineral product was separated from the mold and dried at 85.degree. C. It reproduced the mold surface with all originaldetails of the mold surface intact. The density of the product was 1.4 grams per milliliter, and its hardness was 3-4 (Mohs scale). Theproduct was white and porous, and its external dimensions indicated that the polycondensation took place without any shrinkage ordilation of the material. Chemical analysis of the mineral product gave this molar composition:

which corresponds to the formula of (Na)PSS ##STR3## which has an x-ray diffraction pattern essentially that shown in Table A.

Materials from which the mold may be made include iron, paper, wood and plastics, indeed all materials except aluminum and copper.Even aluminum and copper molds can be used if they are covered with a thin layer of organic resin.

EXAMPLE II

Following the steps described in Example I, we prepared 296 grams of reactant mixture containing 7.5 moles of water, 0.33 moles ofsodium oxide, 0.08 moles of potassium oxide, 1.65 moles silicon dioxide, and 0.41 moles of aluminum trioxide. The source ofpotassium oxide was anhydrous KOH. The oxide-mole ratios of the reactant mixture are set forth in Table E.

TABLE E ______________________________________ (Na.sub.2 O,K.sub.2 O)/SiO.sub.2 0.25 SiO.sub.2 Al.sub.2 O.sub.3 4.02H.sub.2 O/(Na.sub.2 O,K.sub.2 O) 17.30 Na.sub.2 O/Al.sub.2 O.sub.3 0.8 (Na.sub.2 O,K.sub.2 O)/Al.sub.2 O.sub.3 = 1.0 K.sub.2O/Al.sub.2 O.sub.3 0.2 ______________________________________

The reactant mixture, which had the viscosity of a resin, was aged for one hour at ambient temperature (25.degree. C.). To this agedmineral resin we added 280 grams of fine white mullite with a size range between 100 and 150 microns. We poured this mixture intothe same mold used in Example I.

After polycondensation in the mold at 85.degree. C., for 1.5 hours, and following the drying conditions described in Example I, thecured mineral medal had a density of 1.8 grams per milliliter. The diameter of the product was 85.8 millimeters. (The mold's diameterat 25.degree. C. was just 85.4 millimeters. However, the mold had diameter of 85.08 millimeters at the 85.degree. C., molding


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temperature.) Apparently, the cured mineral polymer had the same diameter as the heated mold.

The molded product had a surface hardness of five on the Mohs scale, and the reproduction of the medal surface from the mold wasvery exact.

Chemical analysis of the mineral product gave a mixture of mullite and (Na,K)PSS with a molar composition as follows:

The x-ray powder diffraction pattern is a mixture of the lines characteristic of crystalline mullite and of NaKPSS as set forth in TableA.

Thermogravimetric analysis of NaKPSS gave two endothermic peaks, the first between 150.degree. C., and 200.degree. C., the secondbetween 320.degree. C., and 370.degree. C. The first peak corresponds to the loss of "zeolitic water," amounting to about 9% byweight of the fully hydrated polymer. The second peak corresponds to the loss of hydroxyl groups constituting about 12% by weight ofthe fully hydrated polymer.

The pH of the fully hydrated NaKPSS is about 10 to 10.5, which means that the polymer was free from excess alkali. However, as withother zeolitic materials, the sodium and potassium cations may migrate in the presence of water. This effect vanishes if the NaKPSS isheated to a temperature higher than the second endothermic peak of the thermogravimetric analysis, or higher than 370.degree. C.After this postcuring at a temperature above 370.degree. C., the sodium and potassium cations do not migrate in the presence of water.

Full dehydration and dehydroxylation of NaKPSS transforms a mineral polymer into a product having properties like ceramicmaterials. Its formula ##STR4## corresponds to the molar composition

where x has a value in the range of about 3.5 to about 4.5, and y and z have values up to 1 such that the sum of y and z is 1.

EXAMPLE III

We mixed one kilogram of foundry sand with 50 grams containing 5% by weight of the mineral resin prepared according to ExampleII. The resulting sand/resin mixture was pressed into two molds. One mold was thermoset at 85.degree. C., for a period of 1.5 hours;the second mold was cured at ambient temperature for 15 hours. We obtained two cores suitable for foundry use in which the sandwas bound with the mineral polymer having the following molar composition:

This molar composition corresponds to the molar composition of NaKPSS.

US Patent # 4,472,199

Synthetic mineral polymer compound of the silicoaluminates family and preparation process


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Joseph Davidovits

September 18, 1984

Abstract --- A mineral polymer of the silicoaluminate family has a composition expressed in terms of oxides as follows: where, in thefully hydrated form, "w" is a value at the most equal to 4, "x" is a value in the range of about 4.0 to about 4.2, and "y" is a value in therange of about 1.3 to about 1.52. These mineral polymers are solid solutions which comprise one phase of a potassium polysilicatehaving the formula: and one phase of a potassium polysialate polymer having the following formula: ##STR1## where "n" is the degreeof condensation of the polymer.

Current U.S. Class: 106/813 ; 106/286.2; 106/286.5; 106/600; 106/638; 264/319; 264/333; 423/328.2; 501/153Current International Class: C04B 12/00 (20060101); C01B 33/00 (20060101); C04B 35/63 (20060101); C01B 33/26 (20060101)Field of Search: 423/118,327-330 264/299,313,333 106/288B,85,86,286.2,286.5 252/455Z 501/1,80,153 502/60U.S. Patent Documents: 2972516 // 3012853 // 3056654 // 4349386

Other References:

"IUPAC International Symposium on MacroMolecules", Stockholm 1976, Topic III. ."PACTECIV", Society of Plastic Engineers, U.S.A. preprint pp. 151-154. .Chemical Abstract 86:19049v, Synthetic Kaliophilite, Zhukova, R. S.; Begletsov, V. V., (USSR), Khim Tekrol, (Kiev), 1976, (3), 63-4..Barrer, R. M. "Some Researches on Silicates: Mineral Syntheses and Metamorphoses", Transactions of the British Ceramic Soc., vol.56, No. 4, pp. 155-173, 1957..

Description

This invention relates to a mineral polycondensation process for making cast or molded products at temperatures generally up to about120.degree. C. This process is related to processes for making zeolites or molecular sieves.


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The products of such processes, however, have characteristic three-dimensional frameworks which are successions of tetrahedronsTO.sub.4, where T is silicon, aluminum, gallium, phosphorous or the like. Those products form channels or voids of regular dimensions.The voids are molecular in size. Accordingly, the mineral frameworks can be used to separate organic molecules of different molecularsizes. Those structures also exhibit ion exchange properties. Moreover, those products catalyze several different organicpolymerization systems.

Numerous patents and other references describe methods for making those synthetic minerals, zeolitics and molecular sieves. D. W.Breck's book entitled, "Zeolite Molecular Sieves," published by Interscience in 1974, is a good reference. Generally, those methods arehydrothermal syntheses of silico-aluminate gels in strong, highly concentrated aqueous alkali. The reactant mixture, containing a largeexcess of water, is sealed in a container at constant pressure and temperature. Preferably, the pressure is atmospheric, and thetemperature is in the range of about 25 C. to about 125.degree. C. The reaction continues over more than ten hours until crystallizationof the products occurs. The chemical formula for the resulting synthetic zeolites and molecular sieves may be written as follows:

wherein M is a cation with a valence "n." Many crystalline products have been made in such hydrothermal syntheses. However, theseproducts are very porous and have poor mechanical properties, even when agglomerated with a binder. I have discovered that whenreaction conditions do not favor crystallization or crystal formation, I obtain novel products.

An object of this invention is to provide synthetic mineral products with such properties as hard surfaces (5-7 on the Mohs scale),thermal stability and high surface smoothness and precision. Such products are useful for tooling, and for molding art objects, ceramicsand the like, and building materials.

The main object is to provide a novel mineral polymer, more precisely a novel mineral polymer compound, and to provide a method ofmaking a new mineral polymer compound.

Other objects such as use of this mineral polymer compound as a binder are apparent from this specification and claims.

The names for these novel three-dimensional polymers are set forth in the following publications: "IUPAC International Symposium onMacromolecules," Stockholm, 1976, Topic III; and "PACTEC IV,", Society of Plastic Engineers, U.S.A., preprint page 151. Thesemineral polymers are called polysialates and have this empirical formula:

wherein "z" is 1, 2 or 3; M is a monovalent cation such as potassium or sodium, and "n" is the degree of polycondensation. Where "z"is 1, the mineral polymer has this formula: ##STR2## and is called polysialate or PS for short.

Our new polymer is of the K--PS polymer compound type where "M" is potassium.

A suitable method for distinguishing our new polymers from known polymers is through their X-ray powder diffraction pattern. K--PSpolymer compound has the characteristic x-ray powder diffraction pattern given in Table A below. To obtain this data, we used theDebye-Scherrer method. The radiation used was the K-Alpha doublet of copper.

The X-ray pattern of K--PS is related to that of natural kaliophilite (KAlSiO.sub.4), which corresponds to the general formula of


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polysialate. This natural mineral is not a zeolite, but an anhydrous feldspathoid with the formula: ##STR3## where "w" is a value in therange of 0 to 1.

This distinction is very important. Mineral polymers containing zeolitic water must be dehydroxylated at a temperature up to about400.degree. C. if they are to be used without damage at higher temperature. On the contrary, mineral polymers of the kaliophilite typewill resist thermal shock. Thermal shock resistance is a fast test for distinguishing a zeolitic framework from a feldspathoidic one.

Mineral polymer polysialates K--PS have this chemical formula:

The method of making K--PS comprises preparing a reactant mixture in which the oxide-mole ratios are higher than stoichiometricvalues. For example, the ratio SiO.sub.2 /Al.sub.2 O.sub.3 is in the range of 3.3 to 4.5, instead of 2. These conditions differ from thoseused in a process of making synthetic (Na, K) Poly(Sialate-Siloxo) or (Na, K)--PSS mineral polymers which are described in Frenchpatent application No. 79.22041, and have this empirical formula: ##STR4##

In French application No. 79.22041 and corresponding U.S. patent application Ser. No. 182,571, filed Aug. 29, 1980, now U.S. Pat.No. 4,349,386 the oxide-mole ratios used for making (Na, K)--PSS fall in the range of:

______________________________________ (Na.sub.2 O, K.sub.2 O)/SiO.sub.2 0.20 to 0.28 SiO.sub.2 /Al.sub.2 O.sub.3 3.5 to 4.5H.sub.2 O/(Na.sub.2 O, K.sub.2 O) 15 to 17.5 (Na.sub.2 O, K.sub.2 O)/Al.sub.2 O.sub.3 0.8 to 1.20______________________________________

TABLE A __________________________________________________________________________ Zeolite Z Zeolite G Zeolite WKaliophilite (K)-PS __________________________________________________________________________KAlSiO.sub.4,3H.sub.2 O KAlSi.sub.2 O.sub.6,5H.sub.2 O K.sub.5 Al.sub.5 Si.sub.9 O.sub.28,25H.sub.2 O KAlSiO.sub.4 ##STR5##d(A) I d(A) I d(A) I d(A) I d(A) I -- 9.47 mS 9.99 20 10 halo 10-11.5 halo -- -- 8.17 49 -- -- 7.45 VVS -- 7.09 54 -- -- -- 6.90 m -- -- ---- 5.22 m 5.34 28 -- -- 4.78 vw -- 5.01 56 -- -- -- -- 4.45 21 4.49 35 4.49 m -- 4.32 S 4.28 35 4.28 40 4.27 w -- 3.97 mS -- -- -- -- 3.70 w3.64 20 -- 3.47 m 3.46 S -- 3.52 35 3.52 m 3.29 m -- 3.25 100 3.32 35 3.33 S 3.09 VS 3.11 mw 3.17 75 broad band 3.23 halo 2.97 S2.93 VVS 2.95 71 3.10 100 to 2.82 VS 2.80 w 2.72 53 broad band 2.79 -- 2.59 S 2.54 26 2.61 45 2.56 w 2.35 s 2.29 S 2.40 8 2.24 202.25 vw 2.20 w 2.19 mS 2.18 10 2.13 37 2.17 vw__________________________________________________________________________

However, if the reactant mixture is exclusively composed of a potassium polysilicate, potassium hydroxide (KOH) and alumino-silicateoxide (Si.sub.2 O.sub.5, Al.sub.2 O.sub.2).sub.n, then the mineral polymer produced is not (Na, K)--PSS. The X-ray powder diffractionpattern and the thermogravimetric analysis are different. The X-ray patterns of (Na, K)--PSS are related to those of natural analcime,gismondine, gmelinite and phillipsite, whereas the polymer obtained here is amorphous. Thermogravimetric analysis of this polymergave a loss of water amounting to 5% by weight up to 325.degree. C., the weight remaining constant for higher temperature. Bycontrast, thermogravimetric analysis of (Na, K)--PSS gave a loss of water in the range of 21% to 29% by weight between 100.degree.C. and 500.degree. C. This polymer does not exhibit zeolitic properties. It is brittle, but hard: 5 on the Mohs scale.


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A synthetic kaliophilite KAlSiO.sub.4.0.1H.sub.2 O has been prepared by H. Besson, S. Caillere and S. Henin (Comptes RendueAcademie des Sciences de Paris, Vol. 272, Series D, pp. 2749-2752 (1971)), using silico-aluminate gels and potassium carbonate(K.sub.2 CO.sub.3). The X-ray pattern of this anhydrous synthetic kaliophilite is given in Table A. Its pattern is related to that ofK--PS, but shows a strong line at 3.10 Angstroms, accompanying the broad line at 2.79 to 3.23 Angstroms. Table A also gives X-raypatterns of synthetic zeolites related to the polymer K--PS, such as zeolite Z (or zeolite KF), zeolite G (or zeolite K--G), and zeolite W(or zeolite K--M, K--H). These patterns are given in D. W. Breck's book cited above.

Table B shows the oxide-mole ratios of the reactant mixture used for the synthetic zeolites from Table A.

TABLE B ______________________________________ Zeolite Kalio- Zeolite Z Zeolite G W philite K-PS______________________________________ K.sub.2 O/SiO.sub.2 0.425 0.50 0.6 Excess 0.26 to 0.36 SiO.sub.2 /Al.sub.2 O.sub.3 45 6 2 to 4 4 to 4.2 H.sub.2 O/Al.sub.2 O.sub.3 Excess Excess 75 Excess 12.5 to 23 K.sub.2 O/Al.sub.2 O.sub.3 1.7 2.5 3 Excess 1.12to 1.6 ______________________________________

The method for making K--PS polymeric compound comprises preparing a potassium silico-aluminate/water mixture where thecomposition of the reactant mixture, in terms of oxide-mole ratios, falls within the ranges shown in Table C below.

TABLE C ______________________________________ Oxide-Mole Ratios of the Reactant Mixture______________________________________ K.sub.2 O/SiO.sub.2 0.25 to 0.48 SiO.sub.2 /Al.sub.2 O.sub.3 3.3 to 4.5 H.sub.2O/Al.sub.2 O.sub.3 10 to 25 K.sub.2 O/Al.sub.2 O.sub.3 0.9 to 1.6 ______________________________________

The usual method for preparing this mixture comprises dissolving in water an alumino-silicate oxide, KOH, and a potassiumpolysilicate. The alumino-silicate oxide (Si.sub.2 O.sub.5, Al.sub.2 O.sub.2).sub.n may be prepared from a polyhydroxy-alumino-silicate having the formula (Si.sub.2 O.sub.5, Al.sub.2 (OH).sub.4).sub.n, where the aluminum cation is in the octahedral state and is insix-fold coordination. The polyhydroxy-alumino-silicate is calcined and dehydroxylated at, say, between 550.degree. C. and800.degree. C. The resulting alumino-silicate oxide has the aluminum cation in four-fold coordination and in a tetrahedral position.

Various polyhydroxy-alumino-silicates may be used as the starting material for the preparation of alumino-silicate oxide, includingminerals having basal spacings of about seven Angstroms and having at least one aluminum cation located in the octahedral layers.Examples are alushite, carnat, china clay, lithomarge, neokaolin, parakaolinite, pholenite, endellite, glossecolite, halloysite, milanite,berthierine, fraignotite, grovenite, amesite and chamoisite.

The silico-aluminate mineral polymer compound obtained by polycondensation of a reactant mixture as given in Table C, will have acomposition expressed in terms of oxides as follows:

where, in the fully hydrated form, "w" is a value at the most equal to 4, "x" is a value in the range of about 3.3 to about 4.5, and "y" isa value in the range of about 0.9 to 1.6.

The mineral polymer compound is a solid solution which comprises 35 to 90 parts by weight of a potassium polysilicate (y-1)K.sub.2


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O:(x-2)SiO.sub.2 :(w-1)H.sub.2 O and 10 to 65 parts by weight of the mineral polymer K--PS, which has the formula: ##STR6## andan X-ray pattern related to that of the natural mineral kaliophilite as shown in Table A.

The quantities of the reactants, namely potassium polysilicate, alumino-silicate oxide and potassium hydroxide, fall in the rangesshown in Table C. Preferably, the ratio (K.sub.2 O)/Al.sub.2 O.sub.3 is in the range of about 1.3 to 1.52, and the ratio SiO.sub.2/Al.sub.2 O.sub.3 is in the range of about 4.0 to 4.2. Higher ratios induce a free potassium silicate phase in the solidified polymercompound, and cause potassium silicate migration which can disturb the physical and mechanical properties of the resulting mineralproducts. If the ratio of potassium oxide to aluminum trioxide is lower than 1.1, and the ratio of silicon dioxide to aluminum trioxide islower than 3.7, the solidified polymer compound will have numerous cracks, and cannot be used in the fabrication of molded objects.

By contrast, the oxide-mole ratios of reactant mixtures for synthetic crystalline zeolites Z, G and W are always much higher than thevalues for the K--PS polymer compound, as Table B shows. In particular, water is employed in large excess, and the K.sub.2 Oquantities are much higher.

In the reactant mixture, according to Table C, the quantity of water present equals the sum of solvent water plus the bound water inthe reactants. The reactant mixture is viscous, but is not a gel. Rather, the mixture becomes a mineral resin with unique rheologicalproperties after reacting for at least about one hour at ambient temperature, say 25.degree. C.

After aging, the mineral resin may be used alone, or may be mixed with organic or inorganic additives or fillers. The resin may be usedas a binder or a mineral cement for organic or mineral particles or fibers. The resin is cast, poured, squeezed or vibrated into a moldand heated to a temperature up to about 120.degree. C., but preferably to a temperature in the range of about 60.degree. C. to about95.degree. C. When polycondensation is complete, the solids are separated from the mold and dried at a temperature up to about100.degree. C.

Polycondensation and heating times are a function of the temperature and the heating process used. At an ambient temperature, suchas 25.degree. C., polycondensation requires more than 15 hours. At 50.degree. C., polycondensation requires about four hours; at85.degree. C., about 1.5 hours; and at 95.degree. C., about 0.5 hours. These times may differ, and are often shorter when other heatingtechniques are used. Such other techniques include high frequency, microwave, Joule effect or electrical wires within the reactantmixture itself. Because the reactant mixtures are polyelectrolytes, these heating techniques effect rapid polycondensation and drying.

The pot life of the mineral resin can be as long as two to four hours at ambient temperature depending on the sequence of mixing thereactants. Longer pot life is attained if the potassium hydroxide is not mixed directly with the reactive alumino-silicate oxide solution.In fact, if the alkali is added directly to the alumino-silicate oxide solution, the resulting product differs from the polymers of thisinvention.

The method of preparing our new mineral polymer compound comprises masking either the alumino-silicate oxide or the potassiumhydroxide. Masking of the potassium hydroxide can be effected by mixing the alkali in water with polysilicate, and then adding thissolution to the alumino-silicate oxide. Preferably, we mix the alumino-silicate oxide with aqueous polysilicate, to the exclusion ofalkali, and add this solution to a strong aqueous potassium hydroxide solution. These two reactant mixtures are stable and retain their


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reactivity even after long storage periods. Moreover, these mixtures are easy to handle and store.

Polycondensation is best effected in a closed mold under hydrothermal conditions and in the presence of water. Evaporation of waterfrom the mixture during polycondensation is undesirable. To prevent water evaporation at the surface of a reactant mixture placed inan open mold, the surface can be covered with a thin plastic film or thin layer of a hydrophobic liquid. After heating the mixture in themold, the polycondensed solid is separated from the mold and dried. The molded object has good physical and mechanical properties,including a surface hardness in the range of 5 to 7 Mohs, depending on the nature of the mineral fillers added to the resin. Theprecision of the molded product's surface compares favorably with the quality obtained with such organic resins as epoxies andpolyurethanes.

The following examples illustrate the methods of making the new K--PS polymer compound and some of its properties.

EXAMPLE 1

We prepared 860 grams of a reactant mixture containing 11.33 moles water, 1.630 moles potassium oxide, 4.46 moles of silicondioxide and 1.081 moles of aluminum trioxide. The source of aluminum trioxide is the alumino-silicate oxide prepared bydehydroxylating a natural polyhydroxy-alumino-silicate (Si.sub.2 O.sub.5, Al.sub.2 (OH).sub.4).sub.n. The source of silicon dioxide isthis alumino-silicate oxide and a potassium silicate. The source of potassium oxide is this potassium silicate and potassium hydroxide.The oxide-mole ratios in the reactant mixture are shown in Table D.

TABLE D ______________________________________ K.sub.2 O/SiO.sub.2 0.36 SiO.sub.2 /Al.sub.2 O.sub.3 4.12 H.sub.2O/Al.sub.2 O.sub.3 16.03 K.sub.2 O/Al.sub.2 O.sub.3 1.51 ______________________________________

The reactant mixture, which had the viscosity of a resin, was aged for a period of one hour at ambient temperature (25.degree. C.),then placed under vacuum to eliminate air and gas bubbles. The outgassed resin was poured into a mold.

The surface of the resin in contact with the atmosphere was covered with a thin polyethylene film to prevent water evaporation duringcuring, which was effected at 85.degree. C. in an oven over a period of 1.5 hours.

The hardened mineral product was separated from the mold and dried at 85.degree. C.

The density of the product was 1.7 grams per milliliter, and its hardness was 4.5 on the Mohs scale. The product was white and low inporosity. Physico-chemical analysis of the mineral product gave this molar composition:

which corresponds to the formula of a polymer compound. This polymer compound contains, in a solid solution, one phase of apotassium polysilicate which corresponds to the formula:

and one K--PS which corresponds to the formula: ##STR7## The X-ray powder diffraction pattern is essentially that shown for K--PSin Table A. To obtain this data, we used the Debye-Scherrer method, K-Alpha of doublet copper, in a 57.3 mm chamber.


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The product obtained had many cracks in it. If at least one mineral filler is added to the reactant mixture after, during or even beforeaging, these cracks disappear. The mechanical and physical properties of the molded objects obtained following this process areexcellent. Tensile strength is about 180 kg/cm.sup.2, hardness may reach 7 on the Mohs scale, and linear dilatation coefficient, as afunction of temperature, is in the range of 2 to 5.times.10.sup.-6 m/m/.degree.C.

EXAMPLE 2

Following the steps described in Example 1, we prepared 960 grams of a reactant mixture containing 22.88 moles of water, the othercomponents being unchanged. The oxide-mole ratios of the reactant mixture are set forth in Table D, except H.sub.2 O/Al.sub.2O.sub.3 which was 21.

The fluid reactant mixture was aged for one hour at ambient temperature. Then we added 640 grams of synthetic cordierite (withmullite), with a size range lower than 120 microns. The viscous mixture was poured into a mold and hardened at 85.degree. C. Theproduct had a density of 2.3 grams per milliliter and a surface hardness of 5 on the Mohs scale. Its external dimensions indicated thatpolycondensation took place without any shrinkage.

X-ray diffraction was determined by a different technique, plotting the theta/2 curve under cobalt emission at 1.79 Angstroms. Thepattern showed the very strong lines of cordierite and the middle strong lines of mullite, weak lines at 4.49/4.28/3.53/2.59/2.28/2.16Angstroms and a broad line between 3.38 and 2.80 Angstroms, which is covered with the strong lines of cordierite. This X-raydiffraction pattern is identical to that of K--PS shown in Table A.

EXAMPLE 3

Following the steps described in Example 1, we prepared 792 grams of a reactant mixture containing 13.5 moles of water, the othercomponents being unchanged. The oxide-mole ratios of the reactant mixture are set forth in Table D, except H.sub.2 O/Al.sub.2O.sub.3 which was 12.5.

The fluid reactant mixture was aged for one hour at ambient temperature. Then we added 540 grams of synthetic cordierite (withmullite), with a size range lower than 120 microns, and we followed the steps described in Example 2.

We determined the X-ray diffraction pattern by the same technique as in Example 2 and obtained the same lines for K--PS, plus weaklines at 3.24/2.95/2.88/2.82 Angstroms. These are in the broad amorphous band for K--PS, namely between 2.79 and 3.23, cited inTable A.

The ratios H.sub.2 O/Al.sub.2 O.sub.3 may vary from 10 to 25. Preferably, the ratio is in the range of 14 to 20. Higher ratios increasethe porosity of the solidified product. Lower ratios induce a free alkalinity and cause migrations which can disturb the potassiumsilicate phase in the solid solution of the polymer compound. Preferably, the oxide-mole ratios of the reactant mixture fall within therange in Table E below.

TABLE E ______________________________________ K.sub.2 O/SiO.sub.2 0.30 to 0.38 SiO.sub.2 /Al.sub.2 O.sub.3 4.0 to 4.20


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H.sub.2 O/Al.sub.2 O.sub.3 14 to 20 K.sub.2 O/Al.sub.2 O.sub.3 1.3 to 1.52 ______________________________________

EXAMPLE 4

Following the steps described in Example 1, we prepared 860 grams of a reactant mixture and added 220 grams of muscovite with asize range lower than 120 microns and 90 grams of calcium fluoride (CaF.sub.2) in fine powder form. We obtained a viscous resinwhich we mixed with 1,150 grams of zircon sand. The resulting zircon sand/resin mixture was cast and vibrated in a mold, then heatedat 85.degree. C. for a period of 1.5 hours. The dried product had a density of 3.0 grams per milliliter. It was shiny and had a surfacehardness of 6 on the Mohs scale.

Interpretation of the X-ray diffraction pattern is not easy. The strong lines of zircon and calcium fluoride and the numerous lines ofmuscovite cover practically all the lines of K--PS.

EXAMPLE 5

Following the steps described in Example 1, we prepared a reactant mixture. After aging, the resin was painted on a mold which wasthe negative of a sculpture. During the same period, we mixed five kilograms of flint with a size range from 0.5 to 5 mm, with 0.5kilograms, or 10% by weight of the resin. This mixture was cast and vibrated in the painted mold. The mold was covered with apolyethylene film and cured at ambient temperature (25.degree. C.). Next day, we obtained a sculpture which was separated from themold and had a very fine, hard and shiny surface.

We have used the potassium silico-aluminate reactant mixtures described above in order to make molded objects obtained by theagglomeration of 5 to 95 parts by weight of mineral and/or organic fillers, with 5 to 95 parts by weight of a binder which is a mineralpolymer compound. This mineral polymer compound has a formula with a molar composition as follows:

where, in the fully hydrated form, "w" is a value at the most equal to 4, "x" is a value in the range of about 3.3 to about 4.5, and "y" isa value in the range of about 0.9 to about 1.6.

This mineral polymer compound is a solid solution which comprises 35 to 90 parts by weight of a potassium polysilicate with theformula:

and 10 to 65 parts by weight of a potassium polysialate with the formula: ##STR8## and having an X-ray powder diffraction patternrelated to the natural mineral kaliophilite, as shown in Table A for K--PS.

Molded objects with high thermal shock resistance were obtained by addition of fillers such as muscovite, synthetic or natural alumino-silicate, zircon, chamotte and other ceramics or refractory products.

The molded objects resist the direct action of a flame and may be used at temperatures in the range of 300.degree. C. to 1,200.degree.C. Preferably, they are first dried and dehydrated at a temperature below 350.degree. C. Dehydration and dehydroxylation of themineral polymer compound transforms the molded object into a product having excellent thermal stability properties equivalent to or


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better than ceramic materials. Its composition expressed in terms of oxides is as follows:

where "x" has a value in the range of about 3.3 to about 4.5, and "y" has a value in the range of about 0.9 to about 1.6. These polymercompounds are solid solutions comprising one phase of a potassium polysilicate with the formula:

and one phase of a K--PS polysialate with the formula: ##STR9##

The potassium silico-aluminate reactant mixture described above becomes a mineral resin which can be mixed with at least onemineral and/or organic filler, and used as a binder or cement. These mixtures may also include such additives and fillers as dyestuffs,pigments, reinforcement fibers and water-repelling agents. Polycondensation and setting occur in the range of room temperature up to120.degree. C.

Molded objects of this invention have many uses, depending on the physical, mechanical or chemical properties required. They can beused in industries such as the building industry and may also be used as decoration, taking the form of objects, molds, tools, blocks andpanels.

These molded objects may support several physicochemical, physical or mechanical post-treatments, as well as finishing or coatingoperations. If necessary, the molded objects can be heated to a temperature of at least 325.degree. C. One obtains ceramic-likeproducts having excellent thermal and dimensional stability.

US Patent # 4,509,985

Early high-strength mineral polymer

Davidovits , et al.

April 9, 1985


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Abstract --- An early high-strength mineral polymer composition is formed of a polysialatesiloxo material obtained by adding areactant mixture consisting of alumino-silicate oxide (Si.sub.2 O.sub.5,Al.sub.2 O.sub.2) with the aluminum cation in a four-foldcoordination, strong alkalis such as sodium hydroxide and/or potassium hydroxide, water, and a sodium/potassium polysilicatesolution; and from 15 to 26 parts, by weight, based upon the reactive mixture of the polysialatesiloxo polymer of ground blast furnaceslag. Sufficient hardening for demolding is obtained in about 1 hour with this composition.

Assignee: Pyrament Inc. (Houston, TX)Current U.S. Class: 106/624Current International Class: C04B 14/02 (20060101); C04B 14/04 (20060101); C04B 28/00 (20060101); C04B 28/26 (20060101)

BACKGROUND OF THE INVENTION

The present invention is directed to a mineral polymer composition which is employed for the making of cast or molded products atroom temperatures, or temperatures generally up to 248.degree. F., where the composition has attained sufficient strength to bedemolded within 90 minutes of casting or molding. These high early-strength compositions are obtained by the blending of a mineralgeopolymer, referred to as a polysialate, blast furnace slag, obtained from the making of iron in a blast furnace and possibly, an inertfiller.

The mineral geopolymers are called polysialates, and have the following empirical formula:

wherein "z" is 1, 2 or 3; "M" is a monovalent cation such as potassium or sodium, and "n" is the degree of polycondensation. Where"z" is 1, the mineral geopolymer has the formula: ##STR1## and is called polysialate or PS for short, and is of the K-PS polymercompound type when "M" is potassium. Where "z" is 2, the mineral geopolymer has the formula: ##STR2## and is calledpolysialatesiloxo or PSS for short. When "M" is sodium or a mixture of sodium and potassium, the geopolymer is called (sodium,potassium)polysialatesiloxo or NaKPSS. The chemical formula of NaKPSS may be written as: ##STR3##

The method for making NaKPSS or KPS is described in U.S. Pat. No. 4,349,386 and U.S. application Ser. No. 377,204. It comprisespreparing a sodium silico-aluminate/potassium silico-aluminate water mixture where the composition of the reactant mixture, in termsof oxide-mole ratios, falls within the ranges shown in Table A below.

TABLE A ______________________________________ Oxide-Mole Ratios of the Reactant Mixture______________________________________ M.sub.2 O/SiO.sub.2 0.20 to 0.48 SiO.sub.2 /Al.sub.2 O.sub.3 3.3 to 4.5 H.sub.2O/M.sub.2 O 10.0 to 25.0 M.sub.2 O/Al.sub.2 O.sub.3 0.8 to 1.6 ______________________________________

where M.sub.2 O represents either Na.sub.2 O, or K.sub.2 O or the mixture (Na.sub.2 O,K.sub.2 O).

The usual method for preparing this mixture comprises dissolving in water an alumino-silicate oxide, alkali, and a colloidal silica sol oralkali polysilicate. The alumino-silicate oxide (Si.sub.2 O.sub.5,Al.sub.2 O.sub.2).sub.n may be prepared from a polyhydroxy-alumino-silicate having the formula (Si.sub.2 O.sub.5,Al.sub.2 (OH).sub.4).sub.n, where the aluminum cation is in the octahedral state and is in


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six-fold coordination. The polyhydroxy-alumino-silicate is calcined and dehydroxylated at, say 1112.degree. F. to 1472.degree. F. Theresulting alumino-silicate oxide has the aluminum cation in four-fold coordination and in a tetrahedral position.

Various polyhydroxy-alumino-silicates may be used as the starting material for the preparation of alumino-silicate oxide, includingminerals having basal spacings of about seven Angstroms and having at least one aluminum cation located in the octahedral layers.Examples are alushite, carnat, china clay, lithomarge, neokaolin, parakaolinite, pholenite, endellite, glossecolite, halloysite, milanite,berthiernine, fraignotite, grovenite, amesite, and chamoisite.

The quantities of the reactants, namely colloidal silica sol and/or polysilicate, and strong alkalis such as sodium hydroxide andpotassium hydroxide, fall in the ranges shown in Table A.

After aging, the mineral mixture may be used alone, or may be mixed with inorganic or organic additives or fillers. The mixture may beused as a binder or a mineral cement for organic or mineral particles or fibers. The mixture is cast, poured or squeezed into a mold andheated to a temperature up to about 467.degree. F. but preferably to a temperature in the range of about 140.degree. F. to about203.degree. F. When polycondensation is complete, the solids are separated from the mold and dried at a temperature in the range ofabout 140.degree. F. to about 212.degree. F.

Polycondensation and heating times are a function of the temperature and the heating process used. At an ambient temperature such as77.degree. F., polycondensation requires more than 15 hours. At 122.degree. F., polycondensation requires about four hours; at185.degree. F., about 1.5 hours; and at 203.degree. F., about 0.5 hours. These times may differ and are often shorter when otherheating techniques are used. Such other techniques include high frequency, microwave, Joule effect, or electrical wires within thereactant mixture itself. Because the reactant mixtures are polyelectrolytes, these heating techniques effect polycondensation anddrying very rapidly.

There is a need for a cement which has the high setting and very low volume change characteristics normal for polysialategeopolymers, but which has very early high compressive strengths. This need is particularly acute in the prestress and precast concreteindustry. Considerable savings result from the required strength being obtained at early ages so that construction can continue andthere is a more rapid reuse of molds. There is also a need for such a very early high-strength cement having the high settingcharacteristics of polysialate geopolymers in patching or resurfacing highways and airport runways or in any operation where earlyform removal is desired.

While there have been proposals in the past for a cement having early high compressive strength, none of them have had the earlycompressive strengths required; that is, cement having a compressive strength better than 1,000 psi by 1 hour at 150.degree. F. and6,000 psi by 4 hours at 150.degree. F. when tested in a standard 1 to 2.75 by weight cement-sand mortar, and having the high settingand very low volume change characteristics that are normal for, and are typical of, polysialate geopolymers.

The best early high-strength Portland Cement described in U.S. Pat. No. 4,160,674 is made from a Portland Cement havingsubstantially all of its particles of about 20 microns and smaller. This fine and expensive cement type "Incor" had a compressivestrength of 3,000 psi in 4 hours at a temperature of 150.degree. F.


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The second required component of the high early-strength composition of the present invention is a ground blast furnace slag. Part ofthe steel-making process is in the reduction of iron ore to pig iron in a blast furnace. A by-product of the iron-making operation is blastfurnace slag, the material resulting from the purification of iron ore into pig iron. Blast furnace slags contain, in addition to the lime andmagnesia added to the blast furnace as fluxing material, the impurities previously contained in the iron ore, usually silica, alumina, andminor amounts of other compounds.

The ground blast furnace slag employed is a latent hydraulic product which can be activated by suitable activators. Without anactivation, the development of the strength of the slag is extremely slow. It is also known that the development of the slag necessitatesa pH higher than or equal to 12. The best activators are then Portland Cement, clinker, Ca(OH).sub.2, NaOH, KOH, and waterglass.The 7 day compressive strengths of activated slags with different alkali activators are given in the paper presented by J. Metso and E.Kapans, "Activation of Blast Furnace Slag by Some Inorganic Materials", at the CANMET/ACI First International Conference on theUse of Fly Ash, Silica Fume, Slag and Other Mineral By-products in Concrete", July 31-August, 1983, Montebello, Quebec, Canada.An addition of 4% by weight of NaOH gave a compressive 7 day strength of 12 to 20 MPa (1740 to 2900 psi), and a compressive 28day strength of 22 MPa (3190) psi.

The addition of ground blast furnace slag to the polysialate geopolymers accelerates the setting time, and improves compressivestrength.

BRIEF DESCRIPTION OF THE INVENTION

The present invention is directed to a high early-strength mineral polymer composition, useful as a cement, which has very early highcompressive strength; that is, compressive strength better than 1,000 psi by 1 hour at 150.degree. F. and 6,000 psi by 4 hours at150.degree. F. when tested in a standard 1 to 2.75 by weight cement-sand mortar, and which has the high setting and very low volumechange characteristics that are normal and typical of polysialate geopolymers.

This early high-strength cement composition is obtained by adding to a reactant mixture consisting of alumino-silicate oxide (Si.sub.2O.sub.5,Al.sub.2 O.sub.2) with the aluminum cation in four-fold coordination, strong alkalis such as sodium hydroxide and/orpotassium hydroxide, water and a sodium/potassium polisilicate solution, a certain amount of ground blast furnace slag. To 100 g of areactant mixture having the following oxide-mole ratio:

M.sub.2 O/SiO.sub.2 : 0.21 to 0.36

SiO.sub.2 /Al.sub.2 O.sub.3 : 3.0 to 4.12

H.sub.2 O/M.sub.2 O: 12 to 20

M.sub.2 O/Al.sub.2 O.sub.3 : 0.6 to 1.36

where M.sub.2 O represents either Na.sub.2 O, or K.sub.2 O, or the mixture (Na.sub.2 O, K.sub.2 O), one adds 15 g to 26 g of a fineground blast furnace slag.


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Additional details of both the mineral geopolymers and its use as a cement for making cast or molded products are set forth in thedescription of the preferred embodiments.

Accordingly, it is an object of the present invention to provide a mineral binder of the polysialate type used as a cement, having a veryearly high compressive strength and having very low volume change characteristics that are normal for, and typical of, polysialategeopolymers. A further object of the present invention is the provision of such a very early high compressive strength with the use offine ground blast furnace slag. A further object of the present invention is the provision of a mineral binder of the polysialate typeM.sub.n [(Si--O.sub.2).sub.z --AlO.sub.2 ].sub.n,wH.sub.2 O, wherein "z" is 1 or 2, where M.sub.2 O represents either Na.sub.2 O, orK.sub.2 O or the mixture (Na.sub.2 O,K.sub.2 O).

Employing the compositions of the present invention, cast or molded bodies achieve sufficient strength to be demolded inapproximately 1 hour.

Other and further objects, features and advantages of these mineral geopolymers, such as their uses as binders are apparent from thisspecification and claims.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The method for making NaKPSS or KPS geopolymers is described in U.S. Pat. No. 4,249,386 and U.S. application Ser. No. 377,204,filed Apr. 29, 1982. It comprises preparing a sodium silico-aluminate/potassium silico-aluminate water mixture where the compositionof the reactant mixture, in terms of oxide-mole ratios, falls within the ranges shown in Table A below.

TABLE A ______________________________________ Oxide-Mole Ratios of the Reactant Mixture______________________________________ M.sub.2 O/SiO.sub.2 0.20 to 0.48 SiO.sub.2 /Al.sub.2 O.sub.3 3.3 to 4.5 H.sub.2O/M.sub.2 O 10.0 to 25.0 M.sub.2 O/Al.sub.2 O.sub.3 0.8 to 1.6 ______________________________________

where M.sub.2 O represents either Na.sub.2 O, or K.sub.2 O or the mixture (Na.sub.2 O,K.sub.2 O). The mixture may be used as abinder or a mineral cement for organic particles or fibers. The mixture is cast, poured or squeezed into a mold and heated to atemperature up to about 467.degree. F., but preferably to a temperature in the range of about 140.degree. F. to about 203.degree. F.When polycondensation is complete, the solids are separated from the mold and dried at a temperature in the range of about140.degree. F. to about 212.degree. F.

Polycondensation and heating times are a function of the temperature and the heating process used. At an ambient temperature such as77.degree. F., polycondensation requires more than 15 hours. At 122.degree. F., polycondensation requires about 4 hours; at185.degree. F., about 1.5 hours; and at 204.degree. F., about 0.5 hours.

The following examples illustrate the methods of making the new early high-strength polysialate geopolymers of the NaKPSS or KPStypes, and some of the properties of these cements as well.

EXAMPLE I (CONTROL)


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We prepared 840 g of a reactant mixture containing 17.3 moles of water, 1.438 moles potassium oxide, 4.45 moles of silicon dioxideand 1.08 moles of aluminum trioxide. The source of aluminum trioxide is the alumino-silicate oxide (Si.sub.2 O.sub.5,Al.sub.2O.sub.2).sub.n with Al in four-fold coordination prepared by dehydroxylating a natural polyhydroxy-alumino-silicate (Si.sub.2O.sub.5,Al.sub.2 (OH).sub.4).sub.n with Al in six-fold coordination. The source of silicon dioxide is this alumino-silicate oxide and apotassium silicate. The source of potassium oxide is this potassium silicate and potassium hydroxide. The oxide mole ratios in thereactant mixture are shown in Table B.

TABLE B ______________________________________ K.sub.2 O/SiO.sub.2 0.32 SiO.sub.2 /Al.sub.2 O.sub.3 4.12 H.sub.2O/Al.sub.2 O.sub.3 17.0 K.sub.2 O/Al.sub.2 O.sub.3 1.33 H.sub.2 O/K.sub.2 O 12.03 ______________________________________

We call this reactant mixture standard mixture. To the 840 g of this standard mixture was added 20 g of fine mica, 110 g of finecalcium flouride and 220 g of fine clay kiln dust. This slurry, weighing 1190 g, was added to 2210 g of graded Ottawa sand, and theobtained mixture was cast into standard 2" cube molds, cured 4 hours at 150.degree. F. The compressive strength after 4 hours at150.degree. F. is 6730 psi; other data are given in Table I. Table II gives all volume changes in water and in air. The low volumechange in air of the standard mixture (+0.009) compared with current cement (Type I, Lone Star New Orleans) (-0.074), illustrates thegreat advantage of a geopolymer. However, the standard mixture begins to harden at 150.degree. F. only after 2 hours, and may onlybe demolded after 4 hours. At ambient temperature (say 73.degree. F.), hardening begins after 15 hours and demolding may occur onlyafter 24 hours or better at 48 hours. At 185.degree. F. hardening begins after 40 minutes and demolding occurs after 1 hour and 30minutes. These hardening times are too long for numerous applications, especially when no heat may be applied, or when the moldsand tooling costs are so high that an increase in productivity becomes a necessity.

EXAMPLE II

To the 840 g of the standard mixture of Example I, are added 20 g of fine mica, 110 g of calcium flouride and 220 g of Lone StarMiami ground sidmar slag which has the following characteristics:

______________________________________ MIAMI PLANT GROUND SIDMAR SLAG______________________________________ Glass, % Microscope 70 SiO.sub.2 32.83 Al.sub.2 O.sub.3 11.59 Fe.sub.2 O.sub.3 1.58CaO 41.43 MgO 8.03 TiO.sub.2 0.55 Na.sub.2 O 0.28 K.sub.2 O 0.41 SrO 0.06 SO.sub.3 0.42 S 0.99 Gain on Ignition 0.86 CorrectedLoss 1.12 Hydraulic Index I 1.86 I.sub.H 1.80 ______________________________________

This slurry of Example II, weighing 1190 g, was added to 2200 g of graded Ottawa sand, and the obtained mixture cast into standard2" cube molds. This mixture begins to harden after 21 minutes at 73.degree. F. The compressive strength after 24 hours at 73.degree.F. is 5575 psi. Cured 4 hours at 150.degree. F., the compressive strength is 7140 psi (see Table I), and reaches 8220 psi after 1 day at73.degree. F., the shrinkage in air (Table II) remains low--0.021.

EXAMPLE III

To the 840 g of the standard mixture of Example I, are added 220 g of a fine ground, light weight expanded clay aggregate (used as an


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inert filler), and 130 g of the Miami ground sidmar slag as in Example II. This slurry of Example III, weighing 1190 g, is added to 220 gof graded Ottawa sand. The mixture begins to harden after 45 minutes at 73.degree. F. Compressive strength on 2" cubes cured 4 hoursat 150.degree. F. (Table I), is 8350 psi and reaches 8770 psi after 1 day at 73.degree. F. The shrinkage in air (Table II), remains low at0.015 compared with 0.074 for regular Portland Cement. It is also of interest to note that with this geopolymer mixture of Example III,the compressive strength on 2" cubes, cured 24 hours at 150.degree. F. reaches 10,000 psi.

Table I gives the compressive strength comparison on 2" cubes for the geopolymer standard mixture of Example I, the geopolymermixture of Example III, cements of Lone Star Industries Type I, Type III, Super Incor and Reg. Set II Cement, cured 4 hours at150.degree. F. or at room temperature.

Table II gives the volume change in water or in air after 2 months. Geopolymer mixture shows higher expansion in water than PortlandCement, but the very low shrinkage in air is a very important property.

TABLE I __________________________________________________________________________ COMPRESSIVE STRENGTHCOMPARISON, 2" CUBES, PSI __________________________________________________________________________150.degree. F. for 4 hours Geopolymer Geopolymer Type I (N.O.) Super Reg. Set II Example I Example III Portland Cement IncorCement Cement __________________________________________________________________________ 4 hours 6730 8350 2603000 2200 1 day 6400 8770 2130 8150 3600 7 days 7050 8500 4500 8620 4400 28 days 6900 9000 7200 9720 5200__________________________________________________________________________ No Heat Curing Geopolymer StandardMixture Geopolymer Type I Cement Type III Cement Super Reg. Set II Example I Example II (Miami) (Greencastle) Incor CementCement __________________________________________________________________________ 4 hours -- 3500 -- -- 2000 1800 1day 2000 7920 2000 4500 6600 3800 7 days 4500 8200 5000 6500 8600 4700 28 days 7000 9000 7100 7100 9000 6200__________________________________________________________________________

TABLE II ______________________________________ VOLUME CHANGE IN WATER IN 50% R.H. AIR MIX 2 MONTHS 2MONTHS ______________________________________ Geopolymer Standard +.062 +.009 Example I Geopolymer +.049 -.021Example II Geopolymer +.053 -.015 Example III Type I +.006 -.074 Portland Cement ______________________________________

EXAMPLE IV

We prepared 800 g of a reactant mixture containing 16.7 moles of water, 1.294 moles potassium oxide, 4.22 moles of silicon dioxideand 1.08 moles of aluminum trioxide. The source of the reactants is the same as in Example I. The oxide mole ratios in the reactantmixture are shown in Table C.

TABLE C ______________________________________ K.sub.2 O/SiO.sub.2 0.36 SiO.sub.2 /Al.sub.2 O.sub.3 3.90 H.sub.2O/Al.sub.2 O.sub.3 15.48 K.sub.2 O/Al.sub.2 O.sub.3 1.198 H.sub.2 O/K.sub.2 O 12.90______________________________________

To the 800 g of this reactant mixture, one adds 220 g of a fine ground, light weight, expanded clay aggregate (used as an inert filler),


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and 130 g of the Miami ground sidmar slag. This slurry of Example IV, weighing 1150 g, is added to 2200 g of graded Ottawa sand.Compressive strength on 2" cubes cured 4 hours at 150.degree. F. is 7250 psi, and after storage 7 days at 73.degree. F., 8470 psi.Compressive strength of 2" cubes cured 2 days at room temperature (73.degree. F.) is 6500 psi. The composition of this example beganto harden, and could be demolded, after 60 minutes, at 73.degree. F.

EXAMPLE V

We prepared 732 g of a reactant mixture containing 15.6 moles of water, 1.043 moles of potassium oxide, 3.88 moles of silicon dioxideand 1.08 moles of aluminum trioxide. The sources of the reactants are the same as in Example I. The oxide mole ratios in the reactantmixture are shown in Table D.

TABLE D ______________________________________ K.sub.2 O/SiO.sub.2 0.268 SiO.sub.2 /Al.sub.2 O.sub.3 3.592 H.sub.2O/Al.sub.2 O.sub.3 14.44 K.sub.2 O/Al.sub.2 O.sub.3 0.96 H.sub.2 O/K.sub.2 O 14.90 ______________________________________

To the 782 g of this reactant mixture are added 220 g of a fine ground, light weight, expanded clay aggregate (used as an inert filler),and 130 g of the Miami ground sidmar slag. This slurry of Example V, weighing 1082 g, is added to 2200 g of graded Ottawa sand.Compressive strength on 2" cubes, cured 4 hours at 150.degree. F. is 7935 psi, and after storage for 7 days at 73.degree. F., 8220 psi.Compressive strength of 2" cubes cured 2 days at room temperature (73.degree. F.), is 6650 psi. This composition began to harden, andcould be demolded after about 45 minutes, at 73.degree. F.

In the above Examples III, IV, and V, 130 g of the Miami ground sidmar slag was added to different geopolymer reactant mixtures.The reduction of the ratios SiO.sub.2 /Al.sub.2 O.sub.3 and K.sub.2 O/Al.sub.2 O.sub.3 has a slight influence on the compressivestrength, as shown in Table III.

TABLE III ______________________________________ Compressive strength on 2" cubes cured 4 hours at 150.degree. F.SiO.sub.2 /Al.sub.2 O.sub.3 K.sub.2 O/Al.sub.2 O.sub.3 PSI ______________________________________ 4.12 1.33 8350 3.90 1.1987250 3.592 0.96 7035 ______________________________________

In Example II, 26% per weight of Miami slag was added to the geopolymer reactant mixture; in Example III, 15% of Miami slag; inExample IV, 16.2%; and in Example V, 17.7% by weight was added to the geopolymer reactant mixture.

In fact, another ratio seems to influence the compressive strength. In all above Examples III, IV, V, the H.sub.2 O/K.sub.2 O increases,whereas the compressive strength is decreasing.

EXAMPLE VI

In order to study the influence of water on the compressive strength, we prepared 686 g of a geopolymer reactant containing 13.0moles of water, 1.043 moles of potassium oxide, 3.88 moles of silicon dioxide and 1.08 moles of aluminum trioxide. The sources of thereactants are the same as in Example I. To the 686 g of this geopolymer reactant mixture are added 220 g of a fine ground, light weightexpanded clay aggregate (used as an inert filler), and 130 g of the Miami ground sidmar slag. To this slurry of Example VI are added


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increasing amounts of water, and the obtained mixture is added to 2200 g of graded Ottawa sand. In Table IV is given the relationshipbetween the ratio H.sub.2 O/K.sub.2 O and the compressive strength for the reaction mixture according to this Example VI, which hasthe following oxide mole ratio:

K.sub.2 O/SiO.sub.2 : 0.268

SiO.sub.2 /Al.sub.2 O.sub.3 : 3.592

K.sub.2 O/Al.sub.2 O.sub.3 : 0.96

TABLE IV ______________________________________ Compressive strength on 2" cubes cured 4 hours at 150.degree. F.Variation of water content. ______________________________________ H.sub.2 O/K.sub.2 O 12.46 14.90 16.45 17.52 18.85 20.80psi 4 days 7235 7035 6000 4900 4220 3670 psi 7 days 8420 8220 6280 5480 4850 4100 at 73.degree. F.______________________________________

The compositions of this example began to harden, and could be demolded at times varying from about 30 to about 70 minutes, at73.degree. F.

EXAMPLE VII

In order to demonstrate the major influence of this ratio H.sub.2 O/K.sub.2 O (that is to say, the starting pH of the reactant mixture),we prepared 500 g of a geopolymer reactant mixture containing 8.69 moles of water, 0.719 moles of potassium oxide, 3.308 moles ofsilicon dioxide, and 1.08 moles of aluminum trioxide. The sources of the reactants are the same as in Example I. To the 500 g of thisgeopolymer reactant mixture are added 220 g of a fine ground, light weight, expanded clay aggregate (used as an inert filler), 130 g ofthe Miami ground sidmar slag, and 113 g of water. To this slurry of Example VII is added 2200 g of graded Ottawa sand. The oxidemole ratios of the geopolymer reactant mixture, with water, are shown in Table E:

TABLE E ______________________________________ K.sub.2 O/SiO.sub.2 0.217 SiO.sub.2 /Al.sub.2 O.sub.3 3.062 H.sub.2O/Al.sub.2 O.sub.3 13.18 K.sub.2 O/Al.sub.2 O.sub.3 0.665 H.sub.2 O/K.sub.2 O 20.80______________________________________

Compressive strength of 2" cubes cured 4 hours at 150.degree. F. is 3600 psi and when placed 7 days at room temperature (73.degree.F.), 4000 psi. One obtains the same value with H.sub.2 O/K.sub.2 O equal to 20.80, as in Table III; but in this Example VII, the ratioK.sub.2 O/Al.sub.2 O.sub.3 is 0.665, instead of 0.96 as in Example VI. The most important element is then obviously the H.sub.2O/K.sub.2 O ratio, which determines the pH value of the reacting geopolymer mixture. A low ratio, in the range between 12 and 16yields to high early compressive strength, whereas a big H.sub.2 O/K.sub.2 O ratio, higher than 16, reduced substantially themechanical properties of the geopolymer reactant mixture. Hardening of the composition of this example began in about 70 minutes, at73.degree. F.

EXAMPLE VIII


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We prepared 870 g of a reactant mixture containing 20.0 moles of water, 0.724 moles of potassium oxide, 0.75 moles of sodium oxide,4.45 moles of silicon dioxide and 1.08 moles of aluminum trioxide. The source of sodium oxide is sodium hydroxide. The sources ofthe other reactants are the same as in Example I. The oxide mole ratios in the reactant mixture are shown in Table F.

TABLE F ______________________________________ (K.sub.2 O,Na.sub.2 O)/SiO.sub.2 0.33 SiO.sub.2 /Al.sub.2 O.sub.3 3.592H.sub.2 O/Al.sub.2 O.sub.3 18.6 [K.sub.2 O,Na.sub.2 O]/Al.sub.2 O.sub.3 1.36 H.sub.2 O/(K.sub.2 O,Na.sub.2 O) 13.56______________________________________

To the 870 g of this reactant mixture are added 220 g of a fine ground, light weight expanded clay aggregate (used as an inert filler),and 130 g of the Miami ground sidmar slag. This slurry of Example VII, weighing 1220 g, is added to 2200 g of graded Ottawa sand.Compressive strength on 2" cubes cured 4 hours at 150.degree. F. is 6670 psi, and after storage for 7 days at 73.degree. F., 7870 psi.Curing of the composition of this example began in about 70 minutes, at 73.degree. F.

Compared with the results obtained in Example III, there is a slight reduction in strength from 8350 to 6670 psi (curing 4 hours at150.degree. F.), due to the replacement of 50% of the K.sub.2 O by Na.sub.2 O. Sodium hydroxide is relatively cheaper thanpotassium hydroxide, and results in compressive strengths which are lower, but still interesting for various applications.

EXAMPLE IX

We prepared 781 g of a reactant mixture containing 18.2 moles of water, 1.043 moles of potassium oxide, 3.88 moles of silicon dioxideand 1.08 moles of aluminum trioxide. The sources of the reactants are the same as in Example I. The oxide mole ratios in the reactantmixture are shown in Table G.

TABLE G ______________________________________ K.sub.2 O/SiO.sub.2 0.268 SiO.sub.2 /Al.sub.2 O.sub.3 3.592 H.sub.2O/Al.sub.2 O.sub.3 16.85 K.sub.2 O/Al.sub.2 O.sub.3 0.96 H.sub.2 O/K.sub.2 O 17.25 ______________________________________

To the 781 g of this reactant mixture are added 220 g of fine ground, light weight expanded clay aggregate (used as an inert filler), and130 g of the Miami ground sidmar slag. This slurry of Example IV, weighing 1131 g, is added to 2200 g of graded Ottawa sand. Thecompressive strengths of 2" cubes cured at different temperatures and during different times are given in Table V.

TABLE V ______________________________________ Effect of Time and Temperature, Reactant Mixture Example IX,Compressive Strength on 2" Cubes Temperature Curing Time PSI Stored 7 days at 73.degree. F.______________________________________ (PSI) 100.degree. F. 1 hour.sup. 450 4780 100.degree. F. 4 hours 2630 4620150.degree. F. 1 hour.sup. 1280 5500 150.degree. F. 2 hours 3680 5480 150.degree. F. 4 hours 4900 5480 200.degree. F. 1 hour.sup.4230 4780 ______________________________________

Because of the relatively high H.sub.2 O/K.sub.2 O ratio, the compressive strengths are lower than 6000 psi (cured 4 hours at150.degree. F.), but the 1 hour curing at 150.degree. F. gives a compressive strength higher than 1000 psi, which is high enough fordemolding. Hardening of this composition began in about 60 minutes, at 73.degree. F.


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The amount of slag added to the geopolymer reactant mixture varied in Examples III to VIII from 15.4% to 21% by weight. At thesame time, the amount of water increases. Surprisingly, the increasing of water results in a reduction of the compressive strength,whereas, theoretically it is the opposite which might be expected. Indeed, increasing the water amount improves the dissolution of theslag. Table VI gives the variation of the compressive strength with the slag/water weight ratio of the reactant mixtures of Example VI.

TABLE VI ______________________________________ Compressive strength on 2" cubes, cured 4 hours at 150.degree. F.Variation of the slag/water weight ratio, according to Example VI. Slag/Water PSI ______________________________________ 0.557235 0.46 7035 0.42 6000 0.39 4900 0.36 4200 0.33 3670 ______________________________________

The minimum of 6000 psi early high-strength is obtained with a slag/water weight ratio at least equal to 0.42; at room temperature theslag/water weight ratio determines the setting time.

Table VII gives the setting time at room temperature (73.degree. F.) with the slag/water weight ratio.

TABLE VII ______________________________________ Slag/water weight ratio 0.70 0.55 0.46 0.42 Setting time (73.degree. F.) 12min. 30 min. 45 min. 60 min. ______________________________________

From the above described Examples, the present invention consists in the production of an early high-strength concrete composition,which is obtained by adding to a reactant mixture consisting of alumino-silicate oxide (Si.sub.2 O.sub.5,Al.sub.2 O.sub.2).sub.n withthe aluminum cation in four-fold coordination, strong alkalis such as sodium hydroxide and/or potassium hydroxide, water and asodium/potassium polisilicate solution, a certain amount of ground blast furnace slag. To 100 g of a reactant mixture followingoxide-mole ratio

M.sub.2 O/SiO.sub.2 : 0.21 to 0.36

SiO.sub.2 /Al.sub.2 O.sub.3 : 3.0 to 4.12

H.sub.2 O/M.sub.2 O: 12.0 to 20

M.sub.2 O/Al.sub.2 O.sub.3 : 0.6 to 1.36

where M.sub.2 O represents either Na.sub.2 O, or K.sub.2 O, or the mixture (Na.sub.2 O,K.sub.2 O), one adds 15 g to 26 g of a fineground blast furnace slag. If more than 26 g of ground blast furnace slag is employed, the composition tends to "flash set". While it ismore difficult to use, it can still be employed with higher amounts of slag. The 15 g to 26 g amounts of slag are based upon the reactivepolysialate siloxo mixture, including water.

Tested in standard 1 to 2.75 by weight cement-sand mortar, the polysialate geopolymer/slag mixture used as a cement, yields to earlyhigh compressive strength; that is, compressive strength better than 1000 psi by 1 hour at 150.degree. F. and 6000 psi by 4 hours at150.degree. F. Depending on the slag/water weight ratio, the setting time at room temperature varies from 12 minutes to 60 minuteswith a slag/water weight ratio in the range of 0.70 to 0.42.


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As plotted in Table II, the polysialate geopolymer/slag mixture yields to very low volume change characteristics that are normal andtypical of polysialate geopolymers, such as a shrinkage in air after 2 months, as low as 0.015 compared with the value for regularPortland Cement (0.074).

The foregoing embodiments have been given for the purpose of disclosure and changes can be made therein which are within the spiritof the invention as defined by the scope of the appended claim.

Some Google Search Results

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Ancient Egyptians built Pyramids with concrete blocks, scientists ...Mr Davidovits and his team at the Geopolymer Institute at Saint-Quentin tested the method recently, producing a large block ofconcrete limestone in ten ...www.timesonline.co.uk/article/0,,3-2480751,00.html

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Joseph Davidovits » Milestones in geopolymersAU : Davidovits, J AF : Géopolymère, Saint-Quentin, France SO : CONCRETE INTERNATIONAL, Vol. 16, N°12, PP. 53-58 (1994).TI : Geopolymers: Man-Made Rock ...www.davidovits.info/6/milestones-in-geopolymers - 20k

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Amazon.com: The Pyramids: An Enigma Solved: Books: Joseph ...In fact they could make far better 'concrete' than any that we use today. ... Professor Davidovits is the only scientist to take them apartand reverse ...www.amazon.com/Pyramids-Enigma-Solved-Joseph-Davidovits/dp/0880295554 - 107k

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Philadelphia Inquirer | 12/01/2006 | Are the pyramids concrete?Previously, detractors of the concrete theory have said there weren't enough ... Moreover, after consulting with Davidovits, Barsoumsaid he thinks his ...www.philly.com/mld/philly/news/nation/16137891.htm - 28k

Alternate Theories of Pyramid ConstructionDavidovits provides a brief summation:. I will demonstrate that the pyramid blocks are actually exceptionally high-quality limestoneconcrete -- synthetic ...www.catchpenny.org/theories.html - 17k

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CORDI-Géopolymère - Géopolymère '88 & '99 Tables of ContentFire Safety for Concrete Structures in Tunnels 16. Fire Proof Geopolymeric Cements Joseph Davidovits, Cordi-Géopolymère SA,Saint-Quentin, France ...www.cordi.geopolymere.com/proceedings_gp88-99-2005-content.htm - 29k

Rhymes With RightThis wet “concrete” would have been carried to the site and packed into wooden moulds where it would set hard in a few days. MrDavidovits and his team at ...rhymeswithright.mu.nu/ - 268k

Geopolymeric Agent for Immobilization of Radioactive Ashes after ...File Format: PDF/Adobe AcrobatDavidovits, J., Science in Egyptology Symp., 1984,. pp. 511 ! 520. 22. From Ancient Concrete to Geopolymers, Arts Metiers. Mag.,1993, no. 180, pp. ...www.springerlink.com/index/N266482212476383.pdf

Nabataea: ConcreteWe thank Dr. Davidovits and the Geopolymer Institute for allowing us to use ... Cement and concrete are often thought of as the samething, however, ...nabataea.net/cement.html - 63k


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TU Delft - Making Concrete without using CementFollowing up on work of Davidovits, researchers Hardjito et al. presented an article ... Researchers showed that they could produceconcrete like material, ...pages.ta.tudelft.nl/live/pagina.jsp?id=3f2b62fc-ac12-40e4-84e0-e3513099cb23&lang=en - 16k

Egyptian pyramid construction techniques - Wikipedia, the free ...[edit] Limestone concrete theory. Materials scientist Joseph Davidovits has posited that the blocks of the pyramid are not carvedstone, but mostly a form ...en.wikipedia.org/wiki/Egyptian_pyramid_construction_techniques - 43k

Hydration process of interfacial transition in potassium ...File Format: PDF/Adobe AcrobatDavidovits J. High alkali cements for 21st century concretes. In: Concrete Technology, Past, Present, and Future, SP-144. ACI,Detroit, MI, 1994, pp. ...www.atypon-link.com/TELF/doi/pdf/10.1680/macr.57.1.33.57865

DEVELOPMENT OF SUSTAINABLE CEMENTITIOUS MATERIALSFile Format: PDF/Adobe Acrobat - View as HTMLJ. Davidovits, Douglas C. Comrie, John H. Paterson, and Douglas J. Ritcey. Geopolymeric concretes for environmental protection.Concrete International: ...www.cptechcenter.org/publications/sustainable/lisustainable.pdf

ZNet Commentary: Of Pyramids and SkyscrapersDavidovits succeeded in resynthesizing the polymeric concrete of the ancient Egyptians in a modern laboratory. Whether it was100000 or 1400 people who ...www.zmag.org/Sustainers/Content/2001-09%5C30raptis.cfm - 13k

Abstract8 Davidovits J. High alkali cements for 21st century concretes. In: Concrete Technology, Past, Present, and Future , SP-144. ACI,Detroit, MI, 1994, pp. ...www.atypon-link.com/TELF/doi/xml/10.1680/macr.57.1.33.57865

Pyramid blocks 'poured, not hauled' insists latest study - Irish ...Despite mounting support from scientists, Egyptologists have rejected the concrete claim, made in the 1970s by Joseph Davidovits, aFrench chemist. ...www.unison.ie/irish_independent/stories.php3?ca=10&si=1734625&issue_id=14959

EUROPEAN CONCERTED ACTIONFile Format: PDF/Adobe Acrobat - View as HTML


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Davidovits suggests that this. approach is necessary to prevent the possible ecological disaster from global warming. The. presence ofMCRM in concrete is ...www.empa.ch/plugin/template/empa/*/10928/---/l=

Microsoft PowerPoint - cocoa_2005.pptFile Format: PDF/Adobe Acrobat - View as HTMLDavidovits, J. Journal of Thermal Analysis 1991, 37, 1633. (2). Palomo, A.; de la Fuente, J. I. L. Cement and Concrete Research 2003,33, 281. ...kriven.mse.uiuc.edu/recent/geopolymers/talks/cocoa_2005.pdf

The Building of the Great PyramidDr. Davidovits is the modern patent holder of many geopolymeric rock-making or concrete processes and I talked at length with hisco-author Marjorie Morris ...ezinearticles.com/?The-Building-of-the-Great-Pyramid&id=51916 - 42k

High effective silica fume alkali activatorFile Format: PDF/Adobe Acrobat - View as HTMLDavidovits J 1993 Ceram. Trans. 37 165. Davidovits J 1994 High alkali cements for 21st century con-. cretes, Concrete technologypast, present and future, ...www.ias.ac.in/matersci/bmsapr2004/179.pdf

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Davidovits. J.. The ancient egyptian pyramids-concrete or Rock [J]. ...scholar.ilib.cn/abstract.aspx?A=zgfjskgydk200206003

Applications Of Geopolymer Technology To Waste StabilizationFile Format: PDF/Adobe Acrobat - View as HTMLMoh's scale) (Davidovits and Davidovits, 1987). ... conventional concrete mixing technology, and ... high strength geopolymerconcrete, the soil set ...www.p2pays.org/ref/14/13863.pdf

Impact behavior and microstructural characteristics of PVA fiber ...File Format: PDF/Adobe AcrobatDAVIDOVITS. and. J . DAVIDOVITS. , J. Fire Mater. 21(2) (1997) 67. 6. J . DAVIDOVITS . in “American Concrete Insititue,” editedby P. K. ...


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www.ingentaconnect.com/content/klu/jmsc/2006/00000041/00000010/00006293

Concrete Pyramids[19] Wenskus, J., ”Did the Pharaohs Cheat with Concrete?” R&D Magazine, Dec 1990, p5. [20] Davidovits, J. and Morris, M. ThePyramids, Dorset Press, 1988, ...www.bonisteelml.org/ConcretePyramid1.htm - 37k

Egyptian pyramids actually made of synthetic stone?"Dr. Joseph Davidovits said that the synthetic pyramid stone was made with cement far stronger than ... which binds together the rockand sand in concrete. ...www.science-frontiers.com/sf054/sf054a02.htm - 7k

Towards Making Pre-Mix Concrete Foolproof A John W Harrison, B.Sc ...File Format: PDF/Adobe Acrobat - View as HTMLused by Davidovits (Davidovits 1994). In tec-cement concrete formulations many wastes containing silica and alumina such as fly ashand ground ...www.tececo.com/files/conference_papers/MakingPre-MixConcreteFoolproofUsingTec-CementTechnology310705.pdf

Volcanic Ash in Ancient and Modern Construction — The Thera FoundationAs there is evidence for ancient cement, there is also evidence for even more ancient concrete. According to Davidovits (1987),Farkas (1985) and Starr ...www.therafoundation.org/articles/technology/volcanicashinancientandmodernconstruction - 55k

STUDIES ON REINFORCED LOW – CALCIUM FLY ASH – BASED GEOPOLYMER ...File Format: PDF/Adobe Acrobat - View as HTMLDavidovits, J. (1994) “High-Alkali Cements for 21. st. Century Concretes. in. Concrete Technology, Past, Present and Future.” Inproceedings of V. Mohan ...www.en.kku.ac.th/sirdc/pcg/images/stories/Pdf/8pcg_2...pdf

Concrete InternationalDavidovits says that the pyramids were constructed from synthetic stones made of geopolymeric concrete. To support this theory, hehas produced a concrete ...www.concreteinternational.com/pages/Index.asp?IssueID=243&DepartmentId=

Cambridge 02138 - Harvard Magazine (September-October 2003)Mark Lehnerreplies: Davidovits's hypothesis does not stand up to on-siteobservations. First, if concrete, the blocks certainly were notpouredin molds, ...www.harvardmagazine.com/on-line/090328.html - 46k


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MICROSTRUCTURE AND MICROCHEMISTRY OF FULLY-REACTED GEOPOLYMERS ...File Format: PDF/Adobe Acrobat - View as HTMLJ. Davidovits, “Method for Bonding Fiber Reinforcement on Concrete and. Steel Structures and Resultant Products, U.S Pat. No.5925449, July 20 ...kriven.mse.uiuc.edu/recent/geopolymers/papers/CESP%202003.pdf

Egyptian pyramid construction techniques: Information from Answers.comLimestone concrete theory. Materials scientist Joseph Davidovits has posited that the blocks of the pyramid are not carved stone, butmostly a form of ...www.answers.com/topic/egyptian-pyramid-construction-techniques - 66k

Increasing Coal Fly Ash Use in Cement and Concrete Through ...File Format: PDF/Adobe AcrobatThe use of coal fly ash as a cement replacement in concrete is the most ... Davidovits, J. 1994. Global warming impact on the cementand aggregates ...taylorandfrancis.metapress.com/index/HXRBAH4D1V1UX7QW.pdf

Davidovits., Niclos. European Patent PCT/FR87/00396. ?15?Roy D W, Tamas F D. Proceedings of a conference on hydrolytic cementand concrete ...www.wanfangdata.com.cn/qikan/periodical.Articles/zgfjskgydk/zgfj2002/0206/020603.htm

Davidovits J. Recent progresses in concretes for nuclear waste and uranium waste containment[J]. Concrete International, 1994.16(12):53-58. ...www.wanfangdata.com.cn/qikan/periodical.Articles/jzclxb/jzcl2003/0303/030304.htm

Siloxo -Technology : Geopolymer - Antiquity*Adapted from: Davidovits, J., "Ancient and modern concretes: What is the real difference?," Concrete International, vol. 9, 1987, pp.23-35. ...www.siloxo.com/technology.htm - 12k

Center for By-Products UtilizationFile Format: PDF/Adobe Acrobat - View as HTMLBlended Cements”, Cement and Concrete Research, 2002, pp. 1937-1942. 9. Davidovits, J., “High-alkali Cements for 21. st. CenturyConcretes”, Concrete ...www.uwm.edu/Dept/CBU/Papers/2004%20CBU%20Reports/CBU-2004-06.pdf

Douglas C ComrieFile Format: PDF/Adobe Acrobat - View as HTMLGeopolymeric Concretes, D. Comrie, J. Davidovits, Concrete International, July 1990. • Geopolymer technology and its application to


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waste remediation ...www.chem-mod.com/Doug%20Comrie%20Bio.pdf

Cement Association of Canada -Concrete is required for a pavement that will be exposed to moisture and ... on the polymerization of minerals (Davidovits, Davidovitsand James 1999). ...www.cement.ca/.../e/3156a47568d2612c85256a9000614896?OpenDocument&Start=1&Count=30&Expand=1 - 58k

THE BEHAVIOUR OF GEOPOLYMER PASTE AND CONCRETE AT ELEVATED ...File Format: PDF/Adobe Acrobat - View as HTMLP.K. Mehta (2002) "Greening of the concrete industry for sustainable. development", ACI Concrete International, 24(7), 23-28. 4. J.Davidovits (1993) ...www.en.kku.ac.th/sirdc/pcg/images/stories/Pdf/11PCG_19...pdf

DEVELOPMENT AND PROPERTIES OF LOW-CALCIUM FLY ASH-BASED GEOPOLYMER ...File Format: PDF/Adobe Acrobatcompressive strength of hardened concrete. Davidovits (2002) suggested that it is preferable to mix the sodium silicate solution ...espace.lis.curtin.edu.au/archive/00000623/01/Research_Report_GC1-_2005.pdf

Concrete InternationalTo support this theory, he has produced a concrete that matches the pyramid stones and has accumulated other pertinent evidence.Davidovits discusses his ...www.concreteinternational.com/pages/featured_article.asp?ID=3735

APOTHECARY'S DRAWER WEBLOG: December 2001This is not, however, a new idea; Professor Joseph Davidovits has been postulating this since the 1980s. See Are Pyramids Made outof Concrete? at the ...www.raygirvan.co.uk/apoth/though11.htm - 22k

A New Way to Reduce Global Warming — geopolymeric cementThe price of geopolymeric cement/concrete can be competitive with that of Portland ... The Geopolymer Institute Dr. JosephDavidovits [email protected] ...www.welcomenews.net/geopolymer.html - 8k

Pharoah Crete - Further InformationIt's not a competition between geopolymers and concrete. ... Geopolymer Institute in France, operated by Joseph Davidovits, theauthor of "The Pyramids: An ...www.abc.net.au/quantum/scripts98/9818/pharoahscpt.htm - 9k


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Curtin NewsBytes: Egypt – The origin of gyprock?For the next 12 years, Davidovits researched Egyptian civilisations to ... "It is a natural replacement for concrete: the manufacture ofone metric tonne ...newsbytes.curtin.edu.au/archive/feature-a/fa_Novgyprock.html - 12k

LOW-CALCIUM FLY ASH-BASED GEOPOLYMER CONCRETE: LONG-TERM PROPERTIESFile Format: PDF/Adobe Acrobat - View as HTMLIn this respect, the geopolymer technology proposed by Davidovits (1988a; 1988b). shows considerable promise for application inconcrete industry as an ...espace.lis.curtin.edu.au/archive/00000842/01/Research_Report_GC2__2006.pdf

ABSTRACT. Since the industrial revolution, human activities have ...File Format: PDF/Adobe Acrobat - View as HTMLDavidovits [7] paints a more depressing picture and. points out that if all the fly ash produced was fully utilised in concrete this wouldonly ...www.ukqaa.org.uk/Papers/DundeeCongressEnvBenefitsofPFASearSept2002.pdf

Sustainability and Performance as Key Factors for the Development ...File Format: PDF/Adobe Acrobat - View as HTMLDavidovits J., Comrie D.C., Paterson J.H. and Ritcey D.J., “Geopolymeric Concretes for Environmental Application”, ConcreteInternational, vol. ...www.uwm.edu/Dept/CBU/Papers/2005%20CBU%20Reports/CBU-2005-17.pdf

The Role of Concrete Post Kyoto – The Unrecognized Sequestration ...File Format: PDF/Adobe Acrobat - View as HTMLThis paper demonstrates the potential of the concrete industry to deliver a large ... paper published in World Resources Review in1994 (Davidovits 1994). ...www.tececo.com/files/conference_papers/RoleofConcretePostKyotoUnrecognisedSequestrationSolution050805.pdf

World Mysteries - Popular Experts and AuthorsProfessor Joseph Davidovits is international renown French scientist, ... pyramids were constructed using agglomerated stone(limestone cast like concrete), ...www.world-mysteries.com/pex.htm - 49k

The Cheops mystery targeted with neutronsFile Format: PDF/Adobe Acrobat - View as HTMLFrench professor Joseph. Davidovits is convinced that. the pyramids were built. using blocks of cast stone. made in much the sameway. as concrete. (Photo: ...www.tudelft.nl/live/binaries/6922b368-6e23-4f5f-83d3-5704c656f613/doc/DO05-3-2cheops.pdf


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