FR2831882A1 - GEOPOLYMERIC STONE FOR CONSTRUCTION AND DECORATION, ANALOGUE OF APPEARANCE TO NATURAL STONE - Google Patents

Abstract

Geopolymer stone for construction and decoration comprises 65-95 wt.% rock residues derived from naturally weathered rock and/or eroded detrital rock and 5-35 wt.% of a poly(sialate), poly(sialate-siloxo) and/or poly(sialate-disiloxo) geopolymer binder. An Independent claim is also included for production of the geopolymer stone by hardening a mixture of the rock residues and a geopolymer comprising sodium, potassium and calcium aluminosilicates.

Description

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The present invention relates to a new type of reconstituted stone for use in construction and decoration. This reconstituted stone is called geopolymeric stone because the agglomeration binder is based on mineral geopolymer, consisting of alkaline aluminosilicates, better known as poly (sialate), poly (sialate-siloxo) and / or poly (sialate-disiloxo).

Prior art.

The reconstituted stones are in the prior art manufactured by agglomerating mineral fillers either with organic binders or with hydraulic binders based on lime and portland cement. Stones made with organic binders can not be intended for outdoor use because it is known that the organic resin matrix is not resistant to UV and IR radiation. This type of reconstituted stone is found mainly in the form of artificial marble slabs, inside buildings. Stones reconstituted with hydraulic binders are UV and IR stable and are used outdoors, but their decorative appearance is relatively poor. But, being made of matrices sensitive to chemical attack of acids, these stones, usually based on limestone, are very quickly attacked by atmospheric pollution.

 Binders based on mineral geopolymer, consisting of alkaline aluminosilicates, better known as poly (sialate), poly (sialate-siloxo) and / or poly (sialate-disiloxo), do not have the defects. presented by organic binders and traditional hydraulic binders. They are stable to UV and IR, and are very resistant to acids.

The term poly (sialate) has been proposed to designate aluminosilicate geopolymers.

The sialate network consists of SiO4 and AlO4 tetrahedra alternately linked by oxygen atoms. The cations (Na +, K +, Ca ++, H3O +) present in the structural cavities of the poly (sialate) balance the negative charge of Al3 + in coordination (IV). The empirical formula of Polysialates is: M {- (SiO-A10, wHO, where M is the cation K, Na or Ca and n is the degree of polymerization, z is 1, 2, 3 or more, up to 32. three-dimensional network (3D) polymers are of type:

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<Tb>
<tb> Poly <SEP> (sialate) <SEP> Mn <SEP> - <SEP> (-Si-O-AI-O-) <SEP> n <SEP> M-PS <SEP> If <SEP>: <SEP> Al = l <SEP>: <SEP> 1
<tb> Poly <SEP> (sialate-siloxo) <SEP> Mn- <SEP> (Si-O-Al-O-Si-O-) <SEP> n <SEP> M-PSS <SEP> If <SEP >: <SEP> AI = 2 <SEP>: <SEP> 1
<tb> Poly <SEP> (sialate-disiloxo) <SEP> Mn- <SEP> (Si-O-Al-O-Si-O-Si-O-), <SEP> M-PSDS <SEP> If <SEP>:<SEP> AI = 3 <SEP>: <SEP> 1
<Tb>

minérales, avec les géopolymères, on a réalisé différents objets décoratifs, comme des objets ZD moulés (statues, bas-reliefs). Cependant, la matière finale obtenue ne reproduit pas les caractéristiques d'une pierre naturelle. Plus généralement, la charge minérale a une granulométrie fine, car l'expérience montre que l'emploi de charges de dimension importante (comprise entre 1 mm et 10 mm) s'accompagne irrémédiablement d'un aspect béton . En effet, comme il est fait usage de matériaux broyés et sélectionnés, la forme anguleuse des grains ne permet pas d'obtenir une densification optimale, laissant toujours en évidence une zone non cristalline entre les grains (voir la figure 1). Au contraire, dans le cadre de la présente invention, on utilise des roches résiduelles naturellement altérées, non broyées, permettant de réaliser une pierre dont la structure est reproduite par la figure 2. Geopolymers of the poly (sialate), poly (sialate-siloxo) and / or poly (sialatedisiloxo) type have been the subject of several patents highlighting their particular properties. For example, the French patents FR 2 489 may be mentioned. 290.2. 489,291, 2,528. 818.2. 621,260, 2.659. 319.2. 666.253, 2.758. 323. Using various charges

Minerals, with geopolymers, we realized different decorative objects, like molded ZD objects (statues, bas-reliefs). However, the final material obtained does not reproduce the characteristics of a natural stone. More generally, the mineral filler has a fine grain size, because experience shows that the use of large loads (between 1 mm and 10 mm) is irreparably accompanied by a concrete appearance. In fact, since crushed and selected materials are used, the angular shape of the grains does not make it possible to obtain optimal densification, always leaving in evidence a non-crystalline zone between the grains (see FIG. 1). On the contrary, in the context of the present invention, naturally altered, unmilled residual rocks are used, making it possible to produce a stone whose structure is reproduced in FIG.

suit nous utilisons les définitions géologiques et pétrographiques suivantes tirées de l'ouvrage ZD Zn Précis de Pétrographie de Jean Yung, Masson et Cie Editeurs, Paris, 1969 : - roche altérée : roche ayant subi une altération superficielle principalement due à l'infiltration des eaux acides (eau de pluie, acides humiques). DESCRIPTION OF THE INVENTION The main object of the invention is to manufacture a geopolymeric stone for construction and decoration, having an appearance similar to natural stone. In what

following we use the following geological and petrographic definitions taken from ZD Zn Précis de Petrographie by Jean Yung, Masson et Cie Editeurs, Paris, 1969: - weathered rock: rock having undergone a superficial alteration mainly due to the infiltration of water acids (rainwater, humic acids).

 - residual rock: the superficial alteration gives rise to two kinds of substances, some solid, others passed in solution. Solids accumulated on site form a residual rock.

 - arkose: a variety of feldspathic sandstone in which, next to the quartz grains, the feldspar mineral is in grain the size of which is similar to that of the original granite feldspars.

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 - Pellitic cement sandstone: besides the grains of quartz, there are numerous grains of feldspar, as well as microconglomerate grains of hard rocks, composite grains. The cement is made of quartz particle dust, feldspar, mica, kaolinite ..

 - arena: in regions with a temperate climate, granites are commonly transformed, by superficial weathering, into a sandy rock called the arena.

 - test: shell, shell, shell of shellfish and crustacean limestone.

siloxo) et/ou poly (sialate-disiloxo). Par exemple, les pierres géopolymèriques en grès ZD analogue aux roches naturelles appartenant à la classe des grès à ciment siliceux ou des grès à Zn ciment pellitique sont constituées de 75 à 95% en poids d'arène quartziques et/ou feldspathiques, non broyée et de 5 à 25% en poids de liant roche résiduelle géopolymèrique de type poly (sialate), poly (sialate-siloxo) et/ou poly (sialate-disiloxo). The main object of the invention is the description of geopolymeric stones for construction and decoration, similar in appearance to natural stone, which consist of 75 to 95% by weight of residual rock from a naturally occurring rock. altered, unmilled and from 5 to 25% by weight of poly (sialate) type geopolymeric binder, poly (sialate-

siloxo) and / or poly (sialate-disiloxo). For example, ZD stoneware geopolymer stones similar to natural rocks belonging to the class of siliceous cementitious sandstones or Zn pellitic granite consist of 75 to 95% by weight of quartz and / or feldspathic arena, unmilled and from 5 to 25% by weight of geopolymeric residual binder of poly (sialate), poly (sialate-siloxo) and / or poly (sialate-disiloxo) type.

 The geopolymeric calcareous stones are of calcareous type with foraminifers similar to the natural rocks belonging to the class of limestones with organisms. They consist of 75 to 95% by weight of a mixture of tests and uncrushed sand and 5 to 25% by weight of poly (sialate), poly (sialate-siloxo) and / or poly-type geopolymeric binder. (sialate-disiloxo). Among the rocks with granitic aspect, the geopolymeric stones are of arkose type, that is to say similar to the natural rocks belonging to the class of arkoses. They consist of 75 to 95% by weight of unmilled granitic arena and 5 to 25% by weight of poly (sialate), poly (sialate-siloxo) and / or poly (sialate-disiloxo) geopolymeric binder.

Pour réaliser une pierre selon l'invention il ne faut pas employer de matériaux géologiques tD broyés mécaniquement en usine, comme c'est traditionnellement le cas dans la fabrication des "marbres artificiels". Au contraire, la pierre géopolymèrique selon l'invention est obtenue en utilisant des roches résiduelles qui sont employées telles qu'extraites du sol, ou au plus après avoir subit une simple opération de lavage des poussières. Il n'y a pas de broyage, tout au plus Best ways to achieve the invention

To make a stone according to the invention do not use geological materials tD milled mechanically in the factory, as is traditionally the case in the manufacture of "artificial marbles". On the contrary, the geopolymeric stone according to the invention is obtained by using residual rocks which are used as extracted from the soil, or at the most after having undergone a simple operation of washing the dust. There is no grinding, at most

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une désagrégation des mottes, pour faciliter le lavage et l'élimination des matières parasites z (terre, humus, etc.).

a disintegration of the clods, to facilitate the washing and the elimination of parasitic materials (earth, humus, etc.).

 The geopolymeric stones of the invention as well as their manufacturing process are illustrated by the following Examples. These examples are not limiting on the overall scope of the invention as presented in the claims. All parts shown are by weight.

Example 1: A machine is used daily to make artificial marble tiles or artificial granite. This machine consists of a hydraulic press in which there is also a vibrating table and a vacuum bell. The aggregates are crushed and milled granite with an optimal grain size to leave the least void between the grains. The vibrating table makes it possible to place the grains and the vacuum bell to eliminate the air bubbles included in the binder. For artificial marble, the binder is an organic resin (acrylic or polyester) and for artificial granite, the binder is hydraulic cement. Instead of these traditional binders is now used a geopolymeric cement type (K, Ca) - Poly (sialate-siloxo) as for example that described in French Patent FR 2,666,253.

 80 parts of aggregates are mixed with 18 parts of geopolymeric cement and 2 parts of black pigment. The whole is placed in the mold and then under the vibrating press, and the vacuum is applied. The compressed tile is then allowed to cure at 60 deg. C for 2 hours.

Then we proceed to the finishing operation which consists of sanding and then polishing. An artificial black granite tile, the structure of which is represented in FIG. 1, is obtained: a amorphous phase consisting of cement and fines is clearly distinguished between the angular grains.

On fait un mélange contenant 484 parties de granit broyé dont la granulométrie s'étale de ZD 0.05mm à 7mm, avec 90 parties de ciment géopolymérique (K, Ca)- (poly (sialate-siloxo) et 30 parties d'eau. Ce mélange est introduit dans un moule sous lequel on applique une vibration pour permettre un bon tassement. On fait durcir pendant une journée à la température ambiante et ensuite on démoule. La pierre est ensuite laissée dans un sac plastique fermé, pendant 1 semaine. On découpe à la scie diamantée. La structure de la pierre est similaire à Example 2

A mixture containing 484 parts of crushed granite, the particle size of which is spread from ZD 0.05 mm to 7 mm, with 90 parts of geopolymeric cement (K, Ca) - (poly (sialate-siloxo) and 30 parts of water. The mixture is introduced into a mold under which a vibration is applied to allow a good compaction, is cured for one day at room temperature and then demolded.The stone is then left in a closed plastic bag for 1 week. The structure of the stone is similar to

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 that of Figure 1: there is clearly between the angular grains an amorphous phase consisting of cement and fines.

Example 3
In a heavily weathered granite deposit where highly advanced kaolinization results in a kaolin separation industry, a granite arena is chosen which contains less than 10% by weight of kaolinite. This granitic arena consists of free quartz grains, free feldspar grains, free muscovite mica, and residual kaolinite. A mixture containing 500 parts of this granite arena is made with 100 parts of geopolymeric cement (K, Ca) - (poly (sialate-siloxo) and 30 parts of water, cured at 80 ° C. for 2 hours and then stripped. The stone is then left in a closed plastic bag for 1 week Diamond cutting is done The structure of the stone is similar to that of Figure 2: an extremely dense crystalline structure is obtained, each grain being coated with a thin amorphous layer of kaolinite converted into tecto-alumino-silicate by geopolymerization The stone obtained is of the arkose type.

EXAMPLE 4 The procedure is as in Example 4, but instead of taking the granite arena, the kaolin extraction residue is used. In fact, when the granite arena is rich in kaolin (of the order of 30% by weight for example), this kaolin is extracted by decantation in water. The remaining heavy parts constitute a residual granitic arena containing at most 2% by weight of kaolin. This residue is used as in Example 3. The structure of the stone is similar to that of Figure 2; each grain is coated with a very thin amorphous layer of geopolymeric binder. The stone obtained is of the arkose type.

 To make a limestone geopolymer stone, we will choose a naturally altered shell limestone. For example, to make a nummulite-type foraminiferous limestone, a mixture containing 75 to 95% by weight of naturally weathered, unmilled limestone consisting of free tests and free-testing calcareous sand with 5 to 25% by weight will be cured. a geopolymeric resin of sodium, potassium and calcium aluminosilicates generating, after curing, a geopolymeric binder of the poly (sialate), poly (sialatesiloxo) and / or poly (sialate-disiloxo) type.

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 In the case of fine-textured sandstones, a very weak quartz-bearing arena site will be chosen which easily breaks up by simple pressure. The addition of the geopolymeric cement results in the manufacture of a siliceous cement stoneware or more particularly of a pellitic cement stoneware.

 The geopolymeric stones according to the invention can be used as decorative or protective covering, in statuary and other decorative object. In the construction they can be used as exterior cladding, in the form of tiles, blocks, bricks. You can also put the geopolymeric mixture in the bottom of the mold and pour on either traditional concrete or cellular concrete, or apply a block of dense concrete or cellular already hardened. The connecting element between the geopolymeric stone layer and the dense or cellular concrete core is the geopolymeric binder.

 Of course, various modifications may be made by those skilled in the art methods and geopolymeric stones that have just been described by way of example, without departing from the scope of the invention.

Claims (7)

Claims: 1) Geopolymeric stone for construction and decoration, similar in appearance to natural stone, characterized in that it consists of: a) 75 to 95% by weight of residual rock from a naturally occurring rock weathered, unmilled; b) 5 to 25% by weight of poly (sialate), poly (sialate-siloxo) and / or poly (sialate-disiloxo) geopolymeric binder. 2) geopolymer stone sandstone, according to claim 1), similar to natural rocks belonging to the class of siliceous cement sandstone or sandstone pellitic, characterized in that it consists of: a) 75 to 95% by weight; quartz and / or feldspathic arena weight, unmilled; b) 5 to 25% by weight of geopolymeric residual binder of poly (sialate), poly (sialate-siloxo) and / or poly (sialate-disiloxo) type. 3) Geopolymeric stone foraminiferal limestone, according to claim 1), similar to natural rock belonging to the class of limestones organisms, characterized in that it consists of: a) 75 to 95% by weight of a mixture of tests and calcareous sand, unmilled; b) 5 to 25% by weight of poly (sialate), poly (sialate-siloxo) and / or poly (sialate-disiloxo) geopolymeric binder. 4) arkose-type granite geopolymeric stone, according to claim 1), similar to natural rock belonging to the class of arkoses, characterized in that it consists of: a) 75 to 95% by weight of granite arena unmilled; b) 5 to 25% by weight of poly (sialate), poly (sialate-siloxo) and / or poly (sialate-disiloxo) geopolymeric binder. 5) A method of manufacturing a limestone geopolymer stone according to claim 3), characterized in that when the foraminifer is of nummulite type, this nummulitic limestone is obtained by curing a mixture containing: <Desc / Clms Page number 8>  a) 75 to 95% by weight of naturally weathered limestone, unmilled, consisting of - free tests - calcareous sand with free tests b) 5 to 25% by weight of a geopolymeric resin of sodium aluminosilicates, potassium and calcium generating, after curing, a geopolymeric binder of poly (sialate), poly (sialate-siloxo) and / or poly (sialate-disiloxo) type. 6) A method of manufacturing a geopolymeric granite stone arkose type according to claim 4), characterized in that one obtains this granite stone arkose by curing a mixture containing: a) 75 to 95% by weight of granite arena naturally altered, unmilled, consisting of free quartz grains, free feldspar grains, free mica (muscovite and / or biotite), residual kaolinite, b) 5 to 25% of a geopolymeric resin of sodium, potassium and calcium aluminosilicates generating, after curing, a geopolymeric binder of the poly (sialate), poly (sialate-siloxo) and / or poly (sialate-disiloxo) type. 7) A method of manufacturing a granite geopolymer stone arkose type according to claim 6), characterized in that the granite arena is made of the waste resulting from the extraction of kaolin, from naturally altered granites.