WO2012127079A1 - Produit consolidant, hydrofugeant et anti-taches pour pierres carbonatées et autres matériaux de construction. - Google Patents

Produit consolidant, hydrofugeant et anti-taches pour pierres carbonatées et autres matériaux de construction. Download PDF

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Publication number
WO2012127079A1
WO2012127079A1 PCT/ES2012/000067 ES2012000067W WO2012127079A1 WO 2012127079 A1 WO2012127079 A1 WO 2012127079A1 ES 2012000067 W ES2012000067 W ES 2012000067W WO 2012127079 A1 WO2012127079 A1 WO 2012127079A1
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WO
WIPO (PCT)
Prior art keywords
product
pdms
rock
consolidating
rocks
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Ceased
Application number
PCT/ES2012/000067
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English (en)
Spanish (es)
Inventor
María Jesús MOSQUERA DÍAZ
Juan Francisco ILLESCAS SALINAS
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Universidad de Cadiz
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Universidad de Cadiz
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Filing date
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Publication of WO2012127079A1 publication Critical patent/WO2012127079A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
    • C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
    • C04B41/4966—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones" containing silicon bound to hydroxy groups, i.e. OH-blocked polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/25—Graffiti resistance; Graffiti removing

Definitions

  • Limestone rocks of high purity have a bright white color that makes them an exceptional building material.
  • its application in this field is very limited as a result of its low mechanical resistance and easy staining.
  • the present invention relates to a product, specifically designed for limestone rocks and carbonated rocks in general, which improves its surface properties, making the treated stone substrate an ideal building material for applications such as flooring, facades, cladding and other architectural elements.
  • the new product can be used, with the same applications, on non-carbonated rocks and in general, on any construction material of a porous nature.
  • TEOS tetraethoxysilane
  • the surfactant increases the pore radius of the gel, reducing the capillary pressure responsible for the fracture of the material.
  • alkoxysilanes as a binder and / or rock hydrophobe
  • calcium carbonate slows the sol-gel process, so that the evaporation of the sun occurs before the gelation process occurs in the pores of the rock.
  • Si-OH groups in the rock prevents condensation reactions between the applied product and the altered stone substrate (Wheeler G 2005 Alkoxysilanes and the Consolidation of Stone. The Getty Conservation Institute: Los Angeles, USA) and (Ferreira AP, Delgado J J. Cultural Heritage, 9, 38, 2008).
  • the present invention relates to a product, specifically designed for limestone rocks and carbonated rocks in general, which improves its surface properties, making the treated stone substrate an ideal building material for applications such as flooring, facades, cladding and other architectural elements. .
  • it is a product capable, through a single product and a single application, of: (1) improving mechanical properties, (2) water repellent, (3) increasing the stain resistance of carbonated rocks. (4) facilitate the cleaning of graffiti (anti-graffiti properties).
  • the product applied on the calcareous stone substrate is able to spontaneously polymerize in its pores, forming an organic-inorganic hybrid gel of mesoporous nature and uniform pore diameter.
  • the sol or starting colloidal solution contains, as an active principle, a polydimethylsiloxane with terminal OH groups (its content must be greater than 30% of the total volume of the solution), a silicon oligomer, a neutral catalyst and a non-ionic surfactant.
  • the resulting gel consists of a two-scale topography, consisting of the silicon matrix and the PDMS aggregates.
  • the combination of two roughness scales produces an increase in contact angles and reduces the hysteresis between forward and reverse angle. This reduction of hysteresis generates a decrease in the sliding force of the drop, causing repellent properties in the material.
  • the product of this patent also contains a surfactant that acts as a template for the pores of the gel, causing a mesoporous material and with uniform pores, which does not fracture during its drying stage.
  • FIGURE 1 Pore diameter distribution, according to BJH model, for organic-inorganic hybrid gels prepared in our laboratory.
  • FIGURE 2 FTIR spectra of the gels under study. The figure on the right corresponds to the extension of the indicated spectrum range.
  • FIGURE 4. Optical Microscopy images of the films under study.
  • FIGURE 5. Atomic Force Microscopy images of the films under study.
  • FIGURE 6. Pore diameter distribution of untreated rock and treated with the products under study.
  • FIGURE 7 Average values of puncture resistance as a function of the depth of penetration of the untreated rock and after the application of the selected products.
  • FIGURE 8 Average values of static contact angles and dynamic forward and reverse contact angles for stone surfaces treated with the materials under study.
  • FIGURE 9. Images, obtained by scanning electron microscopy (SEM) of untreated limestone rock surfaces and after treatment with the evaluated products.
  • FIGURE 10 Photographs of stains on the untreated rock surface: (A) without cleaning and cleaning performed (B) 5 minutes after staining, (C) 60 minutes after staining, (D) 24 hours after staining.
  • the product synthesis process includes the following steps: First, the silicon oligomer, the neutral catalyst, the surfactant and the organosiloxane added dropwise are mixed under stirring. Subsequently, the colloidal solution is homogenized by ultrasound, without at any time requiring the addition of solvents to the starting solution.
  • the silicon oligomer can be a commercial consolidant, such as Silres BSOH100 -which contains tetraethoxysilane oligomers and the dibutyltin dilaurate neutral catalyst-, and the Surfactant used in the synthesis may be a primary amine, such as n-octylamine.
  • organosiloxane a polydimethylsiloxane with terminal OH groups can be used.
  • concentration of the neutral catalyst in the colloidal solution must be less than 10% of its total volume to avoid spontaneous gelation of the product, since it must penetrate the pores of the rock before gelation occurs.
  • the silicon oligomer is Silres BSOH100 and the organosiloxane is polydimethylsiloxane with a polymerization degree of 12
  • the proportion of PDMS in the mixture must be equal to or greater than 30% Vol. Lower proportions form fractured gels and also the water repellent that provides The rock is scarce.
  • the next stage of the process is the impregnation of the material to be treated with the prepared colloidal solution.
  • the product can penetrate the substrate by impregnating the surface by spraying or by application by brush or brush.
  • the surface by immersion in a tank containing the sun, or by capillary rise through the surface contact of the product and the underside of the object.
  • co-condensation polymerization of the silicon oligomer and organosiloxane occurs.
  • an organic-inorganic hybrid polymer is formed, consisting of a silica network, in which the PDMS is sandwiched.
  • example 1 the synthesis procedure is described and the characterization of materials containing different proportion of PDMS is performed, between 14 and 56% Vol.
  • example 2 the same materials are deposited, as films, on plates of glass, assessing its hydrophobic properties, morphology and roughness.
  • Example 3 the aforementioned materials are applied to a limestone rock, an evaluation of its effectiveness as a consolidant, hydrophobic and stain repellent is performed.
  • example 4 one of the products is applied to a non-carbonated rock, in particular a granite, in order to check the effectiveness of the product on other types of rocks.
  • a commercial consolidating product, called Silres BSOH100, manufactured by Wacker and consisting of tetraethoxysilane oligomers and a neutral dibutyltin dilaurate catalyst was mixed with polydimethylsiloxane (PDMS).
  • PDMS polydimethylsiloxane
  • PDMS was used, with a polymerization degree of 12 and a percentage of OH groups ranging from 4 to 6% w / w of the total mixture, in four proportions of 14, 28, 42 and 56% of the total volume of the solution .
  • the n-octylamine surfactant was added at a concentration lower than its critical micellar concentration (0.14% of the total volume of the sun).
  • the three components were mixed by magnetic stirring, the PDMS being added dropwise.
  • the viscosity of the colloidal solutions experienced a gradual increase as the PDMS content of the mixture increased.
  • the increase in viscosity did not reach sufficiently high values to create penetration problems in any stone substrate under treatment.
  • the homogeneity of the gels obtained demonstrates that the condensation process is correct and that the PDMS has been perfectly integrated into the structure of the silicon gel.
  • FTIR Infrared Spectroscopy
  • Example 2 The products synthesized and characterized in Example 1 were deposited, as films, on glass plates in order to evaluate their hydrophobicity. They were applied on glass to avoid the alterations that a stone surface could cause on the surface properties of the studied materials, motivated by the roughness of the rock and / or water absorption in the pores of the stone.
  • the hydrophobic behavior of these materials was evaluated by measuring micro-droplet contact angles, using an OCA 15plus model video measuring device, supplied by Datsphysic Instruments. By this method, static angle and dynamic angles of forward and reverse were obtained.
  • the contact angle values obtained for the films under study are shown in Figure 3.
  • photographs of the microdrops are included, corresponding to the dynamic forward and reverse angles obtained.
  • the values of the angles obtained are included in Table 2.
  • Figure 4 shows the images, visualized under the Optical Microscope, of the films deposited on glass plates. Similar to the gels previously characterized, the OH100 and UCA14P films were fractured, while the rest of the materials did not show any fractures. As seen in the images, there is a modification of the morphology of the films as the PDMS content increases. The movie with Lower proportion of PDMS shows a surface with reduced roughness that increases, progressively, by increasing the proportion of PDMS in the film.
  • the product object of the present invention was applied to a limestone rock of a fossiliferous nature, composed of a micritic matrix containing grains of calcium carbonate, fragments of skeletons of mollusks, echinoderms and foraminiferae.
  • the mineralogical composition of the rock obtained by semiquantitative analysis by X-ray diffraction, is calcium carbonate (98.5%) and quartz-a (1.5%).
  • Another series of specimens of the same rock was impregnated with the two commercial products used in the previous examples: Silres BSOH100 consolidant and the Silres BS290 water repellent. The products were sprayed on tiles of dimensions 22X22X2 cm for a period of 1 minute.
  • Table 3 shows the absorption and dry matter values of the different products applied.
  • the dry matter value for the hydrophobic commercial product was significantly lower than the rest of the products evaluated because, only, it is capable of forming a film on the surface of the stone while the rest of the materials penetrate the porous structure of the rock and fill the pores of the stone material.
  • the UCA materials showed a higher dry matter content than the commercial consolidator OH100, the highest values corresponding to products with intermediate content in PDMS (UCA28P and UCA42P).
  • the slight reduction in dry matter observed in the product with the highest proportion in PDMS (UCA56P) could be associated with the higher viscosity of the colloidal solution, which could cause the penetration depth of this product in the rock to be slightly lower.
  • UCA products showed a significantly greater reduction in total porosity (Table 3) than the commercial consolidator OH100, which practically did not reduce the porosity of the rock. From a comparative point of view among UCA products, it is possible to establish that the total porosity gradually decreased with the increase in PDMS content. The largest reduction corresponds to the formulation that contains the highest proportion of PDMS (UCA56P). We discuss this trend in the following terms: the increase in PDMS in the starting solution accelerates gelation, increasing the residue content of the product in areas close to the surface of the rock, which are precisely those evaluated in this test.
  • the data correspond to average values and their corresponding standard deviations.
  • a reduction in the porous volume of the rock (diameter 1 ⁇ ) is observed, which increases as the PDMS content of the product increases.
  • smaller pores appear that show the reduction in pore size that the rock experiences after the mentioned treatments.
  • the consolidating efficacy of the products on the treated stone substrate was evaluated using a microdrill, capable of determining the resistance of the rock based on the drilling depth, called “drilling resistance measurement system (DRMS)", supplied by Synth Technology.
  • DRMS drilling resistance measurement system
  • Untreated rock is a hydrophilic material while the treated rock shows, in all cases, static angles greater than 90 °.
  • the stone surface has a significantly higher roughness than glass, which should increase the value of the contact angle obtained.
  • Figure 10 shows, as an example, photographs of untreated rock surfaces and stone surface treated with UCA56P, after staining and cleaning at the different times established in this study.
  • they are water repellent products, and for this reason, they are more effective when the staining agents have an aqueous base (glue, vinegar, wine and coffee).
  • stains of an aqueous nature it is possible to establish a direct relationship between hysteresis of forward / reverse angles of the products and resistance to staining of the treated surface.
  • Example 2 of this report shows the sliding force values of a drop on the film surface of the products, calculated from the hysteresis values.
  • micro drill used in example 3 of this report to evaluate the mechanical resistance of the rock, did not penetrate the granite substrate. For this reason, the vickers hardness on the untreated rock and after the treatments was evaluated. This test determines the surface hardness of the rock. In addition, the contact angle of the rock was determined before and after the application of the product.
  • the product object of the present invention has an industrial application as a protection treatment for carbonated rocks, and in general for any construction material of porous nature. Specifically, the new product is able to increase the mechanical resistance of the rock and act as a water repellent and anti-stain repellent on the treated stone surface.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention se rapporte à un produit conçu spécialement pour les pierres calcaires et les pierres carbonatées en général, améliorant leur propriétés superficielle et transformant le substrat de pierre traité en un matériau de construction adapté aux applications telles que pavages, façades, revêtements et autres éléments architectoniques. Concrètement il s'agit d'un produit qui permet, au moyen d'un seul produit et d'une seule application, (1) d'améliorer la résistance mécanique superficielle, (2) d'hydrofuger et (3) d'accroître la résistance aux taches, (4) de faciliter l'élimination de peintures (propriétés anti-graffitis). Ce nouveau produit peut être utilisé pour les applications indiquées ci-dessus, sur des pierres non carbonatées et de manière générale sur n'importe quel matériau de construction de caractère poreux.
PCT/ES2012/000067 2011-03-21 2012-03-21 Produit consolidant, hydrofugeant et anti-taches pour pierres carbonatées et autres matériaux de construction. Ceased WO2012127079A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES201100339A ES2388843B2 (es) 2011-03-21 2011-03-21 Producto consolidante, hidrofugante y repelente de manchas para rocas carbonatadas y otros materiales de construcción.
ESP201100339 2011-03-21

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WO2012127079A1 true WO2012127079A1 (fr) 2012-09-27

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WO (1) WO2012127079A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2915424B2 (es) 2020-12-21 2022-12-22 Univ Cadiz Producto para la protección de hormigón y otros materiales de construcción de naturaleza porosa

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2167628T3 (es) * 1996-02-15 2002-05-16 Wacker Chemie Gmbh Revestimientos autoimprimantes de materiales de construccion.
ES2319962T3 (es) * 2000-10-06 2009-05-18 E.I. Du Pont De Nemours And Company Emulsion y producto revestido con ella.
US8097307B2 (en) * 2005-07-30 2012-01-17 Universidad De Cádiz Method of strengthening stone and other construction materials

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2167628T3 (es) * 1996-02-15 2002-05-16 Wacker Chemie Gmbh Revestimientos autoimprimantes de materiales de construccion.
ES2319962T3 (es) * 2000-10-06 2009-05-18 E.I. Du Pont De Nemours And Company Emulsion y producto revestido con ella.
US8097307B2 (en) * 2005-07-30 2012-01-17 Universidad De Cádiz Method of strengthening stone and other construction materials

Also Published As

Publication number Publication date
ES2388843A1 (es) 2012-10-19
ES2388843B2 (es) 2013-12-12

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