WO2012175764A1 - Produit autonettoyant et consolidant pour des roches et d'autres matériaux de construction - Google Patents

Produit autonettoyant et consolidant pour des roches et d'autres matériaux de construction Download PDF

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Publication number
WO2012175764A1
WO2012175764A1 PCT/ES2012/000164 ES2012000164W WO2012175764A1 WO 2012175764 A1 WO2012175764 A1 WO 2012175764A1 ES 2012000164 W ES2012000164 W ES 2012000164W WO 2012175764 A1 WO2012175764 A1 WO 2012175764A1
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WO
WIPO (PCT)
Prior art keywords
gels
product according
particles
rocks
self
Prior art date
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Ceased
Application number
PCT/ES2012/000164
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English (en)
Spanish (es)
Inventor
María Jesús MOSQUERA DÍAZ
Luis Miguel FARIA SOARES PINHO DA SILVA
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Universidad de Cadiz
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Universidad de Cadiz
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Publication of WO2012175764A1 publication Critical patent/WO2012175764A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • 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
    • C11D3/162—Organic compounds containing Si
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3738—Alkoxylated silicones

Definitions

  • the product, object of this patent is able to provide rocks and other building materials with self-cleaning properties by their simple exposure to sunlight. In addition, it is capable of increasing the mechanical strength of the treated stone substrate. Finally, mention that it generates a hydrophobic coating on the rock that prevents the penetration of liquid water, the main vehicle of deteriorating agents.
  • the free radicals formed are capable of oxidizing organic matter, causing water and carbon dioxide as reaction residues.
  • titanium dioxide has been used with multiple applications, including the purification of air and water, as a bactericide and as a self-cleaning agent.
  • titanium dioxide on building materials begins in the early 1990s.
  • Titanium dioxide can be obtained from titanium alkoxides by a simple sol-gel process that ends with the sintering of the titanium coating on the substrate by a calcination process. This last stage of heating at high temperatures (above 450 ° C) promotes the growth of rutile and anatase crystals that have photocatalytic activity. In addition, it favors the adhesion of the gel to the substrate (Houmard M et al Surf. Sci. 602, 3364, 2008).
  • Ti0 2 photocallizer is, without a doubt, the commercial product Aeroxide Ti0 2 P25, marketed by Evonik (Corma A et al. Phys. Chem. Chem. Phys. 10, 769, 2008).
  • the product P25 consists of colloidal particles of titanium dioxide with a pore diameter around 21 nm and a specific surface area of 50 m 2 / g. After the application of P25 on a substrate, it is usually subjected to calcination to achieve sintering of the particles and, consequently, the formation of covalent bonds that give rise to a thermally and mechanically stable coating.
  • Adhesion to the substrate was achieved by integrating colloidal particles of titanium dioxide into a silica network. According to the literature and our own knowledge, to achieve the adhesion and stability of the coating of titanium particles it is essential to perform a sintering process by calcination. In our case, heating at high temperatures should be avoided because many rocks are unstable at these temperatures and also cannot be performed when the product has to be applied in situ in the buildings themselves.
  • the present invention relates to a composite material consisting of titanium particles integrated in a silica gel, which has photocatalytic activity. This new material creates a self-cleaning, consolidating effect on stone substrates and other building materials of a porous nature.
  • it is a product capable of: (1) providing the treated surface with a self-cleaning capacity by simple exposure to sunlight. (2) improve mechanical strength surface of the treated rock and (3) form a cohesive coating capable of adhering to the treated stone substrate.
  • the product that can be applied to the stone substrate by spraying, brush, roller, immersion, capillary ascent or other method is able to spontaneously polymerize on its surface and its pores, forming a silicon-titanium compound gel with self-cleaning capacity.
  • the starting colloidal solution contains a silicon oligomer, colloidal titanium particles and a primary amine in a proportion, relative to the silicon precursor, greater than its critical micellar concentration (eme).
  • VOCs volatile organic solvents
  • FIGURE 1 Scheme of the synthesis performed in the laboratory.
  • FIGURE 2 X-ray diffraction profiles of the xerogels under study.
  • FIGURE 3 - FTIR spectra of the xerogels under study.
  • FIGURE 4. Nitrogen adsorption-desorption isotherms of the xerogels under study.
  • FIGURE 5. Pore diameter distribution, according to BJH model, for the gels evaluated.
  • FIGURE 6. Scanning Electron Microscopy images of the films under study.
  • FIGURE 7. Scanning Electron Microscopy images of the stone surface before and after treatments.
  • FIGURE 8 Scanning Electron Microscopy images of the stone surface after the adhesion test.
  • the left part of each surface corresponds to the untested part and the right part to the surface where the test was performed.
  • EDX spectra are included on the side of each of the surfaces evaluated.
  • FIGURE 9 Average values of resistance to perforation of untreated rock and after the application of the selected products, depending on the depth of penetration.
  • FIGURE 10 Evolution of the color variation of the methylene blue spots on treated stone surfaces as a function of the exposure time to ultraviolet light. MODE OF EMBODIMENT OF THE INVENTION.
  • the synthesis of the product, object of the present invention includes the following steps: First, the silicon oligomer is mixed with the primary amine, then the colloidal particles of titanium dioxide are added. The entire mixing process is carried out by ultrasonic stirring, said stirring being maintained for ten minutes.
  • the silicon oligomer can be TES40 WN (Wacker) and the amine used in the synthesis, n-octylamine. Regarding the required concentrations of each component in the starting colloidal solution, mention that if the polymer precursor is Wacker TES 40 WN and the primary n-octylamine amine, the concentration of surfactant in the initial colloidal solution should be 0.22 M or higher , the critical micellar concentration of said surfactant being around 0.0065 M. For lower concentrations of n-octylamine, P25 aggregation occurs before the sol-gel transition occurs.
  • the next stage of the process is the impregnation of the material to be treated with the prepared sun.
  • the product can penetrate the substrate by impregnating the surface by spraying or by application by brush or brush.
  • spraying or by application by brush or brush.
  • brush or brush In the case of small-sized objects, 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.
  • condensation polymerization of the silicon oligomer occurs, resulting in a silicon-titanium composite.
  • example 1 the synthesis procedure is described and the characterization of the synthesized materials is carried out, in which the proportion of colloidal particles of titanium with respect to the solution was varied between 0 and 2% w / v.
  • Example 2 the same materials are applied to a limestone rock, an evaluation of its ability to adhere to the substrate and its effectiveness as a consolidant, self-cleaning and hydrophobic agent.
  • TES40 WN (hereinafter "TES40"), manufactured by Wacker and consisting of silicon oligomers with the primary amine, n-octylamine, was mixed. The proportion of octylamine with respect to TES40 was 0.37% (v / v).
  • P25 the Aeroxide Ti0 2 P25 colloidal titanium dioxide particles, marketed by Evonik (hereinafter "P25”) were added. Its average particle diameter is 21 nm and its specific surface area is 50 ⁇ 15 m 2 / g.
  • P25 the proportion of P25 with respect to TES40 was varied according to the following proportions: 0, 0.5, 1 and 2% (w / v).
  • the four prepared suns were subjected to ultrasonic stirring (power 125 W / cm 3 ) for 10 minutes. These products were called UCATiO followed by a number that indicates the proportion of titanium in the sun.
  • the gels were dried under laboratory conditions (20 ° C and 60% humidity), their characterization being carried out by means of the tests described in the following paragraphs.
  • FTIR Fourier Transformed Infrared Spectroscopy
  • the textural properties of the gels were evaluated by nitrogen fisisorption, using an Autosorb IQ device from Quantacrome Instruments.
  • Figure 4 shows the adsorption-desorption isotherms and in Figure 5, the pore diameter distributions obtained, using the BJH model.
  • the specific surface, porous volume and pore diameter data are shown in Table 1.
  • the nitrogen fisisorption test was performed on the commercial product P25, obtaining a type IV isotherm with hysteresis H1, typical of a material formed by aggregation of colloidal particles (pore diameter of 28 nm).
  • the gels containing phosphoric acid have type I isotherms, corresponding to microporous materials, with a slight hysteresis, characteristic of a type IV isotherm (mesoporous material). As can be seen in Figure 5, these materials show a distribution of pores located in the boundary between the micro- and mesoporous zone. All UCATiO gels show type IV isotherms, typical of porous materials according to the IUPAC classification, exhibiting a hysteresis type H1, characterized by adsorption and desorption branches practically vertical and parallel to each other.
  • this type of hysteresis is associated with materials formed by spherical particles, with a uniform pore distribution and high connectivity between pores (Kruk, M & Jaroniec M, Chem. Mater., 13, 3169, 2001).
  • porous volume mention that it is inferior, in the entire UCATiP series, to the volumes obtained for octylamine gels, confirming the role played by this surfactant in the formation of the porous network of the gel.
  • octylamine causes an increase in pore size compared to gels that do not contain this surfactant.
  • Figure 6 shows Scanning Electron Microscopy images of the films of the gels under study, obtained by means of a Quanta 200 Microscope from JEOL. At the magnification evaluated, there are significant differences in the morphology of the two series of synthesized gels. In particular, octylamine gels form a continuous and homogeneous film while phosphoric acid gels form a particular kind of aggregate in which a clear discontinuity is observed in the synthesized gels.
  • FTIR spectra Figure 3
  • Example 2 The products synthesized and characterized in Example 1 were applied to a limestone rock of high purity (98.5% calcium carbonate) in order to evaluate the consolidating and self-cleaning efficacy of the materials under study. The products were applied by spraying until saturation on rock specimens with dimensions 5X5X2 cm. The consumption and dry matter values obtained are gathered in Table 2.
  • the percentage of dry matter of the dispersions of P25 in water is significantly lower than that of the soles synthesized in our laboratory. This behavior is associated with the sedimentation of the P25 particles on the stone surface while the suns penetrate the porous structure of the rock, gelling in its pores, and therefore increasing the final percentage of dry matter. From a comparative point of view between gels, the residue of UCATiO gels was slightly higher than that obtained for UCATiP gels.
  • Figure 7 shows photographs, obtained by scanning electron microscopy (Quanta 200 Microscope of JEOL), of the stone surface before and after the application of the products.
  • P25 dipersions and phosphoric acid gels form completely fractured films on stone rocks while gels with octylamine produce homogeneous and fracture-free films that are integrated into the porous structure of the rock.
  • This fact confirms that octylamine is able to lower the capillary pressure of the gel during its drying stage to a sufficiently low value to avoid fracture formation.
  • This reduction in capillary pressure is due to two reasons: (1) decrease in surface tension of the sun. (2) Increase in the pore radius of the gel, as demonstrated in the results obtained by nitrogen fisisorcion.
  • n-octylamine in preventing fracture formation is discussed in more detail in previous publications of our group (Mosquera, MJ et al. Langmuir 2008, 24, 2772; Mosquera, MJ et al. Langmuir 2010, 26 , 6737).
  • the degree of adhesion of the products on the stone substrate was determined by an adhesion test, using a Scoth Magic tape (3M), according to methodology previously described by other authors (Ling L et al. Langmuir, 25, 3260, 2009; Ding , Z et al. Langmuir, 25, 9648, 2009).
  • the treated stone surfaces were subjected in one half of their surface to the adhesion test while the other half remained unchanged. This test simply consisted of placing the tape on the stone surface and then being manually removed, exerting similar pressure in all cases.
  • the changes in the surface of the rock were evaluated by visualization to the Electronic Scanning Microscope (Quanta 200 of JEOL), operating in low vacuum mode.
  • the adhesion of the UCATiP gels is superior to the P25 particles.
  • EDX results show a significant reduction in the percentage of titanium after the test.
  • the proportion of calcium from the stone substrate
  • a significant increase is observed after the test due to the disappearance of the gel surface film that does not contain calcium.
  • the proportion of calcium does not increase after the adhesion test because the titanium particles do not form a homogeneous coating on the surface and therefore, the calcium carbonate present in the rock can be perfectly identified before of the adhesion test.
  • the consolidating efficiency of the products on the stone substrate was evaluated using a microdrill, capable of determining the rock resistance based on the drilling depth, called “drilling resistance measurement system (DRMS)", supplied by Synth Technology.
  • DRMS drilling resistance measurement system
  • drill bits of 4.8 mm in diameter were used with a rotation speed of 200 rpm and penetration speed of 10 mm / min.
  • the drilling profiles obtained are shown in Figure 9.
  • the dispersions of P25 and phosphoric acid gels did not produce any increase in the mechanical strength of the rock.
  • octylamine gels a significant increase in said resistance is observed up to 4 mm penetration.
  • the surfaces treated with P25 particles show a degradation kinetics of methylene blue stains significantly faster than those obtained in silicon / titanium gels.
  • the color reduction of the stain occurs in the first 120 hours of exposure to ultraviolet light, presenting a similar kinetics for the different concentrations of particles evaluated.
  • the degradation kinetics is slower, achieving stability after 620 hours of exposure to ultraviolet radiation.
  • This reduction in photocatalytic kinetics is associated with the lower proportion of titanium in these coatings than in films consisting only of P25.
  • the inclusion of said particles in a silicon network could also reduce said activity. From a comparative point of view between gels, mention that the UCATiO series has a degradation rate higher than that of UCATiP gels.
  • the higher values of specific surface area and pore diameter presented by UCATiO gels with respect to the values obtained for the UCATiP series could be responsible for their greater efficacy as photocatalysts.
  • the stone surface is hydrophilic.
  • the P25 particles also produce hydrophilic surfaces with static angle values similar to the untreated sample, except for the film with the highest proportion of P25, which has a significant reduction in contact angle (by 30 °). This reduction makes it possible to assume that only the dispersion with the highest proportion of particles causes a continuous film on the stone surface.
  • these data reveal the known hydrophilic character of P25 films.
  • the product of the present invention has an industrial application as a rock protection treatment and in general, for the protection of any construction material of a porous nature.
  • the new product is able to increase the mechanical resistance of the rock and form a cohesive coating that adheres to the stone substrate.
  • Said coating has photocalitic activity and, consequently, has a self-cleaning effect in the presence of light.
  • this product is capable of creating a hydrophobic surface on the rock that prevents the penetration of liquid water into its porous structure.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un matériau composite constitué de particules de titane incorporées dans un gel de silice, qui possède une activité photocatalytique. Ce nouveau matériau produit un effet autonettoyant sur des substrats rocheux et d'autres matériaux de construction qui sont poreux. En fait, il s'agit d'un produit qui peut: (1) conférer à la surface traitée un pouvoir autonettoyant par une simple exposition à la lumière solaire; (2) améliorer sa résistance mécanique en surface; (3) former un revêtement cohésif capable de s'accrocher au substrat rocheux traité.
PCT/ES2012/000164 2011-06-24 2012-06-11 Produit autonettoyant et consolidant pour des roches et d'autres matériaux de construction Ceased WO2012175764A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES201100741A ES2394933B1 (es) 2011-06-24 2011-06-24 Producto auto-limpiante y consolidante para rocas y otros materiales de construcción.
ESP201100741 2011-06-24

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WO2012175764A1 true WO2012175764A1 (fr) 2012-12-27

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PCT/ES2012/000164 Ceased WO2012175764A1 (fr) 2011-06-24 2012-06-11 Produit autonettoyant et consolidant pour des roches et d'autres matériaux de construction

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WO (1) WO2012175764A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2610658B1 (es) * 2015-10-28 2018-02-07 Universidad De Cádiz Producto auto-limpiante, descontaminante y consolidante para materiales de construcción

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.
ES2265298B1 (es) * 2005-07-30 2007-12-16 Universidad De Cadiz Procedimiento para consolidar rocas y otros 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.

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.
ES2265298B1 (es) * 2005-07-30 2007-12-16 Universidad De Cadiz Procedimiento para consolidar rocas y otros materiales de construccion.

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ES2394933A1 (es) 2013-02-06
ES2394933B1 (es) 2013-12-11

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