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    • 专利摘要:
    Biocidal and consolidating product for construction materials. The present invention relates to a composite material consisting of copper oxide nanoparticles integrated in a silica gel, which possesses biocidal activity. This new material creates a consolidating, biocidal and hydrophobic effect on construction materials of porous nature. Specifically, it is a product capable of: (1) providing the treated surface with biocide and water repellent capacity, (2) improving its surface mechanical strength, (3) forming a cohesive coating capable of adhering to the treated substrate. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2652140A1
    申请号:ES201600631
    申请日:2016-07-29
    公开日:2018-01-31
    发明作者:Rafael ZARZUELA SÁNCHEZ；María Jesús MOSQUERA DÍAZ；María Luisa Almoraima GIL MONTERO；Jesús Manuel CANTORAL FERNÁNDEZ；Carlos GARRIDO CRESPO；María CARBU ESPINOSA DE LOS MONTEROS
    申请人:Universidad de Cadiz；
    IPC主号:
    专利说明:

     BIOCIDE AND CONSOLIDATING PRODUCT FOR CONSTRUCTION MATERIALS SECTOR OF THE TECHNIQUE. 5 The conservation of construction materials that make up both modern buildings and cultural heritage is a global challenge and involves significant efforts in the development of innovative materials. Construction materials, present in much of contemporary monuments and buildings, are often found in locations exposed to a multitude of processes that cause their deterioration. Biological factors can play a very important role in materials exposed to the outside (Dornieden TH et al., Int Biodeterior Biodegradation, 46, 261,2000; Ortega-Calvo JJ et al., Sci Total Environ., 167, 329 , 2000), especially the damages associated with the action of microorganisms such as bacteria, fungi and algae. The mechanisms of biological attack are varied and generally act in synergy with physical and chemical factors, causing structural and aesthetic damage to building materials. Therefore, it is interesting to develop effective protection strategies against the different degradation agents. 20 The product object of this patent is capable of providing building materials with a porous nature, biocidal properties and increased mechanical resistance. In addition, it is capable of generating a hydrophobic coating on the material that prevents the penetration of liquid water, so that its bioreceptivity decreases and greater resistance to degradation is granted by chemical agents. STATE OF THE TECHNIQUE. Some metal nanoparticles (eg Ag, Cu) are used in different fields for their biocidal activity. The biotoxicity of these systems is generally associated withion release in the medium and its reactivity (C. Loket al., J. Biol. Inorg. Chem., 12, 527, 2007; J. Liu, RH, Environ. Sci. Technol., 44, 2169, 2010 ). The release of these ions occurs in a very localized manner, so they have biocidal effects at concentrations below ppm (Y.L. Wang et al., Carbon, 5 36, 1567, 1998). In the specific case of the biocidal activity of the Cu + and Cu2 + ions, several possible mechanisms have been described: the formation of reactive radical species (JY Kimet al., WaterRes., 42, 356, 2008), the interaction with thiol groups of various biomolecules (L. Macomber et al., Proc. Natl. Acad. Sci. USA 106, 8344, 2009) and the displacement of iron or zinc ions from different proteins or 10 groups containing S atoms (Y.-N. Chang et al., Materials, 5, 2850, 2012). Due to its biocidal activity, there are several applications for applying nanoparticles of Ag or Cu metallic (YZ Wan et al., Carbon, 39, 1607, 2001; S. Zhang et al., Carbon, 42, 3209, 2004; L. Perelshtein et al., Surf. Coat. Technol., 204, 54, 2009; YS Yoshida et al., Biochim. Biophys. Acta, 1210, 81, 1993). 15 Currently, metal nanoparticles are used in different commercial products, such as gauze for wound treatment, anti-odor templates or deodorants. A limitation of the use of metal nanoparticles on building materials is their low interaction with the substrate, which leads to a low durability if no coupling agent is used (F. Bellissima et al., Environ. Sci. Pollut. Res Int., 21, 13278, 2014). A solution to this problem, as proposed in this patent, is to incorporate the particles into a matrix. This achieves two effects: (1) the active component is anchored to the substrate, giving the coating durability. (2) the release of active species occurs at a controlled rate, which reduces losses of the biocidal material through leaching processes. These types of particles have been successfully integrated into various matrices such as plastic polymers (N. Cioffi et al., N. Chem. Mater., 17, 5255, 2005) and hydrogels (S. Cometa et al., J. Bioact. Compat. Polym., 28, 508, 2013). 30 Copper oxide (CuO), like metallic Cu, has biocidal properties. Because of this, it has been used as the active component in paints for the protection of boat hulls against the growth of organisms. As with the reduced form (Cuo), the CuO shows an increase in theBiocidal activity when it is in the form of nanoparticles (O. Bondarenko et al., Environ. Pollut., 169, 81, 2012). Despite showing lower reactivity, CuO nanoparticles have a number of advantages over the metallic form: (1) Their cost is lower, since their production is simpler and does not require inert atmosphere or special storage processes. (2) They have high stability. Cu and Ag nanoparticles are especially sensitive to oxidation, partially oxidizing with atmospheric oxygen. On the other hand, metal nanoparticles are generally photosensitive, which accelerates their oxidation (K. Awazu et al., J. Am. Chem. Soc., 130, 10, 1676,2008). (3) They are more inert, so that they can be incorporated into different matrices without suffering alterations such as total or partial redisolution of the particles. There are works in which CuO nanoparticles have been used on different materials as a biocidal agent: as textile fibers (S. Anita et al., Text. Res. J., 15 81,1081,2011), plastics (K. Delgado et al., Lett. Appl. Microbiol., 53, 50, 2011) or paints (F. Perreault et al., Nanotoxicology,. 8, 374, 2014). However, its use on construction materials is not described, as we propose in the patent presented. The conservation strategies for construction materials, currently used, focus on the use of water-repellent products, based on alkyl siloxanes, and biocides, often applied separately. However, the separate application of these products may cause unwanted interference, reducing their effectiveness (Moreau C. et al., J Cult. Herit., 9, 394, 2008). In addition, the biocidal treatments on most popular building materials, such as quaternary ammonium salts and phenolic compounds such as benzalkonium chloride (Stupar et al., South African J. Bot., 93, 118, 2014), are not of preventive nature, but applied once the material is colonized. Given this situation, it is of special interest to develop products, such as the one proposed in this patent, which can combine the different effects in one application: hydrophobic and biocide. Additionally, a step to improve conservation treatments is the development of products that do notonly act as protection against biological agents, but as consolidators and modifiers of porosity and surface roughness. Apart from the previously mentioned treatments, there are works on the biocidal effect of photoactive products based on Ti02 (C. Kapridaki et al., Prog. 5 Org. Coatings., 76, 400, 2013; Aflori et al., Mater. Sci. Eng. B., 178, 1339,2013). Although this type of treatment has activity, it is totally dependent on the lighting conditions, which may limit its range of application. In recent years, our research group has designed a strategy to avoid fractures in silicon gels that has been the subject of a patent (No. 10 P200501887 / 2) and a publication (Mosquera MJet al, Langmuir, 24, 2772, 2008). This synthesis is based on the addition of a surfactant that acts as a template for the pores of the material, creating a nanomaterial with uniform pore size. This route allows to obtain monolithic gels due to two reasons: (1) The surfactant increases the pore radius of the gel, reducing the capillary pressure responsible for the fracture of the material. (2) The reduction of surface tension caused by the surfactant also reduces the value of capillary pressure. Subsequently, our research team has modified this synthesis process in order to obtain other products with new applications. Specifically, we have designed a consolidating / hydrophobic product by adding a polydimethylsiloxane (PDMS) to the polymeric silicon precursor (TEOS) in the presence of n-octylamine. This product has also been the subject of a patent of invention (No. P200702976). In addition, we have developed a product specifically designed for carbonated rocks, capable of increasing the mechanical resistance of the rock, water repellent and increasing its resistance to staining (Patent application No. P201100339). Finally, the organic solvent has been removed from the synthesis process (1Ilescas J.F., Mosquera M.J., App. Mat. Interf., 4, 4259, 2012). According to the background, the objective of our work, which has originated the present invention patent, focused on the development of a 30 CuO-Si02 composite nanomaterials that combine consolidating properties andbiocides They also have the ability to adhere to the substrate and form a fracture-free coating, improving effectiveness and durability. Based on our previous knowledge, the synthesis was performed in the presence of n-octylamine to avoid the formation of fractures in the coating. The 5 CuO nanoparticles were integrated by adding them in solid form in the synthesis process. With this process the amount of CuO in the product can be modified without introducing water or other reagent into the process, which would modify the final properties. In order to achieve a biocidal material that retains the structural / textural properties of the matrix, it is essential to optimize the content of CuO nanoparticles. It is important that the particles are well dispersed and distributed evenly within the material. In addition, the formulation should promote short gelation times to prevent precipitation of CuO. For this reason, it was necessary to develop an exhaustive 15 research work to obtain the material with the desired properties. In this study it was concluded that products with high concentrations of CuO had less biocidal effect due to agglomeration and precipitation of CuO. 20 DESCRIPTION OF THE INVENTION. The present invention relates to a composite material, consisting of copper oxide nanoparticles (11) integrated in a silica gel, which has biocidal activity. This new material causes a biocidal, consolidating effect and reduces water absorption on building materials of a porous nature. This new material manages to eliminate the inconveniences presented by commercial biocides (discussed in the background of this report). Specifically, it is a product capable of: (1) providing the treated surface with resistance against the growth of microorganisms. (2) improve resistancesurface mechanics of the material and (3) form a cohesive coating capable of adhering to the treated substrate. The product that can be applied on the substrate by spraying, brush, roller, immersion, capillary rise or other method is capable of spontaneously polymerizing on its surface and its pores, forming a Si02-CuO compound gel with biocidal and consolidating capacity. The product is synthesized by a sol-gel process. In an initial stage, a starting sun is synthesized, assisting the process with ultrasound. Said sun, once applied on the substrate, spontaneously gels under ambient conditions, without the need for additional curing treatments. The starting sol contains a silicon oligomer, CuO nanoparticles, water and a primary amine in a proportion, relative to water, greater than its critical micellar concentration (eme). During the synthesis, a small amount of water is added to the starting sun. Two reasons have led to the addition of water: (1) Water acts by accelerating the hydrolysis reaction of the silica precursor. In this way, the obtained sun shows a slight increase in viscosity, but its gelation is also accelerated and the colloidal stability of the copper oxide nanoparticles it contains is increased. Likewise, the sol-gel transition 20 is completed without precipitation or aggregation of the nanoparticles, obtaining uniform gels. (2) Water also affects the structure of the final material, by means of its addition obtaining mesoporous materials with pores of greater size, greater porous volume and greater surface area. Because 25 reverse micelles are formed in the sun. Thirdly, it is important to highlight that the material object of this patent does not contain any volatile organic solvent (VOCs). In this way, contamination problems are avoided by evaporation of these compounds during the application phase.The novelty presented by the process object of this invention compared to other synthesis of biocides already known, is based on the development of a method that allows the inclusion of the CuO particles within the silica matrix that acts as a consolidant. Obviously, the modifications developed in the synthesis process 5 are key to its application as a biocide consolidant. 10 15 20 25 DESCRIPTION OF THE FIGURES FIGURE 1.-FIGURE 2.-FIGURE 3.-FIGURE 4.-FIGURE 5.-FIGURE 6.-Comparison of particle sizes of synthesized soles, obtained by light scattering spectra dynamic (OLS), for increasing amounts of CuO with respect to the silica precursor. CuOOO, without nanoparticles (black). Cu050, 0.05% pN (red), Cu150, 0.150% pN (blue) and Cu150, 0.350% pN (green). Comparison between nitrogen adsorption-desorption isotherms and their corresponding pore distribution for the same material by varying the proportion of water during its synthesis. Schematic representation of the synthesis process. Comparison between nitrogen adsorption-desorption isotherms and their corresponding pore distribution of synthesized materials for increasing amounts of CuO with respect to the silica precursor. CuOOO, without nanoparticles (black). Cu050, 0.05% pN (red), Cu150, 0.150% pN (blue) and Cu150, 0.350% pN (green). HRTEM images of the compounds synthesized for increasing amounts of CuO with respect to the silica precursor. (A) CuOOO, without nanoparticles. (B) Cu050, 0.05% pN, (C) Cu150, 0.150% pN Y (O) Cu150, 0.350% pN. Results obtained by representing the resistance to perforation versus depth, for the untreated sample (fuchsia) and the samples treated with CuOOO products, without nanoparticles5 10 15 FIGURE 7.-FIGURE 8 .- (black). Cu050, 0.05% pN (red), Cu150, 0.150% pN (blue) and Cu150, 0.350% pN (green). Images of the plates containing the synthesized compounds in contact with the cultures. On the right are those of the E. coli bacteria and on the left those corresponding to S. cerevisiae yeast for increasing amounts of CuO, CuOOO, without nanoparticles Cu050, 0.05% pN, Cu150, 0.150% pN and Cu150, 0.350 % pN, after 5 and 7 days of incubation. Results obtained in the bacterial count for E. coli bacteria (right) and S. cerevisiae yeast (left), representing the number of colony forming units (CFU) per milliliter, and the percentage of inhibition for samples treated with quantities increasing CuO, CuOOO, without nanoparticles Cu050, 0.05% pN, Cu150, 0.150% pN and Cu150, 0.350% pN. MODE OF CARRYING OUT THE INVENTION. The synthesis of the product, object of the present invention, includes the following steps: First, the silica precursor is mixed with the 20 CuO nanoparticle powder and dispersed in an ultrasonic bath. The optimal time depends on the equipment used, the volume of synthesis and the proportion of CuO. The CuO scattering process can be monitored with techniques such as dynamic light scattering. An example of a study in which an optimal time of 15 minutes was determined is shown in Figure 1. The primary amine is added to the silica, water and nanoparticle precursor mixture of CuO and the mixture is kept under ultrasonic stirring with a high power probe for 10 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 sun, it is necessary tomention that if the polymer precursor is Wacker TES 40 WN and the primary n-octylamine amine, the concentration of surfactant in the initial sol should be 0.22 M or higher, the critical micellar concentration of said surfactant being around 0.0065 M. lower concentrations of n-octylamine, aggregation and / or precipitation of the nanoparticles occurs before the sol-gel transition occurs. In the case of copper oxide, commercial nanopowders can be used, available in several commercial houses (eg CuO nanopowder childbirth Size <50 nm, Sigma-Aldrich) or nanoparticles prepared in the laboratory. Its proportion in the 10 sun must be between 0.05 and 0.35% w / v, since for higher concentrations there is a significant increase in the agglomeration and precipitation of the CuO particles and also the gels that form They become fragile. The formation of large agglomerates at high CuO loads leads, in turn, to notable color changes in the materials treated with the product. 15 The water content in the sun must be between 0 and 1.67%, being the optimum of the improvement of its characteristics around 0.83% (Figure 2), more water produces an excessively rapid gelation which prevents the application of products to porous materials. 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 means of a roller or brush. In the case of small objects, by immersion in a tank containing the sun, or by capillary ascent by superficial contact of the product with the underside of the object. After impregnation, condensation polymerization of the silicon oligomer occurs, resulting in a CuO-Si02 composite. A scheme of the synthesis process is shown in Figure 3. Next, and in order to illustrate in more detail, the advantages of the products incorporating CuO nanoparticles, results obtained in our research laboratory are described. Specifically, in example 1 the synthesis procedure is described and the characterization of thesynthesized materials, in which the proportion of CuO nanoparticles with respect to the silica precursor was varied between 0.05 and 0.35% pN. In Example 2, the same materials are applied on a porous calcareous rock with a minor proportion of silicon minerals, with an evaluation of its ability to adhere to the substrate and its effectiveness as a consolidator and biocide. EXAMPLE 1 A copper oxide nanopowder (CuO nanopowder childbirth Size <50 nm, Sigma-Aldrich) was mixed with TES40 WN (hereinafter "TES40"), manufactured by 10 Wacker and constituted by silica oligomers, varying the proportions of CuO between 0.05% and 0.35%. The mixture was then subjected to insonation in an ultrasonic bath for 15 minutes (it was determined as the optimal time by DLS measurements as shown in Figure 1). Immediately afterwards, the water and the primary amine, n-octylamine, the proportions of water and octylamine with respect to TES40 were added 0.83% and 0.36% (v / v) respectively. Additionally, a sun without CuO nanoparticles was prepared for comparative purposes. The five suns prepared were subjected to ultrasonic stirring (power 2 W / mL) for 10 minutes. The proportions of the different components (expressed in% w / v with 20 with respect to the silicon oligomer) were 0.28% for n-8 and H20 respectively. In addition, increasing amounts of CuO (0.00%, 0.05%, 0.15% and 0.35%) were added. The nomenclature used indicates the proportion of CuO present in the products. From lowest to highest content of CuO CuOOO, Cu050, Cu150 and Cu350. In order to check if the viscosity of the synthesized soles is suitable for application on building materials, its measurement was performed using a rotational viscometer. The temperature of the experiment was 25 ° C. Table 1 shows the viscosity values obtained.Table 1 Viscosity Appearance time Precipitation (mPa · s) Gelification (hours) CuOOO 4.87 ± 0.03 48 Monolithic N / A Cu050 4.59 ± 0.11 24 Monolithic No Cu150 4.66 ± 0.23 12 Monolithic No Cu350 4.63 ± 0.04 8 Moderate Monolithic * Refers to the presence of precipitate in the xerogel All soles have a Newtonian behavior in the evaluated range (linear regression ¡-2> 0.99). It was observed that the addition of CuONPs slightly decreases S viscosity with respect to the product that does not contain them (CuOOO). However, the increase in the proportion of CuO in the range studied does not produce significant changes. The low viscosity values obtained suggest that the products have the capacity to penetrate the porous structure of construction materials similar to that of commercial products and can be applied to these materials by common techniques (brush, spray, etc.) (Carrascosa et al., Nanotechnology., 27, 095604, 2016; L. Pinho et al., Appl. Catal. B Environ., 178, 144, 2014). Next, all the soles prepared in the laboratory were deposited as a film, by a Pasteur pipette, on plastic Petri dishes. All 15 soles spontaneously gelled under laboratory conditions (25 ° C and 50% humidity). The gelation times, shown in Table 1, decrease significantly as the proportion of CuO increases, taking values ranging from 48 hours for the CuOOO to 8 hours for the Cu350. In addition, the xerogel obtained from the CuOOO compound has a gummy consistency, while the xerogels become more rigid as the amount of CuO increases, which is consistent with obtaining a more crosslinked solid. This effect suggests that the CuO has an active catalytic role in the sol-gel transition. The activity of the CuO in the sol gel process can be explained, taking into account its basic character (R. K. Das et al., Ultrason. Sonochemistry., 26, 210, 2015). On the one hand, theThe presence of Cu2 + ions released by the oxide can accelerate the condensation process since positively charged ions interact with the anions [SiO (OH) xr formed in the basic reaction medium (H. Palza et al., Appl. Surto Sci. , 357, 86, 2015 .; YH Kim et al., J. Phys. Chem. B., 110, 24923, 2006). 5 This leads to a neutralization of repulsive electrostatic forces and can promote the formation of Si02 nuclei by agglomeration (C.C. Huang et al., J. Non. Cryst. Solids., 381, 1, 2013) where condensation thrives. On the other hand, the gelation process was fast enough to avoid the precipitation of CuO for Cu050 and Cu150, since they have a homogeneous appearance (indicating that the 10 CuONPs are uniformly distributed in the siliceous structure). In the case of the material with the highest proportion of CuO (Cu350), precipitation of nanoparticles is observed due to the formation of agglomerates. The data presented demonstrate the suitability of the synthesized compounds for application on building materials. The gelation time is short enough even for on-site applications, and long enough to allow the sun to penetrate the pore network of the material. Next, a study was carried out by Nitrogen Fisisorption and Transmission Electron Microscopy (TEM), in order to determine the influence of the amount of CuO, on the structure of the synthesized compounds. The isotherms and the pore size distribution obtained are shown in Figure 4. All isotherms correspond to type IVa, characteristic of mesoporous solids according to the classification established by the I.U.PAC. (M. Thommes et al., Pure Appl. Chem. 87, 1051, 2015). The hysteresis cycle corresponds to type H2a, gradually changing to type H1, as 2S increases the amount of CuO. According to these results, it follows that increasing the amount of CuO in the compound promotes interconnectivity between the pores. Additionally, in the pore size distribution there is a tendency to the formation of smaller pores in the compounds with larger amounts of CuO. 30 The images obtained by Transmission Electron Microscopy (Figure 5) confirm these results, showing:1) The formation of materials composed of a network of packed nanometric particles, where the particle size tends to decrease (Table 2) as the amount of CuO added increases. This slight decrease in particle size may explain the decrease in pore size, since the formation of smaller particles leads to smaller pores. 10 2) A tendency towards the formation of spherical nanoparticles of Si02, by increasing the CuO content. Particle formation more regularly explains the changes observed in hysteresis cycles. The connectivity between the pores is greater for the more spherical particles. Table 2 Volume Size Surface area particle Si02 * (m2 / g) pore (cc / g) (nm) CuOOO 217.733 0.578 20-30 Cu050 187.089 0.433 15-25 Cu150 268.353 0.579 15-20 Cu350 289.935 0.572 10-15 * Measures in the TEM images The results previously discussed show that CuO plays a predominant role in the sol gel process. The release of Cu2 + ions can IS promote the formation of nucleation centers (Huang et al., J. Non. Cryst. 20 Solids., 381, 1, 2013). A growth per seed explains the progressive decrease in the size of the Si02 particles as the CuO content increases, as the number of nuclei present increases, which causes the increase of Si02 particles produced, preventing their growth.EXAMPLE 2 The products synthesized and characterized in Example 1 were applied on 5X5X2 cm specimens of a limestone rock (45% calcite, 37% dolomite and 7% quartz) with a porosity of 19%, in order to evaluate the consolidating efficacy and Biocide 5 of the materials under study. The products were applied by spraying until saturation was reached and subsequently the excess surface was removed with air. The difference of the values of consumption and dry matter obtained for the different formulations are negligible, being respectively on average 0.52% w / w 0.33% w / w. 10 To evaluate the hydrophobic properties, an important factor in the protection of stone materials that may decrease their bioreceptivity, the static contact angles of water droplets (SCA) and water absorption by capillarity (WAC) of the samples were measured treated, obtaining the percentage of absorbed water (TWU). As observed in Table 3, all treatments show a significant increase in hydrophobic properties with respect to the untreated stone, although there are no notable differences between them. Table 3 --- WAC SCA (0) (kg. M · 2 • h. 1/2)% TWU 5.69 ± Untreated * n / a 5.83 ± 0.85 0.05 0.13 ± CuOOO 99.7 ± 5.4 0.11 ± 0.03 0.03 100.1 ± 0.14 ± Cu050 0.10 ± 0.04 2.7 0.02 0.14 ± Cu150 99.5 ± 2.0 0.11 ± 0.02 0.01 104.1 ± 0.13 ± Cu350 0.10 ± 0.03 0.6 0.02 * Untreated rock absorbs water preventing measurement.Next, using a reflection spectrophotometer for solids, with the following conditions: illuminant D65, observer 100 and CIEL standard * a * b *, the total color differences (6E *) experienced by the samples after application of the samples were determined products, which are collected in Table 4. This 5 parameter is very important since high color changes are perceptible by the human eye and limits the application of products to demanding fields such as heritage conservation (M. Drdácky et al , Mater. Struct., 45, 505, 2012). Table 4 shows how the CuOOO and Cu350 treatments have color difference values above the limit value of human perception (6E *> 5). However, Cu050 and Cu 150 have lower values. 15 In order to evaluate the consolidating effect of the products on the stones, the puncture resistance was measured (Figure 6). All treatments increase the mechanical strength between 10 and 14 mm deep. Table 4 Peeling test Vickers hardness Product AE * (mg / cm2) (Kgf / mm2) CuOOO 5.86 ± 0.45 0.5 ± 0.3 47.5 ± 6.1 Cu050 3.88 ± 0.76 0 , 2 ± 0.1 49.2 ± 6.6 Cu150 2.49 ± 0.78 0.4 ± 0, 1 59.0 ± 3.7 Cu350 9.21 ± 0.39 0.9 ± 0.1 48.7 ± 6.5 The degree of adhesion and cohesion of the products on the stone substrate was determined by measuring Vickers hardness and by adhesion test, using an adhesive tape, according to methodology previously described by other authors (Ling L et al. Langmuir, 25, 3260, 2009; Ding, Z et al. Langmuir, 20 25, 9648, 2009). The treated stone surfaces and their untreated counterpart were subjected to the adhesion test. Said test, called "peeling test", consisted of placing the adhesive tape on the stone surface and then being removed manually, exerting similar pressure in all cases. Table 4 shows the degree of hardness Vickers obtained that inAll cases are larger than the untreated sample, being for the Cu050 and Cu150 samples of the order of 20-24% higher than the untreated sample. These results and the agreement between them confirm the integration of the product inside the stone structure, and its effectiveness as a consolidant. 5 Finally, the biocidal efficacy of the products was evaluated against E. coli bacteria and S. cerevisiae yeast, both in the xerogels and in the treated samples. Figure 7 shows the plates for different times (0-7 days) of contact with the corresponding crops. As can be seen, the turbidity of the medium decreases as the amount of CuO in the compounds 10 increases demonstrating the inhibitory / biocidal effect of the CuNPs embedded in the siliceous matrix. After checking the biocidal effects of the synthesized xerogels, a quantitative test was carried out on the treated samples, to evaluate the biocidal effectiveness. The results obtained (Figure 8), are similar for both microorganisms. It can be seen how the addition of CuO increases its effectiveness with respect to the sample that does not contain CuO. The treatment with Cu150 is the most effective, reaching an inhibition of 86.5% for E. coli and 77.6% for S. cerevisiae. On the other hand, stones treated with Cu350 show a marked decrease in inhibition, with lower values than those obtained with the product 20 Cu050. INDUSTRIAL APPLICATION The product of the present invention has an industrial application as a protection treatment for any construction material of a porous nature. In concrete, the new product is able to increase the surface mechanical strength of the material and form a cohesive coating that adheres to the stone substrate. Said coating has biocidal and hydrophobic activity all 
    权利要求:
    Claims (8)
    [1]
    CLAIMS 1. Consolidating, biocide and hydrophobic product for the treatment of construction materials of a porous nature that comprises: • A silicon oligomer or a hydrolyzed alkoxysilane. 5 • Copper oxide particles. • A non-ionic surfactant in a concentration greater than its critical micellar concentration.
    [2]
    2. Product according to claim 1 where the non-ionic surfactant is a primary amine, preferably n-octylamine. 10
    [3]
    3. Product according to claims 1 and 2, where the concentration of n-octylamine in the starting sol must be 0.22 M or higher.
    [4]
    4. Product according to claim 1, where the concentration of the copper nanoparticles must be such that the proportion varies between 0.05% and 0.35% plv. fifteen
    [5]
    5. Process for obtaining the product according to claims 1 to 4, which consists of mixing a silica oligomer or a hydrolyzed alkoxysilane, with n-octylamine, copper oxide particles, subjecting the mixture to ultrasound stirring.
    [6]
    6. Use of the product according to claims 1 to 5 for the protection of any construction material of a porous nature.
    [7]
    7. Use of the product according to claims 1 to 5 to increase the mechanical resistance of construction materials of a porous nature and form a cohesive coating that adheres to the stone substrate.
    [8]
    8. Use of the product according to claims 1 to 5 to provide a biocidal effect to building materials of a porous nature.
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    公开号 | 公开日
    ES2652140B2|2018-06-01|
    WO2018020058A1|2018-02-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP2367552A1|2008-12-10|2011-09-28|University Of Central Florida Research Foundation, Inc.|Silica-based antibacterial and antifungal nanoformulation|
    ES2423356A1|2012-02-16|2013-09-19|Universidad De Cádiz|Product for protecting and restoring rocks and other construction materials|
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    ES201600631A|ES2652140B2|2016-07-29|2016-07-29|Biocidal and consolidating product for building materials.|ES201600631A| ES2652140B2|2016-07-29|2016-07-29|Biocidal and consolidating product for building materials.|
    PCT/ES2017/000034| WO2018020058A1|2016-07-29|2017-03-22|Biocidal hardening product for construction materials|
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