• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    Composition for the consolidation of carbonated materials, method and uses. The present invention relates to a composition comprising Ca (OH)2 nanoparticles doped with fluorescent nanoparticles and a method that allows the consolidation of carbonated materials, be they constructional or decorative, as well as discern between the areas treated and not treated with the product and assess the degree of penetration of the consolidating treatment under the incidence of ultraviolet lighting, without this implying a visual damage to the consolidated material in the absence of it. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2766074A1
    申请号:ES201831200
    申请日:2018-12-11
    公开日:2020-06-11
    发明作者:Luna Javier Becerra；Partida Ana Paula Zaderenko；Calderón María Del Pilar Ortiz
    申请人:Universidad Pablo de Olavide；
    IPC主号:
    专利说明:

    [0001] COMPOSITION FOR THE CONSOLIDATION OF CARBONATED MATERIALS.
    [0004] FIELD OF THE INVENTION
    [0005] The present invention belongs to the sector of the restoration of any type of construction made of carbonated materials (stone and mortars), specifically to the technical field of new compositions for the consolidation of stones and other carbonated materials
    [0007] BACKGROUND OF THE INVENTION
    [0008] One of the main problems in monuments, constructions and archaeological sites is the loss of cohesion of the constituent materials, especially stone and mortars, which decreases the resistance of the material and its shapes and volumes.
    [0010] To avoid this alteration and provide the material with greater resistance, restorers usually use consolidating substances of diverse chemical nature, such as copolymers, alkoxysilanes, inorganic compounds, among others.
    [0012] These restoration treatments must meet certain requirements, highlighting their compatibility with the original material, their effectiveness and their ability to be discernible from the original. However, the treatments that are commonly used in the sector often suffer from one of these premises. For example, in the case of limestone, silicate-based consolidants, such as tetraethyl orthosilicate (TEOS) or ethylsilicate, have low material compatibility with carbonate matrices and low durability despite their high penetration [1, two].
    [0014] Polymeric consolidants, such as epoxy or acrylic resins, are often incompatible with the stone substrate, causing obstruction of the porous system, generating yellowing or favoring the appearance of biodeterioration [3-6]. Finally, inorganic consolidants, for example lime water, have high compatibility and great durability, albeit with low penetration and effectiveness [5-8].
    [0015] Reducing the size of the calcium hydroxide (Ca (OH) 2) particles to nanometric size, has allowed to improve the penetration of this inorganic consolidant, while maintaining the advantages of lime (compatibility and durability) [9, 10]. Its effectiveness as a pre-consolidant has been widely demonstrated on different types of support, especially on wall paint and stone [1,6,11-13]. However, its effectiveness, when a deep consolidation is required, has turned out to be low, leaving the treatment deposited on the surface, and consequently generating a whitish halo [14-16].
    [0017] This phenomenon is due to the fact that the Ca (OH) 2 nanoparticles tend to migrate to the surface during the solvent evaporation process [2,17]. Furthermore, a direct relationship has been established between the degree of penetration of the treatment and two factors, the pore size of the material to be consolidated and the kinetic stability of the colloid [18]. Controlling the kinetic stability of the colloid has allowed correcting the phenomenon of nanoparticle migration in the solvent evaporation process.
    [0019] In this sense, one of the main premises to follow before applying any consolidation treatment on a good must be to evaluate its effectiveness, ensuring that the precepts mentioned at the beginning of this section are met.
    [0021] Currently, experimentation, sampling and laboratory studies are required to evaluate the real penetration of treatments, with scanning electron microscopy with an X-ray dispersive energy detector (SEM-EDS) being the most common technique for Stratigraphic studies [1,7,19,20]. However, the main problem we found to evaluate the penetration of Ca (OH) 2 nanoparticles in stones and carbonate matrices is the use of materials with a chemical composition based on calcium, impossible to distinguish from the nanoparticles themselves.
    [0023] To avoid this problem, different solutions have been used, such as staining the solvents [21], the use of the phenolphthalein test [17,20] or the use of nanoparticles of different chemical composition as a marker [22]. However, these solutions do not provide a true picture of treatment penetration. For example, the front of the solvent is generally greater than that of the solute it carries.
    [0024] On the other hand, the use of dyes associated with the pH of the sample, that is, pH indicators such as phenolphthalein, can only be used while the pH of the sample is within the range of the indicator turn. In this case, once the carbonation process begins (transformation of Ca (OH) 2 into CaCO3), the initial basic pH (due to Ca (OH) 2) tends to drop until reaching values below the turning point (pKa ) of phenolphthalein, losing its pink coloration.
    [0026] Regarding the third case referring to the use of nanoparticles of different chemical composition as markers, since both the composition and the size of these nanoparticles are different from those of the treatment, it cannot be assumed that they have a similar behavior and, therefore, not they have to have the same penetration into the material.
    [0028] The present invention arises from the need to eliminate and / or minimize these problems, making available a product that allows a penetration analysis of the treatment to be carried out quickly, easily and reliably, without the need to carry out laboratory tests with complex equipment of use and expensive (as is the case with SEM-EDS).
    [0030] To do this, a procedure has been developed that allows the Ca (OH) 2 nanoparticles to be doped with fluorescent nanoparticles, for example, quantum dots or quantum dots (QDs). QDs are characterized by being nanoparticles of only a few nanometers in size that have a high luminescent efficiency [23] and that are widely used in other sectors such as nanosensors, cosmetic products, nano-optical objects, etc. [24.25]. Specifically, ZnO quantum dots, in addition to their potential as nanosensors, are stable, non-toxic, and inexpensive [24,26]. Furthermore, the excellent luminescent properties of embedded quantum dots in matrices such as silica are known [27].
    [0032] The fluorescent nanoparticles, and more specifically the QDs, allow creating a treatment that is easily evaluable, being necessary only to illuminate with ultraviolet light (UV) a cross section of the treated material to determine the actual penetration of the same. They also make consolidation treatments discernible by fluorescence.
    [0033] Compositions comprising Ca (OH) 2 doped with ZnO and TiO2 nanoparticles are known, however, they are only used for antifungal protection of limestone monuments [28].
    [0035] In summary, it can be concluded that the main problem that we find with current consolidants, and specifically with Ca (OH) 2 nanoparticles are:
    [0037] • The treatments currently used for the consolidation of carbonated materials do not meet all the requirements that must be demanded of restoration treatments, especially with regard to their compatibility, effectiveness and ability to be discernible.
    [0038] • Ca (OH) 2 nanoparticles are the most compatible treatment with materials of a carbonated nature. They have proven efficacy for surface pre-consolidation, however, this effectiveness is low when in-depth consolidation is required.
    [0039] • Evaluating the effectiveness of a restoration treatment involves carrying out laboratory tests and the use of complex and expensive equipment, which means that on many occasions such tests are omitted, applying treatments without a guarantee of being effective.
    [0040] • The evaluation of the penetration of a colloid by solvent staining, or the use of markers based on other independent nanoparticles added to the initial colloid, does not guarantee the evaluation of the actual penetration of the treatment.
    [0041] • Consolidation treatments are not discernible, without making a distinction between treated and untreated areas.
    [0043] DESCRIPTION OF THE INVENTION
    [0045] The present invention describes a composition and a method that allows the consolidation of carbonated materials, be they constructional or decorative, as well as distinguishing between the treated and untreated areas with the product and evaluating the degree of penetration of the consolidating treatment.
    [0046] It should be noted that in the present invention, consolidation is understood to be the procedure by which the degree of cohesion of a material is increased, reinforcing and hardening parts of this material that have suffered some kind of deterioration that produces an increase in porosity, cracks or cracks, in short, lack of cohesion of the material.
    [0048] In a first aspect, the invention relates to a composition for the consolidation of carbonated materials comprising Ca (OH) 2 nanoparticles doped with fluorescent nanoparticles. Additionally, this composition allows to analyze in situ the degree of penetration of the consolidant in said material, as well as to make the treatment discernible, thanks to the doping of the Ca (OH) 2 nanoparticles with fluorescent nanoparticles, for example, quantum dots.
    [0050] Another aspect of the present invention is that the fluorescent nanoparticles comprise at least one element of group VI of the periodic system, such as oxygen, sulfur, selenium or tellurium, in combination with at least one transition element, such as zinc or cadmium. .
    [0052] This consolidating treatment complies with the requirements of a conservation product (compatibility, effectiveness and durability), also giving it discernibility thanks to the fluorescence of quantum dots in the presence of ultraviolet light. In this way, the deficiencies detected in the state of the art are avoided, facilitating the work of studying the applicability and effectiveness of the consolidant in different materials, without requiring laboratory tests or the use of complex and expensive equipment in time and money.
    [0054] This is a relevant aspect of the present invention, since the main novelty, compared to the state of the art, is that fluorescent nanoparticles allow evaluating the penetrability of the consolidating treatment, since said particles are attached to the surface of the particles themselves. consolidant (Ca (OH) 2 nanoparticles) and, for this reason, travel with it, offering a truthful and reliable record of the degree of penetration.
    [0056] Another aspect of the present invention is that the composition may additionally comprise alkoxysilanes. Doping with fluorescent nanoparticles not only It does not interfere in the consolidation process, but rather makes it more effective thanks to the use, in a small amount, of an alkoxysilane as a stabilizing agent for quantum dots. Examples of alkoxysilanes used in the present invention are as follows: tetraethyl orthosilicate (TEOS), (3-aminopropyl) triethoxysilane (APTES) and / or (3-aminopropyl) trimethoxysilane (APTMS).
    [0058] Another aspect of the present invention is that a method of consolidation of carbonated materials is provided which comprises the application of the composition of Ca (OH) 2 nanoparticles doped with fluorescent nanoparticles by impregnating the carbonated material from the surface by brush, injection or spraying. , or through total or partial immersion thereof.
    [0060] Another aspect of the present invention is that the consolidation method may comprise an additional step for determining the degree of penetration by UV illumination of the carbonated material. To analyze the penetration in situ of the treatment, it is enough to take a chip from the treated area and analyze the cross section under UV illumination with a wavelength in line with the emission spectrum of the fluorescent nanoparticle used.
    [0062] The main advantage provided by the present invention over the usual consolidation methods is that, in addition to consolidating the material, it allows determining the degree of penetration of the consolidating treatment and, therefore, its effectiveness if a deep consolidation is required.
    [0064] Another aspect of the present invention is that the consolidation method may comprise an additional phase to determine the treated areas from those in which the consolidating treatment has not been applied, making the areas treated by fluorescence of the fluorescent nanoparticles discernible under the incidence of UV lighting, without this being a visual detriment to the consolidated material in the absence of UV light.
    [0066] This aspect is extremely important for heritage assets, so the present invention is of utmost importance in the field of restoration of buildings and other objects of heritage value, according to their chemical nature.
    [0067] Another aspect of the present invention is the use of the composition for the consolidation of carbonated materials.
    [0069] Another aspect of the invention is the use of the composition to determine the degree of penetration of the composition into the carbonated material.
    [0071] A final aspect of the present invention is the use of the composition to make visually discernible areas treated with the composition from those that have not.
    [0072] BRIEF DESCRIPTION OF THE FIGURES
    [0073] Figure 1. Shows the SEM image of the composition of Ca (OH) 2 nanoparticles doped with the quantum dots of ZnO (A) and EDS spectrum of the sample (B).
    [0075] Figure 2. Shows the SEM image of the Ca (OH) 2 nanoparticles doped with the ZnO quantum dots after 2 days of drying (A) and elemental mapping of calcium (B) and zinc (C) performed with EDS.
    [0077] Figure 3. Infrared spectrum of Ca (OH) 2 nanoparticles doped with quantum ZnO dots.
    [0079] Figure 4. Fluorescence spectrum of ZnO quantum dots (A) and image of fluorescence emitted under ultraviolet illumination (B).
    [0081] Figure 5. Shows an image of the surface of the untreated limestone (A), treated with Ca (OH) 2 (B) and after applying the composition of Ca (OH) 2 nanoparticles doped with the quantum dots of ZnO (C). Magnification of the image at 40x obtained by electronic magnifying glass.
    [0083] Figure 6. Shows an image under UV illumination of the cross section of a sample of untreated limestone (A), treated with Ca (OH) 2 (B) and after the application of the composition of doped Ca (OH) 2 nanoparticles. with ZnO (C) quantum dots after 20 days of drying.
    [0085] Figure 7. Shows the SEM image of the sample treated with a composition of Ca (OH) 2 nanoparticles doped by quantum dots of ZnO.
    [0086] DESCRIPTION OF MODES OF REALIZATION
    [0088] Having described the present invention, it is further illustrated by the following examples.
    [0090] Example 1. Obtaining a composition of calcium hydroxide nanoparticles doped with fluorescent zinc oxide nanoparticles
    [0092] In the present example, doping of calcium hydroxide nanoparticles with zinc oxide quantum dots is described. To a solution of zinc acetate in methanol (25 mL, 0.1 M) was added a solution of potassium hydroxide in methanol (10 mL, 2.5 M) under magnetic stirring. Continuously, a dispersion of Ca (OH) 2 nanoparticles in isopropanol (25 mL at 5 g / L concentration) was added and kept under stirring for 1 hour. After confirming the formation of the quantum dots under ultraviolet illumination, 250 pL of APTMS and 500 pL of MilliQ water were added. After the reaction, the pellet of the nanoparticles doped with quantum dots was recovered by centrifugation (5000 rpm, 10 min) and was resuspended in 25 mL of isopropanol for storage.
    [0094] This composition has been characterized by electron microscopy equipped with X-ray dispersive energy spectroscopy (SEM-EDS), Fourier transform infrared spectroscopy (FT-IR) and fluorescence spectroscopy.
    [0096] As can be seen in Figure 1A, the Ca (OH) 2 nanoparticles are characterized by being hexagonal nanoplates with an average size of 100 nm. ZnO quantum dots are small spheres of around 8nm distributed heterogeneously on the surface of Ca (OH) 2 nanoparticles. The presence of Zn was corroborated by EDS analysis, being able to also observe the peaks belonging to the Si, base of the product used for the stabilization of the QDs (Figure 1B). After two days of drying, the formation of the calcite crystals could be observed (Figure 2A), whose size is between 0.5 and 1 pm. The elemental analysis map (Figure 2B-C) allows us to observe that the quantum dots are distributed around these crystals without their presence having interfered with the carbonation process.
    [0097] In the infrared spectrum of the nanocomposite (Figure 3) after 10 days of drying, the vibrational bands characteristic of calcium carbonate (1456 cm-1) and 712 cm-1) [29] and calcite (876 cm-1) are observed by FTIR. ) [30]. Likewise, at 3643 cm-1 the vibrational band corresponding to the O-H bond present in Ca (OH) 2 is appreciable, indicating that the carbonation process has not yet concluded. Finally, the vibrational bands between 450-600 cm-1 have been identified as Zn-O bonds and those located at 890 cm-1 and 1000 cm-1 as the Si-OH and Si-O bonds, respectively. The fluorescence emission spectrum of the quantum dots (Figure 4A) in a suspension in methanol shows multiple bands in the visible, highlighting the peaks at 483 and 525 nm. Figure 4B shows the fluorescence of the described colloid.
    [0099] Example 2. Application of the consolidation method of carbonated materials of the present invention and determination of the degree of penetration
    [0101] The consolidation method was tested on samples of limestone from the quarry located in the municipality of El Puerto de Santa María (Cádiz) and which has been used in relevant historical buildings in southern Spain, such as the cathedral and the Seville city hall. This limestone is characterized by being a bio-calcarenite composed mainly of calcite and silica grains, whose pore diameter is between 10 and 100 gm [31]. Its open porosity was calculated according to the UNE-EN 13755 standard at 14%, while its capillary absorption coefficient calculated according to the UNE-EN 1925 standard was 179 g / m2.s05.
    [0103] For the test, specimens with a size of 2.5 x 2.5 x 2.5 cm were used, each test being carried out in triplicate. Likewise, for comparison, a composition of the present invention was applied, Ca (OH) 2 nanoparticles doped with quantum dots of ZnO (Ca (OH) 2 / ZnO) and another that only contained Ca (OH) 2 nanoparticles.
    [0105] The concentration used was 2.5 g / L of Ca (OH) 2 nanoparticles in isopropanol, making four brush applications of 0.94 mL of product each. The specimens were allowed to dry at room temperature (24oC ± 2) for 20 days.
    [0107] The samples were analyzed by means of photography with UV illumination (A = 254 nm) and visible, electronic magnifying glass, colorimetry, scanning electron microscopy equipped with X-ray dispersive energy spectroscopy (SEM-EDS) and peeling test.
    [0109] The application of both consolidating treatments implied a total increase in color (AE *) calculated according to the formula described in Becerra et al. [32] of around 2, being less than allowed for conservation treatments (<5). Figure 5 shows that, in fact, no change is observed in the surface of the treated material. Aggregates of nanoparticles are also not observed in the images obtained using an electronic magnifying glass (inserted images).
    [0111] The percentage of surface consolidation achieved with respect to the untreated specimens was 71% for the Ca (OH) 2 treatment and 95% for the Ca (OH) 2 / ZnO treatment. In this sense, an increase in the effectiveness of the treatment of 24% can be seen. The presence of ZnO quantum dots allowed analyzing the depth reached by the treatment in a cut of the cross section of the sample (Figure 6C), reaching a penetration of one centimeter.
    [0113] Figure 7 shows the formation of calcite crystals inside the rocky matrix.
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    权利要求:
    Claims (10)
    [1]
    1. Composition for the consolidation of carbonated materials, characterized in that it comprises Ca (OH) 2 nanoparticles doped with fluorescent nanoparticles.
    [2]
    2. Composition according to claim 1, wherein the fluorescent nanoparticles are quantum dots comprising at least one element of group VI of the periodic system in combination with at least one transition element.
    [3]
    3. Composition according to claims 1 to 2, characterized in that it further comprises a stabilizing agent which is an alkoxysilane.
    [4]
    Composition according to claim 3, characterized in that the alkoxysilane is selected from the group consisting of tetraethyl orthosilicate (TEOS), (3-aminopropyl) triethoxysilane (APTES) and / or (3-aminopropyl) trimethoxysilane (APTMS).
    [5]
    5. Method of consolidation of carbonated materials, characterized in that it comprises the application of the composition according to claims 1 to 4 by impregnating the carbonated material from the surface by brush, injection or spraying, or by total or partial immersion thereof.
    [6]
    6. Method of consolidation of carbonaceous materials according to claim 5, characterized in that it can comprise an additional step to discern between the treated and untreated areas by UV illumination of the carbonated material.
    [7]
    7. Method for consolidating carbonaceous materials according to claim 5 or 6, characterized in that it can comprise an additional step for determining the degree of penetration by UV illumination of the carbonated material.
    [8]
    8. Use of the composition according to claims 1 to 4, for the consolidation of carbonated materials.
    [9]
    9. Use of the composition according to claims 1 to 4, to determine the degree of penetration of the composition into the carbonated material.
    [10]
    10. Use of the composition according to claims 1 to 4, to distinguish between the treated and untreated areas with the consolidating composition.
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