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    • 专利摘要:
    Graphene hybrid materials and coatings. The invention relates to a hybrid material that is an electrical conductor, has self-healing capacity, is resistant to mechanical deformation, thermal ablation, corrosión, and oxidation, and has improvements in both toughness and impact resistance. In addition, the invention relates to a coating comprising the hybrid material and a suitable substrate having good adhesion to the material. In addition, the present invention relates to a process for obtaining the hybrid material and the coating system by thermal spray techniques. Finally, the present invention relates to the use of the hybrid material or the coating system as a component or part of a component of protection systems used in aeronautical, aerospace and nuclear plant applications, as well as the use of the hybrid material or the coating as unión interface in electronic and energy systems. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2597157A1
    申请号:ES201530803
    申请日:2015-06-09
    公开日:2017-01-16
    发明作者:Eugenio Santiago GARCÍA GRANADOS；Andrés NISTAL GONZÁLEZ；Mª Antonia SAINZ TRIGO；María Isabel OSENDI MIRANDA；Pilar MIRANZO LÓPEZ
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Aernnova Engineering Division SA；
    IPC主号:
    专利说明:

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    DESCRIPTION
    The invention relates to a warm material, which is an electric conductor, has a self-repairing capacity, is resistant to mechanical deformation, thermal ablation, corrosion, and oxidation, and presents improvements in both toughness and impact resistance. . In addition, the invention relates to a coating system comprising the warm material and a suitable substrate that exhibits good adhesion with the material. Moreover, the present invention relates to the method of obtaining the warm material and the coating system by thermal projection techniques. Finally, the present invention relates to the use of the warm material or the coating system as a component or part of a component of protection systems used in aeronautical, aerospace and nuclear power applications, as well as the use of the warm material or the coating system as a union interface in electronic and / or energy systems.
    STATE OF THE TECHNIQUE
    In the last decade, carbon nanostructures have been considered as reinforcing agents in inorganic matrix composites due to their excellent mechanical, electrical and thermal properties. Specifically, graphene has attracted great attention due to its extraordinary properties [A. K. Geim, K. S. Novoselov, The rise of graphene, Nat. Mater., 6 (2007), 183-191] and the advantages associated with its high specific surface and essentially flat nature. Also, stacks of several layers of graphene (i.e., nanoplatelets, sheets, etc.), with a thickness in the range of 0.3-100 nm, are commercially available fillers for composite materials and, in addition, are potentially less toxic than carbon nanotubes [Y. Zhang, S.F. Ali, E. Dervishi, Y. Xu, Z. Li, D. Casciano, A.S. Biris, Cytotoxicity effects of graphene and single-wall carbon canotubes in neural Phaeochromocytoma-derived PC12 cells, ACS nano, 4 (2010) 3181-3186].
    With the incorporation of graphene-based fillers (GF) in glass-ceramic or glass matrix coatings, similar improvements in properties - electrical, thermal, tribological, mechanical, etc. - can be expected to those observed in ceramic matrix composite materials [H. Porwal, S. Grasso, M.J. Reece, Review of
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    graphene-ceramic matrix composites, Adv. in Appl. Ceram 112 (2013) 443-454]. Vitroceramic and vitreous coatings are effective for the protection of components subjected to corrosion and high temperature oxidation, also showing self-repairing capacity. The incorporation of GF would also add additional thermal and electrical functionalities, improving the performance of these materials. However, research on glass / GF and ceramic / GF glass coatings is still very scarce.
    Some efforts have been made to develop thin films of ceramic compounds - SiO2, TiO2 and hydroxyapatite (HA) - with graphene on metal and vitreous substrates, using different deposition techniques such as spin-coating in English literature of precursors sol-gel [S. Watcharotone, DA Dikin, S. Stankovich, R. Piner, I. Jung, GHB Dommett, G. Evmenenko, SE Wu, SF Chen, CP Liu, S T. Nguyen, RS Ruoff, Graphene-Silica Composite Thin Films as Transparent Conductors, Nano Letters, 7 (2007) 1888-1892], tape cocking [Y. Kusumawati, MA Martoprawiro, Th. Pauporte, Effects of Graphene in Graphene / TiO2 Composite Films Applied to Solar Cell Photoelectrode, J Phys. Chem. C 118 (2014) 9974-9981], electrophoretic deposition [M. Li, Q. Liu, Z. Jia, X. Xu, Yan Cheng, Y. Zheng, T. Xi, S. Wei, Graphene oxide / hydroxyapatite composite coatings fabricated by electrophoretic nanotechnology for biological applications, Carbon, 67 (2014) 185-197], pro cold injection in vado ("cold vacuum spray") and supersonica ("supersonic kinetic spraying") [Y. Liu, Z. Dang, Y. Wang, J. Huang, H. Li, Hydroxyapatite / graphene-nanosheet composite coatings deposited by vacuum cold spraying for biomedical applications: Inherited nanostructures and enhanced properties, Carbon 67 (2014) 250-259, D.Y. Kim, B. N. Joshi, J.J. Park, J.G. Lee, Y.H. Cha, T.Y. Seong, S.I. Nohb, H.J. Ahnc, S.S. Al-Deyabed, S.S. Yoon, Graphene-titania films by supersonic kinetic spraying for enhanced performance of dye-sensitized solar cells, Ceram. Int. 40 (2014) 11089-11097 and J.G. Lee, D.Y. Kim, J.J. Park, Y.H. Cha, J.Y. Yoon, H.S. Jeon, B.K. Min, M. T. Swihart, S. Jin, S.S. Al-Deyab, S.S. Yoon, Graphene-titania hybrid photoanodes by supersonic kinetic spraying for solar water splitting, J. Am. Ceram. Soc., 97 (2014) 36603668]. However, all these works are focused on optoelectronic or biomedical applications. Also with biomedical applications, plasma ford projection has been used in an attempt to produce thicker coatings based on biomaterials of calcium silicate with graphene nanoplaquets (Graphene nanoplatelets, GNPs) [Y. Xie, H. Li, C. Zhang, X. Gu, X. Zheng, L Huang, Graphene-reinforced calcium silicate coatings for load-bearing implants, Biomed. Mater. 9 (2014) 025009 (7pp)]. Finally, coatings of ZrO2 / GNPs compounds have also been produced using atmospheric pressure plasma projection [H. Li, Y. Xie, K. Li, L. Huang, S. Huang, B. Zhao, X. Zheng,
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    Microstructure and wear behavior of graphene nanosheets (GNs) -reinforced zirconia coating, Ceram. Int. 40 (2014) 12821-12829].
    Glasses and vitroceramics based on yttrium aluminosilicates (YAlSiO) are known for their high temperature of glass transition and their good resistance to chemical corrosion [M.J. Hyatt, D.E. Day, Glass Properties in the Yttria-Alumina-Silica System, J. Am. Ceram. Soc. 70 (10) (1987) C283-287], also showing moderate thermal expansion coefficients and high viscosity [M.A. Sainz, P. Miranzo, M.I. Osendi, Sintering behavior and properties of YAlSiO and YAlSiON glass-ceramics, Ceramics International 37 (2011) 1485-1492].
    DESCRIPTION OF THE INVENTION
    The invention relates to a reinforced material, which is an electric conductor, has a self-repairing capacity, is resistant to mechanical deformation, thermal ablation, corrosion and oxidation, and presents improvements in both toughness and impact resistance.
    In addition, the invention also relates to a coating system comprising the hybrid material and a suitable substrate that exhibits good adhesion with the hybrid material. For example, because the protective properties of the hybrid material are of special interest in aeronautical, aerospace and nuclear plants applications, a good adhesion of the hybrid material with the substrates known to those skilled in the art employed in aeronautical, aerospace and technical applications is desirable. nuclear plants.
    Moreover, the present invention relates to the method of obtaining the coating system by thermal projection techniques. The advantages of carrying it out through this procedure are the following:
    - The good dispersion of the graphene-based filler material within the thermally projected granules on the suitable substrate favors the survival of a high proportion of the graphene-based filler material after projection.
    - During the thermal projection, when the fusion of the material occurs, the graphene-based filler material inside the granules migrates to the surface, so that the graphene-based filler material is oriented parallel to the lamellae (flattened drops that form the coating), locating
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    along the interleaves between lamellae, and forming an interconnected network in the coating system.
    An advantage of coating systems is that they are easily replaceable. By means of thermal projection techniques the repair or replacement of the coating system can be carried out on-site.
    Finally, the present invention relates to the use of the hybrid material or of the coating system as a component or part of a component of protection systems, acting as self-repairable materials, electromagnetic shields, thermal or against corrosion, functional coatings provided with electrical conductivity, and / or anti-ice system in aeronautical, aerospace and nuclear power applications, as well as the union interface in electronic and / or energy systems.
    A first aspect of the present invention relates to a dibido material (herein, the material of the invention) characterized in that it comprises:
    • a graphene-based filler material
    • and a glass or a ceramic hob
    and said hybrid material is characterized by forming a stack of glass or glass ceramic lamellae, where graphene-based filler material
    • is oriented parallel to the lamellae,
    • is located in the interleaves between lamellae,
    • forms an interconnected network.
    The term "graphene-based filler material" refers herein to single-layer, low-layer or multilayer structures of graphene oxide, total or partially reduced graphene oxide, or graphene. Said graphene-based filler material it has a thickness between 0.3 and 100 nm. Preferably, for graphene nanoplates the thickness varies between 0.5 and 100 nm.
    Glass and ceramic hobs are thermal and electrical insulators, so that the main objective of adding graphene-based filler material to a glass or hob is to provide thermal and electrical conductivity. The thermal and electrical conductivity is preferably favored in a specific direction, such as the plane in which a graphene-based filler material, such as graphene nanoplates, is oriented.
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    Example of glasses are RE2O3-Al2O3-SiO2, RE2O3 - AlN-SiO2, RE2O3 - Al2O3-Si3N4-SiO2, RE2O3 - Al2O3-SiC-SiO2 and RE2O3 - SiC-AlN-SiO2, where RE is an element of rare earths like La, Gd, Y or Lu.
    Examples of ceramic hobs are RE2O3 - Al2O3-SiO2, RE2O3 - AlN-SiO2, RE2O3 - Al2O3-Si3N4- SiO2, RE2O3 - Al2O3-SiC-SiO2 and RE2O3 - SiC-AlN-SiO2, where RE is an element from rare earths like La, Gd, Y or Lu.
    The hybrid material forms a stacking of the glass or glass ceramic lamellae, where the graphene-based filler material
    • is oriented parallel to the lamellae,
    • is located along the interleaves between lamellae,
    • and forms an interconnected network.
    In a preferred embodiment, the graphene-based filler material is in a volume percentage between 2% and 15% relative to the final volume of the hybrid coating.
    In a preferred embodiment, the glass or hob is in a volume percentage between 85% and 98% with respect to the final volume of the hybrid coating.
    Another aspect of the present invention relates to a coating system (herein, the coating of the invention), characterized in that it comprises
    • the material of the invention,
    • a substrate,
    • and, optionally, an adherent layer located between the hybrid coating and the substrate.
    The coating substrate of the invention is preferably selected from a list consisting of SiC, reinforced SiC composite materials comprising carbon fibers, reinforced carbon composite materials comprising carbon fibers and reinforced Si3N4.
    In a preferred embodiment, the coating has a thickness between 50 ^ m and 500 ^ m, more preferably between 100 ^ m and 200 ^ m.
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    If other substrates were used, for example, substrates with low adhesion to the material of the invention, then, in this coating system an adherent layer located between the hybrid coating and the substrate can be used.
    Examples of adherent layers for substrates with a high coefficient of thermal expansion are layers of silicon or Ni-based alloys such as CoNiCrAlY, NiCoCrAlTaY, NiCrAlY and NiCr.
    Preferably, the adherent layer has a thickness between 50 ^ m and 100 ^ m.
    A further aspect of the present invention relates to the process of obtaining the coating of the invention (herein, process of the invention), which is performed by thermal projection techniques.
    Using thermal projection techniques, the stacking of glass or glass ceramic lamellae is easily achieved. At first, the graphene-based filler material is distributed homogeneously within the granules of the input material and migrates to the surface during thermal projection. Due to the high temperatures some graphene-based fillers disintegrate but a high proportion of them survive. The molten granules (droplets), still with the graphene-based filler material on their surface, reach the substrate and form crushed drops ("splats") and consequently a stack of lamellaselas; the graphene-based filler material is therefore
    • oriented parallel to the lamellae,
    • located along the interleaves between lamellae,
    • and forms an interconnected network.
    The process of the invention comprises the following stages:
    a) adding an aqueous or alcoholic solution comprising the precursors of a glass or a ceramic hob and a dispersant to a mixer, preferably an attrition mill;
    b) adding an aqueous or alcoholic solution comprising the graphene-based filler material and a dispersant to the solution obtained in step a);
    c) drying the homogeneous mixture obtained in step b);
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    d) dispersing the powder mixture obtained in step c) in water together with an organic binder;
    e) obtain granules from the solution obtained in step d);
    and f) deposit the granules obtained in step e) on a substrate or an adhesive or anchoring layer by thermal projection techniques.
    The term "precursor of a glass or a ceramic hob" refers to those materials that participate in the chemical reaction that produces a ceramic or a ceramic hob such as Al2O3, SiO2, RE2O3, where RE is a rare earth element such as La, Gd, Y or Lu), AlN, SiC and
    Si3N4.
    Step a) of the process of the invention refers to the addition of an aqueous or alcoholic solution containing the precursors of a glass or a ceramic glass together with a dispersant to a mixer.
    The alcoholic solution of step a) preferably comprises ethanol or 2-propanol.
    In a preferred embodiment, the dispersant of step a) is selected from the list consisting of any polyelectrolyte such as salts of organic acids and polyethyleneimines, etc. and / or any polysaccharide such as arabic gum, methyl cellulose, carboxymethyl cellulose, etc. or a combination thereof.
    In another preferred embodiment, the dispersant of step a) is in a weight percentage comprised between 0.5% and 4% with respect to the final solution comprising the precursors of a glass or a ceramic hob and a dispersant.
    Step b) of the process of the invention relates to the addition of an aqueous or alcoholic solution comprising the graphene-based filler material and a dispersant to the solution obtained in step a).
    The alcoholic solution of step b) preferably comprises ethanol or 2-propanol.
    In a preferred embodiment, the dispersant of step b) is any polyelectrolyte such as salts of organic acids and polyethyleneimines, etc. and / or any polysaccharide such as arabic gum, methyl cellulose, carboxymethyl cellulose, etc. and / or any ionic surfactant such
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    such as sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, etc. or a combination thereof.
    The aqueous or alcoholic solution comprising the graphene-based filler material and a dispersant mentioned above is prepared by mixing and sonicating simultaneously to disaggregate the graphene-based filler material. Preferably a paddle shaker will be used.
    The addition of an aqueous or alcoholic solution comprising the graphene-based filler material and a dispersant to the solution obtained in step a) should be carried out carefully, avoiding degradation of the graphene-based filler material.
    Step c) of the invention refers to the drying of the homogeneous mixture obtained in step b); In other words, stage c) consists in the elimination of water or alcohol from the homogeneous mixture obtained in stage b). Step c) can be carried out by lyophilization or evaporation.
    Step d) refers to the dispersion of the powder mixture obtained in step c) with water and an organic binder;
    Preferably, the organic binder of step d) is selected from the list consisting of any polysaccharide such as arabic gum, methyl cellulose, carboxymethyl cellulose, etc. and / or any polyalcohol such as polyethylene glycol, butyral polyvinyl, hydroxypropyl, etc. or a combination thereof.
    Preferably, the organic binder of step d) is in a weight percentage between 3% and 10% with respect to the solids content of the final solution.
    Step e) refers to obtaining granules from the solution obtained in step d). The granulation process of step e) is carried out by spray drying or freezing granulation.
    Step f) refers to depositing the granules obtained in step e) on a substrate or an adhesive layer by thermal projection techniques.
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    Examples of thermal projection techniques are atmospheric pressure plasma projection, high velocity thermal projection (high velocity oxyfuel), or flame thermal spraying.
    In a preferred embodiment of the invention, step f) is performed by thermal flame projection.
    If the deposition of step e) is carried out by thermal flame projection, preferably an oxyacetylene gun will be used. The following experimental conditions:
    • the acetylene flow rate in a range between 16 and 27 standard liters per minute (SLPM);
    • the projection distance in a range between 9 and 20 cm;
    • the travel speed of the oxyacetylene gun at an interval between 5 and 10 mm per minute;
    • the vertical displacement between passes of the oxyacetylene gun in a range between 3 and 10 mm;
    • the powder feed rate in a range between 5 and 20 grams per minute are also preferably desirable.
    Another aspect of the invention relates to a process for obtaining the material of the invention, characterized in that it comprises steps a) to f) according to claim 12 and an additional stage g) for separating the substrate and the coating.
    A further aspect of the invention relates to the use of the material of the invention and the coating of the invention as a component or part of a component of a protection system used in aeronautical, aerospace and nuclear applications, and as an electrical conductive coating.
    Examples of protection systems are anti-corrosion systems, thermal shields and electromagnetic interference and anti-ice systems.
    The last aspect of the invention refers to the use of the material of the invention and of the coating of the invention as a connection interface in electronic and / or energy applications.
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    Unless otherwise specified, all the technical and scientific terms used in this document have the same meaning as would be given by an expert in the technique to which this invention belongs. Procedures and materials similar or equivalent to those described herein may be employed in the implementation of the present invention. Throughout the description and the claims, the word "understand" and its variations in no case have the purpose of excluding other technical characteristics, additives, components or stages. Additional objects, advantages and features of the invention will be apparent to those skilled in the art after an examination of the description or through the learning associated with the implementation of the invention. The following examples and drawings are provided as clarification and in no case attempt to limit the present invention.
    BRIEF DESCRIPTION OF THE DRAWINGS
    FIG. 1 shows MEB images of atomized granules of YAS-GNP composition). a) General view of the granules, b) and c) fractured granule at different magnifications and d) detail of a thin GNP (black arrow) inside the granule.
    FIG. 2 shows MEB micrographs of the polished cross sections of a) and b) the YAS coating and c) and d) the YAS-GNP composite coating projected onto SiC substrates.
    FIG. 3 shows MEB micrographs of the fresh fracture (a) and the upper surface (b) of the YAS-GNP coating. The box in (a) shows a GNP with greater magnification.
    FIG. 4 (a) shows an optical image of the polished cross-section of the YAS-GNP coating and (b) a false color image generated by filtering the I / G signal of its Raman spectrum. (c) Average Raman spectra of the original GNP powders, the top surface of the coating and the cross section thereof. Point Raman spectra at positions O and X shown in (a) and (b) are also included.
    FIG 5. shows the conductivity and thermal diffusivity of the YAS and YAS-GNP coatings.
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    FIG 6. shows tests of indentation Vickers at a load of 2.9 N carried out in the cross sections of the YAS and YAS-GNP hforid coatings: (a) hardness (H) and elastic modulus (E); and MEB micrographs showing typical indentation traces for the YAS (b) and YAS-GNP (c and d) coatings. The black and white arrows in d) indicate areas of material removal and crack propagation detention at the GNP interfaces, respectively.
    FIG. 7 shows a MEB image of the polished cross-section of the YAS-GNP composite coating on a C / Cf substrate.
    EXAMPLES
    Example 1: Preparation and characterization of YAS-GNP coatings on SiC substrates.
    1.1. Preparation of YAS-GNP / Si / SiC and YAS / Si / SiC.
    SiC (Hexoloy S.A., Saint-Gobain) commercial and cordierite (Mg2Al4Si5O18) plates of internal production were used as substrates. The SiC plates were subjected to jets of SiC particles of ~ 0.6 mm in diameter (Navarro SiC, Spain) to increase their roughness and favor the adhesion of the coating. On this surface, a Si layer of ~ 56 ^ m thick was deposited by thermal spray using commercial Si powder (Fuse & crushed Si, Amperit® 170.084, H. C. Starck, Germany). As a result of the high surface roughness of the original cordierite plates (Ra = 9 ± 1 ^ m) and its low coefficient of intrinsic thermal expansion (3,510-6 K-1), this substrate did not require any conditioning prior to the projection of the coating.
    The composition YAS 17,5Y2O3-29,5Al2O3-53,0SiO2 (% in moles) was chosen due to its ease of forming glass and its thermal expansion coefficient (CET) being close to that of SiC substrates. High-purity powders (> 99.5%) were used to prepare the vortex composition, in particular Y2O3 (HC Starck, Germany), Al2O3 (SM8, Baikowski, France) and SiO2 (Alfa Aesar, Germany), with a distribution of particle size between 0.5-3.6, 0.3-2.2 and 1.5-21.1 m, respectively. The particle size distribution of SiO2 powders was reduced to 0.4 - 3.4 ^ m by attrition milling in distilled water for 1 hour using Al2O3 grinding media (3 mm diameter balls). As filler material, commercial graphene nanoplates (GNP) from
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    polar character (N008-100-P-10, Angstron Materials Inc., USA) with a nominal length of 5-10 ^ m and a thickness of 50-100 nm, in a concentration of 10% by volume.
    The YAS powders were mixed homogeneously by an attrition mill for one hour and a half in water with 0.4% by weight of a polyelectrolyte dispersant (Dolapix CE 64 CA, Zschimmer-Schwarz, Lahnstein, Germany). Simultaneously, a stable solution of GNP in water with 4% by weight of arabic gum (acacia gum arabic, Sigma-Aldrich) was prepared in an ultrasonic bath (100W, 50 / 60Hz, JP Selecta Ultrasons, Spain) during the minus 30 minutes The suspensions of YAS and GNP were mixed and ground in attrition for another 30 minutes. The solution was granulated by freezing to avoid segregation of the different components. By spray drying, YAS-GNP hybrid granules with size distribution and morphology suitable for the thermal projection process by flame were obtained, using an aqueous solution with a 50% by weight solids content of the granules previously frozen by freezing, mixed with 5% by weight binder (Optapix PS 94, Zschimmer-Schwarz, Germany).
    A similar process was carried out to obtain the original YAS contribution material as a comparison.
    The spray-dried powders were projected using an oxyacetylene gun (CastoDyn DS 8000; Eutectic Castolin, Spain) with a gaseous mixture of O2 and C2H2 in the proportion of 33/24 SLPM (standard liters per minute) and a projection distance of 14 cm. The gun was mounted on an automatic x-y table, which scanned the substrate at a pass speed of 8.3 mms-1, with a distance between consecutive passes of 5 mm. To obtain the coatings a sequence of a surface preheat and two projection passes was used. The feed of the powders was controlled at a rate of 10 gmin-1.
    1.2 Characterization of YAS-GNP coatings.
    1.2.1. Characterization procedures.
    The thermogravimetric analysis (STA 409 NETZSCH, Germany) produced a mass loss of up to 1500 ° C for SD YAS-GNP granules and for the corresponding coating
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    self-supported, previously ground, in air at a heating rate of 10 ° C min -1, in order to estimate the GNP content at each stage of the preparation process.
    The microstructure of the YAS-GNP coatings described in Example 1.1 was examined on the fracture surfaces, top surfaces and polished cross sections of the coatings by scanning electron microscopy with desktop equipment (desktop SEM, TM1000, Hitachi , Japan) and with another field emission (FE-SEM, S-4700 Hitachi, Japan).
    The crystalline phases were analyzed by X-ray diffraction procedures (DRX, D8 Advance, Bruker, USA) in the range of 20 from 10-70 ° with the configuration 0/20.
    Raman spectra were captured on the original GNPs, the top surface and the polished cross section of the warm coating at room temperature using a ^ -Raman imaging system (Alpha300WITec GmbH, Germany) with a laser excitation wavelength of 532 nm . 150 x 150 pixel Raman maps were acquired, registering one spectrum per pixel and using 60 ms of acquisition time, in scanned areas of 45 ^ m * 45 ^ m for the warm coating. For the spectra recorded in the glass matrix, acquisition times of 30 s were used. Raman images of false color were generated by correlating the intensity of the G band (IG) to accurately assign the GNPs.
    Square pieces of the YAS / Si / SiC and YAS-GNP / Si / SiC systems with side dimensions of 8.8 mm and 20 mm were machined to measure the thermal diffusivity in the directions perpendicular and parallel to the surface of the coating, respectively, by the laser pulse procedure (laser-flash method, Thermaflash 2200, Holometrix / Netzsch USA). The total thickness of the pieces was 0.86 mm in both cases, of which -0.20 mm corresponded to the upper glass coating, 0.06 mm to the silicon joint coating and 0.6 mm to the SiC substrate . The pieces were coated with colloidal graphite to increase the absorption of the laser beam. The apparent thermal diffusivity (aapp) of the systems in the perpendicular direction was measured in the atmosphere of Ar as a function of the temperature in the range of 25 to 400 ° C.
    From the measured values of aapp and considering the thermal properties of SiC and Si, the thermal diffusivity of the composite coatings of original YAS and of
    YAS-GNP. From the values to deducted, the density (p) and the specific heat (Cp), are
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    I calculate the thermal conductivity (k) of both coatings using the expression k = apCp.
    The apparent thermal diffusivity in the systems plane was measured at room temperature using special masks that confine the laser pulse in a circle of radius r0 = 2.5 mm in the center of the surface of the piece, while the heat flux Radial is detected on the opposite surface in an inner radius ring 2.2 times R0.
    The electrical conductivity of DC was measured by the procedure of four probes in samples of dimensions 15.5 x 5.5 x 3.0 mm3 machined from hybrid YAS and YAS-GNP coatings projected directly on cordierite insulating substrates. A DC voltage of between 0 and 200 mV (Agilent E3646A DC and Agilent 34401A voltmeter) was applied between two lateral surfaces of the coatings that were previously coated with Ag, the voltage being measured at two internal Ag electrodes separated a distance 5mm L The resistance of the system was calculated from the slope of the I / V curve. Because cordierite is a dielectric material, the conductivity was deduced considering that the effective conduction area, Ae, is defined by the thickness of the coating (~ 0.12 mm) and the width of the sample (3 mm)
    The elastic modulus (E) and hardness (H) were determined in the polished cross sections of the coatings using instrumented Vickers indentation tests (ZHU 2.5; Zwick GmbH & Co. KG, Germany) that simultaneously record the load and the depth of indentation. The elastic modulus of the material is calculated from the reduced modulus obtained using the discharge branch of the load versus displacement curves, considering the properties of the diamond indenter. At least 10 measurements were made with a load of 2.9 N, applied for 5 s, for each sample.
    1.2.2. Results Comparison between YAS-GNP / Si / SiC and YAS / Si / SiC compounds
    As can be seen in Fig. 1a, the contribution material powder (YAS-GNP composition in this case) is composed of rounded granules with an average particle size of ~ 30 ^ m. When observed with a greater increase, the presence of GNP on the surface and inside the warm granules (Fig. 1b-d) is clearly perceived as large structures («5 ^ m) arranged in a circumferential manner. This orientation may be related to a water drag effect when it is ejected from the inside of the atomized drop during drying along with the rotation of the drop due to the air flow
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    hot. In some cases, the GNPs are so thin that certain characteristics can be seen through them (see area indicated with an arrow in Fig. 1d).
    The presence of GNP in the projected coating has been tested by different procedures.
    In the thermogravimetric analysis (ATG) of the spray dried hforid powder of the YAS-GNP composition, two different mass loss processes are observed. The first, with a loss of mass of approximately 5%, occurs between 100 and 500 ° C, and can be associated with the evaporation of wastewater and the burning of the organic additives used left in the granules after the drying process by spraying. The second process involves a loss of mass of 5.7% and occurs between 500 and 900 ° C, and is due to the breakdown of GNPs. This value is very similar to the amount of GNP added (6.1% by weight). The ATG of the YAS-GNP coating consists of a single stage process that starts at 600 ° C with a total mass loss of 2.3%, which is related to the combustion of the GNP. This indicates that organic additives are completely lost during the high temperature projection process while approximately 40% of the added GNPs survive despite the fact that the combustion of O2 / C2H2 in the thermal flame projection process takes place in presence of air and involves gas temperatures above 3000 ° C.
    An ocular inspection of the upper surfaces revealed that the YAS coating was completely white while the YAS-GNP coating was black. The observation of the cross sections (Fig. 2b and c) confirmed that the coatings are continuous and of homogeneous coloration, presenting good adhesion with the Si anchoring layer. The thicknesses of the YAS coating and the YAS-GNP hybrid coating are very similar (197 ± 19 ^ m and 169 ± 10 ^ m, respectively). As shown in Fig. 2b, the YAS coating is formed by a continuous stacking of lamellae and has spherical pores probably associated with the gases trapped in the low viscosity YAS glass during thermal flame projection. On the other hand, this type of residual (spherical) porosity and an elongated dark phase between the flattened ones are clearly observed in the YAS-GNP coating (Fig. 2c).
    As can be seen in Fig. 3, nanoplates are clearly detected on the fracture surface of the YAS-GNP coating, arranged mainly in parallel to the coating surface and along the interleaves between the lamellae. The elderly micrograph
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    Increases shown in the box in Fig. 3a unequivocally confirms the features of a GNP. In addition, the upper surface image (Fig. 3b) also shows some nanoplaquets protruding from the surface of the coating.
    The DRX patterns of the coatings are typical of amorphous materials, except the peak of intense diffraction of the YAS-GNP coating associated with graffiti structures, confirming that the GNPs retain their structure after the thermal projection.
    The Raman study of the YAS-GNP coating is shown in Fig. 4. The spectra of the original GNP and the projected coating, both of the upper surface and of the polished cross-section, show the three characteristic bands of the graffiti structures: D band (-1360 cm-1) associated with the presence of structural defects, the G band (-1595 cm-1) related to the tangential mode of graphene characteristic DC vibration, and the second order D band (2D band, -2717 cm-1) originated by a double resonance process. The background observed in the Raman spectrum of the cross section can be associated with a fluorescence effect due to the presence of porosity and multiple limits.
    Raman spectra of rare earth aluminosilicate glasses usually show a single peak at -950 cm-1 and a shoulder at -450 cm-1. These characteristics are not observed in the average analysis for the YAS matrix due to the high efficiency of Raman emission of the GNP that hides other signals, but they can be perceived in the specific spectrum (point O in Fig. 4), recorded with 30 s integration time. The false color image obtained by filtering the IG signal of the Raman spectrum (Fig. 4) unequivocally confirms the localization of the GNPs in the interleaves between lamellae forming a continuous network. The intensity ratio integrated between the D and G bands (/ d // g) in the average spectrum is 0.48 for the upper surface and 0.35 for the cross section. The same ratio of 0.38 was calculated for point spectra recorded in a region where the maximum intensity of the G band was obtained (point X in Fig. 4a and b). This increase in the ratio / d // g compared to that of the original GNPs shown in Fig. 4c (0,1) may be due to a greater contribution of the defects of the GNP edges, in particular when analyzed the cross sections of the coating.
    The experimental results of the apparent thermal diffusivity measured at room temperature for the YAS / Si / SiC and YAS-GNP / Si / SiC systems in the two configurations
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    studied -perpendicular to and in the plane of the coating- is shown in Table 1. It is clearly observed that the presence of GNPs in the upper coating significantly increases the aapp in both orientations, this increase being 74% for perpendicular orientation and 31% for the parallel.
    Table 1. Apparent thermal diffusivity (aapp) perpendicular and parallel to the surface of the coating for the YAS / Si / SiC and YAS-GNP / Si / SiC systems.
    Perpendicular System (10-5 m s-1) Parallel (10-5 m s-1)
    YAS / Si / SiC 0.27 ± 0.01 2.35 ± 0.05
    YAS-GNP / Si / SiC 0.47 ± 0.02 3.08 ± 0.03
    From the apparent perpendicular thermal diffusivity of the systems, the diffusivity and thermal conductivity values represented in Fig. 5 of the upper YAS and YAS-GNP coatings were calculated using a three layer model. The value of a for the YAS coating varies between 3,510-7 m2 s-1 at room temperature and 3,110-7 m2 s-1 at 400 ° C, and the corresponding k from 0.6 to 0.7 Wm-1K-1 in the same temperature range. These very low values are common for amorphous and vitreous materials. The value of a for the YAS-GNP coating varies between 4,910-7 m2 s-1 at room temperature and 4,110-7 m2 s-1 at 400 ° C, and its corresponding k varies between 0.75 and 0.92 Wm- 1K-1 in the same temperature range.
    These values are ~ 30% higher than those obtained for the YAS coating.
    This increase observed in perpendicular does not correspond to the thermal behavior reported for ceramic compounds of Si3N4 where the GNPs are oriented mainly with their basal plane perpendicular to the main pressing axis of the pulsed current sintering furnace (spark plasma sintering, SPS), where the conductivity and perpendicular thermal diffusivity decrease due to the formation of thermal barriers associated with NGP [14 P. Miranzo, E. Garda, C. Ramirez, J. Gonzalez-Julian, M. Belmonte, MI Osendi, Anisotropic thermal conductivity of silicon nitride ceramics containing carbon nanostructures, J. Eur. Ceram. Soc. 32 (2012) 1847-1854].
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    Thus, the increase measured in the present coatings must be related to the position of the GNPs in the interleaves between lamellae (Figs. 2, 3 and 4), so that they fill the gaps reducing the thermal resistances associated with the numerous interleaves between oriented lamellae.
    Regarding the electrical conductivity at room temperature, the YAS / cordierite system was below the detection limit of the measuring equipment (<10-13 S m-1) while that of the YAS-GNP / cordierite system was fifteen orders of greater magnitude (1.4 102 S m-1), also showing a linear I / V ratio over the entire measurement range. This would test the interconnection of the GNPs throughout the entire coating, in accordance with what was observed in the Raman map of Fig. 4b, and then the percolation limit for the electrical conductivity is below 4% by volume and by Therefore, in the lower limit of the range of values reported for most graphene / ceramic composites (~ 3 - 8 vol.%):
    • Ramirez C, Figueiredo F, Miranzo P, Poza P, Osendi MI. Graphene nanoplatelet / silicon nitride composites with high electrical conductivity. Carbon 50 (2012) 3607-3615.
    • C. Ramirez, S.M. Vega-Diaz, A. Morelos-Gomez A, F. Figueiredo, M. Terrones, M.I Osendi, M. Belmonte, P. Miranzo. Synthesis of conducting graphene / Si3N4 composites by spark plasma sintering. Carbon 57 (2013) 425-432.
    • S. Watcharotone, D.A. Dikin, S. Stankovich, R. Piner, I. Jung, G. H. B. Dommett, G. Evmenenko, S.E. Wu, S.F. Chen, C. P. Liu, S T. Nguyen, R. S. Ruoff, Graphene-Silica Composite Thin Films as Transparent Conductors, Nano Letters, 7 (2007) 1888-1892.
    • O. Jankovsky, P. Simek, D. Sedmidubsky, S. Huber, M. Pumera, Z. Sofer, Towards highly electrically conductive and thermally insulating graphene nanocomposites: Al2O3 graphene, RSC Adv., 4 (2014) 7418-7424.
    In addition, the value obtained from electrical conductivity is in the range of published values for composite ceramic materials with similar additions of GNP (0.4 -1.8 102 Sm-1) [O. Jankovsky, P. Simek, D. Sedmidubsky, S. Huber, M. Pumera, Z. Sofer, Towards highly electrically conductive and thermally insulating graphene nanocomposites: Al2O3 graphene, RSC Adv., 4 (2014) 7418-7424 and Y. Fan , L. Wang, J. Li, J. Li J, S. Sun, F. Chen, L. Chen, W. Jiang, Preparation and electrical properties of graphene nanosheet / Al2O3 composites. Carbon 48 (2010) 1743-1749], with the only exception of a work on a
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    Al2O3 / rGO composite material processed by sol-gel procedures that reports a value greater than 103 Sm "1 with a percolation Kmite of 0.38% by volume [YC Fan, W. Jiang, A. Kawasaki, Highly conductive few- layer graphene-Al2O3 nanocomposites with tunable charge carrier type, Adv. Funct. Mater., 22 (2012), 3882-3889] If this comparison is made only with low dimensional systems, the conductivity of the present coatings is four orders of magnitude greater than that of a thin sheet of SiO2 / graphene (8 10 "2 S m" 1) with a similar proportion of graphene [S. Watcharotone, DA Dikin, S. Stankovich, R. Piner, I. Jung, GHB Dommett , G. Evmenenko, SE Wu, SF Chen, CP Liu, S T. Nguyen, RS Ruoff, Graphene-Silica Composite Thin Films as Transparent Conductors, Nano Letters, 7 (2007) 1888-1892] This extraordinary electrical conductivity allows you to glimpse promising new applications such as shielding against electrical interference High temperature omagnetic (EMI) for the present coatings.
    The mechanical properties of the YAS-GNP coatings were evaluated by Vickers indentation tests (Fig. 6). The YAS-GNP coating shows greater penetration depth (~ 21% increase) and permanent deformation (~ 22%) than the YAS coating for the same indentation load. The H values shown in Fig. 6 indicate that the YAS-GNP hybrid coating shows a lower hardness (4.7 ± 0.5 GPa) (around 30% lower) than that of the YAS coating, due to to the increase in permanent deformation associated with the presence of GNP at the borders between lamellae. A similar trend has been observed for E, which decreases from 98 ± 9 GPa for the YAS coating to 64 ± 10 GPa for the YAS-GNP coating (35% lower). Similar decreases in hardness and elastic modulus due to the addition of graphene nanostructures have been observed in mass ceramic systems [C. Ramirez, P. Miranzo, M. Belmonte, M.I. Osendi, P. Poza, S.M. Vergara-Diaz, M. Terrones, Extraordinary toughening enhancement and flexural strength in Si3N4 composites using graphene sheets, J. Eur. Ceram. Soc. 34 (2014) 161-169 and H. Porwal, P. Tatarko, S. Grasso, C. Hu, A.R. Boccaccini, I. Dlouhy, M.J. Reece Toughened and machinable glass matrix composites reinforced with graphene and graphene-oxide nanoplatelets, Sci. Technol. Adv. Mater. 14 (2013) 055007 (10pp)]. In the present coatings, the localization of the GNP in the intercals between lamellae and the weak union with the surrounding matrix (Fig. 2 and Fig. 3) could favor the shear stress in these intercars. This effect is not necessarily harmful since it increases the deformability of these coatings, which would improve their tolerance to deformations.
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    As can be seen in Fig. 6, indentation traces in the YAS-GNP hforid coating (FIG. 6c and d) show very different characteristics compared to those observed in the YAS coating (FIG. 6b). First, no significant cracks are detected in the vertices of indentation marks; on the other hand, in some cases (Fig. 6c) a highly damaged area of indentation with material removal is observed, while other cases show a damaged area extended around the indentation footprint with signs of shear displacement between adjacent lamellae (indicated with a white arrow in Fig. 6d). All these effects are compatible with a weak union in the interlayer between lamellae, where graphene sheets are located. In the complex field of tensions that develops during indentation, weakly bonded lamellar glides and other dissipative friction effects are plausible, which would limit the spread of the main cracks. In cases where small indentation cracks were generated at the corners of the indentation fingerprint (see black arrows in Fig. 6d) they always stop at the borders with GNP. The observed behavior may be an indication of the improvement of the toughness of the coating due to the presence of GNP.
    Example 2: Preparation of YAS-GNP coatings on substrates C / Cf.
    The same powders described in item 1.1 of Example 1. were projected onto long carbon fiber reinforced carbon substrates (C / Cf, CeraMaterials, NY, USA) on which a Si bonding layer had previously been projected and using the same projection parameters as described in section 1.1 of Example 1. The polished cross-section of said coating system is shown in Fig. 7. The YAS-GNP coating is, as in the previous example, continuous and is well attached to the Si bonding layer, which is very dense and is firmly attached to the C / Cf substrate. The YAS-GNP coating is formed by the stacking of lamellae and a dark phase can be perceived between the flattened lamellae, which can be related, as in the coating described in Example 1, with the presence of graphene nanoplates.
    权利要求:
    Claims (21)
    [1]
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    1. A hforid material, characterized in that it comprises:
    • a graphene-based filler material
    • and a glass or a ceramic hob
    and said hforido material is characterized in that it forms a stacking of glass or glass ceramic lamellae, where the graphene-based filler material
    • is oriented parallel to the lamellae,
    • is located in the interleaves between lamellae,
    • and forms an interconnected network.
    [2]
    2. The hybrid material according to claim 1, wherein the graphene-based filler material is selected from the list consisting of single-layer, low-layer or multi-layer structures of graphene oxide, total graphene oxide or partially reduced, or graphene.
    [3]
    3. The hybrid material according to any one of claims 1 or 2, wherein the graphene-based filler material is between 0.3 and 100 nm thick.
    [4]
    4. The hybrid material according to any one of claims 1 to 3, wherein the glass is selected from a list consisting of RE2O3-Al2O3-SiO2, RE2O3-AlN-SiO2, RE2O3-Al2O3- Si3N4-SiO2, RE2O3-Al2O3 -SiC-SiO2 and RE2O3-SiC-AlN-SiO2, where RE is a rare earth element selected from La, Gd, Y and Lu.
    [5]
    5. The hybrid material according to any one of claims 1 to 4, wherein the ceramic hob is selected from a list consisting of RE2O3-Al2O3-SiO2, RE2O3-AlN- SiO2, RE2O3-A ^ O3-Si3N4-SiO2, RE2O3 -Al2O3-SiC-SiO2 and RE2O3-SiC-AlN-SiO2, where RE is a rare earth element selected from La, Gd, Y and Lu.
    [6]
    6. The hybrid material according to any one of claims 1 to 5, wherein the graphene-based filler material is in a volume percentage comprised between 2% and 15% with respect to the final volume of the hybrid coating.
    [7]
    7. The hforid material according to any one of claims 1 to 6, wherein the glass or the ceramic is in a volume percentage comprised between 85% and 98% with respect to the final volume of the stiffened coating.
    5 8.
    10
    A coating system, characterized in that it comprises:
    • a hybrid material according to any one of claims 1 to 7,
    • a substrate,
    • and, optionally, an adhesion layer located between the hybrid coating and the substrate.
    [9]
    9. The coating system according to the preceding claim, wherein the substrate is selected from a list consisting of SiC, reinforced SiC composite materials comprising carbon fibers, reinforced carbon composite materials comprising carbon fibers and reinforced Si3N4 .
    fifteen
    [10]
    10. The coating system according to any of claims 8 or 9, wherein the coating has a thickness between 50 ^ m and 500 ^ m.
    [11]
    11. The coating system according to the preceding claim, wherein the coating 20 has a thickness between 100 ^ m and 200 ^ m.
    [12]
    12. The coating system according to any one of claims 8 to 11, comprising an adherent layer located between the hybrid coating and the substrate.
    The coating system according to the preceding claim, wherein the silicon layers
    or Ni-based alloys such as CoNiCrAlY, NiCoCrAlTaY, NiCrAlY and NiCr and the adherent layer have a thickness between 50 ^ m and 100 ^ m.
    [14]
    14. A method of obtaining the coating system according to any of the 30 claims 8 to 13, comprising the following steps:
    a) adding an aqueous or alcoholic solution comprising the precursors of a glass or a ceramic hob and a dispersant to a mixer;
    b) adding an aqueous or alcoholic solution comprising the graphene-based filler material and a dispersant to the solution obtained in step a);
    C) drying the homogeneous mixture obtained in step b);
    d) dispersing the powder mixture obtained in step c) in water together with an organic binder;
    e) obtain granules from the solution obtained in step d); Y
    f) deposit the granules obtained in step e) on a substrate or an adherent layer
    5 by thermal projection techniques.
    [15]
    15. The method according to the preceding claim, wherein the dispersant of step a) is selected from a list consisting of a polyelectrolyte, a polysaccharide or a combination thereof.
    10
    [16]
    16. The method according to the preceding claim, wherein the dispersant of step a) is in a weight percentage comprised between 0.5% and 4% with respect to the final solution comprising the precursors of a glass or a ceramic hob and a dispersant.
    fifteen
    [17]
    17. The method according to any of claims 14 to 16, wherein the
    stage b) dispersant is a polyelectrolyte, a polysaccharide, an ionic surfactant or a combination thereof.
    The method according to any one of claims 14 to 17, wherein the
    organic binder of step d) is selected from a list consisting of a polysaccharide, a polyalcohol or a combination thereof.
    [19]
    19. The method according to any of claims 14 to 18, wherein the
    The organic binder of stage d) is in a weight percentage between 3%
    and 10% with respect to the total solids content of the solution.
    [20]
    20. The method according to any of claims 14 to 19, wherein the
    granulation of step e) is carried out by spray drying techniques
    30 or granulated by congelation.
    [21]
    21. The method according to any of claims 14 to 20, wherein the thermal projection techniques of step f) are selected from plasma projection at atmospheric pressure, high velocity thermal projection and thermal flame projection.
    5
    10
    [22]
    22. A method for obtaining the hforid material according to any one of claims 1 to 7, characterized in that it comprises steps a) to f) according to claim 14 and another additional step g) for separating the coating and the substrate.
    [23]
    23. Use of the material of the invention according to any one of claims 1 to 7 or of the
    coating of the invention according to any of claims 8 to 13 as
    component or component part of a protection system used in aeronautical, aerospace and nuclear applications.
    [24]
    24. Use of the material of the invention according to any one of claims 1 to 7 or of the
    coating of the invention according to any of claims 8 to 13 as
    Union interface in electronic and / or energy applications.
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