WO2023187456A1 - Suspension de géopolymère contenant des nanoparticules pour revêtements résistant à la chaleur et procédé pour la production de celle-ci - Google Patents

Suspension de géopolymère contenant des nanoparticules pour revêtements résistant à la chaleur et procédé pour la production de celle-ci Download PDF

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WO2023187456A1
WO2023187456A1 PCT/IB2022/053799 IB2022053799W WO2023187456A1 WO 2023187456 A1 WO2023187456 A1 WO 2023187456A1 IB 2022053799 W IB2022053799 W IB 2022053799W WO 2023187456 A1 WO2023187456 A1 WO 2023187456A1
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layer
geopolymer
suspension
temperature
sample
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PCT/IB2022/053799
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Stefan MICHNA
Jan Novotny
Martin JASKEVIC
Zbynek Cerny
Pavlina ROSYPAL
Jiri PLOCEK
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Univerzita J. E. Purkyne V Usti Nad Labem
Ustav Anorganicke Chemie Av Cr, V.V.I.
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Publication of WO2023187456A1 publication Critical patent/WO2023187456A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/103—Anti-corrosive paints containing metal dust containing Al
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
    • C23C18/127—Preformed particles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C20/00—Chemical coating by decomposition of either solid compounds or suspensions of the coating forming compounds, without leaving reaction products of surface material in the coating
    • C23C20/06—Coating with inorganic material, other than metallic material
    • C23C20/08—Coating with inorganic material, other than metallic material with compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00008—Obtaining or using nanotechnology related materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Definitions

  • Geopolymer suspension containing nanoparticles for heat-resistant coatings and method of the production thereof is a Geopolymer suspension containing nanoparticles for heat-resistant coatings and method of the production thereof.
  • the invention relates to a geopolymer suspension containing nanoparticles for heat-resistant coatings and a method of the production thereof.
  • Inorganic coatings on metallic materials are prepared by a number of physical, electrolytic, or chemical methods. While the hot- or plasma-deposition technologies are highly effective as a top protective layer, the application thereof is highly energy-intensive, and some materials may suffer structural effects due to heating the material during application; therefore, they are not suitable for such materials. In addition, there are sophisticated techniques for coating formation by diffusion processes or vapor-phase deposition of layers. The most common electrolytic methods include the galvanization process. Various technologies of applying aqueous suspensions followed by firing are used for common surface treatments of metallic materials with coatings and enamels.
  • the above shortcomings are largely eliminated by the geopolymer suspension containing nanoparticles for heat-resistant coatings according to the present invention.
  • the summary of the invention is that the suspension contains 20-25% wt. of an aqueous solution of 80-90% wt. phosphoric acid, 25-25% wt. of aluminosilicate, 4, 6-5, 2% wt. of graphite, 5-7% wt. of alumina nanoparticles of a size of up to 90pm, and the remainder is isopropyl alcohol.
  • the aluminosilicate is washed kaolin and/or metakaolin.
  • the ratio of the amount of phosphoric acid to the amount of aluminosilicate is 1.1 to 1.35.
  • a further object of the invention is a method of preparing geopolymer suspension according to the present invention.
  • the method consists in that the aqueous solution of 80 to 90% phosphoric acid is added to 100 ml of isopropyl alcohol, and aluminosilicate is gradually added while stirring at room temperature for 8 to 15 minutes; and after 9 to 15 minutes, graphite as an additive is added at once, and the resulting mixture is homogenized for another 18 to 25 minutes.
  • the geopolymer suspension consists of an acidic aluminosilicate base matrix (aqueous solution with H + ), phosphoric acid solution (H3PO4), and a small amount of graphite (additive) and isopropyl alcohol (CsHgO). Then, this mixture is additionally modified with alumina nanoparticles (AI2O3).
  • aqueous solution with H + aqueous solution with H +
  • phosphoric acid solution H3PO4
  • CsHgO isopropyl alcohol
  • Aqueous suspensions of a mixture of phosphoric acid represent a cheap, environmentally friendly and very simple surface protection application suitable for preparing functional coatings on metallic materials.
  • a wide range of additives can be easily dispersed into the suspensions, providing the coatings with variability in the properties thereof.
  • This flexibility in coating formulation gives the resulting composites new functional properties, particularly in the fields of adhesion and tribology, as well as allows for a broader range of applications.
  • the alumina nanoparticles in the coatings significantly reduce friction compared to the uncoated surface, increase thermal stability, and reduce wear and tear.
  • the suspension exhibits excellent adhesion to metallic materials and can be applied by painting or spraying without the need for firing at high temperatures.
  • the geopolymer needs to be dried at a specific temperature - 180 to 200 °C, the so-called setting, when the emulsion is thermally stabilized. After setting, the resulting surface is maintenance-free, and the stabilized emulsion can only be removed mechanically.
  • the coating stabilized in this way can be used for long-term thermal protection at 500 °C for at least 50 hours and 800 °C for at least 60 minutes.
  • the suspensions are environmentally friendly, long-term stable and affordable.
  • the coatings on metal substrates allow surface modifications of the resulting surfaces' sliding, tribological and thermal properties, thus expanding their functional, i.e. application possibilities.
  • geopolymer emulsion The great advantage of geopolymer emulsion is the long shelf life thereof, which is up to 10-times longer compared to other emulsions.
  • suspension In the case of suspension, there is a small degree of partial separation of the components, but the subsequent homogenization of the mixture, i.e. mixing, is very easy.
  • the guaranteed expiration time is at least 6 months at room temperature when no significant degradation of the mixture has occurred; the total expiration time can be assumed to be much longer.
  • the expiration time of geopolymer suspensions can be further extended through suitable storage at a low temperature of about 4 °C or by forming individual components mixed into the final mixture just before application.
  • This suspension consists in the possibility of application on the surface, where the surface does not need to be chemically or mechanically pre-treated, i.e. degreased, soaked, blasted, preheated, etc.
  • Isopropyl alcohol which is a part of the emulsion, acts as an effective degreaser, and phosphoric acid causes a slight etching of the surface and better adhesion of the coating to the underlying substrate.
  • surface pretreatment e.g. by degreasing using an organic solvent, will positively affect the final surface properties such as adhesion, appearance, etc.
  • the emulsion Before application, the emulsion must be well homogenized by mixing or shaking. In addition, the suspension must be spread thoroughly over the surface when applied by painting, e.g. with a brush, to achieve a very thin layer. It is very preferable as it reduces consumption compared to other types of coatings, such as organic coatings in particular. It has been verified that even with a layer thickness of 40 pm, no surface degradation occurs. The average layer thickness varies between 5 and 20 pm, depending on the application technique during coating. Compared to other common types of coatings, the thickness of the resulting layer is about 10-times thinner. Typically, the organic coatings reach thicknesses of 100 to 200 pm.
  • the options for application to the material surface are the same as for conventional organic compounds, i.e. painting with conventional brushes, air spraying with a spray gun or atomizer, etc.
  • the suspension shows no discoloration and is transparent.
  • the application by spraying will further enhance the aesthetics of the resulting visual surface, but the application by painting achieves perfect aesthetic results of the final surface as well, and such a surface can be used as a visual surface.
  • Another advantage consists of an easy application method by painting.
  • the suspension can be further added with color pigments.
  • Preferable composition of the resulting geopolymer suspension Preferable composition of the resulting geopolymer suspension.
  • Thermal protection of the machine parts surface and the like up to 800 °C for up to 1 hour.
  • a low layer thickness of 5 to 10 pm can be preferably used, which does not significantly affect the final dimensions of the component.
  • the thermal protection can be further improved by layering individual layers or by the appropriate choice of additives added to the suspension to create a coating with application-specific properties.
  • the suspension is environmentally friendly, long-term stable for storage - up to 10-times longer than other emulsions, and usable for application.
  • the guaranteed expiration time is at least 6 months at room temperature.
  • FIG. 1 shows metallographic cut of the base material without coating in section at 200x magnification;
  • Fig. 4 shows the detail at 500x magnification.
  • the analysis of the suspension surface is shown in Fig. 5 at various magnifications.
  • Fig. 6 shows a detail of a section of the geopolymer layer at 500x magnification.
  • FIG. 7 shows the SEM analysis of the layer; the image on the left shows a detail of each layer, and a similar image with the measured layer thickness is shown on the right.
  • Fig. 8 shows a detail of a thick layer at 500x magnification.
  • the SEM analysis of Fig. 9 confirms the very good bonding between the layer and the underlying substrate.
  • Subsequent linear EDS analysis confirmed the composition of the layers, see Fig. 10.
  • the geopolymer layer can be confirmed mainly by the presence of aluminum and phosphorus.
  • the laser scanning microscope images in Fig. 11 show the mark left by a ball after the Tribolab test.
  • Fig. 12 shows the surface of the sample with a thin layer of geopolymer suspension after thermal loading. 3D scan of the surface is shown in Fig.
  • Fig. 13 on the right and detail of the layer section is in Fig. 14.
  • Fig. 15 shows a surface with a thick layer of suspension
  • Fig. 16 on the right shows a 3D scan of the surface.
  • Fig. 17 shows the layer section, where the still perfect adhesion of the layer to the underlying substrate is possible to be verified.
  • Fig. 18 shows the surface of the sample with a thin layer of suspension after thermal loading.
  • Fig. 19 on the right represents a 3D scan of the surface.
  • Fig. 20, then, represents the detail of the layer in the section.
  • Fig. 21 shows a surface with a thick layer of suspension; and
  • Fig. 22 on the right represents a 3D scan of the surface.
  • the integrity and adhesion of the layer can also be observed in the detail of the layer section of Fig.
  • Fig. 24 shows the surface of the sample with a thin geopolymer layer, where it can be seen that the layer integrity was not compromised even at very high burner performance and high temperature.
  • Fig. 25 shows the surface of the sample with a thick layer.
  • Fig. 26 shows the detail of the layer section and the 3D scan on the right.
  • Fig. 27 represents the reference sample without coating.
  • Fig. 28 represents a sample with a thin geopolymer layer.
  • Fig. 29 shows a sample with a thick suspension layer.
  • Fig. 30 represents the reference sample after 60 minutes of heat load.
  • Fig. 31 represents a sample with a thin geopolymer layer.
  • Fig. 32 represents a sample with a thick geopolymer layer.
  • Fig. 33 represents a coating after a very long period of heat load at a high temperature.
  • the emulsion color is bright white; it has a higher viscosity in the form of a gel and contains no sediments.
  • Application to the underlying substrate 4 is very easy, it spreads well, and a very thin layer can be formed.
  • the contained isopropyl alcohol is very volatile and causes very fast drying of the emulsion within about 5 minutes in combination with a thin layer.
  • the emulsion color is bright white; it has the same, i.e. higher viscosity, and contains no sediments. There was a separation of the clear liquid component, which is visible on the surface - about 1/6 of the total volume.
  • the emulsion can be very easily mixed, e.g. Using a glass rod, back to a homogeneous consistency. Application to the underlying substrate 4 is very easy.
  • the emulsion appearance is the same as in the previous cases. There is a separated component that can be very easily mixed into a homogeneous mixture as well. There are no sediments on the bottom, and the viscosity is the same, i.e. a gel. Application and thin layer formation continue to be excellent. Storage at 22°C.
  • the suspension expiration is at least 6 months, even when stored at room temperature (22°C). After 6 months of storage in the refrigerator, the samples showed no changes in color, consistency or subsequent application by coating compared to the original freshly prepared mixture.
  • the emulsion stored in this way can be assumed to have a much longer expiration time without changing the resulting properties.
  • Common structural steel CSN 11375 according to CSN 41 1375 was used as the underlying substrate 4. It is a hot-rolled, non-alloy structural steel suitable for welding, fusion-welded medium- thickness structural and machine components, and is subjected to static and dynamic stresses. The equivalent designation is S235JRG2. This steel was also chosen because of the possible later application thereof as a fire protection for steel beams and fittings in buildings and other infrastructure.
  • the coating was applied to a mechanically untreated surface, leaving a natural oxidation layer on the surface.
  • This method was chosen to verify the possibility of application on an untreated surface and, therefore, to increase the economic efficiency of the application since mechanical or chemical surface treatments are very time-consuming and costly.
  • Coarse dirt was removed from the substrate surface; the substrate surface was degreased with a common organic solvent, usually acetone. Unless it is heavily soiled with grease, the surface has been proven not to be degreased with organic or other solvents necessarily, as the isopropyl alcohol present in the mixture is able to degrease the surface very well during the application of the suspension itself, which contributes to the economic efficiency of the operation.
  • Mechanical or chemical pretreatment of the surface will further improve the mechanical properties of the coating, i.e. coating adhesion, appearance, etc. In this case, it depends on the final specific usage of the surface/component.
  • the suspension is necessary to be thermally stabilized on the substrate surface.
  • the setting takes place for a certain period of time at a given temperature according to the scheme:
  • the layer is insoluble and can only be removed mechanically.
  • a LEXT OLS 500 laser microscope and a Tescan Vega 3 scanning electron microscope with an SEM analyzer were used for the detailed analysis of surfaces and layers. Macroscopically, the resulting set layer is compact, without visible defects or cracks, perfectly follows the underlying substrate 4 and is hardly visible due to minimal thickness and transparency thereof.
  • the surface of the underlying substrate 4 is mechanically untreated having irregularities after rolling.
  • the surface can be seen in Fig. 1 at 200x magnification and in detail at 500x magnification in Fig. 2.
  • Fig. 3 shows metallographic cut of the base material without coating in section at 200x magnification.
  • An oxide layer j_ which reaches a thickness of 10 to 20 pm on average, can be seen on the material surface.
  • Fig. 4 on the left shows the oxide layer 1 thickness and the corrosion 2 of the underlying substrate 4, which is not in the whole sample area but only in particular points to compare the suspension adhesion to the oxidized and partially corroded surfaces.
  • Fig. 4 on the right shows a detail and thickness of the oxide layer from SEM analysis performed on the electron scanning microscope.
  • Fig. 6 on the left shows detail of a section of the geopolymer layer 2 at 500x magnification. It can be observed that the layer is compact and perfectly adhered to the underlying substrate. There is the measured layer thickness on the right, which averages 6.8 pm in the drawing. Generally, the thin layer thickness is between 5 pm and 10 pm, in the case of the thin layer.
  • Fig. 7 shows the SEM analysis of the layer. The drawing on the left shows a detail of each layer - the underlying steel substrate, the oxide layer 1 and the geopolymer layer 3, where the layer structure and its perfect adhesion to the surface can be seen. There is a similar drawing on the right with the measured layer thickness.
  • Thick layer i.e. layer thickness 10 to 30 pm
  • Fig. 8 shows a detail of a thick layer at 500x magnification. Again, good layer adhesion to the substrate and a layer thickness of 26.2 pm can be observed. Generally, the thick layer thickness ranges from 10 pm to 30 pm.
  • Tribological measurements were performed on the UMT TriboLab from Bruker.
  • the geopolymer was applied to pre-prepared test bodies in the form of a steel disc pre-treated according to the device requirements.
  • a disc without geopolymer coating was chosen as a reference sample for comparison.
  • Peripheral speed 0.014 m.s -1
  • the measured friction coefficient values which are more than 2 times lower for the coated component than for the uncoated component, predetermine the coating for use in applications requiring reduced friction and increased wear resistance, such as moving machine parts.
  • the significant reduction in friction and increase in abrasion resistance for the coating is due to the aluminum oxide nanoparticles added to the compound as an additive.
  • Open- flame fire tests were performed on both thin and thick layers to compare them with each other as well as on an uncoated reference sample.
  • a propane -butane burner was used as the fire source. The flame was directed at some distance to the side with the geopolymer coating, and the temperature was measured on the other side, i.e., a K-type measuring thermocouple. The burner performance and flame temperature were controlled according to the specific testing requirement.
  • Fig. 12 shows the surface of the sample with a thin layer of geopolymer suspension after thermal loading. As can be seen, there was no damage to the layer, flaking or scratching, as evidenced by the 3D scan of the surface in Fig. 13 on the right and detail of the layer section is in Fig. 14. [0111] Fig. 15 shows a surface with a thick layer of suspension, and Fig. 16 on the right shows a 3D scan of the surface. Again, it can be observed that there was no damage to the layer adhesion to the substrate. Fig. 17 shows the layer section, where the still perfect adhesion of the layer to the underlying substrate is possible to be verified. [0112] 1) Burner performance: medium
  • the average temperature reached was again lower for the coated sample than for the uncoated reference sample.
  • the resulting temperature reached after 6 minutes was about 619°C for the reference sample.
  • the sample with a thin layer of geopolymer reached a temperature of about 616°C, and the sample with a thicker suspension layer then reached about 614°C, being a temperature reduction by 5°C compared to the reference sample.
  • Fig. 18 shows the surface of the sample with a thin layer of suspension after thermal loading. Even at higher heat load and higher temperature, no damage to the layer occurred.
  • Fig. 19 on the right represents a 3D scan of the surface.
  • Fig. 20 represents then the detail of the layer in the section; it can be observed that there was no damage to the layer adhesion to the substrate even in this case.
  • Fig. 21 shows a surface with a thick layer of suspension; and Fig. 22 on the right represents a 3D scan of the surface. Again, the layer is not damaged by the direct flame of higher temperature. The integrity and adhesion of the layer can also be observed in the detail of the layer section of Fig. 23.
  • Fig. 24 shows the surface of the sample with a thin geopolymer layer, and it can be seen that the layer integrity was not compromised even at very high burner performance and high temperature.
  • FIG. 25 shows the sample surface having a thick layer, and, as in the previous case, it can be seen that the coating withstood the heat load and no flaking or cracking has occurred, which is demonstrated in detail in the next figure 26 along with the detail of the layer in section and the 3D scan on the right.
  • Next Fig. 28 shows a sample with a thin geopolymer layer. There was no damage to the layer by cracking or flaking; the slight damage in the right part of the sample is due to dirt on the substrate surface during suspension application or the layer evaporation, and the layer is still visible on the sample, wherein fine lines caused by the brush during painting can be observed.
  • Fig. 29 shows a sample with a thick suspension layer. The thermally affected area is noticeable. There was no damage to the layer, and it is still clearly visible on the sample - the directed structure after the coating.
  • Fig. 30 shows a sample with a thin geopolymer layer. Even after 60 minutes, the geopolymer coating was not damaged, and the coating still showed excellent adhesion to the underlying substrate.
  • Test time 48 hours
  • the test was carried out in a hardening furnace, where the coated samples having a thin geopolymer layer were heated to 500°C within 2 hours, followed by holding at this temperature for 48 hours. As can be seen from Fig. 33, the coating withstood even a very long period of heat load at high temperature. The coating surface became matted to a certain degree; however, the integrity and adhesion remained unchanged. No cracks or flaking of the coating can be observed.

Abstract

La solution de l'invention est une suspension géopolymère pour revêtements insolubles résistant à la chaleur et à la corrosion sur les surfaces de produits en alliage de Fe, qui contient 20 à 25 % en poids d'une solution aqueuse de 80 à 90 pour cent d'acide phosphorique, 25 à 30 % en poids d'aluminosilicate, 4,6 à 5,2 % en poids de graphite, 5 à 7 % en poids de nanoparticules d'oxyde d'aluminium ayant une taille allant jusqu'à 90 nm et le reste est de l'alcool isopropylique. L'invention fait également référence à la préparation de cette suspension géopolymère, dans laquelle une solution aqueuse de 80 à 90 pour cent d'acide phosphorique est ajoutée à 100 ml d'alcool isopropylique, puis un aluminosilicate est graduellement ajouté et agité à la température du laboratoire pendant 8 à 15 min, et après 9 à 15 min tout en agitant, du graphite et des nanoparticules d'oxyde d'aluminium sont ajoutés une fois comme additifs et le mélange résultant est homogénéisé pendant encore 18 à 25 min.
PCT/IB2022/053799 2022-03-28 2022-04-24 Suspension de géopolymère contenant des nanoparticules pour revêtements résistant à la chaleur et procédé pour la production de celle-ci WO2023187456A1 (fr)

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Citations (3)

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AU2015238291A1 (en) * 2014-03-27 2016-10-06 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method for producing a macroporous and mesoporous geopolymer, with controlled porosity
CN111118490A (zh) * 2019-12-31 2020-05-08 浙江大学 一种耐高温高粘结性能地聚物金属防腐蚀涂层及其制备方法
CN113831102A (zh) * 2021-09-30 2021-12-24 湖南工业大学 连续玄武岩纤维增强磷酸基地质聚合物复合材料及其制备方法

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CN113969070B (zh) * 2020-10-23 2022-10-21 深圳优易材料科技有限公司 一种用于锅炉管护瓦的涂料及其制备方法和应用
CZ2021103A3 (cs) * 2021-03-05 2022-08-17 Univerzita J. E. Purkyně V Ústí Nad Labem Geopolymerní suspenze a způsob její přípravy

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AU2015238291A1 (en) * 2014-03-27 2016-10-06 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method for producing a macroporous and mesoporous geopolymer, with controlled porosity
CN111118490A (zh) * 2019-12-31 2020-05-08 浙江大学 一种耐高温高粘结性能地聚物金属防腐蚀涂层及其制备方法
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