CN114716879B - Intelligent coating material for early warning of damage perception corrosion and application thereof - Google Patents

Intelligent coating material for early warning of damage perception corrosion and application thereof Download PDF

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CN114716879B
CN114716879B CN202210233477.9A CN202210233477A CN114716879B CN 114716879 B CN114716879 B CN 114716879B CN 202210233477 A CN202210233477 A CN 202210233477A CN 114716879 B CN114716879 B CN 114716879B
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organic framework
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corrosion
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CN114716879A (en
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齐锴
范德红
邱于兵
郭兴蓬
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Huazhong University of Science and Technology
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    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • 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
    • C09D5/22—Luminous paints

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Abstract

The invention relates to an intelligent coating material for early warning of damage perception corrosion and application thereof, belonging to the field of anticorrosive coating materials. The fluorescent material comprises a metal organic framework material with a fluorescent effect and a hydrophobic resin, wherein the metal organic framework material with the fluorescent effect is preferably Zr-MOF, tb-MOF or Zn-MOF, and the hydrophobic resin is preferably acrylic resin, epoxy resin or fluorocarbon resin. When the damaged part of the coating does not reach the metal substrate, the metal organic framework material is contacted with an environmental medium to emit fluorescence of one color; when the damaged part of the coating reaches the metal substrate, the metal organic framework material reacts with metal ions generated by the corrosion of the substrate to emit fluorescence of another color. The damage of the coating and the metal corrosion part can be monitored simultaneously according to different fluorescent colors of the coating, so that the damage of the coating is indicated and the occurrence of metal corrosion is warned in advance.

Description

Intelligent coating material for early warning of damage perception corrosion and application thereof
Technical Field
The invention belongs to the field of anticorrosive coating materials, and particularly relates to an intelligent damage-sensing corrosion early-warning coating material and application thereof, in particular to an intelligent damage-sensing corrosion early-warning coating taking a metal organic framework material as a filler and application thereof, and particularly relates to an intelligent damage-sensing corrosion early-warning coating taking a metal ion fluorescent responsive metal organic framework material as a filler and application thereof.
Background
The metal has excellent mechanical property and is widely applied in the industrial fields of aerospace and the like. However, the corrosion problem associated therewith has also attracted a great deal of attention. The metal corrosion reduces the comprehensive performance of the metal material, and brings great loss to national economy. At present, one of the most common metal corrosion protection strategies is to utilize a surface coating technology to prevent a metal substrate from contacting with a corrosive medium, wherein an epoxy coating has the advantages of strong adhesion, high strength, stable chemical properties and the like, and has become one of the most widely applied anticorrosive coatings for metal surfaces. However, when the coating is exposed to a severe environment for a long time, the corrosion resistance is also lowered under the influence of thermal cycles, solar radiation and corrosive chemicals, and even in a very small range, damage of the coating inevitably accelerates corrosion of the metal, but corrosion of the metal under the coating is difficult to observe visually at an early stage, and if measures are not taken in time, a great loss is caused. Therefore, early detection of corrosion is of great significance.
Currently, some detection techniques are used for metal corrosion detection, such as: eddy current testing, ultrasonic testing, thermal image display and the like. These techniques, however, only remain at the physical level to detect the minute defects generated after metal corrosion. Compared with the prior art, the self-warning coating obtained by adding the indicator with the fluorescent characteristic into the coating has the advantages that the damage of the coating and the corrosion of the metal are detected through the change of the fluorescent color, a warning signal can be sent out before the metal structure is damaged, measures can be taken conveniently in time, and the metal is prevented from being further corroded.
Metal-organic frameworks (MOFs) are organic-inorganic hybrid materials with intramolecular pores formed by self-assembly of organic ligands and Metal ions or clusters through coordination bonds. The MOFs with fluorescence characteristics are more used for detecting target molecules/ions in biological cells or sewage, but are rarely used for detecting coating damage and early metal corrosion in an anticorrosive coating at present. Based on the method, the MOFs-based damage perception intelligent coating is developed to be used for detection of coating damage and early metal corrosion, and the method has practical significance.
Disclosure of Invention
The invention solves the problem that a metal coating in the prior art can not give out early warning on metal corrosion, and provides an intelligent damage perception coating material based on metal organic framework filler, which comprises a metal organic framework material with a fluorescent effect and hydrophobic resin. The damage-aware intelligent coating prepared by the invention has excellent anti-corrosion performance, and can monitor the damage of the coating and the metal corrosion condition in real time according to different fluorescent colors of the coating.
According to a first aspect of the present invention, there is provided a coating material based on a metal-organic framework material, comprising a metal-organic framework material having a fluorescent effect and a hydrophobic resin.
Preferably, the metal-organic framework material with fluorescence effect is Zr-MOF, tb-MOF or Zn-MOF.
Preferably, the hydrophobic resin is an acrylic resin, an epoxy resin or a fluorocarbon resin.
Preferably, the particle size of the metal organic framework material is 100nm-500nm.
Preferably, the mass ratio of the metal organic framework material in the coating is 0.5-10%.
According to another aspect of the invention, there is provided a use of any one of the coating materials based on metal-organic framework materials for damage perception and/or corrosion warning coating, wherein the damage and the corrosion of metal parts of the coating are detected according to the difference of the fluorescence color of the coating, so as to indicate the damage of the coating and/or the occurrence of metal corrosion warning.
Preferably, the application is specifically: and uniformly coating the coating based on the metal organic framework material on the surface of the metal material in a blade coating, spin coating or spraying manner, and then curing.
Preferably, the metal material is an aluminum alloy, carbon steel, or copper.
Preferably, the thickness of the coating is 10 μm to 80 μm.
Generally, compared with the prior art, the technical scheme conceived by the invention mainly has the following technical advantages:
(1) The invention discloses a damage perception intelligent coating based on a metal organic framework material as a filler. On one hand, the hydrophobic resin has strong adhesive force, mechanical property and chemical stability, and can isolate the contact of an environmental medium and a metal substrate as a part of a coating, thereby protecting the metal from corrosion. On the other hand, the metal organic framework as a filler provides the coating with fluorescence that is easy to observe. Therefore, the damage perception intelligent coating prepared by the invention has excellent anti-corrosion performance, and can monitor the damage and metal corrosion conditions of the coating in real time according to different fluorescent colors of the coating: when the damaged part of the coating does not reach the metal substrate, the metal organic framework material is contacted with an environmental medium to emit fluorescence of one color; when the damaged part of the coating reaches the metal substrate, the metal organic framework material reacts with metal ions generated when the substrate is corroded to emit fluorescence of another color, and the damaged part of the coating and the corroded part of the metal can be detected simultaneously according to the difference of the fluorescence colors of the coating, so that the damage of the coating is indicated, and the occurrence of metal corrosion is warned. The intelligent coating has the double-function early warning of coating damage and metal corrosion, and has the advantages of simple preparation process, low production price and wide application prospect.
(2) The metal organic framework material has rich light-emitting sources and energy transfer processes, and can be used for detecting various metal ions. Meanwhile, the catalyst has the advantages of large specific surface area, high porosity, abundant active sites and the like, and can be better contacted with a corrosive medium or a corrosive product.
(3) The solvent thermal method used in the invention has simple preparation and synthesis process and stable process, and simultaneously, the raw materials used in the invention can be directly purchased in the market and are easy to obtain.
Drawings
FIG. 1 is a scanning electron microscope image of the metal organic framework material prepared in example 1.
FIG. 2 shows the fluorescence of the metal organic framework material prepared in example 1 under a 365nm ultraviolet lamp in deionized water and an aluminum chloride solution, respectively.
FIG. 3 is the change in fluorescence after soaking the surface of the damage-aware intelligent epoxy resin coating prepared in example 1 at different depths of scratch damage in 3.5% NaCl solution for 12 h.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention relates to a damage perception corrosion early warning intelligent coating based on a metal organic framework material as a filler, which comprises the following steps:
(1) The metal organic framework material is prepared by a hydrothermal/solvothermal method.
(2) And (2) fully stirring and uniformly mixing the metal organic framework material prepared in the step (1) with resin, uniformly coating the mixture on the surface of a metal material in a blade coating, spin coating or spraying mode, and curing at room temperature for 2-3 days to obtain the damage perception intelligent coating.
The metal organic framework material in the step (1) can be Zr-MOF, tb-MOF, zn-MOF and other types, and the average particle size of the particles is 100-500nm. The general preparation method comprises the following steps: mixing metal salt and organic ligand according to a certain molar ratio, ultrasonically dispersing in a solvent, wherein the solvent can be N, N-dimethylformamide, ethanol, methanol, deionized water and the like or a combination thereof, placing the mixed solution at a certain temperature, sealing and reacting for a certain time, and cleaning, purifying and drying to obtain the corresponding metal organic framework material.
And (3) the metal material in the step (2) is a polished metal material. The polishing treatment method comprises the following steps: metals (10 mm multiplied by 4 mm) are polished by sandpaper with 400, 800 and 1200 meshes respectively, and are sequentially put into absolute ethyl alcohol and acetone for ultrasonic treatment for 5-30min so as to remove dirt and grease on the surfaces of the metals. And (4) putting the treated metal material into an oven for drying for later use.
The resin in the step (2) can be acrylic resin, epoxy resin, fluorocarbon resin and the like; the metal material can be aluminum alloy, carbon steel or copper and the like; the metal organic framework material accounts for 0.5-10% of the mass of the coating.
And (3) the damage perception intelligent coating in the step (2) is 10-80 mu m in thickness.
According to the method, the intelligent coating based on metal organic framework material as filler damage perception can be prepared, and the coating is composed of the metal organic framework material and resin. When the damaged part of the coating does not reach the metal substrate, the metal organic framework material is contacted with an environmental medium (water) to emit fluorescence of one color; when the damaged part of the coating reaches the metal substrate, the metal organic framework material reacts with metal ions generated when the substrate is corroded to emit fluorescence of another color, and the damaged part and the corroded part of the coating can be monitored simultaneously according to different colors of the fluorescence of the coating, so that the damaged part of the coating is indicated, and the corrosion of the metal is early warned. The intelligent coating has the double-function early warning of coating damage and metal corrosion, is simple in preparation process and has wide application prospect.
Specifically, zr-MOF is in contact with an environmental medium (water) and emits yellow fluorescence, and the Zr-MOF reacts with aluminum ions generated by aluminum alloy corrosion to emit green fluorescence; tb-MOF is in contact with an environmental medium (water) and emits blue fluorescence, and the Tb-MOF reacts with iron ions generated by corrosion of carbon steel and emits green fluorescence; zn-MOF is in contact with an environmental medium (water) and emits orange fluorescence, and reacts with copper ions generated by copper corrosion to emit purple fluorescence.
Example 1
A preparation method of a damage perception intelligent coating based on a metal organic framework material as a filler comprises the following steps:
(1) 0.54mmol of ZrOCl 2 ·8H 2 Dissolving O in 15mL of DMF, adding 1mL of concentrated hydrochloric acid, then adding 0.74mmol of 2, 5-dihydroxy terephthalic acid, ultrasonically mixing, and then adding 0.1mmol of rhodamine B and ultrasonically mixing to the solutionAnd (5) sounding for 30min. Putting the obtained mixed solution into a polytetrafluoroethylene reaction kettle to react for 12h at 80 ℃, cooling to room temperature, sequentially using DMF and ethanol to centrifugally wash the product for 3 times, and then putting the product into a vacuum drying oven at 60 ℃ for 12h to prepare the metal organic framework material Zr-MOF (UiO- (OH) 2 @ RhB), the microstructure of which is shown in fig. 1, the average particle size is about 200nm.
(2) Aluminum alloys (10 mm. Times.10 mm. Times.4 mm) were polished with 400, 800 and 1200 mesh sandpaper, respectively, and then placed in absolute ethanol and acetone in this order for ultrasonic treatment for 15min to remove dirt and grease on the surfaces of the aluminum alloys. And (5) drying the treated aluminum alloy in an oven for later use. 1.6 percent of UiO- (OH) 2 And @ RhB is added into the epoxy resin, and is stirred for 2 hours and then is uniformly coated on the surface of the treated aluminum alloy by using a film coating machine. The coating was cured at room temperature for 3 days, the thickness being 20 μm after curing. Scratch defects having a depth of 8 μm and 20 μm were respectively made on the epoxy resin coated surface to which the metal organic framework material was added using a scalpel, followed by performing a soaking experiment in 3.5% NaCl solution.
FIG. 2 shows the solution of UiO- (OH) in example 1 under a 365nm UV lamp 2 Fluorescence change before and after mixing the aqueous solution of @ RhB with the aqueous solution of aluminum chloride. As can be seen, under UV conditions, uiO- (OH) 2 The @ RhB aqueous solution exhibited yellow fluorescence, and after mixing with the aluminum chloride solution, exhibited significant green fluorescence.
FIG. 3 is an optical photograph of the surface of the epoxy resin coating with the metal organic framework added thereto in example 1 after the different depth scratches were soaked in 3.5% NaCl solution. As can be seen by fluorescence microscopy: after soaking in 3.5% NaCl solution for 12h, the epoxy resin coating with the metal organic framework material added exhibits macroscopic color change at different depths of scratches, yellow fluorescence at the shallow part of the scratch and green fluorescence at the deep part of the scratch, which is caused by the fact that the aluminum alloy at the shallow part of the scratch is not corroded and the metal organic framework material is contacted with the environmental medium (water) to generate yellow fluorescence during the soaking process of the sample in 3.5% NaCl solution; and the metal organic frame reacts with aluminum ions generated by the corrosion of the aluminum alloy to generate green fluorescence at the deeper part of the scratch, so that the damage of the coating and the metal corrosion can be early warned according to different fluorescence colors.
Example 2
A preparation method of a damage perception intelligent coating based on a metal organic framework material as a filler comprises the following steps:
(1) 0.1mmol of Tb (NO) 3 ) 3 ·6H 2 O was dissolved in a mixed solution of 4mL of ethanol and 4mL of water, 0.1mL of triethylamine was added, and then 0.1mmol of 2- (4-pyridyl) -1H-imidazole-4, 5-dicarboxylic acid was added, followed by ultrasonic mixing. And (3) putting the obtained mixed solution into a polytetrafluoroethylene reaction kettle, reacting for 72h at 120 ℃, cooling to room temperature, washing the product with deionized water for 3 times, and then putting the product into a vacuum drying oven at 55 ℃ for 12h to prepare the metal organic framework material Tb-MOF (Tb-HPyIDC), wherein the average particle size is about 400nm.
(2) Carbon steel (10 mm. Times.10 mm. Times.4 mm) was polished with 400, 800 and 1200 mesh sandpaper, respectively, and then subjected to ultrasonic treatment in absolute ethanol and acetone for 15min in order to remove dirt and grease on the surface of the carbon steel. And (5) putting the treated carbon steel into an oven for drying for later use. Tb-HPyIDC with the mass fraction of 5% is added into acrylic resin, stirred for 2h and then evenly coated on the surface of the treated carbon steel by using a film coater. The coating was cured at room temperature for 3 days, the thickness of the coating after curing being 50 μm. Scratch defects were made to a depth of 10 μm and 50 μm, respectively, on the surface of the epoxy resin coating layer to which the metal organic framework material was added using a scalpel, followed by a soaking experiment in a 3.5% nacl solution.
After 3.5% NaCl solution soaking for 3h, the epoxy resin coating with the metal organic framework material added exhibits macroscopic color change at different depth scratches, blue fluorescence at the shallow part of the scratch and green fluorescence at the deep part of the scratch, which is due to the fact that the carbon steel at the shallow part of the scratch is not corroded and the metal organic framework material generates yellow fluorescence when contacting with the environmental medium (water) during the soaking process of the sample in 3.5% NaCl solution; and at the deeper part of the scratch, the metal organic frame reacts with iron ions generated by the corrosion of carbon steel to generate green fluorescence, so that the damage of the coating and the metal corrosion can be warned according to different fluorescence colors.
Example 3
A preparation method of a damage perception intelligent coating based on a metal organic framework material as a filler comprises the following steps:
(1) Adding 0.987mmol of Zn (NO) 3 ) 2 ·6H 2 Dissolving O in 20mL of deionized water, dissolving 7.904mmol 2-methylimidazole in 20mL of deionized water, ultrasonically mixing, then adding 2mL of CdTe/CdS/ZnS Quantum Dot (QDs) and 10mL of Carbon Dot (CDs) solution into the mixed solution, putting the obtained mixed solution into a polytetrafluoroethylene reaction kettle to react for 2h at 60 ℃, cooling to room temperature, washing the product with deionized water for 3 times, and then putting the product into a vacuum drying box at 50 ℃ for 12h to prepare the metal organic framework material Zn-MOF (QDs/CDs @ ZIF-8) with the average particle size of about 500nm.
(2) Copper sheets (10 mm. Times.10 mm. Times.4 mm) were polished with 400, 800 and 1200 mesh sandpaper, respectively, and then placed in absolute ethanol and acetone in this order for ultrasonic treatment for 15min to remove dirt and grease from the surface of carbon steel. And (5) drying the treated copper sheet in an oven for later use. Adding QDs/CDs @ ZIF-8 with the mass fraction of 10% into fluorocarbon resin, stirring for 2h, and uniformly coating on the surface of the treated copper sheet by using a film coater. The coating was cured at room temperature for 3 days to a coating thickness of 70 μm. Scratch defects of 20 μm and 70 μm in depth were respectively made on the epoxy resin coated surface to which the metal organic frame material was added using a scalpel, followed by a soaking experiment in a 3.5% nacl solution.
After soaking in 3.5% NaCl solution for 6h, the epoxy resin coating with the metal-organic framework material added exhibited macroscopic color changes at different depths of the scratch, orange fluorescence at the lighter part of the scratch, and purple fluorescence at the deeper part of the scratch, since the copper at the shallower part of the scratch did not corrode during the soaking of the sample in 3.5% NaCl solution, and the metal-organic framework material generated orange fluorescence upon contact with the environmental medium (water); and the metal organic frame reacts with copper ions generated by copper corrosion to generate purple fluorescence at the deeper part of the scratch, so that the damage of the coating and the metal corrosion can be early warned according to different fluorescence colors.
It will be understood by those skilled in the art that the foregoing is only an exemplary embodiment of the present invention, and is not intended to limit the invention to the particular forms disclosed, since various modifications, substitutions and improvements within the spirit and scope of the invention are possible and within the scope of the appended claims.

Claims (6)

1. The application of the coating material based on the metal organic framework material in the damage perception and/or corrosion early warning coating is characterized in that the damage and metal corrosion parts of the coating are detected according to the different fluorescence colors of the coating, so that the occurrence of the damage and/or the early warning metal corrosion of the coating is indicated;
the coating material based on the metal-organic framework material comprises a metal-organic framework material with a fluorescent effect and a hydrophobic resin;
the metal organic framework material with the fluorescent effect is Zr-MOF, tb-MOF or Zn-MOF, wherein the ligand of the Zr-MOF is 2, 5-dihydroxyterephthalic acid, the ligand of the object molecule is rhodamine B, the ligand of the Tb-MOF is 2- (4-pyridyl) -1H-imidazole-4, 5-dicarboxylic acid, the ligand of the Zn-MOF is 2-methylimidazole, and the object molecule is CdTe/CdS/ZnS quantum dots and carbon dots;
the coating material containing the Zr-MOF, tb-MOF or Zn-MOF metal organic framework material is respectively used for damage perception and/or corrosion early warning of aluminum alloy, carbon steel or copper.
2. The use according to claim 1, characterized in that said use is in particular: and uniformly coating the coating based on the metal organic framework material on the surface of the metal material in a blade coating, spin coating or spraying manner, and then curing.
3. Use according to claim 2, wherein the coating has a thickness of 10 μm to 80 μm.
4. Use according to claim 1, wherein the hydrophobic resin is an acrylic resin, an epoxy resin or a fluorocarbon resin.
5. Use according to claim 1, wherein the metal organic framework material has a particle size of 100nm to 500nm.
6. The use according to claim 1, wherein the coating comprises from 0.5% to 10% by weight of the metal organic framework material.
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