# US 11,999,623 B2 · Art protection with the use of graphene materials

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- Number: US 11,999,623 B2
- Document ID: US11999623B2
- Status: Granted
- Kind: B2
- Application number: 17/420,034
- Filed: 2019-12-18
- Published: 2022-03-17
- Granted: 2024-06-04
- Earliest claimed: 2018-12-31
- Assignees: Foundation of Research and Technology Institute of Chemical Engineering Sciences (FORTH-ICEHT); Consorzio Interuniversitario Per Lo Sviluppo Dei Sistemi A Grande Interfase (CSGI)
- Applicants: Foundation of Research and Technology Institute of Chemical Engineering Sciences (FORTH-ICEHT); Consorzio Interuniversitario Per Lo Sviluppo Dei Sistemi A Grande Interfase (CSGI)
- Inventors: Costas Galiotis; Piero Baglioni; Giorgos Anagnostopoulos; Maria Giovanna Pastore Carbone; Giovanna Poggi; Konstantinia Papadimitriou; Giorgos Paterakis; Maria Kotsidi; Giorgos Gorgolis
- Web page: https://patentgrep.com/patent/US11999623B2

## CPC

- B32B 37/04: characterised by the partial melting of at least one layer
- C01B 32/186: by chemical vapour deposition [CVD]
- B32B 33/00: Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
- B32B 38/10: Removing layers, or parts of layers, mechanically or chemically
- C09D 7/48: Stabilisers against degradation by oxygen, light or heat
- C23C 16/01: on temporary substrates, e.g. substrates subsequently removed by etching
- C23C 16/26: Deposition of carbon only
- B32B 2307/00: Properties of the layers or laminate
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- C01P 2006/60: Optical properties, e.g. expressed in CIELAB-values
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- 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 (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- 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 (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

The inventive method for applying a protective graphene coating onto a surface, especially onto a two- or three dimensional artwork or colored surface, comprises the following steps: a) depositing, preferably by chemical vapor deposition (CVD), graphene onto a at least one side of a supporting substrate to produce a graphene/substrate composite including a continuous graphene membrane formed on at least one side of said substrate; b) removing the substrate, or lifting off the graphene from the substrate and c) depositing the graphene membrane onto the surface. A protective graphene coating prepared and deposited by this method provides protection for a surface, especially a two- or three-dimensional artwork or a colored surface, against color degradation, especially fading, yellowing and discoloration due to exposure to UV radiation, dirt, dust, moisture, chemical and/or oxidizing agents.

## Claims

### Claim 1

A method for protecting a two- or three-dimensional artwork against color degradation, the method comprising the steps of:
a) depositing graphene onto at least one side of a supporting substrate to produce a graphene/substrate composite comprising a continuous graphene membrane formed on at least one side of said supporting substrate;
b) removing said supporting substrate, or lifting off the graphene membrane from said supporting substrate;
c) depositing the graphene membrane onto the two- or three-dimensional artwork; and
d) removing the graphene membrane without irreversible interference with the artwork.

### Claim 2 (depends on 1)

A method according to claim 1, wherein the supporting substrate is selected from the group consisting of a metal, polymer and non-metal material.

### Claim 3 (depends on 2)

A method according to claim 2, wherein the supporting substrate is selected from the group consisting of a flexible sheet and a foil material.

### Claim 4 (depends on 1)

A method according to claim 1, further comprising the step of:
after step a), applying a supporting layer onto the graphene membrane bearing side of the graphene/substrate composite to produce a supporting layer/graphene/substrate composite.

### Claim 5 (depends on 4)

A method according to claim 4, wherein the supporting layer is selected from the group consisting of a polymer-based backing substrate and adhesive film.

### Claim 6 (depends on 5)

A method according to claim 5, wherein the polymer-based backing substrate or the adhesive film is at least one member selected from the group consisting of a flexible material and transparent.

### Claim 7 (depends on 5)

A method according to claim 5, wherein the polymer-based backing substrate or the adhesive film is at least one member selected from the group consisting of a PET-, PMMA-, and PET/silicone film or membranes.

### Claim 8 (depends on 4)

A method according to claim 4, wherein the supporting layer is a pressure-sensitive adhesive film.

### Claim 9 (depends on 1)

A method according to claim 1, wherein the color degradation is fading, yellowing or discoloration due to exposure to UV radiation.

### Claim 10 (depends on 1)

A method according to claim 1, wherein additionally an oxygen plasma treatment is performed after step a).

### Claim 11 (depends on 1)

A method according to claim 1, wherein, in step c, depositing of the graphene membrane onto the surface is performed via a roll-to-roll coating or unrolling process.

### Claim 12 (depends on 11)

A method according to claim 11, wherein the roll-to-roll coating or unrolling process are performed under at least one of the following conditions:
a temperature of 45 to 70° C., a pressure of 0.1 to 10 MPa, and a rolling speed of 0.1 to 5 mm/sec.

### Claim 13 (depends on 1)

A method according to claim 1, wherein the protective graphene coating is a continuous graphene membrane having dimensions from a few centimeters up to several meters is deposited to fully or at least partially cover the surface or artwork.

### Claim 14 (depends on 1)

A method according to claim 1, wherein in step a) a continuous graphene monolayer or multilayer membrane is formed.

### Claim 15 (depends on 14)

A method according to claim 14, wherein the membrane has a thickness of from 0.33 nm to n×0.33 nm, wherein n is a number of layers in the multilayer membrane.

### Claim 16 (depends on 1)

A method according to claim 1, wherein the surface to be coated exhibits a surface roughness from 1 nm to 10 μm and/or a surface energy of 17 to 64 mN/m.

### Claim 17 (depends on 1)

A method according to claim 1, wherein the surface to be coated comprises a member selected from the group consisting of canvas, paper, cardboard, photographic paper, wood, a polymer, a painting, papyrus, a cover of old music vinyl records, a cover page of a magazine, an interior page of a magazine, a book cover, a page of a book, a mural, artistic masonry and an art installation.

### Claim 18 (depends on 1)

A method according to claim 1, further comprising protection for the artwork against dirt, dust, moisture, chemical and/or oxidizing agents.

### Claim 19 (depends on 1)

A method according to claim 1, wherein applying the supporting layer is performed via a roll-to-roll coating process.

### Claim 20 (depends on 1)

A method according to claim 1, wherein applying the supporting layer is performed via direct compression transfer.

### Claim 21 (depends on 1)

A method according to claim 1, wherein in step a) a graphene monolayer or multilayer membrane is formed, the graphene monolayer or membrane having a thickness of from 0.33 nm to n×0.33 wherein n is a number of layers in the multilayer membrane.