Method for manufacturing of a carbon nanomembrane

Abstract

A method for the manufacture of a carbon nanomembrane is disclosed. The method comprises preparing a metallised polymer substrate and applying on the metallised polymer substrate a monolayer prepared from an aromatic molecule. The aromatic molecule is cross-linked to form a carbon nanomembrane. The carbon nanomembrane is coated by a protective layer and subsequently the carbon nanomembrane and the protective layer are released from the metallised polymer substrate. Finally, the carbon nanomembrane and the protective layer are optionally placed on a support. The protective layer can be optionally removed. The carbon nanomembrane can be used for filtration.

Claims

1. A method for the manufacture of a carbon nanomembrane comprising: preparing an aluminised polymer substrate; applying on the aluminised polymer substrate a monolayer prepared from an aromatic molecule with at least one phosphonic acid group, wherein the aromatic precursor molecules are selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, naphthalene, anthracene, pyrene, bipyridine, terpyridine, thiophene, bithienyl, terthienyl, pyrrole, and combinations thereof; cross-linking by irradiation of the aromatic molecule to form a carbon nanomembrane; protecting the carbon nanomembrane by a protective polymer layer; and removing the aluminised polymer substrate.

2. The method of claim 1, further comprising placing of the carbon nanomembrane with the protective polymer layer on a support layer.

3. The method of claim 2, further comprising removal of the protective polymer layer.

4. The method of claim 1, wherein the aluminised polymer substrate is an aluminised polyethylene terephthalate substrate.

5. The method of claim 1, wherein the protective polymer layer is made of polymethylmethacrylate.

6. The method of claim 1, wherein the protective polymer layer is removed in acetone.

7. The method of claim 1, wherein the protective polymer layer is created by electrospinning a porous polymer.

8. A method for the manufacture of a carbon nanomembrane comprising: preparing a metallised polymer substrate; applying on the metallised polymer substrate a monolayer prepared from an aromatic molecule; cross-linking the aromatic molecule to form a carbon nanomembrane; protecting the carbon nanomembrane by a protective layer; and removing the metallised polymer substrate; wherein the protective layer is created by electrospinning a porous polymer.

Description

DESCRIPTION OF THE DRAWINGS

(1) For a more complete understanding of the present invention and the advantages thereof, reference is now made to the following description and the accompanying drawings, in which:

(2) FIG. 1 shows the method for fabrication according to this disclosure

(3) FIG. 2 shows the precursor molecule

(4) FIG. 3A and FIG. 3B shows the gas separation characteristics of a carbon nanomembrane according to this disclosure (FIG. 3A) and in the prior art (FIG. 3B).

(5) FIGS. 4A, 4B and 4C show diagrams of the carbon nanomembranes during the manufacturing steps

DETAILED DESCRIPTION OF THE INVENTION

(6) The invention will now be described on the basis of the drawings. It will be understood that the embodiments and aspects of the invention described herein are only examples and do not limit the protective scope of the claims in any way. The invention is defined by the claims and their equivalents. It will be understood that features of one aspect or embodiment of the invention can be combined with a feature of a different aspect or aspects and/or embodiments of the invention.

(7) The method for fabrication of the carbon nanomembranes comprises three steps, as shown in FIG. 1.

(8) In a first step 100, a self-assembled monolayer from low molecular aromatic precursor molecules with at least one surface active group is prepared on a substrate of an aluminized polymer foil. The aluminized polymer foil is substantially flat and does not require substantial pre-treatment, unlike the gold layers and the silicon layers known in the art.

(9) The term low-molecular molecules means such compounds that are not in an oligomer or polymer form. The term aromatics includes the term heteroaromatics in this disclosure, i.e. the term aromatics means aromatic compounds that contain no heteroatoms or one or more heteroatoms in at least one aromatic ring. Preferably, the aromatic precursor molecules are elected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, naphthalene, anthracene, pyrene, bipyridine, terpyridine, thiophene, bithienyl, terthienyl, pyrrole, and combinations thereof. The aluminized polymer foil could be, but is not limited to, an aluminized polyethylene terephthalate (PET) film.

(10) This preparation is done by wet chemistry (from a solution) or by organic vapour phase deposition of the precursor molecules onto the substrate. The surface-active group can be e.g. phosphonic acids, alcoxysilanes, alcohols or carboxylic acids. The aluminized polymer foil can be substituted by an aluminium foil if the aluminium foil has the necessary low roughness for a homogeneous formation of a self-assembled monolayer.

(11) It would also be possible to use other metallised polymer foils. For example, it would be possible to use gold or silver instead of aluminium. It would be also possible to use films made of other polymers, such as polyethylene, polyester, polypropylene, polycarbonate, nylon, polyimide, polyaramide (aromatic amides), silane- and siloxane-based polymers like polydimethylsiloxane (PDMS), poly (vinyl trimethyl silane) etc., poly (phenylene oxide), polystyrene, poly (4-methyl pentene-1), polysulfone and others. Aluminium has the advantage that it is comparatively inexpensive. The PET is used as the polymer substrate because one can create a polymer substrate with a surface having a small degree of roughness.

(12) The molecules in the self-assembled monolayer are cross-linked in step 110 by irradiation with low energy electrons (10-1000 eV) or by other irradiation to form a carbon nanomembrane.

(13) The carbon nanomembrane is then released from the aluminized polymer film by means of a protective layer. The CNM/ metallised polymer structure formed in step 110 is first coated with a protective layer, e.g. a layer of polymethylmethacrylate (PMMA) or other polymer in step 120 to form a sandwich structure. The coating can be performed by e.g. spin coating, drop casting, electrospinning Then the edges of the protective layer/CNM/metallised polymer sandwich structure are cut in step 130 and the sandwich structure is let to float or is immersed in step 140 into an aqueous sodium hydroxide solution (preferably 5% concentration) at preferably 50 C. or 60 C. temperature. This basic solution of sodium hydroxide etches simultaneously the aluminium film and the PET film, which allows the separation of the protective layer/CNM structure from the substrate. This is advantageous over the prior art, such as that known from Beyer et al, in which the removal of the gold layer from mica needs to be carried out in two steps

(14) After the aluminium film is completely etched away, the protective layer/CNM structure floats on the liquid/air interface of the solution and can be optionally transferred to a solid or perforated support in step 150 to create a stack. The support can be of any kind, e.g. a porous polymer, a metallic grid, etc.

(15) In a last step 160, the protective layer can be optionally removed. For example, a PMMA-based protective layer could be dissolved by immersion of the stack in acetone.

(16) It is also known that CuCl.sub.2 and KOH can be used as an etchant for the aluminium layer. However, the etching rate is much slower. In the case of CuCl.sub.2 the protective layer/CNM structure does not lift easily off the metallised polymer when the polymer is a PET foil. In this case, an additional slight dipping in 1-5% NaOH solution is necessary to promote the separation of the polymer PET layer from the protective layer/CNM.

(17) Should other metals (Au, Ag, Cu) be used, then a different etchant needs to be used. It is thought, for example, that a gold layer could be removed using aqua regia or an iodine solution.

(18) The substrate used in step 100 is flexible and cheap. The role of the substrate is to reduce the material costs and allow upscaling of the production process.

(19) The surface-active group of the aromatic precursor molecules described in this method is a phosphonic acid, which is known to be very stable in air and in water. Therefore, it does not require special equipment, work under inert atmosphere and preliminary drying and degassing of the organic solvent. These phosphorus-based organic compounds have strong chemical affinity towards aluminium, which rules out the necessity of harsh cleaning of the vessels, used for preparation of the self-assembled monolayer.

(20) The solution for the preparation of the self-assembled monolayer can be handled in air. The formation of the self-assembled monolayer happens in shorter time (e.g. less than 6 hours for a biphenyl-based self-assembled monolayer on the aluminized polymer substrate, in comparison to three days for a biphenyl-based self-assembled monolayer on a gold substrate according to the procedure used to date). The formed self-assembled monolayer from step 100 is more stable in ambient environment.

(21) It has been found that unlike prior art methods the solution does not substantially degrade and can be used multiple times.

(22) The process of releasing the carbon nanomembrane from the substrate does not involve hydrofluoric acid.

(23) FIGS. 4A to 4C show the various manufacturing methods. In FIG. 4A a metallised polymer has a self-assembled monolayer placed on top of the metallised polymer film (step 100). The self-assembled monolayer is then irradiated with electrons to form the CNM/metallised polymer structure (step 110).

(24) FIG. 4B shows the subsequent step in which the CNM/metallised polymer structure is coated with a polymer film as the protective layer (step 120) which is then etched to form a protective layer/CNM structure.

(25) In FIG. 4C the protective layer/CNM structure can be left alone (top path), have a support layer attached (step 150, middle path) and/or then the protective layer can be removed (step 160, lower path).

(26) The carbon nanomembranes can be used as ballistic membranes (separation according to the kinetic diameter of the particles) for gas separation and ultrafiltration. It is possible to control properties like the density and size distribution of intrinsic pores (pores formed during the fabrication without additional efforts like treatment of the substrate or formed membranes by e.g. ion bombardment or etching) by the selection of the precursor molecules and process parameters for the formation of the self-assembled monolayer by analogy with the methods described in ACS Nano, Vol. 7, No 8, 6489-6497.

Example

(27) Preparation of a self-assembled monolayer of the precursor [3-([4-Nitro-1,1-biphenyl]-4-yloxy)-propyl]-phosphonic acid (as shown in FIG. 2) onto an aluminized polyethylene terephthalate film as the substrate with a minimum thickness of the PET film of 75 microns and a thickness of the Al-layer of 14 nm. Preparation was done by immersion of the substrate into a solution of the precursor molecule in technical ethanol.

(28) Crosslinking of the molecules in the self-assembled monolayer by irradiation with low energy electrons (100 eV) with an electron dose of 50 mC/cm.sup.2.

(29) Transfer of thus prepared carbon nanomembrane from the aluminized PET foil to a perforated polymer support. The CNM/Al/PET structure is first protected by a protective layer of polymethylmethacrylate (PMMA) attached to the surface by consecutively spin coating of 50 K and 950 K PMMA solutions. Then the edges of the PMMA/CNM/Al/PET sandwich structure were cut and the sandwich structure was immersed into or let to float on an aqueous 5%-NaOH solution at 60 C. temperature. This basic solution etches simultaneously the aluminium film and the PET film, which allows the separation of the PMMA/CNM structure from the substrate. After the aluminium is completely etched away, the PMMA/CNM structure floats on the liquid/air interface and can be transferred to the porous polymer support. In a last step, the sacrificial PMMA-layer is dissolved by immersion of the stack in acetone.

(30) The so prepared composite membrane (FIG. 3A) is very dense with a permeance of hydrogen lower compared to a traditionally prepared carbon nanomembrane (FIG. 3B). FIG. 3B is taken from M. Ai, S. Shishatskiy, J. Wind, X. Zhang, C. T. Nottbohm, N. Mellech, A. Winter, H. Vieker, J. Qiu, K.-J. Dietz, A. Glzhuser, A. Beyer, Carbon Nanomembranes (CNMs) Supported by Polymer: Mechanics and Gas Permeation, Advanced. Materials 26, 3421 (2014). The cut-off kinetic diameter (gases with a smaller kinetic diameter can pass with high permeance, gases with larger kinetic diameter are hindered) is at around 2.8 also the lowest observed so far. This carbon nanomembrane is a starting point for tuning the gas separation characteristic for specific tasks by changing the structure of the precursor molecules to more complex shapes resulting in different packing densities of the self-assembled monolayers and different diameters of the intrinsic pores. This demonstrates that it is possible to form high quality CNMs (without larger pores) from SAMs, which were formed on the non-atomically flat surfaces. This is something which a person knowing the state of the art would not have expected.