Patent Application
20140183135
The invention is directed to a nanosieve composite membrane, a method for preparing a nanosieve composite membrane, a roll-to-roll apparatus for carrying out the method, and a method for separating a feed flow with particulate matter.
Membranes are widely used in various industrial processes, such as in the field of fluid filtration, gas separation, air cleaning, membrane-reactors etc. By tuning their structural morphology and material composition, membranes can be applied for different purposes. Membranes are usually fabricated porous or dense using organic (e.g. polymer) and/or inorganic (e.g. ceramic) materials. Permeation through membranes usually functions by a pore-based diffusion phenomenon or a solution-diffusion phenomenon depending on their structural morphology.
Fluid filtration can be done based on various characteristics of the particles to be separated like charge, adsorptivity, size, mass, etc., of which size based filtration is the most preferred due to its simplicity and effectiveness. Usually ceramic membranes are most successfully used for filtration (made of e.g. alumina), but have a random porosity with a broad pore-size distribution and also have a multitude of tortuous and dead-end pores.
A solution to this problem is the use of thin, geometrically defined ceramic sieves (microsieve or nanosieve), which have circular non-tortuous perforations with a pre-determined size-distribution and porosity. Moreover, they also have a controllable uniform thickness down to a few tens of nanometers.
Although microsieves (with a pore size defined by a pore diameter of about 2-10 μm) can be fabricated in various ways, the fabrication of nanosieves (with a pore-size of less than 200 nm) is not trivial. Both micro and nanosieves can be fabricated using polymers (Vogelaar et al., Advanced Materials 2003, 15(16), 1385-1389 and Vlassiouk et al., Proceedings of the National Academic Sciences of the United States of America 2009, 106(50), 21039-21044), but they suffer from fouling, swelling, and non-resistance to specific chemicals that are used in filtration processes. Moreover, self-standing polymer nanosieves need to have a thickness in the micrometer scale (or more) for sufficient mechanical strength, but this increases the flow resistance through them.
WO-A-2006/119915 describes a polymeric membrane having a pore diameter in the range of 0.1-100 nm supported by a carrier membrane having a pore diameter of 1-500 μm.
Inorganic nanosieve membranes on the other hand do not have the aforementioned drawbacks. They can be made very thin, strong and chemically stable. Currently, the fabrication of inorganic nanosieves is limited to a silicon wafer based micromachining confined to clean room processing, which makes it expensive and thus hinders its wide applicability. The industrial scalability of inorganic nanosieve production is crucial for cost reduction and to widen its application base.
U.S. Pat. No. 5,968,326 describes a composite membrane comprising an inorganic ion-conducting layer on a cation-selective organic polymer membrane substrate. As possible material for the inorganic ion-conducting layer, this document mentions zeolites.
US-A-2005/0 070 193 describes a sheetlike flexible non-woven substrate having a multiplicity of openings and having a ceramic porous coating. This document further describes the possibility of pre-coating the non-woven with a metal oxide or organosilane adhesion promoter.
US-A-2009/0 069 616 discloses composite membranes comprising a molecular sieve on a polymeric support. The support can have pores or openings in the range of 2 to 100, preferably 20 to 50 nm.
EP-A-1 611 941 describes a membrane on a support for filtering liquid. The disclosure of this document is limited to a banded support structure, having non-porous strips. In addition, the membrane of this document requires a protection layer encapsulating the inorganic membrane and the support.
There remains a need in the art for nanosieves that can be successfully used for filtration and can easily be produced.
Objective of the invention is to provide a nanosieve that overcomes at least part of the problems faced in the prior art.
Further objective of the invention is to provide a nanosieve composite with a polymer membrane support that is protected from degrading (such as in aggressive fluids).
The inventors found that one or more of these objectives can at least partially be met by supporting an inorganic nanosieve layer on a protected porous polymeric support.
Hence, in a first aspect, the invention is directed to a nanosieve composite comprising an inorganic nanosieve layer supported on a porous polymer membrane substrate and an adhesion layer or underlayer between the inorganic nanosieve layer and the polymer substrate, wherein said polymer membrane comprises an inorganic coating such that the polymeric support is sandwiched between the inorganic coating and the inorganic sieve layer, and wherein said inorganic nanosieve layer has an average pore diameter as determined by scanning electron microscopy of 200 nm or less.
The nanosieve composite of the invention provides a geometrically patterned inorganic thin-film nanosieve supported on a macroporous polymer membrane. To protect the polymer support from degrading by aggressive fluids penetrating though the nanopores, the polymer support is provided with a metallic adhesion layer or underlayer between the inorganic nanosieve layer and the polymer substrate The adhesion layer or underlayer may be present only on the support side of the inorganic nanosieve layer. Although the inorganic interlayer (viz. the adhesion layer or underlayer) enhances adhesion, it also serves the purpose of protecting the polymer support from degrading.
The inorganic-polymer-inorganic sandwich design of the invention combines the advantages of the inorganic nanostructured thin-film (such as precise pore definition, ultrathin selective layer, nanoscale robustness and chemical inertness) with the advantages of the polymer support membrane (such as flexibility, rollability, cheapness and industrial scalability. The nanosieve composite is therefore not only useful for air filtration, but also for liquid filtration processes.
The inorganic nanosieve layer can be a ceramic nanosieve layer. Suitable ceramic materials include silicon nitride (Si3N4), SiO2, and Al2O3. The inorganic nanosieve layer can also be a metal (or alloy) nanosieve comprising one or more from the group consisting of chromium, copper, tin, nickel and aluminium.
The average pore diameter of the inorganic nanosieve layer (on the substrate side) as determined by scanning electron microscopy is of 200 nm or less, such as 150 nm or less, preferably 100 nm or less. From a practical point of view, the average pore size of the nanosieve is preferably 1 nm or more, such as 2 nm or more, or 5 nm or more. Other means for measuring the average pore diameter include bubble porosimetry.
Suitably, the inorganic nanosieve layer is applied as a thin film on the polymer membrane support. The inorganic nanosieve layer can, for example, have a thickness in the range of 10-200 nm, such as in the range of 20-150 nm, or in the range of 50-100 nm. Layer thicknesses as defined herein can be determined by techniques well-known to the person skilled in the art, including DekTak profilometry or HR-SEM (high resolution scanning electron microscopy).
The polymer membrane support can suitably be a polymer support. Suitable materials for the polymer membrane include polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyimide or any other polymer, and any mixtures thereof. In order to provide sufficient mechanical support, the polymer membrane support typically has a thickness of at least 1 μm, preferably at least 2 μm more preferably at least 5 μm. From a practical point of view it is not desirable to use a polymer membrane support having a thickness of more than 100 μm. The applied polymer membrane support can advantageously be derived from a polymer foil or web.
The polymer membrane support is porous. The average pore diameter of a porous polymer membrane as determined by bubble porosimetry can suitably be in the range of 1-20 μm, such as in the range of 2-10 μm. Alternatively (or in addition to pores), the polymer membrane support can have periodic grooves or channels. In case the polymer membrane support has grooves or channels, the average groove or channel width is preferably in the range of 1-20 μm, such as in the range of 2-10 μm.
The polymer membrane support in the nanosieve composite of the invention further comprises an inorganic coating. In a special embodiment, the polymer membrane support is sandwiched between inorganic layers. This inorganic coating may be in direct contact with the polymer membrane support. In an embodiment the coverage of the inorganic coating on the polymer membrane is such that essentially no surface of the polymer membrane is exposed after the coating has been applied. This does not necessarily mean that the inorganic coating entirely covers the polymer membrane. The adhesion layer or underlayer will cover parts of the inorganic membrane that are not covered by the inorganic coating.
The inorganic coating may have a thickness in the range of 1-200 nm, such as in the range of 5-150 nm, or in the range of 10-100 nm. These thicknesses are suitable for providing sufficient protection to the polymer membrane.
Suitably, the material of the inorganic coating is the same as the material of the inorganic nanosieve layer. Hence, in a preferred embodiment, the inorganic coating is a ceramic coating, such as a silicon nitride coating. Other materials that may be used for the inorganic coating include metals or alloys. The inorganic coating may therefore also comprise one or more selected from the group consisting of chromium, copper, tin, nickel and aluminium.
The nanosieve composite of the invention further comprises an adhesion layer or underlayer between the inorganic nanosieve layer and the polymer membrane support. This layer may serve to improve the adhesion of the inorganic nanosieve layer onto the polymer membrane support (which is preferably organic) and/or to provide additional protection to the polymer membrane support (such as against aggressive fluids). The terms “adhesion layer” and “underlayer” are well-known to refer to similar layers in the art and can be used interchangeably herein.
Suitably, the adhesion or underlayer layer is a metal layer. The adhesion layer or underlayer can comprise one or more selected from the group consisting of tantalum, chromium, titanium, and molybdenum. The adhesion or underlayer can serve the purpose of protection.
The adhesion layer or underlayer can have a layer thickness in the range of 1-100 nm, such as in the range of 2-70 nm or in the range of 5-50 nm.
Preferably, the nanosieve composite of the invention is flexible. The term “flexible” as used in this application is meant to refer to resilient and capable of being flexed without permanent deformation or rupture. Advantageously, this allows the nanosieve of the composite to be rollable and be processed in a roll-to-roll manufacturing process.
In an embodiment, the nanosieve composite of the invention is transparent. It is preferred that the nanosieve composite of the invention is transparent for ultraviolet radiation. Such an embodiment is highly advantageous in an application wherein the nanosieve composite is used for biofiltration. Filtered microorganisms can then be killed by ultraviolet radiation treatment.
In a further aspect, the invention is directed to a method for preparing a nanosieve composite, preferably one as defined hereinabove, comprising (preferably in the indicated sequence) the steps of
As a polymer substrate a non-porous polymer foil can be applied. The polymer materials can be as defined hereinabove. Optionally, an adhesion layer or underlayer is deposited on the polymer substrate. The adhesion layer or underlayer can, for instance, be deposited on the polymer substrate by an evaporation technique.
In step c) a first layer of inorganic material is deposited onto the polymer substrate or alternatively onto the optional adhesion layer or underlayer. This can suitably comprise a vapour deposition technique (including physical vapour deposition and chemical vapour deposition), such as plasma enhanced chemical vapour deposition. Plasma enhanced chemical vapour deposition has the advantage that a relatively low processing temperature of about 100° C. can be employed.
Perforation of the polymer substrate in step d) may be performed by laser ablation, such as pulsed laser ablation. In accordance with this step the polymer substrate is rendered porous. The perforation of the polymer substrate may result in the polymer substrate having pores, grooves, and/or channels.
In optional step e), part of the adhesion layer or underlayer that is exposed (on the polymer substrate side) after the polymer perforation is removed. In practice, steps d) and e) may be performed in a single step, for instance, by laser ablation. Alternatively, part of the adhesion layer or underlayer can be removed by an etching process, such as plasma etching. Preferably, the part of the adhesion layer or underlayer that is exposed by removal of the polymer perforation is removed in optional step e). In a preferred embodiment, the entire part of the adhesion layer or underlayer that is exposed is removed in step e).
In an embodiment the polymer is perforated after which the optional adhesion layer is applied onto the perforated polymer. Subsequently, part of the adhesion layer in the perforated polymer is removed to expose the first layer of inorganic material in the polymer perforations.
In step f) of the method, a second layer of inorganic material is deposited on the side opposite of the first layer of inorganic material onto said perforated polymer. Advantageously, the same type of inorganic material could be deposited in steps c) and f). Deposition of the inorganic material in step f) can again be suitably performed using a vapour deposition technique (including physical vapour deposition and chemical vapour deposition), such as plasma enhanced chemical vapour deposition.
A photoresist is applied onto the first layer of inorganic material. Various kinds of suitable photoresists are well-known in the field of lithography. Both positive photoresists, as well as negative photoresists may be employed. Preferably, the photoresist is an ultraviolet sensitive resist. A suitable technique for applying the photoresist onto the first layer of inorganic material is by coating such as from coating apparatus, such as a slot-die coater. However, the photoresist can also be applied using a printing process. Typically, the thickness of the photoresist layer is in the range of 50-500 nm, such as in the range of 100-300 nm or 150-250 nm.
After the photoresist has been applied onto the first layer of inorganic material a nanosieve pattern is generated in the photoresist. This may for example be done by lithography techniques, such as nanoimprint lithography or laser-interference lithography. The generated nanosieve pattern is thereafter transferred into the first layer of inorganic material in step i). A suitable technique for carrying out this step is by etching, such as plasma etching and/or chemical etching. Plasma etching can, for example, involve a CF4+O2 mixed mode plasma.
Upon having transferred the nanosieve pattern into the first layer of inorganic material, the photoresist can be removed. This may also be done using a plasma technique, such as using an 02 plasma.
The method of the invention is further clarified by
In an alternative method for preparing a nanosieve composite, the sequence of method steps is altered. This alternative method comprises successively:
Advantageously these methods can be performed using the roll-to-roll approach. This allows an easy and quick fabrication of the nanosieve composites of the invention. Moreover, it enables mass-production.
In a further aspect the invention is directed to an apparatus for manufacturing composite nanosieve membranes, preferably by carrying out the method of the invention.
The apparatus of the invention comprises
The first deposition unit can deposit a first layer of inorganic material onto on surface of the substrate, while the further deposition unit can deposit a second layer of inorganic material on the opposite surface of the substrate. This allows a protection of the substrate by the inorganic material on both surfaces of the substrate.
The apparatus can comprise a third deposition unit, for instance an evaporator, arranged upstream of the first or second deposition unit, for applying a thin metal layer on the first or second substrate surface before applying said inorganic material layer onto said first or second substrate surface. This thin metal layer can, for instance, be an adhesion layer or underlayer as described herein. Alternatively, the adhesion layer can be applied by the first deposition unit.
Preferably, the apparatus is a roll-to-roll apparatus, wherein the apparatus comprises a substrate rewinding system for rewinding the processed substrate, wherein both, the substrate supply and the substrate receiver comprise a frame for rotatably holding a roll of continuous substrate web.
An example of such a roll-to-roll apparatus is shown in
The nanosieve composites of the invention can advantageously be employed in filtration processes, such as an air/gas filtration process, or a liquid filtration process. In particular, the nanosieve composites of the invention are suitable for a liquid filtration process.
Accordingly, in a further aspect the invention is directed to a method for separating a feed flow with particulate matter comprising passing the feed flow over a nanosieve composite of the invention.
When the feed flow with the contaminants is passed over the nanosieve composite of the invention, a permeate (or filtrate) flow will pass through the nanosieve composite, while retentate containing contaminants that are incapable of passing through the nanosieve will remain at the feed side of the nanosieve composite. Due to the flexibility of the polymer membrane support, it may be preferable to provide a macroporous rigid surface for further support.
A specific selection of the polymer membrane support further allows a dual separation. For example, the inorganic nanosieve layer provides a size exclusion, while the polymer membrane support provides an exclusion based on size, hydrophilicity, charge, and the like. Such dual separation is advantageous for decreasing the amount of steps in separation processes.
| Number | Date | Country | Kind |
|---|---|---|---|
| 11163690.8 | Apr 2011 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/NL2012/050283 | 4/26/2012 | WO | 00 | 10/25/2013 |
| Number | Date | Country | |
|---|---|---|---|
| 20140042095 A1 | Feb 2014 | US |
