WO2011117692A1 - Method for the production of polymeric membranes having an ordered arrangement of high-aspect-ratio nanopores, by means of heavy ion bombing - Google Patents

Method for the production of polymeric membranes having an ordered arrangement of high-aspect-ratio nanopores, by means of heavy ion bombing Download PDF

Info

Publication number
WO2011117692A1
WO2011117692A1 PCT/IB2010/056057 IB2010056057W WO2011117692A1 WO 2011117692 A1 WO2011117692 A1 WO 2011117692A1 IB 2010056057 W IB2010056057 W IB 2010056057W WO 2011117692 A1 WO2011117692 A1 WO 2011117692A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer film
nanopores
amplitude mask
layer
film
Prior art date
Application number
PCT/IB2010/056057
Other languages
French (fr)
Inventor
Daniele Pullini
Mauro Sgroi
Original Assignee
C.R.F. Società Consortile Per Azioni
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by C.R.F. Società Consortile Per Azioni filed Critical C.R.F. Società Consortile Per Azioni
Priority to US13/636,000 priority Critical patent/US9376538B2/en
Publication of WO2011117692A1 publication Critical patent/WO2011117692A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/0032—Organic membrane manufacture by inducing porosity into non porous precursor membranes by elimination of segments of the precursor, e.g. nucleation-track membranes, lithography or laser methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/42—Details of membrane preparation apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/08—Patterned membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1076—Micromachining techniques, e.g. masking, etching steps or photolithography
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1079—Inducing porosity into non porous precursors membranes, e.g. leaching, pore stretching
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention regards a method of the type indicated in the preamble of the attached claim 1.
  • a method of this type is disclosed in SU 894 923 Al .
  • Methods for forming nanoporous polymeric membranes without the use of a mask are disclosed in EP 1 849 516 Al and in R.SPOHR, "Radiation measurements", ol . 40, 20 May 2001, pages 191-202.
  • the use of a mask in the heavy ion irradiation of polymeric carriers, for producing holes which do not pass through the carrier, is disclosed in US 2005/230353 Al as well in Yousef H. et al .
  • nanoporous polymeric membranes with high-aspect-ratio nanopores i.e a value exceeding at least 10, and preferably exceeding 100, of the ratio between an axial dimension and a transverse dimension of the nanopores
  • nanopores form a highly ordered arrangement
  • nanostructured objects nanowire sensors, nanostructured electrodes for solar cells and planar optoelectronic devices
  • nanostructured particles materials made of nanocomposites and artificial metamaterials , etc.
  • the method described above characteristically allows producing a random arrangement of through nanopores in polymer layers (for example PC, PA, PP, PBI, PVDF, PEEK, PMMA, PTFE) .
  • the attached figure 1 extracted from the article "Nanoporous ⁇ -PVDF membranes with selectively functionalized pores'", O.Cuscito, M. C. Clochard, S . Esnouf, N.Betz, D . Lairez , Nuclear Instruments and Methods in Physics Research B265 (2007) pages 309-313, shows an example of a membrane obtained through a method of this type.
  • the object of the invention is that of proposing a method capable of obtaining nanoporous polymeric membranes with high-aspect ratio pores, at least exceeding 10, and preferably exceeding 100, obtained according to an ordered arrangement, for example a honeycomb arrangement.
  • the invention regards a method according to the attached claim 1 as well a method according to the attached claim 2.
  • FIG. 2 of the attached drawings shows an SEM (Scanning Electron Microscopy) image of an anodic porous alumina structure.
  • the pores in such structure are arranged regularly according to a honeycomb arrangement, having a hexagonal symmetry.
  • a sufficiently thick anodic porous alumina membrane is interposed between the polymer film and the source of ions, in such a manner that only the ions selected by the pores of the alumina reach the polymer film.
  • any holes mask or matrix used as described above is referred to as an "amplitude mask".
  • amplitude mask is already used in the field of traditional photolithography for describing a mask encoded in such a manner to be entirely opaque, or entirely transparent, to electromagnetic radiation.
  • the same term is used for describing a nanoporous material, wherein the nanopores are obtained at precise positions, i.e. according to an ordered geometric arrangement.
  • the heavy ions may pass through the nanopores of the amplitude mask without the trajectory thereof being altered in a significant manner, while at the non-perforated zones of the amplitude mask the ions are not capable of passing through it.
  • figure 1 has already been described above and it illustrates a nanoporous polymeric membrane with a disordered arrangement of the pores
  • figure 2 is a microphotograph showing the structure of a layer of anodic porous alumina
  • figure 3 is a schematic view of the method for bombing by means of heavy ion beams on a polymer film, according to the prior art
  • figure 4 is a sectional view corresponding to figure 3, showing the bombing step in the method according to the invention, positioned facing the polymer film of an nanoporous amplitude mask,
  • FIGS. 5A, 5B show examples of amplitude masks useable in the method according to the present invention
  • figure 6 shows an embodiment of the method according to the invention, wherein the polymer film is mobile during the bombing by means of heavy ion beams
  • figures 7A, 7B schematically show a further embodiment of the method according to the invention wherein the polymer film is stationary during the bombing by means of heavy ion beams and the amplitude mask is respectively spaced or at contact with the polymer film
  • figure 8 illustrates a further variant wherein one layer of porous alumina is used as a template for making an amplitude mask adhered to the polymer material to be perforated,
  • FIGS 9, 10 illustrate the two further steps of the method according to the invention in the case of this variant.
  • FIGS 11A-11H show the various steps of a further variant of the method according to the invention .
  • Figures 1 and 2 have already been described above.
  • Figure 3 of the attached drawings refers to the prior art wherein a polymer film 1, illustrated in section in the figure, is bombed with heavy ion beams 2 in such a manner to obtain a porous membrane of the type illustrated in figure 1.
  • Figure 4 shows the most important step of the method according to the invention, wherein a prefabricated nanoporous amplitude mask, of suitable elementary composition (metallic, polymeric, ceramic or composite) , is positioned facing the polymer film 1 before bombing by means of the heavy ion beams 2.
  • the amplitude mask indicated in its entirety with reference number 3, has an ordered arrangement of nanopores 3a and has a thickness sufficient to prevent the passage of the heavy ions that are not directed through the pores of the amplitude mask.
  • the polymer film is subjected to the usual etching operation, for fully removing the material at the zones degraded by the heavy ion bombing, and thus obtain a nanoporous polymeric membrane, with high- aspect ratio pores (at least exceeding 10 and preferably exceeding 100) and arranged according to an ordered arrangement, for example a honeycomb arrangement with a hexagonal symmetry.
  • Figure 5A illustrates an example of an arrangement of the nanopores in the amplitude mask used in the method according to the invention.
  • the example refers to the case of an embodiment not forming part of the invention, wherein an anodized porous alumina is used as the amplitude mask.
  • the amplitude mask has a honeycomb nanostructure typical of the anodic porous alumina.
  • the honeycomb-patterned nanopores 4 define microstructures 5 - Z-shaped in the illustrated example - which in turn define a superstructure indicated with reference number 6.
  • Figure 5B illustrates another example of nanostructured amplitude mask having an arbitrary geometry produced by means of “top down nanopatterning” ("Electron beam lithography”, “focused ion beam milling”, “nanoimprint lithography”, “deep UV lithography”) and “bottom up self-assembly of nanoparticles and nanowires”.
  • Figure 6 of the attached drawings schematically shows a first variant of the method according to the invention, wherein the polymer sheet 1 is displaced longitudinally while it is bombed by heavy ion beams 2 coming from a source of ions 7 and passing through an amplitude mask 3.
  • the polymer film 1 is displaced longitudinally, in a plane orthogonal to the direction of the heavy ion beams 2.
  • the amplitude mask 3 remains at a fixed position. This solution allows using the same amplitude mask 3 for several exposures and it is particularly advantageous for perforating a polymer sheet to be unwound during exposure from a roller 8 and wound on a roller 9.
  • Figures 7A and 7B refer to the case wherein the heavy ion bombing instead is performed maintaining the polymer film 1 at a fixed position and positioning the amplitude mask 3 at a short distance from or, respectively, at contact with the film 1.
  • the solution of figure 7A has the advantage of allowing reutilising the same mask 3 for several exposures and it is thus much easier to produce at industrial level. However, it may give rise to some complications related to proper alignment between the ion beam 2, the mask 3 and the polymer substrate 1.
  • the solution of figure 7B guarantees correct alignment of the mask 3, but it does not allow reutilising the same.
  • the porous alumina is used as a template for manufacturing an amplitude mask made of different material, such as for example a high intensity metal (for example copper or lead) , adhered to the polymer material to be perforated.
  • a high intensity metal for example copper or lead
  • Such solution is illustrated in figures 8- 10.
  • deposited on the polymer substrate 1 is a first substrate of material 10 opaque to ions.
  • Deposited on this layer 10 is a second aluminium layer. The aluminium layer is transformed into alumina through anodisation.
  • the material forming the layer 10 is treated chemically through the pores of the anodic porous alumina, specifically for example through anisotropic etching, or through RIE (reactive ion etching) , or through wet etching (in liquid phase) in case the film is tens of nanometres thin, in such a manner to obtain - in the layers 10 - pores 11 at the pores 3a of the anodic porous alumina 3 (figure 9) .
  • the layer 3 of anodic porous alumina is dissolved chemically, and thus the polymer film 1 is bombed by means of heavy ion beams 2 (figure 10) using the layer 10 as an amplitude mask .
  • the porous alumina is used as a template for manufacturing an amplitude mask made of different material.
  • a layer conductive and transparent to the ions e.g. gold, indium and tin oxide, etc
  • deposited on such layer 12 is a thick aluminium layer 3' (figure 11C) which is subsequently anodised to form a layer 3 of anodic porous alumina ( Figure 11D)
  • the thin conductive layer 12 may be used as an electrode for electrodepositing metal (eg.
  • the arrangement of nanowires 13 on the polymer represents the amplitude mask, complementary to that of the anodic porous alumina 3 used for manufacturing thereof, to be exposed to high energy ion beams 2 (Figure 11G) in order to obtain the nanoporous membrane ( Figure 11H) .
  • the step immediately subsequent to obtaining the layer of anodic porous alumina it may be provided for eliminating, if required, the barrier layer at the bottom of the pores by means of chemical etching, in such a manner to define through channels 3a through the layer of anodic porous alumina.
  • the barrier layer is an alumina layer that closes the interface channels between the anodic porous alumina (APA) and the sublayer. Actually, it does not close them completely, i.e. the barrier layer does not insulate the anodisation electrochemical solution from the sublayer, otherwise the anodisation process would not progress.
  • the barrier layer which appears as a plug at the bottom of the pores, is perforated by percolation channels whose diameter is in the order of a nanometer and even smaller. This allows electrical continuity between the anode and cathode and the chemical reaction which transforms aluminium into alumina may occur.
  • the barrier layer is to be removed depends on the suitable balancing between adhesion (the contact area between APA and the sublayer diminishes when the barrier layer is removed) and the conductivity of the electrolytic cell.
  • the nanowires may however, generally, be grown in "plugged" channels to the detriment of a greater cell voltage.
  • the idea on which the present invention is based is that of subjecting a polymer film to bombing by means of heavy ion beams by interposing an amplitude mask between the source of the ions and the polymer film with the aim of obtaining a nanoporous polymeric membrane having a highly ordered arrangement and aspect-ratio of the nanopores .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Toxicology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

A nanoporous polymeric membrane is obtained by bombing a polymer film (1) by means of high energy focused heavy ion beams (2) and subsequently performing chemical etching to remove the portions of the polymer film (1) in the zones degraded by the ion bombing, in such a manner to obtain pores passing through the polymer film (1). The heavy ion bombing is performed after interposing between the source of ions (7) and the polymer film (1), adjacent to the film (1), an amplitude mask (3; 10) having an ordered arrangement of nanopores (3a; 11) and having sufficient thickness to prevent the passage of the heavy ions that are not directed through the pores of said amplitude mask, in such a manner to obtain in the polymer film an ordered arrangement of nanopores having an aspect-ratio at least exceeding 10 and preferably exceeding 100.

Description

"Method for the production of polymeric membranes having an ordered arrangement of high-aspect-ratio nanopores , by means of heavy ion bombing"
***
The present invention regards a method of the type indicated in the preamble of the attached claim 1. A method of this type is disclosed in SU 894 923 Al . Methods for forming nanoporous polymeric membranes without the use of a mask are disclosed in EP 1 849 516 Al and in R.SPOHR, "Radiation measurements", ol . 40, 20 May 2001, pages 191-202. The use of a mask in the heavy ion irradiation of polymeric carriers, for producing holes which do not pass through the carrier, is disclosed in US 2005/230353 Al as well in Yousef H. et al . , "Ion track enabled multiple wire microvia interconnects in printed circuit boards" (from "Nuclear Instruments % methods in Physics Research", Section B: "Beam Interactions with Materials and Atoms", Elsevier, Amsterdam, NL - DOI : 10 , 1016/J . imb .2007.11.014 , vol. 266, no. 8, 1 April 2008 (2008-04-01), pages 1659-1665, XP022658868, ISSN: 0168-583X) and in Metz S. et al . , "Polyimide microfluidic devices with integrated nanoporous filtration areas manufactured by micromachining and ion track technology" (from "Journal of Micromechanics & Microengineering, Institute of Physics Publishing, Bristol GB LNKD-DOI : 10.1088/0960- 1317/14/3/002, vol.14, no. 3, 1 March 2004, pages 324- 331, XP020069627 ISSN: 0960-1317) .
The production of nanoporous polymeric membranes with high-aspect-ratio nanopores (i.e a value exceeding at least 10, and preferably exceeding 100, of the ratio between an axial dimension and a transverse dimension of the nanopores) and wherein the nanopores form a highly ordered arrangement, represents a technological problem yet to be solved. The possible applications of this type of material are numerous and varied. The need for these materials lies in their possible and immediate use in existent systems and devices among which: lithium batteries separators, polymer fuel cells, filtering systems, membranes for microfluidic systems, and as an element for enabling manufacturing other nanostructured objects (nanowire sensors, nanostructured electrodes for solar cells and planar optoelectronic devices) , nanostructured particles, materials made of nanocomposites and artificial metamaterials , etc.
Currently, it is possible to obtain nanoporous membranes by means of a process that provides for bombing polymer films with high energy focused heavy ion beams which degrade the material breaking the chemical bonds along the path of the ions. Subsequently to the bombing step, through a chemical etching process, it is possible to remove the material starting from the degraded zones and obtain through pores which pass through the polymer film ("Track-etched membranes") . Regarding this see R. Spohr, Radiation Measurements , Volume 40, 2005, pages 191-202.
Given that the accelerated ions are propagated in a beam typically through the Gaussian process, the method described above characteristically allows producing a random arrangement of through nanopores in polymer layers (for example PC, PA, PP, PBI, PVDF, PEEK, PMMA, PTFE) .
The attached figure 1, extracted from the article "Nanoporous β-PVDF membranes with selectively functionalized pores'", O.Cuscito, M. C. Clochard, S . Esnouf, N.Betz, D . Lairez , Nuclear Instruments and Methods in Physics Research B265 (2007) pages 309-313, shows an example of a membrane obtained through a method of this type. The object of the invention is that of proposing a method capable of obtaining nanoporous polymeric membranes with high-aspect ratio pores, at least exceeding 10, and preferably exceeding 100, obtained according to an ordered arrangement, for example a honeycomb arrangement.
To obtain such object, the invention regards a method according to the attached claim 1 as well a method according to the attached claim 2.
Further advantageous characteristics of the methods according to the invention form an object of the dependent claims.
The invention exploits the properties of ordered structures such as for example the anodic porous alumina. Figure 2 of the attached drawings shows an SEM (Scanning Electron Microscopy) image of an anodic porous alumina structure. The pores in such structure are arranged regularly according to a honeycomb arrangement, having a hexagonal symmetry. In the case of the abovementioned preferred embodiment, a sufficiently thick anodic porous alumina membrane is interposed between the polymer film and the source of ions, in such a manner that only the ions selected by the pores of the alumina reach the polymer film. Thus this allows, by suitably extending the time of exposure to the ionic beam with respect to the case wherein the alumina mask is not used, degrading the polymer film solely at the alumina pores. The step of chemical etching shall thus produce a nanoporous polymeric structure with symmetry equivalent to that of the porous alumina.
In the present description, and in the claims that follow, any holes mask or matrix used as described above is referred to as an "amplitude mask". The term "amplitude mask" is already used in the field of traditional photolithography for describing a mask encoded in such a manner to be entirely opaque, or entirely transparent, to electromagnetic radiation. In the case of the present invention, the same term is used for describing a nanoporous material, wherein the nanopores are obtained at precise positions, i.e. according to an ordered geometric arrangement. When bombing by means of heavy ion beams, the heavy ions may pass through the nanopores of the amplitude mask without the trajectory thereof being altered in a significant manner, while at the non-perforated zones of the amplitude mask the ions are not capable of passing through it.
Further characteristics and advantages of the invention shall be clear from the description that follows with reference to the attached drawings, strictly provided for exemplifying and non-limiting purposes, wherein:
figure 1 has already been described above and it illustrates a nanoporous polymeric membrane with a disordered arrangement of the pores,
figure 2, also already described above, is a microphotograph showing the structure of a layer of anodic porous alumina,
figure 3 is a schematic view of the method for bombing by means of heavy ion beams on a polymer film, according to the prior art,
figure 4 is a sectional view corresponding to figure 3, showing the bombing step in the method according to the invention, positioned facing the polymer film of an nanoporous amplitude mask,
figures 5A, 5B show examples of amplitude masks useable in the method according to the present invention,
figure 6 shows an embodiment of the method according to the invention, wherein the polymer film is mobile during the bombing by means of heavy ion beams, figures 7A, 7B schematically show a further embodiment of the method according to the invention wherein the polymer film is stationary during the bombing by means of heavy ion beams and the amplitude mask is respectively spaced or at contact with the polymer film,
figure 8 illustrates a further variant wherein one layer of porous alumina is used as a template for making an amplitude mask adhered to the polymer material to be perforated,
figures 9, 10 illustrate the two further steps of the method according to the invention in the case of this variant, and
figures 11A-11H show the various steps of a further variant of the method according to the invention .
Figures 1 and 2 have already been described above. Figure 3 of the attached drawings refers to the prior art wherein a polymer film 1, illustrated in section in the figure, is bombed with heavy ion beams 2 in such a manner to obtain a porous membrane of the type illustrated in figure 1.
Figure 4 shows the most important step of the method according to the invention, wherein a prefabricated nanoporous amplitude mask, of suitable elementary composition (metallic, polymeric, ceramic or composite) , is positioned facing the polymer film 1 before bombing by means of the heavy ion beams 2. The amplitude mask, indicated in its entirety with reference number 3, has an ordered arrangement of nanopores 3a and has a thickness sufficient to prevent the passage of the heavy ions that are not directed through the pores of the amplitude mask. As indicated above, subsequently to such operation, the polymer film is subjected to the usual etching operation, for fully removing the material at the zones degraded by the heavy ion bombing, and thus obtain a nanoporous polymeric membrane, with high- aspect ratio pores (at least exceeding 10 and preferably exceeding 100) and arranged according to an ordered arrangement, for example a honeycomb arrangement with a hexagonal symmetry.
Figure 5A illustrates an example of an arrangement of the nanopores in the amplitude mask used in the method according to the invention. The example refers to the case of an embodiment not forming part of the invention, wherein an anodized porous alumina is used as the amplitude mask. In such case, the amplitude mask has a honeycomb nanostructure typical of the anodic porous alumina. The honeycomb-patterned nanopores 4 define microstructures 5 - Z-shaped in the illustrated example - which in turn define a superstructure indicated with reference number 6.
Figure 5B illustrates another example of nanostructured amplitude mask having an arbitrary geometry produced by means of "top down nanopatterning" ("Electron beam lithography", "focused ion beam milling", "nanoimprint lithography", "deep UV lithography") and "bottom up self-assembly of nanoparticles and nanowires".
Figure 6 of the attached drawings schematically shows a first variant of the method according to the invention, wherein the polymer sheet 1 is displaced longitudinally while it is bombed by heavy ion beams 2 coming from a source of ions 7 and passing through an amplitude mask 3. The polymer film 1 is displaced longitudinally, in a plane orthogonal to the direction of the heavy ion beams 2. During the method, the amplitude mask 3 remains at a fixed position. This solution allows using the same amplitude mask 3 for several exposures and it is particularly advantageous for perforating a polymer sheet to be unwound during exposure from a roller 8 and wound on a roller 9.
Figures 7A and 7B refer to the case wherein the heavy ion bombing instead is performed maintaining the polymer film 1 at a fixed position and positioning the amplitude mask 3 at a short distance from or, respectively, at contact with the film 1. The solution of figure 7A has the advantage of allowing reutilising the same mask 3 for several exposures and it is thus much easier to produce at industrial level. However, it may give rise to some complications related to proper alignment between the ion beam 2, the mask 3 and the polymer substrate 1. The solution of figure 7B guarantees correct alignment of the mask 3, but it does not allow reutilising the same.
According to a first aspect of the invention, the porous alumina is used as a template for manufacturing an amplitude mask made of different material, such as for example a high intensity metal (for example copper or lead) , adhered to the polymer material to be perforated. Such solution is illustrated in figures 8- 10. In this case, deposited on the polymer substrate 1 is a first substrate of material 10 opaque to ions. Deposited on this layer 10 is a second aluminium layer. The aluminium layer is transformed into alumina through anodisation. After eliminating, through chemical etching, the barrier layer at the bottom of the pores typical of the anodic porous alumina - in such a manner to define through channels in the porous alumina - the material forming the layer 10 is treated chemically through the pores of the anodic porous alumina, specifically for example through anisotropic etching, or through RIE (reactive ion etching) , or through wet etching (in liquid phase) in case the film is tens of nanometres thin, in such a manner to obtain - in the layers 10 - pores 11 at the pores 3a of the anodic porous alumina 3 (figure 9) . At this point, the layer 3 of anodic porous alumina is dissolved chemically, and thus the polymer film 1 is bombed by means of heavy ion beams 2 (figure 10) using the layer 10 as an amplitude mask .
According to a second aspect of the invention, the porous alumina is used as a template for manufacturing an amplitude mask made of different material. For example it is possible to deposit on the polymer film 1 (Figure 11A) a layer conductive and transparent to the ions (e.g. gold, indium and tin oxide, etc), as illustrated in figure 11B. Deposited on such layer 12 is a thick aluminium layer 3' (figure 11C) which is subsequently anodised to form a layer 3 of anodic porous alumina (Figure 11D) , The thin conductive layer 12 may be used as an electrode for electrodepositing metal (eg. copper, lead, nickel, gold, platinum) into the pores 3a of alumina 3 (figure HE) , in such a manner to obtain nanowires 13 in the ceramic matrix. By dissolving alumina through chemical etching (Figure 11F) it is possible to obtain an ordered arrangement (with hexagonal symmetry) of nanowires 13 adhering to the polymer sublayer 1 and to the layer 12. In case the length of the nanowires 13 is not excessive (in the order of a micrometre) they remain adhered to the sublayer and they do not tend to bend. The arrangement of nanowires 13 on the polymer represents the amplitude mask, complementary to that of the anodic porous alumina 3 used for manufacturing thereof, to be exposed to high energy ion beams 2 (Figure 11G) in order to obtain the nanoporous membrane (Figure 11H) . In the step immediately subsequent to obtaining the layer of anodic porous alumina it may be provided for eliminating, if required, the barrier layer at the bottom of the pores by means of chemical etching, in such a manner to define through channels 3a through the layer of anodic porous alumina.
However, it is also possible to deposit metals in the pores of the alumina without removing the barrier layer, through pulsed electrodeposition . The barrier layer is an alumina layer that closes the interface channels between the anodic porous alumina (APA) and the sublayer. Actually, it does not close them completely, i.e. the barrier layer does not insulate the anodisation electrochemical solution from the sublayer, otherwise the anodisation process would not progress. The barrier layer, which appears as a plug at the bottom of the pores, is perforated by percolation channels whose diameter is in the order of a nanometer and even smaller. This allows electrical continuity between the anode and cathode and the chemical reaction which transforms aluminium into alumina may occur. Whether the barrier layer is to be removed depends on the suitable balancing between adhesion (the contact area between APA and the sublayer diminishes when the barrier layer is removed) and the conductivity of the electrolytic cell. In other words, the nanowires may however, generally, be grown in "plugged" channels to the detriment of a greater cell voltage.
As clear from the description above, the idea on which the present invention is based is that of subjecting a polymer film to bombing by means of heavy ion beams by interposing an amplitude mask between the source of the ions and the polymer film with the aim of obtaining a nanoporous polymeric membrane having a highly ordered arrangement and aspect-ratio of the nanopores .
Obviously, without prejudice to the principle of thee invention the construction details and embodiments may widely vary with respect to what has been described and illustrated strictly for exemplifying purposes, without departing from the scope of protection of the present invention.

Claims

1. Method for the production of a nanoporous polymeric membrane, wherein a polymer film (1) is bombed by means of high energy focused heavy ion beam (2) and a chemical etching is subsequently performed to remove the portions of said film in the zones degraded by the ion bombing in such a manner to obtain pores passing through the film,
wherein the abovementioned heavy ion bombing is performed after interposing between the source of heavy ions (7) and the polymer film (1), in proximity to the film (1), an amplitude mask (3; 10; 13) having an arrangement of nanopores (3a; 11) and thickness sufficient to prevent the passage of the heavy ions that are not directed through the abovementioned nanopores (3a) of the amplitude mask (3) , in such a manner to obtain a polymer film with a distribution of nanopores ,
characterized in that said amplitude mask (3; 10; 13) has an ordered honeycomb arrangement of nanopores (3a) , so that a corresponding ordered honeycomb distribution of nanopores is obtained in said polymer film (1),
in that said nanopores obtained in the polymer film have un aspect-ratio at least exceeding 10, and in that said amplitude mask (10) is obtained by positioning over said polymer film (1) a layer (10) of material opaque to ions and depositing a layer of aluminium over said opaque layer (10), transforming said aluminium layer into anodic porous alumina by means of an anodisation method, eliminating the barrier layer at the bottom of the pores of the anodic porous alumina through chemical etching, in such a manner to define channels passing through the layer of anodic porous alumina, chemically etching the layer opaque to ions (10) through the pores of the anodic porous alumina in such a manner to obtain in said opaque layer
(10) an ordered arrangement of nanopores (11) corresponding to the arrangement of the pores of the anodic porous alumina and thus using the abovementioned opaque layer (10) with the abovementioned nanopores
(11) as an amplitude mask.
2. Method for the production of a nanoporous polymeric membrane, wherein a polymer film (1) is bombed by means of high energy focused heavy ion beam (2) and a chemical etching is subsequently performed to remove the portions of said film in the zones degraded by the ion bombing in such a manner to obtain pores passing through the film,
wherein the abovementioned heavy ion bombing is performed after interposing between the source of heavy ions (7) and the polymer film (1), in proximity to the film (1), an amplitude mask (3; 10; 13) having an arrangement of nanopores (3a; 11) and thickness sufficient to prevent the passage of the heavy ions that are not directed through the abovementioned nanopores (3a) of the amplitude mask (3) , in such a manner to obtain a polymer film with a distribution of nanopores ,
characterized in that said amplitude mask (3; 10;
13) has an ordered honeycomb arrangement of nanopores (3a) , so that a corresponding ordered honeycomb distribution of nanopores is obtained in said polymer film (1),
in that said nanopores obtained in the polymer film have un aspect-ratio at least exceeding 10, and said amplitude mask (13) is obtained through the following operations:
- positioning over said polymer film (1) a layer (12) conductive and transparent to the ions and then depositing a layer of aluminium (3' ) thereon,
- transforming said aluminium layer into anodic porous alumina (3) by means of an anodisation method,
- using the conductive layer (12) as an electrode for electrodepositing a metal into the pores (3a) of the anodic porous alumina (3) , in such a manner to obtain metal nanowires (13) in the ceramic matrix,
- dissolving the anodic porous alumina (3) through chemical etching in such a manner to obtain an ordered distribution of nanowires (13) adhering to the polymer sublayer (1) and to the conductive layer (12),
said arrangement of nanowires representing the abovementioned amplitude mask which is exposed to the high energy ion beam (2) with the aim of obtaining the nanoporous membrane.
3. Method according to claim 1 or 2, characterised in that the amplitude mask (3) always remains at a fixed position with respect to the beam of heavy ions, while the polymer film (1) is displaced in the longitudinal direction thereof, orthogonally to the beam of heavy ions.
4. Method according to claim 1 or 2, characterised in that both the amplitude mask (3) and the polymer film (1) remain at fixed position during the heavy ion bombing.
5. Method according to claim 4, characterised in that the amplitude mask (3) is maintained spaced from the polymer film (1) .
6. Method according to claim 3, characterised in that the amplitude mask (3) is maintained at contact with said polymer film (1) during the heavy ion bombing .
PCT/IB2010/056057 2010-03-23 2010-12-23 Method for the production of polymeric membranes having an ordered arrangement of high-aspect-ratio nanopores, by means of heavy ion bombing WO2011117692A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/636,000 US9376538B2 (en) 2010-03-23 2010-12-23 Method for the production of polymeric membranes having an ordered arrangement of high-aspect-ratio nanopores, by means of heavy ion bombing

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10425087.3 2010-03-23
EP10425087A EP2386596B1 (en) 2010-03-23 2010-03-23 Method for the production of polymeric membranes having an ordered arrangement of high-aspect-ratio nanopores, by means of heavy ion bombing

Publications (1)

Publication Number Publication Date
WO2011117692A1 true WO2011117692A1 (en) 2011-09-29

Family

ID=42635472

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2010/056057 WO2011117692A1 (en) 2010-03-23 2010-12-23 Method for the production of polymeric membranes having an ordered arrangement of high-aspect-ratio nanopores, by means of heavy ion bombing

Country Status (3)

Country Link
US (1) US9376538B2 (en)
EP (1) EP2386596B1 (en)
WO (1) WO2011117692A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104756284A (en) * 2013-03-20 2015-07-01 株式会社Lg化学 Separator for electrochemical cell and a method of making the same
CN109148795A (en) * 2018-09-08 2019-01-04 佛山皖和新能源科技有限公司 A kind of preparation method of battery composite diaphragm

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20121634A1 (en) * 2012-10-01 2014-04-02 Fond Istituto Italiano Di Tecnologia COMPOSITE MATERIAL INCLUDING POROUS ANODIC ALUMINA AND A POLYMER MATRIX, AND ITS USE FOR DENTAL RESTORATION
CN106582330B (en) * 2016-12-12 2019-05-31 安徽启迪清源新材料有限公司 A kind of filter membrane of oil slick containing heavy metal
CN111816538B (en) * 2020-07-17 2022-03-25 兰州大学 Transmission electron microscope micro-grid based on heavy ion irradiation and preparation method
US11826709B2 (en) * 2021-05-28 2023-11-28 Taiwan Semiconductor Manufacturing Company, Ltd. Filter apparatus for semiconductor device fabrication process
CN113387388B (en) * 2021-06-15 2023-03-07 中国科学院近代物理研究所 Nano porous tungsten trioxide material and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU894923A1 (en) 1980-05-22 1982-04-30 Объединенный Институт Ядерных Исследований Method for producing nuclear filters
US20050230353A1 (en) 2002-07-24 2005-10-20 Manfred Danziger Method and array for processing carrier materials by means of heavy ion radiation and subsequent etching
EP1849516A1 (en) 2004-12-22 2007-10-31 Dressel Pte. Ltd. Company Membrane card and method for the production and use thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5160845A (en) * 1991-03-06 1992-11-03 Stumbo David P Alignment technique for masked ion beam lithography
WO2007051252A1 (en) * 2005-11-03 2007-05-10 The University Of Melbourne Porous polymeric materials and polymer particles for preparation thereof
WO2010085337A1 (en) * 2009-01-21 2010-07-29 Creatv Microtech, Inc. Method of fabrication of micro and nanofilters

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU894923A1 (en) 1980-05-22 1982-04-30 Объединенный Институт Ядерных Исследований Method for producing nuclear filters
US20050230353A1 (en) 2002-07-24 2005-10-20 Manfred Danziger Method and array for processing carrier materials by means of heavy ion radiation and subsequent etching
EP1849516A1 (en) 2004-12-22 2007-10-31 Dressel Pte. Ltd. Company Membrane card and method for the production and use thereof

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 198244, Derwent World Patents Index; AN 1982-94728E, XP002598612 *
METZ S ET AL: "Polyimide microfluidic devices with integrated nanoporous filtration areas manufactured by micromachining and ion track technology; Polyimide microfluidic devices with integrated nanoporous filtration areas", JOURNAL OF MICROMECHANICS & MICROENGINEERING, INSTITUTE OF PHYSICS PUBLISHING, BRISTOL, GB LNKD- DOI:10.1088/0960-1317/14/3/002, vol. 14, no. 3, 1 March 2004 (2004-03-01), pages 324 - 331, XP020069627, ISSN: 0960-1317 *
METZ S. ET AL.: "Polyimide microfluidic devices with integrated nanoporous filtration areas manufactured by micromachining and ion track technology", JOURNAL OF MICROMECHANICS & MICROENGINEERING, INSTITUTE OF PHYSICS PUBLISHING, BRISTOL GB, vol. 14, 2004, pages 324 - 331, XP020069627, DOI: doi:10.1088/0960-1317/14/3/002
O.CUSCITO, M.C.CLOCHARD, S.ESNOUF, N.BETZ, D.LAIREZ: "Nanoporous (3-PVDF membranes with selectively functionalized pores", NUCLEAR INSTRUMENTS AND METHODS IN PHYSICS RESEARCH B265, 2007, pages 309 - 313, XP022349433
R. SPOHR, RADIATION MEASUREMENTS, vol. 40, 2005, pages 191 - 202
R. SPOHR: "status of ion track technology-Prospects of single tracks", RADIATION MEASUREMENTS, vol. 40, 20 May 2001 (2001-05-20), pages 191 - 202, XP002598613 *
R.SPOHR, RADIATION MEASUREMENTS, vol. 40, 2001, pages 191 - 202
YOUSEF H ET AL: "Ion track enabled multiple wire microvia interconnects in printed circuit boards", NUCLEAR INSTRUMENTS & METHODS IN PHYSICS RESEARCH, SECTION - B:BEAM INTERACTIONS WITH MATERIALS AND ATOMS, ELSEVIER, AMSTERDAM, NL LNKD- DOI:10.1016/J.NIMB.2007.11.014, vol. 266, no. 8, 1 April 2008 (2008-04-01), pages 1659 - 1665, XP022658868, ISSN: 0168-583X, [retrieved on 20071122] *
YOUSEF H. ET AL.: "Ion track enabled multiple wire microvia interconnects in printed circuit boards" (from "Nuclear Instruments % methods in Physics Research", Section B: "Beam Interactions with Materials and Atoms", vol. 266, 2008, ELSEVIER, pages: 1659 - 1665

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104756284A (en) * 2013-03-20 2015-07-01 株式会社Lg化学 Separator for electrochemical cell and a method of making the same
JP2015537339A (en) * 2013-03-20 2015-12-24 エルジー・ケム・リミテッド Separation membrane for electrochemical device and method for producing the same
EP2897197A4 (en) * 2013-03-20 2016-06-01 Lg Chemical Ltd Separation membrane for electrochemical device and manufacturing method therefor
US10177359B2 (en) 2013-03-20 2019-01-08 Lg Chem, Ltd. Separator for electrochemical device and method for manufacturing the same
CN109148795A (en) * 2018-09-08 2019-01-04 佛山皖和新能源科技有限公司 A kind of preparation method of battery composite diaphragm

Also Published As

Publication number Publication date
EP2386596B1 (en) 2012-10-17
US9376538B2 (en) 2016-06-28
EP2386596A1 (en) 2011-11-16
US20130011799A1 (en) 2013-01-10

Similar Documents

Publication Publication Date Title
EP2386596B1 (en) Method for the production of polymeric membranes having an ordered arrangement of high-aspect-ratio nanopores, by means of heavy ion bombing
Hao et al. Facile design of ultra-thin anodic aluminum oxide membranes for the fabrication of plasmonic nanoarrays
Apel et al. Fabrication of nanopores in polymer foils with surfactant-controlled longitudinal profiles
US20160009049A1 (en) Nanoporous membranes and methods for making the same
WO2009115230A2 (en) Nanowires and method for the production thereof
Lindeberg et al. Interconnected nanowire clusters in polyimide for flexible circuits and magnetic sensing applications
Rajput et al. Solution-cast high-aspect-ratio polymer structures from direct-write templates
US20140106232A1 (en) Nanoscale three-dimensional battery architecture
DE60019335T2 (en) METHOD FOR PRODUCING PORES IN A POLYMERIC MATERIAL
Wang et al. Electrodeposition of vertically standing Ag nanoplates and nanowires on transparent conductive electrode using porous anodic aluminum oxide template
US20180371631A1 (en) Exposed segmented nanostructure arrays
Amani Hamedani et al. Synthesis and growth mechanism of thin-film TiO2 nanotube arrays on focused-ion-beam micropatterned 3D isolated regions of titanium on silicon
Karim et al. Effect of etching conditions on pore shape in etched ion-track polycarbonate membranes
Kravets et al. A novel technique for fabrication of nanofluidic devices with polymer film formed by plasma polymerization
KR102329300B1 (en) Filtration membrane for trapping microparticles, method for manufacturing same, porous membrane, and method for manufacturing same
US20030020024A1 (en) Method for creating pores and microporous film
Ghenescu et al. Electrical properties of electrodeposited CdS nanowires
AN et al. lll lll a llDl DID lll DIII DD llD lll Dll DID lll 101 llD ll Dl lli
LI et al. aspect-ratio nanopores, by means of heavy ion bombing
DE102005011345A1 (en) Method for producing nanostructure on substrate involves irradiating of defined surface of substrate through ions, introduction of irradiating substrate into a supersaturated solution and removal of substrate form solution
Walewyns et al. Synthesis of patterned freestanding nickel nanowires by using ion track-etched polyimide
Zhang et al. A kind of double-sided porous anodic alumina membrane fabricated with the three-step anodic oxidation method
RU2307066C1 (en) Method for forming single metallic nano-structure in a set of etched channels of track membrane
US10273592B2 (en) Method of forming local nano/micro size structures of anodized metal
Starosta Radiation use in producing track-etched membranes

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10814775

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 13636000

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10814775

Country of ref document: EP

Kind code of ref document: A1