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WO1999022843A1 - Laminated metallized membrane filter - Google Patents

Laminated metallized membrane filter Download PDF

Info

Publication number
WO1999022843A1
WO1999022843A1 PCT/US1998/023321 US9823321W WO9922843A1 WO 1999022843 A1 WO1999022843 A1 WO 1999022843A1 US 9823321 W US9823321 W US 9823321W WO 9922843 A1 WO9922843 A1 WO 9922843A1
Authority
WO
WIPO (PCT)
Prior art keywords
membrane
support
laminate
polymer
polymer membrane
Prior art date
Application number
PCT/US1998/023321
Other languages
French (fr)
Inventor
Mark B. Beisecker
Paul Gagnon
David D. Peterson
Original Assignee
Corning Incorporated
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 Corning Incorporated filed Critical Corning Incorporated
Publication of WO1999022843A1 publication Critical patent/WO1999022843A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
    • B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1692—Other shaped material, e.g. perforated or porous sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2027—Metallic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0471—Surface coating material

Definitions

  • the invention relates to a filter membrane product for separating constituents of a liquid.
  • High energy ions have been used to create narrow tracks of damage in thin polymer films.
  • the tracks may be preferentially etched to make or adjust the size of pores through the film.
  • Such films and foils have many applications including, without limitation, filters and molecular sieves for use in visualizing particulates and organisms collected on the filter surface by imaging techniques such as transmitted light, scanning electron (SEM), epifluorescence (DEFT) and differential interference contrast (DIC) microscopy.
  • Imaging techniques such as transmitted light, scanning electron (SEM), epifluorescence (DEFT) and differential interference contrast (DIC) microscopy.
  • Metallized membranes are polymer membranes that have been coated with a thin layer of metal.
  • the metal may be deposited onto the membrane by several methods including magnetron sputtering techniques, wet chemistry, or vacuum coating methods, such as e-beam or thermal evaporation, for example.
  • Metallized membranes are used in particular as tilters and are ideal for studying particulates or microorganisms that have been collected on the membrane surface by epifluorescence due to the low background emission and high reflectivity of the metal surface. Further, a smooth, flat surface of a metallized track etched membrane is functionally effective for optical and SEM microscopy because it permits stabilizing objects on the membrane surface and restricts them to a very narrow focal plane. Examples of metals that have been used to coat membranes include Cu, Co, Ti, Ni, Ag, Pt, Pd, and Ag.
  • the present invention provides a metallized, laminated track etch membrane.
  • the membrane is comprised of a track-etch filter laminated to a porous rigid support.
  • a metal coating is applied to the exposed surface of the track-etch membrane.
  • the porous support allows for a thicker and mechanically stronger membrane, which in turn allows the membrane to be used in more stringent applications.
  • FIG. 1 shows a partial cross section of the laminated membrane of the present invention.
  • FIG. 2 shows a partially exposed layered view of the membrane of the present invention.
  • a track etch membrane is made by a well known two-step process.
  • the first step is bombardment of a thin (8 ⁇ m -200 ⁇ m) polymer film with energetic heavy ions to create a latent track of damage through the film, and to establish the areal density of pores in the range between 1 pore/cm 2 and IX 10 93 pores/cm 2 .
  • the film is immersed in a strong chemical solution to produce preferential etching along the latent tracks.
  • the result of the process is capillary shaped pores extending through the film.
  • the size of the pore is set by the condition of the chemical etching process both in concentration and temperature of the etchant and exposure time. Typical pore sizes range from 0.02 ⁇ m -14 ⁇ m in diameter.
  • Organic natural or synthetic plastics are suitable for preparing track etch membranes.
  • the following polymers may be named as examples: polyesters, cellulose esters, aliphatic and aromatic polyamides, halogen-containing polymers (such as polyterafluoroethylene, polyvinyl flouride or polyvinylidene chloride), types of polycarbonate, polyimides, polyhydantoins, polyparabanates, polyurethanes, polysulphones, aromatic polyethers, polyethylene oxides and polypropylene oxides, and copolymers and graft polymers thereof.
  • polyesters such as polyterafluoroethylene, polyvinyl flouride or polyvinylidene chloride
  • halogen-containing polymers such as polyterafluoroethylene, polyvinyl flouride or polyvinylidene chloride
  • types of polycarbonate such as polyimides, polyhydantoins, polyparabanates, polyurethanes, polysulphones, aromatic polyethers, polyethylene
  • the thin, track etch membrane filter is next laminated to a porous support material, woven or nonwoven, to gain thickness and mechanical strength.
  • the support material preferably consists of a nonwoven matte of fibers of manmade, polymeric material. Suitable materials for the support include polyolefins, polycarbonate, polyesters, PVDF, nylon, or any other extrudable polymer that may take the general form of a woven or nonwoven matte of fibers.
  • the support and membrane may be attached to each other in a variety of ways.
  • the membrane is composed of a polycarbonate and the support to be attached is composed of a polyolefin
  • the two pieces may be heat bonded together. This is accomplished by heating the polyolefin support above its transition temperature but below the transition temperature of the polycarbonate membrane.
  • One surface of the polyolefin support sheet is contacted with a surface of the membrane film such that the plasticized polyolefin is absorbed into the pores of the polycarbonate membrane.
  • the assembly is then cooled and a mechanical bonding between the polyolefin and the polycarbonate results.
  • thermal integrity of the materials, and thermal compatibility between materials comprising the metallized, laminated membrane is important to product quality. The requirement extends to the membrane and support, and holds through the operations of lamination and metallization.
  • thermal bonding method bonding the polymer membrane material with the support by means of adhesive.
  • a lightweight adhesive web of for example, 5 g/m 2 basis weight, may be interlayered between the support and the membrane.
  • the laminated membrane surface is hydrophilic while the support portion is hydrophobic.
  • Applications will determine the required wetting characteristics of the components. In cases where aqueous fluids at low pressure gradient first come into contact with the hydrophobic support material, initial flow may be limited, or even prevented. In some cases, surface modification treatments imparting hydrophilic characteristics to the hydrophobic support material may be required to achieve a penetrable membrane system.
  • the support material may be hydrophilized by a variety of plasma processes including for example oxygen, nitrous oxide, argon, or neon. The hydrophilization of the support may occur prior to metallization or after metallization of the membrane.
  • the laminated membrane 10 is coated with a thin metal layer 14 covering the top surface.
  • the metal thickness is application dependent, but may range from approximately 100-1500 Angstroms.
  • the coating process may be carried out by any of a variety of known coating techniques including vacuum coating processes such as e-beam or thermal evaporation, wet chemical metalization, or magnetron sputtering techniques, all of which are well known in the art.
  • the metallic ions used are preferably titanium, however in practice any metal including Au, Ag, Ni, Cu, Pt, etc. can be used depending on the process.
  • a membrane surface coated with Ti metal yields approximately 2-3 times lower fluorescence emission compared with plain or dyed membrane surfaces.
  • the mechanical strength imparted by the support aids in the manufacture of the metallized membrane as well as in the metallization of the membrane surface.
  • the support prevents curling of the membrane material, thereby eliminating the need in the past to coat both sides of the membrane material. This allows the membrane material to be run through the metallization equipment only once, thereby reducing cost, time, and risk of damage to membrane.
  • FIG. 1 shows a partial cross section of the laminated membrane system 10 of the present invention.
  • FIG. 2 shows a partially exposed layered view of the membrane filter 10 of the present invention.
  • the present invention is contemplated for use with metallized track etch membranes, but the lamination process may be used in any membrane system where the membrane material itself is necessarily of such a thinness that it may benefit from the added mechanical strength of a porous support.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

A metallized laminated track-etch membrane (10) is disclosed. The membrane (10) is comprised of a track-etch filter (12) laminated to a porous rigid support (16). A metal coating (14) is applied to the exposed surface of the track-etch filter (12). The porous support allows for a thicker and mechanically stronger membrane.

Description

Laminated Metallized Membrane Filter
This application claims the benefit of U.S. Provisional Application No.
60/064173, filed November 4, 1997, entitled Metallized Membrane Filter.
Field Of Invention
The invention relates to a filter membrane product for separating constituents of a liquid.
Background of Invention
High energy ions have been used to create narrow tracks of damage in thin polymer films. The tracks may be preferentially etched to make or adjust the size of pores through the film. Such films and foils have many applications including, without limitation, filters and molecular sieves for use in visualizing particulates and organisms collected on the filter surface by imaging techniques such as transmitted light, scanning electron (SEM), epifluorescence (DEFT) and differential interference contrast (DIC) microscopy. Membranes made from the track-etch process as described in commonly assigned US pat. 5,449,917, for example, necessarily have extreme thinness. This creates difficulties in handling, manufacturing operations, and applications due to static cling and a lack of mechanical strength.
Metallized membranes are polymer membranes that have been coated with a thin layer of metal. The metal may be deposited onto the membrane by several methods including magnetron sputtering techniques, wet chemistry, or vacuum coating methods, such as e-beam or thermal evaporation, for example. Metallized membranes are used in particular as tilters and are ideal for studying particulates or microorganisms that have been collected on the membrane surface by epifluorescence due to the low background emission and high reflectivity of the metal surface. Further, a smooth, flat surface of a metallized track etched membrane is functionally effective for optical and SEM microscopy because it permits stabilizing objects on the membrane surface and restricts them to a very narrow focal plane. Examples of metals that have been used to coat membranes include Cu, Co, Ti, Ni, Ag, Pt, Pd, and Ag.
Summary of Invention The present invention provides a metallized, laminated track etch membrane.
The membrane is comprised of a track-etch filter laminated to a porous rigid support. A metal coating is applied to the exposed surface of the track-etch membrane. The porous support allows for a thicker and mechanically stronger membrane, which in turn allows the membrane to be used in more stringent applications. The lamination and metal deposition processes are key components of the invention.
Brief Description of the Figures
FIG. 1 shows a partial cross section of the laminated membrane of the present invention. FIG. 2 shows a partially exposed layered view of the membrane of the present invention.
Detailed Description of the Invention
A track etch membrane is made by a well known two-step process. The first step is bombardment of a thin (8μm -200 μm) polymer film with energetic heavy ions to create a latent track of damage through the film, and to establish the areal density of pores in the range between 1 pore/cm2 and IX 1093 pores/cm2. In the second step, the film is immersed in a strong chemical solution to produce preferential etching along the latent tracks. The result of the process is capillary shaped pores extending through the film. The size of the pore is set by the condition of the chemical etching process both in concentration and temperature of the etchant and exposure time. Typical pore sizes range from 0.02μm -14 μm in diameter. Organic natural or synthetic plastics are suitable for preparing track etch membranes. The following polymers may be named as examples: polyesters, cellulose esters, aliphatic and aromatic polyamides, halogen-containing polymers (such as polyterafluoroethylene, polyvinyl flouride or polyvinylidene chloride), types of polycarbonate, polyimides, polyhydantoins, polyparabanates, polyurethanes, polysulphones, aromatic polyethers, polyethylene oxides and polypropylene oxides, and copolymers and graft polymers thereof.
The thin, track etch membrane filter is next laminated to a porous support material, woven or nonwoven, to gain thickness and mechanical strength. The support material preferably consists of a nonwoven matte of fibers of manmade, polymeric material. Suitable materials for the support include polyolefins, polycarbonate, polyesters, PVDF, nylon, or any other extrudable polymer that may take the general form of a woven or nonwoven matte of fibers.
The support and membrane may be attached to each other in a variety of ways. For example, if the membrane is composed of a polycarbonate and the support to be attached is composed of a polyolefin, the two pieces may be heat bonded together. This is accomplished by heating the polyolefin support above its transition temperature but below the transition temperature of the polycarbonate membrane. One surface of the polyolefin support sheet is contacted with a surface of the membrane film such that the plasticized polyolefin is absorbed into the pores of the polycarbonate membrane. The assembly is then cooled and a mechanical bonding between the polyolefin and the polycarbonate results. In this embodiment, thermal integrity of the materials, and thermal compatibility between materials comprising the metallized, laminated membrane is important to product quality. The requirement extends to the membrane and support, and holds through the operations of lamination and metallization.
An alternative to the thermal bonding method is bonding the polymer membrane material with the support by means of adhesive. For example, a lightweight adhesive web of for example, 5 g/m2 basis weight, may be interlayered between the support and the membrane. In general, the laminated membrane surface is hydrophilic while the support portion is hydrophobic. Applications will determine the required wetting characteristics of the components. In cases where aqueous fluids at low pressure gradient first come into contact with the hydrophobic support material, initial flow may be limited, or even prevented. In some cases, surface modification treatments imparting hydrophilic characteristics to the hydrophobic support material may be required to achieve a penetrable membrane system. The support material may be hydrophilized by a variety of plasma processes including for example oxygen, nitrous oxide, argon, or neon. The hydrophilization of the support may occur prior to metallization or after metallization of the membrane.
As a further step, and as shown in FIG. 1, the laminated membrane 10 is coated with a thin metal layer 14 covering the top surface. The metal thickness is application dependent, but may range from approximately 100-1500 Angstroms. The coating process may be carried out by any of a variety of known coating techniques including vacuum coating processes such as e-beam or thermal evaporation, wet chemical metalization, or magnetron sputtering techniques, all of which are well known in the art. The metallic ions used are preferably titanium, however in practice any metal including Au, Ag, Ni, Cu, Pt, etc. can be used depending on the process. As an example, a membrane surface coated with Ti metal yields approximately 2-3 times lower fluorescence emission compared with plain or dyed membrane surfaces.
The mechanical strength imparted by the support aids in the manufacture of the metallized membrane as well as in the metallization of the membrane surface. The support prevents curling of the membrane material, thereby eliminating the need in the past to coat both sides of the membrane material. This allows the membrane material to be run through the metallization equipment only once, thereby reducing cost, time, and risk of damage to membrane.
FIG. 1 shows a partial cross section of the laminated membrane system 10 of the present invention. A track etch membrane 12 having a metal coating 14 on its surface, is laminated to a support 16. FIG. 2 shows a partially exposed layered view of the membrane filter 10 of the present invention.
The present invention is contemplated for use with metallized track etch membranes, but the lamination process may be used in any membrane system where the membrane material itself is necessarily of such a thinness that it may benefit from the added mechanical strength of a porous support.
Many modifications and other embodiments will come to the mind of one skilled in the art having the benefit of teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the invention is not to be limited to the specific embodiments disclosed, and that modifications and embodiments are intended to be included within the scope of the appended claims.

Claims

What is claimed is:
1. A laminate membrane system comprising: a polymer membrane having a permeable metallic coating of between 100-1000 Angstroms on a surface thereof; a porous support bonded to said polymer membrane; and, wherein said support adds mechanical strength to said polymer membrane.
2. The laminate membrane system of claim 1 wherein said support is hydrophilic.
3. The laminate membrane system of claim 1 wherein said polymer membrane is a track etch membrane.
4. The laminate membrane system of claim 1 wherein said support is nonwoven.
5. The laminate membrane system of claim 1 wherein said support is substantially rigid.
6. The laminate membrane system of claim 1 wherein said metallic coating comprises titanium metal.
7. The laminate membrane system of claim 1 wherein said polymer membrane is bonded to said support by mechanical bonding.
8. The laminate membrane system of claim 1 wherein said polymer membrane is bonded to said support by an adhesive web.
9. The laminate membrane system of claim 1 wherein said polymer membrane is composed of polycarbonate and said support is composed of a polyolefin.
10. A method of making a laminate membrane system comprising the steps of: a) providing a polymer membrane having two opposing surfaces b) metallizing a first surface with a 100-1000 Angstrom thick coating; and c) bonding said second surface of said polymer membrane to a polymeric support.
11. The method of claim 8 wherein said polymeric support is nonwoven.
12. The method of claim 8 wherein said polymeric support is hydrophilic.
13. The method of claim 8 said polymer membrane is composed of polycarbonate and said support is composed of a polyolefin
14. The method of claim 11 wherein said bonding step is performed by heating the polyolefin support above its transition temperature but below the transition temperature of the polycarbonate membrane such that the transitional polyolefin is absorbed into pores of the polycarbonate, followed by cooling, thereby creating mechanical bonding between the membrane and support.
15. The method of claim 8 wherein said bonding step is performed by interlaying an adhesive web between said support and said membrane, and pressing together.
PCT/US1998/023321 1997-11-04 1998-11-02 Laminated metallized membrane filter WO1999022843A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US6417397P 1997-11-04 1997-11-04
US60/064,173 1997-11-04

Publications (1)

Publication Number Publication Date
WO1999022843A1 true WO1999022843A1 (en) 1999-05-14

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006129722A (en) * 2004-11-02 2006-05-25 Asahi Breweries Ltd Microbe detection membrane filter
WO2007067910A2 (en) * 2005-12-07 2007-06-14 General Electric Company Membrane structure and method of making
US7717271B2 (en) 2005-12-07 2010-05-18 General Electric Company Membrane structure and method of making
EP3115099A1 (en) 2015-07-07 2017-01-11 I3 Membrane GmbH Metal coated polymembrane and method for electrofiltration and electro sorption by means of a metal coated polymembrane
CN106457097A (en) * 2014-04-30 2017-02-22 水务工程设备佛格兰有限公司 Compact electroluminescent laminar element
DE102016125818A1 (en) 2016-12-28 2018-06-28 I3 Membrane Gmbh Process for the separation of charged biologically active substances from liquids and their recovery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2886480A (en) * 1953-12-17 1959-05-12 Siemens Edison Swan Ltd Processes for bonding polymerisable substances
US4715960A (en) * 1983-03-10 1987-12-29 Exxon Research And Engineering Company Method for the modification of polycarbonate membranes, the membranes produced by such method and their use
US4804475A (en) * 1986-05-10 1989-02-14 Bayer Aktiengesellschaft Metallized membrane systems
WO1995013860A1 (en) * 1993-11-12 1995-05-26 Rijn Cornelis Johannes Maria V Membrane filter and a method of manufacturing the same as well as a membrane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2886480A (en) * 1953-12-17 1959-05-12 Siemens Edison Swan Ltd Processes for bonding polymerisable substances
US4715960A (en) * 1983-03-10 1987-12-29 Exxon Research And Engineering Company Method for the modification of polycarbonate membranes, the membranes produced by such method and their use
US4804475A (en) * 1986-05-10 1989-02-14 Bayer Aktiengesellschaft Metallized membrane systems
WO1995013860A1 (en) * 1993-11-12 1995-05-26 Rijn Cornelis Johannes Maria V Membrane filter and a method of manufacturing the same as well as a membrane

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006129722A (en) * 2004-11-02 2006-05-25 Asahi Breweries Ltd Microbe detection membrane filter
EP1811016A1 (en) * 2004-11-02 2007-07-25 Asahi Breweries, Ltd. Membrane filter for microbe detection
EP1811016A4 (en) * 2004-11-02 2009-03-04 Asahi Breweries Ltd MEMBRANE FILTER FOR DETECTION OF MICROBES
WO2007067910A2 (en) * 2005-12-07 2007-06-14 General Electric Company Membrane structure and method of making
WO2007067910A3 (en) * 2005-12-07 2007-10-25 Gen Electric Membrane structure and method of making
US7547393B2 (en) 2005-12-07 2009-06-16 General Electric Company Membrane structure and method of making
US7717271B2 (en) 2005-12-07 2010-05-18 General Electric Company Membrane structure and method of making
US8047382B2 (en) 2005-12-07 2011-11-01 General Electric Company Membrane structure and method of making
US8056731B2 (en) 2005-12-07 2011-11-15 General Electric Company Membrane structure and method of making
CN106457097A (en) * 2014-04-30 2017-02-22 水务工程设备佛格兰有限公司 Compact electroluminescent laminar element
CN106457097B (en) * 2014-04-30 2020-12-29 水务工程设备技术有限责任公司 Filter element and method for the production thereof
US10350552B2 (en) 2014-04-30 2019-07-16 Wta Vogtland Gmbh Filter element and method for the production thereof
US10682612B2 (en) 2015-07-07 2020-06-16 I3 Membrane Gmbh Metal coated polymembrane and method of electrofiltration and electrosorption using a metal coated polymembrane
EP3115099A1 (en) 2015-07-07 2017-01-11 I3 Membrane GmbH Metal coated polymembrane and method for electrofiltration and electro sorption by means of a metal coated polymembrane
US11701618B2 (en) 2015-07-07 2023-07-18 I3 Membrane Gmbh Metal coated polymembrane
WO2018122315A1 (en) 2016-12-28 2018-07-05 I3 Membrane Gmbh Method for separating charged biologically active substances from liquids and the recovery thereof
DE102016125818A1 (en) 2016-12-28 2018-06-28 I3 Membrane Gmbh Process for the separation of charged biologically active substances from liquids and their recovery
CN110177612A (en) * 2016-12-28 2019-08-27 I3薄膜有限公司 Separating charged bioactive substance and its method of recycling from liquid
EP3804841A1 (en) 2016-12-28 2021-04-14 I3 Membrane GmbH Separation process using electrosorption
US11027238B2 (en) 2016-12-28 2021-06-08 I3 Membrane Gmbh Method for separating charged biologically active substances from liquids and the recovery thereof
CN110177612B (en) * 2016-12-28 2022-07-08 I3薄膜有限公司 Separation of charged biologically active substances from liquids and methods for their recovery
CN115069091A (en) * 2016-12-28 2022-09-20 I3薄膜有限公司 Method for separating charged bioactive substances from liquid and recovering the same
CN115069091B (en) * 2016-12-28 2024-06-21 I3薄膜有限公司 Method for separating charged bioactive substances from liquids and recovery thereof

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