CN112973458A - Ion track porous membrane and physical preparation method and application thereof - Google Patents

Ion track porous membrane and physical preparation method and application thereof Download PDF

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CN112973458A
CN112973458A CN202110180823.7A CN202110180823A CN112973458A CN 112973458 A CN112973458 A CN 112973458A CN 202110180823 A CN202110180823 A CN 202110180823A CN 112973458 A CN112973458 A CN 112973458A
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ion
ions
irradiation
membrane material
stretching
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CN112973458B (en
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段敬来
徐国恒
胡正国
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Institute of Modern Physics of CAS
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    • 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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/34—Use of radiation
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses an ion track porous membrane and a preparation method and application thereof. The method comprises the following steps: the membrane material is subjected to ion irradiation and stretching to obtain the membrane material; the irradiation can cause microstructure damage to the material in the irradiation area of the membrane material, and the mechanical strength of the material in the irradiation area is lower than that of the membrane material body; the stretching can transform the structure of the irradiated region material of the membrane material into a pore channel. The preparation method has the advantages of simple method, no use of chemical reagents and ultraviolet light, multiple membrane material types, wide pore density selection range, uniform pore diameter and the like. The ion-track porous membrane prepared by the method has good ion selectivity and flux.

Description

Ion track porous membrane and physical preparation method and application thereof
Technical Field
The invention belongs to the field of materials, and relates to an ion track porous membrane, and a preparation method and application thereof.
Background
Nanoporous membranes are of interest due to their great potential in scientific research and industrial applications including ion separation and water desalination. The polymer membrane has the advantages of firmness, flexibility, easiness in large-scale production and the like, so that the polymer membrane is one of ideal materials for preparing the nano-pores, and the polymer membrane based on the heavy ion tracks is an important technical means for preparing the nano-porous membrane and has a plurality of potential applications. At present, the method for preparing the nanopore by using the heavy ion tracking membrane is only a chemical method, including a chemical etching method and an ultraviolet photolysis method. The precondition for the pore formation by both chemical methods is that the polymer is irradiated with ions and latent ion tracks are formed in the polymer. Wherein, the chemical etching method is to etch the latent tracks by using chemical solution to generate nanopores; the ultraviolet photolysis method is to irradiate the polymer film by using ultraviolet light and make organic molecules in an ion latent track area in the polymer film undergo photodegradation, and the degraded organic molecules are released in the form of gas molecules, so that a nanometer pore channel is formed. However, the diameter of the nanopores obtained by the track chemical etching method is usually large, generally 5 nm or more, so that it is difficult to effectively realize ion and molecule separation, and finally the application of the ion track membrane in the separation field is limited. In addition, chemical etching requires the use of strong acids, strong bases, or strong oxidizing agents, which are likely to cause environmental pollution. For the ultraviolet photolysis method, a nano-sized channel can be prepared by the method, the separation of alkali metal ions and alkaline earth metal ions can be realized, but the ultraviolet irradiation treatment usually needs more than several hours, the efficiency of preparing the pore channel is low, a special ultraviolet irradiation device is needed, the service life of an ultraviolet lamp is limited, and electric energy is consumed. In addition, harmful gases such as carbon monoxide are released to pollute the environment when undergoing a photolysis reaction under ultraviolet irradiation, and the skin, eyes and other parts of the human body are easily damaged when exposed to the ultraviolet environment for a long time.
Therefore, it is important to develop a physical preparation method of the ion-track porous membrane.
Disclosure of Invention
The invention aims to provide an ion track porous membrane and a preparation method and application thereof.
The stress preparation method of the ion track porous membrane provided by the invention belongs to the first physical preparation method of the ion track porous membrane, and has the advantages of simple method, no use of chemical reagents and ultraviolet light, multiple membrane material types, wide pore density selection range, uniform pore diameter and the like. The ion-track porous membrane prepared by the method has good ion selectivity and flux.
The invention provides a method for preparing an ion track porous membrane, which comprises the following steps:
irradiating and stretching the membrane material to obtain the membrane material;
the irradiation can cause microstructure damage to the material in the irradiation area of the membrane material, and the mechanical strength of the material in the irradiation area is lower than that of the membrane material body;
the stretching can transform the structure of the irradiated region material of the membrane material into a pore channel.
Specifically, the method for preparing the ion track porous membrane comprises the following steps:
treating the membrane material by treatment A or treatment B to obtain the membrane material;
the process A comprises the following steps: sequentially performing the irradiation and the stretching;
the processing B comprises the following steps: the stretching is performed simultaneously with the irradiation.
The irradiation is performed by using an ion accelerator or fission fragments.
The pore canal is a through hole with a non-circular section;
the pore density is regulated and controlled by ion irradiation fluence and is the same as the ion irradiation fluence;
the aperture is 0.2-10 nm; in particular 0.684nm-0.800 nm.
The membrane material is plastic and ions are capable of forming ion tracks therein;
the membrane material can be selected from but not limited to PC, PET, PI, PPS, PEEK, PTFE, PVDF, PFA, FEP, E-CTFE and PVF;
the thickness of the membrane material can be selected from, but is not limited to, 2 μm, 4 μm, 5 μm, 6 μm, 12 μm and 30 μm;
in the irradiation step, the irradiated ions can form ion tracks in the membrane material;
the irradiated ion may be selected from, but is not limited to86Kr、129Xe、181Ta and209bi; the irradiated ions are129In the case of Xe, the energy may be specifically 5.98 MeV/u; the irradiated ions are181In the case of Ta, the energy may be specifically 13.5 MeV/u;
the irradiation fluence of the PC film is specifically 5 × 109ions/cm2Or 5X 1010ions/cm2；
The irradiation fluence of the PET film is specifically 1 x 1010ions/cm2Or 5X 1010ions/cm2；
The irradiation fluence of the PI film is specifically 1 × 1010ions/cm2Or 5X 1010ions/cm2；
The radiation fluence of the PPS film is specifically 5 multiplied by 1010ions/cm2；
The PEEK, PTFE, PVDF, PFA, FEP, E-CTFE and PVF fluence are specifically 1 × 1011ions/cm2。
In the stretching step, the stretching ratio is 5-500%; more specifically 10-50% or 10-100% or 20%; the stretching rate can be 0.005mm/s-0.01 mm/s; the stretching direction is unidirectional or multidirectional.
In addition, the ion-track porous membrane prepared by the method and the application of the ion-track porous membrane in material separation also belong to the protection scope of the invention.
Specifically, in the substance separation, the separation target is at least one selected from ions and molecules.
The substance separation specifically comprises the following three separation modes:
a. separating different ions;
b. separating ions from molecules;
c. the different molecules are separated.
The invention selects a physical method to prepare the ion track porous membrane containing the nanometer pore canal. The method breaks through the limitations of a chemical etching method and an ultraviolet photolysis method, has no problems of environmental pollution and the like, and can obviously improve the hole preparation efficiency and reduce the preparation cost. The obtained ion track porous membrane has the characteristics of rich material types, uniform pore diameter, easiness in realizing large-scale preparation and the like, and has important application value.
The preparation method has the advantages of simple method, no use of chemical reagents and ultraviolet light, multiple membrane material types, wide pore density selection range, uniform pore diameter and the like. The ion-track porous membrane prepared by the method has good ion selectivity and flux.
Drawings
FIG. 1 is an I-V curve of different cation solutions.
FIG. 2 is (a) the transport rate of different cations as a function of cationic water and radius; (b) represents an alkali metal ion (Li)+、Na+、K+、Cs+) Selectivity ratio to magnesium ion.
FIG. 3 is an I-V curve of different organic cation solutions.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1
The invention provides a physical preparation method of an ion track porous membrane, which comprises the following steps:
1) cutting a Polyimide (PI) film with the thickness of 12 mu m into a square with the side length of 5.2cm so as to adapt to the irradiation area of an accelerator beam;
2) irradiating the polymer film with heavy ion accelerator to form latent ion tracks in the film129Xe, energy 5.98 MeV/u; the injection amount is 5 x 1010ions/cm2；
3) Cutting the polymer film subjected to heavy ion irradiation into dumbbell-shaped samples, and stretching the irradiated polymer film by using a stretcher, wherein the stretching ratio is 10-50%, and the stretching speed is 0.005-0.01 mm/s; the stretching direction is unidirectional, and the ion track porous membrane provided by the invention is obtained.
Example 2
1) Cutting a polyethylene terephthalate (PET) film with the thickness of 2 mu m into a square with the side length of 5.2cm so as to adapt to the irradiation area of an accelerator beam;
2) irradiating the polymer film by using a heavy ion accelerator, wherein the irradiated ions are181Ta, energy of 13.5MeV/u, fluence of 5X 1010ions/cm2；
3) Cutting the polymer film subjected to heavy ion irradiation into dumbbell-shaped samples, and stretching the irradiated polymer film by using a stretcher, wherein the stretching ratio is 10-100%, and the stretching speed is 0.005-0.01 mm/s; the stretching direction is unidirectional, and the ion track porous membrane provided by the invention is obtained.
Example 3
1) Cutting a polycarbonate film (PC) having a thickness of 30 μm into a shape satisfying irradiation conditions;
2) irradiating the polymer film by using a heavy ion accelerator, wherein the irradiated ions are129Xe or181Ta with an irradiation fluence of 5X 1010ions/cm2；
3) Cutting the polymer film subjected to heavy ion irradiation into a cross-shaped sample, and performing biaxial tension on the irradiated polymer film by using a stretcher, wherein the stretching is performed in one direction by 100%, the stretching ratio in the other direction is continuously changed from 10% to 100%, and the stretching rate is from 0.005mm/s to 0.01 mm/s; the stretching direction is bidirectional, and the ion track porous membrane provided by the invention is obtained.
Example 4
A series of characterizations were performed on the polyimide film PI ion track film obtained in example 1 with a thickness of 12 μm and a draw ratio of 20%.
The PI membrane is clamped between two electrolytic cells, 0.1M different cation electrolytes are added on two sides of the PI membrane, Ag/AgCl electrodes are inserted into the electrolytes on two sides, a Pian meter is used for applying +/-1V bias voltage on two ends of the electrodes to detect ion current, and whether the stretched heavy ion track membrane is conducted or not is verified. FIG. 1 is an I-V curve of different cations at the same concentration. As can be seen, the stretched polymer membrane was conductive, indicating that the physical preparation of the ion-track porous membrane was successful; different cations have different transmembrane currents, which shows that the obtained ion track porous membrane has transmission selectivity on different ions and can realize ion separation.
In order to measure the transmission rate of the PI film to different ions, a commercial H-type electrolytic cell is used, the PI film is clamped between two electrolytic cells, 0.1M electrolyte with different cations and 15mL deionized water are respectively added on two sides of each electrolytic cell, and then 2V voltage is applied to drive the cations to the electrolytic cellOne side of deionized water permeates, samples are collected after a certain time, the concentration of the permeating liquid is measured by ICP-OES, and then the transmission rates of different cations can be obtained through calculation; the selection ratio among different ions can be calculated according to the transmission rates of the different ions; FIG. 2(a) shows the transport rates of different cations, and (b) is alkali metal ion (Li)+、Na+、K+、Cs+) Relative alkaline earth metal ion (Mg)2+) Is selected to the transmission rate, wherein K+With Mg2 +Has a selection ratio of more than 103(ii) a As can be seen from the figure, (a) is the transport rate of different ions, and the transport rate of monovalent ions is much higher than that of divalent and trivalent metal ions, i.e.: k+>Li+>Na+>Cs+>>Ba2+>Ca2+>Mg2+>La3+。
Since the hydrated radius of an organic cation is comparable to its bare ionic radius, measuring the permeability of different sized organic cations is often used as a "ruler" for detecting nanopore size. The size of the ion track nano-pore is detected by using a method for detecting ion current, namely, 0.1M of organic cation aqueous solution with different radiuses and 1 multiplied by 10 are respectively added on two sides of the membrane- 6And (3) adding an Ag/AgCl electrode into the KCl solution of M, and detecting the pore size of the polymer nano porous membrane by measuring transmembrane currents of different organic cations. The organic cation includes tetramethylammonium ion ((Me)4N+Diameter 0.684nm), tetraethylammonium ion ((Et)4N+Diameter 0.800nm), tetrapropylammonium ion ((Pr)4N+Diameter 0.904nm), tetrabutylammonium ion ((Bu)4N+Diameter 0.988nm) and tetrapentylammonium ion ((Pe)4N+Diameter 1.058 nm).
FIG. 3 is an I-V curve of organic cation solutions of different sizes. As can be seen from the figure, (Me)4N+Is significantly larger than organic cations of other sizes, indicating that the nanochannels have a diameter larger than (Me)4N+Diameter less than (Et)4N+The diameter, namely the pore diameter of the nano-pores prepared by the method is mainly distributed between 0.684nm and 0.800 nm.

Claims (9)

1. A method of making an ion-track porous membrane comprising:
irradiating and stretching the membrane material to obtain the membrane material;
the irradiation can cause microstructure damage to the material in the irradiation area of the membrane material, and the mechanical strength of the material in the irradiation area is lower than that of the membrane material body;
the stretching can transform the structure of the irradiated region material of the membrane material into a pore channel.
2. The method of claim 1, wherein: the method for preparing the ion-track porous membrane comprises the following steps:
treating the membrane material by treatment A or treatment B to obtain the membrane material;
the process A comprises the following steps: sequentially performing the irradiation and the stretching;
the processing B comprises the following steps: the stretching is performed simultaneously with the irradiation.
3. The method according to claim 1 or 2, characterized in that: the irradiation is performed by using an ion accelerator or fission fragments.
4. A method according to any one of claims 1 to 3, wherein: the pore canal is a through hole with a non-circular section;
the pore density is regulated and controlled by ion irradiation fluence and is the same as the ion irradiation fluence;
the aperture is 0.2-10 nm; in particular 0.684nm-0.800 nm.
5. The method according to any one of claims 1 to 4, wherein: the membrane material is plastic and ions are capable of forming ion tracks therein;
the membrane material is specifically selected from at least one of PC, PET, PI, PPS, PEEK, PTFE, PVDF, PFA, FEP, E-CTFE and PVF;
in the irradiation step, the irradiated ions can form ion tracks in the membrane material;
the irradiated ions are selected from86Kr、129Xe、181Ta and209at least one of Bi;
the irradiation fluence of the PC film is specifically 5 × 109ions/cm2；
The irradiation fluence of the PET film is specifically 1 x 1010ions/cm2；
The irradiation fluence of the PI film is specifically 1 × 1010ions/cm2；
The radiation fluence of the PPS film is specifically 5 multiplied by 1010ions/cm2；
The PEEK, PTFE, PVDF, PFA, FEP, E-CTFE and PVF fluence are specifically 1 × 1011ions/cm2。
6. The method according to any one of claims 1 to 5, wherein: in the stretching step, the stretching ratio is 5-500%; the stretching direction is unidirectional or multidirectional.
7. An ion-tracking porous membrane prepared by the method of any one of claims 1 to 6.
8. Use of the ion-tracking porous membrane of claim 7 for mass separation.
9. Use according to claim 8, characterized in that: in the substance separation, the separation object is selected from at least one of ions and molecules.
The substance separation specifically comprises the following three separation modes:
a. separating different ions;
b. separating ions from molecules;
c. the different molecules are separated.
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WO2023280263A1 (en) * 2021-07-09 2023-01-12 中国科学院近代物理研究所 Near-perfect light absorber and universal preparation method therefor
CN115738769A (en) * 2022-11-02 2023-03-07 先进能源科学与技术广东省实验室 Polyimide gas separation membrane based on ion beam irradiation modification and application thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023280263A1 (en) * 2021-07-09 2023-01-12 中国科学院近代物理研究所 Near-perfect light absorber and universal preparation method therefor
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CN115738769B (en) * 2022-11-02 2024-01-23 先进能源科学与技术广东省实验室 Polyimide gas separation membrane based on ion beam irradiation modification and application thereof

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