Polyamide flat sheet membranes with microporous surface structure for nanoparticle retention
View Patent ↗The present disclosure provides a flat-sheet polyamide membrane comprising a first major surface and a second major surface and a separation layer and a porous substructure in the cross section of the membrane between the first major and the second major surface, wherein the average pore size diameter in the separation layer is smaller than the average pore size diameters on the first and second major surfaces, wherein the average pore size diameter on the first major surface is larger than the average pore size diameter on the second major surface, wherein the separation layer is closer to the second major surface than to the first major surface. The present disclosure further provides a method for producing such membranes and a use of the membranes for nanofiltration or ultrafiltration purposes.
1. A flat-sheet polyamide membrane comprising a first major surface and a second major surface, a separation layer located between the first and the second major surfaces, and a porous substructure in the cross section of the membrane between the first major and the second major surface; wherein the average pore size diameter in the separation layer is smaller than the average pore size diameters on the first and second major surfaces, wherein the average pore size diameter on the first major surface is larger than the average pore size diameter on the second major surface, wherein the separation layer is closer to the second major surface than to the first major surface; and wherein the first and second major surfaces have a filamentous network-like structure.
2. The membrane according to claim 1 , wherein the maximum of the pore size distribution in the separation layer according to ASTM F316-03 is in the range of from 5 to 50 nm.
3. The membrane according to claim 1 , wherein the surface porosity on the first major surface is larger than the surface porosity on the second major surface.
4. The membrane according to claim 1 , wherein the membrane has a surface porosity on the first major surface of at least 20%.
5. The membrane according to claim 1 , wherein the membrane exhibits a dmax as determined with bubble point IPA of at least 0.01 μm.
6. The membrane according to claim 1 , wherein the transmembrane flow is in the range of from 0.1 to 10 mL/(min·cm2·bar).
7. A method for producing a membrane according to claim 1 , comprising the steps
(i) providing a homogeneous casting solution comprising a polyamide and a solvent system, wherein the casting solution of the polymer component and solvent system has on cooling a critical demixing temperature and a solidification temperature, and a miscibility gap below the critical demixing temperature in the liquid state of aggregation, and wherein the solvent system contains a component A and a component B, which are liquid and can be mixed homogeneously with each other at the dissolving temperature, and wherein a solvent for the polymer component is selected from component A and component B is a non-solvent for the polymer component;
(ii) forming of the casting solution into a film having a first major surface and a second major surface in a forming tool having a temperature above the critical demixing temperature of the casting solution;
(iii) placing the second major of the film onto a conditionable carrier, which is conditioned to a cooling temperature below the solidification temperature, resulting in cooling of the film via the conditionable carrier at such a rate that a thermodynamic non-equilibrium liquid-liquid phase separation into a polymer-rich and a polymer-poor phase takes place, and subsequently, on passing below the solidification temperature, solidification of the polymer-rich phase takes place, forming a membrane structure; at the same time;
(iv) bringing the first major surface of the film into contact with a gaseous atmosphere,
(v) placing the film into a precipitation bath comprising a non-solvent for the polyamide polymer, thereby forming the three-dimensioned porous membrane structure, characterized in that
the conditionable carrier is conditioned to a temperature in the range of from 5 to 45° C.; and wherein the film has a residence time on the conditionable carrier from being casted onto the conditionable carrier until entry into the precipitation bath of at least 10 s.
8. The method according to claim 7 , wherein the conditionable carrier is conditioned to a temperature in the range of from 5 to 30° C.
9. The method according to claim 7 , wherein the casting solution comprises the polyamide in an amount of from 10 to 25 wt. %.
10. The method according to claim 7 , wherein the residence time of the film on the conditionable carrier is at least 15 s.
11. The method according to claim 7 , wherein the residence time is in the range of from 20 to 30 s.
12. The method according to claim 7 , wherein the forming tool exhibits a temperature in the range of from 200 to 240° C.
13. The method according to claim 7 , wherein a difference of the forming tool temperature and the temperature of the conditionable carrier is in the range of from 150 to 250° C.