Materials having improved nonfouling characteristics and method of making same

• US RE33,273 E
• Filed: 11/13/1987
• Issued: 07/24/1990
• Est. Priority Date: 08/18/1982
• Status: Expired due to Term

• Current Assignee: Lois Speaker
• Original Assignee: Georgia Tech Research Corporation (University System of Georgia)
• Inventors: Speaker, Lois M.
• Primary Examiner(s): SPEAR JR, FRANK
• Application Number:
  US07/120,599
• Time in Patent Office: 984 Days
• Field of Search: 210/639, 210/500.2, 424/85, 424/178, 427/369, 427/370
• US Class Current: 210/639
• CPC Class Codes: B01D 67/0088 Physical treatment with compounds, e.g. swelling, coating or impregnation
• CPC Class Codes: B01D 69/122 Separate manufacturing of ultra-thin membranes
• CPC Class Codes: B05D 1/202 Langmuir Blodgett films (LB films)
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures

Abstract

A method of improving the separatory properties of membranes by the deposition of a fluorinated amphiphilic compound in an oriented Langmuir-Blodgett layer on the membranes surface so as to increase membrane selectivity and counteract membrane surface properties leading to fouling during liquid-liquid separations and enhance gas selectivities of membranes used for gas-gas separations. The use of a fluorinated long-chain pyridinium bromide is specifically disclosed.

Claims

1. A method of modifying a surface of a separatory material comprising the step of depositing on said surface .[.a.]. .Iadd.at least one oriented monomolecular .Iaddend.layer of .[.a.]. .Iadd.an essentially water-insoluble .Iaddend.fluorinated amphiphilic molecule .Iadd.which is capable of forming an oriented monomolecular layer and .Iaddend.which is oriented such that the fluorinated portion of said molecule extends outwardly from said surface.

2. A method as claimed in claim 1 wherein said molecule is a fluorinated aromatic heterocyclic bromide.

3. A method as claimed in claim 1 wherein said molecule is fluorinated pyridinium bromide.

4. A method as claimed in claim 1 wherein said layer is a monomolecular Langmuir-Blodgett layer.

5. A method as claimed in claim 1 wherein said molecule is neutral in charge.

6. A method as claimed in claim 1 wherein said molecule has the same electrical charge as said membrane surface.

7. A method as claimed in claim 1 wherein said layer of said molecule is deposited on said surface at a deposition pressure ranging from 30 to 35 mN M^-1.

8. A method as claimed in claim 1 wherein said layer of said molecule is deposited on said surface at a deposition temperature ranging from 1°

to 10°

C.

9. A method as claimed in claim 1 wherein the molecular weight of said molecule ranges from 350 to 700.

10. A method as claimed in claim 1 wherein said molecule is water-insoluble at a deposition pressure ranging from 30 to 35 mN M^-1 and a deposition temperature of 1°

to 10°

C.

11. A method as claimed in claim 1 wherein said separatory material is a semipermeable membrane.

12. A method as claimed in claim 11 wherein said membrane is a liquid-liquid separatory membrane.

13. A method as claimed in claim 11 wherein said membrane is a gas-gas separatory membrane.

14. A method as claimed in claim 1 wherein said separatory material is a resin particle.

15. A method of treating the surfaces of semipermeable membranes which separates a component of a fluid, comprising the steps of:

(a) placing .Iadd.on the surface of a body of water .Iaddend.a film of molecules of .[.a.]. .Iadd.an essentially water insoluble .Iaddend.fluorinated amphiphilic compound .[.on the surface of a body of water.]. .Iadd.which is capable of forming an oriented monomolecular layer.Iaddend.;

(b) compressing said film into an oriented monomolecular layer; and

(c) moving said membrane vertically into and out of said film spread on a water surface a selected number of times whereby said monolayer is transferred onto an exterior surface of said membrane such that the fluorinated portion of said compound is directed toward said fluid.

16. A method as claimed in claim 15 wherein said compound is fluorinated pyridinium bromide.

17. A method of enhancing the selectivity of a selective semipermeable membrane for a component of a mixture introduced to a surface of said membrane, comprising the step of depositing on said surface .[.an.]. .Iadd.at least one .Iaddend.oriented monolayer of .[.a.]. .Iadd.an essentially water insoluble .Iaddend.fluorinated amphiphilic compound .Iadd.which is capable of forming an oriented monomolecular layer and .Iaddend.which exhibits an affinity for said component.

18. A method as claimed in claim 17 wherein said compound is surface-active.

19. A method of modifying the surface of a semipermeable membrane comprising the step of depositing on said surface .[.an.]. .Iadd.at least one .Iaddend.oriented monolayer of .[.a.]. .Iadd.an essentially water insoluble .Iaddend.fluorinated amphiphilic compound .Iadd.which is capable of forming an oriented monomolecular layer and .Iaddend.which has the same charge as said surface.

20. An improvement in a semipermeable membrane of the type having a surface in contact with a fluid to be separated, the improvement comprising .[.a.]. .Iadd.an essentially water insoluble .Iaddend.fluorinated amphiphilic compound .Iadd.capable of forming an oriented monomolecular layer .Iaddend.being deposited on said surface in .[.an.]. .Iadd.at least one .Iaddend.oriented monomolecular Langmuir-Blodgett layer so as to impart non-fouling characteristics to said membrane.

21. An improvement as claimed in claim 20 wherein said compound is fluorinated pyridinium bromide.

22. An improvement as claimed in claim 20 wherein said layer is oriented with the fluorinated portion of said compound directed toward said fluid to be separated.

23. An improvement as claimed in claim 20 wherein said layer is an x-layer of fluorinated pyridinium bromide.

24. A method of preventing the fouling of a semipermeable membrane used for separating dissolved materials from liquids, comprising the step of depositing on the surface of said membrane .[.an.]. .Iadd.at least one .Iaddend.oriented monololecular layer of fluorinated pyridinium bromide prior to the use of said surface in said separating.

25. An improvement in a semipermeable membrane of the type used for separating dissolved materials from liquids, the improvement comprising fluorinated pyridinium bromide being deposited in .[.an.]. .Iadd.at least one .Iaddend.oriented monomolecular layer on the surface of said membrane that is to be in contact with said liquid. .Iadd.

26. A method of modifying a solid surface of a material comprising the step of depositing on said surface at least one oriented monomolecular layer of an essentially water-insoluble fluorinated amphiphilic compound which is capable of forming an oriented monomolecular layer and which is oriented such that the fluorinated portions of the molecules of said compound extend outwardly from said surface. .Iaddend. .Iadd.27. A method as claimed in claim 26 wherein each layer of said fluorinated amphiphilic compound is a monomolecular Langmuir-Blodgett layer. .Iaddend. .Iadd.28. A material having improved non-fouling characteristics, said material including a smooth solid surface having thereon at least one oriented monomolecular layer of an essentially water-insoluble fluorinated amphiphilic compound capable of forming an oriented monomolecular layer, said compound imparting improved non-fouling characteristics to said surface. .Iaddend. .Iadd.29. A material according to claim 28 wherein said layer is a Langmuir-Blodgett layer. .Iaddend. .Iadd.30. A method according to claim 26 wherein said compound is a long chain compound having a fluorinated group and a polar group at opposite ends of said chain, said compound being neutral in charge or having the same charge as that of said surface. .Iaddend. .Iadd.31. A method according to claim 26 wherein said surface is hydrophilic. .Iaddend. .Iadd.32. A material according to claim 28 wherein said compound is a long chain compound having a fluorinated group and a polar group at opposite ends of said chain, said compound being neutral in charge or having the same charge as that of said surface. .Iaddend.