Coatings with controlled porosity and chemical properties

• US 5,224,972 A
• Filed: 04/18/1991
• Issued: 07/06/1993
• Est. Priority Date: 09/11/1990
• Status: Expired due to Fees

• Current Assignee: Sandia Corporation (Martin Marietta Corporation)
• Original Assignee: Sandia Corporation (Martin Marietta Corporation)
• Inventors: Doughty, Daniel H., Bein, Thomas, Frye, Gregory C., Moller, Karin, Brinker, C. Jeffrey
• Primary Examiner(s): SPITZER, ROBERT H
• Application Number:
  US07/686,548
• Time in Patent Office: 810 Days
• Field of Search: 55/67, 55/197, 55/208, 55/270, 55/274, 55/386, 55/389, 55/524, 55/18-21, 55/74, 55/387
• US Class Current: 95/9
• CPC Class Codes: B01D 2253/106 Silica or silicates
• CPC Class Codes: B01D 2253/112 Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
• CPC Class Codes: B01D 2253/308 Pore size
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: G01N 2291/0255 (Bio)chemical reactions, e.g. on biosensors
• CPC Class Codes: G01N 2291/0256 Adsorption, desorption, surface mass change, e.g. on biosensors
• CPC Class Codes: G01N 2291/0422 Shear waves, transverse waves, horizontally polarised waves
• CPC Class Codes: G01N 2291/0423 Surface waves, e.g. Rayleigh waves, Love waves
• CPC Class Codes: G01N 2291/0426 Bulk waves, e.g. quartz crystal microbalance, torsional waves
• CPC Class Codes: G01N 2291/0427 Flexural waves, plate waves, e.g. Lamb waves, tuning fork, cantilever
• CPC Class Codes: G01N 29/022 Fluid sensors based on microsensors, e.g. quartz crystal-microbalance [QCM], surface acoustic wave [SAW] devices, tuning forks, cantilevers, flexural plate wave [FPW] devices microdevices per se B81B
• CPC Class Codes: G01N 30/00 Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation G01N3/00, G01N5/00, G01N7/00, G01N9/00, G01N11/00, G01N13/00, G01N15/00, G01N17/00, G01N19/00, G01N21/00, G01N22/00, G01N23/00, G01N24/00, G01N25/00, G01N27/00, G01N29/00 take precedence
• CPC Class Codes: Y10S 95/902 Molecular sieve

Abstract

Coatings and sensors having both steric and chemical selectivity. Controlled porosity provides the steric selectivity, whereas chemically tailored film properties, using controlled composition or modification by coupling agents, chemical species replacement, or chemical species within pores, provide the chemical selectivity. Single or multiple layers may be provided.

Claims

1. A coating for providing selectivity among different chemical species, the coating comprising:

pores having a predetermined uniform pore size, said predetermined uniform pore size sufficient to prevent analyte species of larger size than said pores from entering said pores and said predetermined uniform pore size sufficient to allow analyte species of smaller size than said pores to enter said pores; and

means for chemically sorbing at least a portion of the analyte species having a smaller size than said pores;

wherein said coating comprises at least one member selected from the group consisting of silicate films, titanate films, zirconate films, alumina films, and hydrous oxide films.

2. The invention of claim 1 wherein said hydrous oxide film comprises at least one member selected from the group consisting of sodium titanate and sodium niobate.

3. The invention of claim 1 further comprising a chemically reactive species attached to the coating, said chemically reactive species reactive to the analyte species to be sorbed within said pores.

4. The invention of claim 1 wherein a portion of surface molecules in said film are replaced with chemically reactive species, said chemically reactive species reactive to the analyte to be sorbed within said pores.

5. The invention of claim 1 wherein said means for chemically sorbing the analyte species comprises providing chemically reactive species adjacent the coating and seated within said pores.

6. The invention of claim 5 wherein said chemically reactive species are trapped within said pores due to their size being larger than the size of the entrance to said pores.

7. The invention of claim 5 wherein said chemically reactive species seated within said pores exhibit selective ion exchange properties.

8. The invention of claim 1 wherein said coating comprises a single layer.

9. The invention of claim 1 wherein said means for chemically sorbing the analyte species comprises such means within said pores.

10. The invention of claim 1 wherein said coating comprises multiple layers.

11. The invention of claim 10 wherein at least one layer provides said pores and at least one other layer provides said means for chemically sorbing the analyte species.

12. A selective chemical sensor comprising said coating of claim 1 disposed on a sensor substrate.

13. The invention of claim 12 wherein said substrate comprises a piezoelectric substrate capable of detecting mass changes resulting from sorption of material thereon.

14. The invention of claim 13 further comprising means for generating an alternating voltage which is applied to an interdigital transducer connected to said piezoelectric surface.

15. A selective chemical sensor system for detecting at least one chemical entity, said system comprising at least two chemical sensors according to claim 12.

16. A method of selectively detecting the presence of a chemical entity within an environment comprising placing a selective chemical sensor according to claim 12 in the environment and detecting changes in the coating resulting from sorption of material thereon.

17. A method according to claim 16 wherein the environment comprises a member selected from the group consisting of gaseous environments and liquid environments.

18. A method of making a selective chemical sensor comprising the steps of:

a) providing a sensor substrate; and

b) disposing the coating of claim 1 on the sensor substrate.

19. The method of claim 18 wherein the step of providing the sensor substrate comprises providing a piezoelectric substrate capable of detecting mass changes resulting from sorption of material thereon.

20. The invention of claim 19 further comprising the step of providing means for generating an alternating voltage which is applied to an interdigital transducer connected to the piezoelectric surface.

21. A coating for providing selectivity among different chemical species, the coating comprising:

pores having a predetermined uniform pore size, said predetermined uniform pore size sufficient to prevent analyte species of larger size than said pores from entering said pores and said predetermined uniform pore size sufficient to allow analyte species of smaller size than said pores to enter said pores;

means for chemically sorbing at least a portion of the analyte species having a smaller size than said pores, said means for chemically sorbing the analyte species comprising chemically reactive species adjacent the coating and seated within said pores; and

wherein said chemically reactive species seated within said pores comprise polyoxometalate species.

22. The invention of claim 21 wherein said chemically reactive species are trapped within said pores due to their size being larger than the size of the entrance to said pores.

23. The invention of claim 22 wherein said chemically reactive species seated within said pores exhibit selective ion exchange properties.

24. A method of making a selective chemical sensor comprising the steps of:

a) providing a sensor substrate; and

b) disposing the coating of claim 21 on the sensor substrate.

25. The method of claim 24 wherein the step of providing the sensor substrate comprises providing a piezoelectric substrate capable of detecting mass changes resulting from sorption of material thereon.

26. The invention of claim 25 further comprising the step of providing means for generating an alternating voltage which is applied to an interdigital transducer connected to the piezoelectric surface.

27. A method of making a coating for providing selectivity among different chemical species, the method comprising the steps of:

a) forming a coating with a predetermined uniform pore size, the predetermined pore size sufficient to prevent analyte species of larger size than said pores from entering said pores and the predetermined uniform pore size sufficient to allow analyte species of smaller size than the pores to enter the pores; and

b) providing means for chemically sorbing at least a portion of the analyte species having a smaller size than the pores;

wherein the step of forming a coating with a predetermined uniform pore size comprises forming at least one film selected from the group consisting of silicate films, titanate films, zirconate films, alumina films, and hydrous oxide films.

28. The invention of claim 27 wherein the step of forming a coating with a hydrous oxide film comprises the step of forming the coating with a member selected from the group consisting of sodium titanate and sodium niobate.

29. The invention of claim 27 wherein the step of forming a coating with a predetermined uniform pore size comprises using sol-gel techniques.

30. The invention of claim 27 wherein the step of providing means for chemical sorption comprises attaching a chemically reactive species to the coating, the chemically reactive species being reactive to the analyte species to be sorbed.

31. The invention of claim 27 wherein the step of forming a film further comprises the step of replacing a portion of surface molecules in the film with chemically reactive species, said chemically reactive species reactive to the analyte to be sorbed within said pores.

32. The invention of claim 27 wherein the step of providing means for chemically sorbing the analyte species comprises providing a chemically reactive species adjacent the coating and seated within the pores.

33. The invention of claim 32 wherein the step of providing a chemically reactive species adjacent the coating and seated within the pores comprises trapping the chemically reactive species within the pores due to their size being larger than the size of the entrance to the pores.

34. The invention of claim 32 wherein the step of providing a chemically reactive species within the pores comprises forming the chemically reactive species from solution.

35. The invention of claim 27 wherein the steps of providing pores having a predetermined uniform pore size and providing means for chemically sorbing the analyte species comprises providing a single layer coating.

36. The invention of claim 27 wherein the steps of providing pores having a predetermined uniform pore size and providing means for chemically sorbing the analyte species comprises providing a multilayer coating.

37. The invention of claim 36 wherein the step of providing a multilayer coating comprises providing at least one layer with pores having the predetermined pore size and at least one other layer with the means for chemically sorbing the analyte species.

38. A method of making a coating for providing selectivity among different chemical species, the method comprising the steps of:

a) forming a coating with a predetermined uniform pore size, the predetermined pore size sufficient to prevent analyte species of larger size than said pores from entering said pores and the predetermined uniform pore size sufficient to allow analyte species of smaller size than the pores to enter the pores; and

b) providing means for chemically sorbing at least a portion of the analyte species having a smaller size than the pores;

wherein the step of forming a coating further comprises the step of replacing a portion of surface molecules in the coating with aluminum as the chemically reactive species, the chemically reactive species reactive to the analyte to be sorbed within the pores; and

wherein the step of replacing a portion of surface molecules in the coating with aluminum comprises using trimethylaluminum to replace surface molecules with aluminum.

39. A method of making a coating for providing selectivity among different chemical species, the method comprising the steps of:

a) forming a coating with a predetermined uniform pore size, the predetermined pore size sufficient to prevent analyte species of larger size than said pores from entering said pores and the predetermined uniform pore size sufficient to allow analyte species of smaller size than the pores to enter the pores; and

b) providing means for chemically sorbing at least a portion of the analyte species having a smaller size than the pores;

wherein the step of providing means for chemically sorbing the analyte species comprises providing a polyoxometalate species as a chemically reactive species adjacent the coating and seated within the pores.