Material for light modulation and manufacturing processes

• US 5,056,899 A
• Filed: 01/10/1990
• Issued: 10/15/1991
• Est. Priority Date: 07/24/1987
• Status: Expired due to Fees

• Current Assignee: Polyvision Corporation (Steelcase Incorporated)
• Original Assignee: Alpine Polyvision Incorporated
• Inventors: Warszawski, Bernard
• Primary Examiner(s): Laroche, Eugene R.
• Assistant Examiner(s): Shingleton, Michael
• Application Number:
  US07/462,977
• Time in Patent Office: 643 Days
• Field of Search: 350/357
• US Class Current: 359/265
• CPC Class Codes: G02F 1/1508 using a solid electrolyte

Abstract

An electrolytic material intended for a process relating to a light-modulating cell involving electrochromic reflection or transmission. The electrolytic material is a homogeneous mixture of solid consistency, comprising at least (a) a water-soluble salt or salts of one metal which can be cathodically deposited from an aqueous solution of one of its ions; (b) one initially water-soluble film-forming polymer resin; and (c) water. The material has ionic conductivity and deformability, and can be formed in a thin continuous layer. It has at least the functions of participating in the erasure of a picture element earlier written in the light-modulating cell, and of enabling the flow of electrical current between a working electrode and a counter-electrode during writing and erasure steps.

Claims

1. A material intended for processes, cells, or devices relating to electrochromic modulation of light by reflection or transmission, the material having ionic electroconductivity and comprising a homogeneous mixture of solid consistency, comprising the following constituents:

a) a hydrosoluble salt or a hydrosoluble mixture of salts of at least one metal which can be cathodically deposited from an aqueous solution of one of its simple or complex ions;

b) at least one initially hydrosoluble film-forming polymer resin;

c) water; and

d) an auxiliary redox couple;

wherein the constituents are selected so as to allow plastic or viscoelastic deformability; and

wherein the material is able to reversibly (1) develop metal or metal alloy deposits by cathodic reduction of at least one depositable metal ion present within the material, and (2) by anodic oxidation, dissolve the deposits and reincorporate into their original state the metal ion or ions produced by this oxidation.

2. The material according to claim 1, wherein the constituents are further selected so as to allow adhesive properties.

3. The material according to claim 1, wherein the initially hydrosoluble film-forming polymer resins are in the proportion of one part by weight to 0.005 to 50 parts of such salts considered in their anhydrous form.

4. The material according to claim 1, wherein the auxiliary redox couple is, in its reduced form, colorless or only slightly colored.

5. The material according to claim 4, wherein the auxiliary redox couple is, in its reduced form, hydrosoluble in the presence of the other hydrosoluble constituents of the material, and forms an homogeneous mixture with the constituents.

6. The material according to claim 1, wherein the metal of the hydrosoluble salts or hydrosoluble mixture of salts is selected from the group consisting of zinc, cadmium, lead, silver, copper, iron, cobalt, nickel, tin, indium, platinum, palladium, gold, bismuth, antimony, tellurium, manganese, thallium, selenium, gallium, arsenic, mercury, chromium, tungsten and molybdenum.

7. The material according to claim 6, wherein copper is associated with at least one other metal selected from the group.

8. The material according to claim 1, wherein the material further comprises at least one hydrosoluble salt of a cation selected from a group consisting of those which cannot be either electro-deposited from an aqueous solution or reduced into a metal.

9. The material according to claim 8, wherein the cation which cannot be electro-deposited from an aqueous solution is selected from a group consisting of the alkali metals, the alkaline-earths, aluminum, beryllium, and rare earths which cannot be electro-deposited from an aqueous solution.

10. The material according to claim 8, wherein the cation which cannot be reduced into a metal is selected from a group consisting of ammonium ion and quaternary ammonium ions.

11. The material according to claim 1, wherein the material further comprises halide anions.

12. The material according to claim 1, wherein the hydrosoluble salt or the hydrosoluble mixture of salts is hygroscopic in the presence of atmospheric humidity.

13. The material according to claim 12, wherein the hydrosoluble salt or the hydrosoluble mixture of salts is further deliquescent in the presence of atmospheric humidity.

14. The material according to claim 1, wherein the ratio of hydrosoluble salts considered in their anhydrous form to water is greater than 0.5.

15. The material according to claim 1, wherein the ratio of hydrosoluble salts considered in their anhydrous form to water is greater than 1.

16. The material according to claim 1, wherein the initially hydrosoluble film-forming polymer resin is selected from a group consisting of polyoxyethylene, polyvinylpyrrolidone, polyvinyl alcohol, the cellulose ethers, sodium alginate, polyacrylic acid and its derivatives, gelatin, gum arabic, polystyrene sulphonic acid and polyacrylamide.

17. The material according to claim 1, wherein the material further comprises at least one dispersed particulate solid.

18. The material according to claim 17, wherein the dispersed particulate solid is a masking and contrasting pigment.

19. The material according to claim 17, wherein the material comprises at least one white pigment such as titanium dioxide.

20. The material according to claim 17, wherein the material comprises at least one colored pigment.

21. The material according to claim 1, wherein the material comprises at least one homogeneously mixed hydrosoluble dye or coloring agent.

22. The material according to claim 1, wherein the material further comprises at least one acid.

23. The material according to claim 21, wherein the acid is selected from a group consisting of hydrochloric acid, hydrobromic acid, acetic acid, perchloric acid, chloric acid, formic acid, nitric acid.

24. The material according to claim 1, wherein the material further comprises at least one cross-linking or vulcanization agent of the resin.

25. The material according to claim 1, wherein the material further comprises at least one complexing agent.

26. The material according to claim 1, wherein the material further comprises at least one agent having a function of favoring formation of a layer and application of a layer of the material.

27. The material according to claim 26, wherein the agent is a surface-active or wetting agent.

35. A process for manufacturing a material according to 1, comprising the following successive steps:

1) fabricating at least one fluid formative composition comprising the constituents of the material and water in quantities allowing a viscosity appropriate for its application as a layer; and

2) acting on the fluid formative composition to obtain the solid consistency of the material.

36. The process according to claim 35, wherein the step of acting on the fluid formative composition comprises evaporation, heat treatment, cross-linking or vulcanization.

28. A material intended for processes, cells, or devices relating to electrochromic modulation of light by reflection or transmission, the material having ionic electroconductivity and comprising a homogeneous mixture of solid consistency, comprising the following constituents:

a) a hydrosoluble salt or a hydrosoluble mixture of salts of at least one metal which can be cathodically deposited from an aqueous solution of one of its simple or complex ions;

b) at least one initially hydrosoluble film-forming polymer resin;

c) water;

d) at least one hydrosoluble salt of a cation selected from a group consisting of those which cannot be either electro-deposited from an aqueous solution or reduced into a metal; and

e) an auxiliary redox couple;

wherein the constituents are selected in a group allowing simultaneously a plastic or viscoelastic deformability and adhesive properties; and

wherein the material is able to reversibly (1) develop metal or metal alloy deposits by cathodic reduction of at least one depositable metal ion present within the material, and (2) by anodic oxidation, dissolve the deposits and reincorporate into their original state the metal ion or ions produced by this oxidation.

37. A process for manufacturing a material according to claim 28, comprising the following successive steps:

1) fabricating at least one fluid formative composition comprising the constituents of the material and water in quantities allowing a viscosity appropriate for its application as a layer; and

2) acting on the fluid formative composition to obtain the solid consistency of the material.

38. The process according to claim 37, wherein the step of acting on the fluid formative composition comprises evaporation, heat treatment, cross-linking or vulcanization.

29. A material intended for processes, cells, or devices relating to electrochromic modulation of light by reflection or transmission, the material having ionic electroconductivity and comprising a homogeneous mixture of solid consistency, comprising the following constituents:

a) a hydrosoluble salt or a hydrosoluble mixture of salts of at least one metal which can be cathodically deposited from an aqueous solution of one of its simple or complex ions, the ratio of the hydrosoluble salts considered in their anhydrous form to water being greater than 1;

b) at least one initially hydrosoluble film-forming polymer resin;

c) water;

d) at least one hydrosoluble salt of a cation selected from a group consisting of those which cannot be either electro-deposited from an aqueous solution or reduced into a metal; and

e) an auxiliary redox couple;

wherein the constituents are selected in a group allowing simultaneously a plastic or viscoelastic deformability and adhesive properties; and

wherein the material is able to reversibly (1) develop metal or metal alloy deposits by cathodic reduction of at least one depositable metal ion present within the material, and (2) by anodic oxidation, dissolve the deposits and reincorporate into their original state the metal ion or ions produced by this oxidation.

39. A process for manufacturing a material according to claim 29, comprising the following successive steps:

1) fabricating at least one fluid formative composition comprising the constituents of the material and water in quantities allowing a viscosity appropriate for its application as a layer; and

2) acting on the fluid formative composition to obtain the solid consistency of the material.

40. The process according to the claim 39, wherein the step of acting on the fluid formative composition comprises evaporation, heat treatment, cross-linking or vulcanization.

30. A material intended for processes, cells, or devices relating to electrochromic modulation of light by reflection or transmission, the material having ionic electroconductivity and comprising a homogeneous mixture of solid consistency, comprising the following constituents:

a) a hydrosoluble salt or a hydrosoluble mixture of salts of at least one metal which can be cathodically deposited from an aqueous solution of one of its simple or complex ions, hygroscopic in the presence of atmospheric humidity, the ratio of the hydrosoluble salts considered in their anhydrous form to water being greater than 1;

b) at least one initially hydrosoluble film-forming polymer resin;

c) water;

d) at least one hydrosoluble salt of a cation selected from a group consisting of those which cannot be either electro-deposited from an aqueous solution or reduced into a metal; and

e) an auxiliary redox couple;

wherein the constituents are selected in a group allowing simultaneously a plastic or viscoelastic deformability; and

wherein the material is able to reversibly (1) develop metal or metal alloy deposits by cathodic reduction of at least one depositable metal ion present within the material, and (2) by anodic oxidation, dissolve the deposits and reincorporate into their original state the metal ion or ions produced by this oxidation.

41. A process for manufacturing a material according to claim 30, comprising the following successive steps:

1) fabricating at least one fluid formative composition comprising the constituents of the material and water in quantities allowing a viscosity appropriate for its application as a layer; and

2) acting on the fluid formative composition to obtain the solid consistency of the material.

42. The process according to claim 41, wherein the step of acting on the fluid formative composition comprises evaporation, heat treatment, cross-linking or vulcanization.

31. A material intended for processes, cells, or devices relating to electrochromic modulation of light by reflection or transmission, the material having ionic electroconductivity and comprising a homogeneous mixture of solid consistency, comprising the following constituents:

a) a hydrosoluble salt or a hydrosoluble mixture of salts of at least one metal which can be cathodically deposited from an aqueous solution of one of its simple or complex ions;

b) at least one initially hydrosoluble film-forming polymer resin;

c) water;

d) at least one hydrosoluble salt of a cation selected from a group consisting of those which cannot be either electro-deposited from an aqueous solution or reduced into a metal; and

e) an auxiliary redox couple;

wherein the constituents are selected in a group allowing simultaneously a plastic or viscoelastic deformability and adhesive properties;

wherein copper associated with at least one metal selected from a group consisting of zinc, cadmium, lead, silver, copper, iron, cobalt, nickel, tin, indium, platinum, palladium, gold, bismuth, antimony, tellurium, manganese, thallium, selenium, gallium, arsenic, mercury, chromium, tungsten and molybdenum; and

wherein the material is able to reversibly (1) develop metal or metal alloy deposits by cathodic reduction of at least one depositable metal ion present within the material, and (2) by anodic oxidation, dissolve the deposits and reincorporate into their original state the metal ion or ions produced by this oxidation.

43. A process for manufacturing a material according to claim 31, comprising the following successive steps:

1) fabricating at least one fluid formative composition comprising the constituents of the material and water in quantities allowing a viscosity appropriate for its application as a layer; and

2) acting on the fluid formative composition to obtain the solid consistency of the material.

44. The process according to claim 43, wherein the step of acting on the fluid formative composition comprises evaporation, heat treatment, cross-linking or vulcanization.

32. A material intended for processes, cells, or devices relating to electrochromic modulation of light by reflection or transmission, the material having ionic electroconductivity and comprising a homogeneous mixture of solid consistency, comprising the following constituents:

a) a hydrosoluble salt or a hydrosoluble mixture of salts of at least one metal which can be cathodically deposited from an aqueous solution of one of its simple or complex ions;

b) at least one initially hydrosoluble film-forming polymer resin;

c) water;

d) at least one hydrosoluble salt of a cation selected from a group consisting of those which cannot be either electro-deposited from an aqueous solution or reduced into a metal;

e) halide anions; and

f) an auxiliary redox couple;

wherein the constituents are selected in a group allowing simultaneously a plastic or viscoelastic deformability and adhesive properties; and

wherein the material is able to reversibly (1) develop metal or metal alloy deposits by cathodic reduction of at least one depositable metal ion present within the material, and (2) by anodic oxidation, dissolve the deposits and reincorporate into their original state the metal ion or ions produced by this oxidation.

45. A process for manufacturing a material according to claim 32, comprising the following successive steps:

1) fabricating at least one fluid formative composition comprising the constituents of the material and water in quantities allowing a viscosity appropriate for its application as a layer; and

2) acting on the fluid formative composition to obtain the solid consistency of the material.

46. The process according to claim 45, wherein the step of acting on the fluid formative composition comprises evaporation, heat treatment, cross-linking or vulcanization.

33. A material intended for processes, cells, or devices relating to electrochromic modulation of light by reflection or transmission, the material having ionic electroconductivity and comprising a homogeneous mixture of solid consistency, comprising the following constituents:

a) a hydrosoluble salt or a hydrosoluble mixture of salts of at least one metal which can be cathodically deposited from an aqueous solution of one of its simple or complex ions;

b) at least one initially hydrosoluble film-forming polymer resin;

c) water;

d) at least one hydrosoluble salt of a cation selected from a group consisting of those which cannot be either electro-deposited from an aqueous solution or reduced into a metal;

e) halide anions; and

f) an auxiliary redox couple;

wherein the constituents are selected in a group allowing simultaneously a plastic or viscoelastic deformability and adhesive properties;

wherein copper is associated with at least one metal selected from a group consisting of zinc, cadmium, lead, silver, copper, iron, cobalt, nickel, tin, indium, platinum, palladium, gold, bismuth, antimony, tellurium, manganese, thallium, selenium, gallium, arsenic, mercury, chromium, tungsten and molybdenum; and

wherein the material is able to reversibly (1) develop metal or metal alloy deposits by cathodic reduction of at least one depositable metal ion present within the material, and (2) by anodic oxidation, dissolve the deposits and reincorporate into their original state the metal ion or ions produced by this oxidation.

47. A process for manufacturing a material according to claim 33, comprising the following successive steps:

1) fabricating at least one fluid formative composition comprising the constituents of the material and water in quantities allowing a viscosity appropriate for its application as a layer; and

2) acting on the fluid formative composition to obtain the solid consistency of the material.

48. The process according to claim 47, wherein the step of acting on the fluid formative composition comprises evaporation, heat treatment, cross-linking or vulcanization.

34. A material intended for processes, cells, or devices relating to electrochromic modulation of light by reflection or transmission, the material having ionic electroconductivity and comprising a homogeneous mixture of solid consistency, comprising the following constituents:

a) a hydrosoluble salt or a hydrosoluble mixture of salts of at least one metal which can be cathodically deposited from an aqueous solution of one of its simple or complex ions, the ratio of the hydrosoluble salts considered in their anhydrous form to water being greater than 1;

b) at least one initially hydrosoluble film-forming polymer resin;

c) water;

d) at least one hydrosoluble salt of a cation selected from a group consisting of those which cannot be either electro-deposited from an aqueous solution or reduced into a metal;

e) halide anions; and

f) an auxiliary redox couple;

wherein the constituents are selected in a group allowing simultaneously a plastic or viscoelastic deformability and adhesive properties;

wherein copper is associated with at least one metal selected from a group consisting of zinc, cadmium, lead, silver, copper, iron, cobalt, nickel, tin, indium, platinum, palladium, gold, bismuth, antimony, tellurium, manganese, thallium, selenium, gallium, arsenic, mercury, chromium, tungsten, and molybdenum; and

wherein the material is able to reversibly (1) develop metal or metal alloy deposits by cathodic reduction of at least one depositable metal ion present within the material, and (2) by anodic oxidation, dissolve the deposits and reincorporate into their original state the metal ion or ions produced by this oxidation.

49. A process for manufacturing a material according to claim 34, comprising the following successive steps:

1) fabricating at least one fluid formative composition comprising the constituents of the material and water in quantities allowing a viscosity appropriate for its application as a layer; and

2) acting on the fluid formative composition to obtain the solid consistency of the material.

50. The process according to claim 49, wherein the step of acting on the fluid formative composition comprises evaporation, heat treatment, cross-linking or vulcanization.