Anti-fog refrigeration door and method of making the same

• US 20060265979A1
• Filed: 04/04/2006
• Published: 11/30/2006
• Est. Priority Date: 09/20/2004
• Status: Active Grant

• Current Assignee: AGC Flat Glass North America Incorporated (AGC, Inc.)
• Original Assignee: AFG Industries Incorporated (AGC, Inc.)
• Inventors: Cording, Christopher R.
• Granted Patent: US 7,891,154 B2
• Time in Patent Office: Days
• US Class Current: 52/204.500
• CPC Class Codes: A47F 3/0434 Glass or transparent panels
• CPC Class Codes: C03C 17/322 Polyurethanes or polyisocyanates
• CPC Class Codes: C03C 17/34 with at least two coatings having different compositions C03C17/44 takes precedence
• CPC Class Codes: C03C 2217/75 Hydrophilic and oleophilic coatings
• CPC Class Codes: C09D 175/04 Polyurethanes
• CPC Class Codes: C09K 3/18 for application to surfaces to minimize adherence of ice, mist or water thereto rendering particulate materials free flowing, in general, e.g. making them hydrophobic B01J2/30; Thawing or antifreeze materials for application to surfaces used in liquids for heat-transfer, heat-exchange or heat-storage or for the production of heat or cold other than by combustion, e.g. radiator liquids, C09K5/00

Abstract

The energy-free refrigeration door of the present application provides a way to control condensation when the door of a refrigeration unit is opened by providing thermal insulation to the door with glass panels which have a low emissivity coating. The door includes a door frame housing and an insulating glass unit comprising inner, middle and outer sheets of glass. A first sealant assembly disposed around the periphery of the inner and middle sheets of glass forms a first chamber between the inner and middle sheets of glass. A second sealant assembly disposed around the periphery of the middle and outer sheets of glass forms a second chamber between the middle and outer sheets of glass. A gas, such as krypton, air, or argon is held in the first and second chambers. The outer sheet of glass and inner sheet of glass each have an unexposed surface that faces the middle sheet of glass. A low emissivity coating is disposed on the unexposed surfaces of the inner and outer sheets of glass so that the glass door as a whole avoids formation of condensation on the outer surface of the outer sheet of the glass door, without the application of electricity to heat the door, while also providing the desired evaporation rate of condensation from the inner side of the inner sheet of the glass door. An anti-fog or anti-frost coating is included on a surface of one of the sheets of glass.

Claims

1. A refrigeration door having an outer surface and adapted to be mounted on a refrigerating compartment, said door comprising:

a first sheet of glass;

a second sheet of glass;

a first sealant assembly disposed around the periphery of said first sheet of glass and said second sheet of glass for maintaining said first sheet and said second sheet in spaced-apart relationship from each other;

a first low emissivity coating adjacent a surface of said first sheet or said second sheet of glass;

an anti-fog or anti-frost coating adjacent a surface of at least one of said sheets of glass; and

a frame secured around the periphery of said insulating glass unit,

wherein the surface having the anti-fog or anti-frost coating thereon is pretreated with a first silane, and said anti-fog or anti-frost coating comprises a second silane, which second silane is different than the first silane.

2. The refrigeration door of claim 1, wherein said first sheet and second sheets of glass, said first sealant assembly, and said first low emissivity coating forming an insulating glass unit having a U value substantially equal to or less than 0.2 BTU/hr-sq ft-F or an emissivity substantially equal to or less than 0.04.

3. The refrigeration door of claim 1, wherein the first silane comprises amino alkyl silicone.

4. The refrigeration door of claim 1, wherein the second silane comprises 3-glycidoxypropyl trimethoxysilane.

5. The refrigeration door of claim 1, wherein the anti-fog or anti-frost coating is applied as a film.

6. The refrigeration door of claim 1, wherein the anti-fog or anti-frost coating is applied as a liquid.

7. The refrigeration door of claim 1, wherein the anti-fog or anti-frost coating has a thickness of about 4 microns to about 20 microns.

8. The refrigeration door of claim 7, wherein the anti-fog or anti-frost coating has a thickness of about 10 microns to about 20 microns.

9. The refrigeration door of claim 8, wherein the anti-fog or anti-frost coating has a thickness of about 12 microns to about 15 microns.

10. The refrigeration door of claim 1, wherein the anti-fog or anti-frost coating is insoluble in water.

11. The refrigeration door of claim 1, wherein the anti-fog or anti-frost coating further comprises a mixture of:

i) a first component comprising about 46% diacetone alcohol, about 4% N-methyl Pyrrolidone, about 4% t-butanol, about 8% Cyclohexane, about 6% 2,4-pentanedione, and about 2% Aromatic 150; and

ii) a second component comprising about 66% polyisocyanate, about 1% free monomeric isocyanates, about 11% xylene, about 11% n-butyl acetate, and about 11% toluene;

wherein the mixture ratio of the first component to the second component is about 100;

40.

12. The refrigeration door of claim 11, wherein the anti-fog or anti-frost coating further comprises a solvent for diluting the mixture.

13. The refrigeration door of claim 12, wherein the solvent is an alcohol.

14. The refrigeration door of claim 13, wherein the alcohol is diacetone alcohol or tertiary butyl alcohol.

15. The refrigeration door of claim 1, wherein the anti-fog or anti-frost coating further comprises a mixture of:

i) a first component comprising about 46% diacetone alcohol, about 4% N-methyl Pyrrolidone, about 4% t-butanol, about 8% Cyclohexane, about 6% 2,4-pentanedione, and about 2% Aromatic 150; and

ii) a second component comprising about 66% polyisocyanate, about 1% free monomeric isocyanates, about 11% xylene, about 11% n-butyl acetate, and about 11% toluene;

wherein the mixture ratio of the first component to the second component is about 100;

about 25-45.

16. The refrigeration door of claim 15, wherein the mixture ratio of the first component to the second component is about 100:

about 30-33.

17. The refrigeration door of claim 16, wherein the mixture ratio of the first component to the second component is about 100:

about 30.

18. The refrigeration door of claim 15, wherein the second silane is present in an amount of about 1% to about 8%.

19. The refrigeration door of claim 15, wherein the second silane is present in an amount of about 6%.

20. The refrigeration door of claim 1, further comprising:

a third sheet of glass;

a second sealant assembly disposed around the periphery of said second sheet of glass and said third sheet of glass for maintaining said second sheet and said third sheet in spaced-apart relationship from each other; and

wherein said insulating glass unit further includes said third sheet of glass and said second sealant assembly.

21. The refrigeration door of claim 20, further including a second low emissivity coating adjacent a surface of said first sheet, said second sheet, or said third sheet of glass.

22. The refrigeration door of claim 2, wherein the U value of said insulating glass unit is effective to substantially prevent the formation of condensation on the outer surface of the door without the application of electricity for heating the outer surface when the interior temperature of the refrigerating compartment is substantially equal to or less than minus zero degrees Fahrenheit;

the temperature of the exterior environment is substantially equal to or greater than seventy-two degrees Fahrenheit; and

the humidity in the ambient environment is substantially equal to or greater than sixty percent.

23. The refrigeration door of claim 22, further comprising:

a first chamber defined by said first sheet of glass, said second sheet of glass, and said first sealant assembly; and

a gas disposed in said first chamber.

24. The refrigeration door of claim 23, wherein said first sealant assembly has a heat transfer rate substantially equal to or less than 1.73 Btu/hr-ft-F.

25. The refrigeration door of claim 23, wherein said gas is selected from the group consisting of argon, krypton, and air.

26. The refrigeration door of claim 1, wherein the interior temperature of the refrigerating compartment is substantially equal to or less than minus twenty degrees Fahrenheit;

the temperature of the exterior environment is substantially equal to or greater than seventy degrees Fahrenheit; and

the humidity in the exterior environment is substantially equal to or greater than sixty percent; and

wherein the outer surface of the door is substantially free of condensation.

27. The refrigeration door of claim 1, wherein the interior temperature of the refrigerating compartment is substantially equal to or less than minus forty degrees Fahrenheit;

the temperature of the exterior environment is substantially equal to or greater than eighty degrees Fahrenheit; and

the humidity in the exterior environment is substantially equal to or greater than sixty percent; and

wherein the outer surface of the door is substantially free of condensation.

28. The refrigeration door of claim 21, wherein:

the first sheet of glass is an inner sheet of glass including a first surface and a second surface, said first surface of said inner sheet being disposed adjacent the interior of the refrigerating compartment;

the third sheet of glass is an outer sheet of glass including a first surface and a second surface, said first surface of said outer sheet being disposed adjacent the exterior environment of the refrigerating compartment;

the second sheet of glass is a middle sheet of glass disposed between said inner and outer sheets of glass;

the first sealant assembly being disposed around the periphery of said inner sheet of glass and said middle sheet of glass for maintaining said inner sheet and said middle sheet in spaced apart relationship from each other;

the second sealant assembly being disposed around the periphery of said middle sheet of glass and said outer sheet of glass for maintaining said middle sheet and said outer sheet in spaced-apart relationship from each other;

the first low emissivity coating being adjacent the second surface of said inner sheet of glass;

the second low emissivity coating being adjacent the second surface of said outer sheet of glass;

said inner sheet, outer sheet, middle sheet, first sealant assembly, second sealant assembly, and said first and second low emissivity coatings forming the insulating glass unit wherein the formation of condensation on said first surface of said outer sheet of glass is substantially prevented without the application of electricity for heating said first surface of said outer sheet of glass.

29. The refrigeration door of claim 28, wherein the anti-fog or anti-frost coating is adjacent the first surface of said inner sheet of glass.

30. The refrigeration door of claim 28, further comprising:

a first chamber defined by said inner sheet of glass, said middle sheet of glass, and said first sealant assembly;

a second chamber defined by said middle sheet of glass, said outer sheet of glass, and said second sealant assembly; and

a gas disposed in said first and second chambers.

31. The refrigeration door of claim 30, wherein:

said inner, said middle, and said outer sheets of glass have a thickness substantially equal to one eighth of an inch;

said inner and said middle sheets of glass being spaced apart a distance substantially equal to one half inch; and

said middle and said outer sheets of glass being spaced apart a distance substantially equal to one half inch.

32. The refrigeration door of claim 30, wherein said first sealant assembly and said second sealant assembly each have a heat transfer rate substantially equal to or less than 1.73 Btu/hr-ft-F.

33. The refrigeration door of claim 32, wherein:

said inner, said middle and said outer sheets of glass having a thickness substantially equal to one eighth of an inch;

said inner and said middle sheets of glass being spaced apart a distance substantially equal to one half inch; and

said middle and said outer sheets of glass being spaced apart a distance substantially equal to one half inch.

34. The refrigeration door of claim 30, wherein said gas in said first chamber and said second chamber are the same.

35. The refrigeration door of claim 30, wherein said gas in said first chamber and said second chamber are not the same.

36. The refrigeration door of claim 30, wherein said first and second low emissivity coatings are selected from the group consisting of a titania based silver and fluorine doped tin oxide.

37. The refrigeration door of claim 30, wherein said first and second low emissivity coatings are applied with a process selected from the group consisting of sputter coating, pyrolytic coating and spray coating.

38. The refrigeration door of claim 30, wherein said frame is formed from a material selected from the group consisting of extruded plastic, aluminum, and fiber glass.

39. The refrigeration door of claim 28, wherein said first sealant assembly and said second sealant assembly each have a heat transfer rate substantially equal to or less than 1.73 Btu/hr-ft-F.

74. The refrigeration door of claim 1, wherein said first sealant assembly is a composite extrusion comprising a combination of polyisobutylene sealant, hot melt butyl sealant, desiccant matrix, rubber shim, and a vapor barrier.

75. The refrigeration door of claim 1, wherein said first sealant assembly is a Comfort Seal sealant assembly.

76. The refrigeration door of claim 20, wherein said second sealant assembly is a composite extrusion comprising a combination of polyisobutylene sealant, hot melt butyl sealant, desiccant matrix, rubber shim, and a vapor barrier.

77. The refrigeration door of claim 20, wherein said second sealant assembly is a Comfort Seal sealant assembly.

40. A method of manufacturing a refrigeration door component having an outer surface, said method comprising the steps of:

providing a first sheet of glass;

providing a second sheet of glass;

providing a first low emissivity coating adjacent a surface of said first sheet of glass or said second sheet of glass;

disposing a first sealant assembly around the periphery of said first sheet of glass and said second sheet of glass to maintain said first sheet and said second sheet in spaced-apart relationship from each other; and

providing an anti-fog or anti-frost coating adjacent a surface of at least one of said sheets of glass, wherein the surface having the anti-fog or anti-frost coating thereon is pretreated with a first silane, and wherein said anti-fog or anti-frost coating comprises a second silane, which second silane is different than the first silane;

said first sheet of glass, said second sheet of glass, and said first sealant assembly forming an insulating glass unit wherein the formation of condensation on the outer surface of the refrigeration door component is substantially prevented without application of electricity for heating the door component.

41. The method of claim 40, wherein said first sheet of glass, said second sheet of glass, and said first sealant assembly define a first chamber;

and further comprising the step of disposing a gas in said first chamber.

42. The method of claim 40, further comprising the steps of:

providing a third sheet of glass;

disposing a second sealant assembly disposed around the periphery of said second sheet of glass and said third of glass for maintaining said second sheet and said third sheet in spaced-apart relationship from each other; and

wherein said insulating glass unit further includes said third sheet of glass and said second sealant assembly.

43. The method of claim 42, wherein said third sheet of glass includes a low emissivity coating adjacent a surface of said third sheet of glass.

44. The method of claim 40, wherein said first sealant assembly has a heat transfer rate substantially equal to or less than 1.73 Btu/hr-ft-F.

45. The method of claim 44, wherein:

said first and said second sheets of glass having a thickness substantially equal to one eighth of an inch; and

said first and said second sheets of glass being spaced apart a distance substantially equal to one half inch.

46. The method of claim 40, further including the step of disposing said insulating glass unit in a door frame.

47. The method of claim 46, wherein said gas is selected from the group consisting of argon, krypton, and air.

48. The method of claim 40, wherein said insulating glass unit has a U value substantially equal to or less than 0.2 BTU/hr-sq ft-F or an emissivity substantially equal to or less than 0.04.

49. The method of claim 40, wherein said low emissivity coating is selected from the group consisting of a titania based silver and fluorine doped tin oxide.

50. The method of claim 40, wherein said low emissivity coating is applied with a process selected from the group consisting of sputter coating, pyrolytic coating and spray coating.

51. The method of claim 42, wherein said first and second sealant assemblies have a heat transfer rate substantially equal to or less than 1.73 Btu/hr-ft-F.

52. The method of claim 44, further including the step of disposing said insulating glass unit in a door frame.

53. The method of claim 40, wherein said first sealant assembly is a composite extrusion comprising a combination of polyisobutylene sealant, hot melt butyl sealant, desiccant matrix, rubber shim, and a vapor barrier.

54. The method of claim 40, wherein said first sealant assembly is a Comfort Seal sealant assembly.

55. The method of claim 42, wherein said second sealant assembly is a composite extrusion comprising a combination of polyisobutylene sealant, hot melt butyl sealant, desiccant matrix, rubber shim, and a vapor barrier.

56. The method of claim 42, wherein said second sealant assembly is a Comfort Seal sealant assembly.

57. The method of claim 40, wherein at least one of said first sealant assembly and said second sealant assembly comprises a warm edge seal.

58. A substantially transparent insulating glass unit door having an outer surface and being for use with a refrigerating compartment residing in an exterior environment and having an interior refrigerating compartment;

said insulating glass unit door comprising;

a first sheet of glass;

a second sheet of glass;

a first sealant assembly disposed around the periphery of said first sheet of glass and said second sheet of glass for maintaining said first sheet and said second sheet in spaced-apart relationship from each other;

a first low emissivity coating adjacent a surface of said first sheet or said second sheet of glass;

an anti-fog or anti-frost coating adjacent a surface of at least one of said sheets of glass, wherein the surface having the anti-fog or anti-frost coating thereon is pretreated with a first silane, and wherein said anti-fog or anti-frost coating comprises a second silane, which second silane is different than the first silane; and

said first sheet of glass, said second sheet of glass, and said first sealant assembly providing the insulating glass unit with a U value effective to substantially prevent the formation of condensation on the outer surface without the application of electricity to heat the outer surface of the insulating glass unit when the interior temperature of the refrigerating compartment is substantially equal to or less than zero degrees Fahrenheit;

the temperature of the exterior environment is substantially equal to or greater than seventy degrees Fahrenheit; and

the humidity in the exterior environment is substantially equal to or greater than sixty percent.

59. The door of claim 58, further comprising:

a third sheet of glass; and

a second sealant assembly disposed around the periphery of said second sheet of glass and said third of glass for maintaining said first sheet and said second sheet in spaced-apart relationship from each other.

60. The door of claim 59, further including a second low emissivity coating adjacent a surface of said first sheet, said second sheet or said third sheet of glass.

61. The door of claim 60 wherein the insulating glass unit has a U value that substantially prevents the formation of condensation on the outer surface when the interior temperature of the refrigerating compartment is substantially equal to or less than minus forty degrees Fahrenheit;

the temperature of the exterior environment is substantially equal to or greater than eighty degrees Fahrenheit; and

the humidity in the exterior environment is substantially equal to or greater than sixty percent.

62. The door of claim 60, wherein said low emissivity coating is effective to cause the insulating glass unit to have a U value substantially equal to or less than 0.2 BTU/hr-sq ft-F.

63. The door of claim 59, wherein said first sealant assembly and said second sealant assembly each have a heat transfer rate substantially equal to or less than 1.73 Btu/hr-ft-F.

64. The door of claim 58, wherein the insulating glass unit has an emissivity substantially equal to or less than 0.04.

65. The door of claim 58, wherein the interior temperature of the refrigerating compartment is substantially equal to or less than minus twenty degrees Fahrenheit;

the temperature of the exterior environment is substantially equal to or greater than seventy degrees Fahrenheit; and

the humidity in the exterior environment is substantially equal to or greater than sixty percent.

66. The door of claim 58, wherein the interior temperature of the refrigerating compartment is substantially equal to or less than minus forty degrees Fahrenheit;

the temperature of the exterior environment is substantially equal to or greater than eighty degrees Fahrenheit; and

the humidity in the exterior environment is substantially equal to or greater than sixty percent.

78. The door of claim 58, wherein said first sealant assembly is a composite extrusion comprising a combination of polyisobutylene sealant, hot melt butyl sealant, desiccant matrix, rubber shim, and a vapor barrier.

79. The door of claim 58, wherein said first sealant assembly is a Comfort Seal sealant assembly.

80. The door of claim 59, wherein said second sealant assembly is a composite extrusion comprising a combination of polyisobutylene sealant, hot melt butyl sealant, desiccant matrix, rubber shim, and a vapor barrier.

81. The door of claim 59, wherein said second sealant assembly is a Comfort Seal sealant assembly.

82. The door of claim 59, wherein at least one of said first sealant assembly and said second sealant assembly comprises a warm edge seal.

67. A refrigeration unit including an insulated enclosure defining a compartment, a cooling system, and a door adapted to be mounted on an opening of said compartment, said door having an outer surface and comprising:

a first sheet of glass;

a second sheet of glass;

a first sealant assembly disposed around the periphery of said first sheet of glass and said second sheet of glass for maintaining said first sheet and said second sheet in spaced-apart relationship from each other;

a first low emissivity coating adjacent the a surface of said first or said second sheet of glass;

said first sheet, second sheet, first sealant assembly, and said first low emissivity coating forming an insulating glass unit wherein the formation of condensation on the outer surface of the door is substantially prevented without the application of electricity for heating said first surface;

an anti-fog or anti-frost coating adjacent a surface of at least one of said sheets of glass, wherein the surface having the anti-fog or anti-frost coating thereon is pretreated with a first silane, and wherein said anti-fog or anti-frost coating comprises a second silane, which second silane is different than the first silane; and

a frame secured around the periphery of said insulating glass unit.

68. The refrigeration unit of claim 67, further comprising:

a third sheet of glass; and

a second sealant assembly disposed around the periphery of said second sheet of glass and said third of glass for maintaining said second sheet and said third sheet in spaced-apart relationship from each other.

69. The refrigeration unit of claim 67, further comprising:

a first chamber defined by said first sheet of glass, said second sheet of glass, and said first sealant assembly;

a second chamber defined by said middle sheet of glass, said outer sheet of glass, and said second sealant assembly; and

a gas disposed in said first and second chambers.

70. The refrigeration unit of claim 68, wherein said first sealant assembly and said second sealant assembly each have a heat transfer rate substantially equal to or less than 1.73 Btu/hr-ft-F.

71. The refrigeration unit of claim 67, wherein the door has an emissivity substantially equal to or less than 0.04.

72. The refrigeration unit of claim 67, wherein the insulating glass unit has a U value substantially equal to or less than 0.2. BTU/hr-sq ft-F.

73. The refrigeration unit of claim 67, wherein said first sealant assembly has a heat transfer rate substantially equal to or less than 1.73 Btu/hr-ft-F.

83. The refrigeration unit of claim 67, wherein said first sealant assembly is a composite extrusion comprising a combination of polyisobutylene sealant, hot melt butyl sealant, desiccant matrix, rubber shim, and a vapor barrier.

84. The refrigeration unit of claim 67, wherein said first sealant assembly is a Comfort Seal sealant assembly.

85. The refrigeration unit of claim 68, wherein said second sealant assembly is a composite extrusion comprising a combination of polyisobutylene sealant, hot melt butyl sealant, desiccant matrix, rubber shim, and a vapor barrier.

86. The refrigeration unit of claim 68, wherein said second sealant assembly is a Comfort Seal sealant assembly.

87. The refrigeration unit of claim 68, wherein at least one of said first sealant assembly and said second sealant assembly comprises a warm edge seal.

88. An anti-fog or anti-frost coating comprising a mixture of:

i) a first component comprising about 46% diacetone alcohol, about 4% N-methyl Pyrrolidone, about 4% t-butanol, about 8% Cyclohexane, about 6% 2,4-pentanedione, and about 2% Aromatic 150; and

ii) a second component comprising about 66% polyisocyanate, about 1% free monomeric isocyanates, about 11 % xylene, about 11% n-butyl acetate, and about 11% toluene;

wherein the mixture ratio of the first component to the second component is about 100;

about 30-33.

89. The anti-fog or anti-frost coating of claim 88, wherein the mixture ratio of the first component to the second component is about 100:

about 30.

90. The anti-fog or anti-frost coating of claim 88, wherein the mixture further comprises a silane.

91. The anti-fog or anti-frost coating of claim 90, wherein the silane comprises 3-glycidoxypropyl trimethoxysilane.

92. The anti-fog or anti-frost coating of claim 91, wherein the silane is present in an amount of about 1% to about 8%.

93. The anti-fog or anti-frost coating of claim 92, wherein the silage is present in an amount of about 6%.

94. The anti-fog or anti-frost coating of claim 88, wherein the anti-fog or anti-frost coating has a thickness of about 4 microns to about 20 microns.

95. The anti-fog or anti-frost coating of claim 94, wherein the anti-fog or anti-frost coating has a thickness of about 10 microns to about 20 microns.

96. The anti-fog or anti-frost coating of claim 95, wherein the anti-fog or anti-frost coating has a thickness of about 12 microns to about 15 microns.

97. A method of forming an anti-fog or anti-frost coating on at least a portion of a substrate, the method comprising:

pretreating at least a portion of the substrate with a first silane;

preparing a mixture of;

i) a first component comprising about 46% diacetone alcohol, about 4% N-methyl Pyrrolidone, about 4% t-butanol, about 8% Cyclohexane, about 6% 2,4-pentanedione, and about 2% Aromatic 150; and

ii) a second component comprising about 66% polyisocyanate, about 1% free monomeric isocyanates, about 11% xylene, about 11% n-butyl acetate, and about 11% toluene;

wherein the mixture ratio of the first component to the second component is about 100;

about 30-33;

applying the mixture to the substrate; and

curing the substrate.

98. The method of claim 97, wherein the mixture does not contain additional solvents.

99. The method of claim 97, wherein the mixture ratio of the first component to the second component is about 100:

about 30.

100. The method of claim 97, wherein the mixture is applied with a single coating step.

101. The method of claim 97, wherein the curing is achieved in a single curing cycle.

102. The method of claim 97, further comprising adding a second silane to the mixture, wherein the second silane is different than the first silane.

103. The method of claim 102, wherein the second silane comprises 3-glycidoxypropyl trimethoxysilane.

104. The method of claim 103, wherein the second silane is present in an amount of about 1% to about 8%.

105. The method of claim 104, wherein the second silane is present in an amount of about 6%.

106. The method of claim 97, wherein the first silane comprises amino alkyl silicone.

107. The method of claim 97, wherein the pretreating comprises preparing a rinse water mixture comprising about 1% or less of the first silane and applying said mixture to said portion of the substrate.

108. The method of claim 107, wherein the rinse water mixture comprises about 0.031% of the first silane.