WO2004092437A2 - Thermal barrier composition - Google Patents

Thermal barrier composition Download PDF

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Publication number
WO2004092437A2
WO2004092437A2 PCT/US2004/010539 US2004010539W WO2004092437A2 WO 2004092437 A2 WO2004092437 A2 WO 2004092437A2 US 2004010539 W US2004010539 W US 2004010539W WO 2004092437 A2 WO2004092437 A2 WO 2004092437A2
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Prior art keywords
titanium
tin
siloxane
thermal barrier
group
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PCT/US2004/010539
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French (fr)
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WO2004092437A3 (en
Inventor
William H. Simendinger, Iii
David William Garrett
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Microphase Coatings, Inc.
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Application filed by Microphase Coatings, Inc. filed Critical Microphase Coatings, Inc.
Priority to EP04749782A priority Critical patent/EP1611264A4/en
Publication of WO2004092437A2 publication Critical patent/WO2004092437A2/en
Publication of WO2004092437A3 publication Critical patent/WO2004092437A3/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the present invention relates to a thermal barrier composition for use on a variety of substrates that are exposed to high temperatures.
  • substrates include pipelines, engine parts including jet engine components, water conduits including tubes in power plants, reactor vessels and exhaust manifolds.
  • Substrates can be subjected to high temperatures causing fatigue, cracking, distortion and the like of the substrate.
  • components of a j et engine or the surrounding parts of the j et can be exposed to temperatures in excess of 1800° F. In such a situation, it is readily apparent that fatiguing or cracking can lead to catastrophic failure.
  • piping used in various manufacturing facilities can be subjected to temperatures in excess of 400° F caused by the liquid or gas passing through the pipe. In such an application, it is preferred that the coating not only provide a thermal barrier but also provide anti-corrosion properties.
  • the thermal barrier composition of the present invention comprises a glassy matrix comprising an alkoxy-functionalized siloxane and a functionally-terminated silane or siloxane, polymethylsilsesquioxane dissolved in a crosslinking agent, and optionally a filler and/or hollow glass microspheres.
  • the glass matrix provides good adhesion to the surface being coated, as well as, toughness, crack resistance, durability, abrasion resistance, heat resistance and stability in the particular environment.
  • the thermal barrier compositions comprises a glassy matrix comprising an alkoxy-functionalized siloxane and a functionally-terminated silane or siloxane, polymethylsilsesquioxane dissolved in a crosslinking agent, and optionally a filler and/or hollow glass microspheres.
  • the thermal barrier composition of the present invention can be coated onto a wide variety of substrates including steel, stainless steel, titanium, aluminum, magnesium and zinc. The coating can withstand continuous use temperatures of 1800°F or higher. Moreover, the composition is resistant to corrosive agents such as nitrogen and sulfur compounds.
  • Suitable alkoxy-functionalized siloxanes include polydiethoxysiloxane, tetraethoxysiloxane, tetramethoxysiloxane, and polydimethoxysiloxane.
  • a preferred alkoxy-functionalized siloxane is polydiethoxysilane.
  • Suitable functionally-terminated silanes or siloxanes include silanol-terminated, vinyl-terminated and amino-terminated silanes or siloxanes such as epoxy-functionalized polydimethylsiloxane, aminopropyltriethoxy silane and silanol-termainated siloxane.
  • the glassy matrix is crosslinked using a titanium or tin catalyst.
  • Suitable catalysts include titanium alkoxides such as titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium propoxide, titanium butoxide, titanium diisopropoxide (bis 2,4- pentanedionate), titanium diisopropoxide bis(ethylacetoacetao) titanium ethylhexoxide, and organic tin compounds such as dibutyl tin diacetate, dibutyltin laurate, dimethyl tin dineodecanoate, dioctyl dilauryl tin, and dibutyl butoxy chlorotin, as well as mixtures thereof.
  • the glassy matrix can be formed by using a Sol-Gel process such as described in U.S. Patent No. 6,313,193, the disclosure of which is incorporated herein by reference in its entirety. Other methods of forming the matrix will be within the skill of one in the art.
  • the polymethylsilsesquioxane (“POSS”) is dissolved in a crosslinking agent preferably titanium isopropoxide. By dissolving in titanium propoxide, up to about 40 percent of the POSS can be dissolved as compared to about 10 percent or less solubility in solvents. In operation, the glassy matrix and the polymethylsilsesquioxane are crosslinked or catalyzed separately so as to avoid premature gelation of the product prior to use.
  • the thermal barrier composition may also optionally include fillers such as, without limitation, glass fibers, fumed silica, mica, kaolin, bentonite, talc, zinc oxides, iron oxides and pigments or other fillers, as will be readily apparent to those skilled in the art.
  • the composition may also include hollow glass microspheres to provide additional heat resistance.
  • hollow glass microspheres Preferably, thin-walled glass microspheres are used. Typically the volume percent of glass microspheres is from about 30 percent to about 80 percent. If the higher amount is used, it is preferable to include milled glass fibers to improve durability.
  • Anti-corrosion agents such as zinc phosphates and zinc salts can also be added.
  • the thermal barrier composition of the present invention can be applied to a substrate by roll-coating, brush, spray coating dipping and the like. It is preferred that the user mix the catalyst with the other components right before or substantially contemporaneously with application to form an interpenetrating polymer network of glass and silicone on the surface of the substrate. Inasmuch as crosslinking occurs via a moisture condensation reaction between ethoxy and hydroxyl groups, the condensation inherently present on the substrate and/or in the atmosphere can be used advantageously.
  • the first step is to dissolve the polymethysilsesquioxane (POSS) into the titanium isopropoxide (TIPO). This is accomplished by mixing the POSS into the titanium isopropoxide and heating at 100°C for 24 hours.
  • POSS polymethysilsesquioxane
  • the second step is to terminate the silanol groups on the ends of the polydimethylsiloxane. This is accomplished by mixing the silanol terminated polydimethylsiloxane with the titanium diisopropoxide (bis-2,4-pentanedionate) and allowing the mixture to crosslink for 1 hour. If this step is not performed, the silanol groups on the polymer will instantly react with the titanium isopropoxide and the system will gel in a matter of seconds.
  • the third step is to add the remaining components to the POSS/TIPO (A component) keeping the titanium diisopropoxide (bis-2,4- pentanedionate)/polydimethylsiloxane mixture out as the B component in an A B system.
  • Example 2 The formulation was manufactured using the same steps as Example 1 except that the POSS did not have to be pre-reacted with the TIPO.
  • the formulation of Example 2 was used in various tests as described below and in Table 1.
  • Example 2 A series of durability tests were performed on the coating composition of Example 2. These tests were designed to simulate real-world events that will test the durability of the coating. The three specific tests performed on the coating composition of Example 2 included: two tool drop tests, a falling sand test, and a 200 lb, 90° pivot test.
  • the first tool drop test consisted of dropping a 106 gram wrench from a height of 48 inches onto a panel coated with the coating composition of Example 2. This test which was repeated multiple times resulted in a dent of about 5mm x 5mm.
  • the second tool drop test consisted of dropping a 783 gram hammer from the same 48 inch height. The tool drop resulted in a dent of about 15mm x 25mm.
  • the falling sand test consisted of dropping 1 gallon of sand from a height of 1.5 feet in a concentrated stream onto the surface of a steel panel coasted with the coating composition of Example 2 mounted 45° to the falling sand.
  • Example 2 demonstrated good abrasion resistance.
  • the third durability test consisted of a 200 lb person standing on a plate coated with the coating composition of Example 2 with all weight on one foot. Then the person pivoted 90°. No damage resulted to the coating composition of Example 2.
  • the test demonstrates the coating composition of Example 2 can be walked on (e.g., a plane wing) with no damage.
  • a titanium plate with a 2.5mm build of the coating composition of Example 2 was prepared.
  • a 3mm wide channel was cut into the coating from the center of the plate to the edge, and a thermocouple was positioned in the channel such that it would be in contact with the titanium plate.
  • the coating composition of Example 2 was applied over the thermocouple to fill the channel and seal the thermocouple at the interface of the coating composition of Example 2 and the titanium plate, producing a sample with the thermocouple counted at the interface of the coating composition of Example 2 and the titanium.
  • Total coating thickness was approximately 3.0mm.
  • the plate was placed onto a steel block and was heated to a temperature of 1057° F by a burner on the turkey fryer.
  • the sample was placed with the coating composition of Example 2 directly in contact with the hot steel block, and allowed to equilibrate for 78 minutes to allow for steady state heat flow.
  • the temperature measurement at the coating composition of Example 2-titanium interface was found to be 720° F with the hot steel measuring 1057° F: a temperature delta of 337° F across the coating composition of Example 2 for a coating that is 3.0mm thick.

Abstract

The thermal barrier composition of the present invention provides a glassy matrix comprising an alkoxy-functionalized siloxane and a functionally-terminated silane or siloxane, polymethylsilsesquioxane dissolved in a crosslinking agent, and optionally a filler and/or hollow glass microspheres.

Description

THERMAL BARRIER COMPOSITION
Related Application This application claims priority to Provisional Application No. 60/461 ,800 filed
April 10, 2003, the disclosure of which is hereby incorporated by reference in its entirety.
Field and Background of the Invention
The present invention relates to a thermal barrier composition for use on a variety of substrates that are exposed to high temperatures. Exemplary substrates include pipelines, engine parts including jet engine components, water conduits including tubes in power plants, reactor vessels and exhaust manifolds.
Substrates, particularly metal substrates, can be subjected to high temperatures causing fatigue, cracking, distortion and the like of the substrate. For example, components of a j et engine or the surrounding parts of the j et can be exposed to temperatures in excess of 1800° F. In such a situation, it is readily apparent that fatiguing or cracking can lead to catastrophic failure. Similarly, piping used in various manufacturing facilities can be subjected to temperatures in excess of 400° F caused by the liquid or gas passing through the pipe. In such an application, it is preferred that the coating not only provide a thermal barrier but also provide anti-corrosion properties.
Summary of the Invention
The thermal barrier composition of the present invention comprises a glassy matrix comprising an alkoxy-functionalized siloxane and a functionally-terminated silane or siloxane, polymethylsilsesquioxane dissolved in a crosslinking agent, and optionally a filler and/or hollow glass microspheres. The glass matrix provides good adhesion to the surface being coated, as well as, toughness, crack resistance, durability, abrasion resistance, heat resistance and stability in the particular environment.
Detailed Description of the Invention
As briefly discussed above, the present invention relates to a thermal barrier composition. The thermal barrier compositions comprises a glassy matrix comprising an alkoxy-functionalized siloxane and a functionally-terminated silane or siloxane, polymethylsilsesquioxane dissolved in a crosslinking agent, and optionally a filler and/or hollow glass microspheres. The thermal barrier composition of the present invention can be coated onto a wide variety of substrates including steel, stainless steel, titanium, aluminum, magnesium and zinc. The coating can withstand continuous use temperatures of 1800°F or higher. Moreover, the composition is resistant to corrosive agents such as nitrogen and sulfur compounds.
Suitable alkoxy-functionalized siloxanes include polydiethoxysiloxane, tetraethoxysiloxane, tetramethoxysiloxane, and polydimethoxysiloxane. A preferred alkoxy-functionalized siloxane is polydiethoxysilane. Suitable functionally-terminated silanes or siloxanes include silanol-terminated, vinyl-terminated and amino-terminated silanes or siloxanes such as epoxy-functionalized polydimethylsiloxane, aminopropyltriethoxy silane and silanol-termainated siloxane.
The glassy matrix is crosslinked using a titanium or tin catalyst. Suitable catalysts include titanium alkoxides such as titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium propoxide, titanium butoxide, titanium diisopropoxide (bis 2,4- pentanedionate), titanium diisopropoxide bis(ethylacetoacetao) titanium ethylhexoxide, and organic tin compounds such as dibutyl tin diacetate, dibutyltin laurate, dimethyl tin dineodecanoate, dioctyl dilauryl tin, and dibutyl butoxy chlorotin, as well as mixtures thereof. The glassy matrix can be formed by using a Sol-Gel process such as described in U.S. Patent No. 6,313,193, the disclosure of which is incorporated herein by reference in its entirety. Other methods of forming the matrix will be within the skill of one in the art.
The polymethylsilsesquioxane ("POSS") is dissolved in a crosslinking agent preferably titanium isopropoxide. By dissolving in titanium propoxide, up to about 40 percent of the POSS can be dissolved as compared to about 10 percent or less solubility in solvents. In operation, the glassy matrix and the polymethylsilsesquioxane are crosslinked or catalyzed separately so as to avoid premature gelation of the product prior to use.
The thermal barrier composition may also optionally include fillers such as, without limitation, glass fibers, fumed silica, mica, kaolin, bentonite, talc, zinc oxides, iron oxides and pigments or other fillers, as will be readily apparent to those skilled in the art. The composition may also include hollow glass microspheres to provide additional heat resistance. Preferably, thin-walled glass microspheres are used. Typically the volume percent of glass microspheres is from about 30 percent to about 80 percent. If the higher amount is used, it is preferable to include milled glass fibers to improve durability. Anti-corrosion agents such as zinc phosphates and zinc salts can also be added.
In operation, the thermal barrier composition of the present invention can be applied to a substrate by roll-coating, brush, spray coating dipping and the like. It is preferred that the user mix the catalyst with the other components right before or substantially contemporaneously with application to form an interpenetrating polymer network of glass and silicone on the surface of the substrate. Inasmuch as crosslinking occurs via a moisture condensation reaction between ethoxy and hydroxyl groups, the condensation inherently present on the substrate and/or in the atmosphere can be used advantageously.
The following specific examples are provided to afford a better understanding of the present invention to those skilled in the art. It is to be understood that these examples are intended to be illustrative only and is not intended to limit the invention in any way.
EXAMPLES
Example 1
1. Formulation wt% Component 6.79 Poly(methylsilsesquioxane)
10.50 Titanium isopropoxide
4.19 Polydiethoxysiloxane
21.00 Silanol-terminated polydimethylsiloxane (4200 g/mol)
7.35 Titanium diisopropoxide (Bis-2,4-pentanedionate) 4.19 Polydiethoxysiloxane
31.49 Mica 325 mesh
13.48 Heucophos ZPO (zinc organophosphate) Corrosion Protection
1.50 Heucorin RZ (zinc salt) Corrosion Protection
2. Manufacturing Steps
The first step is to dissolve the polymethysilsesquioxane (POSS) into the titanium isopropoxide (TIPO). This is accomplished by mixing the POSS into the titanium isopropoxide and heating at 100°C for 24 hours.
The second step is to terminate the silanol groups on the ends of the polydimethylsiloxane. This is accomplished by mixing the silanol terminated polydimethylsiloxane with the titanium diisopropoxide (bis-2,4-pentanedionate) and allowing the mixture to crosslink for 1 hour. If this step is not performed, the silanol groups on the polymer will instantly react with the titanium isopropoxide and the system will gel in a matter of seconds.
The third step is to add the remaining components to the POSS/TIPO (A component) keeping the titanium diisopropoxide (bis-2,4- pentanedionate)/polydimethylsiloxane mixture out as the B component in an A B system.
Example 2
Formulation wt% Component
24.07 Polysilsesquioxane dissolved in titanium isopropoxide and 20% polydiethoxysiloxane
5.42 Epoxy-functionalized polydimethylsiloxane
0.61 Aminopropyltriethoxy silane
16.05 Milled glass fiber
10.57 Hollow glass microspheres
1.20 Dibutyl tin dilaurate
40.12 Isopropyl alcohol
1.78 Titanium dioxide
0.18 Carbon Black
The formulation was manufactured using the same steps as Example 1 except that the POSS did not have to be pre-reacted with the TIPO. The formulation of Example 2 was used in various tests as described below and in Table 1.
Table 1
Figure imgf000006_0001
Durability Testing
A series of durability tests were performed on the coating composition of Example 2. These tests were designed to simulate real-world events that will test the durability of the coating. The three specific tests performed on the coating composition of Example 2 included: two tool drop tests, a falling sand test, and a 200 lb, 90° pivot test.
The first tool drop test consisted of dropping a 106 gram wrench from a height of 48 inches onto a panel coated with the coating composition of Example 2. This test which was repeated multiple times resulted in a dent of about 5mm x 5mm. The second tool drop test consisted of dropping a 783 gram hammer from the same 48 inch height. The tool drop resulted in a dent of about 15mm x 25mm.
The indentions from the tool drop tests are consistent with the energy expected form objects of similar size and mass dropped form a height of 48 inches. No cracking or delamination occurred the coating and the divots can be easily repaired with the coating composition of Example 2.
The falling sand test consisted of dropping 1 gallon of sand from a height of 1.5 feet in a concentrated stream onto the surface of a steel panel coasted with the coating composition of Example 2 mounted 45° to the falling sand.
As a results of this test, the impact zone was abraded in a region about 10mm x 16mm x 0.5 mm. The coating composition of Example 2 demonstrated good abrasion resistance.
The third durability test consisted of a 200 lb person standing on a plate coated with the coating composition of Example 2 with all weight on one foot. Then the person pivoted 90°. No damage resulted to the coating composition of Example 2. The test demonstrates the coating composition of Example 2 can be walked on (e.g., a plane wing) with no damage.
Temperature Delta Data
A titanium plate with a 2.5mm build of the coating composition of Example 2 was prepared. A 3mm wide channel was cut into the coating from the center of the plate to the edge, and a thermocouple was positioned in the channel such that it would be in contact with the titanium plate. The coating composition of Example 2 was applied over the thermocouple to fill the channel and seal the thermocouple at the interface of the coating composition of Example 2 and the titanium plate, producing a sample with the thermocouple counted at the interface of the coating composition of Example 2 and the titanium. Total coating thickness was approximately 3.0mm.
After the coating was cured, the plate was placed onto a steel block and was heated to a temperature of 1057° F by a burner on the turkey fryer. The sample was placed with the coating composition of Example 2 directly in contact with the hot steel block, and allowed to equilibrate for 78 minutes to allow for steady state heat flow.
The temperature measurement at the coating composition of Example 2-titanium interface was found to be 720° F with the hot steel measuring 1057° F: a temperature delta of 337° F across the coating composition of Example 2 for a coating that is 3.0mm thick.
Measure Thermal Conductivity
Thermal conductivity was measured on a free standing coating composition of Example 2 film using the ASTM El 530 standard test method. Measurements were conducted at 105°F, 334°F, and 561°F. The results are listed in the Table 2.
Table 2
Thermal Conductivity Test (ASTM D1530)
Figure imgf000008_0001
In the specification and examples, there have been disclosed typical preferred embodiments of the invention and, although specific terms are employed, they are used in a generic and descriptive sense only and not for purposes of limitation of the scope of the invention set forth in the following claims.

Claims

THAT WHICH IS CLAIMED IS:
1. A thermal barrier coating composition
(a) a glassy matrix comprising an alkoxy-functionalized siloxane and a functionally-terminated silane or siloxane;
(b) polymethylsilsesquioxane dissolved in a crosslinking agent;
(c) optionally, a filler, and
(d) optionally hollow glass microspheres.
2. The thermal barrier coating composition according to Claim 1, wherein the alkoxy-functionalized siloxane is selected from the group consisting of polydiethoxysiloxane, polydimethoxysiloxane, tetramethoxysiloxane and tetraethoxysiloxane and the functionally- terminated siloxane is an epoxy-functionalized polydiethoxysiloxane.
3. The thermal barrier coating composition according to Claim 1, wherein the crosslinking agent is titanium isopropoxide.
4. The thermal barrier coating compositiong according to Claim 1, wherein the filler is selected from the group consisting of fumed silica, mica, kaolin, bentonite, talc, zinc oxides, iron oxides and pigments.
5. The thermal barrier coating composition according to Claim 1 , wherein the glassy matrix is crosslinked using a titanium or tin catalyst.
6. The thermal barrier coating composition according to Claim 5, wherein the titanium or tin catalyst is selected from the group consisting of titatium methoxide, titanium ethoxide, titanium isopropoxide, titanium propoxide, titanium butoxide, titanium diisopropoxide (bis 2,4-pentanedionate), titanium diisopropoxide bis(ethylacetoacetao) titanium ethylhexoxide, dibutyl tin diacetate, dibutyltin laurate, dimethyl tin dineodecanoate, dioctyl dilauryl tin, and dibutyl butoxy chlorotin, and mixtures thereof.
7. The thermal barrier coating composition according to Claim 1, further comprising an anti-corrosion agent.
8. A substrate coated with a thermal barrier composition comprising a glassy matrix comprising an alkoxy-functionalized siloxane and a functionally-terminated silane or siloxane, polymethylsilsesquioxane dissolved in a crosslinking agent, optionally, a filler, and optionally hollow glass microspheres.
9. The substrate according to Claim 8, wherein the substrate is selected from the group consisting of steel, stainless steel, titanium, aluminum, magnesium and zinc.
10. The substrate according to Claim 8, wherein the alkoxy-functionalized siloxane is selected from the group consisting of polydiethoxysiloxane, polydimethoxysiloxane, tetramethoxysilane and tetraethoxysilane and the functionally- terminated siloxane is an epoxy-functionalized polydiethoxysiloxane.
11. The substrate according to Claim 8, wherein the crosslinking agent is titanium isopropoxide.
12. The substrate according to Claim 8, wherein the filler is selected from the group consisting of fumed silica, mica, kaolin, bentonite, talc, zinc oxides, iron oxides, and pigments.
13. The substrate according to Claim 8, wherein the glassy matrix is crosslinked using a titanium or tin catalyst.
14. The substrate according to Claim 13, wherein the titanium or tin catalyst is selected from the group consisting of titatium methoxide, titanium ethoxide, titanium isopropoxide, titanium propoxide, titanium butoxide, titanium diisopropoxide (bis 2,4- pentanedionate), titanium diisopropoxide bis(ethylacetoacetao) titanium ethylhexoxide, dibutyl tin diacetate, dibutyltin laurate, dimethyl tin dineodecanoate, dioctyl dilauryl tin, and dibutyl butoxy chlorotin, and mixtures thereof.
15. The substrate according to Claim 8, further comprising an anti-corrosion agent.
16. A method of forming a thermal barrier composition comprising the steps of
(a) dissolving polymethylsilsesquioxane in a crosslinking agent;
(b) mixing a glass matrix comprising an alkoxy-functionalized siloxane and a functionally-terminated silane with a tin or titanium catalyst to terminate the silanol groups on the end of the siloxane; and
(c) mixing (a) and (b) together.
17. The method according to Claim 16, including adding filler or glass microspheres to the dissolved polymethylsilsesquioxane of step (a) or the mixture of step (c).
18. The method according to Claim 16, wherein the alkoxy-functionalized siloxane is selected from the group consisting of polydiethoxysiloxane, polydimethoxysiloxane, tetramethoxysilane and tetraethoxysilane and the functionally- terminated siloxane is an epoxy-functionalized polydiethoxysiloxane.
19. The method according to Claim 16, wherein the crosslinking agent is titanium isopropoxide.
20. The method according to Claim 16, wherein the filler selected from the group consisting of fumed silica, mica, kaolin, bentonite, talc, zinc oxides, zinc phosphates, iron oxides and pigments.
21. The method according to Claim 16, wherein the titanium or tin catalyst is selected from the group consisting of titatium methoxide, titanium ethoxide, titanium isopropoxide, titanium propoxide, titanium butoxide, titanium diisopropoxide (bis 2,4- pentanedionate), titanium diisopropoxide bis(ethylacetoacetao) titanium ethylhexoxide, dibutyl tin diacetate, dibutyltin laurate, dimethyl tin dineodecanoate, dioctyl dilauryl tin, and dibutyl butoxy chlorotin, and mixtures thereof.
22. The method according to Claim 16, further comprising an anti-corrosion agent.
PCT/US2004/010539 2003-04-10 2004-04-05 Thermal barrier composition WO2004092437A2 (en)

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EP1895552A1 (en) * 2005-01-27 2008-03-05 The Kansai Electric Power Co., Inc. Highly heat-resistant static device for electric power
EP2382221A1 (en) * 2008-12-05 2011-11-02 Rutgers, The State University of New Jersey Compositions and methods for the protection of substrates from heat flux and fire
WO2018033552A1 (en) * 2016-08-19 2018-02-22 Az Electronic Materials (Luxembourg) S.A.R.L. Composition for black matrix and method for producing black matrix using the same
CN112852288A (en) * 2020-12-25 2021-05-28 陕西科技大学 Hydroxyl-containing bridged polysilsesquioxane/SiO2Effective anti-corrosion coating and preparation method thereof
US11512208B2 (en) 2006-08-01 2022-11-29 Rutgers, The State University Of New Jersey Compositions and methods for the protection of substrates from heat flux and fire

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2889185B1 (en) * 2005-07-29 2007-10-12 Rhodia Chimie Sa PROCESS FOR HYDROFUGING AND IMPROVING THE PERLING EFFECT OF CONSTRUCTION MATERIALS
US8186265B2 (en) 2005-08-08 2012-05-29 Ron's Enterprises, Inc. Device to efficiently cook food
US8707857B2 (en) 2005-08-08 2014-04-29 Ronald M. Popeil Cooking device to deep fat fry foods
US20180049590A1 (en) * 2016-04-29 2018-02-22 Alan Backus Devices and methods for supporting and preparing foods
US20080221263A1 (en) * 2006-08-31 2008-09-11 Subbareddy Kanagasabapathy Coating compositions for producing transparent super-hydrophobic surfaces
JP5592795B2 (en) * 2007-10-22 2014-09-17 フレキシブル セラミックス，インク． Fire resistant flexible ceramic resin blends and composite products formed therefrom
US9028969B2 (en) * 2010-07-27 2015-05-12 United Technologies Corporation Composite article having protective coating
US9856400B2 (en) 2012-04-27 2018-01-02 Burning Bush Group, Llc High performance silicon based coating compositions
WO2013170124A1 (en) 2012-05-10 2013-11-14 Burning Bush Group High performance silicon based thermal coating compositions
CN107236453B (en) 2012-07-03 2019-06-11 伯宁布什集团有限公司 Silicon substrate high performance paint composition
US9006355B1 (en) * 2013-10-04 2015-04-14 Burning Bush Group, Llc High performance silicon-based compositions
JP2019119804A (en) * 2018-01-05 2019-07-22 スリーエム イノベイティブ プロパティズ カンパニー Curable composition and optical member
EP3581679B1 (en) 2018-06-01 2021-02-17 Rolls-Royce North American Technologies, Inc. Slurry-based coating system repair
CN109705726B (en) * 2018-12-14 2021-06-04 华东理工大学 Low-density organic silicon heat-insulation-preventing integrated coating and preparation method thereof
CN114702893A (en) * 2022-04-25 2022-07-05 郑州圣莱特空心微珠新材料有限公司 Polyurethane primer and preparation method thereof

Family Cites Families (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5699668A (en) 1980-01-10 1981-08-11 Sumitomo Chemical Co Coating polycarbonate group resin molding article
JPS59109565A (en) * 1982-12-16 1984-06-25 Fujitsu Ltd Coating resin solution and production thereof
JPS60237003A (en) 1984-05-09 1985-11-25 Toshiba Silicone Co Ltd Method of preventing algae propagation
JPS60254034A (en) * 1984-05-30 1985-12-14 Fujitsu Ltd Formation of pattern
US4816288A (en) 1985-05-28 1989-03-28 Ppg Industries, Inc. Primer for adherence to plastic substrates
US4725501A (en) 1985-05-28 1988-02-16 Ppg Industries, Inc. Primer for adherence to plastic substrates
JPS62277475A (en) 1986-05-26 1987-12-02 Yokohama Rubber Co Ltd:The Coating material composition
US4814017A (en) 1986-10-03 1989-03-21 Ppg Industries, Inc. Aqueous organoalkoxysilane/metal oxide sol-gel compositions
US4753827A (en) 1986-10-03 1988-06-28 Ppg Industries, Inc. Abrasion-resistant organosiloxane/metal oxide coating
US5096488A (en) 1988-02-08 1992-03-17 Waitomo Industrial Investments Ltd. Antifouling composition
US4990547A (en) 1988-02-08 1991-02-05 Waitomo Industrial Investments Ltd. Antifouling composition
US5173110A (en) 1988-02-08 1992-12-22 Waitomo Industrial Investments Ltd. Antifouling composition
US5068277A (en) 1989-05-03 1991-11-26 Rhone-Poulenc Inc. Hydrolyzable silicone polymers
JP2952375B2 (en) 1990-03-05 1999-09-27 関西ペイント株式会社 Non-toxic antifouling paint composition
GB9014564D0 (en) 1990-06-29 1990-08-22 Courtaulds Coatings Holdings Coating compositions
GB9115153D0 (en) 1991-07-12 1991-08-28 Patel Bipin C M Sol-gel composition for producing glassy coatings
US5663215A (en) 1991-12-20 1997-09-02 Courtaulds Coatings (Holdings) Limited Coating compositions
US5449553A (en) 1992-03-06 1995-09-12 The United States Of America As Represented By The Secretary Of The Navy Nontoxic antifouling systems
US5298060A (en) 1992-04-03 1994-03-29 Air Products And Chemicals, Inc. Use of silicone resins and fluids to retard marine life buildup on submerged surfaces
US5232996A (en) 1992-05-07 1993-08-03 Lord Corporation Acrylate-terminated polyurethane/epoxy adhesives
US5492730A (en) * 1992-12-28 1996-02-20 Aluminum Company Of America Siloxane coating process for metal or ceramic substrates
US5552466A (en) * 1993-12-17 1996-09-03 Hitco Technologies Inc. Processable silicone composite materials having high temperature resistance
JP3846640B2 (en) 1994-01-20 2006-11-15 東レ・ダウコーニング株式会社 Curable organopolysiloxane composition
US5688851A (en) 1995-09-18 1997-11-18 Ceramal Research & Development Corporation Gel coat and method for manufacture thereof
JP3446505B2 (en) 1996-10-23 2003-09-16 信越化学工業株式会社 Primer composition
US5902851A (en) 1996-12-24 1999-05-11 Matsushita Electric Works, Ltd. Resinous composition for foul releasing coat and coating articles
KR19980079940A (en) 1997-03-05 1998-11-25 후지이 히로시 Rainwater contamination-preventing coating film, coating composition, coating film forming method and coating material
US5958116A (en) 1997-03-14 1999-09-28 Kansai Paint Co., Ltd. Antifouling coating composition
US5939478A (en) 1997-07-21 1999-08-17 Dow Corning Corporation Silicone polyether stabilized silicone latex solvent thickening
US6045869A (en) 1999-01-28 2000-04-04 Gesser; Hyman D. Water-insoluble hydrophilic marine coating and methods
JP2000319582A (en) 1999-03-11 2000-11-21 Kansai Paint Co Ltd Resin composition for coating material
FI105406B (en) 1999-07-05 2000-08-15 Nor Maali Oy Composition for use in painter's paints
US6313193B1 (en) 2000-06-02 2001-11-06 Microphase Coatings Inc. Antifouling coating composition
US6476095B2 (en) 2000-06-02 2002-11-05 Microphase Coatings, Inc. Antifouling coating composition
US6559201B2 (en) 2000-06-02 2003-05-06 Microphase Coatings, Inc. Antifouling coating composition
US6702953B2 (en) * 2000-12-14 2004-03-09 Microphase Coatings, Inc. Anti-icing composition
US6706405B2 (en) * 2002-02-11 2004-03-16 Analytical Services & Materials, Inc. Composite coating for imparting particel erosion resistance

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of EP1611264A4 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1895552A1 (en) * 2005-01-27 2008-03-05 The Kansai Electric Power Co., Inc. Highly heat-resistant static device for electric power
EP1895552A4 (en) * 2005-01-27 2011-06-22 Kansai Electric Power Co Highly heat-resistant static device for electric power
US8993463B2 (en) 2006-08-01 2015-03-31 Rutgers, The State University Of New Jersey Compositions and methods for the protection of substrates from heat flux and fire
US10329433B2 (en) 2006-08-01 2019-06-25 Rutgers, The State University Of New Jersey Compositions and methods for the protection of substrates from heat flux and fire
US11512208B2 (en) 2006-08-01 2022-11-29 Rutgers, The State University Of New Jersey Compositions and methods for the protection of substrates from heat flux and fire
EP2382221A1 (en) * 2008-12-05 2011-11-02 Rutgers, The State University of New Jersey Compositions and methods for the protection of substrates from heat flux and fire
EP2382221A4 (en) * 2008-12-05 2012-07-04 Univ Rutgers Compositions and methods for the protection of substrates from heat flux and fire
WO2018033552A1 (en) * 2016-08-19 2018-02-22 Az Electronic Materials (Luxembourg) S.A.R.L. Composition for black matrix and method for producing black matrix using the same
CN109563372A (en) * 2016-08-19 2019-04-02 Az电子材料（卢森堡）有限公司 The manufacturing method of black matrix composition and the black matrix using it
US10719013B2 (en) 2016-08-19 2020-07-21 Az Electronic Materials (Luxembourg) S.A.R.L. Composition for black matrix and method for producing black matrix using the same
CN112852288A (en) * 2020-12-25 2021-05-28 陕西科技大学 Hydroxyl-containing bridged polysilsesquioxane/SiO2Effective anti-corrosion coating and preparation method thereof
CN112852288B (en) * 2020-12-25 2022-04-29 陕西科技大学 Hydroxyl-containing bridged polysilsesquioxane/SiO2Effective anti-corrosion coating and preparation method thereof

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WO2004092437A3 (en) 2005-06-02
US7687150B2 (en) 2010-03-30
US20060110612A1 (en) 2006-05-25

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