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US20040260018A1 - Thermal barrier composition - Google Patents

Thermal barrier composition Download PDF

Info

Publication number
US20040260018A1
US20040260018A1 US10/814,213 US81421304A US2004260018A1 US 20040260018 A1 US20040260018 A1 US 20040260018A1 US 81421304 A US81421304 A US 81421304A US 2004260018 A1 US2004260018 A1 US 2004260018A1
Authority
US
United States
Prior art keywords
titanium
tin
siloxane
thermal barrier
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/814,213
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English (en)
Inventor
William Simendinger
David Garrett
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Microphase Coatings Inc
Original Assignee
Microphase Coatings Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Microphase Coatings Inc filed Critical Microphase Coatings Inc
Priority to US10/814,213 priority Critical patent/US20040260018A1/en
Assigned to MICROPHASE COATINGS, INC. reassignment MICROPHASE COATINGS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GARRETT, DAVID WILLIAM, SIMENDINGER, WILLIAM H. III
Priority to US10/960,666 priority patent/US7163750B2/en
Publication of US20040260018A1 publication Critical patent/US20040260018A1/en
Priority to US11/324,687 priority patent/US7687150B2/en
Abandoned legal-status Critical Current

Links

Classifications

    • 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 jet engine or the surrounding parts of the jet 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. Pat. 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.
  • a crosslinking agent preferably titanium isopropoxide.
  • titanium propoxide 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.
  • 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
  • TIPO titanium isopropoxide
  • 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.
  • 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
  • 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.
  • Demonstrate coating will create 200° F. 1000° F. Temperature measured at temperature delta. TBC-Ti interface. Durability Perform in-house tests tailored to the a. Simulate 200-lb person standing ASTM High probability that coating will operational environment during Phase I, on a coasted plate and pivoting. D5420-98a have sufficient durability. to determine feasibility. b. Drop tool on coated plate form ASTM 4-feet. D968-93 c. Perform simple abrasion resistance test using falling sand method. Repairability Intentionally damage coated Ti coupons None Repair tests demonstrated that (hammer, scrape). Repair the coupon coating was restored to like-new and assess the quality of the repair by condition. knife adhesion tests and visual inspection. Vibration Use AFRL table vibration that will AFRL AFRL Results indicate high probability provide 160 dB noise and 900° F. that coating will withstand Quartz lamp. vibration environment.
  • 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 5 mm ⁇ 5 mm.
  • 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 15 mm ⁇ 25 mm.
  • 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 As a results of this test, the impact zone was abraded in a region about 10 mm ⁇ 16 mm ⁇ 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.
  • a titanium plate with a 2.5 mm build of the coating composition of Example 2 was prepared.
  • a 3 mm 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 3.0 mm.
  • 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.
  • Example 2-titanium interface 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 3.0 mm thick.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
US10/814,213 2003-04-10 2004-03-31 Thermal barrier composition Abandoned US20040260018A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US10/814,213 US20040260018A1 (en) 2003-04-10 2004-03-31 Thermal barrier composition
US10/960,666 US7163750B2 (en) 2003-04-10 2004-10-07 Thermal barrier composition
US11/324,687 US7687150B2 (en) 2003-04-10 2006-01-03 Thermal barrier composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US46180003P 2003-04-10 2003-04-10
US10/814,213 US20040260018A1 (en) 2003-04-10 2004-03-31 Thermal barrier composition

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US10/960,666 Continuation-In-Part US7163750B2 (en) 2003-04-10 2004-10-07 Thermal barrier composition
US11/324,687 Continuation US7687150B2 (en) 2003-04-10 2006-01-03 Thermal barrier composition

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EP (1) EP1611264A4 (fr)
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EP2207838A4 (fr) * 2007-10-22 2011-11-16 Flexible Ceramics Inc Mélange de résines céramiques flexibles résistant au feu et produits composites formés à partir de celui-ci
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
CN109705726A (zh) * 2018-12-14 2019-05-03 华东理工大学 低密度有机硅防隔热一体化涂层及其制备方法
JP2019119804A (ja) * 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 硬化性組成物及び光学部材
CN114702893A (zh) * 2022-04-25 2022-07-05 郑州圣莱特空心微珠新材料有限公司 一种聚氨酯底涂剂及其制备方法

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US20080221263A1 (en) * 2006-08-31 2008-09-11 Subbareddy Kanagasabapathy Coating compositions for producing transparent super-hydrophobic surfaces
US7955996B2 (en) 2006-08-01 2011-06-07 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
US9028969B2 (en) * 2010-07-27 2015-05-12 United Technologies Corporation Composite article having protective coating
WO2014014542A2 (fr) 2012-04-27 2014-01-23 Burning Bush Group Compositions de revêtements haute performance à base de silicium
US10138381B2 (en) 2012-05-10 2018-11-27 Burning Bush Group, Llc High performance silicon based thermal coating compositions
CN107236453B (zh) 2012-07-03 2019-06-11 伯宁布什集团有限公司 硅基高性能涂料组合物
US9006355B1 (en) 2013-10-04 2015-04-14 Burning Bush Group, Llc High performance silicon-based compositions
JP2018028630A (ja) 2016-08-19 2018-02-22 アーゼッド・エレクトロニック・マテリアルズ（ルクセンブルグ）ソシエテ・ア・レスポンサビリテ・リミテ ブラックマトリックス用組成物、およびそれを用いたブラックマトリックスの製造方法
EP3581679B1 (fr) 2018-06-01 2021-02-17 Rolls-Royce North American Technologies, Inc. Réparation de système de revêtement à base de suspension
CN112852288B (zh) * 2020-12-25 2022-04-29 陕西科技大学 一种含羟基桥连聚倍半硅氧烷/SiO2有效防腐蚀涂层及其制备方法

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Publication number Priority date Publication date Assignee Title
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
EP2207838A4 (fr) * 2007-10-22 2011-11-16 Flexible Ceramics Inc Mélange de résines céramiques flexibles résistant au feu et produits composites formés à partir de celui-ci
US20180049590A1 (en) * 2016-04-29 2018-02-22 Alan Backus Devices and methods for supporting and preparing foods
JP2019119804A (ja) * 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 硬化性組成物及び光学部材
CN109705726A (zh) * 2018-12-14 2019-05-03 华东理工大学 低密度有机硅防隔热一体化涂层及其制备方法
CN114702893A (zh) * 2022-04-25 2022-07-05 郑州圣莱特空心微珠新材料有限公司 一种聚氨酯底涂剂及其制备方法

Also Published As

Publication number Publication date
WO2004092437A2 (fr) 2004-10-28
EP1611264A4 (fr) 2008-02-27
WO2004092437A3 (fr) 2005-06-02
EP1611264A2 (fr) 2006-01-04
US7687150B2 (en) 2010-03-30
US20060110612A1 (en) 2006-05-25

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