WO2001022434A1 - Electrically conductive exothermic coatings - Google Patents
Electrically conductive exothermic coatings Download PDFInfo
- Publication number
- WO2001022434A1 WO2001022434A1 PCT/US1999/021701 US9921701W WO0122434A1 WO 2001022434 A1 WO2001022434 A1 WO 2001022434A1 US 9921701 W US9921701 W US 9921701W WO 0122434 A1 WO0122434 A1 WO 0122434A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrically conductive
- coating composition
- coating
- carbon
- flake
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/90—Electrical properties
- C04B2111/94—Electrically conducting materials
Definitions
- the present invention relates to coatings that are able to evolve heat (exothermic coatings) and more particularly to exothermic coatings that utilize non- metallic particles for achieving remarkable heating characteristics.
- Nishino U.S. Pat. No. 4,714,569 proposes to react a monomer having
- Nahass (U.S. Pat. No. 5,591 ,382) proposes paints for charge dissipation which paints include cylindrical graphite carbon fibrils and a polymeric binder.
- Mahabandi U.S. Pat. No. 5,575,954 proposes conventional metallic and carbon conductive fillers in a unique binder to make a conductive polymer matrix.
- Wakita U.S. Pat. No. 5,567,357 proposes silver-plated copper powder to make a conductive paint.
- Kim proposes metal, metal-coated glass, ceramics, or conductive carbon to prepare conductive coatings.
- Namura proposes a combination of graphite particles, metal particles, and carbon black to prepare conductive coatings.
- Hari U.S. Pat. No. 5,516,546 proposes amorphous or spherical graphite, carbon fiber, metal particles, or mixtures thereof, to prepare conductive coatings.
- Wakabayashi U.S. Pat. No. 5,425,969 proposes a conductive primer for polypropylene that utilizes carbon black, graphite, silver, nickel, or copper.
- Ota (U.S. Pat. No. 5,407,741) proposes to use spherical graphic particles or a diameter of less than 500 ⁇ m to prepare an exothermic conductive coating.
- Ota (U.S. Pat. No. 5,378,533) proposes metallic coated hollow glass spheres to prepare a conductive coating.
- Li (U.S. Pat. No. 5,372,749) proposes a surface treatment for conductive copper powder.
- Rowlette proposes to use a mixture of conductive metal oxide powder and non-conductive particles to prepare an anisotropically electrically conductive coating composition.
- Shrier proposes to use metals, metal alloys, conductive carbides, conductive nitrides, conductive borides, and metal-coated glass spheres to prepare a nonlinear transient over-voltage protection coating.
- Yokoyama U.S. Pat. No. 5,242,511 proposes to a copper alloy powder for use in electromagnetic shielding and similar uses.
- Mio U.S. Pat. No. 4,857,384 proposes to use metal oxide powder in preparing an exothermic conducting paste.
- Gindrup (U.S. Pat. No. 4,624,798) proposes to use metal-coated microparticles in preparing electrically conducting compositions.
- Ellis proposes a blend of graphite, manganese dioxide, and zinc oxide in preparing electrically conductive compositions.
- Neumann proposes to use metallic carbide in preparing paints that have low electrical impedance orthogonal to the plane of the coating.
- the present invention solves many of the problems encountered in the art in formulating non-metallic exothermic coatings.
- the present invention is based on the discovery that different carbon components are required in an electrically conductive exothermic coating in order to avoid break-down (that is, loss of coating properties) and especially if a constant temperature is to be maintained by the coating (self-regulating embodiment). It has been discovered that graphite permits heat to be generated by the coating when energized with a.c. power; however, the heat tends to run away which results in a break down of the coating. Carbon, on the other hand, permits more electrical conductivity by the coating. Both the graphite and carbon should be flake-like in structure. Such a combination of flake-like graphite and carbon pigments in particles sizes of about 1 ⁇ to 500 ⁇ should be used. The amount of such pigments should range from about 10 and 75 weight-% based on the non-volatile solids content of the coating formulation (e.g., without solvent and other components that evolve from the coating during drying and curing operations).
- non-conductive flake-like graphite pigment should be added to the formulation.
- additional conventional spherical carbon up to a 1/3 replacement of the flake-like particle content
- novel coatings are made conventionally by initially forming a pigment grind and then letting down the grind in additional solvent with the incorporation of additives as is necessary, desirable, or convenient.
- the binder should be able to withstand the expected temperatures of the coating and, thus, should be temperature resistant silicone resins, polyamide resins, bis-maleimide resins, and the like.
- Advantages of the present invention include the ability to generate temperatures ranging up to around 850° C. Another advantage is the ability to produce a self-regulating temperature coating. A further advantage is that the inventive coating maintains its coating properties and can be applied, inter alia, by brush, roller coat, reverse roller coat, spray, and the like.
- the inventive paint is unique in its ability to function as a conventional coating with expected coating properties while concomitantly being electrically conductive. Such electrical conductivity further translates into the ability to generate heat (exothermic coating) to the point of being useful in a wide variety of applications, such as, for example, heating of floors, walls, ceilings, roofs, and gutters.
- Further uses include preheating of engine oils in transport vehicles and power plants, local heating of batteries and auxiliary systems, heating cars and tankers carrying oil and other liquids, coal carrying vehicles, and for de-icing of aircraft wings. Additional uses include warming of components subjected to cold temperatures in use, heating of highways and other outdoor structures including, for example, airplane wing de-icing.
- Yet other uses include home/commercial appliances (dryers, irons, clothes presses, space heaters, cooking surfaces such as stoves, hot plates, woks, toasters, water heaters, coffee makers, furnaces, hot tubes, commercial/industrial/home ovens, etc.), medical equipment, as a replacement for resistant heating devices, and the like.
- home/commercial appliances dryers, irons, clothes presses, space heaters, cooking surfaces such as stoves, hot plates, woks, toasters, water heaters, coffee makers, furnaces, hot tubes, commercial/industrial/home ovens, etc.
- medical equipment as a replacement for resistant heating devices, and the like.
- the present invention relies on non-metallic electrically conductive carbon pigments that are flake-like in structure.
- flake-like carbon pigments can be highly
- the flake-like carbon pigments should range in particle size from about 5 to 500 ⁇ . While the amount of such flake-like carbon pigments can be as little as 1 wt-%, amounts up to 75 wt-% can be envisioned, depending upon intended use and other factors. Typically, the more flake-like carbon pigment present, the more conductive the coating is. Measurements have revealed the ability to generate between 1.5 ° and 2.1 ° F heating from the inventive coating for each watt of power inputted to the coating. Moreover, heating can be quite rapid. Water can be boiled in a matter of as little as 60 seconds in a 32 ounce glass dish.
- Another unique feature is the ability of the coating to become scratched, yet still maintain is electrical conductivity and exothermic properties. This makes repair of the coating facile and should prove to be an important characteristic for commercial implementation of the present invention. Since the coating generates such high quantities of heat, the binder used necessarily must be able to withstand such elevated temperatures.
- heat- stable resins should be used including, for example, acrylics, alkyds, cellulosics, epoxies, fluoro-plastics, ionomers, natural rubber, nylons, phenolics, polyamides, polybutadiene, polyesters, polyimides, polypropylene, polyurethanes, silicone resins, silicone rubber, styrene-butadiene; nitrile rubber, polysulphide rubber, vinyl-ethylene, polyvinyl acetate, silicates and polysilicates; hydraulic setting Portland cement, sodium aluminate and gypsum (Plaster of Paris); glass compositions, including glass fruits; ceramic and refractory compositions; and minerals, such as bentonites, and the like.
- additives are incorporated into the formulation in conventional fashion. These additives include, inter alia, opacifying pigments and inert extenders such as, for example, titanium dioxide, zinc oxide, clays such as kaolinite clays, silica, talc, and the like. Additionally, the coating composition can contain corrosion inhibiting pigments, plasticizers, pigment suspending agents, flow leveling agents, catalysts, drying agents, surfactants, tinctorial pigments, and a wide variety of other conventional additives.
- the inventive paint can be applied to a substrate by direct roll coat or curtain coating with or without a knife, reverse roller coat, atomized application, or like conventional techniques. Cure of the coating can be simple air-drying or it can involve baking at a temperature and for a time for cure of the binder system employed, solvents used, and like factors well known to those in the coatings field.
- the electrically conductive exothermic coating then was formed as follows: 6. Apply copper foil electrodes (0.25 in. wide X 2 mil thick X desired length) to substrate to be coated along opposite edges of the surface to receive the coating with adhesive (self-adhesive backing has been used).
- Solder electrical wire leads to the ends of the copper electrodes.
- Printex XE-2 Carbon Pigment A highly conductive carbon pigment, MW of 12, flake-like structure, 1 ,000 ⁇ M grind level, MSDS #1017, Degussa Corporation
- Silicon Carbide AE60 Union Carbide Corporation Silicone Resin "Flame Control" Kern Hi-Tem Coating, No. 850 Series, MSDS #7.06b, high temperature rating (>600 ° F), silicone alkyd resin reduced in xylene, Sherwin Williams Co.
- a coating was compounded from the following ingredients:
- the resulting coating on glass (Pyrex® brand) provided quick heating of 32 oz of water at 0.9 amps (up to 150°-210 ° F) and was stable for several days. There was, however, some spot break-down of the coating.
- a coating was compounded from the following ingredients:
- the resulting coating on glass was highly electrically conductive lts) and provided fairly uniform and rapid heating to the point of run-away oating was not regulated.
- a coating was compounded from the following ingredients:
- the resulting coating on glass (Pyrex®) provided very rapid and uniform heating, high electrical conductivity, and was stable for 10 days at 1.7 amps and 110 volts.
- a coating was compounded from the following ingredients:
- a metal Broaster (metal pan with porcelain coating) pan measuring about 12 cm X 20 cm was coated with a coating of the formulation set forth above at a coating thickness of about 35-55 ⁇ . Leads were connected to the dried coating as described above and then to a POWERSTAT variable automatic transformer (Warner Electric). An Extech 382060 Clamp on power watt meter was employed in the circuit to measure power and a Fluke 52 K/J Infrared Thermometer was used to measure the temperature of the coated Broaster pan. Testing as reported below was conducted at an ambient temperature of about 84.2 ° F. All temperatures reported in this example were obtained in less than 15 minutes after initiation of power to the coating and were sustained for at least 10 minutes. Each voltage test was conducted by starting at ambient temperature and then applying current to obtain the maximum steady-state temperature for that power setting. Thereafter, the sample was cooled to ambient temperature and new power settings were initiated. The data recorded are set forth below.
- Example 5 The coating of Example 5 was used in this experiment also. The same experimental procedure was followed, except that the ambient temperature was 70.2 ° F and the coating was applied to a PYREX brand glass pan with a surface area measuring about 11.4 cm in by 17.1 cm. The data recorded are set forth below.
- a coating was compounded from the following ingredients:
- a metal Broaster pan measuring 13 cm X 30 cm was coated with a thin (about 35-55 ⁇ ) coating of the formulation set forth above and testing conducted as described in the foregoing examples, except that each increased power setting was established immediately after the previous temperature had been stabilized (i.e., the pan was not cooled before each succeeding run). The following data were recorded:
- Example 7 The procedure of Example 7 was repeated for a PYREX brand glass dish measuring about 18 cm X 10 cm with an ambient temperature of about 86 ° F. The coating initially was dried (cured) by subjecting it to 60 V (140 ° F) for 16 hours.
- a coating composition was compounded from the following ingredients:
- the coating was drawn down on a Broaster pan as described in Example 4, above. As an initial test, the coating was able to heat a beaker containing 500 cc of water to boiling in 60 minutes 40 seconds at 4.25 amp at 110 V. Next, the coating was tested (85 ° F ambient temperature) for its electrical conductivity properties with the following data being recorded:
- the coated PYREX dish was filled with 2 quarts of water. The surface was placed on a hot plate and 110 V was applied with a maximum of 3V. This low temperature formula heated the water to 147 ° F for over 8 weeks. The water temperature did not vary more than 1 ° F for the entire two months.
- the water would evaporate every 8 hours, so constant vigilance was taken to keep the water levels up in the dish.
- the experiment finally was terminated when the operator let the dish dry out for a while and the hot dish exploded when water was re-established in the hot dish.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1999/021701 WO2001022434A1 (en) | 1999-09-20 | 1999-09-20 | Electrically conductive exothermic coatings |
EP99949740A EP1236208A1 (en) | 1999-09-20 | 1999-09-20 | Electrically conductive exothermic coatings |
AU62555/99A AU6255599A (en) | 1999-09-20 | 1999-09-20 | Electrically conductive exothermic coatings |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1999/021701 WO2001022434A1 (en) | 1999-09-20 | 1999-09-20 | Electrically conductive exothermic coatings |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001022434A1 true WO2001022434A1 (en) | 2001-03-29 |
Family
ID=22273643
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/021701 WO2001022434A1 (en) | 1999-09-20 | 1999-09-20 | Electrically conductive exothermic coatings |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1236208A1 (en) |
AU (1) | AU6255599A (en) |
WO (1) | WO2001022434A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005036562A1 (en) * | 2003-09-17 | 2005-04-21 | Active Coatings, Inc. | Exothermic coatings and their production |
DE102011007834A1 (en) | 2011-04-21 | 2012-10-25 | Henkel Ag & Co. Kgaa | Mineral composition for the production of electrical heating layers |
ITUB20151080A1 (en) * | 2015-05-27 | 2016-11-27 | Barzaghi S R L | ELECTROTHERMIC COMPOSITION OF WATER BASED CARBON COMPOUNDS AND APPLICATION METHODS |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5549849A (en) * | 1991-08-02 | 1996-08-27 | Carrozzeria Japan Co., Ltd. | Conductive and exothermic fluid material |
-
1999
- 1999-09-20 EP EP99949740A patent/EP1236208A1/en not_active Withdrawn
- 1999-09-20 AU AU62555/99A patent/AU6255599A/en not_active Abandoned
- 1999-09-20 WO PCT/US1999/021701 patent/WO2001022434A1/en not_active Application Discontinuation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5549849A (en) * | 1991-08-02 | 1996-08-27 | Carrozzeria Japan Co., Ltd. | Conductive and exothermic fluid material |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005036562A1 (en) * | 2003-09-17 | 2005-04-21 | Active Coatings, Inc. | Exothermic coatings and their production |
DE102011007834A1 (en) | 2011-04-21 | 2012-10-25 | Henkel Ag & Co. Kgaa | Mineral composition for the production of electrical heating layers |
WO2012143221A1 (en) | 2011-04-21 | 2012-10-26 | Henkel Ag & Co. Kgaa | Mineral composition for producing electric heating layers |
ITUB20151080A1 (en) * | 2015-05-27 | 2016-11-27 | Barzaghi S R L | ELECTROTHERMIC COMPOSITION OF WATER BASED CARBON COMPOUNDS AND APPLICATION METHODS |
Also Published As
Publication number | Publication date |
---|---|
AU6255599A (en) | 2001-04-24 |
EP1236208A1 (en) | 2002-09-04 |
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