WO1995007766A1 - Materiaux a diffusion photonique utilises comme revetements thermoresistants - Google Patents
Materiaux a diffusion photonique utilises comme revetements thermoresistants Download PDFInfo
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- WO1995007766A1 WO1995007766A1 PCT/US1994/010279 US9410279W WO9507766A1 WO 1995007766 A1 WO1995007766 A1 WO 1995007766A1 US 9410279 W US9410279 W US 9410279W WO 9507766 A1 WO9507766 A1 WO 9507766A1
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- slurry
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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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/06—Quartz; Sand
-
- 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
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00112—Mixtures characterised by specific pH values
-
- 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
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
-
- 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
- C04B2111/80—Optical properties, e.g. transparency or reflexibility
Definitions
- the invention relates to heat-resistant coatings for use on substrates and, more particularly to a photon-diffusive coating.
- a solid, opaque substrate (surface) will react to impinging radiation, or heat energy, through the mechanisms of absorption or refection. Energy, if absorbed, may remain in the substrate or leave it through the mechanism of emission.
- the reflection mechanism avoids these problems. Because heat energy does not succeed in penetrating the substrate, the substrate is protected from degradation. For example, a reflective lining in a furnace will radiate energy back to the furnace interior where it can do useful work. In the case of protecting a substrate, the reflected heat would reduce the backside heat temperature of the substrate.
- the instant coating operates on the principle of photon diffusion.
- the composition of instant photon diffusive coating is made from klannerite, which is a hydrothermally altered form of silica containing over 55% cristobalite and tridymite.
- the coating is able to diffuse heat, because of the presence of the minerals cristobalite and tridymite, and they, therefore, are key ingredients in the instant photon diffusive coating formula.
- the coating has a very low indices of refraction, and thus does not capture and subject rays to internal reflection within the crystal structure.
- the mineral has a natural microporosity (e.g., with pores smaller than 0.17 ⁇ m) .
- PDCs photon dispersive coatings
- dispersive coatings have the ability to reflect electromagnetic radiation with negligible absorption. Their ability to diffuse energy is dependent upon the crystal's size and geometry, and orientation of the coating material.
- One of ordinary skill in the art to which this invention most nearly pertains will understand that when a solid is heated, it emits light. Emission occurs because surface atoms or molecules are raised to excited states. As the particles spontaneously return to their stable (ground) energy states, energy is emitted in the form of electromagnetic radiation.
- the emitted radiation typically referred to as thermal radiation, will be distributed over a range of wavelengths, and may result from changes in the electronic, vibrational, and relational states of the atoms and molecules.
- Calcination of the composition results in a breakdown of the stable materials, generally resulting in absorption of heat which is then unavailable to affect the protected substrate.
- Ablation is a process of peeling off exhausted surface layers of insulation to expose new protective layers.
- Intumescence occurs when heat converts a thin coating of a fire-proofing material into a thick insulating barrier. During intumescence, cooling gases are normally released, leaving a reflective multi- cellular foam insulation. Thermal hydrogenation occurs during some calcination reactions when the heat causes release of water of hydration as water vapor.”
- U.S. Patent No. 4,137,198 discloses a foam product intended for use as a construction material with fire-resistant and thermally-insulating properties.
- a block of polymer-hybrid foam composition of this example was subjected to high temperature combustion conditions at flame temperatures of 1800°F. to 2000°F. in gas fired combustion chamber. It was observed that the surface of the polymer-hybrid foam composition developed infra-red reflective chromophores from decomposition of the hybrid foam, which acted as mirrors, reflecting the infra-red rays from the surface of the composition back to the source of the flame.”
- U.S. Patent No. 4,174.711 discloses a fire-resistant enclosure which includes an outer layer intended to reflect infra-red radiation.
- This reflective layer may be chrome plating or gold galvanization.
- the reflective layer is then painted with a coating which burns off when heated, thereby exposing the underlying infra ⁇ red-reflective layer.
- Other materials, in the form of eutectic mixtures are sandwiched behind the infra-red-reflective layer to provide additional heat-resistant and absorbent properties.
- U.S. Patent No. 4,104,427 discloses a laminated fire screen panel to which may be applied an infra-red reflecting coating of either copper, aluminum or a metallic oxide to protect the intumescent fire-retardant material from decomposition and to delay the disposal of the material upon the outbreak of a fire.
- U.S. Patent No. 4,268.581 discloses the use of similar infra-red reflective coatings.
- U.S. Patent No 4,173,668 discloses using an infra-red reflective coating to slow the heating of the intumescent layer, thus prolonging the protection afforded by the fire screen.
- U.S. Patent Nos. 3,935,681 and 4,071,649 disclose fire proof glass work. Each of these references teaches the inclusion of a component which is opaque to or reduces the transmission of infra ⁇ red radiation.
- U.S. Patent No. 4,563,843 discloses the use of silver, gold or copper as an infra-red reflective layer for use in a heat insulation window.
- U.S. Patent Nos. 3,253.008 and 3.345.132 disclose the use of silicon and silica compounds in fire resistance paints and coatings.
- the use of nitrogen-silicon components as flame-proofing agents (column 2, line 62) is disclosed.
- the use of silicic acids as heat insulation materials (column 3, line 60) is disclosed.
- U.S. Patent No. 3.535.130 discloses a paint which chars upon being exposed to fire, liberating water vapor and sulfur dioxide to remove hot gasses and flames.
- U.S. Patent No. 4,097,385 discloses a foaming sealing material contained within a flexible tube which may be placed in openings or cracks. When the tube is heated, the intumescent material contained therewithin expands to close off the opening.
- the intumescent material includes as aqueous alkali metal silicate solution or a gel .
- U.S. Patent No. 4,118.325 discloses a rigid foamed sodium silicate matrix within which unexpanded particulate fillers such as vermiculite or prelite are dispersed. Fire protection is afforded by the silicate foam matrix and by the expansion of the unexpanded mineral in response to the application of heat.
- U.S. Patent No. 4.123,587 discloses an organic foaming agent intended to be included in host materials such as paints, coating compositions and the like. When heated, the composition give off nitrogen gas and/or water.
- the fire-retardant material as taught in this patent is provided in finely ground form which may be dispersed uniformly throughout the host material.
- U.S. Patent No. 4,179.535 discloses a coating composition intended to stabilize and rigidify to prevent the composition from falling away from vertical surfaces during a fire. This patent teaches the use of a slurry of hydrated metal silicate particles and an aqueous alkali metal silicate solution.
- U.S. Patent No. 4,265,806 discloses a tumescent foam flame retardant using organic constituents.
- U.S. Patent No. 4,297,252 discloses the use of sodium aluminate in connection with a sodium silicate foam in order to improve the aging characteristics of the foam.
- U.S. Patent No. 4,338.374 discloses a foam having a self- curing surface which seals to protect the foam from the evaporation of water therefrom.
- U.S. Patent No. 4,442.157 discloses a foaming fire-proofing composition using phenolic resins which decompose to form a stiff foam upon heating.
- U.S. Patent No. 3.347.684 discloses the use of organic fire- retardant pigments in paints. No silicates are used in the disclosed composition.
- U.S. Patent Nos. 3.598.617 and 3,776,741 disclose a composition useful as a coating for resistors in the form of a paint having an orthosilicate base.
- the inclusion of silicon dioxide in a particular combination of particle sizes and proportions is disclosed.
- U.S. Patent No. 4,013,476 discloses a molding material formed from silica and calcium oxide, mineral fibers and other inorganic constituents. The resulting material is non-combustible and may be molded into a variety of shapes and articles.
- U.S. Patent No. 4,097,287 discloses an inorganic film composition useful for the production of non-combustible paints.
- the composition includes a colloidal silica dispersion, aluminum compounds and powered glass.
- U.S. Patent No. 4.137,178 discloses a flame retardant composition form from a phosphorus-nitrogen-silica formula intended to use spent catalyst as part of the formulation.
- the catalyst involved is a polyphosphoric acid held on a silica support.
- U.S. Patent No. 4.114.074 discloses a non-flammable inorganic coating composition, including controlling the shape and size of the aluminum oxide and/or aluminum hydroxide constituents.
- U.S. Patent No. 4.168,175 discloses a fire-retardant using borax and powered glass combined with cellulosic fibers.
- U.S. Patent No. 4,548,891 discloses a coating formed of a photopolymerised titanium composition.
- U.S. Patent No. 2.561.304 discloses the use of silica in paints.
- U.S. Patent No. 4,289.952 discloses a process for controlling the size of powder particles using light and heat energy.
- heat-resistant As used herein, the terms “heat-resistant”, “heat-retardant”, “fire-proof” and “flame-resistant” may be used interchangeably.
- klannerite a silaceous mineral, (a form of hydrated sodium alumino silicate)
- a flame- protective substance e.g., photon-diffusive
- the flame-retardant (i.e., beneficial heat-resistant) properties of the coating are achieved by reflecting energy in the infra-red wavelength region, and this reflectance is achieved by chemical adjustment of the particle size and lattice structure of the klannerite molecules.
- the klannerite is applied in a binder (e.g., latex) and exhibits its infra-red reflective properties after having been subjected to heat.
- a binder e.g., latex
- Use of the coating on a heated substrate, such as a steam pipe, will activate the coating's infra-red reflective properties, while use on normally unheated or ambient articles will not activate these reflective properties until heat is applied.
- the process of manu f acturing the photon diffusive coating generally consists of:
- a particular distribution of particle sizes and structure is achieved by selectively milling and combining different grinds of silica. Theoretically, the milling/combining process creates a molecular lattice structure within which individual molecules of silica are arranged in a close-packing configuration to provide the desired reflectance of infra-red energy.
- T h e present invention contemplates a novel heat-resistant coating and techniques for making and using same.
- klannerite a silaceous mineral (a form of hydrated sodium alumino silicate), is used as a flame-protective (e.g., photon-diffusive) material or coating.
- the flame-protective (i.e., beneficial heat-resistant) properties of the coating are achieved by reflecting energy in the infra-red wavelength region, and this reflectance is achieved by chemical adjustment of the particle size and lattice structure of the klannerite molecules.
- the klannerite is applied in a binder and exhibits its infra-red reflective properties after having been subjected to heat.
- a heated substrate such as a steam pipe
- the coating forms a ceramic bond when heated at a temperature of 500°C for a period of one hour in an oxygen-free environment.
- the process of manufacturing the photon diffusive coating consists of:
- the resulting "slurry" is covered with water (e.g. , sufficient to form a barrier over the surface of the slurry - approximately 33.32 pounds of water), covered (e.g., with a lid), and maintained ("aged") at a temperature of 185 degrees Fahrenheit for a period of 24 hours.
- water e.g. , sufficient to form a barrier over the surface of the slurry - approximately 33.32 pounds of water
- the pH is checked. If the pH is above 12.0, aging is continued by maintaining the slurry at 185 degrees Fahrenheit, and the pH of the slurry is rechecked at 8 hour intervals.
- the slurry is cooled to 120 degrees Fahrenheit. Once cooled, 137 pounds of Lorcon JK 270 (a polysaccharide resin) are added to the slurry and mixed into the slurry at a low speed - ensuring good mixing action. Meanwhile, 33.32 pounds of water and 6.5 pounds of sodium sesquicarbonate are mixed (off line) for approximately five minutes. This mixture is then (after cooling and adding the Lorcon JK 270) added slowly to the batch of slurry.
- Lorcon JK 270 a polysaccharide resin
- Airflex 525BP a latex binder
- the photon diffusive coating mixture of Example 1 is diluted with deionized water in a range of 3-4 (three to four) parts water to one part mixture.
- the diluted mixture is filtered through a suitable filter, such as through a coarse paint strainer, and is then applied to a substrate desired to be coated.
- the preferred dilution is four parts deionized water to one part photon diffusive coating mixture.
- the diluted photon diffusive coating mixture may be applied in any suitable manner to a substrate (surface) to be coated.
- One suitable application technique is simply depositing the diluted coating onto a surface, and using an adjustable doctor blade to meter the thickness of the coating on the surface.
- T h e diluted coating was observed to have a pH of 11.75, and a viscosity of 57KU (as measured according to ASTM test method D- 562) .
- the dry film thickness of the coating on the substrate is 9 mils (average thickness) , although thicker or thinner coatings are contemplated as being within the scope of this invention.
- the coated refractory substrate should be allowed to condition (at room temperature) for approximately twelve hours, then baked, for example, at 950 degrees Fahrenheit for one hour.
- Example 2 The photon diffusive coating mixture of Example 1, applied according to the techniques of Example 2 (to a 9 mil thickness) , was tested for effectiveness as a heat-resistant coating.
- Coated test panels of 0.020 inch thick aluminum were coated and cured as follows:
- test panels were air-dried at 77 degrees Fahrenheit (i.e, room temperature), 50% R.H. (relative humidity), for approximately twelve hours. Then the test panels were subjected to various additional curing steps A-F, as follows:
- A. panels were baked at a temperature of 250 degrees Fahrenheit for a period of one hour;
- the test consisted of subjecting 0.020 inch thick aluminum panels to a direct flame of approximately 3500 degrees Fahrenheit (e.g., such as is generated at the apex of the inner cone of a Bernz-O-Matic propane torch) .
- a direct flame of approximately 3500 degrees Fahrenheit (e.g., such as is generated at the apex of the inner cone of a Bernz-O-Matic propane torch) .
- An un-coated panel burned through within four minutes.
- a coated panel did not burn through after 30 minutes, with the flame directed at the coated side of the panel.
- the reverse side (opposite the flame) of the panel was un- coated, the panel burned through within four minutes.
- the coated panel exhibited the ability to delay the penetration of a high temperature flame through an aluminum panel by over 700%, as compared with an un-coated panel.
- the coating of the present invention effectively prevents burn-through of an aluminum panel when the coating is air-dried for twelve hours (e.g., overnight), and then force-dried at a temperature of 120°F for one hour. It is possible that further curing of the coating occurred in-situ, during the test (i.e., during exposure to heat from the torch). It can also be observed, that force-drying (i.e., baking) of the coating above 250°F can result in undesired blistering of the coating.
- an airless sprayer is recommended, with an appropriate nozzle size (e.g., 0.040 inch) , and further dilution (with water) may be necessary to control spray characteristics, and multiple coats may be required to achieve the desired coating thickness. It is desirable that a monolithic finish be achieved with the coating.
- the coating disclosed herein provides superior results to other coatings.
- high-emissivity coatings absorb heat (energy) and re-radiate it.
- the photon-diffusive coating of the present invention reflects energy rather than absorbing it, thereby reducing heat flow through the coated surface (e.g. , the wall of a furnace) .
- heat can be re fl ected to the interior of the furnace, thereby increasing the efficiency of the furnace and resulting in realizable energy savings.
- the composition of the present invention is made from klannerite mineral, which is a hydrothermically altered form of silica, containing over 55% cristobalite and tridymite. Because of the use of crystobalite and tridymite, the photon diffusive coating has a very low indices of refraction, and thus does not capture and subject rays to internal reflection within the crystal structure. Further, the mineral has a natural microporosity (e.g., with pores smaller than 0.17 ⁇ m) .
- the composition of the present invention has been found to be 85% reflective of radiation in the 0.5 - 5.0 micron (wavelength) range, which is highly effective for reflecting radiant energy at 2200°F (which occurs at approximately 2.0 microns) .
- the photon-diffusive material of the present invention is suitable for use as a heat-resistant coating, and the like, and as a base coat for subsequent intumescent fireproof coatings.
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
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Abstract
La présente invention concerne des compositions de silice, leurs procédés de préparation, et leurs procédés d'utilisation en revêtements thermorésistants notamment. L'invention concerne également l'emploi de ces compositions comme couche de base pour des revêtements intumescents à l'épreuve du feu. En règle générale, dans une réalisation, cette composition est obtenue par réaction des cristaux de silice sur l'hydroxyde de sodium, puis adjonction d'un liant pour agglomérer les cristaux, et enfin chauffage du liant et des cristaux jusqu'à ce que le durcissement soit tel qu'il permette la réflexion des infrarouges. L'invention concerne également les procédés de mélange et de repos des ingrédients devant constituer la composition, ainsi que les procédés d'application de la composition sur la surface du substrat.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU77264/94A AU7726494A (en) | 1993-09-14 | 1994-09-13 | Photon-diffusive materials as heat resistant coatings |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12159393A | 1993-09-14 | 1993-09-14 | |
US08/121,593 | 1993-09-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995007766A1 true WO1995007766A1 (fr) | 1995-03-23 |
Family
ID=22397666
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1994/010279 WO1995007766A1 (fr) | 1993-09-14 | 1994-09-13 | Materiaux a diffusion photonique utilises comme revetements thermoresistants |
Country Status (2)
Country | Link |
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AU (1) | AU7726494A (fr) |
WO (1) | WO1995007766A1 (fr) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4012232A (en) * | 1974-12-23 | 1977-03-15 | Nori Y. C. Chu | Stabilized photochromic materials |
US4046586A (en) * | 1974-08-19 | 1977-09-06 | American Optical Corporation | Stabilized photochromic materials |
US4537636A (en) * | 1982-03-30 | 1985-08-27 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Process for the preparation of nacreous pigments with improved gloss properties, products thereof, and compositions using said pigments |
-
1994
- 1994-09-13 AU AU77264/94A patent/AU7726494A/en not_active Abandoned
- 1994-09-13 WO PCT/US1994/010279 patent/WO1995007766A1/fr active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4046586A (en) * | 1974-08-19 | 1977-09-06 | American Optical Corporation | Stabilized photochromic materials |
US4012232A (en) * | 1974-12-23 | 1977-03-15 | Nori Y. C. Chu | Stabilized photochromic materials |
US4537636A (en) * | 1982-03-30 | 1985-08-27 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Process for the preparation of nacreous pigments with improved gloss properties, products thereof, and compositions using said pigments |
Also Published As
Publication number | Publication date |
---|---|
AU7726494A (en) | 1995-04-03 |
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