Not Applicable
Not Applicable
This invention relates to the formation of fusible coatings or structures (e.g., polymer or polymer composite coatings, or reinforced polymer coatings, as well as polymer, or reinforced polymer structures) via a thermal spray process. In particular, the invention relates to formation of these coatings or structures using a flameless thermal spray process.
Polymer thermal spray systems have been used for depositing thermoplastic, thermoset and radiation-curable materials onto substrates for several decades. Generally, a flame or plasma is projected from a tube and a stream of the polymer (or other fusible powder) is introduced into the projected flame or plasma. In the flame or plasma, the polymer particles are heated and melted, and when they impinge on the surface, they “splat” (flatten) and fuse together to form a more or less continuous coating.
A commercial thermal spray system that uses a gas flame that is available from Xiom, Inc. (Babylon, N.Y.) is the XIOM 5000 Scorpion and the XIOM 1000. Similar units are or have been available from Alamo Supply Company, LTD (Houston, Tex.), model number ASC PG-550, Plastic Flamecoat Systems, Inc (Big Springs, Tex.), Applied Polymer Systems (Boynton Beach, Fla.), and Sulzer Metco, Winterthur, AG, Switzerland.
One major difficulty is the flame or plasma itself. Many polymers degrade in a flame, even when exposed to it for a very short time. In addition, the flame impinging on the target surface can degrade that surface as well. The degradation resulting from oxidation and/or breaking of polymer bonds causes reduction in the physical properties of polymers, as well as the potential inclusion of defects in polymer coatings that are deleterious to their performance or appearance, e.g., burned particles, carbon inclusions, yellowing and discoloration, pinhole defects. As such it is important that thermal methods used to melt, deposit and process polymers as coatings and/or structures do not subject the polymers to harsh oxidation, radical or reactive ion environments that cause charring, or to high temperatures that break or weaken polymer bonds. Thus, the application of polymers for many applications should use the minimum amount of heat during the process in order to preserve the physical properties of the polymers being applied.
The degradation processes related to the use of flames are related to the nature of flames. Flames induce combustion which is a highly exothermic self-sustaining oxidation reaction that in turn produces high temperature flames. The temperature of a flame is primarily dependent on the type of fuel involved in the combustion process and typically ranges from about 1,400 degrees Centigrade (° C.) for a candle to more than 3,000° C. for an oxyacetylene torch. The high temperature of the flame tears apart the vaporized fuel molecules, forming various combustion products and free radicals which react with each other and with the oxidizer involved in the reaction. The high energy of the flame also excites the electrons in some of the transient reaction intermediates such as CH and C2, which results in the emission of visible light as these substances release their excess energy.
The visible part of a flame is extremely rich with chemical reactions and intermediate species, mostly radicals. For example, it has been reported that combustion of natural gas can be modeled using 53 species and 325 elementary reactions. As the temperature decreases beyond the visible part of a flame, most of the highly reactive radicals and ions recombine into less reactive combustion products with stable atomic structures such as CO, CO2, H2O, etc., (for a hydrocarbon based combustion).
During a combustion based polymer thermal spray process, it is desirable to avoid exposure of polymer surfaces to the visible, i.e., highly reactive, part of a flame. The visible part of a flame contains excited species of O, NO, OH, and NH ions. These free radicals can attract hydrogen from polymer surfaces causing surface oxidation and generation of polar oxygenated groups. The oxidation proceeds by a free radical mechanism accompanied by chain scission. Chain scission occurs during free radical propagation yielding polar and mobile scission products. For example, it has been found that hydroxyl, carbonyl, carboxyl, and amide groups are typically found on flame-treated polyethylene. It has been reported that a flame contact period of only 0.01-0.1 second is sufficient to oxidize, i.e., damage, polymer surface to a depth of about 40-90 Angstroms (Å).
For the reasons described above, flame treatment is often used commercially to make polyolefines, polyacetales, and poly(ether terephthalate) printable and bondable by introducing polar oxygenated groups into the thin surface layer. However, during a combustion based polymer thermal spray process, coating unit building blocks are individual powder particles. If the surface of each polymer particle is exposed to an open flame and oxidized, the resulting coating will have an abundance of highly distractive free radicals and mobile scission products distributed throughout the entire coating volume. Such coatings can have significantly shortened service life due to reduced mechanical and barrier properties and an accelerated degradation kinetic. The negative effect of the visible flame on thermally sprayed polymer can be significantly minimized by utilizing thermal energy of lower temperature hot gas occurring downstream and beyond the visible flame zone.
One solution to these aforementioned problems is the use of a flameless system wherein a stream of gas is heated electrically, and the polymer and other particles are introduced into the hot gas stream. This greatly reduces burning and degradation of the coating particles and the substrate. A commercial system using this method is disclosed in PCT patent application publication WO/2008/127227, and is commercially available as the Resodyn PTS1000 system (Resodyn Corporation, Butte, Mont.). Systems to date have used resistive heaters powered by electricity. These systems are less energy efficient than combustible fuel systems, but they avoid exposing the sprayable material to a reactive flame, or plasma, thereby yielding superior results.
For all of its advantages, the use of an electrically resistive heater to transfer heat and melt the polymer or other fusible particles has limitations. In that higher power is required in order to increase the spray output rate, such devices utilize robust sources of electricity and relatively thick copper power cables to avoid undue losses. As a result, while flameless sprayers may achieve improved results, such sprayers are heavier and less portable than their traditional flame- and plasma-based counterparts.
What is needed is a portable, easy to wield system that can spray large quantities of melted, or partially melted, fusible polymer powder particles and/or other materials onto a substrate, which poses reduced risk degradation of such materials while achieving the necessary heat required for melting and fusing the polymer powders and other materials onto a substrate.
The background art is characterized by U.S. Pat. Nos. 3,801,020; 3,958,758; 4,416,421; 4,694,990; 5,236,327; 5,285,967; 5,503,872; 5,932,293 and 7,216,814; by U.S. Patent Applications No. US2006/166153 and US2009/095823; and by International Patent Application No. PCT/US2007/009021; the disclosures of which patents and patent applications are incorporated by reference as if fully set forth herein.
As used herein, the following terms and variations thereof have the meanings given below, unless a different meaning is clearly intended by the context in which such term is used.
“A,” “an” and “the” and similar referents used herein are to be construed to cover both the singular and the plural unless their usage in context indicates otherwise.
“About,” “approximately,” and “in the neighborhood of” mean within ten percent of a recited parameter or measurement, and preferably within five percent of such parameter or measurement.
“Comprise” and variations of the term, such as “comprising” and “comprises,” are not intended to exclude other additives, components, integers or steps.
“Exemplary,” “illustrative,” and “preferred” mean “another.”
In an illustrative embodiment, the invention comprises a thermal spray system for depositing a polymer, or polymer composite coating, or structure onto a target substrate wherein a stream of air is heated by a flame in a defined combustion zone. In this embodiment, means are provided for the introduction of secondary gas flows into and downstream of the combustion zone that cool the combusted gas temperature below a point that would result in the degradation of the fusible polymer powders or other materials being sprayed. In this embodiment, the secondary, or excess, or dilution gas flow, may be adjusted to obtain the desired carrier gas temperature needed to process the polymer, polymer composite, or other material that is chosen for each application. The ability to adjust the carrier gas stream temperature is beneficial for successful application of the thermal spray system, as there are a broad range of fusible materials, each having different temperatures and times at which they can be processed without degradation, yet be sufficiently melted to form the desired coating and/or structure.
In this embodiment, the fusible polymer particles or other materials are introduced into the heated carrier gas stream that melts the particles while propelling them toward the target surface. In this embodiment, the flame is contained within the spray unit and does not come into contact with the target, nor does it come into contact with the fusible polymer powder particles, or other materials being thermally sprayed, or surface being coated. In this embodiment, a means for supplying coating fusible polymer powder, or other materials to the spray gun applicator is provided.
In an illustrative embodiment, the invention is a thermal spray gun, comprising: an exterior surface; an inner chamber located within the exterior surface having a forward end and an aft end; a flame source located within the inner chamber; a first fluid path located within the inner chamber for carrying a combustible mixture to the flame source, wherein the flame source produces a combustion gas when a flame is present; a second fluid path located within the inner chamber for carrying excess gas to a flame produced by the flame source; a third fluid path located between the exterior surface and the inner chamber for carrying a cooling gas to cool the exterior surface and mix with the combustion gas; and a nozzle for introducing a gas-particle mixture into the inner chamber such that the gas-particle mixture is heated by the combustion gas mixed with cooling gas as the gas-particle mixture is propelled through the inner chamber and out of the thermal spray gun. In another embodiment, the flame is anchored at the flame source. In another embodiment, the flame source is a burner plate. In another embodiment, the excess gas is directed towards the flame by a deflector located between the burner plate and the end of the nozzle closest to the forward end of the inner chamber. In another embodiment, the flame source is a perforated tube. In another embodiment, the surface area of perforations per unit length of the tube increases from the aft end of the tube to the forward end of the tube. In another embodiment, the excess gas is sufficient to substantially complete combustion of the combustible mixture. In another embodiment, the excess gas and cooling gas are drawn into the inner chamber by a fluid amplifier located at the forward end of the inner chamber relative to the flame source. In another embodiment, the fluid amplifier employs the Coanda effect. In another embodiment, the flame source is annular and the nozzle projects coaxially through the flame source. In another embodiment, at least a portion of the second fluid path is located between the nozzle and the flame source. In another embodiment, the combustible mixture is produced by a Coanda fluid flow amplifier run by an oxidant gas. In another embodiment, the combustible mixture is substantially stoichiometric with respect to fuel and oxidant present in the combustible mixture. In another embodiment, the source of the gas-particle mixture source is a fluidized bed hopper incorporating a vibrator. In another embodiment, the inner chamber is configured for preventing the flame from contacting the gas-particle mixture. In another embodiment, the gun emits the gases from the inner chamber at a velocity (rate) of less than 100 meters per second (m/s). In another embodiment, the gun emits the gases from the inner chamber at a rate of 15 to 30 m/s.
In another illustrative embodiment, the invention is a method of producing a spray polymer, comprising: introducing a combustible mixture into a flame source located in an inner chamber of a thermal spray gun through a first fluid path, wherein the thermal spray gun includes an exterior surface, and wherein the inner chamber is located within the exterior surface and has a forward end and an aft end; producing a flame at the flame source, thereby producing a combustion gas; introducing excess gas to the flame through a second fluid path located within the inner chamber; introducing a cooling gas to cool the exterior surface and mix with the combustion gas through a third fluid path located between the exterior surface and the inner chamber; introducing a gas-particle mixture into the inner chamber through a nozzle; and heating the gas-particle mixture with the combustion gas mixed with cooling gas as the gas-particle mixture is propelled through the inner chamber and out of the thermal spray gun, thereby producing a spray polymer. In another embodiment, the method comprises anchoring the flame at the flame source. In another embodiment, the method comprises directing the excess gas towards the flame by a deflector located between the flame source and the end of the nozzle closest to the forward end of the inner chamber. In another embodiment, the method comprises introducing an amount of the excess gas sufficient to substantially complete combustion of the combustible mixture and to cool the combustion gas. In another embodiment, the method comprises drawing the excess gas and cooling gas into the inner chamber by a fluid amplifier located at the forward end of the inner chamber relative to the flame source. In another embodiment, the method comprises cooling the nozzle by locating at least a portion of the second fluid path between the nozzle and the flame source. In another embodiment, the combustible mixture is substantially stoichiometric with respect to fuel and oxidant present in the combustible mixture. In another embodiment, the method comprises preventing the flame from contacting the gas-particle mixture.
In yet another illustrative embodiment, the invention is a pre-mixer to generate a fuel-oxidant mixture for a thermal spray gun, comprising: a fluid amplifier having motive flow provided by a motive gas, thereby causing the fluid amplifier to educt an oxidant gas; and a metered inlet for a fuel fluidly connected to the fluid amplifier, wherein the pre-mixer is configured for inputting the fuel-oxidant mixture into the thermal spray gun. In another embodiment, the fuel-oxidant mixture is a substantially stoichiometric mixture. In another embodiment, the fluid amplifier is a Coanda fluid amplifier. In another embodiment, the metered inlet is a jet orifice.
In a further illustrative embodiment, the invention is a burner plate for a thermal spray gun, comprising: a perforated plate; and a second perforated material covering at least a portion of the perforated plate, wherein the burner plate is located within the thermal spray gun to produce a flame for heating gases. In another embodiment, the second perforated material is located around the perimeter of the perforated plate. Here, “around” means in a circle or in circumference.
In a further illustrative embodiment, the invention is a gas-particle mixture source comprising: a fluidized bed hopper incorporating a vibrator.
Further aspects of the invention will become apparent from consideration of the drawings and the ensuing description of exemplary embodiments of the invention. A person skilled in the art will realize that other embodiments of the invention are possible and that the details of the invention can be modified in a number of respects, all without departing from the concept. Thus, the following drawings and description are to be regarded as illustrative in nature and not restrictive.
The features of the invention will be better understood by reference to the accompanying drawings which illustrate exemplary embodiments of the invention. In the drawings:
The following reference numerals are used to indicate on the drawings the parts and environment of an illustrative embodiment of the invention:
Referring to
In this embodiment, material is supplied to spray gun applicator 4 by means of a fluidized bed hopper 6. The rate of supply is controlled by two venturis (not shown). The first venturi transports a stream of the powder material particles in compressed gas from fluidized bed hopper 6 to umbilical 3. The second venturi adds additional transport air to the umbilical 3 and ejects the stream of powder material particles into spray gun 4. Each of the first venturi and second venturi is independently controlled by a different individual stream of compressed gas. Fluidized bed hopper 6 is commercially available in several hopper sizes from a number of manufacturers, such as Powder Parts Inc., Elgin, Ill. 60123.
Referring to
In a preferred embodiment, a combination of vibrator 16 and fluidized bed hopper 6 provides superior powder transport capabilities. The combination is effective at de-agglomerating and fluidizing powders for transport between fluidized bed hopper 6 and spray gun applicator 4 through a powder hose within umbilical 3, with the types of thermoplastic powders used to create thermoplastic fusible coatings.
The thermal spray system described herein may be used for depositing a variety of coating materials, including zinc, aluminum, zinc-aluminum alloy, ferrous metal alloys, copper, copper alloys, ceramics, carbon, graphite and combinations thereof. They may also be used for depositing other materials, such as colorants, electrically conductive materials, fluorescent materials, phosphorescent materials, anti-fouling agents, reflective materials, radar absorbent materials, anti-microbials, microballoons, foaming agents, leveling agents, lubricants, ultraviolet (UV) protectors and combinations thereof. Still other materials suitable for deposition using thermal spray system 4 include thermoplastic or thermoset polymeric materials, such as epoxy resins, polyurethanes, polyethers, nylons, polyesters, polycarbonates, polyethylene, polypropylene, acrylic polymers, polyvinylchloride (PVC) resins, fluorocarbon polymers, ethylenevinylacetate (EVA), ethyleneacrylicacid (EAA), acrylonitrilebutadienestyrene (ABS), polyetheretherketone (PEEK), Polyvinylidenfloride (PVDF), silicones and chemical or physical combinations thereof. Coating materials may be combined with other materials. Particle sizes for the coating materials may range from about 5 microns to about 5,000 microns.
Referring to
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In the embodiment of
A person having ordinary skill in the art would know that a variety of other flame anchoring means are used in flame systems, such as stoves and fueled jets. These flame anchoring means may also be incorporated into embodiments of the invention. Thus, the foregoing examples provide a basic insight into the process of flame anchoring and should not be construed as limitations on the invention.
The heat of combustion at stoichiometric conditions for burning propane in air is 1,980° C. This temperature is too high to be contained by most common refractory materials. For example, high temperature steel alloys have a service temperature of 537° C. Nickel-chromium-iron alloys are used up to 677° C. Even ceramic coated jet engine parts only operate at a maximum temperature of 1,371° C. Therefore, background art flame generating devices are configured so that the flame burns outside the device architecture in free air. For these reasons, in certain embodiments of the invention, in order to contain combustion, film cooling on the flame containment surfaces and heat transfer management are employed.
The desired process temperature for a thermoplastic sprayer device is a hot gas temperature that exits the device in the neighborhood of 700° C., but could range from 100° C. to around 1,000° C. Here, “around” means “approximately” as it is defined above. Most fusible materials are processed in this temperature range. Because combustion temperatures are much higher than preferred fusible material processing temperatures, and to provide a stream of heated carrier gas, in illustrative embodiments of this invention, excess air 12 and cooling gas 13 are introduced to the process during combustion and after combustion is completed.
Referring to
Coanda or attached flow fluid amplifiers are known in the art of fluidics. It is the coupling of a fluid amplifier to a burner or flame tube located within combustion chamber 11 that provides at least two functions. First, excess air 12 serves to complete combustion and begin cooling the flame. Second, the cooling or dilution air 13 serves to further reduce the temperature of the combustion products to achieve the desired flameless hot carrier gas for processing of polymer powders or other materials. Both described functions are accomplished using relatively low quantities of compressed air by means of a Coanda fluid amplifier.
Referring to
Background art venturi style eductors generally do not provide enough primary air to create a stoichiometric mixture and therefore tend to burn rich and require additional oxidant air at the burner. This problem is solved by the applicants by de-coupling the propane gas flow 8, which is typically the motive flow in a pre-mix venturi eductor, from the air venturi and instead using an independent Coanda pre-mix fluid flow amplifier 36, run by primary air 9 and educting additional air 209, in combination with propane fuel gas nozzle 208, e.g., a propane jet orifice, that discharges into the entrance of pre-mix fluid amplifier 36.
Referring to
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Many variations of the invention will occur to those skilled in the art. Some variations include trip plates, trip lips and/or bluff bodies. Other variations call for flame tubes holes or perforated walls, serpentine paths and/or fluid amplifiers with annular nozzles and/or air knives. All such variations are intended to be within the scope and spirit of the invention.
Although some embodiments are shown to include certain features, the applicants specifically contemplate that any feature disclosed herein may be used together or in combination with any other feature on any embodiment of the invention. It is also contemplated that any feature may be specifically excluded from any embodiment of the invention.
This application claims the benefit of U.S. Provisional Patent Application No. 61/205,079, filed Jan. 14, 2009, the disclosure of which patent application is incorporated by reference as if fully set forth herein.
The U.S. Government has a paid-up license in this invention and the right in limited circumstances to require the patent owner to license others on reasonable terms as provided for by the terms of Grant No. FA8651-04-C-0379 awarded by the United States Air Force.
Number | Name | Date | Kind |
---|---|---|---|
3801020 | Mocarski | Apr 1974 | A |
3958758 | Piorkowski | May 1976 | A |
4416421 | Browning | Nov 1983 | A |
4694990 | Karlsson et al. | Sep 1987 | A |
5236327 | Flanagan et al. | Aug 1993 | A |
5285967 | Weidman | Feb 1994 | A |
5503872 | MacKenzie et al. | Apr 1996 | A |
5932293 | Belashchenko et al. | Aug 1999 | A |
7216814 | Gardega | May 2007 | B2 |
20060166153 | Rusch et al. | Jul 2006 | A1 |
20090095823 | Gardega et al. | Apr 2009 | A1 |
Number | Date | Country | |
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61205079 | Jan 2009 | US |