US3770482A - Electrostatic coating method of applying multilayer coating - Google Patents
Electrostatic coating method of applying multilayer coating Download PDFInfo
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- US3770482A US3770482A US00197559A US3770482DA US3770482A US 3770482 A US3770482 A US 3770482A US 00197559 A US00197559 A US 00197559A US 3770482D A US3770482D A US 3770482DA US 3770482 A US3770482 A US 3770482A
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- coating
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- zinc
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/542—No clear coat specified the two layers being cured or baked together
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
- B05D1/06—Applying particulate materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
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- 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
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
-
- 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
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
-
- 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]
- Y10T428/31511—Of epoxy ether
-
- 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]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the powders will be a powder of a film-forming nonconductive organic or inorganic polymer.
- a coating of this powdered composition to a conductive substrate which has a neutral charge or a charge opposite from that of the coating composition powder particles, the powders stratify into distinct layers of different compositions.
- the powders adhere to the substrate because of contact or static electrification for a reasonable length of time and until at least one of the powders can be cured or fused to form the final coating.
- a protective coating of superimposed layers of zinc, epoxy, and polyethylene can be applied to a conductive substrate.
- the electrical charge given to a particle during electrostatic coating may be represented by the following general formula:
- the electric charge thus is dependent upon the field intensity (E,) and on the surface area (and therefore the radius) of the particle.
- E field intensity
- F qE electrostatic force
- the powder With the electrostatic spraying technique, the powder is charged and adheres to a heated or an unheated substrate for a period generally sufficient to permit conveying the'coated object to an oven. A subsequent bake, or curing, process in the oven transforms the powder into a smooth, uniform coating having desired characteristics.
- Some of the main advantages of the electrostatic spraying process are the fact that no solvents are used, and therefore no solvent costs are involved and the coating operation is muchsafer. Generally, any excess powder can'be recovered from the spray booth and reused, which, together with the fact that'very little overspray is encountered, results in al:'
- thermosetting polymers e.g., thermosetting polymers
- powdered metals for decorative effects.
- furniture manufacturers frequently electrostatically spray a mixture of powdered epoxy resin and powdered, flaked aluminum or bronze, the powder mixture containing about 2 percent by weight of metal, on furniture.
- the metal migrates during the baking operation to the surface of the coating, providing an attractive metallic finish.
- French patent 1,261,473 relates to the electrostatic spraying of a polymer such as a cellulose ester.
- the patent discloses that powdered aluminum may be added to the plastic powder to improve the chargeability thereof.
- the French patent makes no mention I of the amount of aluminum powder added to the cellulose ester or polyethylene powder, and it is clear that the patentee must be contemplating relatively small amounts of powdered aluminum, as very small amounts of the finely powdered aluminum should be sufficient to change the chargeability of the polymeric powder.
- This invention relates to a process for electrostatically applying a multilayer coating to substrates in one step.
- the coating comprises a plurality of superimposed, distinct layers of film-forming materials. These film-forming materials are electrostatically applied in admixed powder form, with the electrostatic coating apparatus applying a charge to the powders, which, when the substrate is charged (the substrate may be neutral), is opposite the charge of the'substrate'.
- a conductivesubstrate is electrostatically coated with a mixture of at least two different powders, each powder having an average particle size of less than about 300 microns.
- At least one of the powders is a powder of a film-forming nonconductive organic or inorganic polymer.
- the entire powder mixture coating composition may consistof differentfilm-forming non-conductive organic or inorganic polymers, or one or more components of the coating composition may be a' conductive metal or a conductive non-metal.
- at least one material in the coating composition is' highly conductive.
- the powders are preferentially attracted to the substrate during the electrostatic coating operation, with the material having the greatest charge generally being found adjacent the substrate, and the material 7 having the smallest charge appearing on the outer surface of the coating. It is extremely difficult to accurately measure particle charges, but an approximation of the chargeability of a particular non-conductive material will be furnished by its dielectric constant.
- Two or more powders may be utilized in the coating composition of this invention, provided that the powders of non-conductive materials differ from one another in dielectric constant by a factor of at least 0.1.
- the polymers having the higher dielectric constant value must have a specific gravity which is substantially higher, e.g., at least 0.1 higher, than that of the polymer having the lower dielectric constant value.
- the coating composition is a mixture of said conductive metals and such non-conductive polymers
- the conductive metal should have a specific gravity which is at least three times, preferably four times, that of the nonconductive polymer.
- Conductive non-metals may also be used in the curing compositions of this invention, and, when used in admixture with such non-conductive polymers, should have a specific gravity at least 1.5 times that of the non-conductive polymer.
- the powders used in the coating compositions of this invention form a triboelectric series, e.g., the powders acquire different amounts or degrees of electrostatic charge under similar charging conditions.
- dielectric powders such powders appear to obey Coehns Law, wherein powders of higher dielectric constant values ar more strongly charged than powders of lower dielectric constant values.
- the charging mechanism may be more appropriately described in terms of conductivity.
- the powders used in the compositions of this invention appear to form a series in which the members of such series may be ranked in an order in which the members become increasingly electrophilic.
- the coated substrate is subjected to a treatment to render the coating composition powders immobile.
- a treatment generally results in the fusion of at least one of the coating components, e.g., a thermoplastic polymer, and/or in a chemical treatment or reaction such as to effect at least a partial cure or conversion of at least one of the coating components, e.g., a thermosetting polymer.
- the coating components must have the above differential in dielectric constant values, or chargeability, in order to initially form superimposed layers when applied by electrostatic coating methods. Thereafter, and in accordance with normal electrostatic coating procedures, the substrate, with the charged particles of the coating composition adhering thereto, is placed in a bake oven until the coating composition is transformed, by curing or fusion,,into an integral coating. During this fusion or curing process, the material having the highest dielectric constant, which will generally be deposited in a layer adjacent the substrate, may migrate through other coating components to the surface of the coating if of a similar or lower specific gravity than of the upper layers (those furthest from the substrate).
- the present invention does not contemplate substantial migration of coating components during the fusion or curing process; therefore, it is necessary to maintain the specific gravities of the coating components within the aforesaid ranges in order to prevent substantial migration of one or more coating componentsv
- the coating compositions of the present invention will utilize two or three different components, to produce a resulting two or three layer coating on the substrate. It will, of course, be realized that one component or one final layer in the coating may be itself a mixture of two or more specific materials e.g., tow or more thermoplastic polymers having quite similar dielectric constants and quite similar specific gravi' ties.
- each of the components should differ from the other components by the differentials set forth above as to dielectric constant, or chargeability, and specific gravity.
- the specific gravity of each polymer should differ from the specific gravities of the other polymers by a factor of at least 0.1, preferably by a factor of 0.2.
- the substrate may be of any conductive metal, e.g., iron, steel, copper, aluminum and the like, or may be a conductive non-metal, e.g. carbon, or even may be of a non-conductive material, e.g., a wooden, glass or organic hydrocarbon polymer, which has been rendered at least .partially conductive on at least the surface thereof, e.g., by the application of a conductive coating thereon.
- a conductive coating could be, for instance, colloidal graphite or silver.
- Such substrates are hereinafter referred to as conductive substrates.
- the powder particles will be charged, with the charge being either positive or negative, depending upon the equipment utilized and, to some extent, the particular nature of the powder itself. For instance, it has been found preferable to impart a positive charge to nylon powders.
- the substrate should be neutral or of a charge opposite to the powder to insure that the powder particles will adhere to the substrate until the subsequent heat treatment, backing, fusing or curing operation is completed.
- the substrate maybe merely grounded, in some instances, or an opposite charge may be applied thereto.
- the differential between the charges on the powder particles and on the substrate should be at least sufficient to allow the particles to adhere to the substrate during normal handling operations between the electrostatic coating operation and the bake oven.
- One major advantage of the present invention is in the reduction of atmospheric pollutants and liquid polluting effluents from coating operations. Previous procedure for producing coatings of different components resulted in the discharge of appreciable quantities of polluting materials into the environment, which discharges are reduced or even eliminated by the present invention.
- the average particle size of the polymeric materials in the powder admixture will generally be within the .range of to 70 microns, preferably to 50 microns, and most preferably will average about35 microns in size for electrostatic sprayingapplications. For other types of electrostatic powder applications, different powder sizes will accordingly'be used, as known to the art. For example, in an electrostatic fluidized bedfpolymer powders may be used having particle sizes within the range of 10 to 300 microns.
- At least one powder in the powder admixture be of a highly conductive material.
- the zinc comprise no more than about 7 percent by weight of the powder admixture, preferably less than 6 percent, and most preferably about 5 percent by weight of .zinc is used.
- the zinc concentration may go up as high' as 20 or even percent by weight of the powder admixture.
- the present invention most preferably involves a three-component coating powder system containing from.4 to 30 percent of a metal, i.e. zinc, l0 86 percent of a thermosetting material, i.e. a thermosetting epoxy, and 10 70 percent of a surface layer material, generallyof a thermoplastic nature, e.g. polyethylene or polypropylene.
- a metal i.e. zinc
- l0 86 percent of a thermosetting material i.e. a thermosetting epoxy
- 10 70 percent a surface layer material, generallyof a thermoplastic nature, e.g. polyethylene or polypropylene.
- the preferred ranges for the above components are 5 12 percent, 55 '75 percent and 20 40 percent respectively, all percentages being by weight of the total composition.
- the powders are sprayedwhile suspended in one or more fluids.
- the fluid will be air or other inert gas, but it is possible to use a non-solvent inert liquid in which the coating powders are dispersed.
- the re sulting suspension may be-sprayed upon the substrate, and then the non-solvent is removed during the baking operation.
- the process of thepresent invention produces a final coating upon the substrate, with the final coating containing at least two dissimilar superimposed layers.
- the final coating containing at least two dissimilar superimposed layers.
- the coating components are applied in only one operation, a considerable cost savings will result.
- thermosetting organic polymers or other materials in the coating composition
- various other methods to cure or set organic polymers may be utilized if desired.
- some polyester resins are now being cured instantaneously through the use of electron beams, as is known to the art, and the results obtained with the simple baking operation suggests that the electron beam process may also be used to .cure certain thermosetting polymers.
- organic polymers which are cured by the action of moisture for instance, the moisture cured urethane systems known to the art, is suggested.
- a thermosetting organic polymer e.g. an epoxy, which has an undercatalyzed cure system therein, with a consequential extended pot life. This type of system could function as a simple type of time cure at room temperatures.
- thermoplastic and/or thermosetting polymers in the coating composition will be fused or cured into a film.
- the formation of .a film may be unnecessary and perhaps even undesired. In such situations, it may be necessary only to fuse, for instance, thermoplastic polymer particles to one another.
- the curing or heat treating operation to which the coating compositions is subjected after the electrostatic coating step should convert at least one component of the coating composition into a form which adheres the coating composition, after the electrostatic charge is dissipated, on the substrate.
- a heated substrate can be utilized.
- a heated substrate is not preferred when multiple spray passes are utilized, as the heat from the substrate can fuse or cure the coating material to the point where no further penetration of. various components, e.g. zinc, can be obtained on subsequent passes.
- the baking, or curing, temperature may vary widely,
- the curing temperature will be from about to 1,500F, preferably from 200 to 750F.
- the time required in the bake oven will vary, depending upon the particular temperature utilized, and alsodepending upon the nature of the powder composition.
- the curing temperature may be as short as 10 seconds or even less, and may be as long as several days or even more, but generally such longer cure times are not preferred because of slow production rates and adverse costs caused thereby.
- the cure times will vary from about 1 minute to about 1 hour.
- the temperature-time relationship should be such as to at least partly fuse the thermoplastic powders and/or to at least partly activate, or cure, the thermosetting powders.
- the coating powder moves, under the influence of air pressure, through and from the electrostatic spray gun, it is charged by passing through a high voltage, low amperage field.
- the voltage applied to the spray coating apparatus to produce such field may vary widely, although it is generally preferred to utilize as high a voltage spray is practicably possible.
- the applied voltage was 90,000 volts, which is about the maximum that can be applied with that. particular electrostatic coating equipment.
- Lower voltages may be used, e.g. 30,000 volts, although it is generally preferred to use a voltage of at least 60,000 volts. There is no reason why higher voltages cannot be used if the coating equipment is designed for same.
- the pump and motor pressures can vary considerably, but it has generally been found'suitable to have these pressures about 10 40 lbs per square inch, preferably 25 30 lbs per square inch. Generally, the only adverse effects noted outside the above ranges will be a slower coating rate and some reduction in flow and in the finish gloss appearance of the film.
- the coating composition may also contain conductive non-metals, such as graphite, carbon fibers (whiskers), or the like.
- thermoplastic polymers may be utilized, among which may be mentioned, by way of example, polyethylene and copolymers thereof, polypropylene and copolymers thereof, vinyl resins, nylon and other polyamides, acrylic resins, and the like.
- thermosetting polymers which could be used are powders of polymerizable resins (generally resins which are heat-activated or which are used in conjunction with catalysts) such as epoxys, polyurethanes, polycarbonates, acrylics, crosslinkable vinyl polymers and copolymers and the like.
- the coating composition may also contain inorganic polymers such as silicates, e.g., alkali metal silicates,
- the coating composition of the present invention may be used in the coating composition of the present invention.
- at least one filmforming non-conductive organic polymer either thermoplastic or thermosetting, be included in the coating composition, in an amount of at least 10 percent by weight.
- the coating composition may contain two or three components, and the remaining components are preferably either other nonconductive organic polymers and/or conductive metals.
- the coating composition may contain various fillers or reinforcing agents, such as glass flakes or fibers, or sand or other fine form of silica, or various other fillers commonly used in electrostatic spraying operations.
- Aluminum and bronze are not suitable metal powders for the composition of this invention.
- Aluminum or bronze powders when applied in a composition at a level of about 2 percent by weight or more and in conjunction with an organic polymer, will generally form a metallic layer at the substrate interface. However, upon the subsequent application of heat, the aluminum or the bronze will migrate to the coating surface. The exact mechanism of such migration is not now known, but could be caused by a rapid dissipation of charge, by a leafing effect, by adensity or specific gravity effect, or a combination of these or other factors. In any event, the present invention does not contemplate the use of aluminum or bronze powders as the sole conductive metal powder in the coating compositions of this invention.
- thermosetting polymers for instance, before admixing the polymers with other components such as thermoplastic polymers or metal powders.
- the coating composition of the present invention which produces a plurality of distinct, superimposed layers of coating material on the substrate, may contain one or several conductive metals or nonmetals (as long as the concentration of conductive materials in the final coating composition is such that the may be coating apparatus is not shorted out during operation), one or several thermoplastic polymers, one or several thermosetting polymers, or mixtures thereof.
- the coating composition must contain at least two dissimilar powders, wherein the dissimilar powders have different dielectric constants or degrees of chargeability.
- the dielectric constants of the distinct powders, in the case of non-conductive polymers should vary by at least 0.1 and preferably by at least 0.2.
- epoxy resins generally have a dielectric constant in the neighborhood of 4.0, with polyethylene, polypropylene and acrylic resins having dielectric constants of 2.3, 2.75 and 2.5, respectively.
- the powder may be given either a negative or a positive charge, with the use of a negative charge generally preferred, with the exception of certain polymers, e.g. nylon, to which a positive charge will prefer entially be applied, as known to the art.
- Example I parts by weight of a black epoxy powder, 30 parts by weight of a clear polyethylene powder, 5 parts by weight of zinc dust and 0.15 parts by weight of colloidal silica were dryblended at room temperature until a homogenous blendwas obtained.
- the black epoxy powder (hereinafter sometimes called Black Epoxy Powder No. 3) had the following composition:
- Shell EPON 1004 an by weight epichlorohydrinbisphenol A resin 72 Dicyanamide 2 Dow XD 3540.03 2 amine accelerator Barium sulfate (filler) 23 Carbon black l.8 Monsanto PC 1344,
- the epoxy powder ingredients were dispersed in a high intensity dry blender, thereafter extruded at a temperature of 185-200F, and then reduced to a powder in a hammer mill.
- the resulting powder had the following particle size analysis:
- the Shell EPON 1004 had a Durran softening point of- 95-105, a viscosity (in 40 percent solution in Butyl Carbitol) of 4.6 6.6 poises, an epoxide equivalent (grams of resin containing one gram-equivalent of epoxide) of 875-1 ,025, an epoxide equivalent/100 grams of 0.1 1, and a hydroxyl equivalent/100 grams of 0.34.
- the Dow amine accelerator XD 3540.03 was a free flowing white powder having a total nitrogen content of 63.6 percent by weight.
- the clear polyethylene powder produced by U.S. Industries under the trademark Microthene EN 510 had an average particle size of 12 microns and a density of 0.924.
- the polyethylene appeared to agglomerate with the colloidal silica (which had a particle size of 0.2 microns) which seemed to aid in the chargeability of the polyethylene particles.
- the zinc dust (New Jersey Zinc No. 64) was of galvanizing purity and had an average particle size of 4.8 microns.
- the zinc dust contained 95.7% metallic zinc, 4.2% ZnO, 0.04% Pb, 0.04% Cd, and less than 0.01% Fe. 99.7 percent of the particles passed through a 325 mesh screen.
- the above blended powder composition was sprayed, using a Ransburg Model 322/8446 R-E-PElectrostatic Spray Gun, upon a mild steel panel (6 by 12 by 141 inches) which had been pretreated by shot blasting to provide a 1 mil profile (roughness).
- the spraying was conducted at 78F and 40% RH.
- the voltage applied across the throat of the gun was 90,000 volts and the air pump and the motor pressures of the spray gun were 30 lbs each.
- the steel panel was grounded, and the spray gun was maintained approximately 8 inches from the panel during spraying. An effort was made to maintain only single pass conditions of spraying, with the spray time of approximately 4 seconds, producing an overall coating of about 2 mils on the panel.
- the panel was carefully removed from the spray booth and placed in a bake oven, with an effort made to keep from disturbing the powder adhering to the panel. Th oven was maintained at 300]? for 3 minutes and thereafter the temperature was raised, at a linear rate, for 10 minutes until the oven temperature was 420F. At that point, the panel was removed from the oven and allowed to cool. After cooling, the panel had a generally flat finish, with an essentially clear coat on top overlying a black underlayer.'Zinc could not be visibly detected on the coating surface.
- the coating was scratched and indented and then examined under a microscope (40X). Zinc was detected only at the steel-coating interface.
- the black epoxy and the clear polyethylene were in essentially separate layers over the zinc layer, with the polyethylene layer furthest from the steel panel.
- the three component powder coating composition of this example which is particularly preferred, is attractive for applications wherein a protective coating having size analysis of the resulting epoxy powder was as folexcellent corrosion resistance is required.
- this coating may be used to coat the interior of underground oil or gas pipes.
- the zinc layer produces a galvanized finish on the interior of the pipe, and the epoxy layer overlying the zinc serves to protect the zinc from abrasion, as well as providing an integral coating of high corrosion resistance.
- the polyethylene layer serves as a non-conductor of electrical currents, preventing or minimizing electrolytic corrosion.
- the polyethylene layer provides increased exterior durability, e.g. automobile wheel rims.
- Example II This example was generally similar to Example 1, with the exception that the coating ingredients were applied in two separate spraying operations, with no intermediate baking.
- Example II The Black Epoxy Powder No. 3 (95 parts by weight) and the zinc dust (5 parts by weight) of Example I were sprayed on a steel panel under the spraying conditions described in Example 1. This composition was sprayed for 4 seconds, producing a 2.5 mil coating on the panel. Immediately thereafter, and with no intermediate baking or heating of the panel, a second coating was applied over the first coating. The second coating contained 30 parts by weight of the clear polyethylene powder and 0.15 parts by weight of the colloidal silica of Example I. The polyethylene composition was sprayed on the panel for a total of 5 seconds, producing a 2.0 mil coating.
- the coated panel was placed in an oven having an initial temperature of 300F.
- the temperature was increased at a linear rate for 10 minutes and until the temperature was 420F, at which time the panel was removed from the oven and allowed to cool.
- the panel looked identical to the product of Example 1, and a microscopic examination of a scratched and indented coating also indicated similar results.
- Example 111 The coating powder used in this example had the following composition:
- White Epoxy Powder No. 1 The white epoxy powder (hereinafter sometimes called White Epoxy Powder No. 1) had the following formulation:
- Shell EPON 1004' (similar to that of Example I) 54.4% by weight Dicyanamide 1.3% by weight Amine accelerator (same as Example 1) 1.3% by weight lows:
- the mild steel panel was similar to that of Example I, and the same electrostatic spray gun and spraying conditions were used, except the temperature was 75F and the relative humidity was 42 percent. Immediately after the panel was coated, it was removed from the spray booth, and placed in an oven at 350F for 3 minutes. Thereafter, the oven was rapidly heated to 380F and the panel was held at this temperature for minutes and then removed and allowed to cool. The resulting panelappeared similar in appearance to a panel coated only with White Epoxy Powder No. 1. No zinc was visible on the surface of the panel when examined under a microscope at 40X. One edge of the panel was sanded down and an examination of this edge under a 40X microscope revealed a layer of zinc at the substrate-coating interface.
- the total coating was about 2 mils thick with the zinc layer about 0.2 mil thick.
- the coating of this example could be used in a wide variety of coating apparatus, such as, for instance, as a coating on auto rocker panels, or other auto components, on tubular furniture, shelving, tools, etc., e.g., generally for interior uses, on the interior shell of refrigerators and other household appliances, on off-shore drilling rigs and other applications in marine use, and the like.
- Example IV This example was similar to Example III, except the substrate was a glass panel. The same coating composition was utilized, and the spray conditions were the same as Example Ill.
- the glass panel (6 by 12 inches) was coated with Ransburgs trademarked preparation Ransprep, a colloidal silica composition, which made the glass surface conductive.
- the glass panel was grounded during the epoxy operation.
- the bake schedule used in this example was the same as that used in Example III.
- the panel appeared to be generally similar to the product produced by Example 111.
- An examination of the film surface next to the glass revealed the presence of a continuous zinc layer.
- the outer surface of the coating appeared to be free of zinc when viewed under a 40X microscope.
- Example V This example was similar to Example III except that a larger particle size, and slightly different zinc powder was utilized.
- the coating composition was the same as that used in Example 111, with the exception that the zinc powder (New Jersey Zinc No. 444) had an average particle size of 6.3 microns. 99.3 percent of the zinc passed a 325 mesh screen.
- the zinc powder contained 96.0% metallic zinc, 3.9% ZnO, 0.07% Pb, 0.03% Cd, and less than 0.01% Fe.
- the substrate, spray conditions, and bake schedule were the same as Example III with the exception that the room temperature was 78F and the relative humidity was 40 percent.
- the baked panel had a glossy white appearance, with no zinc visible on the coated surface when viewed under a 40X microscope.
- One edge of the panel was sanded down, and a microscopic examination (40X) of this edge indicated the presence of a zinc layer at the steel-coating interface.
- Example Vl This example was similar to Example V, except that a higher concentration of zinc was used.
- the coating system was of the following composition:
- Example V11 95 parts by weight of a clear epoxy powder and 5 parts by weight of zinc powder (the same as the zinc powder used in Example I) were dry blended at room temperature until a homogenous homogeneous was obtained.
- the clear epoxy powder (hereinafter sometimes called Clear Epoxy Powder No. 2) had the following composition:
- Shell EPON 1004 an by weight epichlorhydrinbisphenol A resin 78.3 Trimellitic dianhydride l 1.7 Stannous octoate 1.4
- the substrate was the same as in Example Ill.
- the spray conditions were the same as Example I", with the exception that the room temperature was F and the relative humidity was 40F.
- a simple bake schedule of 10 minutes at 380F was used. After the baked coated panel had cooled, no zinc could be visibly detected in the epoxy layer.
- the panel had a clear epoxy film overlying the zinc layer which was next to the metal substrate.
- the clear epoxy film was 2 mils in thickness, and the zinc layer was 0.2 mils thick.
- the coating was scratched and indented and then examined under microscope 40X. The zinc layer next to the steel substrate was clearly visible.
- Example Vlll This example relates to a protective coating of polyethylene and zinc applied to a steel substrate.
- the blended powders were applied to a substrate which was similar to that used in Example I.
- the spray conditions were the same as used in Example I.
- the coated panel was baked for 12 minutes in an oven, using an initial temperature of 275F, with the temperature rising, at a linear rate, to 465F at the end of the bake cycle.
- the resulting coating had a slightly textured surface, with a layer of polyethylene overlying a layer of zinc which was adjacent the steel surface.
- the polyethylene layer was about mils thick and the zinc layer was about 0.4 mil thick. It is likely that modification of the above bake schedule would eliminate the textured nature of the coating, if so desired.
- a resulting coating should be useful in a number of applications, including pipe coating, and the coating of metal furniture, fencing, and the like.
- Comparative Example A This example is presented to illustrate that the present invention requires a homogeneous blend of discrete powders.
- Example I 95 parts by weight of clear epoxy powder No. 2 and 5 parts by weight of the zinc powder used in Example I were pebble milled for 16 hours.
- the resulting blended powder appeared to contain agglomerated material, quite likely because of a substantial temperature rise during the pebble milling.
- the powder was electrostatically sprayed upon a steel substrate which was similar to the substrate of Example VII.
- the spraying conditions and the bake schedule were the same as used in Example VII.
- the resulting panel had a 3 mil thick clear coating thereon which contained zinc particles dispersed regularly throughout the film. There was no Stratification of the coating components and no evidence of a continuous layer of zinc.
- this example illustrates that the powders of th different components must be substantially discrete in order to produce a plurality of coating material layers.
- Comparative Examples B and C These examples are presented to illustrate that the use of a conductive metal having a specific gravity below the ranges contemplated by the present invention results in a system wherein the metal migrates to the outer surface of the coating that is, away from the substrate-coating interface.
- Both Examples B and C set forth below involve the coating of solvent washed mild steel panels 4 X 6 X inches, with no preheating.
- the powdered coating composition was sprayed using a Gema Gun, manufactured by Gema A. G., St. Gallen, Switzerland, and distributed by Interrad Corporation, Greenwich, Connecticut.
- the Gema Gun is basically similar to the Ransburg gun used in the preceding examples except the charging electrode is located in the barrel, which is made of plastic/The maximum applied voltage, 52,000 volts, was used in each comparative example.
- the pump and motor pressures were not adjustable on this equipment.
- Comparative Example B A dry blended mixture of a clear epoxy resin powder of less than microns having the following formulation:
- Comparative Example C A dry blended (blended on a roll rack overnight) powder composition consisting of 99.5 percent of the Black Epoxy Powder No. 3 of Example I and 0.5 percent aluminum powder, sold under the trade identification M224 by Alcoa and having an average particle size of 3-30 microns, a density of 2.7 g/c c and a purity of 97 percent, was used in this example.
- the Gema Gun described in Comparative Example A was used in this experiment, and the powder composition was applied to a solvent washed steel panel, 4 X 6 X A inches, with preheating. The composition was sprayed at 8283F and 55-56 percent RH. After coating and before baking, a slight indication of the presence of aluminum was noted on the surface of the panel. After the baking (10 minutes at 400F), the panel had a smooth finish with more aluminum being visible on the surface. The film thickness was 2.8 mils.
- Comparative Example C was repeated, except 2.0 percent aluminum powder was used in the coating composition. After baking, the film which was 2.8 mils thick, was completely silver in color and had a slight roughness. Before baking, the panel appeared similar to those described above.
- Comparative Example C was repeated again, this time with 4.0 percent aluminum powder in the coating composition.
- a film having a coating of 3. 9 mils was obtained which had an extremely rough finish. It was estimated that essentially the total amount of aluminum in the coating composition was on the upper surface of the film, that is, on the side of the film furthest from the substrate.
- a final coated article, or product will have thereon a coating containing superimposed layers of the components of the initial powdered coating composition.
- Such a step might be used wherein an electrostatically applied coating of zinc alone is desired (the zinc alone could not be electrostatically sprayed due to shorting of the electrostatic equipment, but electrostatic spraying might be the only practical method of coating a surface which is in a location difficult to reach).
- a rough guideline will be the strength of the .electrical field through which the powder particles pass in operation of the electrostatic coating apparatus, and the chargeimparted to the conductive substrate (it will be realized that the substrate may merely be grounded,
- a process for applying a corrosion resistant coating comprising a plurality of distinct layers on a conductive substrate, said process comprising electrostatically applying to said substrate a mixture of at least two discrete powders containing up to about 96 percent by weight of one of said powders, said powders selected from the group consisting of:
- the said powders being charged during the electrostatic application, and said substrate having a neutral charge or a charge opposite to that of said powders, whereby said powders stratify in layers on said substrate, and thereafter curing or fusing at least one of said powders, whereby a coating having a plurality of different layers is produced on said substrate.
- said film-forming organic polymer is a mixture of at least one thermoplastic polymer and at least one thermosetting polymer.
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Abstract
Description
Claims (8)
- 2. The process as claimed in claim 1 wherein said mixture contains at least one conductive metal and at least one film-forming non-conductive organic polymer.
- 3. The process as claimed in claim 2, wherein said conductive metal has an average particle size of less than about 50 microns, and is present in said mixture in the amount of about 4 to about 30 percent by weight, and said organic polymer has an average particle size of about 10 to about 300 microns.
- 4. The process as claimed in claim 3, wherein said film-forming organic polymer is a mixture of at least one thermoplastic polymer and at least one thermosetting polymer.
- 5. The process as claimed in claim 4 wherein said powder mixture contains about 5 to about 12 percent by weight of said conductive metal, about 55 to about 75 percent by weight of said thermosetting polymer and about 20 to about 40 percent by weight of said thermoplastic polymer.
- 6. The process as claimed in claim 5 wherein said thermosetting polymer is an epoxy polymer, and said thermoplastic polymer is an ethylene polymer.
- 7. The process as claimed in claim 6 wherein said conductive metal is zinc.
- 8. The process as claimed in claim 6, wherein less than 7 1/2 percent by weight of zinc is in said mixture, based on the total weight of said mixture.
- 9. The process as claimed in claim 8 wherein the average particle size of the zinc is about 4 to about 10 microns.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US19755971A | 1971-01-18 | 1971-01-18 |
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US3770482A true US3770482A (en) | 1973-11-06 |
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US00197559A Expired - Lifetime US3770482A (en) | 1971-01-18 | 1971-01-18 | Electrostatic coating method of applying multilayer coating |
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Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3925580A (en) * | 1973-04-25 | 1975-12-09 | Grow Chemical Corp | Method of spraying a powder paint slurry |
US3926628A (en) * | 1973-05-02 | 1975-12-16 | Fuji Photo Film Co Ltd | Using photoconductive and non-photoconductive powders |
US3937853A (en) * | 1973-07-12 | 1976-02-10 | Anchor Hocking Corporation | Method of making a color decorated, plastic coated glass article |
US3996167A (en) * | 1973-11-09 | 1976-12-07 | Ciba-Geigy Corporation | Antistatic surfaces |
US4244985A (en) * | 1976-04-22 | 1981-01-13 | Armco Inc. | Method of curing thermosetting plastic powder coatings on elongated metallic members |
US4262053A (en) * | 1978-09-19 | 1981-04-14 | Gaf Corporation | Anti-blocking means for dielectric film |
US4381334A (en) * | 1976-11-10 | 1983-04-26 | Pratt & Lambert, Inc. | Zinc-rich powders |
US4565318A (en) * | 1982-09-30 | 1986-01-21 | Canadian Patents & Development Limited | Multi-liquid electrostatic method |
US4670339A (en) * | 1984-06-04 | 1987-06-02 | Advanced Technology Laboratories, Inc. | Electrically conductive thin epoxy bond |
US5000979A (en) * | 1986-03-27 | 1991-03-19 | Avancer Technologies, Inc. | Process for coating a substrate for isolation from hostile environments |
US5334631A (en) * | 1991-07-22 | 1994-08-02 | Akzo N.V. | Powder coating composition containing a resin, a curing agent and zinc |
US5344672A (en) * | 1992-05-14 | 1994-09-06 | Sanderson Plumbing Products, Inc. | Process for producing powder coated plastic product |
US5565240A (en) * | 1992-05-14 | 1996-10-15 | Sanderson Plumbing Products, Inc. | Process for producing powder coated plastic product |
US5795626A (en) * | 1995-04-28 | 1998-08-18 | Innovative Technology Inc. | Coating or ablation applicator with a debris recovery attachment |
US6341420B1 (en) * | 2000-08-02 | 2002-01-29 | Static Control Components, Inc. | Method of manufacturing a developer roller |
US20020088579A1 (en) * | 1998-11-23 | 2002-07-11 | Sven Forsberg | Method of producing a particle or group of particles having a coating of polymers interacting with each other |
US6485550B2 (en) * | 2000-02-17 | 2002-11-26 | Toyographoile Ltd. | Self-sacrifice type metal corrosion inhibitor and a metal corrosion inhibiting method |
US20030211252A1 (en) * | 2002-05-13 | 2003-11-13 | Daniels Evan R. | Method and apparatus for horizontal powder coating |
US6692817B1 (en) | 2000-04-04 | 2004-02-17 | Northrop Grumman Corporation | Apparatus and method for forming a composite structure |
EP1439923A1 (en) * | 2001-11-02 | 2004-07-28 | Static Control Components, Inc. | Method of manufacturing a developer roller |
US6800334B2 (en) * | 2000-02-08 | 2004-10-05 | International Coatings Limited | Powder coating composition incorporating a wax in post-blended form |
US20040237887A1 (en) * | 2002-08-07 | 2004-12-02 | Silver Santandrea | Equipment for preparing for electrostatic painting three-dimensional articles with a predominantly flat extension |
US20080124551A1 (en) * | 2005-02-04 | 2008-05-29 | Basf Aktiengesellschaft | Process For Producing a Water-Absorbing Material Having a Coating of Elastic Filmforming Polymers |
US20080154224A1 (en) * | 2005-02-04 | 2008-06-26 | Basf Aktiengesellschaft | Process for Producing a Water-Absorbing Material Having a Coating of Elastic Filmforming Polymers |
EP2106903A1 (en) * | 2008-02-22 | 2009-10-07 | Hermes Schleifkörper GmbH | Method for scattering friction-inhibiting materials and accompanying device |
US8883264B2 (en) * | 2012-11-01 | 2014-11-11 | Xerox Corporation | Method of powder coating and powder-coated fuser member |
US20160266680A1 (en) * | 2015-03-10 | 2016-09-15 | Xintec Inc. | Chip scale sensing chip package and a manufacturing method thereof |
US20190333664A1 (en) * | 2018-04-27 | 2019-10-31 | Toyota Jidosha Kabushiki Kaisha | Electromagnetic steel sheet |
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US3513012A (en) * | 1963-03-28 | 1970-05-19 | Sames Sa De Machines Electrost | Multilayer coating process |
US3546017A (en) * | 1967-11-07 | 1970-12-08 | Anaconda Wire & Cable Co | Electrodeposition of particulate coating material |
US3607342A (en) * | 1966-11-29 | 1971-09-21 | Fuji Photo Film Co Ltd | Method of development of electrostatic images |
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US2965573A (en) * | 1958-05-02 | 1960-12-20 | Haloid Xerox Inc | Xerographic developer |
US3513012A (en) * | 1963-03-28 | 1970-05-19 | Sames Sa De Machines Electrost | Multilayer coating process |
US3607342A (en) * | 1966-11-29 | 1971-09-21 | Fuji Photo Film Co Ltd | Method of development of electrostatic images |
US3546017A (en) * | 1967-11-07 | 1970-12-08 | Anaconda Wire & Cable Co | Electrodeposition of particulate coating material |
Cited By (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3925580A (en) * | 1973-04-25 | 1975-12-09 | Grow Chemical Corp | Method of spraying a powder paint slurry |
US3926628A (en) * | 1973-05-02 | 1975-12-16 | Fuji Photo Film Co Ltd | Using photoconductive and non-photoconductive powders |
US3937853A (en) * | 1973-07-12 | 1976-02-10 | Anchor Hocking Corporation | Method of making a color decorated, plastic coated glass article |
US3996167A (en) * | 1973-11-09 | 1976-12-07 | Ciba-Geigy Corporation | Antistatic surfaces |
US4244985A (en) * | 1976-04-22 | 1981-01-13 | Armco Inc. | Method of curing thermosetting plastic powder coatings on elongated metallic members |
US4381334A (en) * | 1976-11-10 | 1983-04-26 | Pratt & Lambert, Inc. | Zinc-rich powders |
US4262053A (en) * | 1978-09-19 | 1981-04-14 | Gaf Corporation | Anti-blocking means for dielectric film |
US4565318A (en) * | 1982-09-30 | 1986-01-21 | Canadian Patents & Development Limited | Multi-liquid electrostatic method |
US4670339A (en) * | 1984-06-04 | 1987-06-02 | Advanced Technology Laboratories, Inc. | Electrically conductive thin epoxy bond |
US5000979A (en) * | 1986-03-27 | 1991-03-19 | Avancer Technologies, Inc. | Process for coating a substrate for isolation from hostile environments |
US5334631A (en) * | 1991-07-22 | 1994-08-02 | Akzo N.V. | Powder coating composition containing a resin, a curing agent and zinc |
US5344672A (en) * | 1992-05-14 | 1994-09-06 | Sanderson Plumbing Products, Inc. | Process for producing powder coated plastic product |
US5565240A (en) * | 1992-05-14 | 1996-10-15 | Sanderson Plumbing Products, Inc. | Process for producing powder coated plastic product |
US5795626A (en) * | 1995-04-28 | 1998-08-18 | Innovative Technology Inc. | Coating or ablation applicator with a debris recovery attachment |
US20020088579A1 (en) * | 1998-11-23 | 2002-07-11 | Sven Forsberg | Method of producing a particle or group of particles having a coating of polymers interacting with each other |
US6800334B2 (en) * | 2000-02-08 | 2004-10-05 | International Coatings Limited | Powder coating composition incorporating a wax in post-blended form |
US6485550B2 (en) * | 2000-02-17 | 2002-11-26 | Toyographoile Ltd. | Self-sacrifice type metal corrosion inhibitor and a metal corrosion inhibiting method |
US6692817B1 (en) | 2000-04-04 | 2004-02-17 | Northrop Grumman Corporation | Apparatus and method for forming a composite structure |
US7014883B1 (en) | 2000-04-04 | 2006-03-21 | Northrop Grumman Corporation | Apparatus and method for forming a composite structure |
US6341420B1 (en) * | 2000-08-02 | 2002-01-29 | Static Control Components, Inc. | Method of manufacturing a developer roller |
WO2003043760A1 (en) * | 2000-08-02 | 2003-05-30 | Static Control Components, Inc. | Method of manufacturing a developer roller |
EP1439923A4 (en) * | 2001-11-02 | 2008-09-10 | Static Control Components Inc | Method of manufacturing a developer roller |
EP1439923A1 (en) * | 2001-11-02 | 2004-07-28 | Static Control Components, Inc. | Method of manufacturing a developer roller |
US20030211252A1 (en) * | 2002-05-13 | 2003-11-13 | Daniels Evan R. | Method and apparatus for horizontal powder coating |
US20040237887A1 (en) * | 2002-08-07 | 2004-12-02 | Silver Santandrea | Equipment for preparing for electrostatic painting three-dimensional articles with a predominantly flat extension |
US7051670B2 (en) * | 2002-08-07 | 2006-05-30 | Cefla Soc. Coop. A.R.L. | Equipment for preparing for electrostatic painting three-dimensional articles with a predominantly flat extension |
US20080124551A1 (en) * | 2005-02-04 | 2008-05-29 | Basf Aktiengesellschaft | Process For Producing a Water-Absorbing Material Having a Coating of Elastic Filmforming Polymers |
US20080154224A1 (en) * | 2005-02-04 | 2008-06-26 | Basf Aktiengesellschaft | Process for Producing a Water-Absorbing Material Having a Coating of Elastic Filmforming Polymers |
EP2106903A1 (en) * | 2008-02-22 | 2009-10-07 | Hermes Schleifkörper GmbH | Method for scattering friction-inhibiting materials and accompanying device |
US8883264B2 (en) * | 2012-11-01 | 2014-11-11 | Xerox Corporation | Method of powder coating and powder-coated fuser member |
US20160266680A1 (en) * | 2015-03-10 | 2016-09-15 | Xintec Inc. | Chip scale sensing chip package and a manufacturing method thereof |
US10152180B2 (en) * | 2015-03-10 | 2018-12-11 | Xintec Inc. | Chip scale sensing chip package and a manufacturing method thereof |
US20190333664A1 (en) * | 2018-04-27 | 2019-10-31 | Toyota Jidosha Kabushiki Kaisha | Electromagnetic steel sheet |
US10832841B2 (en) * | 2018-04-27 | 2020-11-10 | Toyota Jidosha Kabushiki Kaisha | Electromagnetic steel sheet |
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