Abstract:
Disclosed is a method of electrolytically separating a paint coating front a metal surface comprising the steps of providing a metal member having a surface having a paint coating thereon and contacting the member with an essentially neutral electrolytic solution. The metal member is made cathodic in an electrolytic cell and current is passed from an anode through the electrolytic solution to the metal member for a time sufficient to cause the paint coating to separate from the metal member.

Description:
BACKGROUND OF THE INVENTION 
     This invention relates to paint removal from metal members such as metal parts, objects and structures and more particularly, it relates to electrolytically assisted removal of paint from large structures such as bridge structures, tanks, ships, airplanes, automobiles and the like. 
     Prior methods of removing paint from large metal surfaces such as surfaces of steel bridge structures and holding tanks include abrasive blasting and chemical stripping. However, abrasive methods have the problem that they result in large amounts of the fragmented paint becoming airborne. This is particularly hazardous when the paint contains heavy metal compounds such as lead and chromate. Environmental regulations provide for stringent controls on the amount of metal such as lead that can escape into the atmosphere or onto surface soil and water. Contamination of water such as river water with paint is particularly troublesome because the metals in the paint can find their way into drinking water. To avoid this type of contamination when blasting, for example, attempts have been made to use enclosures around the structures to be blasted. However, such enclosures tend to be awkward and costly to use and often do not contain the abrasive and paint particles sufficiently well. Thus, hazardous quantities of the paint can still escape into the atmosphere and find their way to the soil and drinking water. Another area of concern is in the removal of paint from metal in confined areas, e.g., in the interior of a ship, where neither airborne particles nor fines are acceptable. In addition, abrasive blasting presents occupational hazards, and personnel must be protected from inhaling and contacting toxic paint constituents. Thus, in order to avoid contamination of the environment, abrasive blasting requires expensive precautions in an attempt to comply with environmental and health regulations. In the case of plastic media blasting of aircraft paints, chromate contaminates the blasting media, making disposal an environmental problem. 
     Another approach to removing paint coatings from metal structures involves the use of organic solvents or caustic solutions for chemical stripping. While the solvents can be effective in removing paint, they contaminate the environment upon evaporation and the escape of volatile organic compounds are restricted by law. Further, solvents have the problem of disposal after being used. The use of caustic solutions has the disadvantage that they are hazardous and require long and weather-dependent soak times to be effective. Thus, there is a great need for a system that avoids these problems. 
     In prior work, the use of electrochemical processes has been suggested for cleaning of metals. For example, Dunn U.S. Pat. No. 1,917,022 suggests the use of an electrochemical process for cleaning metal wherein the work is subjected to electrolytic action in a simple non-cyanide alkaline bath in the presence of metallic ions. According to Dunn, the work may be made either anode or cathode and in either case the dirt is subjected to three distinct cleaning actions; namely, the chemical detergent effect of the alkaline solution; the saponification and emulsification effect; and the mechanical action resulting from the liberation of gases at the work surface. Further, Dunn notes that while the metallic ion concentration may be inaugurated and maintained by the addition to the electrolyte of metal salts such as salts of lead, tin, zinc or cadmium, it is preferred to introduce ions by anodic action on the electrodes. According to Dunn, certain metals will have characteristic advantages and disadvantages. In the case of lead, lead peroxide forms at the anode and with the use of tin, metastannic acid forms. However, the Dunn reference has the disadvantage that it requires an alkaline bath and the addition of heavy metal ions such as lead or cadmium, further aggravating the environmental problem. 
     U.S. Pat. No. 3,900,376 discloses cleaning metal surfaces of elongated metal articles such as rods, bars, strips and wire. The metal articles are passed through an electrolyte such that a gas, e.g., hydrogen, is evolved at the metal surface. A high voltage is applied between the article and an inert anode such that the surface of the article in the electrolyte is completely covered by gas and vapor through which a discharge passes. However, the operation has to be carried out in the region of the current minimum of the current/voltage characteristic which occurs beyond the normal electrolysis regime as the voltage is increased. According to the patent, the high voltage and high current density cause substantial heat generation and the surface of the article is covered with a layer containing both hydrogen and steam. The discharge through the gas and vapor layer causes any scale on the article to flake off. 
     U.S. Pat. No. 2,765,267 discloses a process for stripping flexible films of resin which adhere to underlying metal bases to produce unsupported dielectric layers. The insulating layers are removed from the underlying bases by an electrolytic process in which the base metal is made the cathode in an electrolytic cell, and the insulating layer is forced off the base metal by the pressure of gaseous hydrogen at the junction between the metal and insulation, a distinctly different action than used in the present invention. 
     U.S. Pat. No. 3,457,151 discloses cleaning of an article made of conductive and nonconductive materials such as a printed circuit board, in an electrolytic bath and causing a current to flow in the bath between a cathodic element closely adjacent the board and an anodic element. The scrubbing action of the hydrogen bubbles generated at the cathodic element and at the conductive portions of the board cleans all of the surfaces. 
     U.S. Pat. No. 3,823,080 discloses an electrolytic process for removing a coating from a cathode ray tube mask member, and U.S. Pat. No. 4,439,289 discloses an electrolytic method for removal of magnetic coatings from computer memory disc using a sulfuric acid and glycerin solution. 
     ASTM Designation G95-87, &#34;Standard Test Method for Cathodic Disbondment Test of Pipeline Coatings&#34; and ASTM Designation G8-90 &#34;Standard Test Methods for Cathodic Disbonding of Pipeline Coatings&#34; disclose test methods that cover accelerated procedures for simultaneously determining comparative characteristics of insulating coating systems applied to steel pipe exterior for the purpose of preventing or mitigating corrosion that may occur in underground service where the pipe will be in contact with inland soils and may or may not receive cathodic protection. 
     Other electrolytic cleaning methods are disclosed in U.S. Pat. Nos. 4,493,756; 5,104,501 and 5,232,563. However, it will be seen that there is still a great need for a process for removing paint coatings from metal members such as steel structures, automobiles and aircraft, which does not permit contamination of the environment with heavy metal components such as lead or chromium compounds contained in the protective coating. 
     SUMMARY OF THE INVENTION 
     It is an object of the invention to provide an improved process for removing paint coatings from metal surfaces. 
     It is another object of the invention to provide an improved electrolytically assisted process for removing paint coatings from metal surfaces. 
     Yet, it is another object of the invention to provide an improved electrolytic process for removing paint coatings from metal surfaces using an electrolyte with a substantially neutral pH. 
     And yet, it is another object of the invention to provide an improved electrolytic process for removing paint coatings from metal surfaces which avoids contamination of the environment with caustic or organic chemicals or heavy metals contained in airborne paint dust. 
     These and other objects will become apparent from a reading of the specification and claims appended hereto. 
     In accordance with these objects, there is provided a method of electrolytically separating or inducing the separation of a paint coating from a metal surface comprising the steps of providing a metal member having a surface having a paint coating thereon and contacting the member with an electrolyte having a substantially neutral pH. The metal member is made cathodic in an electrolytic cell and a current is passed from an anode through the electrolyte to the metal member for a time sufficient to cause the paint coating to separate or debond from the metal member. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 is a flow chart illustrating steps in the invention. 
     FIG. 2 shows a paint metal substrate having the contacting electrolyte contained in a layer or blanket in contact with the metal substrate. 
    
    
     DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
     The present invention has particular application to water tanks, bridge structures, aircraft and ships because it assures absence of dust emissions which is prevalent with the use of abrasive blasting. Further, the present invention is particularly suitable for removal of paints from such tanks or structures thereby containing the removed paint constituents without fear of contaminating soil, surface water or air with heavy metals such as lead which may be contained in such paint. It will be appreciated that older structures often contain lead in paints and such paints can still be present on such structures even if re-painted since often it was commonplace to paint over the old paint coatings. In the present invention, there is no need for heavy equipment usually attendant the use of abrasive blasting, enclosures to contain the dust inherent in abrasive blasting, or the use of dust masks by personnel conducting the paint removal operation. Further, the present invention is highly suitable for use in confined spaces such as the interior of ships such as Navy ships. 
     Briefly, in the present invention, the metal surface from which paint is to be removed is contacted with an electrolytic solution to set up an electrochemical cell wherein the metal surface is made cathodic. An anode is associated with the electrolytic solution to complete the cell, and current is passed between the anode and cathode for a time sufficient for the paint to delaminate or separate from the metal surface (FIG. 1). 
     For purposes of the present invention, the electrolytic solution can be any water-based electrolytic solution that is compatible with the metal substrate containing the paint coatings to be removed. The pH of the solution can range from very acidic, e.g., pH of 1 or 2, to very alkaline, e.g., pH of 12 or 13. In certain instances, it is preferred that the solution is utilized at a substantially neutral unbuffered pH and does not contain any metals that can be cathodically reduced in appreciable quantities. Thus, the electrolyte of the present invention does not further contaminate the environment by the use of heavy metals and the like. The electrolyte can comprise a material selected from Na 2  SO 4 , K 2  SO 4 , Na 3  PO 4 , K 3  PO 4  and NaCl. Preferably, the electrolyte is comprised of a single salt. While the electrolyte can be highly alkaline, the preferred electrolyte is substantially neutral. Further, preferably, the electrolyte is a chloride-free electrolyte. 
     The material can be present in the electrolytic solution in the range of 0.01 to 3 mols/l and preferably in the range of 0.1 to 0.7 mols/l with a typical amount being about 0.4  to 0.6 mols/l to provide for the required levels of conductivity. 
     Preferably, the electrolytic solution has a substantially neutral pH. However, the electrolytic solution can have a pH in the range of 3 to 10 and preferably a pH in the range of about 5 to 9. Typically, the pH ranges from about 6 to 8. By the term &#34;substantially neutral pH&#34; is meant a pH range of 3 to 10, preferably 5 to 9 and typically 6 to 8. 
     The temperature at which the method can be used can range from -5° to 60° C., but preferably the electrolytic solution is used at or about ambient temperature. Thus, it will be seen that the method has the advantage that it is not sensitive to weather conditions above freezing. 
     While the inventors do not wish to be bound by any theory of invention, it is believed that the separation or debonding of the paint from the metal surface is primarily chemical in nature. The cathodic reaction such as hydrogen evolution causes a localized higher pH which reacts to debond the coating. Debonding is not primarily caused by stirring or other physical action as occasioned by gas evolution. 
     As noted, the metal surface from which the paint coating is separated or delaminated is made the cathode in an electrolytic cell and the paint coating is contacted on the metal surface by the electrolytic solution. Small objects can simply be dipped into such a solution. When the delaminating or debonding of the paint surface of a large object such as a bridge structure, a water tower or ship is required to be performed in situ, the contact of the surface with electrolyte may be accomplished utilizing a blanket 2 (FIG. 2) saturated with electrolytic solution. In FIG. 2, there is shown a painted metal substrate 4 having a pad or blanket 2 in contact therewith. Blanket 2 may be comprised of any absorbent material that can be saturated with electrolytic solution such that electric current can be passed through the electrolyte. Examples of such blanket materials include: SORBX, available from Matarah Industries, Inc., Milwaukee, Wis., or other spill control materials or other &#34;hydrophyllic&#34; blanket materials such as those available from SPC, Somerset, N.J., or sponge mats available from BREG International, Fredericksburg, Va., all referred to herein as blanket material. As shown in FIG. 2, blanket 2 may have a paper or cloth layer 6 permeable by the electrolyte. Further, paper or cloth layer 6 may have a surface thereof coated with an adhesive which contacts the paint coating. Thus, when the paint coating debonds from the metal surface, it becomes firmly attached to the adhesive. After treatment, the paper layer may be removed with paint fragments to be processed for recovery of metals in the paint. Gaps 14 may be incorporated in larger size blankets to facilitate escape of gas, if the cathodic reaction produces gas such as hydrogen. In addition, blanket 2 may be provided with an electrode mesh 8 such as a wire mesh which can serve as an anode. The anode and cathode are connected by electrical connectors 10 to an electric power source 12 which supplies DC current to the electrodes. It is preferred that electrode mesh 8 be comprised of a flexible material to permit blanket 2 to be wrapped around sharp structures such as beams comprising the bridge structure. Blanket 2 may be held in contact with the painted metal surface by any means that permits electrolytic communication with the painted surface. Magnets, retainers or shrink wrapping may be utilized to bring the blanket in contact with the surface. 
     The anode, as noted, may be comprised of any material that permits electrical contact with the electrolyte and passes current to the cathode to preferably evolve oxygen. Thus, the anode may comprise a metal mesh such as a nickel, stainless steel, graphite screen or cloth, titanium or other materials suitable for anodic use. 
     It will be appreciated that a wide range of electrolytes can be used in conjunction with blanket 2 because substantially all of the electrolytic compounds are contained in blanket 2 during the debonding operation. Thus, almost any suitable electrolyte is contemplated for use with blanket 2. Further, the bonding operation can be carried out to remove paint coatings from any metallic substrate, including but not limited to iron, aluminum, copper, magnesium and titanium based alloys. When debonding paint coatings from aluminum, for example, it may be desirable to use an inhibitor in the electrolytic solution in order to prevent attack of aluminum substrate during the debonding operation. 
     When the electrolyte is in contact with the painted metal surface, a current density is passed at a rate that promotes debonding or delamination of the paint coating from the metal surface. Thus, a current density in the range of 100 to 2000 amps/m 2  may be used with a preferred current density being in the range of 500 to 1000 amps/m 2 . 
     The time for which the electric current is applied can vary depending on the paint coating and the difficulty of debonding. Thus, the time for which the electric current is applied is that which causes debonding. Such times can range from 5 to 120 minutes, preferably 5 to 60 minutes. 
     After the paint coating debonds, it can be collected and processed in a controlled manner to permit recovery of heavy metals. 
     While the invention has been described with respect to metal surfaces, it should be understood that the invention can be applied to other conductive members such as graphite, carbon-carbon composites, and carbon-epoxy composites or other electrically conductive materials having paint coatings thereon such as used in aircraft. The invention has a special advantage when used with such conductive materials because of the low temperature of application, for example, not exceeding 100° C. 
     EXAMPLE 1 
     A test strip having fresh automotive polyester melamine paint coating on a steel substrate was provided with parallel scratches about 1/2-inch from each other. The scratches penetrated the coating to expose steel. The scratches were provided for purposes of facilitating the treatment, providing electrical continuity to initiate the hydrolysis. The test strip was partially immersed in an aqueous solution at room temperature containing 56.8 g/l sodium sulfate, the solution having a pH of 5. A platinum electrode (anode) was placed in the electrolyte about 5 cms from the flat surface of the test strip which was made a cathode. Constant current was applied between the anode and test strip at a current density of 132 mA/cm 2  for 40 minutes. Complete debonding of the paint coating from the steel substrate had occurred where the strip was immersed in the solution. 
     EXAMPLE 2 
     For a second test, a rectangular steel tube covered with an aged, incomplete paint coating (rust spots showing) was partially immersed in an aqueous solution containing 0.3M or 42.62 g/L of sodium sulfate. A platinum electrode (anode) was placed in the solution at room temperature about 3 cms from the steel tube surface, with the steel tube being connected as the cathode. Constant direct current was applied between the anode and the steel tube at an average current density of approximately 38 mA/cm 2  (constant voltage of 35 V) for 30 minutes. The paint coating was completely debonded from the surface of the steel tube. After the electrolytic treatment, rust spots were converted to a black-colored substance. 
     EXAMPLE 3 
     In the third example, a steel substrate having a thick, newly prepared, lead-containing primer coating was covered with a pad soaked with solution containing 0.4M sodium sulfate (pH of 5). A nickel screen was pressed against the pad on the primer coating utilizing magnets. The nickel screen was made the anode and steel substrate was made the cathode. A direct electrical current was applied between the nickel screen and the steel substrate at a current density of 66 mA/cm 2 . After applying the electrical current for 20 minutes, the pad was replaced and the current applied for an additional 20 minutes. After this time period, the primer coating had completely debonded. 
     EXAMPLE 4 
     In a fourth example, a phosphated steel substrate covered with an automotive polyester melamine paint coating was covered with a SORBX2 pad (Matarah Industries) soaked with a 0.4M sodium sulfate solution (pH of 5). A nickel screen was pressed against the pad layer on the paint coating utilizing magnets. The nickel screen was made the anode and the steel substrate was made the cathode. A direct electrical current was applied between the nickel screen and the steel substrate at a current density of 66 mA/cm 2 . After applying the electrical current for 30 minutes, the paint coating had completely debonded. 
     Thus, it will be seen from the examples that paint coatings can be removed effectively from metal substrates providing a paint-free metal surface. The paint fragments are easily collected for proper disposal. 
     While the invention has been described in terms of preferred embodiments, the claims appended hereto are intended to encompass other embodiments which fall within the spirit of the invention.