EP1036221B1 - Formulation d'electroplacage et procede de depot de fer par electroplacage directement sur de l'aluminium ou d'alliages d'aluminium - Google Patents

Formulation d'electroplacage et procede de depot de fer par electroplacage directement sur de l'aluminium ou d'alliages d'aluminium Download PDF

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Publication number
EP1036221B1
EP1036221B1 EP99905554A EP99905554A EP1036221B1 EP 1036221 B1 EP1036221 B1 EP 1036221B1 EP 99905554 A EP99905554 A EP 99905554A EP 99905554 A EP99905554 A EP 99905554A EP 1036221 B1 EP1036221 B1 EP 1036221B1
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Prior art keywords
solution
electroplating
activation
iron
aluminum
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EP99905554A
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German (de)
English (en)
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EP1036221A1 (fr
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John A. Cimermancic
Jerold J. Dallman
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Briggs and Stratton Corp
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Briggs and Stratton Corp
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/20—Electroplating: Baths therefor from solutions of iron

Definitions

  • the present invention relates to the plating of aluminum and aluminum alloy substrates, and more particularly to the plating of aluminum and aluminum alloy substrates with iron.
  • the aluminum or aluminum alloy substrate it is desirable to coat the aluminum or aluminum alloy substrate with a dissimilar metal that is harder than aluminum.
  • a dissimilar metal that is harder than aluminum.
  • an undercoating or intermediate layer such as a nickel layer, is plated onto the substrate prior to plating iron onto the intermediate layer in another separate plating bath. See Phan, Column 3, Lines 3-25.
  • the undercoating layer is required to provide a layer to which the subsequently-plated iron layer will adhere. See Phan, Column 3, Lines 16-22.
  • the iron is not directly plated to the aluminium or aluminium alloy substrate, but is instead plated to an undercoating layer of a different metal which has in turn been plated onto the aluminium or aluminium alloy substrate.
  • US Patent No. 4221639 discloses a method of plating a wall surface of an aluminium alloy cylinder with iron, in which method the wall surface is prepared for electroplating by sequentially degreasing, rinsing, pickling, rinsing, zincating, rinsing, copper striking, and further rinsing.
  • the pickling, zincating and copper striking steps are performed in order to obtain a superior adhesion of a hard iron layer which is electrodeposited from an electoplating bath using a cathode current density which is so high that channels are developed in the iron layer which are of a size to receive lubricant and abrasive dust therein in use.
  • the use of an electroplating bath containing 150-250 g/l of metallic iron and 20-50 g/l of boric acid and have a pH of 0.2 to 0.6 g/l is disclosed.
  • the electroplating formulation and process of the current invention unlike the formulations and methods of US 5516419 and US 4221639, employs an iron plating/activating bath which acts as both the chemical activation bath to activate the aluminium or aluminium alloy substrate and acts as the electroplating bath for depositing a hard iron layer directly onto the aluminium or aluminium alloy substrate.
  • an iron plating/activating bath acts as both the chemical activation bath to activate the aluminium or aluminium alloy substrate and acts as the electroplating bath for depositing a hard iron layer directly onto the aluminium or aluminium alloy substrate.
  • no separate activation bath, no transitory layers, and no separate undercoating layers are needed.
  • This formulation and process is very useful for high volume commercial production.
  • the formulation and process reduce the time and expense involved with the electrodeposition of the iron onto aluminium or aluminium alloy substrates.
  • the resulting iron layer has good hardness and adherence to the substrate, and has exceptional wear resistant characteristics.
  • an activation/electroplating bath solution comprising:
  • a method for electroplating an iron layer onto an aluminium or aluminium alloy substrate cathode from an iron containing anode without the use of an undercoating layer comprising the steps of:
  • One feature and advantage of the current invention is to provide an iron plating formulation and method wherein the iron plating solution acts as both the chemical activation solution for the aluminium or aluminium alloy substrate and acts as the electroplating bath for depositing a hard iron layer directly onto the aluminium or aluminium alloy substrate.
  • Another feature and advantage of the current invention is to provide for plating iron directly onto an aluminium or aluminium alloy substrate without the need of a transitory layer to prevent oxidation of the activated surface of the substrate after activation.
  • Another feature and advantage of the current invention is to plate iron directly onto an aluminium or aluminium alloy substrate without the need of an undercoating.
  • Another feature and advantage of the current invention is to provide an iron coating on an aluminium substrate with the thickness of about 0.25 to about 0.6 mils and a micro-hardness up to about 60 Rockwell C that has exceptional adhesion and wear resistance characteristics.
  • Another feature and advantage of the present invention includes providing for removal of impurities that are dissolved in the electroplating bath on a continuous basis without the need to interrupt the electroplating process.
  • the present invention provides an electroplating formulation and process which employs a mixed iron plating bath used to both chemically activate and to electrodeposit a hard iron layer on an aluminum or an aluminum alloy substrate.
  • a mixed iron plating bath used to both chemically activate and to electrodeposit a hard iron layer on an aluminum or an aluminum alloy substrate.
  • the term 'substrate' means any member or component made of or comprising aluminum or aluminum alloy to which the iron layer will be deposited using the formulation and process of the current invention.
  • the substrate is a piston made of aluminum or aluminum alloy that is for use in an internal combustion engine, but other aluminum or aluminum alloy parts, components, or members may be used as the substrate.
  • the substrate is first cleaned using a non-etching cleaning step.
  • This cleaning step removes particulates, oil, grease, or other matter that may be present on the surface of the substrate as a result of previous machining operations or other handling.
  • Many non-etching methods and compositions generally known may be used in this cleaning step.
  • the cleaning step involves immersion of the substrate into a cleaning bath solution for a sufficient amount of time for the cleaning solution to remove particulate, oil, grease, or other matter from the substrate.
  • the cleaning bath solution is preferably maintained at a temperature of about 140°F (60°C), and the substrate is immersed in the cleaning solution for a sufficient amount of time to allow the part to reach the temperature of the cleaning solution, although this is not critical.
  • times for immersion of the substrate in the cleaning solution range from about 15 seconds to about 2 minutes. However, immersion times outside of this range are workable.
  • the cleaning solution is an alkaline cleaning solution.
  • One suitable cleaning solution is commercially available from Deveco Corporation under the trademark DEVECO 232.
  • the substrate After being cleaned in the cleaning step, the substrate is then rinsed in water to remove excess cleaner.
  • the substrate is then etched in an etching step.
  • the etching step removes excess silicon that may be present on the surface of the substrate, and provides a mechanical tooth on the surface of the substrate that allows for an increased adhesion between the surface of the substrate and the iron coating, as will be seen below.
  • the etching step of the current invention involves immersion of the substrate into an etch bath comprising a suitable etching solution.
  • Typical etching solutions include various combinations of sulfuric, hydrochloric, and hydrofluoric acid. Any of the acid etches known to those skilled in the art for removing excess silicon, removing aluminum oxides and providing for a mechanical tooth on the surface of the substrate may be employed as the etching solution. Preferably, an acid containing fluorine is used for the effective removal of excess silicon.
  • One know acid etch which is suitable for use as the etching solution in the current invention comprises about 50% nitric acid, about 10% hydrofluoric acid, and the remainder being water.
  • the substrate is immersed in the etch bath for an amount of time sufficient to provide for the desired etching results.
  • the substrate is immersed in the etch bath for about 10 to about 50 seconds, and more preferable for about 20 to about 40 seconds. After removing the substrate from the etched bath, it is rinsed with water to remove any excess etching solution.
  • the etching step does remove the aluminum oxides from the surface of the substrate, thereby chemically activating the surface of the substrate. It is at this point where previous formulations and methods, such as the process described in the Phan patent, deposit a transitory protective layer to the surface of the substrate to preserve the activation. For example, in the Phan process, a zinc layer was deposited. Additionally, previous formulations and methods, such as that disclosed in Phan, would then plate an intermediate metal layer, such as nickel, to the surface of the substrate, and then plate iron over the intermediate layer.
  • the substrate is rinsed with water. It is likely that an aluminum oxide layer again forms on the surface of the substrate, thereby deactivating the surface.
  • the activation provided by the etching step need not be maintained in the current invention because, as will be seen below, the electroplating solution of the current invention acts as both an activation and the electroplating solution.
  • the substrate is ready for activation and plating.
  • the substrate is immersed in an activation/electroplating bath.
  • the same bath acts as the activation solution to activate the surface of the substrate and as the iron electroplating solution.
  • the bath includes an aqueous, or a water based, activation/electroplating solution of ferrous ions and other necessary components.
  • the activation/electroplating bath includes the following components:
  • the total Fe +2 content of the electroplating bath is from about 1.0 to about 2.15, and most preferably is about 1.8 moles per liter of solution.
  • the anion associated with the Fe +2 ion is sulfamate, because it is believed that the sulfamic acid that is formed in the bath due to the presence of the sulfamate ion performs, at least partially, the activation function as will be seen below.
  • Barrett SIR One suitable source for iron and ferrous sulfamate is a product called Barrett SIR which is commercially available from MacDermid, Incorporated.
  • the bath also includes a reducing agent to maintain iron in the ferrous state.
  • the reducing agent is needed in an amount sufficient to prevent the oxidation of Fe +2 to Fe +3 .
  • Suitable reducing agents include those known in the art which do not have a significant detrimental effect upon the activation/electroplating function of the bath.
  • the reducing agent is selected from the group consisting of glycolic acid, ascorbic acid, sodium bisulfite, sodium metabisulfite, sodium hydrasulfite, sodium hypophosphite, hydrazine, boric acid, and mixtures thereof.
  • the reducing agent includes glycolic acid, and is employed in a concentration ranging from about 0.01 to about 0.10, more preferably about 0.03 to about 0.05, and most preferably about 0.04 percent by volume of the total solution.
  • One suitable reducing agent is commercially available from MacDermid Incorporated under the name SISR. It is thought that SISR includes from about 0.5 to about 1% glycolic acid, from about 0.1 to about 1% carbon, with the remainder being water.
  • Cl - must also be present in the bath.
  • the Cl - anion serves three important functions in the bath. First, Cl - helps to promote the dissolution of the anode. Second, the Cl - provides for increased conductivity within the bath, thereby increasing the efficiency of the electroplating process. Finally, the Cl - helps in the formation of the iron crystalline structure such that the iron is in a martensitic form.
  • the source for the Cl - is generally a chloride salt that is added to the bath.
  • the source of Cl - is selected from the group consisting of sodium chloride, potassium chloride, ammonium chloride, calcium chloride, and mixtures thereof. More preferably, the source of Cl- is pure sodium chloride.
  • the concentration of Cl- in the bath can range from about 0.17 to about 1.02 moles per liter of solution, and may be between about 0.17 and about 0.34 moles per liter of solution.
  • concentration of Cl- ranges from about 0.34 to about 1.00, and most preferably is about 0.68 moles per liter.
  • a wetting agent is employed in the activation/ electroplating bath solution in an amount sufficient to prevent pitting of the electroplating surface by attachment of hydrogen bubbles during electroplating. This is necessary since hydrogen evolution occurs during the iron deposition on the aluminum cathodes.
  • the wetting agent prevents adherence of hydrogen bubbles on the aluminum cathode that would otherwise cause pitting of the aluminum part or cracking of the iron deposit due to embrittlement.
  • wetting agents may be employed in the practice of the present invention.
  • the wetting agent selected should not significantly interfere with the activation or electroplating function of the bath.
  • the wetting agent used is selected from the group consisting of sodium lauryl sulfate, polyethylene glycol, and mixtures thereof. Most preferably, the wetting agent used is sodium lauryl sulfate.
  • a suitable wetting agent is commercially available from MacDermid Incorporated under the name SNAP-L.
  • the wetting agent generally makes up from about 0.1% to about 0.3% of the total bath by volume. Preferably, the wetting agent makes up about 0.2% of the total bath by volume.
  • ammonium ion are employed in the bath.
  • the ammonium ion is thought to contribute to the hardness of the electroplate without sacrificing ductility. It is believed that the additional ammonium ion acts as a grain refiner and thereby helps to form the crystalline structure of the iron coating.
  • the source of the ammonium ion may be any known source of ammonium that will not have a significant detrimental impact upon the function of the bath.
  • the source of ammonium is selected from the group consisting of ammonium sulfamate, ammonium hydroxide, and mixtures thereof. Most preferably, the source of ammonium in ammonium sulfamate.
  • the ammonium concentration in the bath may be in the range of about 0.08 to about 0.55 moles per liter.
  • the ammonium concentration is from about 0.17 to about 0.40, and most preferably about 0.30 moles per liter.
  • boric acid is employed in the bath to increase the hardness of the electroplate.
  • boric acid may be used as a reducing agent.
  • boric acid also acts to increase the hardness of the electroplate.
  • the concentration of boric acid in the solution may be in the range of about 11 to about 26 grams per liter of the total solution.
  • the boric acid concentration is between about 15 and about 22.5, and more preferably is about 18.7 grams per liter of total solution.
  • the iron plating bath may also include appropriate additional agents, such as wetters, brighteners, and stress reducing agents, and other appropriate agents commonly employed in iron plating, to enhance the plating characteristics.
  • a brightener permits the use of higher current densities, which make it possible to plate the part faster.
  • the composition and concentration of such addition agents are well known in the art.
  • the activating/plating bath is preferably maintained at a pH of about 1 to about 4, more preferably from about 1.5 to about 3.5, and most preferably at a pH of about 2.75.
  • the pH of the plating solution appreciably influences the structure and mechanical properties of the iron deposit. Accordingly, this pH range provides the best combination of desired structural and mechanical properties of the iron deposit.
  • the pH is adjusted with one of sulfamic acid, sulfuric acid, or ammonium hydroxide, or combinations thereof, as appropriate. As the plating process proceeds, and the bath is operating properly, the pH tends to rise slowly.
  • sulfamic acid it is preferable to adjust the rising pH by adding sulfamic acid to the bath to maintain the iron sulfamate characteristics, and maintain the activation characteristics of the bath.
  • other acids may be used to adjust the pH downwardly, but the use of sulfamic acid is preferred to maintain these preferred characteristics of the bath.
  • the activating/plating bath is maintained at a normal bath operating temperature that ranges from about 26.7°C (80°F) to about 76.7°C (170°F).
  • the operating temperatures are about 48.9°C (120°F) to about 60°C (140°F), and most preferably about 54.4°C (130°F).
  • the temperature affects the deposition rates and the internal stresses of the iron deposits. Accordingly, the preferred plating temperature ranges provide the best combination of desired deposit rate and reduced internal stresses of the iron deposit.
  • the substrate is immersed in the plating bath and the plating bath acts to remove the aluminum oxide from the surface of the substrate and thereby activate the substrate.
  • the substrate therefore has a surface which is aluminum or aluminum alloy. It is believed that the sulfamic acid that is formed in the bath due to the presence of the sulfamate ion performs, at least partially, the activation function.
  • the substrate is then electroplated in the same tank and with the same electroplating solution as the activation immediately following activation and directly over the activated substrate.
  • the substrate is made the cathode, and an appropriate iron containing anode is used to complete the circuit.
  • any suitable iron containing anode can be employed. Pure iron, and carbon steel cathodes are preferably used. Most preferably, due to cost and availability, the cathode used in the current invention is a carbon steel cathode.
  • the iron electroplating bath is agitated, for example, by stirring, by mechanical agitation, by bubbling inert gas such as nitrogen through the bath, by plating parts rotating in the bath, or by ultrasonic agitation.
  • agitation using air should be avoided, since this results in excessive oxidation of the Fe(II).
  • a current having a current density between about 1.1 to about 13.2 amps/dm 2 (about 10 to about 120 amps per square foot) is applied on the substrate, as cathode.
  • the current density is between about 2.2 and about 11 amps/dm 2 (about 20 and about 100), and most preferably is about 8.8 amps/dm 2 (80 amps per square foot).
  • the preferred ranges of current density provide the best combination of fast plating time consistent with good visual appearance of the iron plate.
  • the iron is plated directly onto the aluminum or aluminum alloy substrate to a thickness of about 0.005 to about 0.05mm (about 0.0002 to about 0.002 inch).
  • the thickness is between about 0.0063 to about 0.0152mm (about 0.000250 to about 0.000600), and more preferably, between about 0.0089 to about 0.01 mm (about 0.00035 to about 0.0004 inch) in thickness so as to achieve high hardness without increasing internal stresses.
  • the dwell time needed to obtain the desired thickness is inversely proportional to the current density used.
  • the dwell time can range from about 4 minutes to about 30 minutes depending upon the current density used and the desired thickness. For example, if a thickness of 0.0089 mm (0.00035 inches) is desired, and a current density of about 11 amp/dm 2 (about 100 amps per square foot) is used, a dwell time of about 4 minutes is needed. Likewise, if a thickness of 0.0089 mm (0.00035 inches) is desired, and a current density of about 20 2.2 amp/dm 2 (amps per square foot) is used, a dwell time of about 30 minutes is needed.
  • the dwell time is about 6 minutes and 45 seconds at a current density of about 8.8 amps/dm 2 (80 amps per square foot).
  • a current density of about 8.8 amps/dm 2 (80 amps per square foot).
  • shorter or longer times at higher or lower current densities, respectively, may be employed in the practice of the invention to obtain the desired thicknesses.
  • faster rates of iron deposition result in higher hardness of the electroplate. This increased hardness is important for substrates such as pistons used in the lawn and garden industry, where engines typically operate at high grit conditions in which the piston is subject to considerably more abrasion than would be found in most automotive applications.
  • this activation/electroplating formulation and process allows the formation of relatively thick iron layers from about 6.35 to about 15.24 ⁇ m (about 0.25 to about 0.6 mils) that have a micro-hardness up to about 60 Rockwell C.
  • the micro-hardness is in the range of about 50 to about 60 Rockwell C.
  • the part is removed from the activation/electroplating bath and rinsed with cold water to remove excess plating solution.
  • the rinse may then be followed by a step wherein a rust inhibiting or protective agent is applied to the iron coated substrate.
  • a rust inhibiting or protective agent is applied to the iron coated substrate.
  • Conventionally known agents and methods for inhibiting rust and protecting the iron may be used in the current invention.
  • the rust inhibiting application step includes immersion of the iron coated substrate in a rust inhibitor solution containing rust inhibiting agents immediately after rinsing.
  • the rust inhibitor solution contains sodium metasilicate, ethanoamine, alcohols, and a surfactant to prevent flash rusting of the active iron deposited on the substrate.
  • One suitable rust inhibiting solution comprises about 97% water and 3% neutralizing rinse mixture, wherein a suitable neutralizing rinse mixture is commercially available from Broco Products Incorporate of Cleveland, Ohio under the trademark V200NC. The preferred neutralizing rinse mixture provides a completely dry to the touch substrate in addition to the rust protection without the use of another flash plating procedure.
  • This preferred rust inhibiting application step is advantageous over the use of oils or other such agents because if such oils are used near the electroplating bath, or while the substrates are still on the electroplating rack, some of the oils may be inadvertently placed into the electroplating bath. Such oils in an electroplating bath may cause operating problems and electroplating defects. Longer term rust protection means such as soluble oils, mineral oils, greases, etc. can be utilized as off line procedures after the iron plated substrate has been removed from the vicinity of the electroplating bath and apparatus.
  • the apparatus usable to perform the current invention of electroplating iron directly onto the substrate using the above discussed formulations and process are apparatus that are generally well known in the art for use in electroplating.
  • the activation/electroplating bath is maintained in a tank that is made of or lined with a material that is resistant to all of the chemicals used in the bath.
  • the tank is lined with a material such as polyvinyl chloride or polypropylene.
  • the tank must be large enough to accommodate the activation/electroplating bath solution, the substrate to be plated, the anode, and any type of support structure that may be used to support or hold the substrate in the bath.
  • the tank for use in the current invention is about 3 407 litres (900 gallons).
  • a support structure such as a support rack or tree is preferably use to support the substrate throughout the activation/electrodeposition process.
  • the shapes and sizes of such support racks/trees usable in the current invention are well known in the art.
  • the support racks/trees are shaped such that when they are supporting the substrates to be plated, the distance between the center of the substrate being plated and the center line of the anode is about 7 inches.
  • the support rack/tree may include current thieves attached thereto.
  • current thieves attached thereto.
  • the function and placement of current thieves are known in the art for use in other electroplating applications, but their use in the electrodeposition of iron, especially the electrodeposition of iron using the current formulation and method, are thought to be new.
  • the form and function of current thieves as know in the art for use in other applications are generally suitable for use in the current invention.
  • the substrates to be plated with iron are generally placed upon the plating rack/tree. Without the current thieves, the substrates mounted on the ends of the rack/tree would generally receive higher current densities than the substrates near the middle of the rack/tree. As the electrodeposition proceeds, the substrates receiving the higher current densities receive a higher rate of iron deposition. Therefore, a thicker final coating of iron will be deposited on the substrates near the ends of the rack/tree in comparison to those in the middle of the rack/tree.
  • the current thieves are used and act to lessen the current densities in the substrates supported on the ends of the rack/tree, thereby substantially equalizing the amount of current running through all of the substrates mounted on a rack/tree.
  • the substantial equalization of the current densities helps to provide a substantially uniform thickness of iron coating among all of the substrates on a single rack/tree.
  • the current thieves are steel plates mounted at the edges of the support rack/tree.
  • metal impurities may be deposited in the bath.
  • Aluminum and copper from the substrate may be dissolved into the electroplating bath and become impurities within the bath. If the aluminum impurities reach a level of about 20 parts per million within the bath, defects begin to be created in the plating process. Additionally, when copper impurities reach a level of about 10 parts per million in the bath, defects begin to be created in the plating process.
  • the copper and aluminum impurities are removed from the bath by a precipitation step.
  • the pH of the bath is purposefully increased to about 5.5 at which point the aluminum and copper ions precipitate out of solution.
  • the solid aluminum and copper can then be removed from the bath.
  • the ion exchange apparatus includes an ion exchange column that is in fluid communication with the tank containing the activation/electroplating bath.
  • the ion exchange column has a first end and a second end. The first end of the column is interconnected with the tank such that the column is in fluid communication with the tank with a first pipe. The second end of the column is interconnected with the tank such that the column is in fluid communication with the tank with a second pipe.
  • the ion exchange column includes an ion exchange resin contained therein.
  • the ion exchange resin is of a type that will perform ion exchange with the copper and aluminum ions present within the activation/electroplating bath.
  • One suitable ion exchange resin is available from Rohm and Hass Company under the trademark IRC-718.
  • the activation/electroplating bath portion is filtered through the ion exchange column, ion exchange occurs to remove the aluminum and copper ions from the bath.
  • the purified bath is then moved from the opposite end of the ion exchange column and returned to the activation/ electroplating bath tank.
  • aluminum alloy pistons for use in internal combustion engines were used as the substrate.
  • a layer of iron was coated directly onto the aluminum alloy surface of the pistons using a method and activation/electroplating bath embodying the current invention.
  • the aluminum alloy pistons were mounted onto a workbar or rack and put through a cleaning step.
  • the pistons were immersed in a non-etching alkaline cleaner, Deveco 232 at a 3% concentration at 140°F for a period of 4 minutes to loosen and remove any soils, chips, soluble oils or coolants from previous machining operations.
  • the pistons were then rinsed thoroughly with water in two air agitated counterflow rinses to remove any residual cleaner.
  • the pistons were then ready for chemical etching and milling of the surface to provide a mechanical "tooth" for the iron plating.
  • the pistons were submerged in the nitric/hydrofluoric acid mixture for a period of 30 seconds to remove any silica that was present and to roughen the surface until a uniform gray-white matted surface was obtained.
  • the acid utilized in the chemical etching was a mixture of seven volumes of 36° Baume' (52.3% nitric acid) and one volume of 70% Hydrofluoric acid operating at room temperature.
  • the pistons were rinsed twice with water in a counterflow rinsing operation before being placed into an activation/electroplating bath.
  • An activation/electroplating bath solution was prepared by incorporating a ferrous sulfamate concentrate product named Barret SIR, a stabilizer named Barrett SISR, a wetting agent named SNAP-L, each of which is commercially available from MacDermid, Incorporated, and ferrous iron, ammonium sulfamate, sodium chloride, and boric acid.
  • a suitable bath tank, anodes, and filtration equipment was cleaned and leached as known in the art.
  • the required amount of water was added to to the tank, and an the pH of the water was reduced to about 2.5 by adding acid.
  • the required quantity of Barrett SIR was diluted with water in the cleaned tank.
  • the necessary amount of boric acid was added, and then necessary amount of SISR stabilizer was added.
  • the system was then heated to operating temperature, and the required amount of ammonium sulfamate and sodium chloride was added. Thereafter, SNAP-L was added in the required amount, and the solution was brought to operating level with water.
  • the pH was adjusted, as necessary, to about 2.5.
  • the solution was then dummied at 0.2 to 0.5 with mild agitation for several hours while maintaining the pH between about 2.5 and about 3.0.
  • the activation/electroplating bath used in this example had an Fe +2 concentration of 74.9 g/l (10 oz/gal) and a pH of 2.75.
  • Glycolic Acid from the SISR stabilizer, was used as a reducing agent at a concentration of 0.3% by volume.
  • Sodium chloride was used as the source of Cl - and was added at a concentration of 41.2 g/l (5.5 oz/gal).
  • Sodium lauryl sulfate, from the SNAP-L was the wetting agent present in the bath in a concentration of about 0.2% by volume.
  • Ammonia sulfamate was used as the source of ammonium, and was present in the solution in a concentration of 33.7 g/l (4.5 oz/gal).
  • Boric acid was present in the solution at a concentration of 18.7 g/l (2.5 oz/gal).
  • the pistons were then placed into the plating bath.
  • the surface of the aluminum alloy pistons was activated by the bath.
  • Voltage was applied to the workbar and the pistons were plated at a cathode current density 7.7 amps/dm 2 of (70 amps per square foot) for a period of 6 minutes and 45 seconds at a temperature of 54.4°C (130°F).
  • the pistons were plated with the aid of "current thieves" mounted on the work bar to maximize the uniformity of plating for all the pistons which ranges form 72 to 120 on the workbar.
  • the bath pH was maintained at about 2.75 while iron concentration in the bath was maintained at about 74.9 g/l (10 oz/gal). Sulfamic acid was used to maintain pH. The iron concentration was maintained by the annode.
  • the concentration of ammonia sulfamate was maintained at about 33.7 g/l (4.5 oz/gal) and the concentration of sodium chloride was maintained at about 41.2 g/l (5.5 oz/gal).
  • the concentration of the glycolic acid was maintained at about 0.3% by volume and the concentration of the boric acid was maintained at about 18.7 g/l (2.5 oz/gal).
  • the bath was filtered continuously through 25 ⁇ m (25 micron) filters at a rate of three bath turnovers per hour as well as the bath being cleaned of contaminants by an ion exchange process that removes the aluminum and copper dissolved in the bath during electroplating.
  • the ion exchange process utilizes a selective ion exchange resin for removal of the aluminum and copper under the acidic conditions present in the bath.
  • a 1-5% cross-linked strong acid resin is used alternately for removal of the aluminum only.
  • the ion exchange resin is regenerated by acid stripping of the contaminants with hydrochloric acid followed by removal of ferric iron on the resin with a mixture of sodium bisulfite/sodium hydrosulfite followed by putting the resin back into the sodium form fully with sodium chloride.
  • the bath is cleaned by adjustment of the pH to 5.5 with ammonium hydroxide to precipitate the aluminum followed by dummying of the bath to remove the copper and other trace metals that may be present.
  • the pistons were removed from the bath and quickly rinsed with water in a 3 stage counterflow rinse operation that removes the residual plating solution from the pistons.
  • the pistons were then immersed in a commercially available neutralizing alkaline cleaner/rust preventer containing sodium metasilicate at 3% concentration at 71.1°C (160°F) for a period of 30 seconds.
  • the pistons were removed from the bath and excess water is allowed to flash dry from the surface of the pistons before removing them from the workbar.
  • a number of the pistons that were electroplated in the above method were then subjected to various tests.
  • One of these tests included a microhardness measurement perpendicular to the thickness of the electroplate.
  • the microhardness of the iron plating measured between about 50 and 57 Rockwell C.
  • Adhesion tests were also conducted.
  • One adhesion test consisted of slowly heating the electroplated piston to 315°C (600°F) followed by quick immersion into cold) 10°C. (50°F) water.
  • the pistons subjected to this test illustrated no significant loss of adhesion of the iron layer on the aluminum alloy piston even when this test is repeated 20 times in succession on the same piston.
  • Another test included endurance testing whereby an electroplated piston was placed in an engine and the engine was operated at rated speed and full load for a period of 500 hours minimum. The plating on the pistons that were plated in the above process withstood the test, and did not wear through, and galling/seizing of the engine did not occur.

Claims (44)

  1. Solution de bain d'activation/électroplaquage comprenant:
    Fe2+ avec une concentration variant d'environ 0,65 à environ 2,5 moles par litre de solution;
    au moins un anion de sulfamate associé à l'ion Fe2+;
    un agent réducteur dans une quantité suffisante pour prévenir l'oxydation de Fe2+ en Fe3+;
    Cl- dans une quantité suffisante pour favoriser la dissolution de l'anode et augmenter la conductivité de la solution;
    un agent mouillant dans une quantité suffisante pour prévenir la formation de piqûres de la surface d'aluminium électroplaquée;
    de l'acide borique dans une quantité suffisante pour augmenter la dureté de ladite couche de fer; et
    des ions ammoniums dans une quantité suffisante pour augmenter la dureté de ladite couche de fer;
    la solution de bain possédant un pH inférieur à 3,5 et la solution de bain étant utilisée pour l'activation d'un substrat de cathode d'aluminium ou d'alliage d'aluminium et pour l'électroplaquage d'une couche de fer directement sur une surface d'aluminium ou d'alliage d'aluminium de ladite cathode à partir d'une anode contenant du fer.
  2. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle l'agent réducteur est choisi dans le groupe constitué d'acide glycolique, d'acide ascorbique, de bisulfite de sodium, de métabisulfite de sodium, d'hydrosulfite de sodium, d'hypophosphite de sodium, d'hydrazine, d'acide borique et de mélanges de ceux-ci.
  3. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle l'agent réducteur inclut de l'acide glycolique avec une concentration variant d'environ 0,01 à environ 0,10 pour-cent en volume de ladite solution.
  4. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle lesdits ions Cl- présentent une concentration comprise entre environ 0,165 et environ 1,00 mole par litre.
  5. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle lesdits ions Cl- présentent une concentration comprise entre environ 0,330 et environ 1,00 mole par litre.
  6. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle la source desdits ions Cl- dans ladite solution est choisie dans le groupe constitué de chlorure de sodium, de chlorure de potassium, de chlorure d'ammonium, de chlorure de calcium et de mélanges de ceux-ci.
  7. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle l'agent mouillant est choisi dans le groupe constitué de sulfate de lauryle de sodium, de polyéthylèneglycol et de mélanges de ceux-ci, et dans laquelle ledit agent mouillant est présent dans une quantité variant d'environ 0,1 à environ 0,3 pour-cent en volume de la solution.
  8. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle l'agent mouillant est du sulfate de lauryle de sodium.
  9. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle l'agent mouillant présente une concentration comprise entre environ 0,1 et environ 0,3 pour-cent en volume de la solution.
  10. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle la concentration dudit acide borique est comprise entre environ 11 et environ 26 grammes par litre.
  11. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle la concentration desdits ions ammoniums est comprise entre environ 0,08 et environ 0,55 mole par litre de solution.
  12. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle la source desdits ions ammoniums dans ladite solution est choisie dans le groupe constitué de sulfamate d'ammonium, d'hydroxyde d'ammonium et de mélanges de ceux-ci.
  13. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle ladite couche de fer possède une micro-dureté d'au moins environ 50 Rockwell C.
  14. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle ladite couche de fer possède une micro-dureté d'au moins environ 55 Rockwell C.
  15. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle le pH de la solution est compris entre environ 1 et environ 4.
  16. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle le pH de la solution est compris entre environ 1,5 et environ 3,5.
  17. Solution de bain d'activation/électroplaquage suivant la revendication 1, dans laquelle le pH de la solution est compris entre environ 1,5 et environ 2,5.
  18. Procédé pour l'électroplaquage d'une couche de fer sur un substrat de cathode d'aluminium ou d'alliage d'aluminium à partir d'une anode contenant du fer sans utilisation d'une couche sous-jacente, ledit procédé comprenant les étapes consistant:
    à fournir la solution de bain d'activation/électroplaquage comprenant:
    Fe2+ avec une concentration variant d'environ 0,65 à environ 2,5 moles par litre de solution;
    au moins un anion de sulfamate associé à l'ion Fe2+;
    un agent réducteur dans une quantité suffisante pour prévenir l'oxydation de Fe2+ en Fe3+;
    Cl- dans une quantité suffisante pour favoriser la dissolution de l'anode et augmenter la conductivité de la solution;
    un agent mouillant dans une quantité suffisante pour prévenir la formation de piqûres de la surface d'aluminium électroplaquée;
    de l'acide borique dans une quantité suffisante pour augmenter la dureté de ladite couche de fer; et
    des ions ammoniums dans une quantité suffisante pour augmenter la dureté de ladite couche de fer;
    à activer ladite surface de ladite cathode en immergeant ladite cathode dans ladite solution;
    à immerger ladite anode dans ladite solution; et
    à électroplaquer ladite couche de fer sur ladite surface activée d'aluminium ou d'alliage d'aluminium de ladite cathode dans ladite solution.
  19. Procédé suivant la revendication 18, dans lequel l'étape d'électroplaquage inclut un électroplaquage à une densité de courant variant d'environ 1,1 à environ 13,2 Amp/dm2 (environ 10 à environ 120 Amp/ft2) pendant un temps d'arrêt suffisant pour déposer ladite couche de fer sur ladite surface à une épaisseur variant d'environ 0,005 à environ 0,05 mm (d'environ 0,0002 à environ 0,002 pouce).
  20. Procédé suivant la revendication 19, dans lequel ladite étape d'électroplaquage inclut un électroplaquage pendant un temps d'arrêt suffisant pour déposer ladite couche de fer sur ladite surface à une épaisseur variant d'environ 0,0089 à environ 0,01 mm (d'environ 0,00035 à environ 0,0004 pouce).
  21. Procédé suivant la revendication 19, dans lequel ladite étape d'électroplaquage inclut un électroplaquage pendant un temps d'arrêt compris entre environ 4 minutes et environ 30 minutes.
  22. Procédé suivant la revendication 18, dans lequel ladite étape d'électroplaquage inclut un électroplaquage de sorte que ladite couche de fer possède une micro-dureté d'au moins environ 50 Rockwell C.
  23. Procédé suivant la revendication 18, dans lequel ladite étape d'électroplaquage inclut un électroplaquage de sorte que ladite couche de fer possède une micro-dureté d'au moins environ 55 Rockwell C.
  24. Procédé suivant la revendication 18, dans lequel ladite étape de fourniture inclut en outre la fourniture dudit acide borique dans une concentration comprise entre environ 11 et environ 26 grammes par litre.
  25. Procédé suivant la revendication 18, dans lequel ladite étape de fourniture inclut en outre la fourniture desdits ions ammoniums dans une concentration comprise entre environ 0,08 et environ 0,55 mole par litre.
  26. Procédé suivant la revendication 18, dans lequel ladite étape de fourniture inclut en outre la fourniture d'une source desdits ions ammoniums dans ladite solution choisie dans le groupe constitué de sulfamate d'ammonium, d'hydroxyde d'ammonium et de mélanges de ceux-ci.
  27. Procédé suivant la revendication 18, dans lequel ladite étape de fourniture inclut en outre la fourniture de l'agent réducteur choisi dans le groupe constitué d'acide glycolique, d'acide ascorbique, de bisulfite de sodium, de métabisulfite de sodium, d'hydrosulfite de sodium, d'hypophosphite de sodium, d'hydrazine, d'acide borique et de mélanges de ceux-ci.
  28. Procédé suivant la revendication 27, dans lequel ladite étape de fourniture inclut la fourniture d'acide glycolique en tant qu'agent réducteur présent dans ladite solution dans une concentration comprise entre environ 0,01 et environ 0,10 pour-cent en volume de ladite solution.
  29. Procédé suivant la revendication 19, dans lequel ladite étape de fourniture inclut en outre la fourniture desdits ions Cl- dans une concentration comprise entre environ 0,165 et 1,00 mole par litre.
  30. Procédé suivant la revendication 18, dans lequel ladite étape de fourniture inclut la fourniture d'un sel de chlorure en tant que source desdits ions Cl- dans ladite solution.
  31. Procédé suivant la revendication 30, dans lequel ladite étape de fourniture inclut la fourniture dudit sel de chlorure parmi le groupe constitué de chlorure de sodium, de chlorure de potassium, de chlorure d'ammonium, de chlorure de calcium et de mélanges de ceux-ci.
  32. Procédé suivant la revendication 18, dans lequel ladite étape de fourniture inclut en outre la fourniture dudit agent mouillant parmi le groupe constitué de sulfate de lauryle de sodium, de polyéthylèneglycol et de mélanges de ceux-ci.
  33. Procédé suivant la revendication 18, dans lequel ladite étape de fourniture inclut la fourniture dudit agent mouillant dans une concentration comprise entre environ 0,1 et environ 0,3 pour-cent en volume de ladite solution.
  34. Procédé suivant la revendication 18, incluant en outre, avant ladite étape d'activation, les étapes consistant:
    à nettoyer ladite cathode; et
    à attaquer (graver) ladite cathode pour donner des dents mécaniques sur la surface de ladite cathode.
  35. Procédé suivant la revendication 18, incluant en outre les étapes consistant:
    à retirer l'anode de ladite solution après ladite étape d'électroplaquage; et
    à appliquer un inhibiteur de rouille sur la couche de fer.
  36. Procédé suivant la revendication 18, incluant en outre, avant ladite étape d'activation, l'étape consistant à monter ladite cathode sur une structure support avec des écrans voleurs de courant attachés sur celle-ci, et dans lequel ladite étape d'électroplaquage inclut un électroplaquage en présence desdits écrans voleurs de courant.
  37. Procédé suivant la revendication 18, incluant en outre l'étape consistant à maintenir le pH de ladite solution entre environ 1 et environ 4 durant l'étape d'électroplaquage.
  38. Procédé suivant la revendication 37, dans lequel ladite étape de maintien inclut l'ajout d'acide sulfamique, d'acide sulfurique ou d'hydroxyde d'ammonium, comme c'est approprié, pour maintenir le pH.
  39. Procédé suivant la revendication 18, dans lequel l'étape de fourniture inclut en outre ladite solution de bain incluant de l'acide sulfamique.
  40. Procédé suivant la revendication 18, incluant en outre une étape consistant à retirer en continu les impuretés provenant de ladite solution durant l'étape d'électroplaquage en utilisant une colonne échangeuse d'ions en communication de fluide avec ladite solution.
  41. Procédé suivant la revendication 40, dans lequel l'étape de retrait en continu des impuretés inclut la fourniture d'une colonne échangeuse d'ions avec une résine échangeuse d'ions sélective pour le retrait d'aluminium et de cuivre.
  42. Procédé suivant la revendication 41, incluant en outre, après ladite étape d'électroplaquage, l'étape consistant à régénérer ladite résine échangeuse d'ions par une rectification acide.
  43. Procédé suivant la revendication 18, incluant en outre, après ladite étape d'électroplaquage, l'étape consistant à précipiter les impuretés à partir de la solution en augmentant le pH de la solution.
  44. Procédé suivant la revendication 18, dans lequel ladite étape d'immersion inclut en outre la fourniture de ladite anode constituée d'acier au carbone.
EP99905554A 1998-03-02 1999-02-01 Formulation d'electroplacage et procede de depot de fer par electroplacage directement sur de l'aluminium ou d'alliages d'aluminium Expired - Lifetime EP1036221B1 (fr)

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US3347698A 1998-03-02 1998-03-02
PCT/US1999/001999 WO1999045178A1 (fr) 1998-03-02 1999-02-01 Formulation d'electroplacage et procede de depot de fer par electroplacage directement sur de l'aluminium ou d'alliages d'aluminium

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10159890A1 (de) * 2001-12-06 2003-07-24 Federal Mogul Burscheid Gmbh Vorbehandlungsprozess für das Beschichten von Aluminiumwerkstoffen

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6284123B1 (en) * 1998-03-02 2001-09-04 Briggs & Stratton Corporation Electroplating formulation and process for plating iron onto aluminum/aluminum alloys
US9770757B2 (en) 2015-08-13 2017-09-26 GM Global Technology Operations LLC Method of making sound interface in overcast bimetal components
CN112429884A (zh) * 2020-12-03 2021-03-02 淮安中顺环保科技有限公司 一种碱性锌镍合金电镀废水的处理方法

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JPS5551162A (en) * 1978-10-09 1980-04-14 Kioritz Corp Cylinder in aluminum alloy and its preparation
DE69226974T2 (de) * 1991-02-18 1999-05-12 Sumitomo Metal Ind Verwendung von plattiertem Aluminiumblech mit verbesserter Punktschweissbarkeit
US5516419A (en) * 1994-05-26 1996-05-14 Hughes Aircraft Company Hard iron plating of aluminum/aluminum alloys using sulfamate/sulfate solutions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10159890A1 (de) * 2001-12-06 2003-07-24 Federal Mogul Burscheid Gmbh Vorbehandlungsprozess für das Beschichten von Aluminiumwerkstoffen
DE10159890B4 (de) * 2001-12-06 2006-02-16 Federal-Mogul Burscheid Gmbh Verfahren für das Beschichten von Aluminiumwerkstoffen mit Funktionsschichten aus Eisen

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DE69900538D1 (de) 2002-01-17

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