US3537895A - Copper and aluminum pickling - Google Patents

Copper and aluminum pickling Download PDF

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US3537895A
US3537895A US668830A US3537895DA US3537895A US 3537895 A US3537895 A US 3537895A US 668830 A US668830 A US 668830A US 3537895D A US3537895D A US 3537895DA US 3537895 A US3537895 A US 3537895A
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copper
solution
acid
pickling
oxide
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Leslie E Lancy
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LANCY LAB
LANCY LAB Inc
Lancy International Inc
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LANCY LAB
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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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C01B15/037—Stabilisation by additives
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/103—Other heavy metals copper or alloys of copper
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/12—Light metals
    • C23G1/125—Light metals aluminium

Definitions

  • This invention relates to the cleaning or pickling of aluminum, copper, copper alloy and copper plated metals and particularly, to the cleaning of surface portions of metal workpieces for removing copper oxides therefrom.
  • a phase of the invention relates to the removal of copper oxides and the brightening of metal as in the form of a plate or strip workpiece which has been processed, for example, by being subjected to a hot treatment, such as a hot rolling operation.
  • a hot treatment such as a hot rolling operation.
  • the purpose is to remove scale and oxides, such that the strip or plate, after being hot rolled, may be suitably conditioned for further forming, such as by cold drawing or cold rolling.
  • cupric oxide There are two types of copper oxides which are recognized as being formed in hot processed copper containing or surfaced members. They are so-called black or cupric oxide (CuO) and red or cuprous oxide (C11 It has been found that the cuprous oxide forms mainly at lower temperatures and represents an intermediate stage in oxide formation. Basically, the dense black scale produced, for example at hot rolling temperatures, is cupric oxide.
  • CuO black or cupric oxide
  • C11 red or cuprous oxide
  • Another disadvantage of a solution of the above type is that it is impossible to remove dissolved copper from the solution through electrolysis, since the chromic salts inhibit cathode deposition of the copper.
  • the acid is not only wasted and neutralized, as required in waste treating the acid before it can be discharged into a sewage system, but the dissolved copper content is lost from the standpoint of simple reclamation or recovery.
  • chromic acid is highly toxic, it contaminates the rinse waters after pickling and the waters also require meticulous 'waste treatment which further adds to the cost of the operation.
  • the invention relates to the provision and use of cleaning or pickling solutions that will enable the obtaining of bright surfaces on copper, copper containing alloy, and aluminum workpieces which are effectively devoid of metal oxides in the nature of copper oxides. It involves the discovery that there is a tendency, even during an acid pickling or cleaning operation, for cuprous copper oxide to form and adhere to the surface of the workpieces.
  • the invention not only eliminates such a normal tendency, but also makes practical and economical the utilization of hydrogen peroxide in a copper cleaning solution by limiting or restricting its breakdown to that which is essential to the cleaning operation and by making it more effective in its use.
  • the cleaning or pickling is accomplished by a new solution composition and utilization of dissolved ingredients that assures a bright metal surface through the agency of simple procedure in an economical manner to assure a bright surface, irrespective of whether copper predominates or is present in minor amounts.
  • Another object of the invention has been to provide a pickling or cleaning solution which will effectively and efiiciently remove all the copper oxides from a metal surface containing copper and which will simplify the procedure and provide an economical operation;
  • Another object of the invention has been to discover the factors which enter into the presence of copper oxides on a copper or copper alloy metal surface and to develop an improved, simplified and economical process for removing them;
  • a further object of the invention has been to devise a process for removing copper oxides from a copper or copper alloy metal surface in accordance with which the dissolved copper content of the pickling or cleaning solution may be economically recovered;
  • a still further object of the invention has been to develop a new and improved solution for removing copper oxides and new and improved procedure employing such solution, in accordance with which the solution may be rejuvenated and will have a substantially continuous useful life;
  • the figure is a somewhat diagrammatic fragmental section illustrating a workpiece with copper oxides thereon.
  • This view shows a typical metal workpiece 10 that is to be processed in accordance with the invention to remove typical adherent cupric oxide platelets 11 and cuprous oxide powder 12. It will be noted that the cupric oxide 11 tends to enclose, entrap or hold the cuprous oxide 12 along the immediate surface area of the workpiece 10.
  • cuprous oxide not only appears on the surface of the metal after its hot treatment, but that there is a tendency for it to increase by progressive formation thereafter. It has been found that while a small quantity of cuprous oxide may be present in the scale film, when the black or cupric oxide scale is dissolved, an additional electrochemical reduction reaction appears to take place which greatly increases the quantity of cuprous oxide dust that remains on the pickled surface. A cuprous oxide dusty coating in the form of a film remains on the pickled copper surface after a sulfuric acid pickle.
  • Table I The equation of Table I indicates that the cupric ion (Cu++) in contact with metallic copper (Cu) will be reduced to a cuprous ion and that the copper metal is oxidized to the cuprous ion. The one electron lost by the metallic copper is received by the cupric ion. The lower part of the equation (plus and minus electrons) indicates that the cupric electron (Cu++) has received an electron and that the metallic copper (Cu) has lost an electron.
  • the metal surface contributes to the formation of the red copper oxide dust, even during the pickling operation, it has been found that it is unnecessary and undesirable to use an oxidizing agent in sufficient concentration to provide measured oxidizing potential. On the other hand, a small quantity or range of content of oxidizer has been found to avoid reduction by the metal surface and to brake or control the formation by the sulfuric acid of red copper oxide dust.
  • a completely clean and bright copper surface has been obtained by either directly pickling or cleaning in an acid solution in accordance with the invention, or by using the solution as a second step after a sulfuric acid pickle has been employed to remove major quantities of cupric oxide scale.
  • the aqueous pickling solution also containing sulfuric acid provides a maximum economy in a two-step operation.
  • the workpiece is subjected to a sulfuric acid, sulfamic acid or equivalent dissolved acid salt (such as NaHSO aqueous pickling solution or bath in one tank.
  • a sulfuric acid, sulfamic acid or equivalent dissolved acid salt such as NaHSO aqueous pickling solution or bath in one tank.
  • the solution contains about 1% to 40% by volume or 1.84% to 55% or 18 to 550 g./l. by weight of the acid (e.g. 1.84 specific gravity concentrated H and, as an optimum, about 10% to 20% by volume or 17% to 31.6% by weight of the acid in water, and is maintained at an operating temperature of about 80 to 180 F.
  • an aqueous solution is prepared containing peroxide and sulfuric acid in accordance with the invention, and then the workpiece is subjected to the solution in a second tank or bath.
  • a solution is prepared of the same sulfuric acid, sulfamic acid or acid salt content as the first solution, but in a maximum amount of about 55% or 550 g./l. and in a minimum amount of about 1.84% by weight or 18 g./l., hydrogen peroxide (H 0 is added thereto Within a low range of concentration of about 0.1 g./l. up to about 50 g./l. by weight and the solution is maintained at about 80 to 150 F.
  • the quantity is so low in the pickling acid solution that its oxidizing potential does not appreciably raise the electrode potential of the sulfuric acid pickling solution containing, for example 2 to 3 ounces per gallon of copper as dissolved cupric sulfate.
  • the solution is capable of providing a clean copper surface, irrespective of the dissolution of the copper during the pickling operation, and without forming new copper oxide on the metal surface.
  • the pickling solution after it is used, will also contain cupric sulfate. It may contain at least about 1 ounce per gallon of copper as sulfate, and the concentration may go up to the solubility limit of about 9 oz./ gal. of copper as sulfate.
  • a sulfuric pickling solution has been employed containing 5% by volume or 8.8% by weight of sulfuric acid and 17.4 g./l. of copper as cupric sulfate.
  • This solution has an electrode potential measured with gold and glass electrodes at F., of 240 millivolts.
  • the electrode potential was found to be -116 mv. which is not in the oxidizing range.
  • the addition of 0.64% hydrogen peroxide (6.4 g./l. of H 0 gave an electrode potential under similar conditions of 60 mv.
  • An addition of 1% hydrogen peroxide (10 g./l. of H 0 under similar conditions gave an electrode potential of 4 mv.
  • the electrode potential went through the positive side at a concentration of about 12 g./l. of H 0 and that with a concentration of 13.2 g./l. of H 0 the potential was +12 mv.
  • a maximum average Working content of about 1.2%.
  • an electrode potential is avoided that is appreciably on the positive side.
  • hydrogen peroxide may be used in amounts of up to about 50 g./l.
  • the invention essentially differs from previous practices where a general oxidizing condition was desired and was effected by the utilization of chromic acid, hypochlorous acid, perborates, persulfates or hydrogen peroxide, with the range of such agents being relatively high, from about 50 to 60 g./ 1. by weight.
  • the relatively minor concentration that has been found effective for the present process depends on the time available for pickling and the temperature used. As an example, a concentration of 10 g./l. of H represents an optimum, if the pickling is conducted at 120 F. and the available time for reaction is only 30 seconds; the maximum of 50 g./l. of H 0 can be used, if the pickling temperature is about 90 F. and the total time available is only 30 seconds.
  • H 0 about .1% or 1 g./l. of H 0 is suflicient for a bright, smut-free pickling at 120 F. with 4 to 5 minutes time.
  • a pickling solution of 8 to 10% by volume or 13.6 to 17% by weight of sulfuric acid, having a copper concentration of about to 40 g./l. by weight as copper sulfate, within a temperature range of about 90 to 120 F.
  • ethylene glycol In addition to fatty acids, other organic stabilizer compounds containing carboxyl or hydroxyl functional groups that carry polar hydrogen atoms and are not sterically hindered either by themselves or other groups, are glycols such as ethylene glycol.
  • An ethylene glycol type of stabilizer has been found to have an even better stabilizing effect than propionic acid for idle or non-operating solutions containing hydrogen peroxide and, especially with a dissolved iron content.
  • Such an iron content normally has a tendency to drive the peroxide out of the solution by catalyzing breakdown of the peroxide.
  • Propionic and other volatile organic acids have an increased Vapor pressure as the temperature of the pickling solution is increased or if increased heat of the pickling action is not quantatively removed.
  • a stabilizing agent such as glycol which is only lost by drag-out, is advantageous.
  • glycol in addition to having the ability of operating at an elevated temperature (such as 120 to F.) and without an unpleasant odor, permits a faster pickling rate with lower peroxide concentrations or a faster pickling rate in the 1 to 2 second range with 2 to 5% hydrogen peroxide concentrations, if a fast pickling rate is desirable. Elevated temperatures tend to increase spontaneous breakdown of the peroxide and increase vapor pressure of the volatile acids, thus leading 'to loss; this is substantially eliminated by the use of a glycol.
  • ethylene glycol which has good characteristics and which falls within the classification of an organic compound having two or more functional groups that carry polar hydrogen atoms and are not sterically hindered either by themselves or other groups, is represented by the formula CH OH-CH -OH.
  • chloral hydrate which has poor characteristics, does not fall within the classification because of its sterically hindered groups; its formula is:
  • a stabilizing agent or compound of the invention may be used in the solution within a range of 1 to g./l. or .1 to 15% by volume, with an optimum range being within 10 to 20 g./l. or 1 to 2% by volume.
  • the following table illustrates the loss or breakdown of hydrogen peroxide under various conditions including those in which the solution contains no dissolved iron and contains dissolved iron and where the solution is heated up to a temperature of about 150 F.
  • the temperature of treatment should be within the range of about 120 to below 150 F., since at 150 and above, the loss tends to increase greatly (see item 10 of Table V).
  • the pickling acid is made up at 1% to 40% by volume or 1.84% to 55% by weight or 18 to 550 g./l. of sulfuric acid added to water to form an aqueous solution, and containing up to 9 02/ gal. by weight of copper as cupric sulfate, and operated at a temperature between about room temperature (80 F.) and 150 F., with hydrogen peroxide added in concentrations within a range of about 1 g./l. to g./l.
  • a pickling time of a few seconds to 5 to 10 minutes and up to about 30 minutes (or by employing the sulfuric acid pickling solution separately and then passing the workpiece into a second inorganic acid solution made up of the specified concentration of peroxide and holding for the specified time), a great improvement is provided in the resultant copper surface. That is, a copper surface as provided in accordance with the invention, will not be covered with the usual red copper oxide smut and will be clean and bright, such that it is highly suitable for subsequent cold working operations.
  • the dust smut is highly disadvantageous in a workpiece that has to be cold drawn, such as by wire or tube drawing, in that the dust is drawn many times into the metal, where it acts as a foreign inclusion to reduce its tensile strength and conductivity and to, in other ways, impair the quality of the finished product. Also considerable tool wear will result from the loose dust in the lubricant.
  • a further advantage of the invention is that the process lends itself easily to a subsequent or continuous electrolytic recovery of copper dissolved during the pickling operation. With the usual oxidizing agents, such as chromic acid, etc., this cannot be done economically. However, with low concentrations of peroxide used in accordance with my invention, electrolytic refining of the copper can be carried out at nearly 100% efiiciency. Assuming a hydrogen peroxide concentration of 0.4% (4 grams per liter), with the pickling process operated at about 100 F., the plating out of the copper can be carried out at approximately 50% efficiency.
  • the small stream continuously going through the electrolytic recovery cell can be cooled down to 90 F.
  • the plating efiiciency will be about 86%
  • Another feature of the invention is that it allows the continuous use of the bright pickling solution, without the necessity for discarding the used pickle, and without incurring the neutralization costs for waste treatment; at the same time, it enables the recovery of dissolved copper metal in an economical manner, as by ordinary electrolysis.
  • the range of concentration of peroxide serves to prevent or inhibit the transformation of cupric oxide to cuprous oxide, and the formation of cuprous oxide from the copper surface of the workpiece.
  • concentration of hydrogen peroxide is critical from the standpoint of assuring the full dissolving of the cuprous oxide carried by the cupric scale, without being sufiicient to give an active oxidizing action and to prevent the inorganic acid from reacting to form additional cuprous oxide.
  • the use of a stabilizer or inhibitor of the invention restrains the natural breakdown of the peroxide and tends to slow it down in the reaction to assure a most effective and economical employment of the peroxide in the solution.
  • the bubbling or moving of air reduces the consumption of the peroxide.
  • air has a cumulative eifect on the peroxide.
  • the lower limit of 0.1 g./l. of peroxide is made practical with the use of air. It has been found that about 1 g./l. of peroxide is a good working content irrespective of whether oxygen gas is or is not employed.
  • an aqueous pickling or cleaning solution containing inorganic sulfuric or sulfamic acid or equivalent sodium acid sulfate salt is employed at a suitable temperature in an effective amount to react with, dissolve and remove the cupric oxide from the surface of the workpiece.
  • Hydrogen peroxide is employed in the solution in a minor but effective amount to enable the inorganic acid to also remove cuprous oxide and dissolve it in the aqueous solution and to do so without forming additional cuprous oxide and to remove both the cupric and cuprous oxides from the surface of the metal workpiece without forming additional cuprous oxide on the surface.
  • An effective but minor amount of a chemical compound in the nature of an organic stabilizer compound containing functional groups that carry polar hydrogen atoms is dissolved in the aqueous solution and utilized to limit or restrain the breakdown of the hydrogen peroxide, which may be termed its natural breakdown, as distinguished from its breakdown under the reactions or its active operation in effecting the cleaning of the workpiece within the solution.
  • fatty acids and salts thereof found effective for the purpose propionic acid and its salts are particularly effective and represent the optimum, and of glycols, ethylene glycol represents the optimum.
  • the first treatment of the workpiece is employed to remove the substantial portion of the cupric oxide from the surface of the workpiece and the second step is employed to remove any remaining cupric oxide and all of the cuprous oxide so as to provide a bright and clean copper-bearing surface on the workpiece.
  • the two-step procedure is preferred where the cupric oxide is in the form of a heavy layer or encrustation. That is, it shortens the time required for the final cleaning step and, in effect, limits the application of the final treating or pickling solution as to time and temperature and the work load which it has to carry, and thus, is more economical of the amount of hydrogen peroxide and inhibiting chemicals which are employed.
  • the copper which is dissolved in the solution of the final step in the form of copper sulfate can be readily removed by a conventional electrolysis procedure and is removed to keep the sulfate content within practical working limits.
  • the bright pickling or cleaning solution of the invention will contain at least about 1.8% by weight or and 18 g./l. and a maximum of about 55% by weight or 550 g./l. of inorganic concentrated acid in the nature of sulfuric acid, sulfamic acid or the equiva lent acid salt (sodium acid sulfate solution); a good working range is about 1.8% to 20% by weight.
  • the hydrogen peroxide will be provided in the solution within a range of about .1 to 50 g./l. or up to 5% by weight, with the solution maintained at an operating temperature of about to F.; a good working range of H 0 is 1 to 15 g./l. for higher copper bearing workpieces and up to 50 g./l. for lower copper bearing workpieces and for fast action on copper or any alloy and aluminum where the copper content of the solution is lower; a good working range of temperature is about 90 F. to 120 F.
  • the solution may, as previously pointed out, have an oxygen containing gas, circulating, bubbling or moving therethrough to enhance the utilization of the hydrogen peroxide, and will have a minimum of about .l% by volume of the organic stabilizer compound dissolved therein.
  • an organic fatty acid such as formic, acetic, butyric, propionic or equivalent salts thereof
  • a good working range for the fatty acid content is about .5 to 15% by volume and for the stabilizer compounds in general is about .1 to by volume.
  • the stabilizer content is critical for controlling or restraining the breakdown of the hydrogen peroxide in the solution and thus, in conserving it and in enhancing its use.
  • a chelating agent is used in the solution in the minimum amount of .1 oz./gal., with about .1 to 6 oz./gal. or 0.75 to 45 g./l. representing a good working range, and with an optimum of about 1 oz./gal.
  • the chelating agent or compound may be of a common type, such as ethylenediaminetetraacetic acid (EDTA), nitrotriacetic acid N(CH COOH) and ethyleneglycolbis (beta-aminoethyl ether)-N, N-tetraacetic acid (HOOCCH the trademarked line of agents CHELON have been found suitable.
  • Chelating agents which are particularly suitable for a copper containing solution are amines, such as monoamines, diamines, or polyamines as, for example, EDTA or its salts as well as mono, di, tri and tetra sodium salts or modified acids, such as for example N- hydroxyethylene diamine triacetates.
  • a particularly useful agent is disodium ethylenediamine tetra acetate.
  • One phase of the invention rests in the discovery that hydrogen peroxide acts in the presence of copper in an aqueous inorganic acid pickling or cleaning solution to prevent the formation of additional cuprous oxide during the dissolution of cupric oxide.
  • Another phase rests in the discovery that hydrogen peroxide can be conserved, stabilized and enhanced in use in an aqueous inorganic acid containing, metal surface treating solution by providing and employing an organic stabilizing compound in the solution within a minimum content of about 0.1% by volume or 1 g./l.
  • a further phase relates to the determination that the flow of oxygen through a hydrogen peroxide containing aqueous cleaning solution is beneficial.
  • a final phase deals with the discovery that the use of a minimum amount of about 0.1 oz./gal. or 0.75 g./l. of a chelating agent in an aqueous hydrogen peroxide solution used for cleaning copper, copper alloy surfaces would enhance brightness of the surfaces and would assure a bright and clean cleaning or surface conditioning of aluminum and copper containing aluminum alloys.
  • salts of the fatty acids reference is made to equivalent quantities of simple water soluble salts of the fatty acids which after dissolution in the sulfuric acid of the pickling or cleaning solution, will form the fatty acids of which they are derivatives.
  • organic stabilizer compounds such as fatty acids
  • .1 to by volume or 1 to 150 g./l. concentrations are of beneficial value in other solutions (such as etching or pickling solutions) employing sulfuric acid and where a hydrogen peroxide concentration in the order of 1% to 6% by weight is to be used.
  • a pickling solution has been employed for removing cuprous and cupric oxides, copper metal or alloys thereof from a workpiece which, in addition to the inorganic sulfuric or sulfamic acid or equivalent sodium acid sulfate salt content in a concentration of about 1% to 40% by volume or 1.8% to 55% by weight 18 to 550 g./l., contains copper in the form of cupric sulfate when cuprous oxides are to be removed, sulfates of any alloying elements that are to be removed, and an effective amount of hydrogen peroxide as an oxidizing agent.
  • an organic stabilizer compound concentration of about .1 to 15% by volume is important from the standpoint of the hydrogen peroxide, independently of the copper oxide control features encountered in the employment of the copper oxide cleaning solution of my invention.
  • a final stage method of fully removing copper oxides from a copper-containing workpiece which comprises: introducing the workpiece into an aqueous cleaning solution containing an inorganic acid of the class consisting of sulfuric acid, sulfamic acid and equivalent acid salt thereof in the nature of sodium acid sulfate within a concentration range of about 18 to 550 g./l. and utilizing it to dissolve cupric oxide from the surface of the workpiece, providing about 1 g./l. to 50 g./l.
  • a dissolved organic stabilizing compound in the aqueous cleaning solution of the class consisting of benzoic, glycolic and propionic acids; glycerine, ethylene and propylene glycols within a range of about 1 to 150 g./l., employing the stabilizing compound to effectively limit the tendency of hydrogen peroxide to break down in the aqueous solution where the solution may attain an operating level at which it has a dissolved iron content of at least 1 g./l.
  • aqueous solution maintained at a temperature within a range of about to F. during the treatment of the workpiece, and retaining the workpiece in the solution until its surface has a cleanness and brightness representing a condition suitable for cold working.
  • dissolved organic stabilizing compound is limited to the class consisting of glycerine, ethylene and propylene glycols.
  • a final stage cleaning-pickling solution for fully removing copper oxides from copper containing workpieces that comprises an aqueous solution containing: an inorganic acid of the class consisting of sulfuric acid, sulfamic acid and equivalent acid salt thereof in a concentration Within a range of about 18 to 550 g./l. for dissolving cupric oxide from the surface of the workpiece, containing hydrogen peroxide within a range of about .1 to 50 g./l.
  • a cleaning-pickling solution as defined in claim 6 which additionally contains in solution a chelating agent within a range of about .75 to 45 g./l.

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4051057A (en) * 1974-12-13 1977-09-27 Harry Ericson Solutions for cleaning surfaces of copper and its alloys
DE2848475A1 (de) * 1977-11-08 1979-05-10 Dart Ind Inc Die aufloesung von metallen
US4233112A (en) * 1979-06-25 1980-11-11 Dart Industries Inc. Dissolution of metals utilizing an aqueous H2 SO4 -H2 O2 -polysulfide etchant
US4233113A (en) * 1979-06-25 1980-11-11 Dart Industries Inc. Dissolution of metals utilizing an aqueous H2 O2 -H2 SO4 -thioamide etchant
US4233111A (en) * 1979-06-25 1980-11-11 Dart Industries Inc. Dissolution of metals utilizing an aqueous H2 SO4 -H2 O2 -3-sulfopropyldithiocarbamate etchant
US4236957A (en) * 1979-06-25 1980-12-02 Dart Industries Inc. Dissolution of metals utilizing an aqueous H2 SOY --H2 O.sub. -mercapto containing heterocyclic nitrogen etchant
US4401509A (en) * 1982-09-07 1983-08-30 Fmc Corporation Composition and process for printed circuit etching using a sulfuric acid solution containing hydrogen peroxide
US4462861A (en) * 1983-11-14 1984-07-31 Shipley Company Inc. Etchant with increased etch rate
US4557894A (en) * 1982-11-25 1985-12-10 Bicc Public Ltd., Co. Friction-actuated extrusion
US4720306A (en) * 1985-04-16 1988-01-19 Kraftwerk Union Aktiengesellschaft Cleaning method
US4754803A (en) * 1987-02-02 1988-07-05 Phelps Dodge Industries, Inc. Manufacturing copper rod by casting, hot rolling and chemically shaving and pickling
US4770808A (en) * 1985-09-05 1988-09-13 Interox Chemicals Limited Stabilization of metal-containing hydrogen peroxide solutions
US4859281A (en) * 1987-06-04 1989-08-22 Pennwalt Corporation Etching of copper and copper bearing alloys
US4946520A (en) * 1987-02-02 1990-08-07 Phelps Dodge Industries, Inc. Copper rod manufactured by casting, hot rolling and chemically shaving and pickling
US5364549A (en) * 1989-10-05 1994-11-15 Interox Chemicals Limited Hydrogen peroxide solutions
US6036835A (en) * 1997-09-24 2000-03-14 Shipley Company, L.L.C. Method of microetching a conductive polymer on multilayer circuit boards
US6126755A (en) * 1996-10-07 2000-10-03 Solvay Interox Limited Metal surface treatment solutions and process
US6803354B2 (en) 2002-08-05 2004-10-12 Henkel Kormanditgesellschaft Auf Aktien Stabilization of hydrogen peroxide in acidic baths for cleaning metals
EP1839330A2 (en) * 2004-12-23 2007-10-03 Lam Research Corporation Cleaning methods for silicon electrode assembly surface contamination removal
EP3045567A1 (en) * 2015-01-16 2016-07-20 Eural Gnutti S.p.A. Method and plant for the production and pickling of aluminum bars
US20160222519A1 (en) * 2013-10-21 2016-08-04 Atotech Deutschland Gmbh Method of selectively treating copper in the presence of further metal
CN106048627A (zh) * 2016-07-05 2016-10-26 太仓市林源电线电缆有限公司 一种铜铝连接线光亮清洗剂
US10745812B2 (en) * 2017-08-24 2020-08-18 The Boeing Company Methods, systems and apparatuses for copper removal from aluminum desmutting solutions

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US4051057A (en) * 1974-12-13 1977-09-27 Harry Ericson Solutions for cleaning surfaces of copper and its alloys
DE2848475A1 (de) * 1977-11-08 1979-05-10 Dart Ind Inc Die aufloesung von metallen
US4233112A (en) * 1979-06-25 1980-11-11 Dart Industries Inc. Dissolution of metals utilizing an aqueous H2 SO4 -H2 O2 -polysulfide etchant
US4233113A (en) * 1979-06-25 1980-11-11 Dart Industries Inc. Dissolution of metals utilizing an aqueous H2 O2 -H2 SO4 -thioamide etchant
US4233111A (en) * 1979-06-25 1980-11-11 Dart Industries Inc. Dissolution of metals utilizing an aqueous H2 SO4 -H2 O2 -3-sulfopropyldithiocarbamate etchant
US4236957A (en) * 1979-06-25 1980-12-02 Dart Industries Inc. Dissolution of metals utilizing an aqueous H2 SOY --H2 O.sub. -mercapto containing heterocyclic nitrogen etchant
US4401509A (en) * 1982-09-07 1983-08-30 Fmc Corporation Composition and process for printed circuit etching using a sulfuric acid solution containing hydrogen peroxide
US4557894A (en) * 1982-11-25 1985-12-10 Bicc Public Ltd., Co. Friction-actuated extrusion
US4462861A (en) * 1983-11-14 1984-07-31 Shipley Company Inc. Etchant with increased etch rate
US4720306A (en) * 1985-04-16 1988-01-19 Kraftwerk Union Aktiengesellschaft Cleaning method
US4770808A (en) * 1985-09-05 1988-09-13 Interox Chemicals Limited Stabilization of metal-containing hydrogen peroxide solutions
US4754803A (en) * 1987-02-02 1988-07-05 Phelps Dodge Industries, Inc. Manufacturing copper rod by casting, hot rolling and chemically shaving and pickling
US4946520A (en) * 1987-02-02 1990-08-07 Phelps Dodge Industries, Inc. Copper rod manufactured by casting, hot rolling and chemically shaving and pickling
US4859281A (en) * 1987-06-04 1989-08-22 Pennwalt Corporation Etching of copper and copper bearing alloys
US5364549A (en) * 1989-10-05 1994-11-15 Interox Chemicals Limited Hydrogen peroxide solutions
US6126755A (en) * 1996-10-07 2000-10-03 Solvay Interox Limited Metal surface treatment solutions and process
US6176937B1 (en) * 1996-10-07 2001-01-23 Solvay Interox Limited Process for treating a metal surface with an acidic solution containing hydrogen peroxide and a stabilizer
US6036835A (en) * 1997-09-24 2000-03-14 Shipley Company, L.L.C. Method of microetching a conductive polymer on multilayer circuit boards
US6803354B2 (en) 2002-08-05 2004-10-12 Henkel Kormanditgesellschaft Auf Aktien Stabilization of hydrogen peroxide in acidic baths for cleaning metals
EP1839330A4 (en) * 2004-12-23 2010-08-25 Lam Res Corp CLEANING PROCESSES FOR REMOVAL OF CONTAMINANTS FROM THE SURFACE OF THE SILICON ELECTRODE ASSEMBLY
EP1839330A2 (en) * 2004-12-23 2007-10-03 Lam Research Corporation Cleaning methods for silicon electrode assembly surface contamination removal
US20160222519A1 (en) * 2013-10-21 2016-08-04 Atotech Deutschland Gmbh Method of selectively treating copper in the presence of further metal
TWI658135B (zh) * 2013-10-21 2019-05-01 德國艾托特克公司 於其他金屬存在下選擇性處理銅的方法
CN113026020A (zh) * 2013-10-21 2021-06-25 德国艾托特克公司 于其它金属存在下选择性处理铜的方法
EP3045567A1 (en) * 2015-01-16 2016-07-20 Eural Gnutti S.p.A. Method and plant for the production and pickling of aluminum bars
CN106048627A (zh) * 2016-07-05 2016-10-26 太仓市林源电线电缆有限公司 一种铜铝连接线光亮清洗剂
US10745812B2 (en) * 2017-08-24 2020-08-18 The Boeing Company Methods, systems and apparatuses for copper removal from aluminum desmutting solutions

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NL6605461A (xx) 1966-10-28

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