WO2004085707A1 - Solution aqueuse de finissage des metaux, procedes applicables au finissage de composants metalliques, systeme pour nettoyer les composants metalliques, et produits en cuivre finis - Google Patents

Solution aqueuse de finissage des metaux, procedes applicables au finissage de composants metalliques, systeme pour nettoyer les composants metalliques, et produits en cuivre finis Download PDF

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Publication number
WO2004085707A1
WO2004085707A1 PCT/US2004/008668 US2004008668W WO2004085707A1 WO 2004085707 A1 WO2004085707 A1 WO 2004085707A1 US 2004008668 W US2004008668 W US 2004008668W WO 2004085707 A1 WO2004085707 A1 WO 2004085707A1
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WO
WIPO (PCT)
Prior art keywords
finishing
solution
metal component
finishing solution
components
Prior art date
Application number
PCT/US2004/008668
Other languages
English (en)
Inventor
George R Vraciu
Original Assignee
Swagelok Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Swagelok Company filed Critical Swagelok Company
Publication of WO2004085707A1 publication Critical patent/WO2004085707A1/fr

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Classifications

    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00—Brightening metals by chemical means
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00—Brightening metals by chemical means
    • C23F3/04—Heavy metals
    • C23F3/06—Heavy metals with acidic solutions
    • 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

Definitions

  • the invention relates to an improved brass bright dip solution and method for finishing brass components, and more specifically to a chromium-free solution and process for finishing brass components.
  • Brass components such as, for example, fittings
  • a finishing solution removes oxides that form along the surfaces of the brass components, thereby reducing corrosion and making the component more stable for clean environments.
  • copper or zinc can be dissolved in the finishing solution at a greater rate, thereby leaving a copper-enriched surface or a zinc-enriched surface. If it is desirable to have a yellow-gold appearance, the finishing solution should dissolve copper at a higher rate than zinc, thereby leaving a zinc-enriched surface. If it is desirable to have more of an orange tint, the finishing solution should dissolve zinc at a higher rate than copper, thereby leaving a copper-enriched surface.
  • the brass bight dip solution is a finishing solution that leaves components with an oxide-free surface with a yellow-gold luster.
  • the method and solution of the present invention is a chromium free process.
  • the finishing solution is an aqueous solution of organic acid, an oxidizing agent, and an oxidization stabilizer.
  • the finishing solution is comprised of an aqueous solution of citric acid, hydrogen peroxide, and a hydrogen peroxide stabilizer.
  • Another aspect of the present invention is an improved method of finishing metal components, such as brass fittings.
  • the improved process employs a single processing tank and only one rinse cycle.
  • the improved method employs less rinse water, only one process fluid to create, monitor and control, and provides an easier treatment of the used rinse water.
  • Figure 1 is a schematic illustration of a brass finishing process incorporating the present invention.
  • the present invention provides a composition for finishing components, specifically brass components, and an improved method for finishing such components. While the description of the invention is generally directed to brass components, such as, for example, a fitting, other types of components can be finished employing the same solution and process. For example, it is contemplated that the composition and process of the present invention can be employed for finishing various copper alloys, such as, for example, bronze and pewter, zinc alloys, tin alloys, nickel alloys and other such alloys. Furthermore, while the invention is generally described herein as a solution, other compositions are possible, such as, for example, dispersions.
  • the finishing solution is generally comprised of an aqueous solution of an organic acid, an oxidizing agent and an oxidant stabilizer.
  • the aqueous solution is formed with deionized water.
  • the organic acid can be any mild organic acid such as, for example, gluconic acid, salicylic acid, citric acid, or mixtures thereof. However citric acid is preferred. It is preferable to use an organic acid with a pH in the working range of about 0.75 to about 1.65.
  • the oxidizing agent is hydrogen peroxide, however other oxidizing agents can be used.
  • Other oxidizing agents that can be used include inorganic acids, such as, for example, nitric acid, sulfuric acid and phosphoric acid.
  • the oxidant stabilizer can be 244 PCM Stabilizer, which is a mixture of p- hydroxy benzenesulfonic acid and sulfuric acid and proprietary ingredients and made by M.F. Good Company, acetanilide, or other comparable components.
  • the finishing solution is comprised of about 150 to about 250 grams per liter organic acid, about 5 to about 8 percent by volume oxidizing agent, about 4 percent to about 7 percent by volume oxidant stabilizer, and the balance water.
  • the finishing solution is comprised of an aqueous solution of citric acid, hydrogen peroxide, and 244 PCM Stabilizer.
  • the solution can comprise about 50 to about 300 grams per liter of citric acid, or as much as about 600 grams per liter, about 1.5 percent to about 30 percent by volume hydrogen peroxide, about 2 percent to about 7 percent by volume 244 PCM Stabilizer, and the balance deionized water.
  • the 244 PCM Stabilizer can be replaced with about 0.02 to about 0.2 grams per liter of acetanilide.
  • the finishing solution comprises about 150 to about 200 grams per liter of citric acid, about 5 percent to about 8 percent by volume hydrogen peroxide, about 4 percent to about 7 percent 244 PCM Stabilizer, and the balance deionized water. More preferably, the solution finishing comprises about 200 grams per liter of citric acid, about 6.5 percent by volume hydrogen peroxide, about 5 percent 244 PCM Stabilizer, and the balance deionized water.
  • the preferred finishing solution mentioned in this disclosure is ideal for creating a bright yellow-gold luster for brass components. By varying the components, such as by providing a solution that dissolves zinc at a higher rate than copper, brass components can be created with an orange luster.
  • this can be achieved by lowering the citric acid below 100 grams per liter or by replacing the citric acid with nitric acid.
  • this solution or other solutions made by varying the components other alloys, such as, for example, bronze or pewter, can also be finished.
  • the finishing solution may conveniently be made by adding citric acid, in crystalline form, to deionized water at room temperature. The mixture is then stirred until all the citric acid crystals dissolve. The hydrogen peroxide stabilizer is then added to the solution. Finally the hydrogen peroxide is added. The solution is then mixed to form a homogenous solution. Similar solutions can be made in a similar fashion.
  • Figure 1 illustrates a convenient way of finishing brass components with the preferred finishing composition described above.
  • the components are dropped into the process tank 10 filled with the finishing solution.
  • grease, oils, soils, and other contaminants can be removed in an alkaline rinse tank 15 prior to placement of the components into the process tank 10.
  • the finishing solution can be maintained any temperature between its boiling and freezing points, although it is most convenient to operate at room temperature.
  • the finishing tank operates at a temperature between about 60°F and about 90°F, and it is even more preferable to operate the finishing tank at a temperature between about 70°F and about 80°F.
  • one or more tumblers 20 can be placed in the process tank 10.
  • tumbler Any type of tumbler can be used provided it tumbles, turns or otherwise agitates the components.
  • the components are submerged in the solution for a time sufficient to remove the oxides, which is typically between about 30 to about 120 seconds, and more typically about 60 seconds, depending on the degree of finishing desired as well as the concentrations of ingredients in the finishing solution.
  • the components are removed from the process tank 10 and rinsed in one or more rinse tanks 30.
  • three counter-flow rinse tanks using deionized water are used, however the number of rinse tanks used can vary depending on the volume, flow, and purity desired.
  • Rinse water from the rinse tanks can directly contact the metal component, thereby avoiding an acid-treatment step.
  • Water from the rise tanks 30 is then transferred to a treatment facility 35 to remove any contaminants prior to recycling of the water.
  • the treatment facility can provide for treatment of the used rinse water in a single step, as opposed to the multiple treatment steps required by the prior art process.
  • the components are then dried, preferably by one or more forced hot air dryers 40.
  • the resulting finished product is a brass component with a bright yellow-gold luster.
  • the surface of the brass component is essentially oxide free and is zinc enriched.

Abstract

La présente invention concerne un procédé de finissage de composants métalliques tels que des accessoires en laiton. Le procédé fait intervenir une solution de finissage généralement constituée d'une solution aqueuse d'acide organique, un oxydant et un stabilisant d'oxydation. En tant que tel, le finissage du composant métallique peut s'effectuer dans un seul bain de traitement et ne nécessite qu'un unique ensemble de bains rinçages. Ce procédé amélioré permet un traitement plus efficace et économique, tout en utilisant une solution de finissage sans chrome.
PCT/US2004/008668 2003-03-21 2004-03-19 Solution aqueuse de finissage des metaux, procedes applicables au finissage de composants metalliques, systeme pour nettoyer les composants metalliques, et produits en cuivre finis WO2004085707A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US32003203P 2003-03-21 2003-03-21
US60/320,032 2003-03-21

Publications (1)

Publication Number Publication Date
WO2004085707A1 true WO2004085707A1 (fr) 2004-10-07

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PCT/US2004/008668 WO2004085707A1 (fr) 2003-03-21 2004-03-19 Solution aqueuse de finissage des metaux, procedes applicables au finissage de composants metalliques, systeme pour nettoyer les composants metalliques, et produits en cuivre finis

Country Status (1)

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WO (1) WO2004085707A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107099804A (zh) * 2017-05-16 2017-08-29 南京工程学院 一种拉拔铜材表面氧化铜酸洗方法及装置

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2154451A (en) * 1934-12-17 1939-04-18 Du Pont Bright dip
GB1209016A (en) * 1969-06-09 1970-10-14 Lancy Lab Chemical brightening of iron-containing surfaces of work pieces
US3556883A (en) * 1967-07-21 1971-01-19 Mitsubishi Edogawa Kagaku Kk Method for chemically polishing copper or copper alloy
US4051057A (en) * 1974-12-13 1977-09-27 Harry Ericson Solutions for cleaning surfaces of copper and its alloys
JPS5616677A (en) * 1979-07-17 1981-02-17 Mitsubishi Gas Chem Co Inc Treatment of metal surface
US4306933A (en) * 1980-02-11 1981-12-22 Chemline Industries Tin/tin-lead stripping solutions
JPS5864385A (ja) * 1981-10-09 1983-04-16 Tipton Mfg Corp 化学研磨併用のバレル研磨法
US4459216A (en) * 1982-05-08 1984-07-10 Mitsubishi Gas Chemical Company, Inc. Chemical dissolving solution for metals
JPS59196385A (ja) * 1983-04-23 1984-11-07 Shinko Electric Ind Co Ltd 化学研摩液
EP0219945A2 (fr) * 1985-09-05 1987-04-29 Solvay Interox Limited Stabilisation de solutions acides de peroxyde d'hydrogène
DE3619881A1 (de) * 1986-06-13 1987-12-17 Wmf Wuerttemberg Metallwaren Verfahren und mittel zur verbesserung der haftfestigkeit eines metallueberzugs auf einem durch spangebende verformung hergestellten, bleihaltigen messing-formkoerper
EP0457859A1 (fr) * 1989-10-05 1991-11-27 Interox Chemicals Ltd Solutions de peroxyde d'hydrogene.
US6126755A (en) * 1996-10-07 2000-10-03 Solvay Interox Limited Metal surface treatment solutions and process

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2154451A (en) * 1934-12-17 1939-04-18 Du Pont Bright dip
US3556883A (en) * 1967-07-21 1971-01-19 Mitsubishi Edogawa Kagaku Kk Method for chemically polishing copper or copper alloy
GB1209016A (en) * 1969-06-09 1970-10-14 Lancy Lab Chemical brightening of iron-containing surfaces of work pieces
US4051057A (en) * 1974-12-13 1977-09-27 Harry Ericson Solutions for cleaning surfaces of copper and its alloys
JPS5616677A (en) * 1979-07-17 1981-02-17 Mitsubishi Gas Chem Co Inc Treatment of metal surface
US4306933A (en) * 1980-02-11 1981-12-22 Chemline Industries Tin/tin-lead stripping solutions
JPS5864385A (ja) * 1981-10-09 1983-04-16 Tipton Mfg Corp 化学研磨併用のバレル研磨法
US4459216A (en) * 1982-05-08 1984-07-10 Mitsubishi Gas Chemical Company, Inc. Chemical dissolving solution for metals
JPS59196385A (ja) * 1983-04-23 1984-11-07 Shinko Electric Ind Co Ltd 化学研摩液
EP0219945A2 (fr) * 1985-09-05 1987-04-29 Solvay Interox Limited Stabilisation de solutions acides de peroxyde d'hydrogène
DE3619881A1 (de) * 1986-06-13 1987-12-17 Wmf Wuerttemberg Metallwaren Verfahren und mittel zur verbesserung der haftfestigkeit eines metallueberzugs auf einem durch spangebende verformung hergestellten, bleihaltigen messing-formkoerper
EP0457859A1 (fr) * 1989-10-05 1991-11-27 Interox Chemicals Ltd Solutions de peroxyde d'hydrogene.
US6126755A (en) * 1996-10-07 2000-10-03 Solvay Interox Limited Metal surface treatment solutions and process

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 198135, Derwent World Patents Index; Class M14, AN 1981-62934D, XP002291503 *
PATENT ABSTRACTS OF JAPAN vol. 0050, no. 67 (C - 053) 7 May 1981 (1981-05-07) *
PATENT ABSTRACTS OF JAPAN vol. 0071, no. 55 (C - 175) 7 July 1983 (1983-07-07) *
PATENT ABSTRACTS OF JAPAN vol. 0090, no. 59 (C - 270) 15 March 1985 (1985-03-15) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107099804A (zh) * 2017-05-16 2017-08-29 南京工程学院 一种拉拔铜材表面氧化铜酸洗方法及装置

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