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WO1997003167A1 - Acides de decapage inhibes contenant des ions chlorure et zinc - Google Patents

Acides de decapage inhibes contenant des ions chlorure et zinc Download PDF

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Publication number
WO1997003167A1
WO1997003167A1 PCT/US1996/011425 US9611425W WO9703167A1 WO 1997003167 A1 WO1997003167 A1 WO 1997003167A1 US 9611425 W US9611425 W US 9611425W WO 9703167 A1 WO9703167 A1 WO 9703167A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
inhibited
pickling composition
workpiece
composition according
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1996/011425
Other languages
English (en)
Inventor
Gerald A. Black
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Corp
Original Assignee
Henkel Corp
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 Henkel Corp filed Critical Henkel Corp
Priority to BR9609785A priority Critical patent/BR9609785A/pt
Priority to AU65433/96A priority patent/AU6543396A/en
Publication of WO1997003167A1 publication Critical patent/WO1997003167A1/fr
Priority to MXPA/A/1998/000363A priority patent/MXPA98000363A/xx
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/061—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors nitrogen-containing compounds

Definitions

  • This invention relates to the treatment of metal surfaces with aqueous acids to re ⁇ move scale and like materials from the surface, a process commonly known in the art as "pickling", and to aqueous liquid pickling compositions used in such processes, that con ⁇ tain both chloride and zinc ions and an inhibitor.
  • Advantageous inhibitors reduce the rate of dissolution of clean metal as much as possible while reducing the rate of dissolution of surface scale and like contaminating materials as little as possible.
  • One common quantitative method of rating inhibitors used in the art, and in this description below, involves measuring the corrosion rate ofthe met ⁇ al to be pickled in a solution containing the type and concentration of acid to be used for pickling, measuring the corrosion rate in a solution otherwise the same except for adding the inhibitor to be used, and then reporting the results as the percent "protection" ofthe inhibitor.
  • any counterions thus implicitly specified pref- erably are selected from among other constituents explicitly specified in ionic form, to the extent possible; otherwise such counterions may
  • the conveying equipment for the steel objects to be galvanized includes chains or other elements that have the form of a continuous band, and therefore are exposed to both the pickling composition used and to the galvanizing stage, and subsequently return to the pickling zone with zinc on their surfaces.
  • Any such zinc present that contacts the liquid pickling composition usually rapidly dissolves, because the pickling inhibitors that are most effective for inhibiting the dissolution of steel often do not inhibit the dissolution of zinc very effectively.
  • a major object of this invention is to pro ⁇ vide a well inhibited, chloride containing pickling composition that can be used on mixed ferrous and zinciferous surfaces without losing its inhibiting character as rapidly as tria ⁇ zine inhibited hydrochloric acid solutions do when so used. It has been found that nitro- gen containing inhibitors, exclusive of those containing a triazine ring in their molecules, are satisfactory for this purpose
  • a pickling composition according to the invention accordingly comprises, prefer ⁇ ably consists essentially of, or more preferably consists of water and (A) chloride anions; (B) zinc cations;
  • a process according to the invention comprises contacting a metal workpiece to be pickled with a working pickling solution according to the invention as described above.
  • a working pickling solution according to the invention as described above.
  • Pickling compositions according to the invention preferably contain chloride ions in a concentration that is at least, with increasing preference in the order given, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0, 18.0, 19.0, or 20.0 % and independently, primarily for reasons of economy and worker safety and comfort, preferably is not more than, with increasing preference in the order given, 50. 40, 35, 30, or 25 %.
  • the preferred source ofthe chlor ⁇ ide ions is hydrochloric acid, because this supplies both chloride and acid, both of which are needed.
  • pickling compositions according to the invention preferably con- tain zinc ions in a concentration that is at least, with increasing preference in the order given, 0.0001, 0.0002, 0.0005, 0.001 , 0.002. 0.005, 0.008, 0.010, 0.020, 0.030, 0.035, 0.040, 0.045, or 0.048 %
  • pickling compositions according to the invention preferably contain nitrogen-containing inhibitor molecules, exclusive of those that have molecular structures including a triazine ring, in a concentration that is at least, with increasing preference in the order given, 0.0001, 0.0002, 0.0005, 0.001, 0.002, 0.005, 0.008, 0.010, 0.020, 0.030, or 0.035 % and independently, primarily for reasons of economy, preferab ⁇ ly is not more than, with increasing preference in the order given, 5, 3, 2, 1, 0.5, 0.2, 0.1, 0.08, 0.060, 0.055, 0.050, 0.045, or 0.040 %.
  • the nitrogenous inhibitor molecules are preferably selected from the group consisting of alkyl pyridines; hexa ⁇ methylene tetramine; abietyl, hydroabietyl, and dihydroabietyl amines and keto substitut ⁇ ed derivatives thereof, most preferably ketonylated rosin amines as described in U. S. Patent 2,975,125 of Mar. 14, 1961 to Saukaitis et al., the entire disclosure of which, to the extent that it describes ketonylated abietyl, hydroabietyl, and dihydroabietyl amines
  • the inhibitors contain both alkyl aryl polyalkyleneamines and hexamethylene tetramine in a ratio that preferably is at least, with increasing preference in the order given, 0.10: 1.0, 0.15: 1.0,
  • a process according to the invention comprises contacting a metal workpiece to be pickled with a working pickling solution according to the invention as described above, preferably at a temperature that is, with increasing preference in the order given, at least 16, 30, or 38 °C and, ifthe scale to be removed is relatively thick, fast pickling is desired, and adequate protection of workers against the fuming tendency ofthe pick ⁇ ling solution at higher temperatures is provided, more preferably is at least, with increas- ing preference in the order given, 52, 60, 66, 70, 74, 78, or 81 °C and independently pref ⁇ erably is, with increasing preference in the order given, not more than 93, 88, or 83, °C, for a time sufficient to remove scale and other bulk oxide coatings from the workpiece surface.
  • the time of contact for most pickling applications preferably is at least, with increasing preference in the order given, 1, 5, 10, 15, 20, or 25 minutes and independently preferably is not more than, with increasing preference in the order given,
  • RODINE® 51 inhibitor shown in Table 1 contains substantial amounts of triazines, while RODINE® 1 150 inhibitor also shown in Table 1 contains no known triazines but does contain alkyl aryl polyalkyleneamines and hexa- methylene tetramine in a ratio of about 0.38:1.0.
  • a sample of rinse water from a commercial galvanizing plant was obtained. This rinse water is used in the plant to make pickling compositions that contain about 10 % of HCl. Tbis rinse water contains iron and zinc cations at levels of at least about 0.03 % each. Furthermore, pickling compositions inhibited with RODINE® 51 inhibitor at this operation, used to pickle steel to prepare it for galvanizing, initially give satisfactory per ⁇ formance when made with fresh tap water, but soon cease to be satisfactory as continued additions of rinse water containing zinc are added, along with additional concentrated hy ⁇ drochloric acid, to make up for operating losses ofthe pickling compositions. The compositions shown in Table 2 below, some using the above noted practical rinse water containing small amounts of iron and zinc, were attempted, to determine whether obvious precipitation would occur.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

Des inhibiteurs contenant un noyau triazine, lesquels ont été largement vantés dans les techniques actuelles comme étant d'excellents inhibiteurs de compositions décapantes à base d'acide chlorhydrique, ne se sont pas révélés efficaces lors d'une utilisation prolongée quand les composition décapantes peuvent dissoudre des quantités importantes d'ions zinc, car l'inhibiteur précipite comme un solide en présence à la fois d'ions zinc et d'ions chlorure. D'autres inhibiteurs de décapants contenant de l'azote ne présentent pas cet inconvénient et fonctionnent de manière efficace, même en présence de zinc. Des combinaisons d'inhibiteurs de polyalkylèneamine d'alkyle aryle et de tétramine d'hexaméthylène sont particulièrement efficaces.
PCT/US1996/011425 1995-07-13 1996-07-12 Acides de decapage inhibes contenant des ions chlorure et zinc Ceased WO1997003167A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BR9609785A BR9609785A (pt) 1995-07-13 1996-07-12 Composição inibida de decapagem e processo
AU65433/96A AU6543396A (en) 1995-07-13 1996-07-12 Inhibited pickling acids containing chloride and zinc ions
MXPA/A/1998/000363A MXPA98000363A (en) 1995-07-13 1998-01-12 Acids of decapar inhibits containing chloride ions and z

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US112495P 1995-07-13 1995-07-13
US60/001,124 1995-07-13

Publications (1)

Publication Number Publication Date
WO1997003167A1 true WO1997003167A1 (fr) 1997-01-30

Family

ID=21694495

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/011425 Ceased WO1997003167A1 (fr) 1995-07-13 1996-07-12 Acides de decapage inhibes contenant des ions chlorure et zinc

Country Status (6)

Country Link
AR (1) AR002819A1 (fr)
AU (1) AU6543396A (fr)
BR (1) BR9609785A (fr)
CA (1) CA2226887A1 (fr)
WO (1) WO1997003167A1 (fr)
ZA (1) ZA965687B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1302154C (zh) * 2004-11-17 2007-02-28 沈阳黎明航空发动机(集团)有限责任公司 高温合金表面铝硅渗层去除液及应用方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US221200A (en) * 1879-11-04 Improvement in galvanizing metal
US1719168A (en) * 1927-01-11 1929-07-02 Vanderbilt Co R T Pickling of metals, etc.
US3686123A (en) * 1971-04-05 1972-08-22 Kurita Industrial Co Ltd Cleaning composition
US3794603A (en) * 1972-01-17 1974-02-26 Sherwin Williams Co Zn++-benzotriazole-h2so4 corrosioninhibitor
JPS57205320A (en) * 1981-06-12 1982-12-16 Tokai Daigaku Formation of needlelike zinc oxide particle
SU1366858A1 (ru) * 1986-07-09 1988-01-15 Уральское Производственно-Техническое Предприятие "Уралэнергочермет" Способ очистки теплообменных поверхностей от накипи
US5084145A (en) * 1989-04-27 1992-01-28 Sumitomo Metal Industries, Ltd. Method for manufacturing one-sided electroplated steel sheet

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US221200A (en) * 1879-11-04 Improvement in galvanizing metal
US1719168A (en) * 1927-01-11 1929-07-02 Vanderbilt Co R T Pickling of metals, etc.
US3686123A (en) * 1971-04-05 1972-08-22 Kurita Industrial Co Ltd Cleaning composition
US3794603A (en) * 1972-01-17 1974-02-26 Sherwin Williams Co Zn++-benzotriazole-h2so4 corrosioninhibitor
JPS57205320A (en) * 1981-06-12 1982-12-16 Tokai Daigaku Formation of needlelike zinc oxide particle
SU1366858A1 (ru) * 1986-07-09 1988-01-15 Уральское Производственно-Техническое Предприятие "Уралэнергочермет" Способ очистки теплообменных поверхностей от накипи
US5084145A (en) * 1989-04-27 1992-01-28 Sumitomo Metal Industries, Ltd. Method for manufacturing one-sided electroplated steel sheet

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE DERWENT WPI ON DIALOG, Accession No. 83-10476K/05, TOKAI DAIGAKU, "Acicular Zinc Oxide Particles Prodn. by Adding Organic Cpd. Forming Base or Acid by Hydrolysis to Aq. Zinc Salt Soln."; & JP,A,57 205 320, 16 December 1982. *
DATABASE DERWENT WPI ON DIALOG, Accession No. 88-219091/31, URALS URALENERGOCHE, "Scale Removal from Heat Exchanger Surfaces - Involves Washing with Soln. Contg. Hydrochloric Acid, Corrosion Inhibitor, Defoamer, Organic Amino-Phosphonate, Zinc Salt and Water"; & SU,A,1 366 858, 15 January 1988. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1302154C (zh) * 2004-11-17 2007-02-28 沈阳黎明航空发动机(集团)有限责任公司 高温合金表面铝硅渗层去除液及应用方法

Also Published As

Publication number Publication date
MX9800363A (es) 1998-07-31
ZA965687B (en) 1997-02-24
AU6543396A (en) 1997-02-10
AR002819A1 (es) 1998-04-29
BR9609785A (pt) 1999-03-09
CA2226887A1 (fr) 1997-01-30

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