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US1780594A - Acid treatment of metal articles - Google Patents

Acid treatment of metal articles Download PDF

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Publication number
US1780594A
US1780594A US398505A US39850529A US1780594A US 1780594 A US1780594 A US 1780594A US 398505 A US398505 A US 398505A US 39850529 A US39850529 A US 39850529A US 1780594 A US1780594 A US 1780594A
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US
United States
Prior art keywords
acid
metal articles
acid treatment
thio
metal
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.)
Expired - Lifetime
Application number
US398505A
Inventor
Ralph E Lawrence
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.)
Grasselli Chemical Co
Original Assignee
Grasselli Chemical Co
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 Grasselli Chemical Co filed Critical Grasselli Chemical Co
Priority to US398505A priority Critical patent/US1780594A/en
Priority to GB30127/30A priority patent/GB357387A/en
Application granted granted Critical
Publication of US1780594A publication Critical patent/US1780594A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08Iron or steel
    • C23G1/088Iron or steel solutions containing organic acids
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/065Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors sulfur-containing compounds

Definitions

  • non-oxidizing acids are used in different concentrations and under difierent conditions in metal pickling and cleaning operations.
  • the application of my invention to these operations does not necessitate the composition of any material change in the acid baths therein, except the addition to such baths of small amounts of my inhibitors.
  • amounts of A; of 1%, or less of a thioglycollic acid or its derivative is suflicient to insure a far going protection of the metal against attack, or corrosion of the metal itself without affecting the dissolution of acid soluble incrustations on the articles.
  • Some of my novel inhibitors are difficulty soluble in the dilute acid baths used and it is therefor necessary to provide for a uniform distribution of the inhibitor finelydivided form.
  • Tt is a so p 0 mix thmiibitdr'first with a retest; e colloid and -foaming agent.
  • e colloid and -foaming agent When such compounded inhibitors are added to the dilute ,acid they will precipitate uniformly and in fine suspension and insure their' nid'sf'figcientaction.
  • Th-Ffiiciency of inhibitors is conveniently determined by laboratory tests involving the measurement under comparative conditions of the gas evolved from a standard piece of steel immersed in dilute sulfuric acid containing various amounts of the inhibitor.
  • composition of matter for pickling and cleaning metal articles comprising a dian inhibitor of the class of substances comprising thio-glycollic acid and its derivatives containing the radical COOH-CH S.
  • composition of matter for pickling and cleaning metal articles comprising a dilute non-oxidizing acid and a small amount of an inhibitor of the class of substances comprising thio-glycollic acid and its derivatives containing the radical COOHCH finelydispersed throughout said acid.

Landscapes

  • 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)

Description

Patented Nov. 4, 193 b UNITED STATES Examine PATENT OFFICE RALPH E. LAWRENCE, OF
WICKLHFE, OHIO, ASSIGNOR TO THE GRASSELLI CHEMICAL COMPANY, OF CLEVELAND, OHIO, A CORPORATION OF DELAWARE ACID TREATMENT OI METAL ARTICLES Io Drawing.
ooon-ou -s-ri,
It forms easily thio st ers for instance, eth ylt hioglycollic' acid the action of chloracetic adid upon sodium sulfid forms ETCldZ -ooon on. -sson.-ooon,
and this latter, in common with most organic compounds having an S atom between E two C atoms, forms polysulfides by addition of sulfur to the S between the carbon atoms; these compounds are characterized by having in common the same radical:
coon-on.-s,
and it seems that this radical is, in this class of substances, the determining factor in developing the inhibiting property. As a matter of fact thio-glycollic acid, its salts and es -,thio-di-glycollic acid, s, etc., poly-thio-glycollic acids and; similar substances containing in their molecule the radical CO OH--GHz-S display to a varying, and in some instances to a very marked degree, the property of inhibiting the action of acids upon metals.
It is at the present'time understood that the action of the inhibitors generally func- 50 tions mainly in relation to the hydrogen ion throughout the bath in a Application filed October 9, 1929. Serial No. 898,505.
of an acid bath and is practically independent of the anion; this is also believed to be true with the novel inhibitors of my present invention, as I found that the thioglycollic acid and its derivatives display ttdieir inhibiiting afitiondwith various non-ox- 1 izing aci s, suc, as ilute sulfuric hydrochloric, acetic etc., acids, solutions of acid sill fates, e c., acid metal cleaning operations.
Various non-oxidizing acids are used in different concentrations and under difierent conditions in metal pickling and cleaning operations. The application of my invention to these operations does not necessitate the composition of any material change in the acid baths therein, except the addition to such baths of small amounts of my inhibitors. As a rule amounts of A; of 1%, or less of a thioglycollic acid or its derivative is suflicient to insure a far going protection of the metal against attack, or corrosion of the metal itself without affecting the dissolution of acid soluble incrustations on the articles. Some of my novel inhibitors are difficulty soluble in the dilute acid baths used and it is therefor necessary to provide for a uniform distribution of the inhibitor finelydivided form. This is easily achieved by adding it in the form of a water soluble salt or mixing it first W such as suIfur1c. Tt isa so p 0 mix thmiibitdr'first with a retest; e colloid and -foaming agent. Whensuch compounded inhibitors are added to the dilute ,acid they will precipitate uniformly and in fine suspension and insure their' nid'sf'figcientaction.
Th-Ffiiciency of inhibitors is conveniently determined by laboratory tests involving the measurement under comparative conditions of the gas evolved from a standard piece of steel immersed in dilute sulfuric acid containing various amounts of the inhibitor.
The results tabulated below have been obtained from pieces of black, mild steel sheet of about 8 square inches Sui famed at room temperature in 34% sulfuric acid and give the amount of gas evolved in cc.
which are commonly used in Amount of inhibitor 0. 0. 1% 0.05%
- I I I I Hours otimmersion 1 2 6.20 1 2 6, 2o Tbioglycollic acid 3063'; 121; aso Ethy -thio'glyco11ic acid. 3 8 3 4 3 7| 20; 80 5 hio-diglyoollic acid 150, 195 850 Poly-thioglycollic acid 34 60, 200 350 Same am dispersed in 00 B. l
sulfuric acid I s 11 40,57
The evolution of gas in a blank test containing no inhibitor was already considerably more than 400 cc. after 6 hours immersion.
claim: 1. In a process of pickling and cleaning metal articles which comprises subjecting said 15 articles to an acid bath containing as the active pickling and cleaning ingredient a nonoxidizing acid, the step of inhibiting the action of said acid upon the metal by the in corporation into said acid of an inhibitor of the class of substances comprising thio-glycollic acid and its derivatives containing the radical COOHCH S.
2. In a process of pickling and cleaning metal articles which comprises subjecting said. articles to an acid bath containing as the active pickling and cleaning ingredient a nonoxidizing acid, the step of inhibiting the action of said acid upon the metal by the incorporation into said acid of an inhibitor of the class of substances comprising thio-glycollic acid and its derivatives containing the radical GOOHCH S finely dispersed throughout said bath.
A composition of matter for pickling and cleaning metal articles comprising a dian inhibitor of the class of substances comprising thio-glycollic acid and its derivatives containing the radical COOH-CH S.
4. A composition of matter for pickling and cleaning metal articles comprising a dilute non-oxidizing acid and a small amount of an inhibitor of the class of substances comprising thio-glycollic acid and its derivatives containing the radical COOHCH finelydispersed throughout said acid.
In testimony whereof, I afiix my si ature.
RALPH E. LAWRE CE.
US398505A 1929-10-09 1929-10-09 Acid treatment of metal articles Expired - Lifetime US1780594A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US398505A US1780594A (en) 1929-10-09 1929-10-09 Acid treatment of metal articles
GB30127/30A GB357387A (en) 1929-10-09 1930-10-08 Improvements in or relating to the pickling of metals and the like processes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US398505A US1780594A (en) 1929-10-09 1929-10-09 Acid treatment of metal articles

Publications (1)

Publication Number Publication Date
US1780594A true US1780594A (en) 1930-11-04

Family

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Family Applications (1)

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US398505A Expired - Lifetime US1780594A (en) 1929-10-09 1929-10-09 Acid treatment of metal articles

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US (1) US1780594A (en)
GB (1) GB357387A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2989485A (en) * 1958-05-21 1961-06-20 Dow Chemical Co Inhibition of metal corrosion
US3094490A (en) * 1960-12-27 1963-06-18 Amchem Prod Inhibitor composition and method of inhibiting acid attack on metal in the acidizing f wells
US3197403A (en) * 1960-04-04 1965-07-27 Continental Oil Co Acidizing corrosion inhibitor
EP0878605A3 (en) * 1997-05-13 1999-05-19 Halliburton Energy Services, Inc. Use of corrosion inhibited organic acid compositions
EP1008676A3 (en) * 1998-12-10 2000-11-08 CENTRO SVILUPPO MATERIALI S.p.A. Accelerated steel strip pickling process and device for carrying out the process
WO2010055160A3 (en) * 2008-11-17 2010-08-19 Basf Se Acid aqueous thiodiglycol ethoxylate composition and the use thereof in a method for etching metallic surfaces
CN102513220A (en) * 2011-12-21 2012-06-27 大冶有色设计研究院有限公司 Chemical composition for recycling copper concentrate and molybdenum concentrate from copper and molybdenum mixed concentrate pulp

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3037934A (en) * 1958-01-02 1962-06-05 Dow Chemical Co Corrosion inhibition
DE4120305C1 (en) * 1991-06-20 1992-08-27 Mtu Muenchen Gmbh

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2989485A (en) * 1958-05-21 1961-06-20 Dow Chemical Co Inhibition of metal corrosion
US3197403A (en) * 1960-04-04 1965-07-27 Continental Oil Co Acidizing corrosion inhibitor
US3094490A (en) * 1960-12-27 1963-06-18 Amchem Prod Inhibitor composition and method of inhibiting acid attack on metal in the acidizing f wells
EP0878605A3 (en) * 1997-05-13 1999-05-19 Halliburton Energy Services, Inc. Use of corrosion inhibited organic acid compositions
EP1008676A3 (en) * 1998-12-10 2000-11-08 CENTRO SVILUPPO MATERIALI S.p.A. Accelerated steel strip pickling process and device for carrying out the process
WO2010055160A3 (en) * 2008-11-17 2010-08-19 Basf Se Acid aqueous thiodiglycol ethoxylate composition and the use thereof in a method for etching metallic surfaces
US20110232679A1 (en) * 2008-11-17 2011-09-29 Basf Se Use of thioglycol ethoxylate as a corrosion inhibitor
US8901060B2 (en) 2008-11-17 2014-12-02 Basf Se Use of thioglycol ethoxylate as a corrosion inhibitor
CN102513220A (en) * 2011-12-21 2012-06-27 大冶有色设计研究院有限公司 Chemical composition for recycling copper concentrate and molybdenum concentrate from copper and molybdenum mixed concentrate pulp

Also Published As

Publication number Publication date
GB357387A (en) 1931-09-24

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