US1780594A - Acid treatment of metal articles - Google Patents
Acid treatment of metal articles Download PDFInfo
- 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
- Authority
- 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
Links
- 229910052751 metal Inorganic materials 0.000 title description 12
- 239000002184 metal Substances 0.000 title description 12
- 238000010306 acid treatment Methods 0.000 title description 2
- 239000002253 acid Substances 0.000 description 25
- 239000003112 inhibitor Substances 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 8
- 238000005554 pickling Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C23G1/08—Iron or steel
- C23G1/088—Iron or steel solutions containing organic acids
-
- 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
- C23G1/065—Cleaning 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.
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
ID=23575633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US398505A Expired - Lifetime US1780594A (en) | 1929-10-09 | 1929-10-09 | Acid treatment of metal articles |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US1780594A (en) |
| GB (1) | GB357387A (en) |
Cited By (7)
| 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)
| 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 |
-
1929
- 1929-10-09 US US398505A patent/US1780594A/en not_active Expired - Lifetime
-
1930
- 1930-10-08 GB GB30127/30A patent/GB357387A/en not_active Expired
Cited By (9)
| 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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