US3282731A - Embrittlement-free pickling of ferrous metal - Google Patents
Embrittlement-free pickling of ferrous metal Download PDFInfo
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- US3282731A US3282731A US283717A US28371763A US3282731A US 3282731 A US3282731 A US 3282731A US 283717 A US283717 A US 283717A US 28371763 A US28371763 A US 28371763A US 3282731 A US3282731 A US 3282731A
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- acid
- ferrous metal
- embrittlement
- metal
- pickling
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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
- 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
- C23G1/068—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors compounds containing a C=C bond
Definitions
- a conventional method of scale removal involves contacting the material with an aqueous solution of an inorganic acid, typically sulfuric acid, usual- 1y by immersion in a bath thereof. Since the acids employed are capable of dissolving the base metal, .a reac tion which is more rapid than that of oxide dissolution, pitting of the metal results where acid attacks it through discontinuities in the oxide film. Also, after the oxide layer has been removed, continued contact of the metal with the acid results in undesirable dissolution of metal, a condition known as overpickling. Moreover, hydrogen produced in the metal dissolution reaction increases the likelihood of hydrogen embrittlement of the ferrous base, Which latter condition results from absorption of hydrogen by the base metal.
- the present invention concerns inhibited acid pickling solutions capable of controlling acid attack of the base metal, which solutions contain inhibitors which are mark edly effective as Well in preventing hydrogen absorption, with its resulting embrittlement elfect.
- acetylene dicarboxylic' acid is effective when used in the concentration range of 11 to 91 grams per liter of a 2 N sulfuric-acid solution and that propiolic acid is elfective when used in the concentration range of 3.5 to 28 grams per liter of a similar acid solution.
- a method for embrittlement-free pickling of ferrous metal comprising the step of subjecting said metal to an aqueous solution consisting essentially of a strong mineral acid, adapted to pickle ferrous metal, and an acetylenic carboxylic acid selected from a group consisting of acetylene dicarboxylic acid and propiolic acid, the concentration of said latter acid being sufiicient to inhibit dissolution of the ferrous metal and to reduce hydrogen absorption therein.
- a method for embrittlement-free pickling of ferrous metal comprising the step of subjecting said metal to an aqueous solution consisting essentially of a strong mineral acid, adapted to pickle ferrous metal, and acetylene dicarboxylic acid, concentration of said latter acid being sufficient to inhibit dissolution of the ferrous metal and to reduce hydrogen absorption therein.
- a method for embrittlement-free pickling of ferrous metal comprising the step of subjecting said metal to an aqueous solution consisting essentially of a strong mineral acid, adapted to pickle ferrous metal, and propiolic acid,
- 3 4 aqueous solution consisting essentially of a strong mineral 2,993,864 7/1961 Monroe et a1.
- 252-146 X acid adapted to pickie ferrous metal, and propiolic acid, 3,049,496 8/1962 Monroe et a1.
- 252-446 said latter acid being'present in concentration range of 3,114,657 12/1963 Stilwell 252-79.4 about 2 to 15 grams per gram equivalent Weight of pick- FOREIGN PATENTS 468,231 3/ 1943 Italy.
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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)
Description
United States Patent This invention relates to limiting-the hazards of hydro-.
gen embrittlementcand overpickling during removal of oxide scale from' ferrous met-alby acids. 7
Iron and steel products become coated with an oxide scale during their process of manufacture,-the presence of which is objectionable in their further processing, as for example in coating the products or forming them by drawing in dies. A conventional method of scale removal involves contacting the material with an aqueous solution of an inorganic acid, typically sulfuric acid, usual- 1y by immersion in a bath thereof. Since the acids employed are capable of dissolving the base metal, .a reac tion which is more rapid than that of oxide dissolution, pitting of the metal results where acid attacks it through discontinuities in the oxide film. Also, after the oxide layer has been removed, continued contact of the metal with the acid results in undesirable dissolution of metal, a condition known as overpickling. Moreover, hydrogen produced in the metal dissolution reaction increases the likelihood of hydrogen embrittlement of the ferrous base, Which latter condition results from absorption of hydrogen by the base metal.
In order to alleviate the foregoing difliculties, it is common practice to add to the pickling solution an inhibitor for the metal dissolution reaction, thus permitting more selective action in elfecting oxide removal and reducing hydrogen production.
It has been noted that the degree of prevention of hydrogen embrittlement during pickling, resulting with various inhibitors, is unpredictable, some inhibitors even increasing embrittlement.
The present invention concerns inhibited acid pickling solutions capable of controlling acid attack of the base metal, which solutions contain inhibitors which are mark edly effective as Well in preventing hydrogen absorption, with its resulting embrittlement elfect. These results are obtained by the addition, to the picklingacid solutions, of an acetylenic carboxylic acid, which may be acetylene dicarboxylic acid or propiolic acid.
We have found that acetylene dicarboxylic' acid is effective when used in the concentration range of 11 to 91 grams per liter of a 2 N sulfuric-acid solution and that propiolic acid is elfective when used in the concentration range of 3.5 to 28 grams per liter of a similar acid solution.
Additional data, as to approximate useful ranges of inhibitor concentration, are presented in Table I.
TABLE I.GRAMS INHIBITOR PER GRAM EQUIVALENT WEIGHT OF PICKLING ACID Efiective Preferred Range, g. Rangefg.
Acetylene diearboxylic acid 4 to 70 5 to 45 Propiolic acid 1 to 28 2 to The specimens. were pickled at 100 F. for various prese- "Ice cut and vapor degreased with trichloroethylenebefore use.
lected times up to 24'ho u rs byimmersion in either uninhibited 2 N sulfuric-acid solutions or 2 N sulfuric-acid 5. solutions containing various concentrations of inhibitors. .Spec1mens were weighed prior to pickling and' -aft'erjextraction' of the'hydrogen absorbed during pickling. The hydrogen concentration in pickled steel was determined by warmextraction at 160 C, a'ccordingtothe'method described; by R.M. Hudsonyl. K. Magor, and G. L. Stragand (-J. .An1er..Ceram. Soc. 41,23 l 9 58 v TABLE IL-METAL nrssoLu'rroN AND HYD ROGEN Pro" UP IN 2 NORMAL sULrURro-Aom SOLUTIONA'I) 100i Weight Loss, Hydrogen Ab- Inhibitor mgjcrn. sorbed, ceJlOOg. Inhibitor 'Conc.,
4 hr. 24 hr. 4, hr. 24 hr.
None 0 21.1 130. 2 8. 3 19.1 I 5. 7 11. 4 75. 5 3.1 10.1 11.4 2.1 19.5 1. 5 2. 9 Acetylene dicarboxylic acid; 22.8 3.8 28.6 0.7 1.1 .45. 6 3.4 10. 4 0.9 0.8 91.2 2.7 13. 0 0.7 0.6 136.8 2.1 26.0 1. 7 4.2 0.7' 5.3 59.9 5.6 8.6 3. 5 1.7 3. 9 1.6 1. 7 Propiolic acid 14. 0 0. 6 2. 6 0. 7 1. 1 28.0 3.0 6. 5 1.0 1.1 56.0 6.1 18.2 1.7 1.3
It will be appreciated that the foregoing concentration ranges and specific examples are illustrative only, to permit ready practice of the invention, and that such variations in concentrations and combinations of ingredients as would occur to those familiar with the art to which this invention appertains are included herein and are within the scope of the following claims.
We claim:
1. A method for embrittlement-free pickling of ferrous metal comprising the step of subjecting said metal to an aqueous solution consisting essentially of a strong mineral acid, adapted to pickle ferrous metal, and an acetylenic carboxylic acid selected from a group consisting of acetylene dicarboxylic acid and propiolic acid, the concentration of said latter acid being sufiicient to inhibit dissolution of the ferrous metal and to reduce hydrogen absorption therein.
2. The method of claim 1 in which said pickling acid is sulfuric acid.
3. A method for embrittlement-free pickling of ferrous metal comprising the step of subjecting said metal to an aqueous solution consisting essentially of a strong mineral acid, adapted to pickle ferrous metal, and acetylene dicarboxylic acid, concentration of said latter acid being sufficient to inhibit dissolution of the ferrous metal and to reduce hydrogen absorption therein.
4. A method for embrittlement-free pickling of ferrous metal comprising the step of subjecting said metal to an aqueous solution consisting essentially of a strong mineral acid, adapted to pickle ferrous metal, and propiolic acid,
I the concentration of said'latte'r' acid'being sufficient to in* ling acid.
3 4 aqueous solution consisting essentially of a strong mineral 2,993,864 7/1961 Monroe et a1. 252-146 X acid, adapted to pickie ferrous metal, and propiolic acid, 3,049,496 8/1962 Monroe et a1. 252-446 said latter acid being'present in concentration range of 3,114,657 12/1963 Stilwell 252-79.4 about 2 to 15 grams per gram equivalent Weight of pick- FOREIGN PATENTS 468,231 3/ 1943 Italy. References Cited by the Examiner QTHER REFERENCES UNITED STATES PATENTS Raphael, Acetylenic Compounds in Organic Synthesis, 3/1944 Giloy s 252-446 X Academic Press Inc., pub, New'York, 1955, pp. 81 and 82. .8/1959 Mayhew et a1.. 106-14 10 7 19 1 Monroe et 1 '252 14 JOHN H. MACK, Prlmary Examiner. 7/ 1961 Monroe et 252146'X R. MIHALEK, Assistant Examiner.
Claims (1)
1. A METHOD FOR EMBRITTLEMENT-FREE PICKING OF FERROUS METAL COMPRISING THE STEP OF SUBJECTING SAID METAL TO AN AQUEOUS SOLUTION CONSISTING ESSENTIALLY OF A STRONG MINERAL ACID, ADAPTED TO PICKLE FERROUS METAL, AND AN ACETYLENIC CARBOXYLIC ACID SELECTED FROM A GROUP CONSISTING OF ACETYLENE DICARBOXYLIC ACID AND PROPIOLIC ACID, THE CONCENTRATION OF SAID LATTER ACID BEING SUFFICEINT TO INHIBIT DISSOLUTION OF THE FERROUS METAL AND TO REDUCE HYDROGEN ABSORPTION THEREIN.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US283717A US3282731A (en) | 1963-05-28 | 1963-05-28 | Embrittlement-free pickling of ferrous metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US283717A US3282731A (en) | 1963-05-28 | 1963-05-28 | Embrittlement-free pickling of ferrous metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3282731A true US3282731A (en) | 1966-11-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US283717A Expired - Lifetime US3282731A (en) | 1963-05-28 | 1963-05-28 | Embrittlement-free pickling of ferrous metal |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3413159A (en) * | 1964-12-24 | 1968-11-26 | Atomic Energy Commission Usa | Process of simultaneously cleaning and coating uranium surfaces |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2344404A (en) * | 1939-10-21 | 1944-03-14 | Giloy Franz | Corrosion preventing agent |
| US2899391A (en) * | 1959-08-11 | Corrosion preventive compositions | ||
| US2993862A (en) * | 1956-08-02 | 1961-07-25 | Dow Chemical Co | Acetylenic glycols as corrosion inhibitors |
| US2993864A (en) * | 1956-08-02 | 1961-07-25 | Dow Chemical Co | Ethynylcyclohexyl compounds as corrosion inhibitors |
| US2993863A (en) * | 1956-08-02 | 1961-07-25 | Dow Chemical Co | Halogenated propargyl alcohols as corrosion inhibitors |
| US3049496A (en) * | 1959-04-30 | 1962-08-14 | Dow Chemical Co | Propargyl compounds as corrosion inhibitors |
| US3114657A (en) * | 1960-08-29 | 1963-12-17 | John W Stilwell | Composition and method for cleaning and stripping metals |
-
1963
- 1963-05-28 US US283717A patent/US3282731A/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2899391A (en) * | 1959-08-11 | Corrosion preventive compositions | ||
| US2344404A (en) * | 1939-10-21 | 1944-03-14 | Giloy Franz | Corrosion preventing agent |
| US2993862A (en) * | 1956-08-02 | 1961-07-25 | Dow Chemical Co | Acetylenic glycols as corrosion inhibitors |
| US2993864A (en) * | 1956-08-02 | 1961-07-25 | Dow Chemical Co | Ethynylcyclohexyl compounds as corrosion inhibitors |
| US2993863A (en) * | 1956-08-02 | 1961-07-25 | Dow Chemical Co | Halogenated propargyl alcohols as corrosion inhibitors |
| US3049496A (en) * | 1959-04-30 | 1962-08-14 | Dow Chemical Co | Propargyl compounds as corrosion inhibitors |
| US3114657A (en) * | 1960-08-29 | 1963-12-17 | John W Stilwell | Composition and method for cleaning and stripping metals |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3413159A (en) * | 1964-12-24 | 1968-11-26 | Atomic Energy Commission Usa | Process of simultaneously cleaning and coating uranium surfaces |
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