US2708184A - Tincture of iodine as acid pickling inhibitor - Google Patents
Tincture of iodine as acid pickling inhibitor Download PDFInfo
- Publication number
- US2708184A US2708184A US274677A US27467752A US2708184A US 2708184 A US2708184 A US 2708184A US 274677 A US274677 A US 274677A US 27467752 A US27467752 A US 27467752A US 2708184 A US2708184 A US 2708184A
- Authority
- US
- United States
- Prior art keywords
- iodine
- tincture
- inhibitor
- pickling
- bath
- 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
- 229910052740 iodine Inorganic materials 0.000 title claims description 29
- 239000011630 iodine Substances 0.000 title claims description 28
- 229940098465 tincture Drugs 0.000 title claims description 15
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title description 25
- 238000005554 pickling Methods 0.000 title description 15
- 239000003112 inhibitor Substances 0.000 title description 14
- 239000002253 acid Substances 0.000 title description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- -1 FERROUS METALS Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 235000019441 ethanol Nutrition 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 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
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
Definitions
- Dilute non-oxidizing acids such as sulfuric, hydro chloric, phosphoric, acetic, formic and the like are com monly used in pickling and metal cleaning operations.
- many inhibitors are known, including the halides upon which the present inventors are filing herewith companion patent applications Serial Number 274,675 and 274,676. It is also well known, however, that ethanol increases the rate of attack of pickling acids against the base metals.
- tincture of iodine we mean the ordinary product available on the market which contains about 7% iodine, potassium iodide and 5% water made up to 100% with ethyl alcohol, in accordance with the definition given in standard reference works.
- Ethanol and iodine evidently exert a synergistic influence on each other.
- the inhibiting properties of iodine are enhanced and the tendency of ethanol to increase the rate of attack of the etching acid is completely overcome.
- the synergistic effect can clearly be seen from the following examples.
- Example 1 Pieces of SAE 1010 steel were pickled in beakers containing 5% sulfuric acid, about 1 N. Two pieces were treated in acid containing no inhibitor and were utilized as controls in both this and the following examples. A third-piece of the steel was pickled in 5% sulfuric acid to which 0.002% iodine had been added. A fourth piece was pickled in 5% sulfuric acid containing 0.1% of a 2% tincture or a total iodine content of 0.002%.
- Percentage retardation where Lu is the rate of weight lossof a piece of metal during pickling in an uninhibited bath and L1 is the rate of loss of weight from apiece of .the same metal under.- going pickling in an inhibited bath.
- Example 2.--Tests were run as in Example 1 except that 0.02% of iodine inhibitor was used. This percentage was obtained, 1) by adding 0.02% of I2 directly to the pickling bath; (2) by adding 1% of a 2% commercial tincture of iodine; and (3) by adding 1% of a 2% ethanol tincture made up in the laboratory. Results obtained are summarized in Table 2.
- Example 3 The tests of Examples 1 and 2 were repeated utilizing, however, a concentration of 0.10% iodine. This concentration was obtained (1) by adding 0.10% I2 directly to the pickling bath and again (2) by adding 5% of a 2% commercial tincture of iodine to the bath. Results obtained are shown in Table 3.
- a composition of matter for pickling ferrous metals consisting essentially of an aqueous solution of sulfuric acid carrying dissolved therein a sufiicient amount of a tincture of iodine to provide iodine to the extentof between about 0.002% and about 0.1% by weight of said solution.
- a composition of matter consisting essentially of a non-oxidizing acid bath for pickling metals, said bath carrying dissolved therein a corrosion inhibiting agent comprising approximately ten parts of ethanol and one part of iodine, said inhibitor constituting not more than 5% by weight of said bath.
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
United States Patent TINCTURE-OF IODINE AS AGID 'PICKLING INHIBITOR Karl F. Hager, Huntsville, Ala. ;Morris Rosenthal, Alexandria, Va., assignors to the United States of America as represented by the Secretary of the Army No Drawing. Application March 5,1952,
Serial 'No. 274,677 6 Claims. (Cl. 252147) improved inhibitor for acid pickling. Other objects of the invention will be evident hereinafter.
Dilute non-oxidizing acids such as sulfuric, hydro chloric, phosphoric, acetic, formic and the like are com monly used in pickling and metal cleaning operations. For such acids many inhibitors are known, including the halides upon which the present inventors are filing herewith companion patent applications Serial Number 274,675 and 274,676. It is also well known, however, that ethanol increases the rate of attack of pickling acids against the base metals.
We have discovered that, contrary to expectation, even a 2% solution of iodine in ethanol added in small amounts to a pickling acid is an eifective inhibitor. In fact, this solution is a much more effective inhibitor than the iodine disclosed alone in the companion cases. For example 0.1% of a 2% tincture of iodine in a nonoxidizing pickling acd, a total of 0.002% iodine content, is a better inhibitor than 0.002% pure iodine dissolved in the same acid. By tincture of iodine we mean the ordinary product available on the market which contains about 7% iodine, potassium iodide and 5% water made up to 100% with ethyl alcohol, in accordance with the definition given in standard reference works.
Ethanol and iodine evidently exert a synergistic influence on each other. As a result of this joint influence the inhibiting properties of iodine are enhanced and the tendency of ethanol to increase the rate of attack of the etching acid is completely overcome. The synergistic effect can clearly be seen from the following examples.
Example 1.-Pieces of SAE 1010 steel were pickled in beakers containing 5% sulfuric acid, about 1 N. Two pieces were treated in acid containing no inhibitor and were utilized as controls in both this and the following examples. A third-piece of the steel was pickled in 5% sulfuric acid to which 0.002% iodine had been added. A fourth piece was pickled in 5% sulfuric acid containing 0.1% of a 2% tincture or a total iodine content of 0.002%.
Weight loss determinations may be made directly or, since the hydrogen evolved is proportional to the iron dissolved, by determination of the volume of hydrogen produced. The latter method was followed in this case with the results given in Table 1. All experiments were run without stirring at ambient temperature for twentyfour hours.
The percentage retardation caused by the added inhibitor was calculated from the formula:
Percentage retardation= where Lu is the rate of weight lossof a piece of metal during pickling in an uninhibited bath and L1 is the rate of loss of weight from apiece of .the same metal under.- going pickling in an inhibited bath.
Table 1 Percentage Percentage Test No. Inhibitor Added Iodine Retarda- Gontent tion 1 0.002% I: 0.002 33 2 0.1% of 2% tincture." 0.002 57 The synergistic efiect obtained from mixing iodine and ethanol is obvious from the figures in the fourth column of Table 1.
Example 2.--Tests were run as in Example 1 except that 0.02% of iodine inhibitor was used. This percentage was obtained, 1) by adding 0.02% of I2 directly to the pickling bath; (2) by adding 1% of a 2% commercial tincture of iodine; and (3) by adding 1% of a 2% ethanol tincture made up in the laboratory. Results obtained are summarized in Table 2.
Table 2 Percentage Percentage Test No Inhibitor Added Iodine arde- Oontent tion 0.02 It 0. 02 1% ofa 2% Com. Tincture.. 0.02 95 1% of 2% Lab. Tincture 0. 02 90 The reciprocal synergistic influence of iodine and ethanol upon each other is again evident from the fourth column of the table.
Example 3.-The tests of Examples 1 and 2 were repeated utilizing, however, a concentration of 0.10% iodine. This concentration was obtained (1) by adding 0.10% I2 directly to the pickling bath and again (2) by adding 5% of a 2% commercial tincture of iodine to the bath. Results obtained are shown in Table 3.
Table 3 Percentage Percentage Test No. Inhibitor Added Iodine etarda- Content tion 6 0.10% 12 0. 1 7 5% ofa 2% Com. Tincture.. 0. 1 91 non-oxidizing pickling acid and water, said composition carrying dissolved therei'na sufiicient amount of a tincture of iodine to provide iodine to the extent of between about 0.002% and about 0.1% by weight of said composition.
2. A composition of matter for pickling ferrous metals consisting essentially of an aqueous solution of sulfuric acid carrying dissolved therein a sufiicient amount of a tincture of iodine to provide iodine to the extentof between about 0.002% and about 0.1% by weight of said solution.
3. The method of inhibiting corrosion of ferrous metal articles in a non-oxidizing acid pickling bath which comprises supplying to said bath a small but effective quantity of tincture of iodine.
4. A composition of matter consisting essentially of a non-oxidizing acid bath for pickling metals, said bath carrying dissolved therein a corrosion inhibiting agent comprising approximately ten parts of ethanol and one part of iodine, said inhibitor constituting not more than 5% by weight of said bath.
References Cited in the file of this patent UNITED STATES PATENTS 453,129 Reeser May 26, 1891 1,809,041 Jenkins et a1. June 9, 1931 2,399,134 Miller et al. Apr. 23, 1946 2,477,181 Holman July 26, 1949 OTHER REFERENCES Pharmaceutical Formulas, vol. 1, 11th ed., The Chemist and Druggist, 1944, London, page 629.
Claims (1)
- 2. A COMPOSITION OF MATTER PICKING FERROUS METALS CONSISTING ESSENTIALLY OF AN AQUEOUS SOLUTION OF SULFURIC ACID CARRYING DISSOLVED THEREIN A SUFFICIENT AMOUNT OF A TINCTURE OF IODINE TO PROVIDE IODINE TO THE EXTENT OF BETWEEN ABOUT 0.002% AND ABOUT 0.1% BY WEIGHT OF SAID SOLUTION.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US274677A US2708184A (en) | 1952-03-03 | 1952-03-03 | Tincture of iodine as acid pickling inhibitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US274677A US2708184A (en) | 1952-03-03 | 1952-03-03 | Tincture of iodine as acid pickling inhibitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2708184A true US2708184A (en) | 1955-05-10 |
Family
ID=23049177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US274677A Expired - Lifetime US2708184A (en) | 1952-03-03 | 1952-03-03 | Tincture of iodine as acid pickling inhibitor |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2708184A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2827367A (en) * | 1955-08-30 | 1958-03-18 | Texas Instruments Inc | Etching of semiconductor materials |
| US3030311A (en) * | 1959-08-24 | 1962-04-17 | Dow Chemical Co | Mineral acid inhibitors |
| US3161598A (en) * | 1961-12-11 | 1964-12-15 | Geld Isidore | Method and composition for chemical rust removal |
| US3249547A (en) * | 1958-05-19 | 1966-05-03 | Monsanto Co | Inhibition of acidic corrosion by use of a combination of a sugar and an iodide or bromide salt |
| US3296149A (en) * | 1964-09-25 | 1967-01-03 | Hooker Chemical Corp | Corrosion-inhibiting composition of mixture of molasses, potassium iodide and metal salt of a fatty acid |
| US4851149A (en) * | 1985-11-13 | 1989-07-25 | Henkel Corporation | Non-toxic acid cleaner corrosion inhibitors |
| WO2016093952A1 (en) * | 2014-12-08 | 2016-06-16 | Saudi Arabian Oil Company | Inhibiting toxicity of acid systems used for treating metals |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US453129A (en) * | 1891-05-26 | Compound for dehorning cattle | ||
| US1809041A (en) * | 1930-02-03 | 1931-06-09 | Swann Res Inc | Inhibitor |
| US2399134A (en) * | 1943-02-24 | 1946-04-23 | Aluminum Co Of America | Method of removing oxide coating from aluminum surfaces |
| US2477181A (en) * | 1942-07-06 | 1949-07-26 | Turco Products Inc | Composition and method for cleaning aluminum preparatory to spot welding |
-
1952
- 1952-03-03 US US274677A patent/US2708184A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US453129A (en) * | 1891-05-26 | Compound for dehorning cattle | ||
| US1809041A (en) * | 1930-02-03 | 1931-06-09 | Swann Res Inc | Inhibitor |
| US2477181A (en) * | 1942-07-06 | 1949-07-26 | Turco Products Inc | Composition and method for cleaning aluminum preparatory to spot welding |
| US2399134A (en) * | 1943-02-24 | 1946-04-23 | Aluminum Co Of America | Method of removing oxide coating from aluminum surfaces |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2827367A (en) * | 1955-08-30 | 1958-03-18 | Texas Instruments Inc | Etching of semiconductor materials |
| US3249547A (en) * | 1958-05-19 | 1966-05-03 | Monsanto Co | Inhibition of acidic corrosion by use of a combination of a sugar and an iodide or bromide salt |
| US3030311A (en) * | 1959-08-24 | 1962-04-17 | Dow Chemical Co | Mineral acid inhibitors |
| US3161598A (en) * | 1961-12-11 | 1964-12-15 | Geld Isidore | Method and composition for chemical rust removal |
| US3296149A (en) * | 1964-09-25 | 1967-01-03 | Hooker Chemical Corp | Corrosion-inhibiting composition of mixture of molasses, potassium iodide and metal salt of a fatty acid |
| US4851149A (en) * | 1985-11-13 | 1989-07-25 | Henkel Corporation | Non-toxic acid cleaner corrosion inhibitors |
| WO2016093952A1 (en) * | 2014-12-08 | 2016-06-16 | Saudi Arabian Oil Company | Inhibiting toxicity of acid systems used for treating metals |
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