US1981109A - Metal pickling process - Google Patents
Metal pickling process Download PDFInfo
- Publication number
- US1981109A US1981109A US628274A US62827432A US1981109A US 1981109 A US1981109 A US 1981109A US 628274 A US628274 A US 628274A US 62827432 A US62827432 A US 62827432A US 1981109 A US1981109 A US 1981109A
- Authority
- US
- United States
- Prior art keywords
- metal
- acid
- pickling
- pickling process
- inhibitor
- 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
- 239000002184 metal Substances 0.000 title description 30
- 229910052751 metal Inorganic materials 0.000 title description 30
- 238000005554 pickling Methods 0.000 title description 14
- 238000000034 method Methods 0.000 title description 9
- 239000002253 acid Substances 0.000 description 19
- 239000003112 inhibitor Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 150000003462 sulfoxides Chemical class 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 6
- -1 ferrous metals Chemical class 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 3
- HTMQZWFSTJVJEQ-UHFFFAOYSA-N benzylsulfinylmethylbenzene Chemical compound C=1C=CC=CC=1CS(=O)CC1=CC=CC=C1 HTMQZWFSTJVJEQ-UHFFFAOYSA-N 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000016499 Oxalis corniculata Nutrition 0.000 description 1
- 240000007019 Oxalis corniculata Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 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
- C23G1/04—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
- the present invention relates to the cleaning and preservation of metallic surfaces wherein the metal is in contact with a liquid of an acid nature. More particularly, the invention relates to the prevention of excessive pitting and embrittlement of a metal when subjected to a pickling process by treatment with a dilute solution of a non-oxidizing acid.
- Certain objects of the present invention are to prevent the acid pickle liquor from attacking clean portions of the surface of a metal; to obviate over-pickling, embrittlement and pitting of the articles treated; to minimize the amount of metal lost in pickling; to increase the efiiciency of the pickling operation; to prolong the effective life of the pickling bath; and particularly to facilitate the pickling operation.
- the metal is treated with a dilute acid to remove oxides such as rust, scale. and other deposits, after which the metal is preferably washed with water and dipped into "an alkaline bath to remove the last traces of free acid.
- the acid removes the rust and scale, but unfortunately, from the pickling standpoint, unless some agent to prevent such action is present, it attacks the cleaned metal itself thereby causing loss of metal and producing an evolution of hydrogen as, which escapes into theain carrying with it a fine spray cifthje afi d l ia uor frorn'fii pickling bath and'pi'ififi'c'ihi'aii'atnfdsphere possessing corrosive properties and one which is injurious to health and damaging to equipment.
- a regulating agent or ingredient which acts to restrain the action of the acid from attacking clean metal but assists in removing the rust, scale and other deposits, or in other words the regulator or inhibitor causes the acid selectively to remove such materials without appreciably attacking the clean portions of the metal under treatment.
- the pickle regulator or inhibitor as disclosed in the present application comprises an organlfi ides to sulfoxide.
- the followingsulmxides have proved Ty effective as solvent i lilntor: bgngyl: sulfoxide, dibenzylsulfoxide, diphenylenesulfoxide, polymerized diethylenesulfoxide, thioanthrenesulfoxide. of e aliphatic N mustang-pe m metal'iicklifi'g.
- the sulfoxides maybe employed as inhibitors with advantage in a number of operations, as for example, in the commercial pickling of iron and steel, in the removal of rust of corrosion products from the interior of piping where it is inconvenient to dismantle the piping, in the preparation of metals for electroplating where it is desirable to remove oxides and other corrosion products without removing the free metal and particularly without injuring the surface of the metal.
- the sulfoxides to be very efiicient inhibitors where employed in the acid treatment of ferrous metals, but also in the treatment of otmals, such as g1 hf tin afidfi'llifiiinium.
- the amount of inhibitor employed will, of course, vary in accordance with the requirements of the operator. For example, in the pickling of heavy, cheap materials, such as, for instance, iron castings, an inhibition of '75 to 90% might be quite satisfactory to the pickler, while in the case of relatively valuable material, such as the finer grades of iron or seamless tubing, the pickler might be dissatisfied with less than 99% or even better inhibition.
- the amount of inhibition varies somewhat with the kind and amounts of inhibitor employed, although any measurable quantity of inhibitor will produce some retardation of solution.
- Twitc ells reagent aldehyde condensation products of naphthol sulfonic acids, petroleum sludge acids. some of the higher aldehydes, watersglnble EaEbohydrates, etc.
- the process oi treating metals which comprises subjecting the metal to a non-oxidizing acid solution containing an aliphatic sulfoxide.
Description
1.04- uumruol uuno,
Patented Nov. 20, 1934 UNITED STATES PATENT OFFICE METAL PICKLmG PROCESS No Drawing. Application August 10, 1932, Serial No. 628,275. In Germany August 14, 1931 10 Claims.
The present invention relates to the cleaning and preservation of metallic surfaces wherein the metal is in contact with a liquid of an acid nature. More particularly, the invention relates to the prevention of excessive pitting and embrittlement of a metal when subjected to a pickling process by treatment with a dilute solution of a non-oxidizing acid.
' Certain objects of the present invention are to prevent the acid pickle liquor from attacking clean portions of the surface of a metal; to obviate over-pickling, embrittlement and pitting of the articles treated; to minimize the amount of metal lost in pickling; to increase the efiiciency of the pickling operation; to prolong the effective life of the pickling bath; and particularly to facilitate the pickling operation. Other and further objects of the invention will be apparent from the following description and accompanying table.
In the art of pickling, the metal is treated with a dilute acid to remove oxides such as rust, scale. and other deposits, after which the metal is preferably washed with water and dipped into "an alkaline bath to remove the last traces of free acid. The acid removes the rust and scale, but unfortunately, from the pickling standpoint, unless some agent to prevent such action is present, it attacks the cleaned metal itself thereby causing loss of metal and producing an evolution of hydrogen as, which escapes into theain carrying with it a fine spray cifthje afi d l ia uor frorn'fii pickling bath and'pi'ififi'c'ihi'aii'atnfdsphere possessing corrosive properties and one which is injurious to health and damaging to equipment.
By the present invention, these objectionable features of the pickling process are substantially overcome or reduced to a minimum. To accomplish to as great an extent as possible the objects set forth in accordance with the presentinvention, there is added to the pickling bath, a regulating agent or ingredient which acts to restrain the action of the acid from attacking clean metal but assists in removing the rust, scale and other deposits, or in other words the regulator or inhibitor causes the acid selectively to remove such materials without appreciably attacking the clean portions of the metal under treatment.
The pickle regulator or inhibitor as disclosed in the present application, comprises an organlfi ides to sulfoxide. The followingsulmxides have proved Ty effective as solvent i lilntor: bgngyl: sulfoxide, dibenzylsulfoxide, diphenylenesulfoxide, polymerized diethylenesulfoxide, thioanthrenesulfoxide. of e aliphatic N mustang-pe m metal'iicklifi'g.
The sulfoxidesmaybe employed as inhibitors with advantage in a number of operations, as for example, in the commercial pickling of iron and steel, in the removal of rust of corrosion products from the interior of piping where it is inconvenient to dismantle the piping, in the preparation of metals for electroplating where it is desirable to remove oxides and other corrosion products without removing the free metal and particularly without injuring the surface of the metal. We have found the sulfoxides to be very efiicient inhibitors where employed in the acid treatment of ferrous metals, but also in the treatment of otmals, such as g1 hf tin afidfi'llifiiinium.
The amount of inhibitor employed will, of course, vary in accordance with the requirements of the operator. For example, in the pickling of heavy, cheap materials, such as, for instance, iron castings, an inhibition of '75 to 90% might be quite satisfactory to the pickler, while in the case of relatively valuable material, such as the finer grades of iron or seamless tubing, the pickler might be dissatisfied with less than 99% or even better inhibition. The amount of inhibition varies somewhat with the kind and amounts of inhibitor employed, although any measurable quantity of inhibitor will produce some retardation of solution.
It is sometimes advantageous to mix with the as of the aromatic series In enera l a ll prg anic,snlfoxides t5 as well inhibitor a substance which will aTise the former ttTreadflybecome wet with acid, or which will tend to disperse -1 quickly and thoroughly throughout the acid. Any of the substances ordinarily used for dispersing materials in an acid medium may be applied, such for example as cell ,sulfi.te pitch, Turkey red oil,
Twitc ells reagent, aldehyde condensation products of naphthol sulfonic acids, petroleum sludge acids. some of the higher aldehydes, watersglnble EaEbohydrates, etc.
The following table shows the results of some tests made with the addition of different sulfoxpickling baths at different temperatures.
The tests were performed by using band iron pieces of 8x1.6x0.075 cm. and having a weight of about 5 grams; as acidfllccs pf sulfuric acid ofnzofizujoncentration weiexmployed and iiftestwas executed with.0.l% of sulfoxide calciflated on the metal.
- Reaction Temper- Decrease Kind oisulioxide me time inweigm Hour: C. Grams Benzylsulfoxide 2 60 0.02
cancm-s-cmmm 2 s0 0.025
Di henylsulfoxide 8.mso.m g 88 3g Diphenylenesulioxide 2 60 0. 02
\ S II 0 x Pol erized diethylenesulloxide Hrs-01 Z 33 $31.,
Thioanthrenesulioxide 2 60 0. 04
O \O E No addition l 27 A test executed with only 0.01 gram of a sulfoxide gave the following result:
We do not wish to be limited to the specific sulfoxides listed above, which it should be understood are given only as examples; nor do we wish to be limited to the amounts of inhibitor or conditions under which the inhibitor is used Nor do we wish to be limited to any particular acid since any acid normall q operations ma m On the contr ry, esire our invention to be limited only as defined in the appended claims:
We claim:-
1. The process of treating metals, which comprises subjecting the metal to a non-oxidizing acid solution containing an organic sulfoxide.
2. The process of treating metals, which comprises subjecting the metal to a non-oxidizing acid solution containing an aromatic sulfoxide.
3. The process of treating metals, which comprises subjecting the metal to a non-oxidizing acid solution containing benzylsulfoxide.
4. The process oi treating metals, which comprises subjecting the metal to a non-oxidizing acid solution containing an aliphatic sulfoxide.
5. The process of treating metals, which comprises subjecting the metal to a non-oxidizing acid solution containing polymerized diethylenesulfoxide.
6. A solution of the type adapted for the acid treatment of metals which contains an organic 10. A solution of the type adapted for the acid treatment of metals which contains polymerized diethylenesulfoxide.
, ALBERT KLAMROTH.
HANS AHRENS.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE405690X | 1931-08-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1981109A true US1981109A (en) | 1934-11-20 |
Family
ID=6421969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US628274A Expired - Lifetime US1981109A (en) | 1931-08-14 | 1932-08-10 | Metal pickling process |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US1981109A (en) |
| BE (1) | BE390398A (en) |
| FR (1) | FR741086A (en) |
| GB (1) | GB405690A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2483499A (en) * | 1944-12-08 | 1949-10-04 | Standard Oil Dev Co | Lube oil additives and preparation thereof |
| US2818388A (en) * | 1954-01-04 | 1957-12-31 | Stepan Chemical Co | Corrosion inhibition |
| US2956956A (en) * | 1954-02-10 | 1960-10-18 | Dehydag Gmbh | Inhibitors for acid solutions employed in the surface treatment of metals |
| US3357924A (en) * | 1964-08-13 | 1967-12-12 | Aquitaine Petrole | Corrosion inhibitor |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4304681A (en) * | 1980-09-15 | 1981-12-08 | Shipley Company, Inc. | Novel stripping composition for positive photoresists and method of using same |
-
0
- BE BE390398D patent/BE390398A/xx unknown
- FR FR741086D patent/FR741086A/fr not_active Expired
-
1932
- 1932-08-10 US US628274A patent/US1981109A/en not_active Expired - Lifetime
- 1932-08-11 GB GB22529/32A patent/GB405690A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2483499A (en) * | 1944-12-08 | 1949-10-04 | Standard Oil Dev Co | Lube oil additives and preparation thereof |
| US2818388A (en) * | 1954-01-04 | 1957-12-31 | Stepan Chemical Co | Corrosion inhibition |
| US2956956A (en) * | 1954-02-10 | 1960-10-18 | Dehydag Gmbh | Inhibitors for acid solutions employed in the surface treatment of metals |
| US3357924A (en) * | 1964-08-13 | 1967-12-12 | Aquitaine Petrole | Corrosion inhibitor |
Also Published As
| Publication number | Publication date |
|---|---|
| GB405690A (en) | 1934-02-12 |
| BE390398A (en) | |
| FR741086A (en) | 1933-02-04 |
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