US3660253A - Steel pickling bath - Google Patents
Steel pickling bath Download PDFInfo
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- US3660253A US3660253A US45929A US3660253DA US3660253A US 3660253 A US3660253 A US 3660253A US 45929 A US45929 A US 45929A US 3660253D A US3660253D A US 3660253DA US 3660253 A US3660253 A US 3660253A
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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
- C23G1/08—Iron or steel
- C23G1/085—Iron or steel solutions containing HNO3
Definitions
- the steel strip base material which has been cold rolled to gage, annealed, and usually given a temper roll, is cleaned of dirt and oil, and pickled in dilute mineral acid. After pickling, the strip is thoroughly rinsed in water and then introduced into an electrotinning bath. Pickling, preceding electrotinning is usually performed in an aqueous solution of approximately 3 to 5 weight percent sulfuric acid.
- Electrotinplate can be made from either an alkaline or an acid plating bath with the latter type gaining favor due to the greater speed at which acid tinplate can be produced.
- alkaline tinplate has generally been considered to have corrosion resistance superior to that of acid tinplate. This superiority is of particular importance in the shelf life of unlacquered tin cans containing the more corrosive types of acid food, such as fruit juices.
- Prior art acid tinplate used for such acid foods often fails after a relatively short shelf life.
- Grade K is now used by certain can manufacturers to designate that tinplate grade which meets requirements of can shelf life for the more corrosive acid types of food and beverages, including citrus fruits and tomatoes.
- Grade I(" tinplate must have an iron solution value" (ISV) of not more than 20.
- Iron solution value represents the dissolved iron in micrograms in a test solution of sulfuric acid containing ammonium-thiocyanate and hydrogen peroxide, after exposure of one side of a tinplate sample of specific dimensions to 50 milliliters of the test solution in a closed jar for 2 hours at 80 F.
- the ISV test is the subject of a discussion in Corrosion," Vol. 12, No. 9, Sept. 1956, pp. 23-30, the test being described in Appendix B The Iron Solution Test" at p. 29.
- Grade I(" tinplate must have, additionally, an alloy-tin couple" (ATC) value of not more than 0.12.
- the alloy tin couple value represents the current flow in microamperes per square centimeter between a tin anode and the tin-iron alloy of a tinplate sample, after immersing a tinplate sample of specific dimensions, from which the free tin has been removed, in citrus juice for hours.
- ATC alloy-tin couple
- a further test of importance for Grade K tinplate is the pickle lag," i.e. the time between the immersion of a steel strip in a pickling solution and the time the strip begins to pickle.
- This test is of particular importance in an acid plating line because of the increased speed involved in this type of line.
- the testing procedure for determining pickle lag entails immersing a detinned specimen in 6 N. hydrochloric acid at 90 C. and measuring the time lapse before a steady rate of iron dissolution, or hydrogen evolution, is attained. The test procedure is discussed in Tinplate Testing" (May 1960) by W. E. Hoare,Tin Research Institute, Middlesex, England.
- Grade K" tinplate should have a pickle lag of no more than 10 seconds.
- the method of this invention comprises pickling a cold rolled annealed strip, from which dirt and oil have been removed, in a heated aqueous solution of from 0.5-1.5 weight percent nin'ic acid, calculated as nitrate (NO ion, and from 2.5-20 weight percent sulfuric acid (l00% H).
- a heated aqueous solution of from 0.5-1.5 weight percent nin'ic acid, calculated as nitrate (NO ion, and from 2.5-20 weight percent sulfuric acid (l00% H
- the strip is held in the pickling solution, for a predetermined time period, after which the pickling solution is thoroughly rinsed from the strip.
- the strip is then ready for plating.
- the improved tinplate obtained by the use of the pickling bath composition and method of this invention is unexpected. Neither sulfuric nor nitric acid pickling baths alone will provide a steel base, which, when tinplated, will consistently pass Grade I(" test requirements.
- Cold rolled, annealed steel strip having a gage of 0.0082 inch, and a carbon content of 0.08 weight percent, is cleaned cathodically in an aqueous solution of alkaline cleaner, as is well known to those skilled in the art. Thereafter, the strip is thoroughly rinsed with water and passed through rubbercoated squeegee rolls. The strip is then introduced into an aqueous pickling bath, at a bath temperature of approximately F., comprising 10 grams per liter (1 weight percent) nitric acid and 50 grams per liter (5%) sulfuric acid. The strip remains in the pickling bath for approximately 5 seconds. It is then withdrawn, thoroughly rinsed with water, and excess water removed by passing the strip through rubber-coated squeegee rolls. The thus pickled and. rinsed strip is then passed through an acid electrotinning line where the strip is coated with tin and subsequently flow brightened.
- Blackplate test pieces were made up in the form of cylinders. Each cylinder had a diameter of 6 inches and a height of 6 inches, the cylinder being subjected, to a height of 5 inches, to the test procedure given below.
- the test procedure comprised fixing each cylindrical test piece in a vertical position on a rotating current conducting head, after which the test cylinder was cleaned electrolytically in a proprietary alkaline cleaning solution (Pennsalt 86-B), rinsed in water, pickled, rinsed, plated electrolytically with tin on both sides from an acid plating bath and rinsed.
- a number of thus treated cylinders were then cut up into panels having a dimension of 4 inches by 17.5 inches. The panels were flow brightened in an induction furnace, and from these panels, specimens were obtained upon which determinations were made for iron solution values.
- Series 111 and IV compared with Series V and VI show that an increase in temperature tends to lower the ISV value, other factors being the same.
- a comparison of Series III with Series V and Series IV with Series VI shows that an increase in percent HNO tends to lower ISV values, other factors being the same.
- the last two series (VII AND VIII) show that an increase in percent H 50 also tends to lower the ISV value, other factors being the same.
- the bath is operable with a sulfuric acid concentration up to 200 g./1. (20.0%), the preferred range for sulfuric is from 3 to 7.5 weight percent, as the faster pickling rate with higher concentrations of sulfuric acid may cause undesirable etching, with consequent loss of brightness of the strip surface.
- the temperature of the pickling bath for best performance preferably should be from about to F. Temperatures above this range may be used; however, the temperature should be maintained below the point at which undesirable etching occurs and at which acid would be lost by excessive volatilization.
- the pickling time is also a variable, dependent on bath composition, bath temperature and pickling line speed, but generally is between about 2 to about 5 seconds.
- the method for the production of electro-plated strip which comprises the steps of a. pickling cold rolled annealed steel strip in an aqueous solution of about 0.5 to 1.5 weight per cent nitric acid calculated as nitrate (N05) ion and about 2.5 to 7.5 weight per cent sulfuric acid calculated as 100% H 50 above about 150 F.,
- step (a) is maintained for a time and at a temperature sufficient to produce an ion solution value not exceeding 20 micrograms.
- step (a) is maintained for a period of from about 3 to 5 seconds at a temperature from about 150 to 180 F.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
A method and bath for cleaning and conditioning steel prior to tinplating in which the strip is pickled in a dilute aqueous solution of nitric and sulfuric acids. The pickled strip, when tinplated, has improved corrosion resistance.
Description
United States Patent Rauch, Jr. et al.
STEEL PICKLING BATH Stewart E. Rauch, Jr.; Edward H. Mayer, both of Bethlehem, Pa.
Inventors:
us. Cl ..204/34, 134/2, 204/37 T int. Cl ..C23g 1/08 Field 0: Search I 34/2; 204/29, 34, 37 T References Cited UNITED STATES PATENTS 9/1969 Rauch ..204/34 FOREIGN PATENTS OR APPLICATIONS 458,940 5/1936 Great Britain 204/29 Primary Examiner-John H. Mack Assistant Examiner-W. I. Solomon Attorney-Joseph J. O'Keefe [57] ABSTRACT A method and bath for cleaning and conditioning steel prior to tinplating in which the strip is pickled in a dilute aqueous solution of nitric and sulfuric acids. The pickled strip, when tinplated, has improved corrosion resistance.
3 Claims, No Drawings BACKGROUND OF THE INVENTION Mn P S Si Ni Cu .12 max .60 max .015 max .05 max .01 max .04 max .06 max the remainder being essentially iron.
In the production of electrotinplate, the steel strip base material, which has been cold rolled to gage, annealed, and usually given a temper roll, is cleaned of dirt and oil, and pickled in dilute mineral acid. After pickling, the strip is thoroughly rinsed in water and then introduced into an electrotinning bath. Pickling, preceding electrotinning is usually performed in an aqueous solution of approximately 3 to 5 weight percent sulfuric acid.
Electrotinplate can be made from either an alkaline or an acid plating bath with the latter type gaining favor due to the greater speed at which acid tinplate can be produced. However, in the tinplate industry alkaline tinplate has generally been considered to have corrosion resistance superior to that of acid tinplate. This superiority is of particular importance in the shelf life of unlacquered tin cans containing the more corrosive types of acid food, such as fruit juices. Prior art acid tinplate used for such acid foods often fails after a relatively short shelf life.
This observed difi'erence in corrosion characteristics between alkaline and acid electrotinplate has led to the establishment of certain standards, which govern the use of electrotinplate for specific use.
The term Grade K is now used by certain can manufacturers to designate that tinplate grade which meets requirements of can shelf life for the more corrosive acid types of food and beverages, including citrus fruits and tomatoes.
To meet Grade K requirements, tinplate must pass several tests. Grade I(" tinplate must have an iron solution value" (ISV) of not more than 20. Iron solution value represents the dissolved iron in micrograms in a test solution of sulfuric acid containing ammonium-thiocyanate and hydrogen peroxide, after exposure of one side of a tinplate sample of specific dimensions to 50 milliliters of the test solution in a closed jar for 2 hours at 80 F. The ISV test is the subject of a discussion in Corrosion," Vol. 12, No. 9, Sept. 1956, pp. 23-30, the test being described in Appendix B The Iron Solution Test" at p. 29.
Grade I(" tinplate must have, additionally, an alloy-tin couple" (ATC) value of not more than 0.12. The alloy tin couple value represents the current flow in microamperes per square centimeter between a tin anode and the tin-iron alloy of a tinplate sample, after immersing a tinplate sample of specific dimensions, from which the free tin has been removed, in citrus juice for hours. The ATC test is discussed in Corrosion, Vol. 17, No. 2, Feb. 1961, pp. 106-414, and the test is described in Appendix A Detailed ATC Procedure at pp. 1 13-1 14.
A further test of importance for Grade K tinplate is the pickle lag," i.e. the time between the immersion of a steel strip in a pickling solution and the time the strip begins to pickle. This test is of particular importance in an acid plating line because of the increased speed involved in this type of line. The testing procedure for determining pickle lag entails immersing a detinned specimen in 6 N. hydrochloric acid at 90 C. and measuring the time lapse before a steady rate of iron dissolution, or hydrogen evolution, is attained. The test procedure is discussed in Tinplate Testing" (May 1960) by W. E. Hoare,Tin Research Institute, Middlesex, England. Preferably, Grade K" tinplate should have a pickle lag of no more than 10 seconds. Heretofore tinplate made from steel which has been treated by a prior art pickling solution, i.e. generally sulfuric acid, has not consistently met Grade K requirements.
SUMMARY OF THE INVENTION It is a primary object of this invention to provide a treatment for cold rolled, annealed steel strip, which when subsequently electrotinned and flow brightened, will have a low iron solution value.
It is a further object to provide a treatment for cold rolled, annealed steel strip, which when subsequently electrotinned and flow brightened, will have improved ATC values.
It is another object of this invention to provide for the aforementioned strip a treatment wherein the pickle lag time is reduced.
It is another object of this invention to provide a treatment for cold rolled, annealed steel strip, which steel when tinplated will pass the aforementioned Grade 1( requirements.
It is another object of this invention to provide a pickling bath composition which will accomplish the above named objects.
The method of this invention comprises pickling a cold rolled annealed strip, from which dirt and oil have been removed, in a heated aqueous solution of from 0.5-1.5 weight percent nin'ic acid, calculated as nitrate (NO ion, and from 2.5-20 weight percent sulfuric acid (l00% H The strip is held in the pickling solution, for a predetermined time period, after which the pickling solution is thoroughly rinsed from the strip. The strip is then ready for plating.
The improved tinplate obtained by the use of the pickling bath composition and method of this invention is unexpected. Neither sulfuric nor nitric acid pickling baths alone will provide a steel base, which, when tinplated, will consistently pass Grade I(" test requirements.
DESCRIPTION OF THE PREFERRED EMBODIMENT The preferred method by which this invention can be performedis given in the following detailed description.
Cold rolled, annealed steel strip, having a gage of 0.0082 inch, and a carbon content of 0.08 weight percent, is cleaned cathodically in an aqueous solution of alkaline cleaner, as is well known to those skilled in the art. Thereafter, the strip is thoroughly rinsed with water and passed through rubbercoated squeegee rolls. The strip is then introduced into an aqueous pickling bath, at a bath temperature of approximately F., comprising 10 grams per liter (1 weight percent) nitric acid and 50 grams per liter (5%) sulfuric acid. The strip remains in the pickling bath for approximately 5 seconds. It is then withdrawn, thoroughly rinsed with water, and excess water removed by passing the strip through rubber-coated squeegee rolls. The thus pickled and. rinsed strip is then passed through an acid electrotinning line where the strip is coated with tin and subsequently flow brightened.
By use of the pickling method just described, followed by electrotinning and flow brightening, we have produced tinplate having an iron solution value not exceeding 20, and an alloy-tin couple value not exceeding 0. 12.
The outstanding improvement in ISV and improvement in ATC value obtained with the nitric-sulfuric acid pickling bath and method, as against results obtained with conventional sulfuric acid pickling, for comparative samples, tinned from the same acid lines is shown from test results comparing the two pickling procedures.
For the comparative tests, box annealed 0.0082 inch gage blackplate having a carbon content of 0.08% was-used. Blackplate test pieces were made up in the form of cylinders. Each cylinder had a diameter of 6 inches and a height of 6 inches, the cylinder being subjected, to a height of 5 inches, to the test procedure given below.
The test procedure comprised fixing each cylindrical test piece in a vertical position on a rotating current conducting head, after which the test cylinder was cleaned electrolytically in a proprietary alkaline cleaning solution (Pennsalt 86-B), rinsed in water, pickled, rinsed, plated electrolytically with tin on both sides from an acid plating bath and rinsed. A number of thus treated cylinders were then cut up into panels having a dimension of 4 inches by 17.5 inches. The panels were flow brightened in an induction furnace, and from these panels, specimens were obtained upon which determinations were made for iron solution values.
The following table contains the results of tests run.
TABLE I Pickling ISV g. Bath Temp. of Fe/disk Test Composition F.) Average Series 1 (Average) of 10 samples I-INO;,, 10 gm./l. I 150 57 Series 11 (Average) of 10 samples H 50 50 grn./1. 150 35 Series III (Average) H 80 50 gm./l. of 10 Samples HNO 5 gm./l. 150 20 Series IV (Average) H 50 50 gm./l. of samples HNO,-,, 5 gm./l. 175 14 Series V (Average) H 50 50 gm./l. of 10 samples I-INO 10 gm./1. 150 17 Series V1 (Average) H 50 50 gm./l. of 10 samples) HNO;,, l0 gm./l. I75 11 Series VII (Average) H 80 100 gm./1. of 10 samples HNO l0 gm./l. 175 6 Series VIII (Average) H SO 200 gm./l. of 10 samples HNO 10 gm./l. 175 7 The preceding table shows the improved ISV properties of the combination of sulfuric and nitric acid pickling baths. Series I in which nitric acid was used, and Series II in which sulfuric acid was used, show ISV values well above the value of 20 established as the maximum allowable for Grade I(" tinplate. Series 111 and IV compared with Series V and VI show that an increase in temperature tends to lower the ISV value, other factors being the same. A comparison of Series III with Series V and Series IV with Series VI shows that an increase in percent HNO tends to lower ISV values, other factors being the same. The last two series (VII AND VIII) show that an increase in percent H 50 also tends to lower the ISV value, other factors being the same.
All the 18V values represent an average of 10 samples. These samples were, in each series, from five test cylinders which were then run in duplicate.
While the bath is operable with a sulfuric acid concentration up to 200 g./1. (20.0%), the preferred range for sulfuric is from 3 to 7.5 weight percent, as the faster pickling rate with higher concentrations of sulfuric acid may cause undesirable etching, with consequent loss of brightness of the strip surface.
In addition, the following two tests were made of steel samples in a production line test. In the first test, samples were taken from edges and centers of 14 coils of tin plate. These samples were treated in a sulfuric acid heated bath. In the second test, sodium nitrate was added to the above bath to bring the nitrate concentration (NO ion to 1%, the equivalent of 10 gm./l., and the bath temperature was raised to 180 F. 12 coils samples were then pickled in this second bath, wherein all other operating conditions were the same as for the first test. The results of these tests are given in Table 11 below.
TABLE II lSV ATC Pickle Temp. pg. of micro- Lag Solution F.) Fe/disk amp/sq.cm. Seconds H 5% (Average of 14 samples) 20 .044 7 t. 5% (Average of 12 samples) HNO 1% 180 11 .028 4 The above test shows the improvement in ISV, ATC, and pickle lag achieved by the bath and method of our invention over that of the prior art sulfuric acid bath.
In the practice of our invention the temperature of the pickling bath for best performance preferably should be from about to F. Temperatures above this range may be used; however, the temperature should be maintained below the point at which undesirable etching occurs and at which acid would be lost by excessive volatilization. The pickling time is also a variable, dependent on bath composition, bath temperature and pickling line speed, but generally is between about 2 to about 5 seconds.
It is also possible in the bath and method of this invention to substitute an alkali nitrate for nitric acid as a source of nitrate ions.
Other variations are also possible without departing from the scope of the novel concepts of this invention, such as the use of continuous annealed in place of box annealed plate. Also, this invention is suitable in the production of alkaline tinplate as well as the acid tinplate of the examples.
We claim:
I. The method for the production of electro-plated strip which comprises the steps of a. pickling cold rolled annealed steel strip in an aqueous solution of about 0.5 to 1.5 weight per cent nitric acid calculated as nitrate (N05) ion and about 2.5 to 7.5 weight per cent sulfuric acid calculated as 100% H 50 above about 150 F.,
b. rinsing said strip, and
c. electrotinning said strip.
2. The method as claimed in claim 1 wherein step (a) is maintained for a time and at a temperature sufficient to produce an ion solution value not exceeding 20 micrograms.
3. The method as claimed in claim 1 wherein the pickling in step (a) is maintained for a period of from about 3 to 5 seconds at a temperature from about 150 to 180 F.
Claims (2)
- 2. The method as claimed in claim 1 wherein step (a) is maintained for a time and at a temperature sufficient to produce an ion solution value not exceeding 20 micrograms.
- 3. The method as claimed in claim 1 wherein the pickling in step (a) is maintained for a period of from about 3 to 5 seconds at a temperature from about 150* to 180* F.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US4592970A | 1970-06-12 | 1970-06-12 |
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US3660253A true US3660253A (en) | 1972-05-02 |
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US45929A Expired - Lifetime US3660253A (en) | 1970-06-12 | 1970-06-12 | Steel pickling bath |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5234542A (en) * | 1992-03-04 | 1993-08-10 | Macdermid, Incorporated | Composition and process for stripping tin from copper surfaces |
DE19959749A1 (en) * | 1999-12-11 | 2001-06-28 | Rasselstein Hoesch Gmbh | Producing tinplate of greater corrosion resistance is achieved by rolling, annealing, pickling and high purity tin coating, producing intermediate boundary layer |
US20110017361A1 (en) * | 2008-01-22 | 2011-01-27 | Thyssenkrupp Steel Europe Ag | Method for Coating a Hot-Rolled or Cold-Rolled Steel Flat Product, Containing 6-30% wt. Mn, with a Metallic Protective Layer |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB458940A (en) * | 1935-08-20 | 1936-12-30 | Richard Thomas & Co Ltd | Improvements in or relating to the production of coatings of tin or tin alloys on metal articles |
US3468768A (en) * | 1966-07-05 | 1969-09-23 | Bethlehem Steel Corp | Surface treatment of steel electrotinning stock |
-
1970
- 1970-06-12 US US45929A patent/US3660253A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB458940A (en) * | 1935-08-20 | 1936-12-30 | Richard Thomas & Co Ltd | Improvements in or relating to the production of coatings of tin or tin alloys on metal articles |
US3468768A (en) * | 1966-07-05 | 1969-09-23 | Bethlehem Steel Corp | Surface treatment of steel electrotinning stock |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5234542A (en) * | 1992-03-04 | 1993-08-10 | Macdermid, Incorporated | Composition and process for stripping tin from copper surfaces |
DE19959749A1 (en) * | 1999-12-11 | 2001-06-28 | Rasselstein Hoesch Gmbh | Producing tinplate of greater corrosion resistance is achieved by rolling, annealing, pickling and high purity tin coating, producing intermediate boundary layer |
DE19959749C2 (en) * | 1999-12-11 | 2003-06-18 | Rasselstein Hoesch Gmbh | Process for producing tinplate with high corrosion resistance |
US20110017361A1 (en) * | 2008-01-22 | 2011-01-27 | Thyssenkrupp Steel Europe Ag | Method for Coating a Hot-Rolled or Cold-Rolled Steel Flat Product, Containing 6-30% wt. Mn, with a Metallic Protective Layer |
US8506731B2 (en) * | 2008-01-22 | 2013-08-13 | Thyssenkrupp Steel Europe Ag | Method for coating a hot-rolled or cold-rolled steel flat product containing 6-30 wt% Mn |
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