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
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
  • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
  • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
• • 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
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F15/00—Other methods of preventing corrosion or incrustation
• • 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
  • C23G1/086—Iron or steel solutions containing HF
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D2261/00—Machining or cutting being involved

Definitions

• the present invention relates to a method of treating austenitic stainless steels and articles fabricated from such steels.
• the present invention more particularly relates to a method of treating at least a portion of a surface of austenitic stainless steels and articles fabricated from such steels a surface of austenitic stainless steels and articles fabricated from such steels to enhance their corrosion resistance.
• the present invention also is directed to austenitic stainless steels and articles fabricated from such steels that are produced using the method of the invention.
• the invention finds application in, for example, the production of corrosion resistant strip, bars, sheets, castings, plates, tubings, and other articles from austenitic stainless steels.
• the corrosion resistance of stainless steels is controlled by the chemical composition of the surface presented to the environment.
• Open-air annealing a heat-treating operation commonly used in the production of stainless steels, is known to produce a chromium- depleted layer near the metal surface, under a chromium-rich oxide scale. Failure to remove both of these surfaces is known to impair the corrosion performance of stainless steels.
• Mechanical processes such as grit blasting or grinding, have been employed to remove the chromium-rich scale.
• the chromium-depleted layer is generally removed by chemical means, namely, by acid pickling.
• pickling involves immersing the steel in an acidic solution, commonly an aqueous solution of nitric acid (HNO 3 ) and hydrofluoric acid (HF), for a period of time, preferably much less than 60 minutes.
• an acidic solution commonly an aqueous solution of nitric acid (HNO 3 ) and hydrofluoric acid (HF)
• HNO 3 nitric acid
• HF hydrofluoric acid
• the acidic solution may be at an elevated temperature, preferably a temperature at which the acidic solution is not highly volatile. It is generally known that pickling of highly corrosion- resistant stainless steels requires particular care and attention because these materials are known to pickle slowly, thereby making removal of the chromium-depleted layer difficult.
• the present invention provides a method of enhancing the corrosion resistance of austenitic stainless steels and articles produced from the steels.
• the method includes removing sufficient material from at least a portion of a surface of the steel such that corrosion initiation sites present on the surface are eliminated or are reduced in number to an extent greater than has heretofore been achieved in conventional austenitic stainless steel processing. Removal of material from the steel surface may be accomplished by any known method suitable for removing material from a surface of a steel. Such methods include, for example, grit blasting, grinding, and/or acid pickling. Acid pickling, for example, occurs under conditions that are aggressive (stronger pickling solution and/or longer pickling time, for example) relative to conventional pickling conditions for the same steel.
• the method of the invention may provide austenitic stainless steels having a critical crevice corrosion temperature (“CCCT"), as defined herein, of at least around 13.5°C greater than steels of the same composition that have been pickled and otherwise processed in a conventional manner.
• CCCT critical crevice corrosion temperature
• UNS N08367 commercially available as AL-6XN® and AL-6XN PLUSTM from Allegheny
• the method of the present invention obviates the significant increase in cost, and also the concerns over phase stability, that would be associated with such increases in alloying additive content.
• the present invention therefore, provides an economical way of significantly improving the corrosion resistance properties of austenitic stainless steels, without changing the chemical composition of the steels.
• FIGURES 1 (a) - (d) illustrate the results of a bolted multiple crevice test, the TC Cor 2 crevice test defined herein, performed at various temperatures on a UNS N08367 alloy manufactured and acid cleaned in a conventional manner;
• FIGURE 2 is a scanning electron micrograph of a surface of a UNS N08367 alloy manufactured and acid cleaned in a conventional manner
• FIGURES 3(a) through 3(d) illustrate the results of a bolted multiple crevice test, the TC Cor 2 crevice test defined herein, performed at various temperatures on a UNS N08367 alloy after undergoing a treatment that enhances corrosion resistance and which is an embodiment of the method of the present invention
• FIGURE 4 is a scanning electron micrograph (SEM) of a surface of a UNS N08367 alloy after undergoing a treatment that enhances corrosion resistance and which is an embodiment of the method of the present invention
• FIGURE 5 is an SEM of a surface of a UNS N08367 alloy manufactured and acid cleaned in a conventional manner after undergoing the ASTM G 150 test;
• FIGURE 6 is an SEM of a surface of a UNS N08367 alloy after undergoing a treatment that enhances corrosion resistance and which is an embodiment of the method of the present invention, and after being subjected to the ASTM G 150 test;
• FIGURE 7 is an SEM of a surface of a UNS N08367 alloy after undergoing a treatment that enhances corrosion resistance and which is an embodiment of the method of the present invention, and after being subjected to the ASTM G 150 test;
• FIGURE 8 is a plot of the pickling time, in minutes, required to achieve a CCCT of at least 43°C (110°F) relative to the weight % ratio of HF to HNO 3 in the pickling solution.
• the present invention provides a method of enhancing the corrosion resistance of austenitic stainless steels and articles produced from the steels. The method includes removing sufficient material from at least a portion of a surface of the steel such that corrosion initiation sites present on the surface are eliminated or are reduced in number to an extent greater than has heretofore been achieved in conventional austenitic stainless steel processing. Removal of material from the steel surface may be accomplished by any of a variety of methods, including grit blasting, grinding, and/or acid pickling. The method of the invention provides improvement in the corrosion resistance of a steel without the need to modify the steel's chemical composition. The method may be applied on austenitic stainless steel in any form, including strip, bar, plate, sheet, casting, tube, and other forms.
• the present invention is especially beneficial for enhancing the corrosion resistance of austenitic stainless steels that will be used in particularly corrosive environments.
• Austenitic stainless steels used in such applications typically are comprised of, by weight, 20 to 40 % nickel, 14 to 24 % chromium, and 4 to 12 % molybdenum.
• the composition of one such steel, UNS N08367, which is considered in the following tests, is set forth in Table 1.
• the relative pitting resistance of a stainless steel can be correlated to alloy composition using the Pitting Resistance Equivalent number (PREN).
• PREN Pitting Resistance Equivalent number
• the PREN provides a prediction, based on composition, of the resistance of a stainless alloy to chloride-induced localized corrosion attack.
• the typical UNS N08367 composition shown in Table 1 has a PRE N of 47.5, while the maximum PRE N of a UNS N03867 alloy is 52.6.
• TC Cor 2 crevice test To compare the difference in the corrosion resistance capabilities of a UNS N03867 alloy processed in a conventional manner with the same alloy that has undergone a treatment that is within the method of the present invention, alloy samples were tested to measure CCCT utilizing a TC Cor 2 crevice test. This test is often specified when steel products are being qualified for severely corrosive applications.
• the TC Cor 2 test is a bolted multiple crevice test which will be generally familiar to one of ordinary skill.
• the TC Cor 2 test in particular, entails exposing a steel sample to a 10% FeCl 3 -6H 2 O solution for an exposure time of 72 hours.
• Delrin washers in accordance with the ASTM G78 specification, are bolted to the test sample to create artificial crevices on the sample surface. All TC Cor 2 testing used herein was performed after applying a torque of 58 inch-lbs to fasten the washers to the samples surfaces. To determine the threshold temperature for crevice attack, samples were tested over a range of temperatures. With plate samples, crevice attack is considered present if the weight loss of the sample is greater than 0.0002 grams/cm 2 or if the depth of corrosive attack is greater than 0.0015 inches. Historically, the expected results of the TC Cor 2 for austenitic stainless steels could be predicted based on alloy composition.
• TC Cor 2 crevice testing was performed on samples of UNS N08367 steel processed in a conventional manner, including a mill anneal and an acid cleaning under typical processing conditions.
• the results of the TC Cor 2 testing, at temperatures ranging from 32.2°C (90°F) to 46°C (115°F) are set forth in Figure 1(a) through 1(d).
• failures were experienced at all temperature measurements, including those conducted at temperatures as low as 32.2°C (90°F). Those results are consistent with what would be expected by the results of Equation 2, above.
• Figure 2 illustrates the surface of a UNS N08367 steel processed in a conventional manner.
• the typical as-received mill surface seen in Figure 5 appears to have a very active surface condition present on the surface of the steel.
• the morphology of this attack suggests that this more active surface condition may serve as the weak link in the corrosion resistance of the alloy.
• Figure 3(a) through 3(d) illustrates the improved corrosion resistance achieved according to an embodiment of the method of the present invention.
• the typical as-received mill steel surface was sandblasted and then lightly pickled with a relatively weak acid and short exposure time.
• this surface treatment produced substantial improvement in corrosion performance over specimens that were only acid cleaned.
• the sandblasted and pickled specimens passed the TC Cor 2 crevice test at 48.8°C (120°F), which is the highest temperature that was evaluated and which is well above 27°C (80.6°F), the CCCT result predicted by Equation 2 for a steel having the composition of UNS N08367 steel.
• the ECPT is a sensitive method of ranking an alloy's resistance to chloride pitting.
• the test includes holding steel samples at a constant potential of 700 mV (vs. SCE) while the temperature of the specimen and test solution are increased at a rate of 1°C per minute.
• the measurements reported herein were performed in a Gamry Flex Cell using the Gamry CMS 110 Critical Pitting Test System.
• the electrolyte used in the testing consisted of 1 M NaCI and the cell was purged with 99.99% nitrogen gas during testing.
• the ECPT is defined as the temperature at which the current increases above 100 ⁇ A/cm 2 and stays above this threshold current density for 60 seconds.
• the acid cleaned mill surface shows the least resistance (lowest ECPT).
• the corrosion resistance is improved.
• the samples used to w obtain the ECPT results were examined by a scanning electron microscope to see if the initiation sites for corrosive attack could be identified.
• the attack on the surface of the acid cleaned sample is shown in Figure 5.
• the initiation sites consist of regions that are preferentially attacked, thereby resulting in a very unusual etch pattern.
• the morphology of the attack suggests the presence of a more active surface condition that serves as the weak link in the corrosion resistance of the steel.
• the sites for corrosion attack on the surface of a steel treated according to one embodiment of the present invention, wherein the surface was sandblasted and pickled, are shown in Figure 6. As is apparent, these sites consist of isolated angular pit-like cavities.
• the SEM of the surface of a steel treated according to another embodiment of the invention is shown in Figure 7. As Figure 7 illustrates, the surface of the ground and acid-cleaned specimen has spherical pitting widely distributed across the surface of the specimen. The reason for the wide spread pitting on this specimen is because this sample was exposed to higher temperatures which nucleated many more sites of attack.
• a predicted 13.5-20 °C increase in CCCT could be achieved by modifying the composition of the UNS N03876 alloy to include an additional 4 weight % chromium or, alternatively, an additional 1.2 weight % molybdenum. Beyond the cost implications of such alloying additions, enhancing corrosion resistance of the UNS N03867 alloy by the foregoing alloying additions would not be practical due to the phase instability that would result.
• the pickling time required to achieve at least a CCCT of 43°C (110°F) was plotted as a function of the weight % ratio of HF to HNO 3 in the pickling solution.
• the resulting plot is shown in Figure 8.
• This plot shows that the pickle time required to enhance the corrosion resistance is indirectly proportional to the ratio of the weight % HF to weight % HNO 3 in the pickling bath.
• the minimum pickling time, in minutes, required to achieve a CCCT of at least 43°C (110°F) is approximately equal to 55(x) "1 0443 , where (x) is the weight ratio of HF to HNO 3 in the pickling solution. It is expected that similar plots can be developed for use with different bath chemistries.
• the present invention may be used with any austenitic stainless steel to enhance the corrosion resistance of the steel relative to the corrosion resistance achieved by processing the steel in a conventional manner.
• the above data shows that the actual corrosion resistance of samples of an austenitic stainless steel treated by the method of the present invention is significantly greater than that of the same steel processed using a conventional acid treatment.
• the present method may be used to provide austenitic stainless steels, and articles fabricated from those steels, which have corrosion resistance properties not previously achieved in steel with the same chemical composition.
• the method of the invention may be used with articles of any type fabricated from austenitic stainless steels. Such articles include, for example, strip, bars, plates, sheets, castings, and tubing.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
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• Mechanical Engineering (AREA)
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• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
• ing And Chemical Polishing (AREA)

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