Cleaning should always come first. Grease, coolant or other shop debris must be thoroughly cleaned from the surface to obtain the best possible corrosion resistance. Machining chips or other shop dirt can be wiped carefully off the part. A commercial degreaser or cleanser may be used to clean off machining oils or coolants. Foreign matter such as thermal oxides may have to be removed by grinding, or by methods such as acid pickling.
Sometimes a machine operator might skip the basic cleaning, assuming erroneously that by simply immersing the grease-laden part in an acid bath, both cleaning and passivating will take place simultaneously. That doesn’t happen. Instead, the contaminating grease reacts with the acid to form gas bubbles. These bubbles collect on the surface of the workpiece and interfere with passivation.
Even worse, contamination of the passivating solution, sometimes with high levels of chlorides, can cause a “flash attack” as shown in Figure 1. Instead of obtaining the desired oxide film with a shiny, clean, corrosion-resisting surface, the flash attack causes a heavily etched or darkened surface—a deterioration of the very surface that passivation is designed to optimize.
Parts made from martensitic stainless steels [which are magnetic, with moderate corrosion resistance and capable of yield strengths up to about 280 ksi (1930 MPa)] are hardened at a high temperature and then tempered to secure the hardness and mechanical properties desired. Precipitation hardenable alloys (which offer a better combination of strength and corrosion resistance than the martensitic grades) may be solution treated, partially machined, aged at lower temperatures, then finish machined.
In such cases, the parts must be thoroughly cleaned with a degreaser or cleanser to remove any traces of cutting fluid before heat treating. Otherwise, cutting fluid remaining on the parts will cause excessive oxidation. This condition can result in undersized parts with a pitted finish after the scale is removed by acid or abrasive methods. If cutting fluids are allowed to remain on parts that are bright hardened, as in a vacuum furnace or protective atmosphere, surface carburization may occur, leading to a loss of corrosion resistance.
Passivating Baths
After thorough cleaning, the stainless steel part is ready for immersion in a passivating acid bath. Any one of three approaches can be used—nitric acid passivation, nitric acid with sodium dichromate passivation and citric acid passivation. Which approach to use depends on the grade of stainless steel and prescribed acceptance criteria.
More resistant chromium-nickel grades can be passivated in a 20 percent-by-volume nitric acid bath (Figure 2). As indicated in the same table, less resistant stainless grades can be passivated by adding sodium dichromate to the nitric acid bath to make the solution more oxidizing and capable of forming a passive film on the surface. Another option, used in place of nitric acid plus sodium dichromate, is to increase the concentration of nitric acid to 50 percent-by-volume. The sodium dichromate addition and the higher nitric acid concentration both reduce the chance of undesirable flash attack.
The procedure for passivating free-machining stainless steels (also shown in Figure 2) is somewhat different from that used with the non-free-machining stainless grades. That is because the sulfides of sulfur-containing free-machining grades are partially or totally removed during passivation in a typical nitric acid bath, creating microscopic discontinuities in the surface of the machined part.