BACKGROUND OF THE INVENTION Aluminum parts are widely used in the aerospace, aircraft, and automobile industries. In many cases, aluminum parts must be cleaned and etched prior to being inspected using a penetrant dye process. The current practice is to clean parts manually with a solvent wipe and then perform a chemical etching on the parts in an immersion tank. There has been a long-standing need to combine the cleaning and etching steps in a single stable tank immersion instead of in multiple steps. By using a single stable tank immersion, the cleaning and etching results will be improved, manufacturing costs will be reduced, and the amount of solvent emissions will be minimized. The term"hybrid etch" refers to the combination of cleaning and etching in a single tank.

There is a commercially-available prior art liquid cleaning and etching concentrate (described in more detail below) which performs the cleaning and etching functions well when the solution in the tank is fresh. However, as the solution ages in service, the etch rate becomes too slow and a hard insoluble scale is formed in the bottom of the tank which makes it difficult to clean the tank. The prior art concentrate contains the following components:

(a) 11-55 grams/liter of phosphoric acid; (b) 11-55 grams/liter of hydrogen fluoride (HF) (hydrofluoric acid); (c) 110-165 grams/liter of sulfamic acid (H3NO3S) ; (d) 110-165 grams/liter of propylene glycol monomethyl ether (a solvent); and (e) balance water.

In commercial practice, the above concentrate is supplied in 55-gallon drums and is added to a tank which is one-half full of deionized water. Thus the concentrate is diluted on a 1: 1 basis. Accordingly, the bath in the tank will contain the following constituents: (a) 5.5-27. 5 grams/liter of phosphoric acid; (b) 5.5-27. 5 grams/liter of hydrogen fluoride; (c) 55-82.5 grams/liter of sulfamic acid; (d) 55-82.5 grams/liter of propylene glycol monomethyl ether; and (e) balance water.

As described above, an aqueous solution of the prior art product performs the cleaning and etching functions well when the solution in the tank is fresh, but as the solution ages in service, the etch rate becomes too low and a hard insoluble scale is formed in the bottom of the tank which makes it difficult to clean the tank. An applicable process specification, BAC 5786 (a process specification of The Boeing Company), requires a minimum etch rate of 0.8 mils per side per hour. BAC 5786 is incorporated herein by reference.

Previous efforts by others to stabilize the etch rate were not successful. In addition, previous efforts by others to keep the scale from forming were not successful.

Therefore, there is an unmet need in the art for a process for cleaning and etching that stabilizes the etch rate and that prevents scale from forming. The present invention meets this need.

03-1027 PCT SUMMARY OF THE INVENTION The present invention is a process for combined chemically cleaning and etching parts made of aluminum and/or aluminum alloys. An exemplary embodiment of the present invention includes: (a) providing a cleaning and etching solution including: (1) 5-35 grams/liter of phosphoric acid; (2) 5-35 grams/liter of hydrogen fluoride; (3) 55-95 grams/liter of sulfamic acid; (4) 55-95 grams/liter of glycol ether; and (5) balance water; (b) contacting the parts with the solution for a time sufficient to achieve the desired amount of cleaning and etching; (c) periodically measuring the etching rate of the solution; (d) when the etching rate is below the required minimum rate, adding sufficient hydrogen fluoride to restore the etching rate above the required minimum rate; and (e) periodically adding sufficient sulfamic acid to prevent the formation of scale made of hydrated aluminum fluoride.

In accordance with aspects of the invention, another exemplary embodiment of the present invention is a process for combined chemically cleaning and etching parts made of aluminum and/or aluminum alloys including: (a) providing a cleaning and etching solution including: (1) 5-35 grams/liter of phosphoric acid; (2) 5-35 grams/liter of hydrogen fluoride; (3) 120-220 grams/liter of sulfamic acid; (4) 55-95 grams/liter of glycol ether; and (5) balance water; (b) contacting the parts with the solution for a time sufficient to achieve the desired amount of cleaning and etching; (c) periodically measuring the etching rate of the solution; (d) when the etching rate is below the required minimum rate, adding sufficient hydrogen fluoride to restore the etching rate above the required minimum rate; and (e) periodically adding sufficient sulfamic acid to prevent the formation of scale made of hydrated aluminum fluoride.

In accordance with further aspects of the invention, another exemplary embodiment of the present invention is a solution for combined chemically cleaning and etching parts made of aluminum and/or aluminum alloys including: (a) 5-35 grams/liter of phosphoric acid; (b) 5-35 grams/liter of hydrogen fluoride; (c) 120-220 grams/liter of sulfamic acid; (d) 55-95 grams/liter of glycol ether; and (e) balance water.

DETAILED DESCRIPTION OF THE INVENTION Embodiments of the present invention solve both of the problems presented by the prior art. That is, embodiments of the present invention stabilize the etch rate and prevent scale from forming when cleaning and etching parts made of aluminum and/or aluminum alloys. The term"aluminum"will be used to refer to aluminum and/or aluminum alloys.

03-1027 PCT The following non-limiting examples illustrate the present invention.

Example 1 In Example 1, the starting solution contains the following constituents: (a) 5-35 grams/liter of phosphoric acid; (b) 5-35 grams/liter of hydrogen fluoride; (c) 55-95 grams/liter of sulfamic acid; (d) 55-95 grams/liter of glycol ether (solvent); and (e) balance water.

The preferred concentrations are 25-35 grams/liter of phosphoric acid, 25-35 grams/liter of hydrogen fluoride, 80-95 grams/liter of sulfamic acid, and 80-95 grams/liter of glycol ether (solvent).

The solvent is used in the solution in order to clean the aluminum parts by removing any soil that may be on them. The preferred solvent is propylene glycol monomethyl ether. The process is run at ambient temperature. The aluminum parts are immersed in the solution for the time that is sufficient to etch a specified amount.

The etching rate of the solution is measured periodically. When the etching rate falls below the required rate of 0.8 mils per side per hour, it is no longer within the applicable process specification, BAC 5786. About 0.5-1. 3 grams per liter of HP are added in order to restore the etch rate above 0.8 mils/side/hr. (This is accomplished, for example, by adding 1.0-2. 6 grams/liter of 49% by wt. reagent grade hydrofluoric acid.) This amount of HF addition was discovered after extensive etch rate testing. Titration results indicated there was a high acidity level, but the fluoride level did not correspond accordingly. There were no maintenance procedures available for the complex reactions occurring in the acid solution.

However, the HF additions do not mitigate the formation of scale in the tank. X- ray diffraction analysis indicated that the hard scale is primarily hydrated aluminum fluoride. After further research, it was discovered that sulfamic acid must be added in order to prevent the formation of hydrated aluminum fluoride. It was discovered that an adequate concentration of sulfamic acid is needed in order to chelate or otherwise bind with aluminum ions. Aluminum ions are generated during the etching process. Thus, an

03-1027 PCT addition of about 7-28 grams/liter of sulfamic acid is added periodically in order to compensate for the sulfamic acid that is bound by the chelating activity. The addition of sulfamic acid can be performed when additional HF is added to the solution or the sulfamic acid can be added at other times. The requirement is to periodically add sufficient sulfamic acid to prevent the formation of scale made of hydrated aluminum fluoride.

Example 2 In Example 2, the starting solution contains the following constituents: (a) 5-35 grams/liter of phosphoric acid; (b) 5-35 grams/liter of hydrogen fluoride; (c) 120-220 grams/liter of sulfamic acid; (d) 55-95 grams/liter of glycol ether (solvent); and (e) balance water.

The preferred starting concentrations are 25-35 grams/liter of phosphoric acid, 25- 35 grams/liter of hydrogen fluoride, 120-130 grams/liter of sulfamic acid, and 80-95 grams/liter of glycol ether.

The solvent is used in the solution in order to clean the aluminum parts by removing any soil that may be on them. The preferred solvent is propylene glycol monomethyl ether. The process is run at ambient temperature. The aluminum parts are immersed in the solution for the time that is sufficient to etch a specified amount.

The etching rate of the solution is measured periodically. When the etching rate falls below the required rate of 0.8 mils per side per hour, it is no longer within the specification. About 0.5-1. 3 grams per liter of HF are added (accomplished, for example, by adding 1.0-2. 6 grams/liter of 49% by wt. reagent grade hydrofluoric acid) in order to restore the etch rate to above 0.8 mils/side/hr.

In this example, the solution is started with an excess of sulfamic acid in order to prevent the formation of hydrated aluminum fluoride. As explained above, it was discovered that an adequate concentration of sulfamic acid is needed to prevent the formation of hydrated aluminum fluoride. Thus, an addition of about 7-28 grams/liter of sulfamic acid is added periodically in order to compensate for the sulfamic acid that is bound by the chelating activity. The addition of sulfamic acid can be performed when additional HF is added to the solution or the sulfamic acid can be added at other times.

The requirement is to periodically add sufficient sulfamic acid to prevent the formation of scale made of hydrated aluminum fluoride.

Unless indicated otherwise, in stating a numerical range for a compound or a temperature or a time or other process matter or property, such a range is intended to specifically designate and disclose the minimum and the maximum for the range and each number, including each fraction and/or decimal, between the stated minimum and maximum for the range. For example, a range of 1 to 10 discloses 1.0, 1.1, 1.2... 2.0, 2.1, 2.2,... and so on, up to 10.0. Similarly, a range of 500 to 1000 discloses 500, 501, 502,... and so on, up to 1000, including every number and fraction or decimal therewithin."Up to x"means"x"and every number less than"x", for example, "up to 5"discloses 0. 1, 0. 2, 0.3,..., and so on up to 5. 0.

While the preferred embodiments of the invention have been illustrated and described, as noted above, many changes can be made without departing from the spirit and scope of the invention. Accordingly, the scope of the invention is not limited by the disclosure of the preferred embodiments. Instead, the invention should be determined entirely by reference to the claims that follow.