US20230063860A1

US20230063860A1 - Copper treatment additive

Info

Publication number: US20230063860A1
Application number: US17/892,056
Authority: US
Inventors: Rod P. Sniadecki
Original assignee: Acs Enterprises D/b/a American Chemical LLC
Current assignee: Acs Enterprises D/b/a American Chemical LLC
Priority date: 2021-08-24
Filing date: 2022-08-20
Publication date: 2023-03-02
Also published as: WO2023028088A3; WO2023028088A2

Abstract

A copper treatment additive and methods are provided for applying copper to base metal effectively and efficiently while requiring a reduced frequency of replacing a treatment bath of copper sulfate solution. The copper treatment additive comprises an acidic, liquid mixture for use with a solution of copper sulfate and sulfuric acid to produce a strongly adherent, uniform metallic copper coating on steel. The copper treatment additive includes a first portion of Polyethylene Glycol 3350, a second portion of 4,4′-Methylene Dianiline; and a third portion of 31.45% Hydrochloric Acid. The copper coating has been observed to facilitate wire drawing processes and enhance characteristics associated with welding and decorative wire.

Description

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application claims the benefit of U.S. Provisional Patent Application No. 63/236,515, filed Aug. 24, 2021, the contents of which are hereby incorporated by reference in its entirety.

FIELD

Embodiments of the present disclosure generally relate to metalworking. More specifically, embodiments of the disclosure relate to a composition of matter and methods for a copper treatment additive for applying copper to base metal effectively and efficiently while requiring a reduced frequency of replacing a bath of copper sulfate solution.

BACKGROUND

Wire drawing is a metalworking process used to decrease the cross-section of a wire by pulling the wire through one or more drawing dies. Applications for wire drawing include electrical wiring, cables, welding wires, tension-loaded structural components, springs, paper clips, spokes for wheels, strings for musical instruments, and the like. Wire drawing typically is performed at room temperature and thus is classified as a cold working process. In some instances, however, wire drawing may be performed at elevated temperatures for large wires to reduce forces.
Lubrication during the wire drawing process is essential for maintaining a good surface finish and improving die longevity. Lubrication may be achieved by way of a pump that floods the dies with a suitable lubricant, such as oil. For example, wet drawing includes completely immersing dies and wire or rod in lubricants during the wire drawing process. Further, dry drawing includes passing the wire or rod through a container of lubricant so as to coat the surface of the wire or rod in preparation for the wire drawing process. In another example, metal coating includes coating the wire or rod with a soft metal that acts as a solid lubricant during the wire drawing process. In many instances, the wire may be immersed in a copper sulfate solution to deposit a film of copper that forms a kind of lubricant. In some classes of wire, the copper film is left on the wire after the final drawing to prevent rust and allow easy soldering.
A drawback to conventional wire immersion techniques is that large baths of copper sulfate solution must be changed every 1-3 days to maintain an effective adhesion of copper to the wire. Embodiments herein provide a copper treatment additive that prevents corrosion, oxidation, and other such issues on the surface or substrate of metal in manufacturing processes, such as wire drawing. The copper treatment additive of the present disclosure enables copper to be applied to base metal effectively and efficiently without a need for dumping the bath of copper sulfate solution as often, thereby reducing waste treatment and increasing cost savings.

SUMMARY

A copper treatment additive and methods are provided for applying copper to base metal effectively and efficiently while requiring a reduced frequency of replacing a treatment bath of copper sulfate solution. In various embodiments, the copper treatment additive comprises an acidic, liquid mixture for use with a solution of copper sulfate and sulfuric acid to produce a strongly adherent, uniform metallic copper coating on steel. The copper treatment additive includes a first portion of Polyethylene Glycol 3350, a second portion of 4,4′-Methylene Dianiline; and a third portion of 31.45% Hydrochloric Acid. The copper coating has been observed to facilitate wire drawing processes and enhance characteristics associated with welding and decorative wire.
In an exemplary embodiment, a copper treatment additive for applying copper to a base metal comprises: a first portion comprising Polyethylene Glycol 3350; a second portion comprising MDA; and a third portion comprising Hydrochloric Acid.
In another exemplary embodiment, the additive comprises an acidic, liquid mixture for use with a solution of copper sulfate and sulfuric acid to produce a strongly adherent, uniform metallic copper coating on steel. In another exemplary embodiment, the third portion comprises 31.45% Hydrochloric Acid.
In an exemplary embodiment, a method for preparing a batch of a copper treatment additive comprises: adding water to a 400-gallon stainless-steel tank; introducing Hydrochloric Acid; adding MDA to the stainless-steel tank; introducing Polyethylene Glycol 3350; mixing at a moderate speed; and adding additional water.
In another exemplary embodiment, adding water comprises adding 250 gallons to the stainless-steel tank. In another exemplary embodiment, adding the water includes setting a mixer comprising the stainless-steel tank to a slow setting.
In another exemplary embodiment, introducing Hydrochloric Acid includes gradually introducing 15 gallons of Hydrochloric Acid into the stainless-steel tank. In another exemplary embodiment, introducing Hydrochloric Acid includes allowing the mixer to slowly stir the contents of the stainless-steel tank.
In another exemplary embodiment, adding MDA includes adding 25 kg of MDA to the mixture of water and acid in the stainless-steel tank. In another exemplary embodiment, introducing Polyethylene Glycol 3350 includes adding 50 lbs. of Polyethylene Glycol 3350 into the stainless-steel tank.
In another exemplary embodiment, mixing at the moderate speed includes mixing for about 20 minutes. In another exemplary embodiment, adding additional water includes allowing the mixture to slowly stir for about IO minutes.
In an exemplary embodiment, a method for preparing a copper treatment bath comprises: building up the copper treatment bath; adjusting operations based on the type of metal to be treated; testing copper concentration of the copper treatment bath; testing free acid concentration in the copper treatment bath; and testing a concentration of copper treatment additive.
In another exemplary embodiment, building up the copper treatment bath includes filling a suitably sized tank to three quarters full of water. In another exemplary embodiment, filling includes adding about 46 lbs. (4 gal) of 66 Deg Be Sulfuric Acid followed by adding about 20 lbs. of Copper Sulfate Pentahydrate followed by adding about 9.5 lbs. (1.2 gal) of a copper treatment additive for each I00 gallons of the copper treatment bath.
In another exemplary embodiment, adjusting operations includes immersing wire to be treated in the copper treatment bath at a temperature ranging between about 70° F. and 170° F. for a length of time sufficient to produce a uniform copper coating on the wire. In another exemplary embodiment, adjusting operations includes establishing the temperature and the length of time that provide the best operating conditions for the type of metal to be treated and the requirements of a wire drawing process to be performed.
In another exemplary embodiment, testing the copper concentration includes increasing the copper concentration by adding 2 lbs. of copper sulfate pentahydrate for each I00 gallons of the copper treatment bath. In another exemplary embodiment, testing the free acid concentration includes increasing the free acid concentration by adding 4.7 lbs. (1 L) of 66 Deg Be Sulfuric Acid for each I00 gallons of the copper treatment bath.
In another exemplary embodiment, testing the concentration of copper treatment additive includes producing a predetermined volume of precipitate during a specific time period. In another exemplary embodiment, testing the concentration of copper treatment additive includes increasing the concentration of copper treatment additive in proportion to the volume of precipitate produced.
These and other features of the concepts provided herein may be better understood with reference to the drawings, description, and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block diagram illustrating an exemplary embodiment of a copper treatment additive for applying copper to base metal, according to the present disclosure;

FIG. 2 is a flow chart illustrating an exemplary embodiment of a method for preparing a batch of a copper treatment additive, according to the present disclosure; and

FIG. 3 is a flow chart illustrating an exemplary embodiment of a method for preparing an exemplary embodiment of a copper treatment bath in accordance with the present disclosure.

While the present disclosure is subject to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the drawings and will herein be described in detail. The invention should be understood to not be limited to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present disclosure.

DETAILED DESCRIPTION

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. It will be apparent, however, to one of ordinary skill in the art that the invention disclosed herein may be practiced without these specific details. In other instances, specific numeric references such as “first portion,” may be made. However, the specific numeric reference should not be interpreted as a literal sequential order but rather interpreted that the “first portion” is different than a “second portion.” Thus, the specific details set forth are merely exemplary. The specific details may be varied from and still be contemplated to be within the spirit and scope of the present disclosure. The term “coupled” is defined as meaning connected either directly to the component or indirectly to the component through another component. Further, as used herein, the terms “about,” “approximately,” or “substantially” for any numerical values or ranges indicate a suitable weight or volume tolerance that allows the part or collection of items to function for its intended purpose as described herein. For example, in some instances a variation of up to 10%, as a non-limiting example, in the stated amount may constitute the appropriate degree of “about.” Of course, depending on the intended purpose, the variation may even be larger as determined by one of ordinary skill in the art.
Wire drawing is a metalworking process used to decrease the cross-section of a wire by pulling the wire through one or more drawing dies. Lubrication during the wire drawing process is essential for maintaining a good surface finish and improving die longevity. Lubrication may be achieved by way of a pump that floods the dies with a suitable lubricant, such as oil. In many instances, the wire may be immersed in a copper sulfate solution to deposit a film of copper that forms a kind of lubricant. A drawback to conventional wire immersion techniques, however, is that large baths of copper sulfate solution must be changed every 1-3 days to maintain an effective adhesion of copper to the wire. Embodiments herein provide an inhibitor that enables copper to be applied to base metal effectively and efficiently without a need for dumping the bath of copper sulfate solution as often, thereby reducing waste treatment and increasing cost savings.
FIG. 1 is a block diagram illustrating an exemplary embodiment of a copper treatment additive 100 for applying copper to base metal, according to the present disclosure. The copper treatment additive 100 generally comprises an acidic, liquid mixture for use with a solution of copper sulfate and sulfuric acid to produce a strongly adherent, uniform metallic copper coating on steel. The copper coating has been observed to facilitate wire drawing processes and enhance characteristics associated with welding and decorative wire.
As shown in FIG. 1 , a batch (for this example, 400-gallons) of the copper treatment additive 100 includes a first portion 104 comprising Polyethylene Glycol 3350, a second portion 108 comprising 4,4′-Methylene Dianiline (MDA), and a third portion 112 comprising Hydrochloric Acid. Preferably, the third portion 112 comprises 31.45% Hydrochloric Acid. In one embodiment, the first portion 104 comprises one 50-lb. bag of Polyethylene Glycol 3350. In some embodiments, the first portion 104 may include an additional 20 lbs. of Polyethylene Glycol 3350, without limitation. In an embodiment, the second portion 108 comprises one 25 kg bag of MDA. In some embodiments, however, the second portion 108 may include an additional 20 lbs. of MDA, without limitation. Further, in some embodiments, the third portion 112 comprises 15 gallons of 31.45% Hydrochloric Acid.
FIG. 2 is a flow chart illustrating an exemplary embodiment of a method 120 for preparing a batch of the copper treatment additive 100, according to the present disclosure. The method 120 may begin at step 124 wherein about 250 gallons or water are added to a 400-gallon stainless steel or equivalent acid resistive tank. It is contemplated that the steel tank may include a mixer that is configured to mix or stir contents within the steel tank. In an embodiment, the mixer is set to a slow setting while the 250 gallons of water are added to the steel tank. With the mixer slowly stirring the contents of the steel tank, 15 gallons of Hydrochloric Acid may be gradually introduced into the steel tank in step 128.
In step 132, the MDA may be added to the tank. In an embodiment, 25 kg of MDA may be added to the mixture of water and acid in the steel tank. Next, in step 136, 50 lbs. of Polyethylene Glycol 3350 may be introduced into the steel tank. As may be required, additional MDA and Polyethylene Glycol 3350 may be added to the mixture in the steel tank, as described above. Once the prescribed quantities of MDA and Polyethylene Glycol 3350 have been added to the steel tank, the mixer may be increased to a moderate speed for example, for about 20 minutes to advantageously mix the contents within the steel tank.
Once the contents of the steel tank are sufficiently mixed, as described above, in step 140 additional water may be added to the mixture. In an embodiment, step 140 comprises turning down the mixer to the slow setting, adding water to the rim of the steel tank, and allowing the mixture to slowly stir for about 10 minutes. Once sufficiently to a slight amber hue.
FIG. 3 is a flow chart illustrating an exemplary embodiment of a method 160 that comprises preparing the copper treatment bath 100 in accordance with the present disclosure. The method 160 begins at a step 164 comprising building up the copper treatment bath. In step 164, a suitably sized tank may be filled to three quarters full of water. For each 100 gallons of working volume, about 46 lbs. (4 gal) of 66 Deg Be Sulfuric Acid may be added, followed by adding about 20 lbs. of Copper Sulfate Pentahydrate, followed by adding about 9.5 lbs. (1.2 gal) of the copper treatment additive 100 discussed with respect to FIG. 1 .
As shown in FIG. 3 , the method 160 includes a step 168 comprising adjusting operations based on the type of metal to be treated with the copper treatment additive 100. In some embodiments, wire to be treated may be immersed in the copper treatment bath, described with respect to step 164, at a temperature ranging between about 70° F. and 1 70° F. The wire may be immersed for a sufficient length of time to produce a uniform copper coating on the wire. In general, there is a broad range of both time and temperature that may be used to treat various metals. It is contemplated that the best operating conditions will depend largely on the type of metal being treated and the requirements of the particular wire drawing process to be performed. Once time and temperature have been established, adjustments may be made according to the specific requirements.
In step 172, the copper concentration in the copper treatment bath may be tested and adjusted as needed. In some embodiments, optional testing step 172 may be implemented. This step 172 includes pipetting a 10 ml sample into a 400 ml beaker, adding 50 ml of water and 3 ml of reagent solution 46, and then boiling gently for about 5 minutes. Once the cooled to room temperature, 5 ml of reagent solution 102 may be added, followed by slowly adding between 3 grams and 6 grams of reagent solution 101 while stirring until a pale milky gray color is obtained. Next, 2 grams of reagent 103 may be added, followed by 10 drops of indicator 10. Finally, the copper concentration may be determined by titrating with titrating solution 104 to a pale milky gray endpoint. The volume of titrating solution 104 used, expressed in a number of milliliters, represents the copper concentration value in points. Preferably, the copper concentration ranges between about 6.0 points and about 9.5 points. The copper concentration of the copper treatment bath may be increased by one point by adding 2 lbs. of copper sulfate pentahydrate for each 100 gallons of the copper treatment bath.
Step 176 can be another optional testing step. In step 176, the free acid in the copper treatment bath may be tested and adjusted as needed. In some embodiments, step 176 includes pipetting a 10 ml sample into a 150 ml beaker and then titrating with titrating solution 89 to the formulation of a permanent precipitate that does not dissolve with stirring. The volume of titrating solution 89 used, expressed in a number of milliliters, represents the free acid value in points. The free acid value advantageously ranges between about 12 points and about 14 points. The free acid concentration of the copper treatment bath may be increase by one point by adding 4.7 lbs. (1 L) of 66 Deg Be Sulfuric Acid for each 100 gallons of the copper treatment bath.
As shown in FIG. 3 , the method 160 concludes with another optional step 180 wherein the concentration of copper treatment additive 100 in the bath may be tested. In some embodiments, a mixture of 40 ml of water and a 50 ml sample may be added to a 100 ml stoppered, graduated cylinder. The mixture may be mixed thoroughly by inverting the cylinder 5 or 6 times and then positioning the cylinder on a level surface for substantially 10 minutes. A level of precipitate within the cylinder is to be read within the remaining 0.5 minutes of the required elapsed time. Experimental observation has shown that the mixture should produce 16 ml of precipitate in 10 minutes. If the volume of precipitate is greater than 16 ml, then no additional copper treatment additive 100 needs to be added to the copper treatment bath. However, if the volume of precipitate is less than 16 ml, then for each milliliter less than 16 ml, 0.8 lbs. (380 ml) of the copper treatment additive 100 should be added for every 100 gallons of the copper treatment bath.
In view of the above disclosure, it is understood the weight or volume of the material quantities listed above can be proportionately altered to produce less or more of the copper treatment additive. As a non-limiting example, for a 200 gal. quantity, the respective ingredients/materials can be halved. Therefore, various changes and modification to the above “recipe(s)” can be made and are understood to be within the scope of this disclosure.
While the invention has been described in terms of particular variations and illustrative figures, those of ordinary skill in the art will recognize that the invention is not limited to the variations or figures described. In addition, where methods and steps described above indicate certain events occurring in certain order, those of ordinary skill in the art will recognize that the ordering of certain steps may be modified and that such modifications are in accordance with the variations of the invention. Additionally, certain of the steps may be performed concurrently in a parallel process when possible, as well as performed sequentially as described above. To the extent there are variations of the invention, which are within the spirit of the disclosure or equivalent to the inventions found in the claims, it is the intent that this patent will cover those variations as well. Therefore, the present disclosure is to be understood as not limited by the specific embodiments described herein, but only by scope of the appended claims.

Claims

What is claimed is:

1. A copper treatment additive for applying copper to a base metal, the additive comprising:

a first portion comprising Polyethylene Glycol 3350;

a second portion comprising MDA; and

a third portion comprising Hydrochloric Acid.

2. The additive of claim 1, wherein the additive comprises an acidic, liquid mixture for use with a solution of copper sulfate and sulfuric acid to produce a strongly adherent, uniform metallic copper coating on steel.

3. The additive of claim 1, wherein the third portion comprises 31.45% Hydrochloric Acid.

4. A method for preparing a batch of a copper treatment additive, comprising:

adding water to an acid resistant tank;

introducing Hydrochloric Acid;

adding MDA to the tank;

introducing Polyethylene Glycol 3350;

mixing at a predetermined speed; and

adding additional water.

5. The method of claim 4, wherein the adding water comprises adding 250 gallons to the tank.

6. The method of claim 5, wherein the adding water further comprises setting a mixer in the tank to a slow setting.

7. The method of claim 4, wherein the introducing Hydrochloric Acid includes gradually introducing 15 gallons of Hydrochloric Acid into the tank.

8. The method of claim 7, wherein the introducing Hydrochloric Acid includes allowing the mixer to slowly stir the contents of the tank.

9. The method of claim 4, wherein the adding MDA includes adding 25 kg of MDA to the tank.

10. The method of claim 4, wherein the introducing Polyethylene Glycol 3350 includes adding 50 lbs. of Polyethylene Glycol 3350 into the tank.

11. The method of claim 4, wherein mixing at the moderate speed includes mixing for about 20 minutes.

12. The method of claim 4, wherein the adding additional water includes allowing the mixture to slowly stir for about 10 minutes.

13. A method for preparing a copper treatment bath, comprising:

building up the copper treatment bath;

adjusting operations based on the type of metal to be treated;

testing copper concentration of the copper treatment bath;

testing free acid concentration in the copper treatment bath; and

testing a concentration of copper treatment additive.

14. The method of claim 13, wherein building up the copper treatment bath includes filling a suitably sized tank to three quarters full of water.

15. The method of claim 14, wherein filling includes adding about 46 lbs. (4 gal) of 66 Deg Be Sulfuric Acid followed by adding about 20 lbs. of Copper Sulfate Pentahydrate followed by adding about 9.5 lbs. (1.2 gal) of a copper treatment additive for each 100 gallons of the copper treatment bath.

16. The method of claim 13, wherein adjusting operations includes immersing wire to be treated in the copper treatment bath at a temperature ranging between about 70 deg. F. and 170 deg. F. for a length of time sufficient to produce a uniform copper coating on the wire.

17. The method of claim 16, wherein testing the copper concentration includes increasing the copper concentration by adding 2 lbs. of copper sulfate pentahydrate for each 100 gallons of the copper treatment bath.

18. The method of claim 13, wherein testing the copper concentration includes increasing the copper concentration by adding 2 lbs. of copper sulfate pentahydrate for each 100 gallons of the copper treatment bath.

19. The method of claim 13, wherein testing the free acid concentration includes increasing the free acid concentration by adding 4.7 lbs. (1 L) of 66 Deg Be Sulfuric Acid for each 100 gallons of the copper treatment bath.

20. The method of claim 13, wherein testing the concentration of copper treatment additive includes producing a predetermined volume of precipitate during a predetermined time period.

21. The method of claim 20, wherein testing the concentration of copper treatment additive includes increasing the concentration of copper treatment additive in proportion to the volume of precipitate produced.