Metal pretreatment composition containing zirconium, copper, zinc and nitrate and related coatings on metal substrates

Abstract

A pretreatment composition for metal that provides enhanced corrosion resistance, enhanced paint adhesion and reduced chip damage to a wide variety of metal substrates. The pretreatment is also cleaner because it is based on zirconium rather than zinc phosphates. The pretreatment coating composition in use preferably comprises 50 to 300 parts per million (ppm) zirconium, 0 to 100 ppm of SiO.sub.2, 150-2000 ppm of total fluorine and 10-100 ppm of free fluorine, 150 to 10000 ppm of zinc and 10 to 10000 ppm of an oxidizing agent and has a pH of 3.0 to 5.0, preferably about 4.0. The coating composition can optionally include 0 to 50 ppm of copper. The suitable oxidizing agents can be selected from a large group.

Claims

1. A metal pretreatment coating composition comprising the following components: 50 to 300 ppm of zirconium; 10 to 50 ppm of copper; 10 to 100 ppm of SiO.sub.2; 150 to 2000 ppm total fluorine; 10 to 100 ppm free fluorine; 600 to 7900 ppm zinc; and 10 to 10,000 ppm of an oxidizing agent; and having an acidic pH; wherein at least one oxidizing agent is nitrate, present in an amount of from 600 to 10,000 ppm and said components are selected such that the coating composition is capable of depositing an amount of zirconium and a coating thickness that are both less than an otherwise identical coating composition that is devoid of zinc under the same process conditions.

2. The metal pretreatment coating composition according to claim 1 comprising 75 to 300 ppm of zirconium, 10 to 40 ppm of copper and 20 to 100 ppm of SiO.sub.2.

3. The metal pretreatment coating composition according to claim 1 wherein said oxidizing agent comprises at least one of a nitrite ion or salt, an inorganic peroxide, a permanganate ion or salt, a persulfate ion or salt, a perborate ion or salt, a chlorate ion or salt, a hypochlorite ion or salt, a vanadate ion or salt, a vanadyl ion or salt, a ceric ion or salt, a tungstate ion or salt, a stannic ion or salt, a hydroxylamine, a nitro-compound, an amine oxide, hydrogen peroxide, or a mixture thereof.

4. The metal pretreatment coating composition according to claim 3 wherein said oxidizing agent comprises at least one of ammonium nitrate, sodium nitrate, potassium nitrate, sodium nitrite, sodium peroxide, potassium permanganate, sodium persulfate, sodium perborate, sodium chlorate, sodium hypochlorite, sodium vanadate, vanadyl sulfate, ceric sulfate, ceric ammonium sulfate, ceric ammonium nitrate, sodium tungstate, stannic fluoride, hydroxylamine, hydroxylamine sulfate, sodium nitrobenzene sulfonate, sodium m-nitrobenzene sulfonate, and N-methylmorpholine N-oxide.

5. The metal pretreatment coating composition according to claim 3 wherein said oxidizing agent comprises hydrogen peroxide present in an amount of from 10 to 30 ppm.

6. The metal pretreatment coating composition according to claim 1 having a pH of about 3.0 to about 5.0.

7. The metal pretreatment coating composition according to claim 1 wherein said oxidizing agent comprises hydrogen peroxide present in an amount of from 10 to 30 ppm and has a pH of about 3.5 to about 4.5.

8. The metal pretreatment coating composition according to claim 1 wherein said oxidizing agent further comprises an ion or salt of sulfate present in an amount of from 600 to 10000 ppm.

9. The metal pretreatment coating composition according to claim 1 wherein Zn is present in an amount of 900 ppm or more and the oxidizing agent is present in an amount greater than 5000 ppm.

10. The metal pretreatment coating composition according to claim 1 wherein zinc is present in an amount greater than 5000 ppm and the oxidizing agent also contains hydrogen peroxide.

11. The metal pretreatment coating composition according to claim 1 wherein the composition comprises 50-300 ppm of zirconium, 10-50 ppm of copper, 10-100 ppm SiO.sub.2, 150-2000 ppm total fluorine, 10-100 ppm free fluorine, 1200 to 4800 ppm zinc, and 3000 to 10,000 ppm nitrate.

12. The metal pretreatment coating composition according to claim 1 wherein the composition comprises 100-200 ppm Zr, 10-40 ppm Cu, 10-100 ppm SiO.sub.2, 150-1100 total fluorine, 10-100 ppm free fluorine, 900-5000 ppm Zn, and 2000-10,000 ppm nitrate.

13. The metal pretreatment coating composition according to claim 1 wherein zinc is present in an amount of from 600 to 4800 ppm.

14. The metal pretreatment coating composition according to claim 1 wherein the pretreatment composition contains only further metal ions selected from the group consisting of sodium, potassium, tin, vanadium and cerium.

15. The metal pretreatment coating composition according claim 1, wherein zinc is present in an amount of from 600 to 4800 ppm and the oxidizing agent is present in an amount of 900 to 7000 ppm.

16. The metal pretreatment coating composition according to claim 1, wherein zinc is present in an amount of from 600 to 3000 ppm.

17. The metal pretreatment coating composition according claim 1, wherein zinc is present in an amount of from 600 to 2400 ppm.

18. The metal pretreatment coating composition according claim 1, wherein zinc is present in an amount of from 900 to 3000 ppm.

19. The metal pretreatment coating composition according claim 1, wherein zinc is present in an amount of from 900 to 2700 ppm.

20. The metal pretreatment coating composition according claim 1, wherein the nitrate is present in an amount of from 1,000 to 10,000 ppm.

21. The metal pretreatment coating composition according claim 1, wherein the nitrate is present in an amount of from 5500 to 10,000 ppm.

22. A metal pretreatment coating composition consisting of: 50 to 300 ppm of zirconium, 10 to 50 ppm of copper, 10 to 100 ppm of SiO.sub.2, 150 to 2000 ppm total fluorine, 10 to 100 ppm free fluorine, 600 to 7900 ppm zinc, and 10 to 10,000 ppm of an oxidizing agent.

23. The metal pretreatment coating composition according to claim 22 wherein hydrogen peroxide is present as an oxidizing agent in an amount of from 10 to 100 ppm.

24. A metal pretreatment coating composition comprising: 50 to 300 ppm of zirconium, 10 to 50 ppm of copper, 10 to 100 ppm of SiO.sub.2, 150 to 2000 ppm total fluorine, 10 to 100 ppm free fluorine, 600 to 7900 ppm zinc, and 10 to 10000 ppm of an oxidizing agent, and wherein the pretreatment composition contains only further metal ions selected from the group consisting of sodium, potassium, tin, vanadium and cerium, wherein said components are selected such that the coating composition is capable of depositing an amount of zirconium and a coating thickness on a metal substrate that are both less than an otherwise identical coating composition that is devoid of zinc under the same process conditions.

25. The metal pretreatment coating composition according to claim 24 wherein zinc is present in an amount of from 600 to 4800 ppm.

26. The metal pretreatment coating composition according to claim 24, wherein zinc is present in an amount of from 600 to 3000 ppm.

27. The metal pretreatment coating composition according claim 24, wherein zinc is present in an amount of from 600 to 2400 ppm.

28. The metal pretreatment coating composition according claim 24, wherein zinc is present in an amount of from 900 to 3000 ppm.

29. The metal pretreatment coating composition according claim 24, wherein zinc is present in an amount of from 900 to 2700 ppm.

30. The metal pretreatment coating composition according to claim 24, wherein said oxidizing agent comprises at least one of a nitrite ion or salt, an inorganic peroxide, a persulfate ion or salt, a perborate ion or salt, a chlorate ion or salt, a hypochlorite ion or salt, a vanadate ion or salt, a vanadyl ion or salt, a ceric ion or salt, a stannic ion or salt, a hydroxylamine, a nitro-compound, an amine oxide, or a mixture thereof.

31. The metal pretreatment coating composition according claim 24, wherein at least one oxidizing agent is nitrate, present in an amount of from 600 to 10,000 ppm.

32. The metal pretreatment coating composition according claim 24, wherein said oxidizing agent comprises an ion or salt of sulfate present in an amount of from 600 to 10,000 ppm.

Description

DETAILED DESCRIPTION

(1) The present invention is directed toward improved conversion pretreatment coating compositions for coating a variety of metal substrates to provide corrosion resistance to the substrates. In particular the metal substrates that can be passivated, provided with enhanced corrosion resistance, by the pretreatment coating compositions of the invention include cold rolled steel (CRS), hot-rolled steel, stainless steel, steel coated with zinc metal, zinc alloys such as electrogalvanized steel (EG), galvalume, galvanneal (HIA), and hot-dipped galvanized steel (HDG), aluminum alloys such as AL6111 and aluminum plated steel substrates. The invention also offers the advantage that components containing more than one type of metal substrate can be passivated in a single process because of the broad range of metal substrates that can be passivated by the pretreatment coating compositions of the invention.

(2) The inventive pretreatment is zirconium based and thus is cleaner than phosphate based pretreatments. It can be substituted in a normal pretreatment process without significant changes to the process. Preferably the pretreatment coating composition comprises: 50 to 300 ppm of zirconium, 0 to 100 ppm of SiO.sub.2, 0 to 50 ppm of copper, 150 to 2000 ppm of total fluorine, 10 to 100 ppm of free fluorine, 150 to 10000 ppm of zinc and 10 to 10000 ppm of an oxidizing agent. The pretreatment coating composition has an acidic pH of preferably 3.0 to 5.0, more preferably from 3.5 to 4.5. The oxidizer agent can include oxidizing ions and salts thereof and may include a mixture of oxidizing agents. Especially preferred in the present invention is use of nitrate salts and ions as the oxidizing agent. Examples of suitable nitrates include ammonium nitrate, sodium nitrate and potassium nitrate. Other oxidizing agents, as ions or salts, that are expected to be able to replace or enhance the function of the nitrate ion include: nitrite ion, inorganic peroxides, permanganate ion, persulfate ion, perborate ion, chlorate ion, hypochlorite ion, vanadate ion, vanadyl ion, ceric ion, tungstate ion, stannic ion, hydroxylamines R.sub.2—NOH, nitro-compounds R—NO.sub.2, amine oxides R.sub.3—NO and hydrogen peroxide. Examples of useful sources of these include: sodium nitrite, sodium peroxide, potassium permanganate, sodium persulfate, sodium perborate, sodium chlorate, sodium hypochlorite, sodium vanadate, vanadyl sulfate, ceric sulfate, ceric ammonium sulfate, ceric ammonium nitrate, sodium tungstate, stannic fluoride, hydroxylamine, hydroxylamine sulfate, sodium nitrobenzene sulfonate, sodium m-nitrobenzene sulfonate, and N-methylmorpholine N-oxide. The oxidizing agent is preferably present in the pretreatment coating composition at a level of from 10 to 10000 ppm, the most preferred levels are determined in part by their redox potential in that oxidizers with a higher redox potential can be used at lower levels. For example, hydrogen peroxide can be used at levels of from 10 to 30 ppm, whereas nitrate or sulfates are preferably used at levels of from 600 to 10000 ppm.

(3) The pretreatment coating composition can be used in the standard processes for metal pretreatment. These generally involve an initial cleaning of the metal substrate with an acidic or alkaline cleaner. Examples include the Parco® Cleaners such as 1533 or 1523 which are typically applied via spray, immersion bath or both for 60 to 120 seconds at about 50° C. per the manufacture's directions. Other alkaline or acidic metal cleaners are also expected to work in the present invention. The cleaning step is generally followed by several warm water rinses with city water and deionized water. After these rinses the pretreatment coating of the present invention is applied via spray, immersion bath or both for a period of time generally ranging from 60 to 120 seconds. Typically, the exposure occurs at temperatures of about 25° C. After exposure to the pretreatment coating composition the substrate is generally again rinsed with warm deionized water and blown dry. After the pretreatment coating in the industry the substrates are often covered in an electrocoating and then painted with a topcoat. The electrocoatings are available from many sources and often include a post application baking step to dry the film in place. The typical electrocoating film thicknesses are from about 0.7 to 1.2 mils in thickness. After the electrocoating the substrates are often painted with a topcoating system. These systems typically include a primer coating, a paint basecoat and then a clearcoat. Typical dry film thicknesses for these topcoats are from 0.9 to 1.3 mils dry film thickness.

(4) Substrates coated with the pretreatment coating of the present invention alone or after electrocoating and perhaps topcoating are typically tested for corrosion resistance in standardized testing protocols. The substrates with coatings are scribed down to the substrate level and then exposed to various humidity levels, temperatures and salt sprays. Often the pretreatment coatings are tested for their effects on paint adhesion to the substrates. In this testing the substrate is first cleaned and coated with the pretreatment coating. Then an electrocoating is applied followed by a topcoating. The panels are then subjected to mechanical stresses such as being stored at very low temperatures well below freezing and then having gravel flung at it at high pressure to simulate road debris. The amount of paint chipping and other damage is then observed. The goal is to develop pretreatment coating compositions that enhance corrosion resistance and paint adhesion to a variety of substrates.

(5) A new pretreatment designed in accordance with the present invention will result in enhanced corrosion protection, enhanced paint adhesion of subsequently applied electrocoatings and topcoatings and lower zirconium incorporation than past pretreatments. The pretreatment according to the present invention has as important elements the presence of zinc and an oxidizing agent. The oxidizing agent can be selected from a large group including nitrate salts and ions as the oxidizing agent. Examples of nitrates include ammonium nitrate, sodium nitrate and potassium nitrate. Other oxidizing agents, as ions or salts, that can replace the function of the nitrate ion include: nitrite ion, inorganic peroxides, permanganate ion, persulfate ion, perborate ion, chlorate ion, hypochlorite ion, vanadate ion, vanadyl ion, ceric ion, tungstate ion, stannic ion, hydroxylamines R.sub.2—NOH, nitro-compounds R—NO.sub.2, amine oxides R.sub.3—NO and hydrogen peroxide. Examples of useful sources of these include: sodium nitrite, sodium peroxide, potassium permanganate, sodium persulfate, sodium perborate, sodium chlorate, sodium hypochlorite, sodium vanadate, vanadyl sulfate, ceric sulfate, ceric ammonium sulfate, ceric ammonium nitrate, sodium tungstate, stannic fluoride, hydroxylamine, hydroxylamine sulfate, sodium nitrobenzene sulfonate, sodium m-nitrobenzene sulfonate, and N-methylmorpholine N-oxide. The oxidizing agent is preferably present in the pretreatment coating composition at a level of from 10 to 10000 ppm, the most preferred levels are determined in part by their redox potential in that oxidizers with a higher redox potential can be used at lower levels. For example, hydrogen peroxide can be used at levels of from 10 to 30 ppm, whereas nitrate is preferably used at levels of from 600 to 10000 ppm. The oxidizing agents can be used alone or in combination with each other. Of course, it will be understood that the coating composition of the present invention can be provided as a concentrated composition that is diluted with water prior to use to produce the recited levels of the components.

(6) The pretreatment coating composition of the present invention finds use as a pretreatment coating for a wide range of metal substrates and provides enhanced corrosion resistance to the substrates and enhanced paint adhesion. The treated metal substrates are used in many products including automotive, aeronautics, appliance and other manufacturing industries. Preferably when diluted to usage levels the pretreatment coating composition according to the present invention has the composition detailed below in TABLE 1.

(7) TABLE-US-00001 TABLE 1 Zr, Cu, SiO.sub.2, F, total F, free Zn, Oxidizer ppm ppm ppm ppm ppm ppm ppm pH Using 50- 0-50 0-100 150- 10-100 150- 600- 4.00 nitrate 300 2000 10000 10000 oxidizer Using 50- 0-50 0-100 150- 10-100 150- 600- 4.00 sulfate 300 2000 10000 10000 oxidizer Using 50- 0-50 0-100 150- 10-100 150-  10- 4.00 other 300 2000 10000 10000 oxidizers

(8) Surprisingly, the present invention provides for enhanced corrosion protection and improved paint adhesion despite resulting in much thinner pretreatments coating layers than the prior systems.

EXAMPLES

(9) The standard pretreatment coating process for all of the data, unless otherwise noted, was as described below in TABLE 2 using the pretreatment coating compositions. The Parco® Cleaner 1533 is an alkaline cleaner available from Henkel Adhesive Technologies. The control pretreatment coating composition was a zirconium based pretreatment coating composition with no zinc and a very low level of NO.sub.3.

(10) TABLE-US-00002 TABLE 2 Treat- Time, Temperature Stage ment Product Application seconds ° C. 1 Clean Parco ® Spray 120 50 Cleaner 1533 2 Rinse Water Spray 60 38 3 Rinse Deionized Spray 60 25 water 4 Pre- Test Immersion 120 25 treatment pretreatment solution 5 Rinse Deionized Spray 60 25 water

(11) In a first series of experiments a control pretreatment coating composition with no zinc and a very low level of nitrate was supplemented with various levels of zinc and nitrate, and applied to a variety of substrates. The pretreatment coating compositions are detailed below in TABLE 3. Pretreatment example 1 is the control pretreatment coating composition. Pretreatments 2 to 5 have increasing amounts of zinc and nitrate added to them.

(12) TABLE-US-00003 TABLE 3 Pretreatment Zr, Cu, SiO.sub.2, F, total F, free Zn, NO.sub.3, example ppm ppm ppm ppm ppm ppm ppm pH 1 control 150 20 50 360 35 0 100 4.00 2 150 20 50 360 35 600 1600 4.00 3 150 20 50 360 35 1200 3000 4.00 4 150 20 50 360 35 1800 4200 4.00 5 150 20 50 360 35 2400 5500 4.00

(13) The pretreatments were applied, as described above, to the following substrates: cold rolled steel (CRS); electrogalvanized steel (EG); hot-dipped galvanized steel (HDG); galvanneal steel (HIA); and the aluminum alloy AL6111. As an initial measure the zirconium coating weight in milligrams per meter squared on each substrate was determined by X-ray fluorescence and the results are presented below in TABLE 4. In general, as the levels of zinc and nitrate increased the zirconium coating weight was reduced on all of the tested substrates.

(14) TABLE-US-00004 TABLE 4 Zirconium Coating Weight, mg/m.sup.2 Pretreatment CRS EG HDG HIA AL6111 1 control 130 290 240 230 50 2 100 230 200 210 50 3 50 150 110 120 30 4 60 170 120 120 40 5 60 150 90 130 30

(15) In a next series of experiments another control pretreatment coating, Bonderite® 958 (B-958), was also incorporated so that the performance of the pretreatments of the present invention could also be compared to an industry standard zinc phosphate based pretreatment, B-958. All of the samples were pretreated as described in TABLE 2 above except for the Bonderite® 958 sample, which was treated per the manufacture's instructions. The pretreated samples were then coated with cathodic electrocoat primer, scribed to substrate level and then placed in corrosion testing as described below. The electrocoating was with BASF electrocoat CathoGuard® 310X with an application time of 2 minutes at a temperature of 90° F. (32.2° C.) and an application voltage of 230 Volts. The samples were baked at 320° F. (160.0° C.) for 20 minutes and resulted in a dry film thickness of 0.8 to 1.1 mils. Panels of each pretreatment after electrocoating were subjected to 40 continuous corrosion cycles that were 24 hours each as described below. A pH 6 to 9 salt mist spray comprising 0.9% by weight sodium chloride, 0.1% by weight calcium chloride, and 0.25% by weight sodium bicarbonate was prepared. The test panels were placed in an environment of 25° C. and 40 to 50% relative humidity (RH). Over the first 8 hours the panels were misted with the salt mist spray at time 0, 1.5 hours, 3 hours, and at 4.5 hours. After the first 8 hours the panels were subjected to 49° C. and 100% RH with a ramp up from 25° C. and 40 to 50% RH over the first hour. The panels showed visible water droplets on them. The last 8 hours of the 24 hour cycle was to ramp up to 60° C. and down to less than 30% RH over a 3 hour period and then hold these conditions for another 5 hours. This completed one 24 hour cycle and the panels were subjected to 40 total cycles. The panels were evaluated for average corrosion creep from the scribe line and maximum corrosion creep from the scribe line in millimeters. The results are presented below in TABLE 5A and 5B.

(16) TABLE-US-00005 TABLE 5A HDG CRS, EG HDG maxi- average CRS average EG average mum Pre- creep maximum creep maximum creep creep treatment mm creep mm mm creep mm mm mm B-958 2.8 3.8 1.0 1.7 0.7 1.6 control 1 3.7 7.2 1.0 2.0 1.0 2.4 control 2 4.8 6.6 1.5 3.0 1.2 2.8 3 3.6 6.3 0.9 3.0 0.6 0.8 4 2.9 5.0 0.9 2.0 0.6 1.7 5 2.6 3.8 1.1 2.1 0.9 2.0

(17) TABLE-US-00006 TABLE 5B HIA HIA AL6111 AL6111 average maximum average maximum Pretreatment creep mm creep mm creep mm creep mm B-958 control 0.9 1.5 0.5 0.6 1 control 0.9 1.5 0.5 0.5 2 0.7 1.3 0.6 0.7 3 0.9 1.3 0.6 0.7 4 0.7 0.8 0.5 0.5 5 0.7 0.9 0.5 0.5

(18) The results show that the pretreatments according to the present invention show improved anti-corrosion performance on CRS, HDG, HIA, and AL6111 substrates, but no real change on EG. In some cases, the pretreatments of the present invention performed as well as B-958 and increasing levels of zinc and nitrate seemed to perform better.

(19) In a next series of tests panels coated with the pretreatments were then finish coated with BASF Topcoat system to produce panels having a pretreatment, electrocoat, primer, base paint coat, and clear coat. The BASF Topcoat system comprised a primer of PUA1177C powder, a basecoat of R98WU321S, a clearcoat of R10CG060S and produced a total film thickness of 5.0 to 8.0 mils, and a basecoat thickness of 1.0 to 1.2 mils. The panels were then tested for their resistance to paint chipping using a gravelometer as known in the industry. The basic protocol was as follows: the 100 by 300 millimeter test panels were placed at −30° C. for 4 hours; then put into a gravelometer and 1 pint of gravel having a size such that it fell through a 16 millimeter screen and was retained on a 9.5 millimeter space screen was thrown at it using an air pressure of 70 pounds per square inch (0.48263 mega Pascal). The panel was removed, dust and condensation moisture were wiped off of the panel. The panel was then covered with a 100 millimeter strip of masking tape, pressed firmly and then the tape was removed to pull off loose chips and paint. The panels were then visually examined and the extent of chip damage compared to photographic standards. The damage was rated from 0 to 10 with 0 being failure and extensive chip damage and 10 being no visible chip damage. In addition, the average chip diameter was determined in millimeters. The results are presented below in TABLE 6A and 6B. The pretreatments of the present invention performed very well on the chip testing. The present invention pretreatments performed better than the control pretreatment and at the highest levels of zinc and nitrate they performed as well as the industry standard B-958. This data shows that for many substrates the pretreatments of the present invention improve paint adhesion compared to a control pretreatment.

(20) TABLE-US-00007 TABLE 6A CRS EG HDG average average average CRS chip EG chip HDG chip damage diameter damage diameter damage diameter Pretreatment rating mm rating mm rating mm B-958 9 2 9 4 9 2 control 1 control 7 5 8 4 8 4 2 7 5 9 2 9 2 3 8 4 9 3 9 3 4 9 2 9 3 9 3 5 9 2 9 2 9 3

(21) TABLE-US-00008 TABLE 6B HIA AL6111 HIA average chip AL6111 average chip damage diameter damage diameter Pretreatment rating mm rating mm B-958 control 9 3 10 0 1 control 9 3 10 0 2 9 3 10 0 3 9 3 10 0 4 9 3 10 0 5 9 2 10 0

(22) For the next series of experiments another series of pretreatment compositions were prepared as detailed below in TABLE 7. The pretreatments were then applied to CRS and the zirconium coating weight in milligrams per meter squared was determined. In addition, the coating thicknesses in nanometers (nm) and atomic percentages (At %) of several key elements in the coatings were determined by X-ray photoelectron spectroscopy for several of the coatings. These results are presented below in TABLE 8.

(23) TABLE-US-00009 TABLE 7 Pretreatment Zr, Cu, SiO.sub.2, F, total F, free Zn, NO.sub.3, example ppm ppm ppm ppm ppm ppm ppm pH  6 control 150 20 50 200 15 0 100 4.00  7 150 20 50 400 35 600 1600 4.00  8 150 20 50 500 35 1200 3000 4.00  9 150 20 50 500 35 1800 4200 4.00 10 150 20 50 500 35 2400 5500 4.00 11 150 20 50 500 35 3000 6800 4.00

(24) TABLE-US-00010 TABLE 8 Coating Zr wt thickness, Pretreatment (mg/m.sup.2) nm Zr At % Fe At % Cu At % Zn At %  6 control 101 65 24 12 8 0  7 83 50 20 16 9 0.5  8 54 45 16 18 10 1.5  9 45 10 30 11 18

(25) The data show several interesting trends. As demonstrated above as the levels of zinc and nitrate increase the coating weight of zirconium goes down. The data also shows that the levels of zinc and nitrate also affect coating thickness and atomic make up. The increasing levels of zinc and nitrate decrease the coating thickness. Increasing levels of zinc and nitrate also result in less zirconium in the coating as shown before but also more iron and more copper. In addition, there is some incorporation of zinc into the coating.

(26) In the next series of tests, the coatings from TABLE 7 or B-958 were applied to CRS panels and the panels were subjected to a variety of corrosion testing protocols after being scribed. In a 30 cycle test the panels were subjected to 30 cycles of a 24 hour testing protocol similar to that described above. The salt misting spray comprised 0.9% by weight sodium chloride, 0.1% by weight calcium chloride, and 0.075% by weight sodium bicarbonate. The first 8 hours the panels were kept at 25° C. and 45% RH and misted 4 times during the 8 hours as described above. The panels were then put at 49° C. and 100% RH for the next 8 hours. The final 8 hours were at 60° C. and less than 30% RH. The cycle was carried out for a total of 30 times. The panels were then evaluated for average corrosion creep and maximum corrosion creep in millimeters from the scribe. The panels were also tested for 500 or 1000 hours using ASTM B117 protocol. The results are presented below in TABLE 9. The results demonstrate that the pretreatments prepared according to the present invention perform better in cyclic corrosion testing than the control pretreatment.

(27) TABLE-US-00011 TABLE 9 30 ASTM ASTM 30 cycle B117 ASTM B117 ASTM cycle maxi- 500 hr B117 1000 hr B117 average mum average 500 hr average 1000 hr Pre- creep creep creep maximum creep maximum treatment mm mm mm creep mm mm creep mm B-958 2.5 3.6 1.7 2.6 2.6 3.4 control 6 6.5 8.3 4.9 7.6 15.6 26.7 control 7 4.8 5.3 1.7 2.7 4.1 6.7 8 4.5 5.6 1.5 2.2 4.2 6.8 9 3.9 5.0 1.7 2.4 5.4 8.4 10 3.7 4.4 1.7 2.1 4.0 5.9 11 3.5 4.1 1.6 2.0 3.8 5.6

(28) Several of these pretreatments were also tested in a gravelometer test. For these tests the CRS panels with pretreatment applied were then covered with either the BASF Topcoat system as described above or the DuPont Topcoat system. The DuPont Topcoat system used primer 765224EH, basecoat 270AC301, clearcoat RK8148 and produced a dry total film thickness of 5.0 to 8.0 mils, and a dry basecoat thickness of 1.0 to 1.2 mils. The panels were subjected to the gravelometer test and the number of chips in a 4 inch by 6 inch (10.2 cm by 15.2 cm) section of each panel were determined. In addition, the average chip diameter in millimeters was determined. The results are shown below in TABLE 10. The pretreatments according to the present invention were significantly better than the control pretreatment. The number of chips was significantly lower and the chips were smaller with pretreatments according to the present invention. As the amount of zinc and nitrate were increased the pretreatment was more effective.

(29) TABLE-US-00012 TABLE 10 DuPont BASF BASF DuPont average number average chip number chip diameter of diameter Pretreatment of chips mm chips mm B-958 control 5 1.7 8 1.6 6 control 12 2.2 9 1.8 7 10 1.7 7 1.9 8 6 1.6 6 1.8

(30) In the next series of experiments the nitrate was replaced with sulfate as the counter ion to determine if this counter ion can replace nitrate. The pretreatment compositions are presented below in TABLE 11. The pretreatments were applied to CRS panels and several parameters were measured. The zirconium coating weight in milligrams per meter squared was determined and reported in TABLE 12 below. Also, the 30 cycle corrosion testing as reported in TABLE 9 above was performed in the panels except the panels were run for 31 cycles instead of 30. The results are presented below in TABLE 12 in terms of average corrosion creep from scribe and maximum corrosion creep from scribe in millimeters.

(31) TABLE-US-00013 TABLE 11 Pretreatment Zr, Cu, SiO.sub.2, F, total F, free Zn, SO.sub.4, example ppm ppm ppm ppm ppm ppm ppm pH 12 control 150 20 50 200 15 0 0 4.00 13 150 20 50 400 35 600 900 4.00 14 150 20 50 400 35 1200 1800 4.00 15 150 20 50 400 35 1800 2600 4.00 16 150 20 50 400 35 2400 3500 4.00 17 150 20 50 400 35 4800 7000 4.00

(32) TABLE-US-00014 TABLE 12 Zr Average Maximum Pretreatment mg/m.sup.2 creep mm creep mm B-958 control 3.0 3.4 12 control 94 5.8 8.0 13 70 6.4 9.5 14 71 4.5 6.7 15 76 4.5 6.1 16 75 4.9 6.5 17 65 4.0 4.9

(33) The results demonstrate that sulfate also functions with zinc to reduce zirconium coating weight, although not to the same extent as nitrate. The data also demonstrate that the sulfate and zinc combination is effective in enhancing the corrosion resistance of the pretreatment such that it is almost as effective as the standard B-958.

(34) In the next series the effect of nitrate alone in the absence of zinc was tested in a series of pretreatments as detailed below in TABLE 13. The pretreatments were applied to CRS panels and tested as described above for 31 cycles and the average and maximum creep from scribe were determined and reported below in TABLE 14. The results demonstrate that higher levels of nitrate alone have the ability to also enhance the corrosion protective effect of zirconium based pretreatment coatings, although to a lesser extent than zinc.

(35) TABLE-US-00015 TABLE 13 Pre- F, F, treatment Zr, Cu, SiO.sub.2, total free Zn, NH.sub.4, NO.sub.3, example ppm ppm ppm ppm ppm ppm ppm ppm pH 18 control 150 20 50 200 15 0 100 0 4.00 19 150 20 50 400 35 0 600 1500 4.00 20 150 20 50 400 35 0 1000 3000 4.00 21 150 20 50 400 35 0 1800 6000 4.00

(36) TABLE-US-00016 TABLE 14 Average Maximum Example Creep, mm Creep, mm B-958 Control 3.0 3.4 18 control 5.8 8.0 19 6.1 9.6 20 4.8 7.7 21 3.8 5.5

(37) In the next series of experiments another set of pretreatment compositions was prepared as detailed below in TABLE 15. The compositions were applied to CRS and then tested for corrosion resistance via the 30 cycle procedure described above. The results are presented in TABLE 16 below. The results demonstrated the effects of increasing zinc and nitrate. In general, increasing the zinc at a constant nitrate level enhanced corrosion performance and increasing the nitrate at a constant zinc level also did so.

(38) TABLE-US-00017 TABLE 15 Pretreatment Zr, Cu, SiO.sub.2, F, total F, free Zn, NO.sub.3, example ppm ppm ppm ppm ppm ppm ppm pH 22 150 15 50 200 35 0 1000 4.00 23 150 15 50 285 35 150 1000 4.00 24 150 15 50 550 35 600 1000 4.00 25 150 15 50 1600 35 2400 1000 4.00 26 150 15 50 200 35 0 6000 4.00 27 150 15 50 285 35 150 6000 4.00 28 150 15 50 550 35 600 6000 4.00 29 150 15 50 1600 35 2400 6000 4.00 30 150 15 50 200 35 0 10000 4.00 31 150 15 50 285 35 150 10000 4.00 32 150 15 50 550 35 600 10000 4.00 33 150 15 50 1600 35 2400 10000 4.00

(39) TABLE-US-00018 TABLE 16 Pretreatment Average Maximum example Creep, mm Creep, mm B-958 Control 3.5 5.4 22 7.4 10.6 23 5.3 8.1 24 6.4 9.7 25 5.1 7.4 26 6.1 9.0 27 3.6 5.0 28 5.5 7.1 29 4.8 7.5 30 5.9 9.0 31 5.2 7.2 32 5.2 6.9 33 4.5 7.2

(40) In another series of tests, the pretreatments described below in TABLE 17 were applied to CRS panels. The coating weigh of zirconium was determined and reported below in TABLE 18. Panels were also further treated to electrodeposition with DuPont electrocoat 21 and DuPont “3 wet” Topcoat. The coated panels were then subjected to the 30 cycle corrosion test described above and the results are presented below in TABLE 18. Again, the presence of zinc and nitrate enhanced corrosion protection of the pretreatment.

(41) TABLE-US-00019 TABLE 17 Zr, Cu, SiO.sub.2, F, total F, free Zn, NO.sub.3, ppm ppm ppm ppm ppm ppm ppm pH 34 150 5 50 200 15 0 100 4.00 control 35 150 5 50 200 15 600 1600 4.00 36 150 5 50 200 15 1800 4200 4.00

(42) TABLE-US-00020 TABLE 18 Zirconium coating weight Maximum Pretreatment mg/m.sup.2 creep mm B-958 control 9.8 34 control 60 6.8 35 67 5.1 36 64 6.2

(43) In another series of experiments the treatment protocol was changed as shown below in TABLE 19 using the pretreatments described in TABLE 20 on ACT CRS panels. The control pretreatment B-958 was also included. The zirconium coating weights in mg/m.sup.2 were determined and are reported below in TABLE 21. A multiple of panels for each condition were then coated with a BASF electrocoat of CathoGuard® 800 and a BASF Topcoat system as described below. The application time of the CathoGuard® 800 was 2 minutes at 92° F. (33.3° C.) with an application voltage of 250 Volts. The bake time was 20 minutes at 350° F. (176.7° C.). The dry film thickness of CathoGuard® 800 was 0.8 to 1.1 mils. The BASF Topcoat system was a primer of R28WW216F, a basecoat of R98WW321, and a clearcoat of R10CG060B which produced a total dry film thickness on the substrate of 5.0 to 8.0 mils. The samples were then tested for corrosion resistance as described above for samples 6-11 except the exposure was for 28 cycles. The corrosion results are reported below in TABLE 22. The results again show that the pretreatment according to the present invention reduced the zirconium coating weight and enhanced the corrosion resistance of panels using another electrocoating and topcoat system.

(44) TABLE-US-00021 TABLE 19 Treat- Application Application Stage ment Product Application time (sec) temp. (° C.) 1 Clean Parco ® Spray 60 50 Cleaner 1523 2 Clean Parco ® Immersion 120 50 Cleaner 1523 3 Rinse City water Spray 60 38 4 Rinse Deionized Spray 60 25 water 5 Pre- Pretreatment Immersion 120 25 treatment 6 Rinse Deionized Spray 60 25 water

(45) TABLE-US-00022 TABLE 20 Pretreatment Zr Cu SiO.sub.2 F total F free Zn NO.sub.3 example ppm ppm ppm ppm ppm ppm ppm pH 37 control 150 10 50 200 35 0 100 4.00 38 150 10 50 200 35 600 6000 4.00

(46) TABLE-US-00023 TABLE 21 Pretreatment example Zr coating weight mg/m.sup.2 37 control 70 38 87

(47) TABLE-US-00024 TABLE 22 Pretreatment example Maximum creep mm B-958 5.6 37 control 11.5 38 6.5

(48) In a final series of examples, the effect of including the oxidizing agent hydrogen peroxide in the present invention was tested. The treatment protocol was changed as shown below in TABLE 23 using the pretreatments described in TABLE 24 on ACT CRS panels. The control pretreatment B-958 was also included. The zirconium coating weights in mg/m.sup.2 were determined and are reported below in TABLE 25. A multiple of panels for each condition were then coated with a BASF electrocoat of CathoGuard® 310X as described above for examples 1-5. The dry film CathoGuard® 310X thickness was 0.8 to 1.1 mils. The samples were then tested for corrosion resistance as described above for samples 6-11 except the exposure was for 31 cycles. The corrosion results are reported below in TABLE 26. The results show that hydrogen peroxide alone reduced the zirconium coating weight, reduced the average and maximum corrosion creep. The results further show that when hydrogen peroxide is combined with the elevated zinc and elevated nitrate the pretreatment coating compositions of the present invention were even more effective in reducing average and maximum corrosion creep.

(49) TABLE-US-00025 TABLE 23 Application Application Treat- Application time temperature Stage ment Product method seconds ° C. 1 Clean Parco ® Spray 120 50 Cleaner 1533 2 Rinse City water Spray 60 38 3 Rinse Deionized Spray 60 25 water 4 Pre- Pretreatment Immersion 120 25 treatment 5 Rinse Deionized Spray 60 25 water

(50) TABLE-US-00026 TABLE 24 Zr Cu SiO.sub.2 F total F free Zn NO.sub.3 H.sub.2O.sub.2 Example ppm ppm ppm ppm ppm ppm ppm ppm pH 39 150 10 50 200 35 0 100 0 4.00 control 40 150 10 50 200 35 0 100 10 4.00 41 150 10 50 200 35 0 100 20 4.00 42 150 10 50 200 35 0 100 30 4.00 43 150 10 50 200 35 600 1600 0 4.00 44 150 10 50 200 35 600 1600 10 4.00 45 150 10 50 200 35 600 1600 20 4.00 46 150 10 50 200 35 600 1600 30 4.00

(51) TABLE-US-00027 TABLE 25 Example Zr coating weight mg/m.sup.2 39 control 130 40 112 41 94 42 106 43 94 44 120 45 103 46 113

(52) TABLE-US-00028 TABLE 26 Average Maximum creep Example creep mm mm B-958 2.1 2.7 39 control 2.9 4.9 40 2.8 4.1 41 2.5 3.3 42 2.2 3.3 43 3.3 4.5 44 2.3 4.0 45 1.9 3.5 46 2.0 3.0

(53) The foregoing invention has been described in accordance with the relevant legal standards, thus the description is exemplary rather than limiting in nature. Variations and modifications to the disclosed embodiment may become apparent to those skilled in the art and do come within the scope of the invention. Accordingly, the scope of legal protection afforded this invention can only be determined by studying the following claims.