Confidential September 15, 2006 T-4569 P-5051 Nanotechnology Paint Pretreatment Evaluation Introduction: A direct comparison study has been conducted at the Technical Center on several new paint pretreatments which are broadly described as being in the category of “nanotechnology”. These pretreatments are touted as options for replacing the current heavy metal pretreatments zinc phosphate, iron phosphate and hexavalent chrome containing sealers. The benefits of using the new nanotechnology pretreatments are that they do not contain heavy metals or phosphates, and the pretreatments may be used at ambient temperatures, therefore no heating of the bath is required. Test Description: This test compared seven of the new pretreatments from four suppliers against the current zinc and iron phosphate pretreatments. Clean, bare, unpolished steel ACT panels were sent to four separate companies, three of which supplied two products for testing while the fourth company supplied only one. The panels were taken to Valspar in East Moline, Illinois and painted. There were three separate paints used for this test. They were an acrylic e-coat, a spray urethane with a urethane top coat, and a spray alkyd. Two standard tests were performed to evaluate the corrosion protection provided by these products. They were the ASTM B117 Neutral Salt Spray and the GM9540P Scab test. In preparation for the corrosion tests all panels were scribed down the center of the panel for a length of 4”. ASTM B117: The panels were placed in a salt spray chamber where there is a solution of 5% NaCl (sodium chloride) dissolved in reverse osmosis purified water sprayed into the chamber causing a continual salt fog to envelop and condense on the panels. The panels were exposed for 192, 240, 336, 504, and 720 hours in the chamber. The panels were then removed and measured per the ASTM standard. GM9540P: Another set of panels were placed in a cyclic corrosion chamber containing a solution of 0.9% NaCl (sodium chloride), 0.1% CaCl2 (calcium chloride), and 0.25% NaHCO3 (sodium bicarbonate) in reverse osmosis purified water. The panels were exposed for 10, 20, and 40 cycles. Each cycle lasts for 24 hours consisting of three eight

hour periods. The first eight hour period sprays the solution on the panels for 20 minutes every 70 minutes. The second eight hour period is a continuous fog of only reverse osmosis water. The final eight hour period is a hot dry period where the humidity is between 20% and 30% and the temperature is maintained at 60oC. The panels were then removed and measured in the same manner as the salt spray panels. Results: The results of creep from the scribe for the two tests are presented graphically in the next six graphs. See the last page titled “Legend for Graphs” for notes indicating the respective line colors corresponding to each supplier’s products.

ASTM B117 Salt Spray: Acrylic E-coat: The graph below titled “E-coat Acrylic Salt Spray Results” shows that all of the products, except for Bulk Chemical Inc.’s ECLPS 2400 and Henkel’s Bondrite NT1, performed comparable to the zinc and iron phosphates. As the time increased a greater separation is noticed between the grouping of products. The two Coral products are comparable with the zinc and iron phosphates throughout the duration of the testing. The 336 and 504 hour creep results for the Bondrite NT1 (brown)and the ECLPS 2400 (red) are much higher than the 720 hour results. We suspect that this could indicate a problem with contamination of the panels that these tests were taken from. Upon receipt of the panels from the companies after pre-treating, the panels were punched with a code for identification. While the code was being applied gloves were not worn possibly allowing for skin oils to come into contact with the panels. This is a potential reason for the poor performance of these products relative to the remainder of the data collected.

E-coat Acrylic Salt Spray Results

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Urethane with Urethane Top Coat: The graph below titled “Spray Ureth/ Ure TC Salt Spray Results” shows that the zinc phosphate performs better and more consistently than the rest of the products. The Henkel’s Bondrite NT1 with Parcolene 95 C performs comparable to the iron phosphate. The other products have an increasing creep with respect to time.

Spray Ureth/ Ure TC Salt Spray Results

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Alkyd: The graph below titled “Spray Alkyd TC Salt Spray Results” shows that Henkel’s Bondrite NT1 with Parcolene 95C performed comparable to the zinc phosphate while the iron phosphate performance was only slightly worse. The rest of the products performed rather poorly in comparison. Due to the size of the panels, 30mm was the maximum measurable creep. Anything beyond 30mm was indeterminable as to whether the creep was from the edge of the panel or from the scribe.

Spray Alkyd TC Salt Spray Results

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GM9540P Scab Corrosion Test: Acrylic E-coat: The graph below titled “E-coat Acrylic GM9540P Scab Test Results” shows that all of the products performed comparable at a low number of cycles. As the number of cycles increased the products begin to form two comparable groups. The better of these groups contained the zinc and iron phosphates as well as the two Coral products; Eco-Treat and Eco-Treat M. The only other product not in the second grouping was BCI ELCPS 2400 which had much more creep than all of the other products.

E-coat Acrylic GM9540P Scab Test Results

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Urethane with urethane top coat: The graph below titled “Spray Ureth/ Ure TC GM9540P Scab Test Results” shows that the zinc phosphate performed better overall. At 40 cycles the Coral product performs comparable to the zinc phosphate. All of the other products excluding BCI’s ECLPS 2400 are grouped between 3.8 and 5.5 mm of creep. The ECLPS 2400 is higher at 40 cycles but comparable prior to this.

Spray Ureth/ Ure TC GM9540P Scab Test Results

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Alkyd: The graph below titled “Spray Alkyd GM9540P Scab Test Results” shows that at lower cycles the zinc phosphate performs better than the rest of the products. However at 40 cycles there is not much discrimination among the products tested. The only product that is not grouped with the rest is the ECLPS 2400 from BCI.

Spray Alkyd GM9540P Scab Test Results

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Conclusion: The results of this test vary widely between the types of paints and the two tests performed. There was no pretreatment with the exception of the current products (iron and zinc phosphates) that performed well in all of the different combinations. Of the products being tested the Henkel product, Bondrite NT1 with Parcolene 95C performed the best on average over the variety of tests. Some of the variability in the results may have been caused from handling damage such as body oils from the operator’s hands as well as panels that rusted prior to receipt. Even though there was variability in the results several of the products tested performed comparably to the iron phosphate pretreatment. This study does not include a cost comparison but it is our general understanding that the initial cost may be slightly higher for these new pretreatments. However, with the advantages of low bath heating costs and no heavy metal disposal issues our results indicate that further testing is warranted and these products should be considered for use in our paint systems. One suggestion is that testing multiple panels rather than single panels with each pretreatment, paint, and standard would have provided for a statistical analysis of the data collected ensuring more reliable results. Samuel J. Brownlee Deere & Co. Technical Center Intern - Summer 2006

Data Table for Salt Spray and GM9540P Results (mm Creep From Scribe):

Salt Spray Corrosion GM 9540P Scab Panel # Pretreatment Paint Substrate 192 Hr 240 Hr 336 Hr 504 Hr 720 hr 10 Cycles 20 Cycles 40 Cycles

A11 BCI #1 e-coat Acrylic Clean 6.5 1.8 3.6 5.1 7.9 3.4 5.6 6.8 A12 BCI #1 Spray Ureth/ Ure TC Clean 1.9 2.8 2.8 3.3 8.5 1.3 3.1 4.3 A13 BCI #1 Spray Alkyd Clean 20.2 22.0 30.0 30.0 30.0 2.3 2.8 2.1 A21 BCI #2 e-coat Acrylic Clean 7.4 4.6 15.1 22.0 11.0 3.9 7.9 20.4 A22 BCI #2 Spray Ureth/ Ure TC Clean 2.6 3.8 5.6 7.3 7.5 0.6 2.4 7.0 A23 BCI #2 Spray Alkyd Clean 25.2 20.5 30.0 30.0 30.0 3.5 4.8 4.9 B11 Chemetall #1 e-coat Acrylic Clean 3.8 1.6 3.0 3.1 3.9 3.2 4.1 5.5 B12 Chemetall #1 Spray Ureth/ Ure TC Clean 2.2 4.0 4.4 2.8 12.8 2.4 2.2 4.8 B13 Chemetall #1 Spray Alkyd Clean 18.6 10.6 20.2 30.0 30.0 2.5 2.8 2.5 C11 Coral #1 e-coat Acrylic Clean 1.4 1.4 1.8 2.0 2.4 1.6 2.5 2.5 C12 Coral #1 Spray Ureth/ Ure TC Clean 3.8 4.8 5.4 6.6 8.3 1.3 3.2 5.3 C13 Coral #1 Spray Alkyd Clean 23.5 21.6 24.3 25.3 30.0 1.9 8.1 1.9 C21 Coral #2 e-coat Acrylic Clean 1.6 2.0 1.6 2.3 3.0 2.0 3.6 3.5 C22 Coral #2 Spray Ureth/ Ure TC Clean 4.1 5.4 6.5 7.0 13.6 2.3 3.0 2.4 C23 Coral #2 Spray Alkyd Clean 17.0 23.5 28.3 30.0 30.0 2.8 3.4 2.4 D11 Henkel #1 e-coat Acrylic Clean 2.0 2.5 14.0 19.5 8.8 10.0 5.4 6.0 D12 Henkel #1 Spray Ureth/ Ure TC Clean 4.1 2.6 3.8 6.5 6.0 2.1 3.1 5.5 D13 Henkel #1 Spray Alkyd Clean 20.0 20.5 29.0 30.0 30.0 2.0 2.8 2.1 D21 Henkel #2 e-coat Acrylic Clean 4.6 6.5 3.1 3.5 5.3 2.6 4.0 5.8 D22 Henkel #2 Spray Ureth/ Ure TC Clean 1.4 2.0 2.2 2.9 3.1 0.1 3.5 4.3 D23 Henkel #2 Spray Alkyd Clean 3.4 4.3 5.3 4.6 12.5 1.5 2.9 2.5 E11 Iron Phos e-coat Acrylic B1000 P60 1.9 1.6 4.3 5.1 3.0 2.0 3.5 3.1 E12 Iron Phos Spray Ureth/ Ure TC B1000 P60 1.9 2.9 3.6 2.9 3.0 0.1 3.6 3.8 E13 Iron Phos Spray Alkyd B1000 P60 6.2 7.0 8.5 9.3 22.5 1.8 2.1 1.9 F11 Zinc Phos e-coat Acrylic B952 P99 0.8 0.0 1.6 3.1 2.4 1.5 1.8 2.9 F12 Zinc Phos Spray Ureth/ Ure TC B952 P99 0.0 0.0 0.4 1.2 1.4 0.0 0.9 2.0 F13 Zinc Phos Spray Alkyd B952 P99 1.9 2.8 4.1 5.8 8.1 0.3 0.5 2.8

Supplier Product Supplier Product BCI #1 ECLPS 1900 Coral #1 Eco-Treat BCI #2 ECLPS 2400 Coral #2 Eco-Treat M Chemetall #1 Oxsilan 9810 Henkel #1 Bondrite NT1 Henkel #2 Bondrite NT1 & Parcolene 95C

Legend for Graphs

Line Name Line Color Supplier Product

A1 Red BCI ECLPS 1900 A2 Red BCI ECLPS 2400 B1 Blue Chemetall Oxsilan 9810 C1 Light Blue Coral Eco-Treat C2 Light Blue Coral Eco-Treat M D1 Brown Henkel Bondrite NT1 D2 Brown Henkel Bondrite NT1 &

Parcolene 95C

Iron Yellow Iron Phosphate Zinc Green Zinc Phosphate

Corrosion graphs by paint type

- Each company is a different color

- Diamond represents first product

- Square represents second product

Panel Code Product Paint BCI #11 ECLPS 1900 E-coat Acrylic

BCI #12 ECLPS 1900 Spray Urethane with Urethane Topcoat

BCI #13 ECLPS 1900 Spray Alkyd BCI #21 ECLPS 2400 E-coat Acrylic

BCI #22 ECLPS 2400 Spray Urethane with Urethane Topcoat

BCI #23 ECLPS 2400 Spray Alkyd Chemetall #11 Oxsilan 9810 E-coat Acrylic Chemetall #12 Oxsilan 9810

Spray Urethane with Urethane Topcoat

Chemetall #13 Oxsilan 9810 Spray Alkyd Coral #11 Eco-Treat E-coat Acrylic

Coral #12 Eco-Treat Spray Urethane with Urethane Topcoat

Coral #13 Eco-Treat Spray Alkyd Coral #21 Eco-Treat M E-coat Acrylic

Coral #22 Eco-Treat M Spray Urethane with Urethane Topcoat

Coral #23 Eco-Treat M Spray Alkyd Henkel #11 Bondrite NT1 E-coat Acrylic

Henkel #12 Bondrite NT1 Spray Urethane with Urethane Topcoat

Henkel #13 Bondrite NT1 Spray Alkyd

Henkel #21

Bondrite NT1 & Parcolene 95C E-coat Acrylic

Henkel #22

Bondrite NT1 & Parcolene 95C

Spray Urethane with Urethane Topcoat

Henkel #23

Bondrite NT1 & Parcolene 95C Spray Alkyd

Iron #11 Iron Phosphate E-coat Acrylic

Iron #12 Iron Phosphate

Spray Urethane with Urethane Topcoat

Iron #13 Iron Phosphate Spray Alkyd

Zinc #11 Zinc Phosphate E-coat Acrylic

Zinc #12 Zinc Phosphate

Spray Urethane with Urethane Topcoat

Zinc #13 Zinc Phosphate Spray Alkyd