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

20.0

15.0
A1
A2
Creep (mm) B1
C1
C2
10.0 D1
D2
Iron
Zinc

5.0

0.0
0 100 200 300 400 500 600 700 800
Time (hr)
 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

15.0

12.5

10.0 A1
A2
Creep (mm) B1
C1
7.5 C2
D1
D2
Iron
5.0 Zinc

2.5

0.0
0 100 200 300 400 500 600 700 800
Time (hr)
 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

30.0

25.0

20.0 A1
A2
Creep (mm) B1
C1
15.0 C2
D1
D2
Iron
10.0 Zinc

5.0

0.0
0 100 200 300 400 500 600 700 800
Time (hr)
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

20.0

15.0
A1
A2
Creep (mm) B1
C1
C2
10.0 D1
D2
Iron
Zinc

5.0

0.0
0 5 10 15 20 25 30 35 40 45
Cycles
 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

8.0

6.0

A1
A2
Creep (mm) B1
C1
4.0 C2
D1
D2
Iron
Zinc

2.0

0.0
0 5 10 15 20 25 30 35 40 45
Cycles
 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

10.0

8.0

A1
A2
Creep6.0
(mm) B1
C1
C2
D1
D2
4.0
Iron
Zinc

2.0

0.0
0 5 10 15 20 25 30 35 40 45
Cycles
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
Spray Urethane with Urethane
BCI #12 ECLPS 1900 Topcoat
BCI #13 ECLPS 1900 Spray Alkyd
BCI #21 ECLPS 2400 E-coat Acrylic
Spray Urethane with Urethane
BCI #22 ECLPS 2400 Topcoat
BCI #23 ECLPS 2400 Spray Alkyd
Chemetall
#11 Oxsilan 9810 E-coat Acrylic
Chemetall Spray Urethane with Urethane
#12 Oxsilan 9810 Topcoat
Chemetall
#13 Oxsilan 9810 Spray Alkyd
Coral #11 Eco-Treat E-coat Acrylic
Spray Urethane with Urethane
Coral #12 Eco-Treat Topcoat
Coral #13 Eco-Treat Spray Alkyd
Coral #21 Eco-Treat M E-coat Acrylic
Spray Urethane with Urethane
Coral #22 Eco-Treat M Topcoat
Coral #23 Eco-Treat M Spray Alkyd
Henkel #11 Bondrite NT1 E-coat Acrylic
Spray Urethane with Urethane
Henkel #12 Bondrite NT1 Topcoat
Henkel #13 Bondrite NT1 Spray Alkyd
Bondrite NT1
& Parcolene
Henkel #21 95C E-coat Acrylic
Bondrite NT1
& Parcolene Spray Urethane with Urethane
Henkel #22 95C Topcoat
Bondrite NT1
& Parcolene
Henkel #23 95C Spray Alkyd
Iron
Iron #11 Phosphate E-coat Acrylic
Iron Spray Urethane with Urethane
Iron #12 Phosphate Topcoat
Iron
Iron #13 Phosphate Spray Alkyd
Zinc
Zinc #11 Phosphate E-coat Acrylic
Zinc Spray Urethane with Urethane
Zinc #12 Phosphate Topcoat
Zinc
Zinc #13 Phosphate Spray Alkyd