Final Report - Strategic Environmental Research and Development ...

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Table of Contents Table of Contents .…………………….…………………………………………….....… i List of Acronyms …………….……………………………………………....………….. ii List of Figures …………….……………………………………………....……………... iv List of Tables …………….……………………………………………....…………..….. xxvi Keywords …………….……………………………………………....………………….. xxx Acknowledgements …………………………………….………………………............... xxxi 1. Executive Summary ………………………………….……………………….............. 1 2. Project Background ………………………………….………………………............... 4 3. Objective ……………………….………………………………....…………………... 11 4. Technical Approach ………………………………….……………………….............. 12 5. Results and Accomplishments ……………………….……………………….............. 13 5.1 Task 1: Fundamental Studies of the Trivalent Chrome Process (TCP) ………….. 14 5.2 Task 2: Mechanisms of Selected Inhibitors ………………………………………. 62 5.3 Task 3: Active Inhibition, Barrier Properties and Adhesion ……………………... 92 5.4 Task 4: Paint Adhesion Strength and Mechanism ………………………………... 168 5.5 Task 5: Inhibitor Activation and Transport in the Primer Layer …………………. 207 5.6 Task 6: Interactions Between Polymer Matrix, Pigment, Surface Treatment and Alloy …………………………......................................................... 258 5.7 Task 7: Characterization of Local Environments in Coating Systems …………… 339 6. Concluding Summary ……………………………….……………….……….............. 361 Appendix 1. Team Members ……………………….……………………………............ 366 Appendix 2. List of Scientific/Technical Publications ………………………….............. 367 i
List of Acronyms AES Atomic Emission Spectroscopy (p. 234) AES Auger Electron Spectroscopy (p. 236) AFM Atomic Force Microscopy AFOSR Air Force Office of Scientific Research ANN krf t N laiciNrlaicifitrA ASTM American Society for Testing and Materials BFM Breakpoint frequency method BT Blister test CCC Chromate conversion coating CE Counter electrode CEC Cation Exchange Capacity CI Constant Infusion CP Constant Pressure CPE Constant Phase Element DBES Doppler broadening of energy spectra DD Degreased and deoxidized DDTCP Degreased and deoxidized + TCP DOI Direct optical interrogation EC Equivalent circuit EDAX/EDXS Energy Dispersive Analysis by X-rays/Energy Dispersive X-ray Spectroscopy EDS Energy Dispersive Spectroscopy EIS Electrochemical Impedance Spectroscopy FIB Focused ion beam FTIR Fourier transform infrared spectroscopy GBT Galvanic Blister Test GC/MS Gas chromatography / mass spectroscopy ICP Inductively coupled plasma IMC Intermetallic Compound MSDS Materials Safety Data Sheet NAVAIR Naval Air Systems Command (of the U. S. Navy) NCP Non-Chromium Process NMR Nuclear Magnetic Resonance OCP Open circuit potential OES Optical emission spectroscopy OLI short for OLI Systems, Inc. OP Optical Profilometer ORR Oxygen reduction reaction OSU Ohio State University PALS Positron Annihilation Lifetime Spectroscopy PVA Polyvinyl alcohol PVB Polyvinyl buterol ii
Page 1 and 2: FINAL REPORT Scientific Understandi
Page 3: This report was prepared under cont
Page 7 and 8: List of Figures Figure 1.1. Figure
Page 9 and 10: Figure 1.21. Figure 1.22. Figure 1.
Page 15 and 16: Figure 3.11. Cathodic polarization
Page 19 and 20: Figure 4.12. Average Roughness of R
Page 21 and 22: Figure 5.4. Figures 5.5. Apparatus
Page 23 and 24: Figure 5.36. Figure 5.37. R paramet
Page 25 and 26: Figure 6.23. Two commercial samples
Page 27 and 28: Figure 7.1. a) instrumental configu
Page 29 and 30: List of Tables Table 1.1. Table 1.2
Page 31 and 32: Table 6.4. Processing parameters fo
Page 33 and 34: Keywords 1. Al alloys 2. Non-chroma
Page 35 and 36: 1. Executive Summary This report su
Page 37 and 38: the role of electrophoresis in inhi
Page 39 and 40: occurring at low pHs and release at
Page 41 and 42: were obtained by a post treatment w
Page 43 and 44: 4. G.O. Ilevbare, J.R. Scully, J. Y
Page 45 and 46: 3. Objective The primary objective
Page 47 and 48: 5. Results and Accomplishments In t
Page 49 and 50: powder, slurried with ultrapure wat
Page 51 and 52: TCP-coated AA2024-T3. A Kratos AXIS
Page 53 and 54: X-ray Photoelectron Spectroscopy (X
Page 55 and 56:
Potential (V vs. Ag/AgCl) -0.2 -0.3
Page 57 and 58:
Signal Intensity (counts/s) assessi
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Al (including both Al 0 and Al 3+ c
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TEM or during sample preparation, s
Page 63 and 64:
Potential (V vs. Ag/AgCl) and uncoa
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5.1.4.8 Effects of Aging on the Fil
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Intensity (counts/s) Concentration
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|Z| 0.01Hz (ohm cm 2 ) |Z| 0.01Hz (
Page 71 and 72:
The artificial scratch cell was als
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Raman intensity, a.u. 4000 880 3500
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Figure 1.24. Raman spectra for the
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peak at 520 cm -1 and an intense Cr
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Figure 1.28. Plots of the intensity
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Figure 1.30. (A) Video micrograph o
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The Zr and O signals arise from the
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Figure 1.35. (A) Corrosion potentia
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Table 1.1. Corrosion current (i cor
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additional pitting. The TCP coating
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Figure 1.41. Cr(VI) peak intensity
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Work is ongoing to understand how t
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9. L. Li, D-Y. Kim and G. M. Swain,
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carefully rinsed with DI water, air
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decrease to a net anodic current in
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Potential (mV vs. SCE) Potential (m
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i (A/cm 2 ) Immediately after silic
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Page 107 and 108:
Potential (mV vs. SCE) Rp (ohm.cm 2
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Page 111 and 112:
2.4.4 In situ AFM Scratching Result
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Figure 2.31. In situ AFM scratching
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(2.3) Figure 2.35. Specie diagram f
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concentration and the silicon to ca
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analysis coupled with XPS revealed
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5.2.4.4 In Situ AFM Scratching Befo
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esults in the formation of silicate
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26. P. Schmutz and G.S. Frankel, J.
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Pr 3+ , Y 3+ showed [12] an order o
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0.1M NaCl solution with varying con
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8.7 through pH 12.6 due to the lowe
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(b) (c) 99
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immersed in Ce 3+ remained bright w
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S phase and dissolution of Al matri
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Corrosion rate, i corr (A/cm 2 ) 6x
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I L (microA) 600 500 400 300 NC (-8
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than that of chromate[35]. Historic
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coupon was immersed with the polish
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5.3.2.4 Results 5.3.2.4.1 Speciatio
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(c) Figure 3.8. Speciation diagram
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E vs. SCE (V) -0.70 -0.75 -0.80 -0.
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E vs. SCE (V) 1000 rpm E vs. SCE (V
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Chemical quantification showed a me
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(a) (b) Figure 3.15. (a) (top) SEM
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E vs. SCE (V) E vs. SCE (V) E vs. S
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-Z" (ohm) -Z" (ohm) -Z" (ohm) -Z" (
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(Figure 3.8b). However, no effect o
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CPS CPS CPS x 2 14 10 12 10 8 6 4 2
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CPS CPS 100 95 90 85 80 75 70 x 10
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I k L 0. 2 1 2 AnFC B D 2 3 O 1
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i -800 (A/cm 2 ) 10 -4 NaCl NaCl+5
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Corrosion rate ( 1/R p ) ohm -1 cm
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particles compared to zinc-free sol
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and Zn bentonite compounds have red
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2) Deoxidizing for 3 minutes in an
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Scintag (now ThermoARL) Pad-V TM an
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Table 3.5. Characterization of bent
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Zn 2+ cation release (meq/100g) Pr
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(a) (b) (c) Figure 3.33. (a) An exp
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|Z| (ohm) Phase angle (degrees) 5.3
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|Z| at 0.01 Hz (ohm.cm 2 ) Pore Res
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|Z| at 0.01 Hz (ohm.cm 2 ) |Z| at 0
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pigmented coatings exhibited partia
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5.3.3.6 Conclusions 1. Exchange ben
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39. M. Mahdavian and M. M. Attar, P
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100. F.Liebau, Structural Chemistry
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of the coated sample, which is tigh
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Lubricant Blue (Struers) was used f
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good grip on the dolly, the equipme
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Pressure (kPa) r (mm) Pressure x Ra
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Pressure x Radius (kN/m) plateau bu
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Pressure x Radius (kN/m) Pxr (KN/m)
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Average Roughness (m) In contrast,
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Adhesion Strength (J/m 2 ) PVB PVB
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Pressure (kPa) Constant Infusion up
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(a) (b) (c) (d) Figure 4.19. Coatin
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Min. Potential (V vs SHE) Min. Pote
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Pressure (kPa) exposure in hot wate
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Engineering Stress (MPa) slope of t
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Adhesion Strength (J/m 2 ) ASTM D33
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Pressure (kPa) Pressure (kPa) Radiu
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Adhesion Strength (J/m 2 ) Pressure
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Table 4.7. Adhesion Strength values
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Non-Cl./Deox. No CC Cleaned/Deox. N
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5.4.5 Conclusions and Implications
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5.5 Task 5: Inhibitor Activation an
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solution for equilibration at contr
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Table 5.2. Techniques applied to sp
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The capacitance was determined by E
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combination with zinc molybdate, a
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Concentration, mmol / L Final pH te
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Alkaline affects praseodymium solub
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MoO 4 2- ) inhibition to the system
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Zinc molybdate is reported to be si
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The presence of a salt that has no
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This approach yields two figures of
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Inhibitor mapping of the Hentzen 16
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The molybdate loss in the strontium
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The capacitance dC is given by 0 (
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2 C( r, t) C( r )[1 r 2 exp( D nt
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-thea (degree) logIZI (Ohm-Cm 2 ) P
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Capacitance (F) respectively. The c
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Capacitance (F) Weight gain (g) For
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Normalized Capacitance Change Norma
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Potential V (Ag/AgCl) Corrosion rat
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5.5.4.7 Nanopore structure characte
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Normaalized Transport Rate (g/m^2_d
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S-Parameter S-Parameter Penetration
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S-Parameter S-Parameter Penetration
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R-parameter R-parameter Penetration
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5. T. M. Letcher, “Thermodynamics
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pigment of CaSiO 3 with initial pH
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allowed a comparison of the differe
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The solution resistance (R sol ) va
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Theta [degrees] theta |Z| [ohm] 10
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C [F/cm2] Rcorr [ohm*cm2] 7075-AHN
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C [F/cm 2 ] Rcorr [ohm*cm 2 ] Rcorr
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Visual TTF [hours] Table 6.2. Param
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of Metallast pre-treatment, which h
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Prediction of the TTF obtained by A
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5.6.2 Electrochemical Impedance Spe
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5.6.2.2.1 Coating system descriptio
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Table 6.4. Processing parameters fo
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population of total TTF vectors th
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components of the impedance and the
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Figure 6.17. EIS spectra for sample
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Figure 6.18. Kaplan-Meier survival
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Maximum c i range Maximum ci range
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The type and number of input neuron
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Predicted TTF The BFM method, intro
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The most significant variables to i
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5.6.3 Characterization of Pigment D
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of sputtering gold and carbon paint
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Figure 6.26. Cross-sectional view o
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Figure 6.28. EDX maps of primer cro
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Figure 6.31. EDX maps of primer cro
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In Figure 6.34, Ca and Si existed a
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Table 6.8. Average percentage resid
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strictly limited due to the barrier
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Figure 6.37. Coating systems in det
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Each corrosion volume of scribed ar
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Corrosion Area (mm 2 ) 1200 1000 80
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Corrosion Area (mm 2 ) Corrosion Ra
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Corrosion Rate (mm/yr) Corrosion Vo
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Corrosion Area (mm 2 ) corrosion ra
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corrosion rate (mm/yr) Corrosion Vo
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Corrosion Volume (mm/yr) Corrosion
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ate, PPG CA7233 coated samples had
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Appendix 6B Table 6B.1. Corrosion v
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Table 6B.3. Corrosion rate of sampl
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Table 6B.5. Corrosion area of sampl
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5.7. Task 7: Characterization of Lo
Page 375 and 376:
at 65C. After using DI water to rin
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Transmission Mode Conduct EIS measu
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Cdl(F/cm 2 ) Rp(.cm 2 ) relatively
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pit bottom area (cm 2 ) pit bottom
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2days 2days 1mm 1mm 7days 7days Pit
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(a) (b) Si Si O Al Na Ca K Si Al-Cu
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Pit 1 and pit 2 as shown in Figure
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In these experiments, Deft primers
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For the case of as-deposited thin f
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3. L. Balazs, Physica E, 54, 1183-1
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and subsequently re-oxidized in two
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not represent true adhesion strengt
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• The pit morphology in 0.5 M NaC
Page 401 and 402:
Appendix 2. List of Scientific/Tech
Page 403 and 404:
“The Secret Life of Chromate Free
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