Electroformed Nanocrystalline Coatings An Advanced Alternative to Hard-Chrome Electroplating PP-1152

1. Electroformed Nanocrystalline Coatings An Advanced Alternative to Hard-Chrome ElectroplatingPP-1152 Dr. Maureen J. Psaila-Dombrowski, McDermott Technology, Inc. Douglas E. Lee, Babcock & Wilcox Canada Dr. Jonathan L. McCrea, Integran Technologies Dr. Uwe Erb, University of Toronto HCAT Meeting, Toronto, Ontario September 26, 2002

2. Contents • Technical Objective • SERDP Program Overview • Background • Results Since Orlando Meeting • Summary

3. Technical Objective • Develop an environmentally benign advanced nanocrystalline Co-based coating technology that: • Is compatible with conventional electroplating infrastructure • Will produce coatings that meet or exceed the overall performance of hard chrome (hardness, wear, fatigue, corrosion, and thermal stability) • Has costs similar to or less than life-cycle cost of existing hard chrome electroplating processes • Will be applied to non-line-of-sight surfaces

4. Program Overview Three Phases • Phase I Technology Viability Assessment • Completed • Phase II Coating Optimization • Completed • Phase III Extension to Complex ID Shapes • In Progress

5. Program Plan

6. Background • Synthesized Co-P, Co-Mo and Co-Fe nano alloys • Synthesized and Optimized Co-Fe,Co-Fe-P, Co-Fe-Zn and Co-Fe-Zn-P nano alloys • Optimized Co-P alloy • Cobalt chloride/ortho-phosphoric/phosphorous acid bath • Plating efficiency >90% • Grain size 12-15 nm • As-deposited hardness 700 VHN • Deposition rate 2-8 mills/hr • Precipitation hardenable • Good salt spray results • High Taber wear results (CS 17) • Good pin-on-disk results

7. Process Cost Initial Study Update

8. Results • Process scale-up completed (2L to 50L) • Activation procedure developed for high carbon steel substrates • Adhesion tests performed as per ASTM B571-91 • Bend Test for Ductility performed as per ASTM B489-85 • Low Temperature Annealing Treatments Performed • 191°C anneal shows little increase in hardness • 250°C anneal (4 hr) increases hardness to ~800 VHN

9. Adhesion Test • ASTM B571-97 • No peeling and/or flaking of the coating from the substrate under low magnification (4x) - 30% elongation (bending)

10. Ductility

11. Abrasive Wear (Taber)

12. Sliding Wear • Experimental Set-up (Ball-on-Disk) • CSEM Tribometer • Static member - 6mm alumina (Al2O3) Ball (1800VHN) • 10 N Load • 1000 meter total sliding distance • 20 mm wear track diameter • 10cm/s sliding velocity • Profile measured using stylus profilometer

13. Material Hardness (VHN) Coefficient of Friction Wear Volume Loss (mm3/N/m) x 10-6 Standard Samples Mild Steel 150 0.73 18.2 Tool Steel 250 0.75 13.1 Hard Chrome 1208 0.70 11.87 Nanocrystalline Samples Nano Cobalt 500 0.35 10.7 Nano Co~2%P 728 0.53 5.5 Nano Co~4%P 745 0.48 6.4 Nano Co~4%P (HT) 1013 0.44 5.3 Nano Co~6%P 733 0.45 7.1 Nano Co~10%P 719 0.50 6.2 Sliding Wear

14. Sliding Wear

15. Fatigue Testing • 4340 HCAT specimens acquired from Metcut • Plated by Integran and ground by Metcut • Testing underway at MTI .25”

16. Fatigue Test Matrix

17. H2 Embrittlement • ASTM F-519 Type 1a Specimens acquired from Smith & Williston • Plated by Integran • Testing underway at MTI

18. Initial H2 Embrittlement Test Matrix

19. Electrochemical Testing • Establish electrochemical behaviour Co EHC plate Ni 200 Nano Co-2-3wt%P (4340) Nano Co Nano Co-4-5wt%P (4340) • Linear polarization resistance scan (LPR) • Potentiodynamic scan (PDS) per ASTM G61 • 3.56 wt% NaCl, room temperature • Determine corrosion rate and potential for pitting • Testing in process at MTI

20. NLS Application • Mockups designed and fabricated • Blind and through cylinders • Pins • External lugs • Anode design study in progress • Consumable Co electrode • Fixed graphite electrode Optical Micrograph - 13 mil Nano Co 2-3wt%P coating on 1” ID

21. Process Data Summary

22. Property Data Summary