Transcript Electroformed Nanocrystalline Coatings: An Advanced

DoD
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DOE Strategic Environmental Research
and Development Program
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Electroformed Nanocrystalline Coatings
An Advanced Alternative to
Hard-Chrome Electroplating
PP-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
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Contents
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Technical Objective
SERDP Program Overview
Background
Results Since Orlando Meeting
Summary
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Technical Objective
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Develop an environmentally benign advanced
nanocrystalline Co-based coating technology that:
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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
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Program Overview
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Three Phases
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Phase I
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Completed
Phase II
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Technology Viability Assessment
Coating Optimization
Completed
Phase III Extension to Complex ID Shapes
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In Progress
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Program Plan
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GFY00
Phase I: Technological Viability Assessment
1. Alloy Synthesis
2. Material Characterization
3. Impact Assessment
4. Reporting/Management/Go-No Go
Phase II: Coating Application Optimization
5. Alloy Optimization
6. Mechanical Properties Testing
7A. Material Performance Testing
8. Reporting/Management/Go-No Go
Phase III: Extension to Complex Shapes
7B. Material Performance Testing
9. Process Scale-up and Optimization
10. Production Part ID Applications
11. Production Part Evaluation
12. Reporting/Management/Final Report
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GFY01
GFY02
GFY03
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Background
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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
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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
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Process Cost
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Initial Study Update
Plating
Process
Nominal
Plating
Efficiency
(%)
Consumables
Relative
Consumable Cost
(by weight)
Relative
Power Cost
(by weight)
Total
Relative
Process Cost
Chrome(VI)
25
Cr2O3
1.00
1.00
1.00
Conventional Ni
90
Ni
0.70
0.08
0.44
Nano Co
>90
Co
1.83
0.08
1.09
Nano Co-3wt%P
>90
Co
H3PO2
2.21
0.08
1.31
Nano Co-30%Fe
75
Co, Fe
1.35
0.10
0.82
Nano Co30%Fe-1.5%P
55
Co, Fe
H3PO2
1.67
0.13
1.02
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Results
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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 B48985
Low Temperature Annealing Treatments Performed
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191°C anneal shows little increase in hardness
250°C anneal (4 hr) increases hardness to ~800 VHN
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Adhesion Test
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ASTM B571-97
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No peeling and/or flaking of the coating from the substrate under
low magnification (4x) - 30% elongation (bending)
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Ductility
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8.00
ASTM B489 Bend Tests (July2002)
Elongation in Bending (%)
7.00
ASTM B489 Bend Tests (May2002)
6.00
5.00
4.00
3.00
2.00
1.00
0.00
0.00
1.00
2.00
3.00
4.00
Wt% P in Deposit
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5.00
6.00
7.00
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Abrasive Wear (Taber)
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Grain Size
TWI
(CS-10)
Pure Co
12 nm
20.4
Co-1.2wt%P
Co-3.5wt%P
6 nm
15 nm
14.5
11.0
--
1.0
Composition
EHC
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Sliding Wear
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Experimental Set-up (Ball-on-Disk)
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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
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Sliding Wear
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Material
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Hardness
(VHN)
Coefficient
of Friction
Wear Volume Loss
(mm3/N/m) x 10-6
Mild Steel
150
0.73
18.2
Tool Steel
250
0.75
13.1
Hard Chrome
1208
0.70
11.87
Standard Samples
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
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Sliding Wear
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Disk / Pin Material
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Coefficient of Friction
(µ)
Plate Volume Wear
3
(mm /Nm)
Hard Chrome / Al2O3
0.699
11.9 x 10
-6
Low
Hard Chrome /
WC
0.693
11.0 x 10
-6
Mild
Hard Chrome /
Mild Steel
0.871
Negligible
Nano Co-2-3%P /
Al2O3
0.480
6.4 x 10
-6
Low
Nano Co-2-3%P /
WC
0.518
5.5 x 10
-6
Low
Nano Co-2-3%P /
Mild Steel
0.695
6.1 x 10
-6
Low
Note: As deposited surface polished with 800 grit paper
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Ball Wear
Severe
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Fatigue Testing
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4340 HCAT specimens
acquired from Metcut
Plated by Integran and
ground by Metcut
Testing underway at
MTI
SM
.25”
3.69”
Section to
be plated
0.625”
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Fatigue Test Matrix
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Coating
Grit Blast
Peen
Final Ground Thickness
No.
Specimens
Bare
No
No
N/A
12
Bare
No
Yes
N/A
12
Nano Co 2-3% P
Yes
Yes
0.003
6
Nano Co 4-5% P
Yes
Yes
0.003
6
Nano Co
Yes
Yes
0.003
6
R = -1, Air
Stress levels (ksi/Hz): 175 (5), 150 (5), 125 (29), 110 (29)
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H2 Embrittlement
and Development Program
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ASTM F-519 Type 1a
Specimens acquired
from Smith & Williston
Plated by Integran
Testing underway at
MTI
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Initial H2 Embrittlement
Test Matrix
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Coating
Composition
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Thickness
Bare
Nano
Co 2-3wt%P
Nano
Co 4-5wt%P
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Number of Specimens
191°C /
191°C /
No Bake
12 hours 24 hours
3
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Total # of
Specimens
3
0.004”
4
4
4
12
0.004”
4
4
4
12
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Electrochemical
Testing
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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
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NLS Application
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Mockups designed and
fabricated
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Blind and through cylinders
Pins
External lugs
Anode design study in
progress
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Consumable Co electrode
Fixed graphite electrode
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Optical Micrograph - 13 mil Nano
Co 2-3wt%P coating on 1” ID
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Process Data Summary
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Bath Chemsitry
Efficiency
Deposition Rate
Thickness
As-Deposited Appearance
Microstructure
Relative Process Cost
Emission Analysis
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Nanocrystalline Co-P Alloy
Hard Chrome
Co 2-5wt%P
(CoCl2 / H3PO4 / H3PO3)
Cr
2(CrO3 / SO4 )
85-95%
15-35%
Up to 8 mil per hour
Up to 1.6 mil per hour
Demonstrated up to 0.020”
Typically < .005”
Pit / Pore Free
Microcracked
Nanocrystalline
(avg. g.s. = 8 -15nm)
-
1.3
1.0
Below OSHA limits
6+
Cr
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Property Data Summary
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Nanocrystalline Co-P
Hard Chrome
As-Deposited
600-700 VHN
800-1200 VHN
HT @ 250°C
700-800 VHN
-
HT @ 400°C
1000-1200 VHN
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2 – 7 % Elongation
<.1%
400°C
-
27 mg / 1000 cycles (CS-17)
11 mg / 1000 cycles (CS-10)
3.2 mg / 1000 cycles (CS-17)
1.0 mg / 1000 cycles (CS-10)
5-6 x 10-6 mm3/Nm
(Alumina Ball on Nano Co-P Disk)
9-11 x 10-6 mm3/Nm
(Alumina Ball on Cr Disk)
Protection Rating 7 @ 1000 hrs
Protection Rating 2 @ 1000 hrs
In process
In process
10-15 ksi (Tensile)
Cracked – Exceeds cohesive strength
Hydrogen Embrittlement
In process
Yes – min bake 14 hrs
Fatigue
In process
Fatigue Debit
Hardness
Ductility
Thermal Stability
Wear
Abrasive (Taber)
Adhesive
(Pin-on-disk)
Corrosion
Salt Spray
Poteniodynamic
Internal Stress
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