Transcript Electroformed Nanocrystalline Coatings: An Advanced

DoD
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DOE Strategic Environmental Research
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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
August 30, 2001
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Contents
Improving Mission Readiness Through
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Technical Objective
Nanocrystalline Materials
SERDP Program Overview
Phase I Results
Phase II Optimization
Phase II Next Step
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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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Introduction
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Introduced 20 years ago
Enhanced volume fraction of the boundary
component
Superior mechanical properties
Produced by a variety of techniques:
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Physical and chemical vapor phase processing
Mechanical attrition
Crystallization of amorphous precursors
Electrochemical methods
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Synthesis
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Electrodeposited via conventional electroplating techniques
Single step process
Fully dense material - chemically homogeneous
Pure metals, binary/ternary alloys, composite materials
Broach choice of alloying constituents and bath chemistry
Pulsed power supply to favour nucleation of grains instead of
grain growth
Fixed or consumable anodes
Plated or freestanding material with a broad range of thickness
(1 to 1mm)
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Structure
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Solid, fully dense
electrodeposits (virtually
zero porosity)
Grains and well
characterized grain
boundaries (similar to
conventional
polycrystalline materials)
3 to 100nm grain size
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Mechanical Properties of Conventional and Nanocrystalline Nickel
Conventional †
Nano-Ni
100nm
Nano-Ni
10nm
Yield Strength, MPa (25oC)
103
690
>900
Yield Strength, MPa (350oC)
–
620
–
Ultimate Tensile Strength, MPa (25oC)
403
1100
>2000
Ultimate Tensile Strength, MPa (350oC)
–
760
–
Tensile Elongation, % (25oC)
50
>15
1
Elongation in Bending, % (25oC)
–
>40
–
Modulus of Elasticity, GPa (25oC)
207
214
204
Vickers Hardness kg/mm2
140
300
650
Work Hardening Coefficient
0.4
0.15
–
Fatigue Strength, MPa (108 cycles/air/ 25oC)
241
275
–
Wear Rate (dry air pin on disc), µm3/µm
1330
–
7.9
0.9
–
0.5
Property
Coefficient of Frictionality (dry air pin on disc)
† ASM Metals Handbook, ASM International, Metals Park, OH. Vol. 2, p. 437 (1993)
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Program
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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
in process
Phase III Extension to Complex Shapes
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next year
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Phase I Results
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Go/No Go Nanocrystalline Material Data
Alloy I
Alloy II
Alloy III
Co-P
Co-Mo
Co-Fe-P
(0 to 5wt%P) (0 to 1wt%Mo) (15-30%Fe,2.5%P)
1) Grain size (nm)
2) Microhardness (VHN)
3) Thermal Stability (C)
4) Coating Thickness/
Integrity
8-14
575-820*
485
≤ 0.010”
No
Pits/Pores
8-14
~575
up to 497
≤ 0.002”
N/A
15-25
520-900**
425
≤ 0.05”
No
Pits/Pores
*Hardness increases up to 1100 when heat treated 5 minutes @ 450C
**Hardness increases up to 1250 when heat treated 10 minutes @ 400°C
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Phase II
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Select most promising alloy (Co-Fe-P) and optimize
composition, grain size and deposition process
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cleaning and activation procedures
plating procedure
heat treatment procedure
grinding/polishing procedure
Apply to high strength and low strength carbon steel
substrates (.003 to .010” thickness)
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Phase II
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Define formal testing requirements and conduct tests. Include pertinent
requirements from existing HCAT protocols and program data. Meet or
exceed hard chrome performance requirements.
 Mechanical testing
 hardness
 tensile strength
 ductility
 adhesion
 coefficient of friction
 Performance testing
 fatigue
 corrosion
 embrittlement
 wear
Go / No-go decision
Reports and Review
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Phase III
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Extension to Complex Shapes
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Adapt processes and develop equipment for DoD non-lineof-sight applications
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Suitable anodes
Fluid delivery system
Optimized rate of deposition and coating quality
Apply optimized alloy composition developed in Phase I and
II to an actual DoD part/s for DoD evaluation
Identify coating inspection technique
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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
7. Material Performance Testing
8. Reporting/Management/Go-No Go
Phase III: Extension to Complex Shapes
9. Process Optimization
10. Anode and Production Equipment Design
11. Production Part Application
12. Material Performance Evaluation
13. Reporting/Management/Final Report
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GFY01
GFY02
GFY03
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Co-Fe alloy
Variation of electrical parameters (I avg, pulse time, frequency)
Cobalt chloride-ferrous sulphate bath chemistry
Results
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Electrodeposits demonstrated typical Hall-Petch strengthening
behaviour
Fe concentration in deposit not affected by pulse conditions
No definitive trend of hardness vs peak current density
Build up rates increased with increasing duty cycle but were below
expectations, but increased with addition of conducting salts
Experienced Fe depletion problems with bath aging
Samples made for salt spray corrosion and taber wear tests
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Co-Fe-P alloy
Studied variation of electrical parameters, pH and metal
ion/conducting salt additions
Managed Fe depletion with complexing and reducing agents
Cobalt chloride-ferrous sulphate bath chemistry with
hypophosphorous acid addition
Results
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Higher current densities increased Fe concentration in deposits. P content
independent of current density
Fe content increased with pH; P content decreased with pH
Grain size decreased with increasing P content
Plating rate significantly increased (.002 to .005”/hour) by conductive salt
addition (NaCI) and higher average current density; not increased by
higher metal ion concentration
Samples made for salt spray corrosion and taber wear tests
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Taber Wear Screening Test Results
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Tests performed per ASTM D4060, ASTM C501 and MIL-A8625F
Nanocrystalline Co and Co-P alloys have higher Taber
indices
Nanocrystalline Co-Fe-P alloys show significantly improved
Taber indices. Higher Fe and higher hardness better
60-70% Fe concentration represents limit for lowest wear
coefficient
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45
0wt%Fe
20wt%Fe 30wt%Fe
50wt%Fe
Taber Wear Index (mg/1000 cycles)
40
Co-3%Fe
510VHN
60wt%Fe
35
30
Co-32%Fe
340VHN
25
100wt%Fe
Co-19%Fe,1%P
467VHN
20
Co-29%Fe,3%P
884VHN
15
Co-Fe Alloys
Cobalt Alloys
10
Iron Alloys
5
Co-89%Fe,2%P
706VHN
0
0
0.001
0.002
0.003
0.004
0.005
Inverse Hardness (1/VHN)
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0.006
0.007
0.008
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Salt Spray Screening Test (ASTM B117)
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>1200 hour exposure evaluated to ASTM D610 galleries
Nanocrystalline Co and Co-P alloys performed very well.
Heat treatment did not degrade corrosion performance.
Thicker coating performed better
Nanocrystalline Co-Fe on Co-Fe-P alloys performed very
poorly.
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ASTM B117 Testing
Carbon Steel Substrate
10
WC-Co HVOF - .004"
T400 HVOF - .004"
9
Hard Cr EP - .004"
ASTM B537 Ranking
8
Nano-Ni - .002"
NiLoP- .002"
7
Nano-Co - .002"
6
CoLoP- .002"
CoLoFeP- .002"
5
CoHiFeP- .002"
4
Note: Data for WC-Co,
T400 and Hard Chrome per
“Replacement of
Chromium Electroplating
Using HVOF Thermal
Spray Coatings”, Sartwell
et. Al.
3
2
1
0
0
200
400
600
800
1000
1200
Exposure Time (hours)
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1600
1800
2000
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Investigate alternative alloy additions
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Co-Fe-Zn
 grain size: 4 to 29 nm
 VHN: 500-600 as deposited
 Plating rate: .004 - .006”/hour
 Salt water corrosion: Co ~20% Fe ~20% Zn
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Co-Fe-Zn-P
Co-Fe-W
Establish sliding wear performance
Procure fatigue and hydrogen embrittlement test
specimens
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