electrodeposited inconel and stellite like coatings for improved … · 2017-11-18 ·...
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S.H.VijapurT.D.HallE.J.TaylorM.E.Inman
M.Brady(ORNL)
Electrodeposited Inconel and Stellite like Coatings for Improved Corrosion
Resistance in Biocombustors
slide 2
Problem/ Oppurtunity • Advantages of state of the art combustion systems
– Higher Efficiency • Reduce CO2 and poisonous gas emissions • Lower Fuel Cost
• Challenge: – Requires higher operating temperatures – Potentially requires the use of exotic process
streams • Supercritical CO2 • Supercritical Steam
– Must be durable to range of burnable materials • Wood, Gas, Coal, Waste ….
! Need to develop novel material systems to durably perform in these
environments
slide 3
Direct Current Electrodepositable Materials (from Literature)
Ia IIa IIIa IVa Va VIa VIIa VIII Ib IIb IIIb IVb Vb VIb VIIb ο1 H
2 He
3 Li
4 Be
5 B
6 C
7 N
8 O
9 F
10 Ne
11 Na
12 Mg
13 Al
14 Si
15 P
16 S
17 Cl
18 Ar
19 K
20 Ca
21 SC
22 Ti
23 V
24 Cr
25 Mn
26 Fe
27 Co
28 Ni
29 Cu
30 Zn
31 Ga
32 Ge
33 As
34 Se
35 Br
36 Kr
37 Rb
38 Sr
39 Y
40 Zr
41 Nb
42 Mo
43 Tc
44 Ru
45 Rh
46 Pd
47 Ag
48 Cd
49 In
50 Sn
51 Sb
52 Te
53 I
54 Xe
55 Cs
56 Ba
57 La
72 Hf
73 Ta
74 W
75 Re
76 Os
77 Ir
78 Pt
79 Au
80 Hg
81 Tl
82 Pb
83 Bi
84 Po
85 At
86 Rn
Electrodeposition is a scalable cost efficient technique to obtain surfaces with controllable physical, catalytic, and structural properties. These properties can potentially be enhanced and cost effectively scale to production levels Eliaz, N., et al., “Induced Codeposition of Alloys of Tungsten, Molybdenum and Rhenium
with Transition Metals” Modern Aspects of Electrochemistry 42 Springer, NY, (2008), p 191, Ch. 4
slide 4
Direct Current Electrodepositable Alloy Materials from Water Based Solution (from Literature)
AuPt X
Ir XRe X
W X XSb X X
Sn X X X XIn X X X
Cd X X X X X XAg X X X X X X X X X
Pd X X X XRh X X X X X X
Ru X X X XMo X X X X
Zr XSe X X X X
Zn X X X X X X X X X X XCu X X X X X X X X X X X X X
Ni X X X X X X X X X X X X X X X XCo X X X X X X X X X X X X X X
Fe X X X X X X X X X X X X XMn X X X X X X X X X X
Cr X X X X X X X X X X XV X X X X X
Ti X X X X X X
With Alloy materials the composition may also be varied to obtain the variance in the desired physical properties • Electrical Resistance • Wear Resistance • Thermal Resistance • Thermal Expansion Match
Eliaz, N., et al., “Induced Codeposition of Alloys of Tungsten, Molybdenum and Rhenium with Transition Metals” Modern Aspects of Electrochemistry 42 Springer, NY, (2008), p 191, Ch. 4
slide 5
Global Initiative
• Why: – Nearly 4.3 Million deaths a year are due to smoke inhalation
• Incomplete combustion producing CO and carcinogens – Nearly $40 Billion spent annually on fuel sources
• Some families spend up to 2 hr a day or 1/3 of income acquiring fuel
– 1 Billion Tons of CO2 year from open fires
! Must improve burning efficiency ! Must operate at higher
temperatures ! Must design low cost material
systems to durably perform in these environments
Create more efficient, longer lasting, cleaner, and cost effective cookstoves for use in burning biomaterials
slide 6
DOE Focus Program on Low Cost CoatingsProblem:
– Biomass combustion reactors are subjected to various corrosive attacks due to the wide range of potential materials that will be burned in them, including:
• Gasoline, grass and other carbon based waste
– These give off mixtures of: • Alkali halides (fly ash particulate) • Halogen Acids • Water • Sulfur and Nitrogen Oxides
Potential Solutions: 1. Replace the composition of the internal materials used within bio-
combustors. " Corrosion resistant SS, Ni Alloys, or Co alloys (THESE ARE COST PROHIBITIVE)
2. Apply a high value coating to existing bio-combustors or lower cost steels. " Coating could consist of corrosion resistant alloys like Stellite 21 or Inconel 740
slide 7
Objective of Program• Develop a cost effective, scalable, and flexible electrodeposition based
coating process that can be applied to the corrosion sensitive regions of existing and next generation bio-combustors – Ni and Co based alloys have been shown to possess excellent alkali/
halide attack resistance – Co based alloys have been shown to possess sulfidation resistance – Mo additions into the metal alloys also seem to improve corrosion
resistance and high temperature stability. – Cr improves temperature stability and corrosion resistance in high
temperature systems Alloy Co Ni Cr Fe Mo W
Inconel® 740 20 (base) 25 0.5 – Inconel® 718 - (base) 19 25 3 - Haynes® 25 (base) 10 20 – 15 Stellite® 21 (base) 3 29 6 –
slide 8
Experimental Plan Outline• Substrate:
– Low cost ferritic or austenitic steels • 304 SS, 410 SS, 441 SS; 1” x 4” dual sided
• Coating compositions – [Co/Ni] – Cr – [Mo/Fe] (composition variance)
• Testing Parameters: – CTE (quick CTE test at Faraday within muffle furnace) – Coating composition
• XRF – High temperature corrosion test at 700°C in Air
• 500 hr Salt Spray (Remove after every 100 hr for weight and reapplication)
• High salt loading (3 mg/cm2) and low salt loading (1 mg/cm2) – Cross-sectional SEM analysis of oxidation
slide 9
Electrolyte Development• Used a Hull Cell to Rapidly design electrolyte and
processing conditions to deposit binary and ternary alloys consisting of [Ni/Co]-Cr-[Mo/Fe]
• Used XRF to measure the deposit composition
Distance from high current
edge, cm
Elemental composition, % Cr Co
1 17.2 82.0 3 7.7 91.5
Standard Cr3+ plating solution + 43.13 g/L CoSO4⋅7H2O (0.154 M Co2+)
Distance from high current
edge, cm
Elemental composition, %
Cr Co 3.8 2.3 93.5
Standard Cr3+ plating solution + 21.65 g/L CoSO4⋅7H2O (0.077 M Co2+)
Anode
Cathode6.3 cm
12.8 cm
4.8 cm
slide 10
Compositional Screening: Ni-Cr and Ni-Co-Cr w/ Hull Cell
Hull Cell study shows that a wide range of potential deposit composition can be obtained controlling the Ni concentrations
slide 11
Compositional Screening: Ni-Cr-Fe w/ Hull Cell
slide 12
Compositional Screening: Ni-Co-Cr-Mo w/ Hull Cell
Alloy Co Ni Cr Mo Inconel® 740 20 (base) 25 0.5 Stellite® 21 (base) 3 29 6
slide 13
Scale up to 1” x 4” Coupons• Using the electrolyte designed within the Hull Cell study and approximate applicable current
densities we transitioned to coupon studies • Cell
– 3: 1” x 4” samples prepared simultaneously – 29 L cell Volume – FARADAYIC®
Flow Assembly* • Samples prepared
– Pure Ni (Wood’s bath) • Varying Thickness
– Pure Cr (1411 and 1318) • Varying Thickness
– NiCr (Varying Ni Conc. / Thickness) • 1411 • 1318
– NiCrFe (Thickness) • 1411 • 1318
− NiCoCr and CoCr (Varying Thickness) − 1411
*Gebhart, L.E., and Taylor, E.J., U.S. Patent 8,329,006, December 11, 2012.
slide 14
As Plated Samples
NiCrFe
NiCoCr NiCr
Ni: 25, Cr: 20, Co:55
CoCr
Cr: 15, Co:85 Cr: 20, Co:80
slide 15
Corrosion Studies Baseline• 100 h salted oxidation [~3 mg/cm2 - high salt loading and 1
mg/cm2 – low salt loading: sea salt applied to surface from 3.5 w/w% solution prior to corrosion test]
• Five consecutive 100 h salted oxidation • Thermal Cycle
– Ramping from room temperature to 100°C at 10°C/min – Dwelling at 100°C for 30 minutes – Ramping from 100°C to 450°C at 1-2°C/min – Dwelling at 450°C for 60 min – Ramping from 450°C to 700°C at 10°C/min – Dwelling at 700°C for 100 hours – Ramping from 700°C to room temperature at 10°C/min
slide 16
Comparison Between Substrates and Coated Parts after 500h Salted Oxidation Trials [1 mg/cm2]
Cross-Sections Post 500 h Cycle
Surface Images Post 500 h Cycle Mass-Loss Post 500 h Cycle
Ni
304 SS
316 SS
Panels A/B
slide 17
Comparison Between Substrates after 500 h Salted Oxidation Trials with High Salt Loading [3 mg/cm2]
Surface Images Post 500 h Cycle Mass-Loss Post 500 h Cycle
SS substrates 100h Salted oxidation 500h Salted oxidation
SS substrates 100h Salted oxidation 500h Salted oxidation
60Ni-40Cr
70Ni-20Cr-10Al
Ni
500h Salted oxidation
slide 18
Comparison Between Substrates and Coated Parts after 500h Salted Oxidation Trials with High Salt Loading [3 mg/cm2]
Surface Images Post 500 h Cycle
Mass-Loss Post 500 h Cycle SS441/1411/60Ni-40Cr
Coated 100h 500h
SS441/1411/25Ni-20Cr-55Co
Coated 100h 500h
SS441/1318/60Ni-40Cr
Coated 100h 400h
SS410/1318/60Ni-40Cr
Coated 100h 400h
slide 19
Corrosion Performance Overview
~ 50 w/w% NiCr alloys improve corrosion resistance of the base SS substrate by at least 70% potentially leading to a 3.4 fold
cookstove lifetime improvement
• Pure Cr and Ni deposit do not maintain adhesion during salted corrosion studies
• 60/40 ish NiCr and NiCoCr (25/55/20) mixtures seem to have the best corrosion resistance (dependent on thickness)
• Ternary (Ni/Cr/Fe) deposits did not maintain adhesion during oxidation study (presumably to CTE mismatch)
Composition-Electrolyte Base
Salted oxidation (500 h)
Cr - 1411 − Cr - 1318 −
Ni - Wood’s plating − NiCr - 1411 P NiCr - 1318 O P
NiFeCr - 1411 − NiFeCr - 1318 − CoCr - 1411 −
NiCoCr - 1411 P
slide 20
Baseline Economic Analysis for Exemplar Component
• Estimate using Cookstove Design from Literature
Patent Application# PCT/US2013/068809
0.61 ft2 internal area exposed to biocombustor
hot zone
$/lb Density (lb/in3)
Cost per Volume of Material ($/in3)
Cost per Area Assume 1/8” Thick Material ($/
ft2)
Cost of 0.61 ft2 exemplar component (Fig Right)
718 IN $ 21.79 0.297 $ 6.47 $ 116.49 $ 71.06 625 IN $ 18.29 0.305 $ 5.58 $ 100.41 $ 61.25 Haynes 25 $ 48.75 0.33 $ 16.09 $ 289.58 $ 176.64 316L SS $ 2.69 0.285 $ 0.77 $ 13.80 $ 8.42 304 SS $ 1.61 0.285 $ 0.46 $ 8.26 $ 5.04 Hastelloy C-22 $ 18.96 0.314 $ 5.95 $ 107.16 $ 65.37 Stellite® 21 $ 54.75 0.301 $ 16.48 $ 296.62 $ 180.94 Stellite® 6 $ 54.03 0.305 $ 16.48 $ 296.62 $ 180.94
Bulk Wrought Material Pricing
slide 21
Initial Electrodeposition Based Economic Analysis
• Base material cost: $5.04 • Coating cost is a function of the
number of units produced
Line No. Plant Parameters 10,000 Units 100,000 Units 1,000,000 Units 1 Cylinder Size 0.61 ft2 0.61 ft2 0.61 ft2 2 Run Time (sec) 7200 7200 7200 3 Total Units/Hr 2 16 128 4 Total Hours worked per day 24 24 24 5 Units/Day (24 hr.) 48 384 3072 6 Days worked per year 348 348 348 7 Units/Yr. (348 days) 16,704 133,632 1,069,056 8 Plating Line Cost ($/unit) $0.48 $0.06 $0.06 9 Material Cost ($/unit) $2.03 $1.29 $1.24 10 Labor Cost ($/unit) $12.52 $1.56 $0.39 11 Total Cost ($/unit) $15.03 $2.91 $1.69
Coating Cost Estimate Patent Application# PCT/US2013/068809
slide 22
Overall Conclusions• Demonstrated a wide range of [Co/Ni] – Cr – [Mo/Fe] alloy coating
compositions can produced • Demonstrated process scalability from a Hull Cell to flat coupons • Demonstrated the potential of specific coatings to surpass 500 h accelerate high
temperature corrosion testing – 50 w/w% NiCr alloys improve corrosion resistance of the base SS
substrate by at least 70% potentially leading to a 3.4 fold cookstove lifetime improvement
• Demonstrated that the process maybe an economically viable approach for improve cook stove biocombustor lifetimes – Cost estimate for 50 w/w% NiCr coating is $2.93/ in3 or $1.69 per 4 mil
coating on a 0.61 ft2 component produced at 1,000,000 units per year – This would realize a 89% cost reduction compared to base IN625
materials
slide 23
Next Steps
• Evaluate the potential of other alloy systems – Co-Ni-Cr – Ni-Cr-Mo/W – Addition of Si or Al to the deposit
• Validate performance in combustion test rigs at ORNL
slide 24
Special thanks to all our team members for their support
THANK YOU FOR YOUR ATTENTION!
QUESTIONS?
Contact Information:Santosh Vijapur, Tim Hall, Maria Inman, or EJ Taylor
Ph: 937-836-7749 Email: santoshvijapur@faradaytechnology.com
timhall@faradaytechnology.commariainman@faradaytechnology.com
jenningstaylor@faradaytechnology.com
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