thin-film surface engineering - nfpa surface engineering frank kustas, phd senior research scientist...
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Thin-Film Surface Engineering
Frank Kustas, PhD
Senior Research Scientist IV, AMP Lab
Assistant Director, Surface Engineering Research Center
South Dakota School of Mines and Tech (SDSM&T)
Chief Technology Officer
NanoCoatings, Inc. Rapid City SD
4/3/2017 1
2
SDSM&T AMP Lab Surface Processing Range
Physical Vapor Deposition - CVD
• Very Dense, Smooth Surface
• High Hardness and Toughness
• Low Friction
• Virtually Any Material
• Net Shape / No Final Finishing
Thin-Film:
nm – tens of m (0.002 in.) Thicker:
m (0.0005 in.) – hundred m (0.004 in.)
Thick-Film / Repair
hundreds of m – tens of mm (>1.0 in.)
Hybrid AP-CVD / Nanospray
• Non-Vacuum Process
• Oxide / Nanoparticle Layers
• Superhydrophobic / Icephobic
Plasma Electrolytic Oxidation
• Immersion; Non-Line-of-Sight
• Crystalline Oxides; High Hardness
• No Through-Thickness Porosity
• “Green” Electrolytes
Cold Spray
• No Melting of Powder
• Low Heat Input Into Substrate
• Very High Adhesion
• No Limit on Thickness
• Deposit Virtually Any Metal
• Deposition on Metallic and
Non-Metallic Surfaces
Atmospheric CVD of silica Nanoparticle spray
Laser Powder Deposition
• Fuse Metal/Ceramic Powder to Metal Surfaces
• Low Heat Input into Substrate
• Superior Adhesion, Abrasion and Corrosion Resistance
4/3/2017 2
SDSM&T Surface Engineering
Research Center (SERC)
• What is it ? – A new 3-Year SD Board of Regents (SDBOR) R&D
collaboration grant to foster developments in Surface Engineering (SE) - Global market in SE > $100B annually; impacts all industrial sectors
- 3 SD institutions (SD Mines (Lead), South Dakota State, Univ. of SD)
• Goals: 1. Develop new multi-institution research collaborations to increase R&D
grant awards and spur economic development (start-ups, jobs) in SD
2. Provide training for undergraduate and graduate students in SE
3. Increase our research capacity in SE
• Approach: 1. Human resource development (new faculty, new course content)
2. Acquisition of new research instrumentation
3. Build strong and sustainable collaborative research partnerships
4/3/2017 3
SERC Collaborations
• Incorporate established faculty/research staff with complementary
expertise in: 1) SE technology, 2) advanced matls/manuf., 3) advanced
materials characterization
4/3/2017 4
Application Driven:
1) Biomedical
2) Energy
3) Environment
Define Industry
Needs / “Pain”
Solution(s)
Cold Spray Technology
Research Partners
Equipment • VRC Gen III Cold Spray
System • 1000 psi & 850 ∘C • Robotic or Hand-held capable
• 400 sq. ft. spray booth • 6-axis motion system • 3-axis motion system • Powder processing equipment • Tecnar cold spray velocimeter • Metallographic Evaluation • Wear & Corrosion Testing • Mechanical Testing
Research Efforts
20
µm
CP
Ti
Al 2024
• Process Development • Materials Characterization • Equipment Development
• Modeling • Repair Applications • Commercialization &
Transition
Contact Information:
Christian Widener, PhD
AMP, SDSM&T
Christian.Widener@
sdsmt.edu
(605) 394-6924
Dye Penetrant Test Showing Benefits of Process Control
10-3-16
Contact Information:
Joshua Hammel
AML, SDSM&T
Joshua.Hammell@
sdsmt.edu
605-394-5245
• ASTM G65(B) 3-15mm3 Volume Loss
• Abrasion resistance is process dependent and can be tailored
• Abrasion characteristics on the order of common hard facing alloys with less added weight and lower COF when lubricated
0
20
40
60
80
100
120
140
Aver
age
Ad
just
ed V
olu
me
Loss
(m
m3)
ASTM G65B Abrasion Data
AR400 Astralloy Mangabraze Stoody 101HC NT-60 NTCr-70SP BAM
10-3-16
4/3/2017 8
1. Enhanced Physical Vapor Deposition (PVD) &
Chemical Vapor Deposition (CVD)
2. High Voltage Anodize: Plasma Electrolytic Oxidation
(PEO)
3. Atmospheric Plasma CVD (AP-CVD) & Ultrasonic
Spray of Nanoparticles
Thin Film Coating Technologies
PVD – CVD Processing
• Ar ion (+) bombardment of metal-target (-) ejects atoms that deposit on
substrate. Thin-film (<50 m (0.002 in.), but recently up to 400 m thick
• Attributes: 1. Low film porosity, excellent adhesion, high hardness and toughness
2. Deposit virtually any material; metals, ceramics, polymers
3. Grow nanostructured coatings, multilayers, alloys, in-situ
4. No final-finishing required
5. 2nd source for Ar+ plasma generation; increases ion-bombardment by 5-10X
6. Addition of CVD precursor
PVD Process; Courtesy SwRI
W-filament
4/3/2017 9
Coatings Fabricated by T-PVD Method
4/3/2017 10
• BAM: Al-Mg-B14 with and w/o TiB2 addition (3rd hardest material)
• TiN / SiCN nanostructured coatings (high hardness and toughness)
• TiC / amorphous carbon (a-C) (low-friction, fretting-resistance)
• CrN (excellent salt-spray corrosion resistance), TiN
• WS2 (higher-temp. low-friction solid-lubricant)
• Energetic Metal-Multilayer Materials
• Quasicrystalline Alloys, High-Entropy Alloys/Compounds
App.
App.
Example Industry Case Study-1
4/3/2017 11
Paint-spray system pump-shaft wear/failure • SS shafts coated with nitride coatings (CrN, TiN) using
arc-deposition process.
• During use, pump leakage/failure. Large scratches
observed on shaft surfaces.
Optical image of failed shaft SEM image of failed shaft
Example Industry Case Study-1
4/3/2017 12
• Arc-deposited coatings exhibit large particles which
dislodged and acted as abrasive-particles damaging the
hard coating.
SEM top-view image SEM cross-section image showing embedded particles
Mechanical Property Comparisons
4/3/2017 13
• Hardness and modulus measured by nanoindenter at SDSM&T
• T-PVD BAM coatings offer higher Figures of Merit (FOM) H/E and H3 /
E2 than arc-deposited coatings.
Coating Hardness (H), GPa Modulus (E), GPa H/E(2) H3 / E2 (2)
CrN (CAT-ARC) (1) 20.2 282.1 0.072 0.104
TiN (CAT-ARC) (1) 24.1 447.4 0.054 0.070
BAM (NTC-F, ARC) 22.1 323.6 0.068 0.100
BAM; T-PVD #A27 (#A46) 27.9 345.0 0.081 0.183
BAM; T-PVD #A30 28.2 338.1 0.083 0.195
BAM & Ti ML #A48 (~50%Ti)
58.6nm / 55.5nm
23nm BAM; 131nm BAM
16
(12.5, 12.9)
210
(217, 196)
0.076
0.093
BAM & Ti ML #A58 (#A57);
585.6nm / 55.5nm
26 280 0.093 0.224
BAM & 2% SiCN;
T-PVD; #A28
24.8 302.4 0.082 0.167
NCI CrN (avg. of 4)
T-PVD
24.6 3.95 352.1 47.17 0.070 0.121
NCI TiN-SiCN (5% Si) 26.7 283.5 0.094 0.236
Notes: (1): Commercial product; (2) H/E = relative deformation (or strain) capability
H3 / E2 = relative resistance to plastic deformation
SEM Images of BAM Coating Cross-Sections
4/3/2017 14
NTC-F Arc-deposited BAM coating SDSMT/NCI T-PVD BAM coating
Debris from silicon wafer
Coating
NTC-F
T-PVD
Ra, nm (in)
227.4 (8.95)
44.0 (1.73)
SD, nm (in)
62.42 (2.46)
32.5 (1.28)
BAM #A29 vs. 4620 Steel; “Light” Mineral Oil
• Test Conditions: 1) A29: constant-load (~59 ksi) vs. bare 4620 steel ring.
• No coating failure for A29 BAM vs. bare 4620 steel ring.
• Similar performance under PAO-Grease Lub.
4/3/2017 15
Wear factor:
1.50E-06 mm3/Nm
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0 200 400 600 800 1000
Time Duration, Seconds
Co
eff
icie
nt
of
Fri
cti
on
Pure BAM Coating #A46, Dry Sliding-Friction
Test Conditions: 1) 17 RPM (3 cm/s sliding rate); 2) Stepped load test
3) 5-min. test durations; 4) RT laboratory air, 5) unlubricated, 6) vs. non-coated
4620 steel ring.
• No failure of coating observed
4/3/2017 16
Pure BAM Coating #A46, Wear Scar; No Failure
Leading
Edge
Fe-oxide (~Fe2O3);
O: 62.2 a/o, Fe: 20.3 a/o.
“Wear-Scar” in
BAM Coating
4/3/2017 17
Example DoD Case Study-2
4/3/2017 18
• Sliding and fretting-wear applications such as propulsion-system
components (brgs., gears), lubricant-free weapon parts, air-foil brgs.
V-22 Osprey, other rotorcraft
Proprotor
Al Transfer/Debris on M50 Steel
Bearing Flange
Shaker-table
Test simulation
Low Friction/Wear TiC / C-Gr
PVD Coatings for Fretting-Wear Appl.
4/3/2017 19
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0:00:00 1:12:00 2:24:00
Time; hr:min:sec
CO
F
#75, Ti/C(ramp)ML, TiC(ramp)&Gr,
P:2.9mt
#73, Ti/C(step) ML, TiC(ramp)&Gr
#75: Smaller wear scar dia.,
but same sliding speed; P: 2.9mt
Unless Noted:
Ti bond layer,
P=2.5 mt,
Bias: -70V
#56 Graded TiC & Gr (3-hr Test)
Wear Factor: 1.8E-6 mm3/Nm
• HRC60 Steel Ball vs. TiC & Gr Graded Coatings on M50 Steel Showing COF
Reduction With Time; 1.29 GPa (187 Ksi) Initial Stress, Unlubricated, RT Air
Good Fretting-Wear Resistance of TiC / C-Gr
PVD Coatings
4/3/2017 20
• Simulated fretting-wear test with bending bar and mechanically-
bolted washers (slip at washer-bar interfaces).
A. Voevodin et al., Tribology Transactions 38 (1995) 4 829.
DoD Case Study 3; Replace Cd, Cr Plate
4/3/2017 21
Post Salt-Fog (168-hr)
(24-hr)
Navy SBIR Contract N68335-10-C-0132
Pre Salt-Fog
Al-W (#448) Co-sputtered coating
Al-Fe-Cr-Cu
Coating (24-hr)
Al-Co-Ce
(24-HR)
Post Salt-Fog (168-hr)
(24-hr)
Navy SBIR Contract N68335-10-C-0132
Pre Salt-Fog
Al-W (#448) Co-sputtered coating
Al-Fe-Cr-Cu
Coating (24-hr)
Al-Co-Ce
(24-HR)
Navy SBIR Contract N68335-10-C-0132
Pre Salt-Fog
Al-W (#448) Co-sputtered coating
Al-Fe-Cr-Cu
Coating (24-hr)
Al-Co-Ce
(24-HR)
Salt-spray resistance of PVD coatings
as replacements for Cd-plate
• Replacement of Cd and Cr-plating for aircraft landing-gear hooks
and small-arm-weapons sliding components, respectively.
- Al & W (Mo, Cr), Al-Co-Cr // Reactive-PVD CrN
Salt-spray resistance (24-hr exposure) of reactive-PVD
coatings of CrN as replacement for Cr-plate.
(Army SBIR Contract: W15QKN-06-C-0103)
Applications for PVD-CVD
4/3/2017 22
• Cutting-tools: drills, taps, dies, barrel rifling-tools, etc.
• Precision mechanical assembly components: gears, bearings.
• Machinery components: cold-spray feeder-plate assembly,
hydraulic fracturing valve seats (thicker coating), engine blades
(thicker coating)
• Biomedical prostheses components: articulating surface,
implanted stems
Biomedical joint Fracking valve seat Integrated blade-disk (Blisk) Rifling tool
Status of T-PVD Method
4/3/2017 23
• Method developed and patented by Southwest Research Institute (SwRI)
- Unique method for second-source generation of Ar+ plasma
• Engineered Coatings, Inc. (ECI) subcontracted with SwRI to set up the process in
a large PVD chamber. NanoCoatings, Inc. (NCI) licensed technology from ECI.
• ECI / NCI have the rights to use the technology for R&D. If the technology
becomes commercial, SwRI expects compensation.
• SwRI subcontracted with Mustang vacuum to build a
commercial-level PEMS system: • Turn-key automated system with 4 – 36 in. long
cathode sputter sources and dual rotation planetary stage.
• Carousels for mounting large number of parts.
Plasma Electrolytic Oxidation (PEO)
• Anodic (+) polarization of substrate at high voltage (>400V) 1. Conversion of substrate results in excellent adhesion, wear resistance
2. Crystalline-oxide: Increased hardness (3-5X ) over “hard” anodize
3. Non-columnar structure results in greater corrosion resistance
4. Incorporate functional materials into oxide (solid lube, toughener)
5. Part immersion in green electrolyte; reduced number of process steps.
6. Non-line-of-sight processing of complex-shaped parts
PEO Process Cycle, Univ. of Cambridge, UK
4/3/2017 24
PEO Operation (“Sparking”); Coated Tube
Microstructure, Hardness of PEO
Coatings
Crystalline structure () offers higher hardness, wear-resistance
4/3/2017 25
Amorphous surface for hard-anodize
HV=491 HV=1309
Crystalline surface ( = -Al2O3) for PEO #30
*
* * *
*
PEO Coating Morphology
• Dual structure (top: partially-porous, bottom: dense). Ability to convert complex
shapes.
• Controllable surface porosity (frequency) can incorporate micron-nanoparticles
or liquid / grease lubrication.
Reduced exposure of base material
for PEO treatment
Curran, Trans. Inst. Met. Finish,
89/6 (2011) 295 4/3/2017 26
Top surface view showing porosity
PEO Applications to Steels-1
• Primarily performed on “value-added” metals, Al, Ti, Mg, Ta that form
adherent, stable oxides.
• But recent R&D has shown process can be applied to low-C, high-alloy
(SS) steels.
4/3/2017 27 NCI Patent Pending
High -Al2O3
Content
Corrosion Resistance for PEO
Treated Steels
• Preliminary NaCl electrochemical corrosion tests show promise
4/3/2017 28 NCI Patent Pending
Higher
Corrosion
Resistance
PEO Applications to Steels-2
• PEO application to aluminized or cold-sprayed steel (e.g., low-C)
4/3/2017 29 NCI Patent Pending
PEO Treated 6061-Al Cold-Sprayed Steel
Steel
CS 6061 Al
Alumina
PEO Treated Aluminized (Al-Si) Steel
NCI DOE STTR Phase 1 Program;
Award DE-SC0013768
Improved Corrosion Resistance for PEO Alumina
Coatings on Steel
• PEO of aluminized and cold-sprayed steel. Significant reductions in corrosion
rate, compared to bare steel and aluminized surface. • 3.5 wt.% NaCl, Ag/AgCl reference electrode; Pt counter electrode, scan rate=2mV/s.
4/3/2017 30 NCI Patent Pending
Sample Description Corrosion
Potential(mV)
Corrosion Current
Density(A/cm2)
Corrosion
Rate (mpy)
1018 Carbon Steel -542 5.51 x 10-5 24.6
PEO coated 3003 Al -49 2.10 x 10-7 0.09
PEO coated AA 6061 cold
sprayed steel substrate
Aluminized Steel
-60
-658
1.66 x 10-7
4.06 x 10-3
0.06
1.73
More
Noble
Lower
Corrosion
Rate
Applications for PEO-Treatment
• Applications where traditional anodize cannot provide desired
wear, corrosion resistance, and other properties: 1. Oil/gas exploration & drilling equipment: hydraulic fracturing
2. Food-processing equipment
3. Biomedical prostheses
4. Off-road, motor sports parts
5. Consumer products: cookware, cooking utensils
6. Aerospace and aeronautic components: engine blades/blisks
• Applications where line-of-sight (LOS) coating technology cannot
provide uniform coating application
4/3/2017 31 Fracking valve seat Turbine-engine blisk section Mine fan blades
Plasma-CVD / Nano-Spray Technology
• Atmospheric-Plasma Chemical-Vapor-Deposition (AP-CVD) & Ultrasonically-
Agitated, Atomized-Spray of Nanoparticles 1. Non-vacuum process
2. Unique method to “glue” nanoparticles in multilayered coating or co-deposit
AP-CVD / Nanospray Process Cycle
Ultrasonically-Atomized Spray of
Nanoparticles, Sono-tek
Atmospheric-Plasma CVD of
Silica; UCLA
Before After Sonication
Nanomultilayer Coating
Video of fluid spray
ECI MDA SBIR Program 4/3/2017 32 NCI Patent Pending
Properties of AP-CVD/Spray Coatings
• Excellent hot acid-corrosion resistance, abrasion to diamond particles;
anti-tamper resistance.
• Hydro- to superhydrophobic, and icephobic surfaces
Hydro-, Superhydrophobic, Icephobic behavior
Hydro; WCA~125 Superhydro; WCA>150
NCI Icephobic Non Icephobic
Video of water repulsion
Survival of Coated Die Pad to
260C Sulfuric Acid; MDA SBIR
Applications
NCI Patent Pending 4/3/2017 33 ECI MDA SBIR Program
Summary
• SDSM&T/NCI offers a unique combination of surface engineering
capabilities to fabricate coatings that range from the nm to the tens of mm.
• Triode-Physical Vapor Deposition – Chemical Vapor Deposition (PVD/CVD)
method to produce wear and corrosion resistant coatings. 1. Moving-mechanical components; Fine-dimension gears, bearings, slides,
flaps, valve parts, fan blades.
2. Cutting and forming tools
• Plasma Electrolytic Oxidation (PEO): Wear and corrosion resistance. 1. Moving-mechanical components; Bushings, gears, plates, wire/cable
2. Incorporation of solid-lubricant additives to reduce friction, ensure system
operation during a loss-of-lubricant event. Additives to increase toughness.
• AP-CVD / Ultrasonic, Atomized Spray of Nanoparticles: Superhydro- and
ice-phobic surfaces. 1. Turbine-engine leading-edge components, drone flight surfaces.
2. Naval-ship surfaces and components.
3. Anti-tamper protection. 4/3/2017 34
Appendix
4/3/2017 35
• BAM: Al-Mg-B14 with and w/o TiB2 addition (3rd hardest material)
• TiN / SiCN nanostructured coatings (high hardness and toughness)
• TiC / amorphous carbon (a-C)
• Doped Diamond-like carbon (DLC) coatings (low friction under sand
contaminated oil conditions)
• CrN (excellent salt-spray corrosion resistance), TiN
• Multilayer Nitride / WS2 (higher-temp. low-friction solid-lubricant)
• Energetic Metal-Multilayer Materials
• Quasicrystalline Alloys, High-Entropy Alloys/Compounds
Fine-Grain PVD-CVD TiN/SiCN Coatings
4/3/2017 36
GS=366.5 nm 11.4 nm
TEM Micrograph of nc-(Al1-xTix)N/a-Si3N4), by High-Temp. CVD,
Showing Nearly -Equiaxed TiN Nanocrystals of ~3-4 nm. Jilek et al,
Plasma Chem. And Plasma Process V. 24, N. 4, Dec. 2004.
Rockwell Indentation; Adhesion, Toughness
4/3/2017 37
Indent Classification (Munz, W-D et al, J. Vac. Sci. Technol. A 11 (5) (Sep/Oct 1993) 2583-2589)
• Simple method to evaluate coating adhesion and relative coating/substrate
interfacial toughness
- Application of Rockwell C-brale indenter, loaded to 60, 100, 150 kg loads
Rockwell Indents; NTC-F BAM; T-PVD TiNSiCN
4/3/2017 38
ARC BAM
T-PVD
TiNSiCN
Local Cohesive Failure Within Coating
Good Scratch Adhesion of TiN/SiCN
4/3/2017 39
Acoustic Emission Signal Spikes (Green)
Excellent Scratch Adhesion With No Coating / Substrate Failure; 1-10N load, 1 mm/min, 3 mm total scratch length.
Good Sand Erosion Resistance of TiN-
SiCN
• Nanostructured coatings offer good toughness and sand-erosion
resistance. Application to blades, blisks for turbine-engines, valve
seats for hydraulic-fracturing pumps.
4/3/2017 40
Sand-erosion test data for bare and TiN/SiCN-coated 4130 steel;
CMU Unconventional Energy Center Grant
Si-DLC Solid Lubricant Coating
• Test Conditions: 1) Stepped-load (stress) test to study load-carrying capability.
No lubrication, RT air.
• Si-DLC film survived up to 1.37 GPa (199 ksi) contact stress without failure.
4/3/2017 41
Cr-doped DLC Solid Lubricant Coating
• Test Conditions: 1) Constant-load (stress) test under contamination environment.
• Thicker Cr-DLC film survived sand-contaminated oil lubricant without failure.
4/3/2017 42
4/3/2017
DoD Case Study 4; Wide Temp. Range
Solid Lubrication
• Solid-lubricant coatings desired for engine control components
and air-foil bearings that experience high service temperatures.
• ECI/SwRI Approach: Investigate dry-machining multilayer nitride
coatings. Low friction from lubricious oxides.
LMC JSF STOVL NASA
4/3/2017
Nanomultilayered Coatings
• Alternating layers of TiAlCrN / WN
Bilayer thickness controlled by power and rotation rate.
#369; ~14.5 nm Bilayer #361; ~265 nm Bilayer
4/3/2017
Reduced COF for Nanomultilayers
-0.10
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
0 10 20 30 40 50 60
Time (min)
CO
F (
N/N
)
~0.6
Bare Pyrowear vs. Si3N4 Ball
• COF Comparison:
~35% reduction (0.6 to 0.38) at RT
Comparable COF with WS2 cap layer
TiAlCrN / (Ti-W-Ti)N On
Pyrowear vs. Si3N4 Ball
-0.10
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0 10 20 30 40 50 60 70
Time (min)
CO
F (
N/N
) ~0.38
-0.10
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0 10 20 30 40 50 60 70
Time (min)
CO
F (
N/N
)
With WS2 cap at 483C ECI #371 Pyro 483C;
ball wear scar, 35X
TiAlCrN / WN vs. Si3N4 Ball