M4-NUWC Overview Fontaine.pdf

Advanced Unmanned Undersea Vehicle
Energy Solutions
Presented by: Dr. Joe Fontaine
11 th Electrochemical Power Sources
R&D Symposium
July 13 – 16, 2009
Baltimore, MD
Principal Investigators:
Dr. Alan Burke
Dr. Louis Carreiro
Mr. Eric Dow
Dr. Charles Patrissi
Mr. Christian Schumacher
Dr. Craig Urian

Science &
Technology
Naval Undersea Warfare Center
Division Newport
Mission
Development
INNOVATION
Acquisition
Support
Fleet
Support
Prototyping Undersea Warfare Analysis
Test & Evaluation
� Provide research, development, test and evaluation, engineering, analysis and
assessment, and fleet support capabilities for:
• submarines, autonomous underwater systems, and offensive and defensive
undersea weapon systems, and
� Steward existing and emerging technologies in support of undersea warfare

•
Joint / Coalition Battlespace Management
•
Ship / Shore Training Tools
•
Tactical Analysis & Decision Support
Towed Arrays
Comms
ASW Modules
For USVs
Division Newport Contributions to
USW Technology
Towed Array
Handlers
Advanced Sensors
• Smart Skins
• Nanosensors
Hull Arrays
Distributed Undersea Networks
Littoral Combat Ship
with Mission Modules
Surface Ship Sonar
Surface Ship USW Offensive & Defensive Systems
Including Torpedo Recognition & Alertment
Sonar Systems
Harbor Defense Systems
Torpedo Tubes
Supercavitating
Torpedoes Weapons
Periscopes,
Antennas &
Imaging Systems
Sail Arrays
CMs
CCS, FCS
Tomahawk Integration
Launchers
0010100101001010
Towed Array
Handlers
Towed Arrays
UUVs
Undersea Comms
At Speed & Depth

People
Bird’s Eye View of NUWCDIVNPT
• 2544 Civilian employees
• The nation’s experts on USW
• Highly educated & dedicated to
Fleet excellence
• 75% are Scientists & Engineers;
44% have advanced degrees
Customers
• Scientific sponsors
• Fleet
• Navy Program sponsors
• Intelligence community
• Defense industry
• Non-defense industry
• Foreign Navies
Facilities
• Highly specialized for USW
• Have full life cycle
application
• Reduce cost, risk, and
development time
• Make use of state-of-the-art
simulations and networking
• 256 Acres
75% Of Our Workforce are Engineers and Scientists
Advanced Degrees - 136 PhD’s (7%) and 711 Master’s (37%)

Science and Technology for:
Shock Analysis
and Testing
NUWC Autonomous Systems and
Technology Department
– Torpedoes
– Autonomous Undersea Vehicles (AUVs)
– Countermeasures/Counterweapons
System Development, Integration and Test
– AUVs
– Mobile ASW Targets
– Undersea Defense Systems
Acquisition and In-Service Engineering
– AUVs
– Mobile ASW Targets
– Undersea Defense Systems
Electric Torpedoes
Science & Technology
AUVs & Mobile Targets
Undersea Defense Systems

Autonomous Undersea Vehicles

•
•
Propulsion and Energy Thrust
Historically focused on both high power and
energy dense air independent systems
– Active participant from 6.1 to 6.3
–
Level of effort ranging from developer to technical
evaluator at the component to system level
Prime movers
– Thermal
–
•
•
•
Electric
•
Piston gas expander engines
Turbines
Advanced thermal cycles
Permanent Magnet Brushless DC motors
• Power electronics/motor controller

•
Propulsion and Energy Thrust
(cont.)
Energy sources
–
–
Thermal based systems
•
• Chemical stored energy
Electrochemical
• Batteries
–
–
• Fuel cell development
– Semi-Fuel cells
– SOFC
– Borohydride
Mon/bi-propellant development and T&E
Technical evaluation: Zn-AgO, Li-ion
Development: Al-AgO, Li-H2O

Advanced Air-Independent Energy
Solutions for Unmanned Undersea Vehicles
Specific energy, Wh/kg
1375 Wh/kg = TNT
Challenges to meeting UUV
power requirements include:
• Air-independent operation
• Refuelability
• Multi-mission capability
• Stealth
• Safety
• Environmentally benign
• Endurance (high energy
density)
• Weight/volume constraints
• Buoyancy
• Start-up
• low/no signature
* David Linden Handbook of Batteries, 2nd ed, 1995
Existing Commercial Sector and Conventional Energy
Sources will NOT meet the Navy UUV Future Requirements

SOFC

•
•
•
Fuel Flexibility
–
–
–
–
Benefit of SOFC Powered UUV
Pure H2 not required for operation
Hydrocarbon fuels (diesel-type) can be utilized &
rapidly refueled
Internal reforming of light hydrocarbons within fuel cell
stack
Tolerates impurities such as carbon monoxide and
sulfur (ppm level)
High Efficiency, 55-65%
– (based on LHV of fuel conversion to electricity)
Noble metal catalysts not required for electrodes
and fast reaction kinetics at electrodes

•
•
Government
– ONR -
–
–
– NASA -
Industry
–
–
–
– TDA -
–
–
–
–
Benefit of SOFC Powered UUV
Refuelable Fuel Cells for UUV’s
DoE/NETL - Testing of SOFC Stacks for SECA Program
Internally funded fuel development effort
LOX/Methane Solid Oxide Fuel Cell
Versa Power Systems - SOFC stack evaluation
Delphi Corporation - SOFC stack evaluation
Innovatek - Fuel processing
CO2 high-temperature sorbent and Phase II reformer
R&D Dynamics - high-temperature blower for anode gas
recycle
NexTech, SBIR Phase II JP10 based system
MSRI Phase II Stack development
SBIR Phase I JP-10 based energy system
ceramatec
•
• Fuel Cell Energy
• Innovatek

SOFC Stack Test Stand
Versa Power Systems

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•
Broad Fuel Comparisons
Energy Content (LHV)
Fuel Flashpoint,ºC MP,ºC MJ/L MJ/kg
Methanol 12
-98
15-18
19-22
Ethanol 13
-114
18
23
Gasoline -7.2
-58 (aviation) 31-34
42-46
Diesel 40-50 -20 to 5 (cloud) ~36-40 42-47
Liquid H2 (no tank) -252 (BP) 8
121
LNG (no tank)
-164(BP) 21
51
2015 H2 Storage Goal (9wt% systems basis) 10-15
10
Glycerin 176
~ 17 22
18
Coal
13-25 15-30

Fuel Processing (Reformers)
Catalytic Partial Oxidation (CPOX )
•
•
•
CmHn + m/2 O 2
Exothermic Reaction -
n/2 H 2
+ mCO + heat
no additional heating required for heating inlet
Fast Kinetics - reformer starts and achieves operating temperature quickly
Air-dependent Operation -
Steam Reforming
•
•
CmHn + mH2O + heat (m+n/2) H2 further studies needed to consider pure O 2
+ mCO
Endothermic reaction - requires heat for reaction and fuel/water
evaporation
-
-
Heat is supplied from fuel cell exhaust gases and CO2 scrubber
Steam can be supplied by SOFC product gases (anode recycle)
More hydrogen produced per mole of fuel than in CPOX
feed
• Air-independent operation & 15% reduction in O 2 consumption vs. combustion

•
•
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•
NUWC SOFC Test Facility
& Prototype SOFC Cell Stack w/Reformer
The Naval Undersea Warfare Center (NUWC) Division Newport is
providing independent testing and evaluation of solid oxide fuel cell
(SOFC) stacks being developed under DOE’s Solid State Energy
Conversion Alliance (SECA) program.
This testing targets SOFC performance in an air-independent
environment, which simulates operating conditions of Unmanned
Undersea Vehicles (UUVs).
Through an IA w/DOE, FY09 Testing of Versa SOFC stacks (28 cell)
will demonstrate upwards of 1 kW with Reformed S-8 and Pure O2.
FY08 Testing of Delphi SOFC stacks (30 cell) demonstrated
upwards of 1 kW using Reformed S-8 and Pure O2 under Closed
Loop Anode gas recirculation conditions.

•
•
30-Cell
NUWC SOFC Lab System
Demo
Delphi Stack integrated with:
1) InnovaTek’s Steam Reformer
2) TDA Research’s CO2 Sorbent
3) R&D Dynamics’ High Temperature Blower
Benchmarks achieved in first Demo:
– > 75% S-8 Utilization
– > 90% Oxygen Utilization
– > 50% Efficiency (PSOFC / S-8 LHV) *
– > 1 kW
Delphi Stack, 30-cell
All achieved
simultaneously in
initial proof-of-
concept study
(several hours of
operation).
C m H m Hn + n + m H 2 O 2 O (g) + (g) + heat (m+n/2) H 2 + 2 + m CO R&D Dynamics
* Furnace power neglected

28-cell Versa Power Systems SOFC
Stack

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In house Laboratory Independent
Research (ILIR) Fuel Development Effort
Develop a carbide fuel system (CFS) for use with a
solid oxide fuel cell (SOFC) that has the ability to
generate a hydrocarbon fuel and sequester/store
carbon dioxide efficiently
Demonstrate the ability of the CFS to co-generate
acetylene and hydrogen and to trap/store carbon
dioxide
Establish parameters for processing acetylene gas
Integrate CFS with fuel processor, SOFC and BoP
for unmanned underwater vehicle (UUV) propulsion
applications

•
•
•
CaC 2(s) + 2H 2 O (l)
Acetylene Generation
C 2 H 2(g) + Ca(OH) 2(aq)
Highly exothermic reaction (DH = -120 kJ/mole)
Reaction kinetics affected by:
– Temperature
– Purity of CaC2 – Particle size of CaC2 – Rate of addition of water to CaC2 (or CaC2 to water)
Storage of C2H2 under low pressure (less than 2
atm)

Carbide / Hydride Fuel System
CaC 2(s)
CaH 2(s)
+ 4H2O (l) C2H2(g) + 2H2(g) + 2Ca(OH) 2(aq)
C 2 H 2 + 2H 2 + nH 2 O
Hydrogenation
Reactor and
Steam Reformer
2CO + 5H 2 + (3+n)H 2 O
3.5 O 2 (recycle)
Gas Generation Chamber
SOFC
2H 2 O (l)
+
Q Burner
2CaCO 3(s)
2CO 2 + (8+n)H 2 O
and residual fuel gases
2CO 2 + (8+n)H 2 O

SOFC Stack Performance
Fuel: Acetylene reformate Oxidizer: Oxygen

•
•
•
Summary of SOFC Effort
Continued independent evaluation of third party
stacks and components at various levels of
integration for both ONR and DOE/SECA
Acetylene and Hydrogen mixture generated
using Carbide Fuel Source (CSF)
Cell stack operated on acetylene reformate
Principal Investigators:
Dr. Alan Burke and Dr. Louis Carreiro

Sodium Borohydride Based
Fuel Cells

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•
•
NaBH 4
Objective:
–
/ H2O2 Fuel Cell Program
Develop a low temperature, aqueous fuel/oxidant,
refuelable, energy conversion system using either
Direct topology or PEM based external decomposition
Task:
–
Evaluate the different technical approaches of this
fuel/oxidant combination
Goal:
–
Identify a technology path that will deliver a system
energy density of > 300 Wh/kg for a 21” UUV energy
section at 2kW

Reaction Chemistries:
Direct Electro oxidation/reduction
1. Alkaline Anolyte and Catholyte
Anode BH 4 -
Cathode HO 2 -
+ 8OH -
�
+ H2O + 2e- Overall 4HO 2 - + BH4 - �
BO 2 -
�
+ 6H2O + 8e- 3OH -
2. Alkaline Anolyte / Acid Catholyte
Anode BH 4 -
Cathode 4H2O2 + 8OH -
+ 8H +
�
Overall 4HO 2 - + BH4 - �
+ 8e -
BO 2 -
�
1.24 V
0.87 V
BO 2 - + 2H2 O + 4OH - 2.11 V
+ 6H2O + 8e- 8H2O 1.24 V
1.77 V
BO 2 - + 2H2 O + 4OH - 3.01 V
Key to this chemistry is to minimize the amount of caustic and acid needed to preserve the two pH
levels of the respective electrolytes. Use of an anion exchange membrane or bi-polar membrane
may be the key enabler but electro-osmotic drag will be difficult to compensate for.

Oxidation of BH 4 -
Anode BH 4 -
Reaction Chemistries:
/ Reduction of O 2 via H 2
+ 8OH -
�
BO 2 -
O 2
3. Alkaline Anolyte and Catholyte
Cathode 2O 2
+ 4H2O + 8e- Overall 2O 2 + BH 4 - �
�
+ 6H2O + 8e- 8OH -
decomposition
1.24 V
0.41 V
BO 2 - + 2H2 O + 4OH - 1.64 V
4. Alkaline Anolyte / Acid Catholyte
Anode BH 4 -
Cathode 2O 2
+ 8OH -
+ 8H +
Overall 2O 2 + BH 4 - �
�
+ 8e -
BO 2 -
�
+ 6H2O + 8e- 4H2O 1.24 V
1.23 V
BO 2 - + 8H2 O 2.47 V

Reaction Chemistries:
Oxidation / Reduction of H 2
5a. BH 4 - Decomposition
BH 4 -
+ 2H2O �
BO 2 -
+ 4H 2
5b. H 2 O 2 Decomposition
2H2O2 �
O 2
+ 2H2O O 2 via decomposition
5c. H 2 /O 2 Electro-Oxidation/reduction
(acid environment)
Anode 2H 2
Cathode O 2
�
+ 4H +
4H +
Overall 2H 2 + O 2 �
+ 4e -
+ 4e -
�
2H2O 0.00 V
1.23 V
2H 2 O 1.23 V
This chemistry would support a Proton Exchange Fuel Cell (PEMFC)

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•
•
Direct Borohydride System
Background
Objective: investigate and develop a liquid refuelable DBFC
ONR 332 sponsored program
Collaborative effort between Dstl and NUWC to
increase the understanding and science of the DBFC
Parallel approaches taken in demonstrator
development
O2 Dstl
–
–
•
MEA topology with indirect O2 reduction
NUWC
•
•
Cell topology based
–
–
–
–
Electrodeposited Pd/Ir anode
Electrodeposited Pd/Ir cathode
Cation exchange membrane
DuPont N115
Direct reduction and oxidation of H2O2 PEM
H 2
and NaBH 4
DBH/HPFC
25%
NaBH 4
60%
H2O2 Solution
waste

single cell potential (V)
1.00
0.90
0.80
0.70
0.60
0.50
IV Comparison of 3 Systems
0.40
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
current density (A/cm^2)
PEMFC @ 50C (O2/H2)
DB-DHP-FC @ 25C
DB-O2-FC @ 60C

energy density (Wh/kg)
340
320
300
280
260
240
220
200
System Level Energy Density
Calculations of 3 Systems @ 2kW
180
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
current density (A/cm^2)
PEMFC @ 50C (O2/H2)
DB-DHP-FC @ 25C
DB-O2-FC @ 60C

•
Current Efforts
Study Reaction Chemistry 2
– Alkaline BH -
4
–
–
/ anion exchange membrane / H2O2 (pH

single cell potential (V)
1.80
1.60
1.40
1.20
1.00
0.80
0.60
0.40
0.20
Preliminary 2kW System Modeling of
Reaction 2 Using Literature IV Data
PEMFC @ 50C (H2/O2)
DBH-DHP (pH

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Future Efforts
Analyze the technological maturity and practicality
of H2/O2 PEMFC operating off of decomposed
borohydride and decomposed hydrogen peroxide
Investigate powdered storage of borohydride to
increase system energy density
– Conceptual analysis
Perform system level analysis and component level
experimentation of both PEM and Gen 2 fuel cells
–
–
System engineering to determine volume/mass
constraints
System safety analysis
• Working with strong oxidizing and strong reducing compounds
Principal Investigator: Dr. Craig Urian

Li –
Lithium-Seawater Battery Development
Charles J. Patrissi, Ph.D. / Christian R. Schumacher, M.S.
seawater battery
Anode: Li Li + + e- Cathode: 2H20 + 2e- Cell: Li + H2O Li +
H 2
+ OH- + ½
+ 2OH -
H 2 (gas)
Theoretical Energy Storage of Li-seawater battery:
8570 Wh / kg of Li
4600 Wh / L of Li
(Al-H 2 O ~ 4380 Wh/kg (Theor.)) (Mg-H 2 O ~ 4120 Wh/kg (Theor.))
NUWCDIVNPT
Li anode pouch
Flexible
Pouch
Material
Water proof
electrolyte
Key Enabler: Water proof electrolyte membrane
• Li-ion conductor
• Funding: NAVSEA / ONR
• Ceramic Glass
• Target: low power sensors
Li pouch anode
• FY09
• Fabricated at NUWCDIVNPT
– Demonstrate pouch anode in
• Up to 96% coulombic efficiency in seawater (70
the ocean
psig to date)
– Shelf stability
• Low power density
– Cathode development
Seawater battery
– Fundamental studies toward
– High energy density
increased power
– Potentially safer to store than COTS Li – Increased hydrostatic pressure
batteries (no cathode)

Academia (ULI)
Additional Basic
Research
–Stevens Inst. Tech - Microplasma Reforming of Acetylene
–UConn - Fuel Cell Performance using H2O2 Reformate as
an Oxidant
–UConn – Button Cell operation using logistic fuels
–Virginia Tech – Grated Anode (sulfur tolerance)

A
outlet
Electrolyte Flow
Reference Electrode
Development of Nano/ Microstructured
Electrodes for Increased Performance
of Electrochemical Energy Sources
Counter Electrode
Technical Approach:
B
100 µm
Working electrode
electrolyte
inlet
Inert
laminar flow
plate
•Quantify Mass transport coefficient, Km, •Characterize the effects of:
-fiber density, fiber length, surface roughness
K m
= (D/ δ L
) = I L
AnFC B
D =Diffusion Coefficient
δL =Boundary Layer
Thickness
IL =Limiting Current
A =Active Surface Area
n =# of Electrons Transferred
F =Faraday’s constant
CB =Bulk concentration of
electroactive species
Objectives:
•Engineer a general, broad-range solution to increasing
battery and fuel cell performance across many systems
•Achieve this by focusing on enhancing the mass transfer of
a high efficiency electrode
•Understand/ Define operating parameters for NUWC’s
Carbon Microfiber Array (CMA) Electrode
•Tailor CMA for specific applications depending on energy
and power requirements
Payoff:
•Increase Range and Duration of Stealth Missions that are
Energy Limited such as:
-Sea Based Sensors
-Undersea Distributed Network Systems
-Unmanned Undersea Vehicles
Investigators:
Christian Schumacher, MS
Charles Patrissi, PhD
Funding:
ILIR (FY07) $100K
ILIR (FY08) $100K
ILIR (FY08) $100K

Microplasma Reforming of Acetylene for SOFC Aboard
UUVs Student: E. Lennon, PI: R. Besser, Navy Mentor: A. A.
Burke
elennon@stevens.edu, rbesser@stevens.edu
Non-Thermal Microplasma
S&T OBJECTIVES
Examples:
•
Microplasma chips fabricated by Besser’s group
running with inert gases (nitrogen & neon) in batch
mode.
APPROAC
•H
•
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Characterize VI behaviors of microplasmas to
determine device efficiencies under various chip
geometries & input settings.
Design next generation flow-thru microplasma
chips & fabricate at Cornell Nanotechnology
Facility (CNF).
Assess hydrogen generation from C2H2 microplasma chips in a closed-loop carbide fuel
processing system via measurement of
conversion, yield, selectivity, & process
efficiencies (all potentially improved by high
electron density in microplasma).
•
•
Determine if microplasma reforming of acetylene
(C2H2) is a viable fuel processing option for H2 delivery to UUV SOFC.
Determine if viable, under what conditions
microplasma reforming of acetylene (C2H2) performs best.
Compare microplasma fuel reforming for UUVs
to existing reforming technologies.
Accomplishments Jun’08 – May‘09
• Completed H2 O2 decomposition project &
submitted manuscript to Journal of Power
Sources.
• Completed microplasma fuel processing lit review.
• Reviewed VI data of inert gas microplasmas &
analyzed characteristics for batch chips.
• Integrating mass spec into current experimental
Upcoming setup. Work Jun’09 – May’10
• Complete microplasma flow-thru chip design .
• Fabricate next generation microplasma flow-thru
chips at CNF.
• Run experiments of acetylene reforming with
microplasma chips to quantify hydrogen

APPROACH
•
•
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•
Fuel
H 2 O + O 2 from
decomposed
H 2 O 2
Fuel Cell Performance using Decomposed Hydrogen
Peroxide as the Oxidant
John R. Izzo Jr., Wilson K. S. Chiu, University of Connecticut,
wchiu@engr.uconn.edu
Louis G. Carreiro, A. Alan Burke, Naval Undersea Warfare Center, Newport RI
SOFC
anode
electrolyte
cathode
Develop model to predict SOFC performance
for various oxidant stream compositions.
Validate model via cathode polarization tests on
button cells.
Characterize H2O2 to identify impurities.
Determine extent of LSM cathode degradation
using SEM, EDS, XRD and polarization data.
Couple fuel cell with H2O2 micro-chemical
reactor and optimize cathode for the oxidant
feed stream.
% Change in � at x* =1
Voltage (V)
Performance (modeling)
-2
-1.8
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
50 um
400 um
100 um
300 um
200 um
300 200 um um
400 100 um um
50 um
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Oxidant Molar Water Content
Testing (experiments)
1.2
1
0.8
0.6
0.4
0.2
0
0 0.1 0.2 0.3 0.4 0.5 0.6
Current Density (A/ cm2)
850C
800C
750C
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
Power Density (W/ cm2)
ACCOMPLISHMENTS AND PLANS
•
•
•
S&T OBJECTIVES
•
•
•
Understand behavior of air-independent fuel
cells for UUV propulsion applications.
Study the effect of a decomposed H2 on fuel cell performance and durability.
Cathode model coupling gas and charge transport
developed and validated.
LSM cathode exposed to H2O, N2 at 750 ˚C and
characterized with SEM, EDS and XRD.
Baseline polarization experiment performed.
• Perform additional polarization experiments while
varying H2O content in oxidant stream.
• Refine competitive sorption mechanism with O2 and H2O to describe O2 reduction kinetics in model.
O 2
stream
Develop Solid Oxide Fuel Cell (SOFC) system
model and experimental setup for validation with
button cell testing.

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•
•
Conclusion
Energy storage is the limiting factor for these next generation
systems
– New technology development must be tempered by:
• Safety (personnel and platform)
• Robust
• Long shelf life
• Pressure tolerant system
• Total ownership cost
Fuel Cell technology has the potential to greatly increase UUV
mission time compared with current battery technology.
High energy dense low power batteries key enablers for
Distributed Netted Sensors
Main challenges for UUV application:
–
–
–
Fuel & Oxygen Storage Density (liquids preferred, potential Solid NaBH4 dissolution)
Stack reliability for multiple thermal/Electrochem cycles & 1000’s of hours operation
Minimal startup requirements

ONR Sponsors:
•
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Dr. Michele Anderson
Ms. Maria Mederios
DOE (NETL) Sponsor
• Mr. Wayne A. Surdoval
Acknowledgments
NUWC Members:
•
•
•
•
•
•
•
•
Mr. Delmas Atwater
Dr. Alan Burke
Dr. Louis Carreiro
Mr. Eric Dow
Dr. Joseph Fontaine
Mr. Christian Schumacher
Dr. Charles Patrissi
Dr. Craig Urian

Thank you, Questions?
Contact information: joseph.fontaine@navy.mil