Project Title: Passive Oil Collection System

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Patent Application for “Passive oil collection and recovery system”. All types of oil spill ... collector has a designed recovery rate that is at least 10 times superior to the rates of the best ...... The collected information will be stored in hard drive.
Proposal Prepared in Response to Gulf of Mexico Research Initiative Request for Proposals: Individual Investigators or Collaborative Efforts

LOI Submission Number: GoMRl2012-ll-331 Project Title:

Passive Oil Collection System

Institution Name and Location:

Auburn University

Principal Investigator and Contact Information:

Dr. Vitaly Vodyanoy

2. Project Summary Efficient and economical oil collection device which recovers oils and other materials of the surface waters by using physical principles that have never been used in oil skimmers. The design of novel device strongly exceeds other commercial skimmers in the areas of recovery rate, volume, and economy. The device was invented by Auburn University scientists after the explosion of the BP deep-water oil rig. Auburn University has submitted non-provisional US Patent Application for “Passive oil collection and recovery system”. All types of oil spill bring serious threat to human and animal health, cause ecological problems, devastate the economic lives of the affected communities because their waters can no longer sustain aquatic life. This reality creates a strong global demand for the fast, efficient and economical oil clean up by oil skimmers. The fact that only 3% oil leaked during the Deep Horizon disaster was collected by oil skimmers indicates that oils skimmers of much higher capabilities are needed. Unlike other skimmers, the proposed device has no moving parts, pumps, filters, adsorbents, belts, brushes, disks or other attributes. It does not need any motors or electrical power. Having no moving parts they have the highest mechanical efficiency and durability. The 10-m oil collector has a designed recovery rate that is at least 10 times superior to the rates of the best contemporary skimmers. The average designed consumption energy of the passive collectors is 100 times smaller than that of the other skimmers. In contrast with other skimmers, they produce no noise or pollution. The novel oil collection vessel has a dual function: it works as an oil recovery device and as a collection tank. A single 10-meter vessel can store 524 metric tons of oil. No other conventional skimmers have a collection tank of such capacity. The oil contained by a single device is equivalent to 5.4 million kilowatt-hour (kWh) that can provide electricity for an average house in USA for 486 years, or save about $604,666. At such capacity and designed oil recovery rate, only five 10-m vessels could collect and hold all daily oil escaped from Deep Horizon rig. Only 3% oil leaked during this disaster was collected by oil skimmers. If during the same time the oil were collected with Passive Oil Collectors, which have 10 folds higher collection efficiency, more than $130 million could be saved by the oil costs alone. Taking in account very low energy consumption and high volume of Passive Oil Collectors, the saving could be much greater. The objective of this work is to define and characterize effects of physical and environmental conditions on the oil recovery rate and oil % collected by the Passive Oil Collection Devices from water surface in order to determine the most effective device design and range of use for maximum efficiency and economy. Our 36 month effort contains following tasks: (1) Characterize oil collection properties (flow rate and oil %) as function of oil viscosity and degree of oil dispersion (range of oil droplet dimensions). (2) Determine dependence of flow rate and oil %oil on film thickness and vessel velocity. (3) Define effects of temperature, wind, and wave‟s action on the oil collection properties by the Passive Oil Collection Devices. Our efforts will start with the unique oil collection idea and theoretical models, through laboratory tests that will be examined against a major concept and theoretical calculations. The R&D efforts will result in the simple solution of a very old problem – foundation of the versatile oil collection device that is very efficient, of high volume, excellent % of oil recovery, very economical, durable, no noise, no pollution, environmentally friendly, and capable producing a broad economic impact in the oil clean up industry by strong protection of health, life, and environment. The research team includes researchers with expertise in physics, interface film technology, engineering design and strong laboratory experience. The combination of the expertise is ideal for the development of fundamental knowledge, investigation, design, and optimization of this complex system. Collectively, our experience and preliminary results position us well to undertake the work that we propose.

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3. Table of contents Contents 1. Cover Sheet ............................................................................................................................................ 1 2. Project Summary ................................................................................................................................... 2 3. Table of contents ................................................................................................................................... 3 4. Project Description................................................................................................................................. 3 a. Research Objectives and Goals of the Project ............................................................................. 3 a1. Timeline Table .............................................................................................................................. 4 b. Approach ............................................................................................................................................. 4 b1. Preliminary Results ..................................................................................................................... 4 b2. Methods....................................................................................................................................... 10 b3. Role of key personnel ............................................................................................................... 13 c. Qualifications .................................................................................................................................... 14 c1. PI‟s Qualifications ..................................................................................................................... 14 C2. Graduate Students .................................................................................................................... 14 C3. Metrics of progress for evaluating personnel involved in the Project. .............................. 14 d. Data Management Objectives........................................................................................................ 15 e. Supplementary Objectives ............................................................................................................. 15 5. Facilities, Equipment, and Other Resources ................................................................................... 15 6. Budget and Budget Justification ........................................................................................................ 16 6a. Annual budget for each of the one to three years of proposed research. ............................ 16 6b. Budget justification ........................................................................................................................ 26 7. References Cited ................................................................................................................................. 28 8. Personnel: ............................................................................................................................................. 29 9. Current and Pending Support ............................................................................................................ 31

4. Project Description a. Research Objectives and Goals of the Project The objective of this work is to define and characterize effects of physical and environmental conditions on the oil recovery rate and oil % collected by the Passive Oil Collection Devices from water surface in order to determine the most effective device design and range of use for 3

maximum efficiency and economy. Our 36 month effort contains following tasks: (1) Characterize oil collection properties (flow rate and oil %) as function of oil viscosity and degree of oil dispersion (range of oil droplet dimensions). (2) Determine dependence of flow rate and oil % on film thickness and vessel velocity. (3) Define effects of temperature, wind, and wave‟s action on the oil collection properties by the Passive Oil Collection Devices. The ultimate goal of this research project is to create the versatile oil collection device that is very efficient, of high volume, excellent % of oil recovery, very economical, durable, no noise, no pollution, environmentally friendly, and capable producing a broad economic impact in the oil clean up industry by strong protection of health, life, and environment. a1. Timeline Table Tasks Year 1 Year 2 Year 3 Task #1. Characterize oil collection properties as function of oil viscosity and degree of oil dispersion. Subtask 1. Produce laboratory prototype of oil collecting x vessel (two vessels). Subtask 2. Characterize oil water emulsions. x x Subtask 3. Produce a level adjustable mechanical x x clamp for the vessel positioning (two units). Subtask 4. Measure and define oil collection rate and % x x oil dependence on oil viscosity and dispersion. Task #2. Determine dependence of flow rate and oil % oil on film thickness and vessel velocity. Subtask 1. Build a water tank with continuous water x x x x x movement along an oval flume. Water velocity, temperature control, wind, and wave action. Subtask 2. Measure and define oil collection rate and % x x x x oil dependence on film thickness and velocity. Task #3. Define effects of temperature, wind, and wave’s action on the oil collection properties by the Passive Oil Collection Devices. Subtask 1. Determine temperature dependence of oil x x collection properties. Subtask 2. Define wind weathering effects on oil x x collection properties. Subtask 3. Characterize wave action and optimal x x vessel geometry x x x Final technical report

b. Approach b1. Preliminary Results b1.1. Passive oil collection device. The Passive Oil Collection Device is an efficient, simple, durable, and economical oil skimmer. It collects and recovers crude, refined, animal, vegetable oils, and other floating materials from surface waters. The device is composed of the collection vessel, the flotation system, and the vessel positioning system. The water-filled sealed vessel is positioned above the spilled oil so that the oil entrance opening is leveled with the oil layer on the water surface. The oil moves upward into the vessel displacing the water due to the lower density of the oil. After the vessel is filled, the collected oil 4

is exchanged with water, and the device is ready for a new oil collection. The device has no moving parts, pumps, filters, adsorbents, belts, brushes, disks or other attributes of the conventional oil skimmers. The device efficiently collects oil in complete silence; you can hear your watch ticking. b1.2. Physical principles governing operation of the Passive Oil Collection Device After the explosion of the BP deep-water oil rig on 20th April 2010 the wellhead, located in the deep ocean floor 5,000 below the surface, burst open and millions of gallons of hot oil rushed to the surface. After reaching the surface the oil rapidly spread, killing animals, marine life, poisoning water and air. The large amount of oil escaping from the ocean floor moves up with a speed of about 60 meters per minute and, even in the case of the 2010 BP leak of 1500 m deep, it reached the surface in 25-30 minutes. Oil moves up because it is lighter than water and it stops its vertical movement at the air/water interface since it is much heavier than air (Figure 1.1). A vessel open at one end, filled with water and inverted with the opening submerged into oil layer, holds the water inside as a result of balanced water pressures outside and inside. (Figure 1.2). The oil beneath the vessel rushes in and fills the vessel replacing water (Figure 1.3). The last picture reminds a very famous Figure 1 Oil moves upward in water experiment of Torricelli. In 1643 Evangelista Torricelli created a 1 m long tube, sealed at the top end, filled it with mercury, and set it vertically into a basin of mercury. The column of mercury fell to about 76cm, leaving a Torricellian vacuum at the top of the tube. The column‟s height fluctuated with changing atmospheric pressure. This was the first functional barometer. If we replace mercury with water we will conceive a physical principle of a very efficient and simple oil collection method. Atmospheric Pascal„s A vessel of any shape, open at one end and filled with water, when inverted into water Pressure pressure with the opening submerged, will result in the H creation of a low pressure area (Figure 2). If surface of the surrounding water is covered with oil (or any other liquid that has density less than water) the oil will go through the P=gH vessel‟s opening toward the lower pressure area at the top due to the density differential. As the oil moves into the vessel it will displace an equal volume of water from within the vessel.

Figure 2. Physical principles of oil collection

The pressure of the water column in the inverted vessel is calculated by Pascal‟s law and does not depend on shape of the vessel: P=gH, where ρ is the fluid density, g is acceleration due to gravity ~9.8 m/s2; H is a column a fluid column height in meters, P is a pressure in Pa (N/m2). According to Pascal equation, for 10 m column we have P=103 kg/m3×9.8 m/s2×10 m=105 N/m=1 atm 5

It means that 10-m water column can be equilibrated by atmospheric pressure (a water weight/m2=atmos. pressure). Therefore, the vessel can hold water inside the vessel if the water column height is equal or less than 10 meters. This condition limits the height of the vessel by the impressive 10 meters. b1.3. How much oil can be collected by the Passive Oil Collection Device? It is easy to calculate that a two and one-half meter-device can collect 51.5 barrels of oil. The device of 10 meters in diameter can collect 3296 barrels of oil ($332,980 as of 1/11/12). 3296 barrels of oil are equivalent to 5.4 millions of kilowatt-hour (kWh). The electricity consumption by an average house in USA is 920 kwh/month [1].Thus one 10-m collecting device can amass the oil that provides electricity for an average house in USA for 486 years, or save about $604,666. The vessel volume increases sharply as function of vessel diameter. When we increased the vessel diameter by 4, the volume is increased by 64 times. The collected volume increases as a vessel diameter to the power of 3. During the Deep Horizon Explosion, oil was leaking from the well head at the flow rate of 13002650 cubic meters of crude per day [2]. A 10-m Passive Oil Collection Device can collect 524 cubic meters of oil. Thus only five 10-m devices would be required to capture and hold all of the daily oil leaked from the well.

b1.4. How fast oil can be collected from the water surfaces by the Passive Oil Collection Device? When the vessel is filled with water and positioned so that the open mouth is immersed into the oil layer on the surface of water, the oil flows into the vessel replacing the internal (prime) water. The oil layer in most cases is a water emulsion of oil droplets [3]. Using Eq (1) (page 10) with Δρ/ρ = 0.13 (for an oil with a density of 0.89 mg/mL and seawater at 1.025 mg/mL), ν = 1.07×10−6 m2/s and g = 9.81 m/s2, droplets with a diameter of 6000 µm will rise with a velocity (wv) of 0.14 Figure 1. Calculated oil flow rate as a function m/s. This value agrees well with experimental data [4]. of oil droplet size and the opening diameter. From Eq (2) (page 11) one can calculate a vertical flow rates for different diameters of vessel opening. It is clear that the collecting rate increases as the opening diameter to the power of two. It also increases when oil droplet size increases (Figure 3). For example, 1 m diameter vessel with 20 cm opening can fill 138 gallons of oil from a thick layer of oil (droplet diameter of ~6000 μm) emulsion for ~140 seconds with rate of 60 gallons/min. Ten-m vessel with 4 m opening can collect 138,425 gallons from the same layer for ~5 minutes at the rate of 27,870 gallons/min (6,330 cubic meters per hour). It is important to notice that a flow rate does not depend on diameter of container, but increases as an opening diameter to the power of 2. During the Deep Horizon Explosion, oil was leaking from the well head at the flow rate of 13002650 cubic meters of crude per day. The maximum flow rate of the oil that escaped from the rig corresponds to 110 cubic meters per hour. The collection flow rate by the ten-m vessel with 4 m opening is 6,330 cubic meters per hour. Therefore, the oil collection by 10-m vessel is ~60 times faster than the oil leak. According to our theoretical estimate the filing time of our 10-m vessel is 5 minutes. Even if we are wrong with our estimate by two orders of magnitude and filing time is not 5, but rather 500 minutes, or ~21 hours, five 10-m vessels, 524 m3 each could collect and hold all daily oil escaped from Deep Horizon rig. 6

b1.5. Energy Consumption. The passive oil collection is not really free. The vessel needs to be filled with water and to be positioned just above the oil/water surface. These processes consume energy and it can be used to estimate energy consumption of this method. Let us make an imaginary experiment. We put an empty sphere vessel with opening up on the water surface of the water pool, which is deep enough to fully submerge the vessel. Then, position the vessel opening with the water level allowing water to fill the vessel. During filling the container is submerging by gravity. The water filled container is positioned below the water surface with opening up. The filled container is rotated 180o around the horizontal symmetry axis (until opening is facing downward). The water filled container then is positioned below the water surface with opening down. Finally, the water filled container must be lifted until opening is on the oil/water surface. Using Archimedes‟ buoyancy principle and gravitational potential energy definition, we can estimate the potential energy change (E) from the vessel position just below to just above the water/air interface: E=(m+M/2)gd, where d is vessel diameter, g is acceleration due to gravity ~9.8 m/s2, m and M are masses of empty and full vessel, respectively. There are some other vessel filling and positioning procedures but the energy consumptions are approximately the same. Using this equation together with Eqs (1) (Page 10)and (2) (page 11) we can calculate that 1 m diameter, 40 cm opening staining steel sphere (55 kg) can provide 63 m3/h oil flow rate and can collect 524 kg of oil at the energy consumption of 0.0016 kwh/m3. The weir oil skimmer of similar productivity will spend 400 times more energy. There is no need for a pump to unload the oil that is collected by the Passive Oil Collection Device. To unload the device we could use the same physical principles that we use for oil collection. The collecting vessel is connected with the barrel on the service vessel and the collected oil is exchanged with water. b1.6. Experimental validation of the passive oil collection concept We have examined the concept with one laboratory experiments and one prototype field experiment. In the laboratory experiment we elevate the water-filled vessel to align the vessel opening with the oil layer (Figure 4 A). Collection begins and the oil stream enters the vessel filling it up (Figure 4 B). The oil movement stops when the vessel is full of oil.

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Figure 4. Oil collection with 125 ml laboratory separatory funnel. A. The water-filled vessel is positioned with opening down, above water /oil level. B. Oil enters the vessel through the opening and replaces water. C. The vessel is filled with oil.

The filling process is quite rapid and depends only on diameter of the mouth. Oil enters the vessel and replaces water. The process occurs naturally, so there is no moving parts, pumps,

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sorbents, etc. Only two driving forces derived from gravity and atmospheric pressure are in action. Both are almost FREE. We spent a small amount of energy when we lift the water filled vessel above the water/oil level. This experiment validates the passive oil collection principles and clearly demonstrates the lifting of spilled oil into collective vessel. The process of oil collection is illustrated by this link: https://www5.vetmed.auburn.edu/~vodyavi/1 Principle.Copy.01.mov A passive oil collection prototype field experiment. A simple pontoon oil collection system was composed of a 15-gallon plastic translucent barrel with 4-inch opening in middle of a barrel cylinder and a pontoon that holds a barrel with adjustable strips (Figure 5 A). The barrel was filled with water and positioned with an opening at a water surface in a small pool (~6-m diameter) (Figure 5 B). Two full buckets of oil (~11 gallons) were spilled in the pool (Figure 5 C) and collection began (Figure 5 D). To facilitate oil collection, the pontoon was moved by hand around a pool surface with an average velocity of ~ 0.1 m/s. In 10 minutes collection was interrupted, the barrel was rotated 180o opening up and oil was drawn out by hand with a glass can (Figures 10 E-G). Ten gallons of oil was recovered. The recovery rate measured by the amount of recovered oil in this experiment was 6.3×10-5 m3/s. Using the pool geometry we estimated that after oil spreading the created film was quite thin (~1500 microns). Using Eq. 3 (page 11), a horizontal oil velocity, at , g=9.8 m/s2, ρ/ρ=0.11, h=1.5×10-3 m, is equal 4.4×10-2 m/s. From Eq. 4 (page 11), the horizontal flow rate, at the opening diameter was 4 inches, Fh= πwh dh= 2.07 ×10-5 m3/s. The flow rate due to the device movement with average velocity wm=0.1 m/s, Fhm=πwmdh=4.71×10-5 m3/s. The total collection flow Ft= Fh+ Fhm=2.07 ×10-5+4.71×10-5=6.8×10-5 m3/s. This theoretical flow rate agrees well with the experimental value of 6.3×10-5 m3/s. The optimal vessel velocity for this case is calculated with Eqs. (9) (page 12) and (1) wo=dwv/4h=0.5 m/s. The optimized flow rate for the optimal velocity is estimated by Eq (10), Fo= wv×πd2/4=2.4×10-4 m3/s. This analysis indicates that movement of collecting vessel over oil layer in this experiment with an optimized velocity would increase the flow rate by a factor of 5. Thus, for thin oil layers the oil flow can be significantly enhanced if collecting device (or water with oil layer) moves. This field experiment validates the principles of passive oil collection for relatively large oil quantity. The test also shows successful oil collection from a thin oil layer, and gives a way to enhance the recovery rate by a horizontal movement of collection vessel. The experimental results agree well with predictions of theoretical model.

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Figure 5. A passive oil collection prototype field experiment. A. Schematics of collecting system. The barrel has an oil collecting opening on the bottom of the barrel. The position of the barrel is controlled by hand adjustable strips. B. The collecting barrel is filled with water and positioned above the water surface opening down touching the water surface. C. Oil is spilled in a pool. D. The device collects oil. E-H. The collected oil is drawn out by hand.

b1.7 Comparison of the Passive Oil Collection Device with commercial oil skimmers. The contemporary oil skimmers occupy a very competitive field. There are many manufacturers of oil skimmers. For each type of skimmer the manufacturers have different sizes and models of the equipment. Different manufacturers produce similar devices, each one with its own design and standard of quality and name. The majority of skimmers collect oil from a film on water that is naturally created on the water air interface due to the gravity forces and density difference between oil and water. The light oil comes to water surface and makes a film.

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Skimmers are generally classified in following four groups based on their principles of operation (oil collection and oil recovering) Weir, Oleophilic, Mechanical and Vacuum [5]. 1. Weir skimmers represent a major group of skimmers. The weir operates at the interface of the oil with the water allowing the oil to flow into the skimmer. The weir mechanically separates a top layer of oil from water. An adjustment of a weir position minimizes the quantity of water recovered. The weir skimmers normally have a pump that continually passes oil and water through device, an adjustable weir that separate oil from water, and holding tank. 2. Oleophilic surface skimmers, sometimes called sorbent surface skimmers, use a surface to which oil can adhere to remove the oil from the water surface. This oleophilic surface can be in the form of a disc, drum, belt, brush, or rope, which is moved through the oil on the top of the water. A wiper blade or pressure roller removes the oil and either deposits it into an onboard container or the oil is directly pumped to storage facilities on a barge or on shore. The oleophilic surface itself can be steel, aluminum, fabric, or plastics such as polypropylene and polyvinyl chloride [5]. 3. Mechanical skimmers include belts with paddles, metallic and plastic toothed disks, collection buckets and drums. They all depend on physical action to bring the oil into the skimmer. 4. Vacuum skimmers use a vacuum or slight differential in pressure to remove oil from the water surface. Often the „skimmer‟ is only a small floating head connected to an external source of vacuum, such as a vacuum truck. The head of the skimmer is simply an enlargement of the end of a suction hose and a float. Passive oil collection skimmers do not belong to any of the above groups of skimmers, and represent independent oil collecting devices. The passive collection vessel is filled with water and positioned above the water/oil surface, so that a vessel opening is leveled with the oil layer allowing a continuous liquid connection between inside and outside liquids. The internal liquid is contained inside the vessel as the liquid weight is equilibrated by a force of atmospheric pressure. As soon as connection made, the oil from a water surface under the opening comes up inside the vessel replacing the internal water. The process continues until the entire vessel is filled with oil. The operation principles of the passive collection are different from those of weir skimmers, which use pump suction and mechanical weir for collecting and recovering oil. They are also very different from the principles of oleophilic skimmers that use mechanical movement and oleophilic surfaces for collection and separation of oil from water. The passive oil collectors differ from mechanical skimmers, which use mechanical movement and mechanical means for oil entrapment. And finally, the passive collectors are very dissimilar to vacuum skimmers, which utilize negative pressure to collect oil. b2. Methods The objective of this work is to define and characterize effects of physical and environmental conditions on the oil recovery rate and oil % collected by the Passive Oil Collection Devices from water surface in order to determine the most effective device design and range of use for maximum efficiency and economy. b2 1. Tasks (1) Characterize oil collection properties (flow rate and oil %) as function of oil viscosity, degree of oil dispersion (range of oil droplet dimensions), oil film thickness, and vessel velocity. Rationale. Nineteen century mathematician and physicist Sir George Gabriel Stokes derived an equation that can describe a vertical velocity (wv) of oil droplets that depends on the droplet diameter (d), the normalized density difference between water and oil ( ρ/ρ), gravitational acceleration (g) and the water viscosity (ν): wv=( ρ/ρ)gd2 /18ν (1) 10

The vertical flow rate (Fv) then is proportional to the opening surface area S: Fv=wv×S= wvπd2/4 (2) Experimental design. We will build laboratory prototype of 8 inches diameter transparent vessel with 4 inches opening. An oil-resistant rectangular plastic container 16(L)x16(W)x12(H) inches will be used for artificial sea water and oil layer. The vessel filled with water will be positioned and maintained above the oil layer with the adjustable mechanical clamp. High and low viscosity motor oils, transmission liquid, and a raw crude oil from the Texas Raw Crude (Midland TX) will be used for the oil collection experiments. The crude oil will be artificially weathered by enforced evaporation under a fume hood for two weeks. The oil/water emulsions will be prepared as following: The oil samples will be mixed individually with salt water in the mixing containers with the Excella E24 New Brunswick Incubator Shaker (Available in our lab). The ratio of crude oil to salt water will be ~ 1:2. Alternatively, emulsions will be prepared with the variable speed 169953 GE Blender. Artificial seawater with 30 ppt salinity will be prepared by dissolving an appropriate amount of sodium chloride into distilled water. The samples of the emulsions will be stored in glass jars for 7 days to confirm the stability. The experiments will be carried out at room temperature (~25 o C). The oil viscosity will be measured by the Stokes methods using velocity of a test ball in the bulk oil and in the oil monolayer [6-8]. The rapid evaluation of oil viscosity will be carried out by the HARDV-III Brookfield Digital Rheometer. The percent of water in oil will be measured by Varian 4100 FTIR Microscope (Available in our lab). The content of oil can be calculated by the absorbance at the wave number parting for 2930cm-1 (stretching vibration of C-H of CH2 group), 2960cm-1(stretching vibration of C-H of CH3 group) and 3030cm-1(stretching vibration of C-H of aromatic ring). Main vibrations of water are 1643.5, 2127.5 and 3404.0 cm-1. The oil droplet size and distribution will be analyzed by High Resolution Light Microscope and Image Pro-Plus 2.0 software (Media Cybernetics, Bethesda, MD) available in our laboratory [9, 10]. The oil flow rate and oil % will be experimentally measured and compared with our and literature theoretical models [3, 4, 7, 8, 11]. Expected results. The experiment will determine the working viscosity range and % of oil recovery for passive collection devices that will allow the most optimal usage during oil spills. b2. 2. Task (2). Determine dependence of flow rate and oil %oil on film thickness and vessel velocity. Rationale. The Eqs (1) and (2) are true for relatively thick oil layers or when the removed oil from the water surface is rapidly replenished by the underwater source. When oil that is directly under the vessel‟s opening is moving upward, the empty space is getting filled either by the underwater source or by horizontal oil layer movement that percolates under the opening. If the oil layer is very thin, then the limiting factor for filling vessel with oil is the horizontal flow rate. Therefore for thin oil layers the oil flow is directly proportional to the opening perimeter and therefore to the opening diameter. To estimate an oil flow rate for thin oil layers we can use equation for horizontal oil velocity (wh) derived for the inertia-gravity spreading of oil on water [12]: , (3) where g is gravitational acceleration, h – layer thickness,  is experimentally found constant = 1.2, and ρ/ρ – the normalized density difference between water and oil, which is found to be equal to the fraction of the oil thickness floating above the mean water level [12]. The horizontal flow rate (Fh) then can be estimated from the equation: Fh= πwh dh (4) where d is an opening diameter. For thin oil layers, the oil flow into vessel can be facilitated by a horizontal movement of collecting device. While the thin oil layer under the vessel opening is moved into vessel, the 11

device moves horizontally over the fresh oil layer. It is easy to estimate the contribution of device movement to the horizontal flow rate: Fhm=πwmdh (5) where wm is a device velocity. It is clear that device moment is beneficial only for thin oil layers when Fv >>Fh . The oil volume (V) under the opening is a function of the opening diameter (d) and oil layer thickness (h): V=πd2h (6) The time needed to lift this volume of oil into the vessel (t) at the vertical flow rate Fv is equal t=V/Fv (7) Substituting V and Fv in Eq. (7) from Eqs (6) and (2), respectively we have t=4h/wv (8) During this time (t) when the oil under the opening could be fully depleted the device should move forward at least the distance that is equal to the opening diameter (d), to be positioned over the fresh oil spot. Thus the optimal velocity (wo) of the device movement is wo=d/t=dwv/4h (9) Substituting device velocity (wm) in Eq. (5) with the optimal velocity (wo) from Eq. (9) we can find the optimal flow rate (Fo) of the device moving with the optimal velocity over thin oil layer Fo= wvπd2/4=Fv (10) Eq. (10) shows that collection vessel movement with the optimal velocity allows the substantial collection enhancement that is equal to the vertical flow rate. The range of vessel velocities (wm ) that can facilitate the collection flow rate is 0< wmwo .Therefore, the total flow rate (Ft) in case of thin oil films with a device moving with velocity wm can be described as following: Ft= Fh+ Fhm= πwh dh+ πwmdh= πdh(wh+wm)= πdh( + wm) (11) When wm= wo Fto= Fv+Fh= wvπd2/4+ whπdh=πd(wvd/4+whh) (12) where wv and wh are described by Eqs (1) and (3), respectively. Experimental design. We will build the oval water tank 120(L)x60(W)x12(H) inches similar to that described in [13]. The water flume will be 16(W)x12(H) inches (Figure 6). Approximately 640 liters of artificial seawater will be circulating in the 6.2 meter long flume. The tank will be connected to the refrigerated/heated circulator through water inlet and outlet (4) and (5). The tank is also provided with underwater propeller (6), electronic thermometer (7) and wave cam (8). The tank will be included under transparent oval cover with two air fans making a wind tunnel (not shown). The tank will be filled with water and combining action of water circulator and propeller provide a desired water velocity in the water channel. Two water filled Figure 6. Experimental set up for oil film collection properties. 1, 2 - vessel will be positioned above the water level in tank‟s ports 1 ports for collection vessels; 3and 2 (Figure 6). Than oil will be spread onto water surface in refrigerated/heated circulator; 4, tank at thickness of 0.1, 1, 5, 10, and 25 mm and oil collection 5-water inlet, outlet, respectively; 6-water propeller; 7-thermometer; flow rate and %oil will be measured at various velocities of water and oil layer. (Instead of moving vessel, the oil layer will 8-wave cam. be moved relatively to the stationary vessels). Expected results. The experiment will result in characterization oil collecting properties for oil layers of different thickness and define the oil layer (or vessel) velocity to maximize oil collection for thin layers.

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b2.3. Task 3. Define effects of temperature, wind, and wave‟s action on the oil collection properties by the Passive Oil Collection Devices. Rationale. Because viscosity of liquids strongly depends on temperature [14] the oil collection properties is also a strong function of viscosity has been known for all types of oil collection devices as viscosity affects both the oil loading as well as the flow rate of oil across the water surface. Additionally, wind and wave action are important factors in oil collection from spills. The waves are specifically important for oil collection by Passive Collection Devices: during oil collection the vessel opening needs to be in contact with water/oil surface in order to be able to hold inside liquids. If wave action throws up the vessel and opening is shortly exposed to air, the vessel can lose some of the “prime” water or collected oil. A fluid outflow from a vessel turned upside-down was calculated theoretically [15] and was shown depends on ratio of the opening diameter and height of the vessel (d/h). In experiments of this task we will experimentally determine the optimal d/h ratio for certain wave amplitudes. Experimental design. We will use the experimental set up shown in Figure 6. The oil collection parameters will be measured for the same oil samples that were used in Task #1. Oil collection properties will be examined with two 8 inch-diameter vessels with openings varied from 1 to 5 inches in diameter, temperature from 5 to 35 oC, wind – from 0-10 m/s, waves of ~12 and 18 cm height and various wavelengths. The water temperature will be controlled by the refrigerated/heated circulator and oil collection will be monitored for the freshly spread oil layers and for oil layers first weathered by wind. Waves will be generated by a flap-type wave-maker. The wave-maker is linked to an adjustable cam. Wave-heights are altered by controlling the strokes of the cam, and wave frequency is controlled by the rotational speed of the cam [16]. Expected results. The work will result in characterization of oil recovery by Passive Collection Devices at different temperatures, and simulated real environmental conditions at sea: wind and waves. We determine the most effective geometry (d/h, opening diameter to height ratio) of collective vessels to work at sea. The research effort of this work will summarize the development, laboratory testing, and performance of newly designed passive oil collectors that were not used before. Preliminary results of this work make us anticipate to strongly increase the oil collecting efficiency, recovery rate, percent of oil recovery, capability to collect thin oil layers, capability to work without operator and work at night. Improvement in oil recovery will result in better preparedness to new spills at sea and better efficiency of oil recovery for other types of oil spills. It will reduce number of recovery systems, personnel on standby, equipment maintenance, and consequently will reduce overall costs of oil recovery.

b3. Role of key personnel Institution

PI

Research Topic/Goal

Role

Auburn University

Dr. V. Vodyanoy

Passive oil collection devices, design, optimization and tests.

Project Leader

Associate Postdoctoral And Graduate students Dr. R. Guntupalli (mechanical engineer, postdoctoral fellow) Mr. O. Pustovyy (Assistant Researcher, optics, design and manufacturing) Ms. L. Globa (Associate researcher, oil sample preparation and testing). Two Graduate Students, TBD

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c. Qualifications c1. PI’s Qualifications Vitaly Vodyanoy, PI, MS in Physics, PhD in Biophysics. Experience: Extensive expertise in film technology; $12 millions of extramural funds, 41 PhD and MS students who completed their work, 8 postdoctoral scholars sponsored, more than 90 refereed publications, 10 book chapters, 52 Patents, (20 US patents, 32 Foreign patents), 9 US Patents commercialized, 3 commercial products marketed. Received 2000 Pfizer Award for Research Excellence, 2006 R&D 100, 2007 R&D 100 Awards, 2007 Nano 50 Award, 2008 Rice Alliance for Technology and Entrepreneurship Award. Auburn University Alumni Professor, 2007-2012. Auburn University Creative Research Award, 2005; Auburn University Distinguished Graduate Faculty Lecturer, 2005; Auburn University B.F. Hoerlein Research Award, 2011. Directed Federal Projects: National Science Foundation BNS 81-13761 (Planar Lipid Bimolecular Membrane); US Army Research Office DAALO3-86-G-0131; DAAL03-88-K -077; and DAAL03-90-G (Reconstitution of olfactory receptors in membranes). Federal Aviation Administration FAA -93-G-058 (Membrane Biosensor). DARPA MDA972-00-1-0011 (Molecular Switches); ARMY-DAAD05-02-C0016 (Preservation of Biological Materials; High Resolution Light Microscope). C2. Graduate Students Graduate students will be involved in all research activities related to the project. The will work under supervision of PI. C3. Metrics of progress for evaluating personnel involved in the Project.

Participants Personnel Role

Activity Progress Task1 Task2 Task 3 Task 1 Task 2 Task 3 Subtasks Subtasks Subtasks Subtasks Subtasks Subtasks 1 2 3 4 1 2 1 2 3 1 2 3 4 1 2 1 2 3 V. Vodyanoy PI x x x x x x x x x R. Guntupalli Co-I x x x x x ts O. Pustovyy Co-I x x x x x L. Globa Co-I x x x x x x GRA1 GRA x x x x x x x x x GRA2 GRA x x x x x x x x x Columns of the table represent participants, activity and progress of the project. X – represent the involvement of the person in the activity of particular task and subtask. The individual evaluation of the personnel involved in particular subtasks will be entered in the table as the project progresses. We will use the following labels: t- competed on time; l- took longer time, ssatisfactory, and u-unsatisfactory. For example, the work of Dr. Guntupalli on Subtask 3 of Task 1 was labeled as accomplished on time (t) and satisfactorily (s). 1. The PI is personally responsible for the whole project and project components. 2. PI and Co-Is are engaged in everyday communication on the current status of the work. The PI and Co-Is will share all scientific information obtained in this project. 3. Topical meetings of the PI and Co-Is to discuss progress of work, problems, make decision on scientific direction are scheduled for every two weeks, and in the case of urgency the meetings are called when needed.

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d. Data Management Objectives 1. In the course of project the accumulated data will be saved as MS Word, MS Excel, and PDF formats. Video recordings will be saved in four major formats: AVI, MPEG-4, WMV, and MOV. High resolution photographs will be saved JPEG format. Data analysis will be carried out with Microcal Origin Statistical Package. The collected information will be stored in hard drive storages, and backed up by the AU CVM data storage facility. Additionally, each investigator keeps daily records of all research activities in the individual laboratory notebooks. Data will be used for reports, presentations, and publications. All data will be available to the Research Board and available to the public through the GoMRI AU website. 2. We will follow guidelines on accessing and sharing data, security, and intellectual property of the Auburn University Office of Contracts and Grants. 3. The PI will interface for the research program and reporting of results with the Research Board. The interactions between the Research Board and the PI will include participation in meetings including an annual meeting with the Research Board. PI will prepare quarterly and annual reports to the Research Board. PI will also maintain full records of all PIs publications, presentations, and reports, which will be available for the GoMRI AU. 4. PI plans to publish all results in highly rated scientific journals and to present new materials in the regional, national, and International meetings. 5. There is no technical data or computer software that would have any disclosure restrictions. Non-provisional US Patent Application No. 2A09.1-321, 2011 “Passive oil collection and recovery system” has been filed.

e. Supplementary Objectives PI intends to make presentation related to oil spills and oil collection in Tuskegee University and local community colleges.

5. Facilities, Equipment, and Other Resources Equipment The PIs have total of 2100 sq. ft of dedicated laboratory space and equipment essential for the proposed work. All laboratories are located within one research building on the campus of Auburn University. These laboratories are also equipped with nanotechnology instruments, high resolution optical microscopy, and analytical and chemical work. Additionally, all members of team have access to the Alabama Nano Science and Technology Center and the Material research and education center of Auburn University. Major Equipment/Instrumentation in PIs’ laboratories: Two fully equipped chemical benches. Two SterilGard III (SG 403 Baker Hoods) The Baker Company; Allegra 21 R Centrifuge Beckman coulter; S4 180 Bucket rotor Beckman coulter ; Microfuge 18 Centrifuge Beckman coulter; Isotemp Standard Incubator 600 Series Fisher Scientific; Thermolyne Heavy-Duty Bench top, Muffle Furnase; (100-1200* C) Fisher Scientific Mini Protean 3 System Bio-Rad; Sterilizer EC 6000 Barnstead Thermolyne; Heater model# 2001 Barnstead Thermolyne; Isotemp ceramic top Stirring hot plate Fisher Scientific; Pipetman (5 units) Rainin instrument; C-24 incubator Shaker New Brunswick Scientific; Direct Q Millipore water purification system. Beckman L8-70M Ultracentrifuge. Nanotechnology: Pneumatic Pico Pump PV800; Mechanex BB-CH-PC computerized pipet puller; Stoelting DC-3K motorized 15

micromanipulator with X,Y,Z-controller; Devices for measurements small currents, membrane capacitance and temperature monitoring; Chamber for solvent-free bilayers of large surface area on GS-34 vibration isolated laboratory bench., computers. Two fully computerized KSV 2200 and 3000 Langmuir-Blodgett Systems (KSV Chemical, Finland) for oil layer surface studies... Q-sense E4 sensor system. The systems designed for the monolayer and multilayer thin film techniques. DNA electrophoresis, Bio-Rad apparatus for blotting, Bio-Rad low pressure chromatography Econo System. Optics/Microscopy in PIs’ laboratories: Nanofilm EP3 Spectral Ellipsometer; Varian 4100 FTIR Microscope. Ocean Nano-drop Spectrometer. UNICO Model SQ4802 spectrophotometer. SpectroThree Olympus research microscopes (BH-2, BX-50, BX-51) equipped with the Aetos Technologies CytoViva 150TM high resolution illumination system, Olympus BH-2 fluorescence microscope, Burleigh Atomic force microscope, SLM-Aminco spectrofluorometer, 5 TMS optical tables, Sony color video printer, Sony 9500 MD video recorder. IMAGING SOFTWARE: Apple‟s Imovie, Apple‟s Final Cut Express 1.1, Sony Vegas MovieStudio 4.0, Adobe Photoshop CS, CADMAX Solid Master, AnalySIS Imager 3.2, Image-Pro Plus 2.0, Nero Express 2, The GIMP 2.2.3, Origin 6.0, Carl Zeiss Imaging Systems, NI IMAQ6.1 for LabVIEW, Ocean Optics Software for Spectrometers; Imaging cameras: SONY DXC – C33, SONY DXC – S500, ZEISS AxioCam HRC, OptroNics DEI – 470, ColorView III.

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7. References Cited [1] EIA, How much electricity does an American home use?, U.S. Energy Information Administration http://www.eia.gov/tools/faqs/faq.cfm?id=97&t=3, 2008. [2] Wikipedia, Deepwater Horizon explosion, The Free Encyclopedia, Available at http://en.wikipedia.org/wiki/Deepwater_Horizon_explosion. accessed 2/3/2012. [3] F.H. Chen, P.D. Yapa, Estimating the oil droplet size distributions in deepwater oil spills, Journal of Hydraulic Engineering-Asce, 133 (2007) 197-207. [4] D.G. Seol, T. Bhaumik, C. Bergmann, S.A. Socolofsky, Particle image velocimetry measurements of the mean flow characteristics in a bubble plume, Journal of Engineering Mechanics-Asce, 133 (2007) 665-676. [5] M. Fingas, Weather Windows for Oil Spill Countermeasures, in: http://www.arlis.org/docs/vol1/191092451.pdf (Ed.), Environmental Technology Centre Environment Canada, Anchorage, Alaska, 2007. [6] H.R. Kruyt, Colloid Science, Elsevier, New York, 1952. [7] M. Fingas, B. Fieldhouse, Formation of water-in-oil emulsions and application to oil spill 28odeling, Journal of Hazardous Materials, 107 (2004) 37-50. [8] M. Fingas, B. Fieldhouse, Studies on crude oil and petroleum product emulsions: Water resolution and rheology, Colloids and Surfaces a-Physicochemical and Engineering Aspects, 333 (2009) 67-81. [9] V. Vodyanoy, O. Pustovyy, A. Vainrub, High resolution light microscopy of nanoforms, in: SPIE Proc. , 2007 pp. 1-12. [10] A. Vainrub, O. Pustovyy, V. Vodyanoy, Resolution of 90 nm (lambda/5) in an optical transmission microscope with an annular condenser, Opt Lett. , 31 (2006) 2855-2857. [11] S. Menta, Making and breaking of water in crude oil emulsions, MS THESIS, in, Texas A&M University 2005. [12] R. Chebbi, Inertia-gravity spreading of oil on water, Chemical Engineering Science, 55 (2000) 4953-4960. [13] P. Brandvik, J. Resby, P. Daling, F. Leirvik, J. Fritt-Rasmussen, Meso-scale weathering of oil as a function of ice conditions. , in, SINTEF Materials and Chemistry, Trondheim, Norway, 2010, pp. 112. [14] O.O. Okoturo, T.J. VanderNoot, Temperature dependence of viscosity for room temperature ionic liquids, Journal of Electroanalytical Chemistry, 568 (2004) 167-181. [15] V. Skakauskas, P. Katauskis, G. Simeonov, On a Fluid Outflow from a Bottle Turned Upside-Down, Nonlinear Analysis: Modelling and Control, 11 (2006) 277-291. [16] A. Lal, M. Elangovan, CFD Simulation and Validation of Flap Type Wave-Maker, World Academy of Science, Engineering and Technology, 46 (2008) 76-82.

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