1. Field of the Invention
The present invention relates generally to fueling stations for dispensing natural gas to vehicles and, more particularly, to fueling stations having the capacity to provide and dispense both compressed natural gas (CNG) and liquified natural gas (LNG) on-demand.
2. State of the Art
Natural gas is a known alternative to combustion fuels such as gasoline and diesel. Much effort has gone into the development of natural gas as an alternative combustion fuel in order to combat various drawbacks of gasoline and diesel including production costs and the subsequent emissions created by the use thereof. As is known in the art, natural gas is a cleaner burning fuel than many other combustion fuels. Additionally, natural gas is considered to be safer than gasoline or diesel since natural gas rises in the air and dissipates, rather than settling as do other combustion fuels. However, various obstacles remain which have inhibited the widespread acceptance of natural gas as a combustion fuel for use in motor vehicles.
To be used as an alternative combustion fuel, natural gas is conventionally converted into compressed natural gas (CNG) or liquified (or liquid) natural gas (LNG) for purposes of storing and transporting the fuel prior to its use. In addition to the process of converting natural gas to CNG or LNG, additional facilities and processes are often required for the intermediate storage of, and the ultimate dispensing of, the natural gas to a motor vehicle which will burn the natural gas in a combustion process.
Conventional natural gas refueling facilities are currently prohibitively expensive to build and operate as compared to conventional fueling facilities. For example, it is presently estimated that a conventional LNG refueling station costs approximately $350,000 to $1,000,000 to construct while the cost of a comparable gasoline fueling station costs approximately $50,000 to $150,000. One of the reasons for the extreme cost difference is the cost of specialized equipment used in handling, conditioning and storing LNG which is conventionally stored as a cryogenic liquid methane at a temperature of about −130° C. to −160° C. (−200° F. to −250° F.) and at a pressure of about 25 to 135 pounds per square inch absolute (psia).
An additional problem inhibiting the widespread acceptance of natural gas as a combustion fuel for motor vehicles is that, currently, some motor vehicles which have been adapted for combustion of natural gas require CNG while others require LNG thus requiring different types of fueling facilities for each. For example, LNG facilities conventionally dispense natural gas from storage tanks wherein the natural gas is already conditioned and converted to LNG. The LNG is often conventionally delivered to the storage tanks by way of tanker trucks or similar means. On the other hand, CNG facilities often draw natural gas from a pipeline or similar supply, condition the natural gas and then compress it to produce the desired end product of CNG.
Some efforts have been made to provide LNG and CNG from a single facility. For example, U.S. Pat. No. 5,505,232 to Barclay, issued Apr. 9, 1996 is directed to an integrated refueling system which produces and supplies both LNG and CNG. The disclosed system is stated to operate on a small scale producing approximately 1,000 gallons a day of liquefied or compressed fuel product. The Barclay patent teaches that a natural gas supply be subjected to passage through a regenerative purifier, so as to remove various constituents in the gas such as carbon dioxide, water, heavy hydrocarbons and odorants prior to processing the natural gas and producing either LNG or CNG. Thus, as with conventional CNG facilities, it appears that the system disclosed in the Barclay patent requires location in close proximity to a natural gas pipeline or similar feed source.
Additionally, the system disclosed in the Barclay patent requires the natural gas to be processed through a liquefier regardless of whether it is desired to produce LNG or CNG. The requirement of an on-site liquefier may unnecessarily increase the complexity and cost of constructing a natural gas refueling facility, thus keeping the facility from being a realistic alternative to a conventional gasoline fueling facility.
Another example of a combined LNG and CNG fueling facility is disclosed in U.S. Pat. No. 5,315,831 to Goode et al, issued May 31, 1994. The Goode patent discloses a fueling facility which includes a volume of LNG stored in a cryogenic tank. LNG is drawn from the storage tank and dispensed to vehicles as required. CNG is produced by drawing off a volume of the LNG from the storage tank and flowing the LNG through a high-efficiency pump and a vaporizer system, which CNG is then dispensed to a vehicle as required.
While the Goode and Barclay patents disclose integrated fileling stations which purportedly provide the capability of dispensing LNG and/or CNG, improvements to such facilities are still desired in order to make such fueling facilities efficient, practical and comparable in costs of construction and operation relative to conventional gasoline fueling facilities.
In view of the shortcomings in the art, it would be advantageous to provide an integrated fueling system which is able to dispense LNG, CNG or both on demand and which is of simple construction, provides simple, efficient operation and otherwise improves upon the current state of the art.
In accordance with one aspect of the present invention a fueling station is provided. The fueling station includes at least one pump configured to boost a pressure of a volume of liquefied natural gas (LNG) supplied thereto including at least one pressurized output configured to supply pressurized LNG. At least one diverter valve is operably coupled to the at least one pressurized output of the at least one pump, wherein the at least one diverter valve is configured to selectively divert the flow of any pressurized LNG flowing from the at least one pressurized output of the at least one pump between a first flow path and a second flow path. At least one LNG dispensing unit is in fluid communication with the first flow path. A vaporizer is in fluid communication with the second flow path. The vaporizer is configured to receive and convert pressurized LNG to compressed natural gas (CNG). At least one CNG dispensing unit in fluid communication with the vaporizer.
In accordance with another aspect of the invention another fueling station is provided. The fueling station includes a multiplex pump configured to boost the pressure of volume of liquified natural gas (LNG) supplied thereto. The multiplex pump includes at least two pistons wherein each piston has an individual pressurized output configured to provide a supply of pressurized LNG. At least one LNG dispensing unit is disposed in selective fluid communication with the pressurized output of each of the at least two pistons of the multiplex pump. A vaporizer, configured to receive and convert LNG to compressed natural gas (CNG), is placed in selective fluid communication with the pressurized output of each of the at least two pistons of the multiplex pump. At least CNG dispensing unit in is disposed in fluid communication with the vaporizer.
In accordance with another aspect of the present invention a natural gas fueling facility is provided. The fueling facility includes a source of saturated liquified natural gas (LNG) such as a cryogenic storage tank containing a volume of saturated natural gas. The fueling facility further comprises at least one fueling station. The fueling station includes a multiplex pump in fluid communication with the source of saturated LNG. The multiplex pump includes at least two pistons wherein each piston has an individual pressurized output configured to provide a supply of pressurized LNG. At least one LNG dispensing unit is disposed in selective fluid communication with the pressurized output of each of the at least two pistons of the multiplex pump. A vaporizer, configured to receive and convert LNG to compressed natural gas (CNG), is placed in selective fluid communication with the pressurized output of each of the at least two pistons of the multiplex pump. At least CNG dispensing unit is disposed in fluid communication with the vaporizer.
In accordance with a further aspect of the present invention, a method is provided for dispensing natural gas fuel. The method includes providing a supply of saturated liquified natural gas (LNG) at a first pressure to a pump. The saturated LNG is passed through a pump to increasing the pressure of the saturated LNG to a second elevated pressure. A first flow path is provided between the pump and an LNG dispensing unit. A second flow path is provided between the pump and a compressed natural (CNG) dispensing unit. LNG is selectively passed through the first flow path, the second flow path or through both the first and the second flow paths. The pressure of any LNG flowing through the first flow path is reduced to an intermediate pressure, at least a portion of which reduced pressure LNG is subsequently dispensed through the LNG dispensing unit. Any LNG flowing through the second flow path is vaporized to produce CNG therefrom, at least a portion of which CNG is dispensed through the CNG dispensing unit.
The foregoing and other advantages of the invention will become apparent upon reading the following detailed description and upon reference to the drawings in which:
Referring to
With both fueling stations 102A and 102B being substantially similar in construction and operation, reference only to the components of the first fueling station 102A will be made for sake of convenience and simplicity. The storage tank 104 is coupled to the pump 106 which, depending on current demand, provides pressurized LNG to either an LNG dispensing nozzle 108 for dispensing into a vehicle's tank, or to a vaporizer 110 for conversion of the LNG to CNG through the addition of thermal energy thereto. The vaporizer 110 is coupled with a CNG outlet 112 which is coupled to a CNG dispensing device (not shown in
With continued reference to
It is noted that, while the exemplary embodiment of the present invention shows a cold box 114 housing various components, such components may each be individually insulated from the surrounding environment and from one another instead of, or in addition to, the placement of such components within a cold box 114. It is further noted that various valves, piping, tubing or other components associated with the production of CNG (such components being set forth in greater detail below herein) may also be insulated depending, for example, on the environment in which the fueling facility is placed in service.
The fueling stations 102A and 102B may be mounted on a skid 116 such that the entire fueling facility 100 may be prefabricated and then transported to a specific site. The skid 116 may be fabricated as a single unit or may include individual skids 116A and 116B each associated with individual fueling stations 102A and 102B respectively. In the exemplary embodiment shown in
It is noted that, while the exemplary fueling facility 100 is shown to include two fueling stations 102A and 102B supplied by a common storage tank of saturated LNG, other embodiments are contemplated and will be appreciated by those of ordinary skill in the art. For example, additional fueling stations may be coupled with the storage tank 104 depending, for example, on the capacity of the storage tank 104. Alternatively, the fueling facility 100 may include a single fueling station if so desired. It is also noted that while the fueling stations 102A and 102B of the exemplary fueling facility 100 are each shown to include a single LNG dispensing nozzle 108 and a single CNG outlet 112, the fueling stations 102A and 102B may employ multiple LNG nozzles 108 and/or multiple CNG outlets 112 if so desired and in order to meet anticipated demands.
Referring now to
If a demand for LNG is initiated, the pressurized LNG flows from the pump 106, through a mixer 130, the function of which shall be discussed in more detail below, through a flow meter 132 and may be dispensed from an LNG dispensing nozzle 108 to a vehicle tank 134. A circulation line 136 (recirculation line) may circulate unused or excess LNG back to the storage tank 104 from the LNG flow path 126.
A bypass line 138 may be provided to enable the diversion of a volume of LNG from the feed line 120 around the pump 106 and into the LNG flow path 126 such as, for example, during start up of the pump at the initiation of a demand for LNG at the LNG dispensing nozzle 108. A check valve 140 may be placed in the bypass line 138 to prevent any pressurized LNG which may be present in the LNG flow path 126, such as from the pump 106 after start-up thereof, from flowing back to the storage tank 104 through the feed line 120.
If a demand for CNG is initiated, pressurized LNG flows from the pump 106 through the CNG flow path 128. The CNG flow path 128 includes a vaporizer 110 which transfers thermal energy to the natural gas so as to produce CNG from the pressurized LNG. CNG exits the vaporizer 110 and passes through a mixer 142, the function of which shall be described in more detail below, through a meter 144 and is dispensed to a CNG vehicle tank 146 through the CNG dispensing nozzle 112. While, if desired, the CNG produced from the LNG may be placed in an adequately rated pressure vessel 148 and stored for future dispensing into a CNG vehicle tank 146, an advantage of the present invention is that intermediate storage of CNG is not required for the fueling of CNG vehicles. Rather, the CNG may be produced and dispensed on-demand from the LNG supply. In other words, the CNG may flow substantially directly from the vaporizer 110 to the CNG outlet 112 and/or associated CNG dispensing unit. It is to be understood that “substantially directly” allows for a diversion of some of the CNG flowing from the vaporizer 110 as well as the introduction of one or more additives to the CNG flowing from the vaporizer 110. Rather, the term “substantially directly” indicates that intermediate storage is not required or utilized between the production of the CNG by the vaporizer 110 and the dispensing thereof to a vehicle's fuel tank.
Referring now to
As indicated above, LNG is provided from a storage tank 104 (not shown in
The feedline 120 may be diverted into one of two bypass lines 138A and 138B (as there are two independent LNG dispensing nozzles 108A and 108B in the presently described embodiment shown in
Each of the supply lines 168A-168C is configured to supply an individual one of the three pistons 170A-170C of the triplex-type pump 106. Similarly, each of the pistons 170A-170C pumps pressurized LNG into an associated pressure line 172A-172C. Additionally, individual vent lines 174A-174C are coupled with each piston 170A-170C and provide a flow path 176 back to the tank 104 (not shown) through appropriate valving and piping. The pump may also include a pressure relief valve 175 to prevent over pressurization and potential failure of the pump 106.
The pressure lines 172A-172C provide pressurized LNG to either or both of the LNG flow paths 126A and 126B, to the CNG flow path 128, to all of the aforementioned paths simultaneously, or to any combination thereof through the appropriate control of various valves and flow control mechanisms as set forth below. Considering first the LNG side of the fueling station, pressurized LNG may flow through diverter valves 178A-178C, each of which in the exemplary embodiment may include a normally open ¾″ control valve rated for service at approximately 5,000 psia and at −240° F. The pressurized LNG passes through any combination of the diverter valves 178A-178C depending on demand. Due to lack of back pressure the pressurized LNG may experience a drop in pressure to, for example, approximately 300 psia as it passes through the diverter valves 178A-178C.
It is noted that the pump 106 need not produce an elevated pressure (e.g., 5,000 psia) but, rather, may provide pressurized LNG at the pressure needed to deliver LNG to a vehicle's tank. Thus, for example, the pump 106 may produce pressurized LNG at a pressure of, for example, approximately 300 psia which, thus does not necessarily experience a reduction in pressure as it passes through the diverter valves 178A-178C. However, the pump 106 may still build up the pressure of any LNG diverted to the vaporizer 110 to a desired pressure (e.g., 5,000 psia) while providing LNG at a “reduced” pressure (as compared to that diverted to the vaporizer 110) to the LNG flow paths 126A and 126B.
In one exemplary scenario, the pump 106 may be producing LNG through the pressurized output lines 172A-172C at a pressure of approximately 300 psia. If, for example, diverter valves 178A and 178B are open and diverter valve 178C is closed, LNG flows through diverter valves 178A and 178B to the LNG flow paths 126A and 126B at a pressure of approximately 300 psia while LNG is diverted by diverter valve 178C to the vaporizer and builds to a desired pressure (e.g., 5,000 psia). In such a scenario, energy is conserved by pumping LNG at the pressure which is required to dispense LNG to a vehicle's tank, while independently building pressure of diverted LNG to a required pressure for the conversion of the LNG to CNG in the vaporizer 110.
Returning to LNG side of the fueling station 102A, any LNG exiting the diverter valves 178A-178C is then directed through either, or both, of LNG control valves 180A and 180B. LNG control valve 180A controls the supply of LNG through the first LNG flow path 126A while LNG control valve 180B controls the supply of LNG through the second LNG flow path 126B. Thus, through proper actuation of the LNG control valves 180A and 180B, the LNG may be directed to flow through a specified one of the LNG flow paths 126A and 126B or to both simultaneously. Exemplary LNG control valves 180A and 180B may include a normally closed 1″ on/off control valve rated for service at approximately 300 psia and at −240° F. Such control valves 180A and 180B may also function as diverter valves depending, for example, on the operational configuration of the fueling station 102A.
As the LNG flow paths 126A and 126B are substantially similar, only one of the flow paths 126A is described in further detail for sake of convenience and simplicity in description and illustration. LNG flowing from the control valve 180A may be mixed with a defined volume of CNG from diverted CNG line 182A to control the temperature of the LNG flowing through the LNG flow path 126A. The warmed LNG then flows through a mass flow meter 184A, through another control valve 186A which may be configured similar to LNG control valves 180A and 180B, and finally through LNG dispensing nozzle 108A to a vehicle's LNG tank 134 (see
Sensors, such as a temperature sensor 188A and a pressure transducer 190A, may be placed in the LNG flow path close to the dispensing nozzle 108A to monitor the characteristics of LNG being dispensed and to assist in controlling the production of an dispensing of LNG. For example, the temperature of LNG within the LNG flow path 126A may be monitored to assist in controlling the flow rate of any CNG injected thereinto by way of CNG warming line 182A.
The LNG flow path may also include a pressure relief valve 194A so as to maintain the pressure in the LNG flow path 126A at or below a defined pressure level. An exemplary pressure relief valve may include a 1″ pressure relief valve rated for service at approximately 300 psia and at −240° F.
A user interface and display unit 196A may be operatively coupled with the fueling station 102A such that a user may initiate demand of LNG through LNG dispensing nozzle 108A and to monitor the progress of fueling activities. Another user interface and display unit 196B may be associated with the dispensing of fuel from the LNG dispensing nozzle 108B. Similarly, while not specifically shown in
Referring back to LNG flow path 126A, a circulation line 136A may be used to circulate excess LNG back to the tank 104 (see
It is noted that the fueling station may be configured to utilized one of various techniques. For example, when not dispensing LNG fuel to a vehicle's tank, the pump 106 may continue produce a pressurized output and the output may be circulated through the LNG flow paths 126A and 126B such as described above herein. Either or both of the LNG dispensing units 108A and 108B may be coupled with an associated inlet receptacle 200A and 200B to circulate LNG through the associated recirculation lines 198A and 198B and, ultimately, back to the tank 104. Since substantially continuous circulation of LNG through the dispensing units 108A and 108B and associated inlet receptacles 200A and 200B may cause the LNG nozzles 192A and 192B to freeze up after a period of time, control valves 186A and 186B may be used to stop flow through the dispensing units 108A and 108B and circulate the LNG back through circulation lines 136A and 136B respectively.
It is additionally noted that, the fueling station 102A may be configured for passive cooling, meaning that the pump 106 need not be operated to in order to circulate LNG through the LNG flow paths 126A and 126B. For example, the elevation head of the LNG supply (e.g., within the LNG tank 104) may be sufficient to cause LNG to flow through the supply lines 168A-168C and through a bypass associated with each piston 170A-170C of the pump 106. Any LNG flowing through the bypass of the pump 106 would then flow through the LNG paths 126A and 126B and subsequently circulate, for example, through circulation lines 136A and 136B back to the tank. Thus, the present invention may take advantage of the head of the LNG supply to render passive cooling to the various component of the fueling station 102A without the need to expend energy in the operation of the pump 106.
Still referring to
It is noted that the configuration of the fueling station 102A and, more particularly, the LNG flow path, enables LNG to be provided at a vehicle's LNG tank at a relatively high pressure of up to, for example, approximately 300 psia and at a relatively cold temperature of, for example, −240° F. Significantly, this enables the collapsing of an existing vapor head formed within a vehicle's LNG tank rather than requiring the purging of any vapor within the vehicle's LNG tank prior to introducing the LNG therein.
Referring back to the bypass lines 138A and 138B, LNG provided from the storage tank 104 (see
Still referring to
A small amount of LNG, which is supplied through an LNG cooling line 210, may be mixed with CNG leaving the vaporizer 110 to lower the temperature thereof. In one embodiment, for example, as much as four (4) gpm may diverted through the cooling line 210 for mixture with the CNG to control the temperature thereof. Sensors, such as a temperature sensor 212 and/or a pressure transducer 214, may be positioned in the CNG flow path 128 to monitor characteristics of the CNG flowing therethrough and to assist, for example, in controlling the amount of LNG being mixed with the CNG exiting the vaporizer. The amount of LNG being mixed with CNG may be controlled by a control valve 216 such as, for example, a ½″ normally closed control valve rated for service at approximately 5,000 psia.
As noted above, a portion of CNG may similarly be diverted to warm LNG prior to the dispensing thereof. In diverting a portion of CNG, a pilot controlled pressure regulating valve 218 may be used to reduce the pressure of the CNG prior to its mixing with LNG. An exemplary pressure regulating valve 218 may be configured to reduce the pressure of the CNG from approximately 5,000 psia to approximately 300 psia with a flow rate capacity of approximately 800 scfm. After a portion of CNG is directed through the pressure regulating valve 218, the reduced pressure CNG may be split into two warming lines 182A and 182B for warming LNG in LNG flow paths 126A and 126B respectively. Control valves 220A and 220B may be used to distribute and otherwise control the flow of reduced pressure CNG to the warming lines 182A and 182B. Exemplary control valves may include a ¾″ normally closed proportional control valves rated for service at a pressure of approximately 300 psia and at a temperature of −240° F.
Various additives may be also introduced into, and mixed with, the CNG as it flows through the CNG flow path 128. For example, upstream of the branch containing the pressure regulating control valve 218, a source of odorant 222 may be coupled with the CNG flow path 128 to introduce and mix odorant therewith. The odorant may be added to the CNG to assist in the detection of any CNG which may leak from a vehicle's CNG tank, piping, engine or from some other storage vessel.
A source of lubricant 224 may also be coupled with the CNG flow path 128 to introduce and mix lubricant therewith. The lubricant may be added to the CNG for purposes of lubricating various motor vehicle components during processing and combustion of the gas. For example, the lubricant may be added to provide necessary lubrication of an injection device or similar fuel delivery system associated with a motor vehicle consuming and combusting CNG as will be appreciated by those of ordinary skill in the art.
The CNG flow path 128 carries CNG to a CNG dispensing unit 226 which may be coupled to a CNG outlet 112 and is configured for dispensing of the CNG fuel into a vehicle's CNG tank. The CNG dispensing unit 226 may include, for example, a 1000 or 5000 Series Dispenser or a 5000 Series Fleet Dispenser commercially available from ANGI Industrial LLC, of Milton, Wis. Such exemplary CNG dispensing units may include integrated filters, multiple dispensing hoses or nozzles, and have integrated controllers associated therewith. Such dispensers may be configured to accommodate a flow rate substantially equivalent to, or greater than, the output of the vaporizer 110.
As discussed above, while not necessary with the present invention, CNG may also be dispensed to a storage facility 148 (see
A vapor bleed line 228 is coupled to the CNG path 128 and is further coupled with a vapor return line 230. The vapor return line 230 is configured to receive any vapor bled off from the CNG dispensing unit 226, which may include vapor bled off a vehicle's CNG tank and fed back through the CNG dispensing unit. Vapor drawn off from these two lines 228 and 230 may be combined and through a pressure regulator 231 fed to a vapor management system which may include, for example, circulation back into the storage tank 104 (
Further examples of an appropriate vapor management system may include for example, metering the gas back into a residential grid, use of the gas as a fuel for on site heating needs, further compression of the gas for use as vehicle fuel, or simply venting of the gas to the atmosphere as allowed by applicable regulations.
As set forth above, LNG may be circulated back to the storage tank 104 (see
While the example set forth in
Referring first to
Referring to
Referring to
Referring to
Referring now to
With any of the above exemplary embodiments, the flow of the pressurized LNG is multiplexed in the sense that it is capable of being diverted between the vaporizer 110 (and associated CNG flow path 128) and the LNG flow path 126 including the ability to divert substantially all of the pressurized LNG to either destination, as well as the ability to fractionally divide the flow of the pressurized LNG between the two destinations in substantially any desired combination (e.g., 70% vaporizer/30% LNG flow path; 40% vaporizer/60% LNG flow path; etc.).
The configuration of the exemplary fueling station 102A as illustrated in
If the substantially simultaneous dispensing of both CNG and LNG is required, then a portion of the pressurized LNG is diverted through LNG diversion line 208. For example, one or more diverter valves 178A-178C may be closed, or partially closed, to cause pressurized LNG to flow through LNG diversion line 208 rather than to the control valves 180A and 180B and the corresponding LNG flow paths 126A and 126B. The pressurized LNG may then pass through the vaporizer 110 for production of CNG as set forth above herein.
If only CNG is desired, substantially all of the pressurized LNG may be diverted through LNG diversion line 208 by appropriate actuation of diverter valves 178A-178C to produce a greater volume of CNG. It is noted, that the phrase “substantially all” is used above in discussing the flow of pressurized LNG when the dispensing of either only LNG or only CNG is desired. It is to be understood that the use of the term “substantially all” recognizes that a small amount of pressurized LNG may be diverted off for purposes of temperature control. For example, if only the dispensing of LNG is required, a small volume of pressurized LNG may be diverted through the vaporizer 110 to be injected into, and mixed with, the LNG through CNG warming lines 182A and 182B if so required.
The fueling station 102A of the present invention further enables the dispensing of natural gas fuel in a thermally and cost efficient manner. For example, the integrated dispensing of LNG and CNG maintains the LNG in a relatively cold state and helps to avoid cool down runs as required in conventional fueling stations wherein cold LNG must be circulated through the system for a period of time in order to cool down the various components prior to dispensing the fuel into a vehicle's tank. Moreover, such a configuration provides passive cooling with an open supply of LNG through the pump 106 which may be circulated back to the tank 104 (
Additionally, it has been estimated that the production and dispensing of CNG in accordance with the present invention provides as much as 20 to 1 savings as compared to the conventional production, transportation, storage and ultimate dispensing of CNG to motor vehicles for combustion thereby.
While the invention may be susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and have been described in detail herein. However, it should be understood that the invention is not intended to be limited to the particular forms disclosed. Rather, the invention includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the following appended claims.
The present application is a divisional of pending U.S. patent application Ser. No. 10/435,166, filed on May 9, 2003.
This invention was made with United States Government support under Contract No. DE-AC07-99ID13727 and Contract No. DE-AC07-05ID14517, awarded by the United States Department of Energy and pursuant to National Science Foundation Contract No. 9972817. The United States Government has certain rights in the invention.