Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C1/00—Making non-ferrous alloys
  • C22C1/04—Making non-ferrous alloys by powder metallurgy
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
  • B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
  • B22F10/10—Formation of a green body
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
  • B22F10/60—Treatment of workpieces or articles after build-up
  • B22F10/64—Treatment of workpieces or articles after build-up by thermal means
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
  • B22F10/60—Treatment of workpieces or articles after build-up
  • B22F10/66—Treatment of workpieces or articles after build-up by mechanical means
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
  • B22F12/50—Means for feeding of material, e.g. heads
  • B22F12/55—Two or more means for feeding material
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P10/00—Technologies related to metal processing
  • Y02P10/25—Process efficiency

Definitions

• SBIR Small Business Innovation Research
• NSF National Science Foundation
• thermoelectric materials specifically a method to form materials from a raw material in the form of a slurry into a solid.
• Embodiments of this include method of forming thermoelectric materials across a substrate, as part of a process of forming a thermoelectric device.
• thermoelectric cooling and generation require electrically conducting solids of high quality.
• Thermoelectrics require materials with a high z, or thermoelectric figure of merit.
• the thermoelectric figure of merit z is defined as S 2 /p ⁇ where S is the Seebeck coefficient, p is the electrical resistivity and ⁇ is the thermal conductivity.
• thermoelectric (TE) materials should have a degree of crystallinity and low resistance between crystal grains.
• Room temperature TEs are often made using alloys of Bismuth and Tellurium, e.g., the Bi 2 T e 3 family.
• Bi 2 Te S is highly anisotropic, putting a premium on proper crystal orientation in order to achieve high z, and thereby a high performance cooler or generator.
• thermoelectric cooling technique based on transient effects that in one of its embodiments includes a slurry.
• This slurry is thermoelectric in nature, participating actively in the operation of the device in a slurry form.
• This invention does not describe the use of slurry materials as a raw material or as a component in an intermediate step in the formation and organization of conducting materials, such as thermoelectric materials.
• thermoelectric materials by the creation of nanowires. These are aligned wires but are formed by the use of a template material that is filled by vapor deposition and other means.
• This patent covers a variety of material formulations in this template type method of formation, without claim to the construction and organization of solids or composite systems by slurries.
• United States Patent Number 6,692,652 to Takao (2004) describes the creation of perovskite-type alkali-pentavalent metal oxide compounds with a polycrystalline nature. These are organized with crystal planes in parallel from particle constituents. These may be composed of K, Na, L, Nb, Sb, or Ta, with no claim to method of organization. Slurry use is described, but the methods for dispersing across a substrate and annealing in place are not described.
• United States Patent Number 6,806,218 to Itahara (2004) similarly claims slurry based creation methods for thermoelectric materials, but claims materials based on elements including Co Sn Mn. Organization techniques are not presented.
• Embodiments of the present invention are related to forming solids from a slurry containing solid particles, including techniques to densify these materials and form them in ordered arrays of elements, as part of a process of forming a thermoelectric device.
• Embodiments of the present invention include a method and process for creating solid materials from raw materials that are composed of particles.
• thermoelectric materials may be manufactured in ordered arrays of individual solid elements. These elements may be formed in ordered arrays across a substrate, as part of a process for creating a working thermoelectric device.
• these materials may be densified in place, on a substrate. Densification of thermoelectric materials is a key step in the creation of high performance materials for use in thermoelectric devices.
• FIG. 1 shows a schematic cross section view of a thermoelectric device.
• FIG. 2 shows a lower substrate on which a thermoelectric device is to be formed.
• FIG. 3 shows a lower substrate with electrical interconnections formed and patterned.
• FIG. 4 shows a patterned mold layer formed across the substrate and interconnections.
• FIG. 5 shows a p-type thermoelectric slurry being dispensed into mold cavities by a dispensing head.
• FIG. 6 shows a n-type thermoelectric slurry being dispensed into mold cavities by a dispensing head.
• FIG. 7 shows low density thermoelectric materials on a substrate, formed in a mold layer, and covered with a capping layer.
• FIG. 8 shows low density thermoelectric materials that are encapsulated by mechanically compliant materials on a mechanically rigid substrate, placed in a pressure vessel.
• FIG. 9 shows the densified and cured thermoelectric materials on a substrate.
• FIG. 10 shows condensed an annealed n and p-type thermoelectric material in mold cavities on a substrate.
• FIG. 11 shows top electrical interconnections used to create an electrical circuit through the thermoelectric elements.
• FIG. 12 shows an optional top substrate that may be attached using solder or thermally conductive adhesives.
• FIG. 13 illustrates the principle of electrophoretic deposition.
• FIG. 14 illustrates an example of depositing thermoelectric particles in cavities in a mold using electrophoretic or dielectrophoretic deposition.
• FIG. 15 through FIG. 20 illustrate an example of a fabrication sequence involving depositing p-type and n-type thermoelectric particles in cavities in different mold layers using electrophoretic or dielectrophoretic deposition.
• thermoelectric elements 3 : n-type thermoelectric elements
• thermoelectric slurry low potential electrical lead
• mold layer open cavity : dispensing head for p-type thermoelectric slurry : p-type thermoelectric slurry being dispensed : p type thermoelectric slurry filling a cavity : dispensing head for n-type thermoelectric slurry : n-type thermoelectric slurry being dispensed : n-type thermoelectric slurry filling a cavity : condensed and annealed n-type thermoelectric material : condensed and annealed p-type thermoelectric material : solder or thermally conductive adhesive : capping layer : pressure vessel : a liquid or gas : a gas or mechanical ram for applying pressure : pressure applied to the pressure vessel using a high pressure gas or mechanical ram: isostatic, or spatially uniform pressure applied on the outside surface of the material placed in the pressure vessel : low potential electrostatic plate : high potential electrostatic plate : positively charged particles : negatively charged particles : Thermoelectric
• FIG. 1 shows a schematic cross section view of a thermoelectric device according to an embodiment of the present invention.
• a substrate 1 is used on which to build the structure. Electrically conducting materials that serve as electrical interconnections 2 are formed on the substrate 1.
• N-type thermoelectric elements 3 are formed in physical and electrical contact with the lower electrical interconnections 2.
• P-type thermoelectric elements 4 are formed in physical and electrical contact with the lower electrical interconnections 2.
• Electrically conducting materials form upper electrical interconnections 5, in physical and electrical contact with the n-type and p-type thermoelectric elements 3, 4.
• An upper substrate 6 is in physical contact with the upper electrical interconnections 5. This is the typical structure of a thermoelectric device, whether it is a thermoelectric cooler or a thermoelectric generator.
• thermoelectric cooler When operating as a thermoelectric cooler, an electrical interconnection is held at high electrical potential 7 while another is held at low electrical potential 8, allowing electrical current to flow in series up the n-type elements 3 and down the p-type elements 4, passing through the upper and lower electrical interconnections 2, 5.
• thermoelectric device of the type shown in FIG. 1 may proceed according to an inventive method as shown in FIG. 2 through FIG. 12.
• the thermoelectric device may be fabricated on a lower substrate 1 on which.
• the lower substrate is a high thermal conductivity material and is compatible with high volume microelectronic assembly, such as a silicon wafer or a high thermal conductivity PCB board.
• electrically conducting materials may be formed and patterned to form electrical interconnections 2 on the substrate 1.
• the electrically conducting materials may be formed using standard microelectronic manufacturing methods including sputtering, electrode position, and screen printing.
• the electrically conductive materials may be patterned, e.g., using photolithography, shadow masks, or by screen printing.
• the electrically conductive materials preferably have high electrical conductivity, and are compatible with the process by adhering well to the substrate 1 and have limited diffusion into thermoelectric materials. Examples of applicable conductive materials include, but are not limited to, copper, nickel, aluminum, and tungsten.
• a mold layer 10 may be formed across the lower substrate 1 and interconnections 2.
• This mold layer 10 is patterned to create an array of open cavities 11. These cavities 11 are located where thermoelectric elements are to be formed at a later stage of the manufacturing process.
• the mold layer may 10 be formed using standard semiconductor process materials such as spin photo resist, dry-film photo resist, and polyimide.
• the cavities 11 may be formed by mechanical impressions from a negative mold, or by photolithography.
• FIG. 5 shows a p-type thermoelectric slurry 21 being dispensed into mold cavities 11 by a dispensing head 20.
• the thermoelectric slurry is formed by mixing particles of solid thermoelectric material with a carrier fluid.
• This carrier fluid can be one of several liquids, including propylene glycol, ethylene glycol, water, alcohol, etc.
• a dispensing head 20 is positioned over the open cavities 11 in the mold layer 10 where a p-type element is to be formed, and dispenses a precise amount of slurry.
• the dispensing head 20 may be based on technology developed for high throughput dispensing of inks and glues, such as ink jet and pneumatic injection heads.
• the dispensing head 20 may be located precisely and may include multiple heads operating in parallel to increase throughput of slurry deposition across the substrate 1. Open cavities where n-type elements are to be formed are left empty.
• a n-type thermoelectric slurry 31 may be dispensed into remaining open mold cavities 11 by a dispensing head 30.
• the deposition of the n-type slurry 31 fills the open cavities, creating an array of alternating n and p type slurries across the mold layer.
• the dispensing head 30 can be composed of multiple heads in parallel to increase the throughput of slurry deposition across the substrate.
• an array of dispensing heads can be used that is composed of multiple n and p type slurry dispensing heads, allowing both materials to be dispensed across the substrate in a high throughput fashion.
• thermoelectric materials 21, 31, may particles made from thermoelectric materials that are the same or similar to current materials used for operation near room temperature.
• n-type thermoelectric materials include, but are not limited to alloys (also known as solid solutions) of Bismuth (Bi), Tellurium (Te), and sometimes Selenium (Se).
• alloys also known as solid solutions
• Bismuth Bismuth
• Te Tellurium
• Se Selenium
• an alloy of Bi(2)Te(2.7)Se(0.3) where the numbers in parentheses indicate the relative proportions of each element, may be used in an n-type slurry.
• p-type thermoelectric materials include, but are not limited to, are usually alloys of Bi, Antimony (Sb), and Te.
• an alloy of Bi(0.5)Sb(l .5)Te(3) may be used in a p-type slurry.
• the particles in the slurries 21, 31 may be of any suitable size, e.g. from several nanometers in diameter (more than 1 nanometer) to tens of microns (less than 100 microns).
• low density thermoelectric materials 32, 22 formed on the substrate 1 in the mold layer 10 may be covered with a capping layer 60 prior to undergoing a densification and curing process.
• a carrier fluid may first be removed from the slurries that form the low density thermoelectric materials 32, 22, e.g., by the application of heat and/or reducing the ambient pressure, leaving a cluster of low density thermoelectric solids 32, 22.
• the capping layer 60 and the mold layer 10 may be formed using spin coated or dipped materials that are much more mechanically compliant than the rigid substrate 10.
• the capping layer 60 covers the low density thermoelectric materials 32, 22 all across the substrate, encapsulating them.
• the low density thermoelectric materials 32, 22 that have been encapsulated by mechanically compliant materials 10, 60 on the mechanically rigid substrate 1 may be placed in a pressure vessel 70.
• the pressure vessel 70 may be filled with a liquid or a gas 71, and high pressure 73 is applied to the inside of the vessel using a high pressure gas or mechanical ram 72.
• the submerged substrate 1, thermoelectric materials 32, 22, mold layer 10, and capping layer 60 experience a uniform pressure 74 on their outside surfaces. Since the substrate 1 is much more mechanically rigid that the other materials, it deforms very little. However, the compliant mold and capping layers 10, 60 and the low density thermoelectric materials 32, 22 deform.
• This applied pressure compresses the thermoelectric materials 32, 22, and densifies them.
• This process may also include the application of heat to the system, in a process similar to hot isostatic pressing, influencing the thermoelectric properties of the thermoelectric elements.
• FIG. 9 shows the densified and cured thermoelectric materials on a substrate after the removal from the pressure vessel 73. Due to the application of isostatic pressure in the pressure vessel, the thermoelectric materials 40, 41 are highly compressed, and have a smaller volume than before. This process allows these individual elements that are arrayed across the substrate to each be compressed uniformly, creating a high quality, uniform thermoelectric device manufacturing process.
• the mold layer 10 may be removed, and the device may be annealed at high temperature to further enhance the thermoelectric properties of the thermoelectric materials 3, 4.
• the mold layer 10 may be reapplied to facilitate subsequent manufacturing. Specifically, as shown in FIG. 10 the mold layer may be formed around condensed an annealed n and p-type thermoelectric material 40, 41 in mold cavities on the substrate 1.
• FIG. 11 shows top electrical interconnections 5 used to create an electrical circuit through the thermo- electric elements.
• Electrically conducting materials may be formed using standard microelectronic manufacturing methods including sputtering, electrodeposition, and screen printing.
• the conducting materials that form the interconnections 5 may be patterned using photolithography, shadow masks, or by screen printing.
• the conducting materials that make up the interconnections 5 are characterized by high electrical conductivity, and have limited diffusion into the thermoelectric materials. Examples of suitable materials for the top electrical interconnections 5 include copper, nickel, aluminum, and tungsten.
• an optional top substrate 6 may be attached using solder or thermally conductive adhesives 50.
• the top substrate 6 provides a stable surface on which the device to be cooled may be attached, or that may be attached to a heat source (in the case of power generation).
• the mold layer 10 can optionally be removed by chemical wet etching or other means.
• Embodiments of the present invention allow for thermoelectric devices to be formed in a highly manufacturable process, as many elements, and therefore many devices may be processed across a single substrate in parallel.
• Electrical interconnections 2 are formed using wafer scale deposition and patterning techniques, creating uniform and precise structures across a substrate 1 , as shown in Fig. 3.
• microelectronic assembly techniques allow cavities 11 to be formed in a mold layer 10 that are located accurately with respect to the position of the electrical interconnections 2, as seen in Fig. 4. These cavities 11 become the receptacle for the thermoelectric slurries (21, 31) that are injected or dispensed by an automated print head (Figs. 5 and 6).
• thermoelectric material precursors (21, 31) may be delivered in the form of particles dispersed in a carrier fluid.
• thermoelectric materials are critical for a viable product, and a key to embodiments of the invention is the ability to perform a densification and high temperature anneal (or cure) to each individual element in place across the substrate.
• Figs. 7 and 8 illustrate how the carrier fluid can be removed by the application of heat and/or reducing the ambient pressure, and each individual element can be encapsulated in a capping layer 60.
• isostatic pressure By applying isostatic pressure to the entire system, as shown in Fig. 8 the loosely packed thermoelectric precursors 32, 22 are compressed into highly dense solids (3,4 in Fig. 9). This is accomplished by submerging the system in a liquid or gas 71 filled chamber 70 and increasing the pressure 73.
• Isostatic pressure 74 compresses the system on all sides of the system, and since the mold layer 10 and capping layer 60 are mechanically compliant materials, and the substrate 1 is a rigid material, the thermoelectric elements 32, 22 are highly compacted. This pressing may be done at ambient temperature, or at elevated temperature. The thermoelectric properties of the elements 3, 4 are further improved by curing or annealing them at high temperature, as shown in Fig. 9. This process may necessitate removing the mold layer 10, depending on the nature of the mold layer 10 and the annealing conditions.
• Fig. 10 The volume production process continues, as shown in Fig. 10 with the reapplication of a mold layer 10, as needed.
• Upper electrical interconnections 5 are formed using standard microelectronic fabrication and patterning processes, and a top substrate 6 may be attached as the application requires (Fig. 11 and 12). This top substrate is attached by reflowing solders 50 or by the use of high thermal conductivity adhesives 50.
• thermoelectric materials are dispersed in a slurry and deposited on the wafer just where they are needed, there is little raw material waste. This is a significant advantage over alternatives where large thermoelectric crystals are sawed into pieces, creating waste, or where thermoelectric materials are deposited over an entire wafer and then selectively etched. Both of these alternatives are very wasteful processes, and dramatically increase costs.
• isostatic pressure is experienced on all the outer surfaces, allowing each element to experience the same pressure. This allows for a high uniformity in the thermoelectric element formation process, and greatly reduces the potential for the substrate to break or crack.
• thermoelectric device processes can be greatly improved over traditional hand-made thermoelectric device processes.
• electrophoretic or dielectrophoretic methods may be used to deposit these materials.
• Dielectrophoretic and Electrophoretic deposition are related approaches that are used to deposit materials such as paints in a variety of applications and phosphor particles in the manufacture of CRT televisions and other displays. These two techniques may also be applied to the deposition of patterned thin and thick film thermoelectric materials. Electrophoretic deposition describes the movement of charged particles in an applied electric field towards a surface. As the particles impact the surface they form a desired layer or film. As shown in FIG. 13 two plates 75, 76 separated by a gap of width w have an electrical potential V applied between them. The region between the plates may be approximated to have a uniform electric field with a strength of V/w. Particles 77, 78 with both positive and negative charge are shown in the region between the plates.
• Positively charged particles 77 experience an electrophoretic force towards the plate 75 with low electrical potential, and negatively charged particles 78 experience a similar force towards the high potential plate 78.
• a uniform electric field is shown in FIG. 13 for the sake of example, this is not a requirement for the movement of charged particles 77, 78.
• the movement of the particles largely follows the direction of the field lines E, altered by other forces such as gravity, viscous drag, etc.
• particles of thermoelectric material may be negatively charged and dispersed in a fluid between a positively charged substrate 1 part and a negatively charge plate. The thermoelectric particles are drawn to the substrate by the electric field E filling the cavities in the mold.
• Dielectrophoretic deposition describes the movement of uncharged particles in an applied non-uniform electric field. Movement of these uncharged particles requires that the dielectric constant of the particles and the medium in which they reside to be different.
• a particle with no net charge in a nonuniform field undergoes an internal charge separation due to its presence in an electrical field, e.g., the particle has a surplus of positive charges at the side near low electrical potential, and a surplus of negative charges at the side near the high electrical potential. Since the particle is in a nonuniform electric field, either the positive or negatively charged region will be in a region of higher electric field strength. As such, there is a net electrostatic force on the particle that causes the particle to move.
• the net force may cause the particle to move towards the low potential electrode or the high potential electrode, based on the relative polarizability of the particle with respect to the medium. If the particle is more polarizable than the medium, it will experience net force towards the high electrical field region. This is the case, for example, of a metallic particle (high dielectric constant) in a medium such as isopropyl alcohol (moderate dielectric constant). The opposite is true for particles of low polarizability (low dielectric constant), such as plastic in a medium with higher polarizability, such as isopropyl alcohol.
• thermoelectric materials Either electrophoresis or dielectrophoresis may be applied to the deposition of thermoelectric materials into massively parallel arrays.
• An example of deposition of suspended particles into patterned mold materials in order to create solid thermoelectric elements is shown in FIG. 14.
• a substrate 1 is prepared with a mold layer 10, also known as a template.
• the template is made of a material having a low dielectric constant, such as photo resist. Since the dielectric constant is lower than the fluid in which the thermoelectric particles 79 are dispersed, the electric field lines E from a curved electrode 80 preferentially flow into the open cavities 11, to the substrate 1. As such, charged or uncharged thermoelectric particles largely follow these electric field lines into the open cavities 11 in the template 10, by means of electrophoretic or dielectrophoretic deposition.
• Such techniques may be applied to deposition of the n-type and/or p-type slurries in the open cavities 11.
• the open cavities 11 may be formed and filled in two stages by electrophoretic or dielectrophoretic deposition.
• a first mold layer 81 may be formed and a first group of open cavities 82 may be formed in the first mold layer 81 (e.g., by photolithography) over lower electrical connections 2 on a lower substrate 1.
• the open cavities 82 may be filled with one polarity (e.g., p-type) thermoelectric material 83 by electrophoretic or dielectrophoretic deposition, as shown in FIG. 16. Subsequently, the first mold layer 81 may be removed as shown in FIG.
• a second mold layer 84 may be formed and a second group of open cavities 85 may be formed in the second mold layer 84 over the lower electrical connections 2, but in different locations than the thermoelectric material 83 as shown in FIG. 18.
• the second group of open cavities 85 may then be filled with an opposite polarity (e.g., n-type) thermoelectric material 86 by electrophoretic or dielectrophoretic deposition as shown in FIG. 19.
• the second mold layer 84 may then be removed as shown in FIG. 20. Subsequent fabrication may then proceed as described above with respect to FIG. 10 through FIG. 12.
• thermoelectric elements may be formed on a substrate in a massively parallel manner.
• Thermoelectric elements may be formed by the described method from particle raw materials dispersed in a fluid (e.g., a slurry) in a manner resulting in little wasted raw material.
• a fluid e.g., a slurry
• the relative dielectric constants of particles, suspending fluid, and template material allow the flow of particles to be designed such that they deposit to a high degree only in the cavities formed by the template.
• the size and length of the thermoelectric elements can be controlled by the design of the template layer, composition of the thermoelectric slurry, and (for electrophoretic or dielectrophoretic deposition) applied electric field, and the time of deposition.

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• 2008
  • 2008-04-29 EP EP08747119A patent/EP2145348A1/de not_active Withdrawn
  • 2008-04-29 US US12/111,873 patent/US20080274004A1/en not_active Abandoned
  • 2008-04-29 WO PCT/US2008/061912 patent/WO2008137429A1/en active Application Filing

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