US20100139885A1 - Sintered diamond heat exchanger apparatus - Google Patents
Sintered diamond heat exchanger apparatus Download PDFInfo
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- US20100139885A1 US20100139885A1 US12/330,644 US33064408A US2010139885A1 US 20100139885 A1 US20100139885 A1 US 20100139885A1 US 33064408 A US33064408 A US 33064408A US 2010139885 A1 US2010139885 A1 US 2010139885A1
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- sintered diamond
- elements
- tubes
- insulating
- sintered
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/02—Constructions of heat-exchange apparatus characterised by the selection of particular materials of carbon, e.g. graphite
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02G—HOT GAS OR COMBUSTION-PRODUCT POSITIVE-DISPLACEMENT ENGINE PLANTS; USE OF WASTE HEAT OF COMBUSTION ENGINES; NOT OTHERWISE PROVIDED FOR
- F02G1/00—Hot gas positive-displacement engine plants
- F02G1/04—Hot gas positive-displacement engine plants of closed-cycle type
- F02G1/043—Hot gas positive-displacement engine plants of closed-cycle type the engine being operated by expansion and contraction of a mass of working gas which is heated and cooled in one of a plurality of constantly communicating expansible chambers, e.g. Stirling cycle type engines
- F02G1/053—Component parts or details
- F02G1/057—Regenerators
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D17/00—Regenerative heat-exchange apparatus in which a stationary intermediate heat-transfer medium or body is contacted successively by each heat-exchange medium, e.g. using granular particles
- F28D17/02—Regenerative heat-exchange apparatus in which a stationary intermediate heat-transfer medium or body is contacted successively by each heat-exchange medium, e.g. using granular particles using rigid bodies, e.g. of porous material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D7/0008—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits for one medium being in heat conductive contact with the conduits for the other medium
- F28D7/0025—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits for one medium being in heat conductive contact with the conduits for the other medium the conduits for one medium or the conduits for both media being flat tubes or arrays of tubes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D7/16—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D7/16—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation
- F28D7/1615—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation the conduits being inside a casing and extending at an angle to the longitudinal axis of the casing; the conduits crossing the conduit for the other heat exchange medium
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02G—HOT GAS OR COMBUSTION-PRODUCT POSITIVE-DISPLACEMENT ENGINE PLANTS; USE OF WASTE HEAT OF COMBUSTION ENGINES; NOT OTHERWISE PROVIDED FOR
- F02G2257/00—Regenerators
Definitions
- the invention relates to improvements in heat transfer materials. More particularly, this invention relates to the use of sintered diamond material for heat exchangers and regenerators.
- Heat exchangers are used in many applications including heating units, cooling units, engines and many other applications.
- heat exchangers are used in Stirling engines such as those found in, by way of example only, U.S. Pat. No. 7,076,941
- Such Stirling engines also use regenerators which are specialized heat exchangers.
- heat transferring materials in their heat exchangers and regenerators such as aluminum, copper, brass, or stainless steel. While these heat exchanges are adequate for some uses, an improved heat exchanger is needed which has a higher thermal conductivity. Higher thermal conductivity results in more efficient heat transfer and reduced energy loss.
- heat transferring materials are needed with a high thermal diffusivity for the efficient transfer of heat energy.
- the present invention relates to the use of heat exchanging material constructed of sintered natural or synthetic diamond powder or particles.
- Synthetic diamonds have been manufactured for over half a century. In one manufacturing process, a natural diamond sliver is placed in a chamber under 58,000 atmospheres of pressure at 1500 degrees Celsius. The sliver of natural diamond is bathed in a molten solution of graphite and a catalyst. Carbon precipitates onto the diamond sliver. Using this process, a three carrot diamond can be grown in just a few days. Through this and other methods, over 100 tons of synthetic diamonds are manufactured each year. These synthetic diamonds are used for various industrial and commercial applications. For example, synthetic diamonds are used in drill bits, cutting blades and grinding wheels.
- Diamond particles such as natural or synthetic diamond dust are a byproduct of some of these applications and the diamond dust is readily available in many different sizes. This dust could be a byproduct of processes using natural or synthetic diamonds.
- the sintered diamond dust can be made of particles of various sizes from extremely fine powder to more coarse particles.
- the diamond dust can be found from commercially available sources in particle sizes ranging from 0.025 microns to 100 microns.
- diamond dust can be purchased in these size ranges from Advanced Abrasives Corporation of Pennsauken, N.J.
- the cost of diamond dust generally depends on the size of the diamond particles, and the finer the powder, the less expensive it is. Thus, fine powder can be used to form many desired shapes and configurations.
- Diamonds have one of the highest coefficients of thermal conductivity of any material.
- Sintered diamonds have a coefficient of thermal conductivity of nearly 8 watts/cm° C., making it an ideal heat exchanging medium.
- the use of irregularly shaped particles increases the surface area of the formed or finished sintered diamond heat exchanging material.
- the process of sintering diamond involves placing the fine powder or particles in a mold. The mold is then placed in an ultra high temperature press and heated to a temperature in the range of 2000 degrees Fahrenheit under a pressure in the range of hundreds of pound per square inch. At this temperature and pressure, the diamond powder is fused together. It is within the scope of the present invention to mix the diamond powder with other materials such as boron carbide, silicon carbide or other materials before sintering.
- sintered diamond can refer to pure sintered diamond, or sintered diamond which also includes other materials mixed with the diamond powder. The diamond could be natural or synthetic.
- the sintered diamond material can be formed into many desired shapes including tubes, screens, mesh, disks, granules, or other possible shapes. Where necessary, passages can be formed in the finished sintered diamond heat exchanging materials to allow fluid to flow through. For example, if the sintered diamond is formed into a disk, fluid passages can be formed directly in the disk.
- the sintered diamond can be formed into various shapes depending on the required application.
- the sintered diamond can be adapted to be used with a regenerator of a Stirling engine.
- a regenerator is a temporary repository of heat during certain cycles of the Stirling engine. Heated fluid flows through in one direction, and heat is transferred to the regenerator material. Relatively colder fluid flows through the regenerator in the other direction and picks up the heat energy left behind when the heated fluid flowed through.
- the diamond material can be formed into circular disks resembling mesh material. It will be understood by those of ordinary skill in the art that the disks need not be circular, but can take many different shapes.
- the material could be made into thin disks which resemble wire mesh heat exchanging material. In this case, the mesh-like disks would be separated by thin insulating layers (with holes for fluid flow) that would keep heat from being conducted from one end of the regenerator to the other. In one example embodiment, the disks would be on the order of 1 ⁇ 8 inch thick.
- the sintered diamond material can be formed into small, irregular pieces of sintered diamond material. These irregular pieces can be packed into a space between insulating disks, and the fluid flow would be between and around these pieces.
- the diamond particles When used for a heat exchanger, the diamond particles can be formed into shapes having two flow passages therethrough.
- the use of two sets of passages is well known in heat exchangers. As fluid flows through one set of passages, heat is transferred to the heat exchanger material. The heat is then transferred to the fluid flowing through the other set of passages. The two sets of passages are isolated from one another so that the two streams of fluid do not mix with one another.
- a regenerator in one example embodiment, includes a housing.
- the housing includes a plurality of sintered diamond elements having a fluid passage therethrough.
- a plurality of insulating elements are spaced between the sintered diamond elements and also have a fluid passage therethrough.
- the fluid passages of the insulating elements are in fluid communication with the fluid passages of the sintered diamond elements.
- the sintered diamond elements can comprise irregularly shaped diamond dust particles sintered together such that the sintered diamond elements are porous.
- the sintered diamond elements can include a plurality of disks placed adjacent one another between the insulating elements.
- the sintered diamond elements can be made from diamond particles of between 0.001 and 500 microns, for example.
- the sintered diamond elements are made by placing the particles in a mold and subjecting the particles to high temperature and pressure as is known in the diamond sintering art.
- each of the sintered diamond elements and each of the insulating elements have an opening therethrough, for example through the center of the sintered diamond elements and the insulating elements. Insulating material can be placed within each of the openings of the sintered diamond elements and each of the insulating elements.
- a heat exchanger in another example embodiment of the invention, includes a housing containing a plurality of sintered diamond elements.
- the plurality of sintered diamond elements have first and second fluid passages associated therewith which are isolated from one another.
- the sintered diamond elements could be, for example mesh constructed of sintered diamonds. Alternatively, or in addition, the sintered diamond elements could be made as disks of sintered diamonds having passages therethrough.
- the sintered diamond elements include a plurality of tubes of sintered diamond. One fluid flow is through the tubes and a second fluid flow is between the plurality of tubes.
- the sintered diamond elements include a first plurality of tubes and a second plurality of tubes. The first plurality of tubes forms a first fluid passage and the second plurality of tubes forms a second fluid passage.
- FIG. 1 is an exploded perspective view of one embodiment of the present invention
- FIG. 2 is another exploded perspective view of the invention of FIG. 1 ;
- FIG. 3 is a perspective view of another embodiment of the present invention.
- FIG. 4 is a front elevation view of the invention of FIG. 3 ;
- FIG. 5 is a perspective view of another embodiment of the present invention.
- FIG. 6 is an end view of another embodiment of the present invention.
- FIG. 7 is a front elevation view of the invention of FIG. 6 ;
- FIG. 8 is a cross-sectional view of another embodiment of the present invention.
- FIG. 9 is a cross-sectional view of another embodiment of the present invention.
- FIG. 10 is a cross-sectional view of another embodiment of the present invention.
- FIG. 11 is an end view of the invention of FIG. 10 ;
- FIG. 12 is an end view of another embodiment of the present invention.
- FIG. 13 is a cross-sectional view of the invention of FIG. 12 ;
- FIG. 14 is an end view of another embodiment of the present invention.
- FIG. 15 is a cross-sectional view of the invention of FIG. 14 ;
- FIG. 16 is a simplified representation of a sintered diamond molding apparatus
- FIG. 17 is a simplified representation of a sintered diamond top mold
- FIG. 18 is a simplified representation of a sintered diamond bottom mold
- FIG. 19 is a simplified representation of another sintered diamond top mold
- FIG. 20 is a simplified representation of another sintered diamond bottom mold
- FIG. 21 is a simplified representation of a side cross-sectional view of sintered diamond top and bottom molds shown separated from one another;
- FIG. 22 is a simplified representation of a side cross-sectional view of sintered diamond top and bottom molds shown together;
- FIG. 23 is a simplified representation of a side cross-sectional view of sintered diamond tubes after molding has taken place.
- FIG. 24 is a simplified representation of the process of molding sintered diamond.
- FIGS. 1 through 11 illustrate various embodiments of the present invention.
- the heat exchanger 10 includes a housing 12 .
- the housing 12 is shown as cubic in configuration for illustration purposes only. It will be understood by those skilled in the art that the housing 12 can be made in many possible shapes.
- the housing 12 has walls 14 , 16 , 18 and 20 , shown again in the particular configuration for illustration purposes.
- Sintered diamond tubes 22 are placed within the housing 12 . The length and diameter of sintered diamond tubes 22 are a matter of design choice, depending on the heat transfer and flow and pressure and temperature requirements for a particular application.
- the tubes 22 are held in position by faceplates 24 and 26 which have holes 28 through which the tubes 22 extend. Fluid (not shown) can flow through the tubes 22 in the direction of arrow 30 . Walls 14 and 18 have fluid holes 32 and 34 respectively. Fluid can flow into and out of holes 32 and 34 in the direction of arrow 36 . As fluid flows through tubes 22 , heat is transferred to or from the tubes 22 . A second isolated fluid flow through holes 32 and 34 travels around and between tubes 22 . This fluid flow either picks up or delivers heat to the tubes 22 depending on the relative temperatures of the fluid flowing within and around the tubes 22 . Because the tubes 22 are made of sintered diamond, a highly efficient heat exchanger is created.
- FIGS. 3 and 4 show another example embodiment of a heat exchanger 50 .
- a housing 52 is shown as cubic in configuration for illustration purposes only.
- the housing 52 can be made in many possible shapes.
- the housing 52 has walls 54 , 56 , 58 , and 60 , again shown in the particular configuration for illustration purposes.
- Sintered diamond tubes 62 are placed within the housing 52 .
- the length and diameter of sintered diamond tubes 62 are a matter of design choice, depending on the heat transfer requirements for a particular application.
- the tubes 62 are held in position by walls 56 and 60 which have holes 68 through which the tubes 62 extend.
- Fluid (not shown) can flow through the tubes 62 in the direction of arrow 70 .
- Ends 74 and 78 have fluid holes 82 and 84 respectively.
- Fluid can flow into and out of holes 82 and 84 .
- heat is transferred to or from the tubes 62 .
- a second isolated fluid flow through holes 82 and 84 travels around and between tubes 62 . This fluid flow either picks up or delivers heat to the tubes 62 depending on the relative temperatures of the fluid flowing through and around the tubes 62 .
- FIG. 5 shows another example embodiment of a heat exchanger 150 .
- a housing 152 is shown as cubic in configuration for illustration purposes only. It will be understood by those of skill in the art that the housing 152 can be made in many possible shapes.
- the housing 152 has walls 154 , 156 , 158 and 160 , shown again in the particular configuration for illustration purposes.
- Sintered diamond tubes 162 and 163 are placed within the housing 152 . The length and diameter of sintered diamond tubes 162 and 163 are a matter of design choice.
- the tubes 162 are held in position by walls 156 and 160 which have bores 168 through which the tubes 162 extend.
- tubes 163 extend through ends 174 and 178 which have bores 169 therethrough.
- Fluid (not shown) can flow through the tubes 162 in the direction of arrow 170 .
- a second, isolated flow of fluid flows through tubes 163 in the direction of arrow 171 . If the fluid flowing through tubes 162 has a higher temperature than the fluid flowing through tubes 163 , heat is transferred to the fluid flowing through tubes 163 . If the fluid flowing through tubes 163 has a higher temperature than the fluid flowing through the tubes 162 , heat is transferred to the fluid flowing through tubes 162 . Because the tubes 162 and 163 and the housing are made of sintered diamond, the heat is transferred very efficiently.
- FIGS. 6 and 7 illustrate a regenerator 210 in accordance with an example embodiment of the present invention. It will be understood by those of skill in the art that the particular configuration of the regenerator 210 is shown for illustration purposes only and that various other configurations of the regenerator are possible.
- An outer housing 212 is provided with flanges 214 and 216 . Depending on the particular application, the housing could be made from metal, such as, for example, aluminum, brass, or steel.
- the flanges 214 and 216 include bolt holes 218 for attaching the regenerator 210 to other parts of a system.
- the regenerator 210 includes an insulating layer 220 made of any suitable insulating material.
- a sintered diamond heat exchanging medium 230 is provided.
- the sintered diamond heat exchanging medium 230 is shown as a series of rings 232 .
- the rings 232 are separated by insulating material 234 to prevent heat transfer in the direction of fluid flow illustrated by line 240 . Because the sintered diamond heat exchanging medium 230 has such a high coefficient of thermal conductivity, heat would rapidly spread from one end 242 of the regenerator 210 to the opposite end 244 without insulating material 234 .
- the sintered diamond heat exchanging medium 230 and the insulating material 234 are porous such that fluid (not shown) can flow in the direction of line 240 .
- a regenerator works by heated fluid flowing in one direction, for example direction 240 A. The heated fluid flows through the sintered diamond heat exchanging medium 230 and transfers its heat to the sintered diamond heat exchanging medium 230 .
- relatively cooler fluid flows in the direction 240 B.
- the relatively hotter sintered diamond heat exchanging medium transfers heat to the cooler fluid flowing in direction 240 B.
- an insulating core 250 is provided such that the diameter of the regenerator matches other components in the system without providing excess regeneration capacity.
- FIG. 8 illustrates another embodiment of a regenerator 310 using sintered diamond heat exchanging medium 330 .
- An outer housing 312 is provided with flanges 314 and 316 . Again, depending on the particular application, the housing could be made from, for example, metal, such as aluminum, brass, or steel.
- the regenerator 310 includes an insulating layer 320 made of any suitable insulating material. The choice of insulating material will depend on the application in which the regenerator 310 is used and could include a polymer or ceramic material for example.
- a sintered diamond heat exchanging medium 330 is provided.
- the sintered diamond heat exchanging medium 330 is shown as a quantity of granules 332 packed between insulating material 334 to prevent heat transfer in the direction of fluid flow illustrated by line 340 .
- the granules 332 are sized such that spaces 336 are present between granules 332 .
- the spaces 336 allow for fluid to flow between and around the granules 332 .
- the insulating material 334 is porous to allow fluid to flow through the insulating material 334 .
- An insulating core 350 is provided for use in some applications.
- FIG. 9 illustrates another embodiment of a regenerator 410 in accordance with an example embodiment of the present invention.
- An outer housing 412 is provided with flanges 414 and 416 .
- the regenerator 410 includes an insulating layer 420 made of any suitable insulating material.
- a sintered diamond heat exchanging medium 430 is provided.
- the sintered diamond heat exchanging medium 430 is shown as multilayered sintered diamond mesh 432 .
- the mesh 432 is separated by insulating material 434 to prevent heat transfer in the direction of fluid flow illustrated by line 440 . Because the sintered diamond heat exchanging medium 430 has such a high coefficient of thermal conductivity, heat would rapidly spread from one end 442 of the regenerator 410 to the opposite end 444 without insulating material 434 .
- An insulating core 450 is provided to adjust the capacity of the regenerator 410 .
- FIGS. 10 and 11 illustrate another embodiment of a regenerator 510 in accordance with an example embodiment of the present invention.
- An outer housing 512 is provided with flanges 514 and 516 .
- the regenerator 510 includes an insulating layer 520 made of any suitable insulating material.
- a sintered diamond heat exchanging medium 530 is provided.
- the sintered diamond heat exchanging medium 530 is shown as sintered diamond wire-like mesh 532 .
- the wire-like mesh 532 is separated by insulating material 534 to prevent heat transfer in the direction of fluid flow illustrated by line 540 .
- An insulating core 550 is provided if needed for the particular application.
- FIGS. 12 and 13 illustrate another embodiment of a regenerator 610 in accordance with an example embodiment of the present invention.
- An outer housing 612 is provided to house the internal components of the regenerator 610 .
- the regenerator 610 includes a sintered diamond heat exchanging medium 630 .
- the sintered diamond heat exchanging medium 630 is shown as sintered diamond tubes 632 .
- Sections of tubes 632 can be separated by insulating material (not shown) such as fiberglass insulation material, or other insulating material, to prevent heat transfer in the direction of fluid flow illustrated by line 640 . Fluid flows through the tubes 632 and through the insulating material from one end of the regenerator 610 to the other, as will be readily appreciated by one of ordinary skill in the art.
- FIGS. 14 and 15 illustrate another embodiment of a regenerator 710 in accordance with an example embodiment of the present invention.
- An outer housing 712 is provided to house the internal components of the regenerator 710 .
- the regenerator 710 includes a sintered diamond heat exchanging medium 730 .
- the sintered diamond heat exchanging medium 730 is shown as a sintered diamond spiral 732 .
- Sections of the spiral 732 can be separated by insulating material (not shown) such as fiberglass insulation material, or other insulating material, to prevent heat transfer in the direction of fluid flow illustrated by line 740 . Fluid flows through the sections of the spiral 732 and through the insulating material from one end of the regenerator 710 to the other, as will also be readily appreciated by those of skill in the art.
- FIG. 16 is a simplified representation of a sintered diamond molding apparatus 810 .
- the molding apparatus 810 includes a top mold 812 mounted to a plate 813 and a bottom mold 814 mounted to a plate 815 , which is in turn mounted to a base 824 .
- the apparatus includes a means 820 for pressing the top mold 812 and the bottom mold 814 together, shown for representation purposes only as actuated by a handle 816 .
- a heat source 818 is also provided for the sintering process.
- the temperatures required for the process will necessitate a much more complex heating system than the one illustrated.
- the diamond material (not shown) is placed in the bottom mold 814 , and the top mold 812 and the bottom mold 814 are brought together under pressure.
- the top mold 812 and bottom mold 814 are heated by the heat source 818 to sinter the diamond material.
- FIGS. 17 and 18 illustrate the top mold 812 and the bottom mold 814 .
- the top mold 812 has pins 830 .
- the bottom mold has cylindrical cavities 832 . The difference between the outside diameter of the pins and the inside diameter of the cavities determines the wall thickness of the sintered diamond tubes created by the molds 812 and 814 .
- FIGS. 19 and 20 illustrate another embodiment of a top mold 912 and a bottom mold 914 .
- the top mold 912 has pins 930 .
- the bottom mold has cavities 932 in the shape of wire mesh. The difference between the size of the pins 930 and the size of the cavities 932 determines the wire size of the sintered diamond mesh created by the molds 912 and 914 .
- FIGS. 21 through 23 illustrate a schematic representation of a cross-section of molds 812 and 814 of the present invention.
- the top mold 812 has pins 830 .
- the bottom mold 814 has cylindrical cavities 832 .
- the pins 830 are sized to fit within the cavities 832 such that tubes 834 are created after the sintering process.
- FIG. 21 illustrates the top mold 812 separated from the bottom mold 814 .
- FIG. 22 illustrates the top mold 812 nested inside the bottom mold 814 .
- FIG. 23 illustrates the bottom mold 814 with the top mold 812 removed and the tubes 834 formed in the cavities 832 .
- FIG. 24 represents a schematic of the molding process.
- Sintered diamond dust 870 and optionally a binding agent 872 are mixed using a mixing process represented by cylinder 874 .
- the blended material 876 is injected into a bottom mold 878 through an injection molding apparatus 880 .
- the top mold 882 is forced down into the bottom mold 878 and the blended material 876 is heated while the pressure is applied. This sintering process is well known in the art.
Abstract
A heat exchanging medium is provided which is constructed out of sintered diamond. The medium can be formed into various desired shapes such as tubes, mesh, screens, granules or the like. The sintered diamond forms the heat transfer medium of a heat exchanger or regenerator.
Description
- The invention relates to improvements in heat transfer materials. More particularly, this invention relates to the use of sintered diamond material for heat exchangers and regenerators.
- Heat exchangers are used in many applications including heating units, cooling units, engines and many other applications. For example, heat exchangers are used in Stirling engines such as those found in, by way of example only, U.S. Pat. No. 7,076,941, Such Stirling engines also use regenerators which are specialized heat exchangers. Typically, such engines use heat transferring materials in their heat exchangers and regenerators such as aluminum, copper, brass, or stainless steel. While these heat exchanges are adequate for some uses, an improved heat exchanger is needed which has a higher thermal conductivity. Higher thermal conductivity results in more efficient heat transfer and reduced energy loss. In addition, heat transferring materials are needed with a high thermal diffusivity for the efficient transfer of heat energy.
- There remains a need for improved heat exchangers and regenerators which have higher thermal conductivity than heat exchangers and regenerators of the past.
- The present invention relates to the use of heat exchanging material constructed of sintered natural or synthetic diamond powder or particles. Synthetic diamonds have been manufactured for over half a century. In one manufacturing process, a natural diamond sliver is placed in a chamber under 58,000 atmospheres of pressure at 1500 degrees Celsius. The sliver of natural diamond is bathed in a molten solution of graphite and a catalyst. Carbon precipitates onto the diamond sliver. Using this process, a three carrot diamond can be grown in just a few days. Through this and other methods, over 100 tons of synthetic diamonds are manufactured each year. These synthetic diamonds are used for various industrial and commercial applications. For example, synthetic diamonds are used in drill bits, cutting blades and grinding wheels.
- Diamond particles such as natural or synthetic diamond dust are a byproduct of some of these applications and the diamond dust is readily available in many different sizes. This dust could be a byproduct of processes using natural or synthetic diamonds. The sintered diamond dust can be made of particles of various sizes from extremely fine powder to more coarse particles. For example the diamond dust can be found from commercially available sources in particle sizes ranging from 0.025 microns to 100 microns. For example, diamond dust can be purchased in these size ranges from Advanced Abrasives Corporation of Pennsauken, N.J. The cost of diamond dust generally depends on the size of the diamond particles, and the finer the powder, the less expensive it is. Thus, fine powder can be used to form many desired shapes and configurations.
- Diamonds have one of the highest coefficients of thermal conductivity of any material. Sintered diamonds have a coefficient of thermal conductivity of nearly 8 watts/cm° C., making it an ideal heat exchanging medium. The use of irregularly shaped particles increases the surface area of the formed or finished sintered diamond heat exchanging material. The process of sintering diamond involves placing the fine powder or particles in a mold. The mold is then placed in an ultra high temperature press and heated to a temperature in the range of 2000 degrees Fahrenheit under a pressure in the range of hundreds of pound per square inch. At this temperature and pressure, the diamond powder is fused together. It is within the scope of the present invention to mix the diamond powder with other materials such as boron carbide, silicon carbide or other materials before sintering. As used herein, sintered diamond can refer to pure sintered diamond, or sintered diamond which also includes other materials mixed with the diamond powder. The diamond could be natural or synthetic.
- The sintered diamond material can be formed into many desired shapes including tubes, screens, mesh, disks, granules, or other possible shapes. Where necessary, passages can be formed in the finished sintered diamond heat exchanging materials to allow fluid to flow through. For example, if the sintered diamond is formed into a disk, fluid passages can be formed directly in the disk. The sintered diamond can be formed into various shapes depending on the required application. For example, the sintered diamond can be adapted to be used with a regenerator of a Stirling engine. A regenerator is a temporary repository of heat during certain cycles of the Stirling engine. Heated fluid flows through in one direction, and heat is transferred to the regenerator material. Relatively colder fluid flows through the regenerator in the other direction and picks up the heat energy left behind when the heated fluid flowed through.
- In one example embodiment of the present invention, the diamond material can be formed into circular disks resembling mesh material. It will be understood by those of ordinary skill in the art that the disks need not be circular, but can take many different shapes. The material could be made into thin disks which resemble wire mesh heat exchanging material. In this case, the mesh-like disks would be separated by thin insulating layers (with holes for fluid flow) that would keep heat from being conducted from one end of the regenerator to the other. In one example embodiment, the disks would be on the order of ⅛ inch thick.
- In another embodiment, the sintered diamond material can be formed into small, irregular pieces of sintered diamond material. These irregular pieces can be packed into a space between insulating disks, and the fluid flow would be between and around these pieces.
- When used for a heat exchanger, the diamond particles can be formed into shapes having two flow passages therethrough. The use of two sets of passages is well known in heat exchangers. As fluid flows through one set of passages, heat is transferred to the heat exchanger material. The heat is then transferred to the fluid flowing through the other set of passages. The two sets of passages are isolated from one another so that the two streams of fluid do not mix with one another.
- In one example embodiment, a regenerator includes a housing. The housing includes a plurality of sintered diamond elements having a fluid passage therethrough. A plurality of insulating elements are spaced between the sintered diamond elements and also have a fluid passage therethrough. The fluid passages of the insulating elements are in fluid communication with the fluid passages of the sintered diamond elements. The sintered diamond elements can comprise irregularly shaped diamond dust particles sintered together such that the sintered diamond elements are porous. Alternatively, or in addition, the sintered diamond elements can include a plurality of disks placed adjacent one another between the insulating elements. The sintered diamond elements can be made from diamond particles of between 0.001 and 500 microns, for example. In one example embodiment, the sintered diamond elements are made by placing the particles in a mold and subjecting the particles to high temperature and pressure as is known in the diamond sintering art.
- In some example embodiments, each of the sintered diamond elements and each of the insulating elements have an opening therethrough, for example through the center of the sintered diamond elements and the insulating elements. Insulating material can be placed within each of the openings of the sintered diamond elements and each of the insulating elements.
- In another example embodiment of the invention, a heat exchanger includes a housing containing a plurality of sintered diamond elements. The plurality of sintered diamond elements have first and second fluid passages associated therewith which are isolated from one another. The sintered diamond elements could be, for example mesh constructed of sintered diamonds. Alternatively, or in addition, the sintered diamond elements could be made as disks of sintered diamonds having passages therethrough.
- In another embodiment, the sintered diamond elements include a plurality of tubes of sintered diamond. One fluid flow is through the tubes and a second fluid flow is between the plurality of tubes. In another example embodiment, the sintered diamond elements include a first plurality of tubes and a second plurality of tubes. The first plurality of tubes forms a first fluid passage and the second plurality of tubes forms a second fluid passage.
- Embodiments and applications of the invention are illustrated by the attached non-limiting drawings. The attached drawings are for purposes of illustrating the concepts of the invention and may not be to scale.
-
FIG. 1 is an exploded perspective view of one embodiment of the present invention; -
FIG. 2 is another exploded perspective view of the invention ofFIG. 1 ; -
FIG. 3 is a perspective view of another embodiment of the present invention; -
FIG. 4 is a front elevation view of the invention ofFIG. 3 ; -
FIG. 5 is a perspective view of another embodiment of the present invention; -
FIG. 6 is an end view of another embodiment of the present invention; -
FIG. 7 is a front elevation view of the invention ofFIG. 6 ; -
FIG. 8 is a cross-sectional view of another embodiment of the present invention; -
FIG. 9 is a cross-sectional view of another embodiment of the present invention; -
FIG. 10 is a cross-sectional view of another embodiment of the present invention; -
FIG. 11 is an end view of the invention ofFIG. 10 ; -
FIG. 12 is an end view of another embodiment of the present invention; -
FIG. 13 is a cross-sectional view of the invention ofFIG. 12 ; -
FIG. 14 is an end view of another embodiment of the present invention; -
FIG. 15 is a cross-sectional view of the invention ofFIG. 14 ; -
FIG. 16 is a simplified representation of a sintered diamond molding apparatus; -
FIG. 17 is a simplified representation of a sintered diamond top mold; -
FIG. 18 is a simplified representation of a sintered diamond bottom mold; -
FIG. 19 is a simplified representation of another sintered diamond top mold; -
FIG. 20 is a simplified representation of another sintered diamond bottom mold; -
FIG. 21 is a simplified representation of a side cross-sectional view of sintered diamond top and bottom molds shown separated from one another; -
FIG. 22 is a simplified representation of a side cross-sectional view of sintered diamond top and bottom molds shown together; -
FIG. 23 is a simplified representation of a side cross-sectional view of sintered diamond tubes after molding has taken place; and -
FIG. 24 is a simplified representation of the process of molding sintered diamond. - Throughout the following description specific details are presented to provide a more thorough understanding to persons skilled in the art. However, well-known elements may not have been shown or described in detail to avoid unnecessarily obscuring the disclosure. Accordingly, the description and drawings are to be regarded in an illustrative, rather than a restrictive, sense.
-
FIGS. 1 through 11 illustrate various embodiments of the present invention. Referring toFIGS. 1 and 2 , an exploded view of aheat exchanger 10 illustrating one embodiment of the present invention is shown. Theheat exchanger 10 includes ahousing 12. Thehousing 12 is shown as cubic in configuration for illustration purposes only. It will be understood by those skilled in the art that thehousing 12 can be made in many possible shapes. Thehousing 12 haswalls Sintered diamond tubes 22 are placed within thehousing 12. The length and diameter ofsintered diamond tubes 22 are a matter of design choice, depending on the heat transfer and flow and pressure and temperature requirements for a particular application. Thetubes 22 are held in position byfaceplates holes 28 through which thetubes 22 extend. Fluid (not shown) can flow through thetubes 22 in the direction ofarrow 30.Walls fluid holes holes arrow 36. As fluid flows throughtubes 22, heat is transferred to or from thetubes 22. A second isolated fluid flow throughholes tubes 22. This fluid flow either picks up or delivers heat to thetubes 22 depending on the relative temperatures of the fluid flowing within and around thetubes 22. Because thetubes 22 are made of sintered diamond, a highly efficient heat exchanger is created. -
FIGS. 3 and 4 show another example embodiment of aheat exchanger 50. Ahousing 52 is shown as cubic in configuration for illustration purposes only. Thehousing 52 can be made in many possible shapes. Thehousing 52 haswalls Sintered diamond tubes 62 are placed within thehousing 52. The length and diameter ofsintered diamond tubes 62 are a matter of design choice, depending on the heat transfer requirements for a particular application. Thetubes 62 are held in position bywalls holes 68 through which thetubes 62 extend. Fluid (not shown) can flow through thetubes 62 in the direction ofarrow 70. Ends 74 and 78 havefluid holes holes tubes 62, heat is transferred to or from thetubes 62. A second isolated fluid flow throughholes tubes 62. This fluid flow either picks up or delivers heat to thetubes 62 depending on the relative temperatures of the fluid flowing through and around thetubes 62. -
FIG. 5 shows another example embodiment of aheat exchanger 150. Ahousing 152 is shown as cubic in configuration for illustration purposes only. It will be understood by those of skill in the art that thehousing 152 can be made in many possible shapes. Thehousing 152 haswalls Sintered diamond tubes housing 152. The length and diameter ofsintered diamond tubes tubes 162 are held in position bywalls tubes 162 extend. Similarly,tubes 163 extend throughends bores 169 therethrough. Fluid (not shown) can flow through thetubes 162 in the direction ofarrow 170. A second, isolated flow of fluid flows throughtubes 163 in the direction ofarrow 171. If the fluid flowing throughtubes 162 has a higher temperature than the fluid flowing throughtubes 163, heat is transferred to the fluid flowing throughtubes 163. If the fluid flowing throughtubes 163 has a higher temperature than the fluid flowing through thetubes 162, heat is transferred to the fluid flowing throughtubes 162. Because thetubes -
FIGS. 6 and 7 illustrate aregenerator 210 in accordance with an example embodiment of the present invention. It will be understood by those of skill in the art that the particular configuration of theregenerator 210 is shown for illustration purposes only and that various other configurations of the regenerator are possible. Anouter housing 212 is provided withflanges flanges regenerator 210 to other parts of a system. Theregenerator 210 includes an insulatinglayer 220 made of any suitable insulating material. The choice of insulating material will depend on the application in which theregenerator 210 is used and could include a polymer or ceramic material for example. A sintered diamondheat exchanging medium 230 is provided. In this illustrated embodiment, the sintered diamondheat exchanging medium 230 is shown as a series ofrings 232. Therings 232 are separated by insulatingmaterial 234 to prevent heat transfer in the direction of fluid flow illustrated byline 240. Because the sintered diamondheat exchanging medium 230 has such a high coefficient of thermal conductivity, heat would rapidly spread from oneend 242 of theregenerator 210 to theopposite end 244 without insulatingmaterial 234. The sintered diamondheat exchanging medium 230 and the insulatingmaterial 234 are porous such that fluid (not shown) can flow in the direction ofline 240. As is known to those of skill in the art, a regenerator works by heated fluid flowing in one direction, forexample direction 240A. The heated fluid flows through the sintered diamondheat exchanging medium 230 and transfers its heat to the sintered diamondheat exchanging medium 230. In another cycle, relatively cooler fluid flows in thedirection 240B. The relatively hotter sintered diamond heat exchanging medium transfers heat to the cooler fluid flowing indirection 240B. In some applications, an insulatingcore 250 is provided such that the diameter of the regenerator matches other components in the system without providing excess regeneration capacity. -
FIG. 8 illustrates another embodiment of aregenerator 310 using sintered diamondheat exchanging medium 330. Anouter housing 312 is provided withflanges regenerator 310 includes an insulatinglayer 320 made of any suitable insulating material. The choice of insulating material will depend on the application in which theregenerator 310 is used and could include a polymer or ceramic material for example. A sintered diamondheat exchanging medium 330 is provided. In this illustrated embodiment, the sintered diamondheat exchanging medium 330 is shown as a quantity ofgranules 332 packed between insulatingmaterial 334 to prevent heat transfer in the direction of fluid flow illustrated byline 340. Thegranules 332 are sized such thatspaces 336 are present betweengranules 332. Thespaces 336 allow for fluid to flow between and around thegranules 332. The insulatingmaterial 334 is porous to allow fluid to flow through the insulatingmaterial 334. An insulatingcore 350 is provided for use in some applications. -
FIG. 9 illustrates another embodiment of aregenerator 410 in accordance with an example embodiment of the present invention. Anouter housing 412 is provided withflanges 414 and 416. Theregenerator 410 includes an insulatinglayer 420 made of any suitable insulating material. A sintered diamondheat exchanging medium 430 is provided. In this illustrated embodiment, the sintered diamondheat exchanging medium 430 is shown as multilayeredsintered diamond mesh 432. Themesh 432 is separated by insulatingmaterial 434 to prevent heat transfer in the direction of fluid flow illustrated byline 440. Because the sintered diamondheat exchanging medium 430 has such a high coefficient of thermal conductivity, heat would rapidly spread from oneend 442 of theregenerator 410 to theopposite end 444 without insulatingmaterial 434. An insulatingcore 450 is provided to adjust the capacity of theregenerator 410. -
FIGS. 10 and 11 illustrate another embodiment of aregenerator 510 in accordance with an example embodiment of the present invention. Anouter housing 512 is provided withflanges regenerator 510 includes an insulatinglayer 520 made of any suitable insulating material. A sintered diamondheat exchanging medium 530 is provided. In this illustrated embodiment, the sintered diamondheat exchanging medium 530 is shown as sintered diamond wire-like mesh 532. The wire-like mesh 532 is separated by insulatingmaterial 534 to prevent heat transfer in the direction of fluid flow illustrated byline 540. An insulatingcore 550 is provided if needed for the particular application. -
FIGS. 12 and 13 illustrate another embodiment of aregenerator 610 in accordance with an example embodiment of the present invention. Anouter housing 612 is provided to house the internal components of theregenerator 610. Theregenerator 610 includes a sintered diamondheat exchanging medium 630. In this illustrated embodiment, the sintered diamondheat exchanging medium 630 is shown as sintereddiamond tubes 632. Sections oftubes 632 can be separated by insulating material (not shown) such as fiberglass insulation material, or other insulating material, to prevent heat transfer in the direction of fluid flow illustrated byline 640. Fluid flows through thetubes 632 and through the insulating material from one end of theregenerator 610 to the other, as will be readily appreciated by one of ordinary skill in the art. -
FIGS. 14 and 15 illustrate another embodiment of aregenerator 710 in accordance with an example embodiment of the present invention. Anouter housing 712 is provided to house the internal components of theregenerator 710. Theregenerator 710 includes a sintered diamondheat exchanging medium 730. In this illustrated embodiment, the sintered diamondheat exchanging medium 730 is shown as asintered diamond spiral 732. Sections of thespiral 732 can be separated by insulating material (not shown) such as fiberglass insulation material, or other insulating material, to prevent heat transfer in the direction of fluid flow illustrated byline 740. Fluid flows through the sections of thespiral 732 and through the insulating material from one end of theregenerator 710 to the other, as will also be readily appreciated by those of skill in the art. -
FIG. 16 is a simplified representation of a sintereddiamond molding apparatus 810. Themolding apparatus 810 includes atop mold 812 mounted to aplate 813 and abottom mold 814 mounted to aplate 815, which is in turn mounted to abase 824. The apparatus includes ameans 820 for pressing thetop mold 812 and thebottom mold 814 together, shown for representation purposes only as actuated by ahandle 816. Those of ordinary skill in the art will readily appreciate that the pressures required to sinter the diamond are much greater than can be produced by hand. Aheat source 818 is also provided for the sintering process. Again, those of ordinary skill in the art will readily appreciate that the temperatures required for the process will necessitate a much more complex heating system than the one illustrated. In concept, the diamond material (not shown) is placed in thebottom mold 814, and thetop mold 812 and thebottom mold 814 are brought together under pressure. Thetop mold 812 andbottom mold 814 are heated by theheat source 818 to sinter the diamond material. -
FIGS. 17 and 18 illustrate thetop mold 812 and thebottom mold 814. Thetop mold 812 haspins 830. The bottom mold hascylindrical cavities 832. The difference between the outside diameter of the pins and the inside diameter of the cavities determines the wall thickness of the sintered diamond tubes created by themolds -
FIGS. 19 and 20 illustrate another embodiment of atop mold 912 and abottom mold 914. Thetop mold 912 haspins 930. The bottom mold hascavities 932 in the shape of wire mesh. The difference between the size of thepins 930 and the size of thecavities 932 determines the wire size of the sintered diamond mesh created by themolds -
FIGS. 21 through 23 illustrate a schematic representation of a cross-section ofmolds top mold 812 haspins 830. Thebottom mold 814 hascylindrical cavities 832. Thepins 830 are sized to fit within thecavities 832 such thattubes 834 are created after the sintering process.FIG. 21 illustrates thetop mold 812 separated from thebottom mold 814.FIG. 22 illustrates thetop mold 812 nested inside thebottom mold 814.FIG. 23 illustrates thebottom mold 814 with thetop mold 812 removed and thetubes 834 formed in thecavities 832. -
FIG. 24 represents a schematic of the molding process.Sintered diamond dust 870 and optionally abinding agent 872 are mixed using a mixing process represented bycylinder 874. The blendedmaterial 876 is injected into abottom mold 878 through aninjection molding apparatus 880. Thetop mold 882 is forced down into thebottom mold 878 and the blendedmaterial 876 is heated while the pressure is applied. This sintering process is well known in the art. - It is to be understood that the exemplary embodiments are merely illustrative of the present invention and that many variations of the above-described embodiments can be devised by one skilled in the art without departing from the scope of the invention.
Claims (18)
1. A regenerator for exchanging heat energy between a reciprocating fluid flow and a heat storage medium comprising:
a housing;
the heat storage medium including a plurality of sintered diamond elements within the housing, the plurality of sintered diamond elements having a fluid passage therethrough;
a plurality of insulating elements within the housing and spaced between the sintered diamond elements, the insulating elements having a fluid passage therethrough, the fluid passage of the insulating elements in fluid communication with the fluid passage of the sintered diamond elements.
2. The apparatus of claim 1 wherein the sintered diamond elements comprise irregularly shaped diamond dust particles sintered together such that the sintered diamond elements are porous.
3. The apparatus of claim 1 wherein the sintered diamond elements comprise a plurality of disks placed adjacent one another between the insulating elements.
4. The apparatus of claim 1 wherein the sintered diamond elements comprise a plurality of plates placed adjacent one another between the insulating elements.
5. The apparatus of claim 1 wherein the sintered diamond elements comprise a plurality of tubes placed adjacent one another between the insulating elements.
6. The apparatus of claim 1 wherein the sintered diamond elements are made from diamond particles of between 0.001 and 500 microns.
7. The apparatus of claim 1 wherein the sintered diamond elements are made by placing diamond particles in a mold and heating the particles to sufficient temperature to fuse the particles together.
8. The apparatus of claim 7 wherein the mold has cavities shaped in the form of wire-like mesh.
9. The apparatus of claim 7 wherein the mold has cavities shaped in the form of tubes.
10. The apparatus of claim 1 wherein each of the sintered diamond elements have an opening therethrough and each of the insulating elements have an opening therethrough, and further including an insulating material within each of the openings of the sintered diamond elements and each of the insulating elements.
11. The apparatus of claim 10 wherein the openings in the sintered diamond elements and the openings of the insulating elements are substantially through the center of the sintered diamond elements and the insulating elements.
12. A heat exchanger for exchanging heat energy between a first fluid flow and a second fluid flow comprising:
a housing;
a plurality of sintered diamond elements within the housing, the plurality of sintered diamond elements having a first fluid passage associated therewith and a second fluid passage associated therewith, and the first fluid passage is isolated from the second fluid passage.
13. The apparatus of claim 12 wherein the sintered diamond elements comprise a plurality of tubes of sintered diamond and wherein the first fluid passage is through the plurality of tubes and the second fluid is between the plurality of tubes.
14. The apparatus of claim 12 wherein the sintered diamond elements comprise a first plurality of tubes and a second plurality of tubes the first plurality of tubes forming the first fluid passage and the second plurality of tubes forming the second fluid passage wherein the first plurality of tubes and the second plurality of tubes are embedded in a block of sintered diamond.
15. The apparatus of claim 12 wherein the sintered diamond elements are made from diamond particles of between 0.001 and 500 microns.
16. The apparatus of claim 12 wherein the sintered diamond elements are made by placing diamond particles in a mold and heating the particles to sufficient temperature to fuse the particles together.
17. The apparatus of claim 12 wherein the mold has cavities in the shape of tubes.
18. A regenerator for exchanging heat energy between a reciprocating fluid flow and a heat storage medium comprising:
a housing;
an insulating core;
the heat storage medium including a plurality of sintered diamond elements within the housing and surrounding the insulating core, the plurality of sintered diamond elements having a fluid passage therethrough;
a plurality of insulating elements within the housing and spaced between the sintered diamond elements, the insulating elements having a fluid passage therethrough, the fluid passage of the insulating elements in fluid communication with the fluid passage of the sintered diamond elements.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/330,644 US20100139885A1 (en) | 2008-12-09 | 2008-12-09 | Sintered diamond heat exchanger apparatus |
CN2009801490679A CN102245996A (en) | 2008-12-09 | 2009-12-03 | Sintered diamond heat exchanger apparatus |
AU2009333674A AU2009333674A1 (en) | 2008-12-09 | 2009-12-03 | Sintered diamond heat exchanger apparatus |
PCT/US2009/066563 WO2010077551A2 (en) | 2008-12-09 | 2009-12-03 | Sintered diamond heat exchanger apparatus |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/330,644 US20100139885A1 (en) | 2008-12-09 | 2008-12-09 | Sintered diamond heat exchanger apparatus |
Publications (1)
Publication Number | Publication Date |
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US20100139885A1 true US20100139885A1 (en) | 2010-06-10 |
Family
ID=42229769
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/330,644 Abandoned US20100139885A1 (en) | 2008-12-09 | 2008-12-09 | Sintered diamond heat exchanger apparatus |
Country Status (4)
Country | Link |
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US (1) | US20100139885A1 (en) |
CN (1) | CN102245996A (en) |
AU (1) | AU2009333674A1 (en) |
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Also Published As
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AU2009333674A1 (en) | 2010-07-08 |
WO2010077551A3 (en) | 2011-02-17 |
WO2010077551A2 (en) | 2010-07-08 |
CN102245996A (en) | 2011-11-16 |
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