WO2014194138A1 - Diode thermique épicatalytique - Google Patents

Diode thermique épicatalytique Download PDF

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Publication number
WO2014194138A1
WO2014194138A1 PCT/US2014/040089 US2014040089W WO2014194138A1 WO 2014194138 A1 WO2014194138 A1 WO 2014194138A1 US 2014040089 W US2014040089 W US 2014040089W WO 2014194138 A1 WO2014194138 A1 WO 2014194138A1
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WO
WIPO (PCT)
Prior art keywords
gas
thermal diode
epicatalytic
heat transfer
cavity
Prior art date
Application number
PCT/US2014/040089
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English (en)
Inventor
Daniel P. SHEEHAN
Original Assignee
Sheehan Daniel P
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US14/289,322 external-priority patent/US9212828B2/en
Application filed by Sheehan Daniel P filed Critical Sheehan Daniel P
Priority to KR1020157036821A priority Critical patent/KR20160034856A/ko
Priority to AU2014274104A priority patent/AU2014274104A1/en
Priority to EP14803740.1A priority patent/EP3003547A4/fr
Priority to CN201480038411.8A priority patent/CN105473218B/zh
Publication of WO2014194138A1 publication Critical patent/WO2014194138A1/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24V—COLLECTION, PRODUCTION OR USE OF HEAT NOT OTHERWISE PROVIDED FOR
    • F24V30/00—Apparatus or devices using heat produced by exothermal chemical reactions other than combustion
    • 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
    • F28D15/00—Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F23/00—Features relating to the use of intermediate heat-exchange materials, e.g. selection of compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J15/00—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor
    • B01J15/005—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates

Definitions

  • the subject matter described herein generally relates to managing heat flow, and in particular to devices that create and maintain a steady-state temperature differential.
  • waste heat generated by a vehicle engine can be directed to the vehicle's interior to provide heating during the winter months
  • fossil fuel e.g., gasoline, coal, oil, etc.
  • ETD Epicatalytic Thermal Diode
  • the ETD spontaneously: i) creates and maintains a temperature difference between two separated surfaces of the ETD; and ii) mediates efficient steady-state heat flow across the ETD, in the direction of (i.e., up) the temperature gradient.
  • the structure of the ETD thermomechanically and chemically optimizes both the creation and maintenance of the temperature gradient and the flow of heat.
  • ETD devices comprise one or more ETD cells, connected in series and/or parallel.
  • adjacent ETD cells share one or more components for increased efficiency of operation and/or reduced production costs.
  • an ETD cell comprises first and second surfaces with a cavity between them configured to hold a gas.
  • the surfaces chemically interact with the gas such that the gas dissociates at a faster rate proximate to the first surface than it does proximate to the second surface.
  • a greater amount of heat is absorbed or released (depending on whether the dissociation reaction is endothermic or exothermic, respectively) proximate to the first surface than proximate to the second surface. Consequently, a steady-state temperature differential between the first surface and the second surface is created and maintained.
  • the ETD cell further comprises first and second heat transfer surfaces connected and substantially parallel to the first and second surfaces respectively.
  • the heat transfer surfaces are connected to the side of the corresponding surface that is opposite the cavity.
  • the heat transfer surfaces are configured to conduct heat to and/or from the corresponding surface.
  • FIG. (figure) 1A is a diagram illustrating an epicatalytic reaction that results in a temperature differential between two surfaces, according to one embodiment.
  • FIG. IB is a side-view of a single ETD cell in which the reaction of FIG. 1A may occur, according to one embodiment.
  • FIG. 2 is an isometric view of a system configuration including multiple ETD cells in parallel, according to one embodiment.
  • FIG. 3 is side-view representation of a system configuration combining three layers of ETD cells in series, according to one embodiment.
  • FIG. 4 is diagram illustrating an apparatus for testing combinations of materials and gasses to determine their suitability for use in an ETD cell, according to one
  • FIG. 5 is a flow chart illustrating an exemplary method of determining the suitability of a particular gas-surfaces combination for use in an ETD cell, according to one embodiment.
  • FIG. 6 is a flow chart illustrating an alternate method for determining the suitability of a particular gas-surface combination for use in an ETD cell, according to one embodiment.
  • Embodiments of an ETD utilize a process involving (at least) two spatially separated surfaces that are chemically active with respect to a gas enclosed between them, the gas undergoing a generic dissociation reaction AB ⁇ A + B.
  • FIG. 1A illustrates an embodiment of this process that uses two parallel surfaces 120 & 140.
  • the two (or more) surfaces 120 & 140 exhibit most behaviors of traditional heterogeneous catalysts, but deviate on one standard principle of catalysis.
  • the surfaces 120 & 140 alter the gas phase equilibrium due to the dominance of surface effects over the bulk properties of the gas in the cavity 130 between the surfaces.
  • the surfaces 120 & 140 are referred to herein as "epicatalysts" and a process based on such surfaces is referred to as “epicatalysis” and/or an “epicatalytic process.”
  • a first one of the surfaces 140 is predisposed to the dissociation half-reaction (meaning AB ⁇ A + B) compared with a second one of the surfaces 120.
  • the second surface 120 is comparatively predisposed to the recombination half-reaction (meaning A + B ⁇ AB), relative to the first surface 140.
  • proximate is used herein with regards to the gas and a surface to mean that the monomers and/or dimers of the gas are within about 10 Angstroms of the surface, including being on the surface.
  • the cavity 130 contains the gas, which can freely move within the cavity.
  • This flow of gas between the two surfaces 120 & 140 carries net thermal and chemical energy, resulting in a steady-state temperature differential between the two surfaces.
  • the dissociation reaction is endothermic and the
  • the dissociation reaction is endothermic, it should be noted that in some embodiments, the dissociation reaction is exothermic. In such embodiments, the surface that favors dissociation 140 will be warmer than the surface that favors recombination.
  • FIG. IB is a cutaway side-view illustrating the general structure of an ETD cell 100, according to one embodiment.
  • Multiple ETD cells 100 can be combined in various ways to achieve desired effects, some examples of which are discussed in greater detail below, with reference to FIGS. 2 and 3.
  • the ETD cell 100 includes a first surface 140 and a second surface 120, each supported by a corresponding heat transfer surface 110 and aligned substantially parallel to each other. Separation between the surfaces 120 & 140 is maintained by a plurality of separators 160, of which two are shown. Thus, a cavity 130 is formed between the surfaces 120 & 140, which contains the gas.
  • the ETD cell 100 In other embodiments, other geometries that maintain a substantially constant separation between two or more surfaces are used for the ETD cell 100, such as nested cylinders, nested spheres, spirals, and the like. In some embodiments, one or both of the surfaces 120 & 140 also serve as the corresponding heat transfer surface 1 10. In yet further embodiments, the surfaces 120 & 140 are not arranged with substantially constant separation, for example, at an angle of 45 degrees relative to one another, or with one of the surfaces being substantially curved relative to the other.
  • Gases useful with the disclosed apparatus are those which exist as a dimer, AB, but also as individual monomers, A and B. Further, the gases useful with the disclosed apparatus are selected based on their interaction with the specific surfaces 120 and 140. As disclosed above, a gas useful with particular surfaces 120 and 140 is one that is predisposed to dissociation at the first of the two surfaces as compared to the second and predisposed to recombination at the second surface as compared to the first. In one embodiment, the gas is chosen based on the stability of the individual monomers A and B, the strength of bond between the components in the dimer AB, and the vapor pressure of the gas at the operating temperature of the ETD device (e.g., at or near room temperature).
  • the gas is selected such that the vapor pressure of the gas is sufficient for the chemical cycle to operate when the gas is at the ETD's operating temperature.
  • gases with relatively low molecular weight e.g., less than about 200 amu
  • gases with relatively low molecular weight can be used in some embodiments intended for room temperature operation.
  • gases have net intermolecular forces and energies that are comparable to ambient thermal energies, and thus, an appreciable amount of dissociation occurs in ambient conditions.
  • gasses of higher molecular weight a significant proportion of the molecules tend to liquefy or solidify at room temperature, resulting in the cavity 130 not containing a sufficient amount of the gas in the vapor phase for the reaction cycle to be maintained.
  • the stability of the individual monomers and the strength of bond of the dimer for the selected gas are such that the surface effects due to the surfaces 120 & 140 dominate over gas phase equilibrium behavior when the ETD device is at the operating temperature.
  • the dimer AB is bonded by a relatively weak bond, such that the dimer can thermally dissociate at or near room temperature, resulting in an appreciable amount (e.g., 10%) of the gas existing in the dissociated species at any given time.
  • gas dimers with hydrogen bonds (HyB), halogen bonds (HaB), and van der Waals bonds (vdWB) are used. Both homodimers (gases where monomers A and B are the same) and heterodimers (gases where monomers A and B are different) are used in various embodiments.
  • Hydrogen bonded dimers are molecules comprising two monomers joined with one or more hydrogen bonds.
  • Hydrogen bonded dimers for which dissociation and recombination rates vary in proximity to a surface include, but are not limited to: low molecular weight carboxylic acids, alcohols, aldehydes, ketones, ethers, esters, acyl halides, amides, and amines.
  • low molecular weight carboxylic acids include, but are not limited to: low molecular weight carboxylic acids, alcohols, aldehydes, ketones, ethers, esters, acyl halides, amides, and amines.
  • lone pair electrons available from F, O, N, and sometimes S, working in concert with hydrogen atoms attached to electronegative elements will result in a dimer that exhibits epicatalytic behavior when in proximity to appropriate surfaces.
  • embodiments may employ as the gas: formic acid, acetic acid, methanol, ethanol, formaldehyde, ammonia, dimethyl ketone, methylamine, dimethylamine, dimethyl ether, water, acetamide, methylthiol, cyanogens, hydrogen cyanide, hydrogen fluoride, hydrogen sulfide, cyanomethane, formamide, aminomethanimine, hydrogen chloride, cyanoethane, carbon monoxide, carbon dioxide, sulfur dioxide, and nitrogen oxides, as well as heterodimer combinations of the monomers of these molecules.
  • Halogen bonded dimers are molecules comprising two monomers joined with one or more halogen bonds.
  • low molecular weight halogen bonded molecules containing Fluorine, Chlorine, Bromine, or Iodine exhibit epicatalytic behavior.
  • embodiments may employ as the gas: mono-halogen methane, di-halogen methane, tri-halogen methane, tetra-halogen methane, halogenated ethane, and halogenated versions of the hydrogenated species above, as well as heterodimer combinations of the monomers of these molecules.
  • Van der Waals bonded dimers are molecules comprising two monomers joined with one or more Van der Waals bonds. Unlike the HyB and HaB dimers above, many types of Van der Waals bonded dimers exhibit an appreciable amount of dissociation significantly below room temperature. Those skilled in the art will recognize that in various applications, based on the above considerations, embodiments may employ as the gas: noble gas dimers (e.g., Argon, Xenon), methane, ethane, propane, and nitrogen.
  • noble gas dimers e.g., Argon, Xenon
  • gases other than those listed above are used.
  • some covalently bonded gases such as di-borane and nitrogen tetroxide, have bonds that are weak enough for a significant proportion of the gas to be in the dissociated state when at or near room temperature.
  • the gas is described herein as a dimer for convenience, it should be noted that in some embodiments the gas is a trimer or higher-order molecule comprising multiple monomers bound by one or more of the bond types described above.
  • additional factors are taken into account when selecting a gas for the cavity 130 including the chemical properties of the gas, the availability/price of the gas, the toxicity of the gas, and the like.
  • the heat transfer surfaces 110 give mechanical stability and support to the surfaces 120 and 140.
  • the heat transfer surfaces 1 10 are also impermeable to the gas and make up part of a sealed container that retains the gas.
  • one or both of the surfaces 120 & 140 also serve as the corresponding heat transfer surface 1 10.
  • an ETD system contains a plurality of ETD cells 100, with the individual cells sharing the gas throughout a plurality of connected cavities 130. One such system is described in further detail below, with reference to FIG. 2.
  • the outer surfaces of the heat transfer surfaces 1 10 include, in various embodiments, surface features (e.g., fins, roughness, etc.) in order to increase heat transfer via conduction and convection. Additionally, the outer surfaces are, in some embodiments, faced (e.g., painted black) in order to maximize heat transfer via radiation.
  • the outer surfaces can include one or more of anodized aluminum, carbon black, carbon nanotube forests, and the like, in order to provide efficient radiative heat transfer into and out of the cell 100.
  • the heat transfer surfaces 110 are thermally conductive (e.g., having a high thermal conductivity and being physically thin) and mechanically strong. Examples of materials with these properties include mylar, kevlar, aramid, metal foil, and the like. Being thermally conductive allows heat to easily enter the ETD cell 100 through the first heat transfer surface 110A, and be harvested from the ETD cell at the second heat transfer surface 1 10B. Being mechanically strong allows the heat transfer surfaces 1 10 to provide good mechanical support of the surfaces 120 & 140, thus ensuring that the functional geometry of the ETD cell 100 is substantially maintained under stress.
  • the heat transfer surfaces 110 may be constructed from identical or different materials with the desired properties, depending on the specific embodiment. For example, the material used for each heat transfer surface 1 10 can be chosen to ensure effective binding with the corresponding surface material.
  • the heat transfer surfaces 110 are macroscopically flexible, as well as being mechanically strong over shorter length scales. Consequently, a sheet of ETD cells can be manipulated to form cylinders, spirals, wrappings, and other such structures, as desired for a particular application.
  • the heat transfer surfaces have low emissivity on the inner facing surfaces (e.g., mirrored) to reduce back radiative heating of the cooler surface 140 by the warmer surface 120.
  • the relationship between the emissivities (and absorptivities) of the heat transfer surfaces 1 10 and the surfaces 120 & 140 is optimized to further reduce the amount of back radiative heating achieved by mirroring alone.
  • the choice of materials for the surfaces 120 & 140 is based, at least in part, by the specific gas in the cavity 130, and in particular, how the dissociation/recombination reaction rates of the specific gas is altered by proximity to the chosen materials for the surfaces.
  • a material that favors dissociation of the gas is selected for the first surface 140.
  • a material that (relatively) favors recombination of the gas is selected for the second surface 120.
  • the geometry of one or both surfaces 120 and 140 is tailored to increase the number of interactions between the gas and surface, and hence increase the corresponding dissociation or recombination rate.
  • the surface 120 or 140 may be rippled, grooved, roughened, dendritic, or otherwise configured (e.g., coated in a carbon nano-tube forest) to increase the surface area available for gas-surface interaction.
  • the geometry of the pair of surfaces 120 and 140 is tailored such that the proportion of incoming dimers that dissociate at the dissociating surface is approximately equal to the proportion of monomer pairs that recombine and the recombination surface.
  • the material used for the dissociating surface 140 competes with the monomers of the gas for attraction, thus reducing the number of monomers that recombine proximate to the dissociating surface and consequently increasing the overall dissociation rate.
  • the dissociating surface 140 interacts too strongly with the monomers they may stick to the surface. If this occurs, the monomers become unavailable to participate in the chemical cycle, which can prevent the establishment of a steady-state temperature differential.
  • the material used for the dissociating surface 140 should be one that has appreciable dissociative desorption activity with respect to the particular dimer used, meaning both that an appreciable portion of dimers incident on the surface dissociate and an appreciable portion of the resulting monomers leave the region proximate to the surface.
  • all dimers incident on the dissociating surface 140 undergo dissociative desorption.
  • practical systems typically have a dissociative desorption ratio (the percentage of incident dimers for which dissociation occurs and the resulting monomers leave the region proximate to the dissociating surface 140) of less than 100%.
  • the dissociative desorption ratio is between 0.01% and 90%. In another embodiment, the dissociative desorption ratio is between 0.1% and 90%.
  • the dissociative desorption ratio is between 0.1% and 50%. In a further embodiment, the dissociative desorption ratio is between 0.1 and 10%. In other embodiments, other dissociative desorption ratios occur, depending on the specific gas and materials used, as well as the ETD operating temperature and pressure.
  • Example material classes that exhibit this property include (but are not limited to): metals, ceramics, metal oxides, nitrides, and halides, as well as functionalized organic polymers and other high molecular mass molecules that exhibit functionalized surfaces.
  • noble metals e.g., Au, Ag
  • transition metals e.g., Fe, Ni, Cu
  • refractory metals e.g., W, Re, Mo
  • alumina A1203
  • magnesia MgO
  • titania Ti02
  • silica nitrocellulose, aramid, nylon, rayon, or polymethylmethacrylate (PMMA).
  • the dissociating surface 140 also interacts with the gas such that the gas dissociates proximate to the dissociating surface at a greater rate than it does proximate to the recombining surface 120.
  • the dissociating surface 140 surface-chlorinated polyethylene, surface- chlorinated polypropylene, or Teflon.
  • Another class of materials that are used as the dissociating surface 140 in some embodiments that use vdWB, HaB, or HyB gases is doped semiconductors.
  • doped semi-conductors include silicon and germanium doped with one or more of: chlorine, fluorine, nitrogen, oxygen, barium, and caesium.
  • the recombining surface 120 facilitates recombination of the monomers back into dimers, thus, the material selected for the recombining surface interacts with the monomers in a manner that favors recombination, e.g., by influencing the distribution of the charge of the monomers.
  • the recombining surface 120 binds the monomers lightly, e.g., by weak HyB, HaB, or VdWB. Consequently, interactions between gas monomers and the recombining surface 120 do not dominate over the formation of bonds between the monomers, thereby creating dimers.
  • the recombinative desorption ratio is between 0.01% and 90%. In another embodiment, the recombinative desorption ratio is between 0.1% and 90%. In yet another embodiment, the recombinative desorption ratio is between 0.1% and 50%. In a further embodiment, the recombinative desorption ratio is between 0.1 and 10%. In other embodiments, other recombinative desorption ratios occur, depending on the specific gas and materials used, as well as the ETD operating temperature and pressure.
  • Non-polar, organic surfaces such as high molecular weight hydrocarbons, organosilanes, chloro-polymers, and unfunctionalized polymers.
  • Those skilled in the art will recognize that in various applications, based on the above considerations embodiments may employ, as the recombining surface 120: polyethylene, polypropylene, paraffin, natural rubber, or polyethers.
  • fluoropolymers exhibit suitable properties for use as the recombining surface 120, including homo-polymers and co-polymers fabricated from:
  • chlorotrifluoroethylene chlorotrifluoroethylene.
  • recombining surface 120 polyvinylfluoride, polyvinylidene fluoride, polytetrafluoroethylene, perfluoroalkoxy polymer, polyethylenechlorotrifluoroethylene, Viton, perfluoropolyether, or perfluorosulfonic acid.
  • graphene and its allotropes e.g., graphite, carbon nanotubes
  • graphite, carbon nanotubes also exhibit these properties and can be used for the recombining surface 120, in combination with an appropriate gas.
  • Another class of materials that are used as the recombining surface 120 in some embodiments that use vdWB, HaB, or HyB gases is doped semiconductors.
  • doped semiconductors By doping a semiconductor with electronegative or electropositive species, sites are created that interact with the monomers in a manner that encourages recombination.
  • doped semi-conductors include silicon and germanium doped with one or more of: chlorine, fluorine, nitrogen, oxygen, barium, and caesium
  • the separation between the surfaces 120 & 140 is less than (or of the order of) the mean free path for collision or reaction for the gas-phase dissociation- recombination reaction (AB ⁇ A + B).
  • the mean free path for collision or reaction for the gas-phase dissociation- recombination reaction (AB ⁇ A + B).
  • gas pressures for gas pressures of about 0.01 - 10 atmospheres, corresponding separations in the range of about 10 - 0.01 microns can be used. In other embodiments, gas pressures as low as 0.001 and as high as 40 atmospheres are used, corresponding to separations in the range of about 100 - 0.0025 microns.
  • the surfaces 120 & 140 have a high thermal conductivity and are physically thin (e.g., 1-lOnm) in order to aid the transfer of heat in and out of the ETD cell 100.
  • the surfaces 120 & 140 have a high surface area (e.g., rough or dendritic) to maximize chemical reactivity per unit area and are optically thin (e.g., less than IR wavelength) so that the optical character of the heat transfer surfaces 110 dominates radiation transfer in the interior of the ETD cell 100.
  • the plurality of separators 160 maintains the desired separation between the active surfaces 120 & 140.
  • the material and structure of the separators 160 are selected to keep the amount of thermal conduction across the cavity 130, via the separators, as low as possible. In the embodiment shown in FIG. IB, this is accomplished by using separators 160 that are thin columns with rounded tips to minimize the area of contact with the heat transfer surfaces 110. In other embodiments, different shaped separators 160 are used, such as spherical micro-particles. Although in the embodiment shown, the separators 160 abut the heat transfer surfaces 1 10, in other embodiments the separators abut and/or are embedded in the surfaces 120 & 140 (e.g., as shown in FIG. 3).
  • the separators 160 are mechanically strong enough and adequately spaced to maintain the separation between the surfaces 120 and 140 at close to the desired value when the ETF cell 100 is stressed.
  • the separators 160 also have a low thermal conductivity to minimize thermal back-conduction from the cooler surface 120 to the warmer surface 140.
  • the separators 160 have low emissivity (e.g., mirror-like) so as to not absorb internal radiation.
  • the gas in the cavity 130 is acetic acid
  • the dissociating surface 140 is polymethyl methacrylate
  • the recombining surface 120 is polyethylene.
  • the gas is formamide
  • the dissociating surface 140 is partially surface-chlorinated polyethylene
  • the recombining surface 120 is polypropylene.
  • the gas is ammonia
  • the dissociating surface 140 is alumina ceramic
  • the recombining surface 120 is polystyrene.
  • the gas is formic acid
  • the dissociating surface 140 is polymethyl methacrylate
  • the recombining surface 120 is polyethylene.
  • FIG. 4 illustrates an apparatus 400 for testing combinations of materials and gasses to determine their suitability for use in an ETD cell, according to one embodiment.
  • the apparatus 400 includes a black body cylinder 420 inside a vacuum vessel 410.
  • the body of the vacuum vessel 410 is a stainless steel cylinder with a diameter of approximately 30 centimeters (cm) and a length of approximately 40 cm
  • the black body cylinder 420 is a cylinder with a diameter of approximately 0.64 cm and a length of approximately 10 cm constructed from tungsten or rhenium foil (with a thickness of approximately 26 microns).
  • the vacuum vessel is diffusion pumped to a base pressure of approximately 10 "6 Torr.
  • An inner portion 425 of the black body cylinder 420 (e.g., the central 2.5 cm portion) is sealed off with a pair of alumina discs 422
  • a cylindrical electrode 442 (e.g., a tantalum electrode) is attached to the interior surface of each end of the black body cylinder 420.
  • the electrodes 442 are attached to a variable power supply 440 via a pair of wires 445.
  • the black body cylinder and its contents can be ohmically heated.
  • the equilibrium temperature of the black body cylinder 420 and its contents can thus be controlled by varying power supplied by the variable power supply 440.
  • variable power supply 440 wires 445, and electrodes 442 are omitted.
  • mechanisms for refrigerating the black body cylinder 420 are provided to enable the testing of materials for low temperature epicatalytic behavior.
  • thermocouples 430 are positioned inside the black body cylinder 420 and fed through the holes in the alumina discs 422 such that a central portion of each thermocouple 430 is located within the inner portion 425.
  • the first thermocouple 430A is coated with a material that is a candidate for being predisposed to the dissociation half- reaction with respect to a particular gas
  • the second thermocouple 430B is coated with a material that is a candidate for being predisposed to the recombination half-reaction (relative to the first material) with respect to the same gas.
  • Each thermocouple is connected to a corresponding thermocouple gauge 450 via a wire 435.
  • thermocouple gauge 450A connected to the first thermocouple monitors the temperature of the first thermocouple
  • the second thermocouple gauge 450B monitors the temperature of the second thermocouple.
  • the thermocouple gauges 450 might be a pair of channels on a data-logger that will monitor and record the temperature of the thermocouple once a second.
  • thermocouples 430 are subject to four heat transfer channels: 1) heat conduction along the wires 435, 2) black body radiation, 3) heat convection by gasses present in the cavity, and 4) gas dissociation/recombination reactions (i.e., epicatalytic effects).
  • gas dissociation/recombination reactions i.e., epicatalytic effects
  • FIG. 5 illustrates an exemplary method 500 of determining the suitability of a particular gas-surfaces combination for use in an ETD cell, according to one embodiment.
  • the method 500 is described from the perspective of the method being performed using the apparatus 400 shown in FIG. 4. However, in other embodiments, different testing apparatus are used. In various embodiments, some of the steps of the method 500 are performed in a different order and/or in parallel. Some embodiments of the method 500 include additional and/or different steps.
  • the pair of thermocouples 430 are placed within the black body cylinder 420. As described above with reference to FIG. 4, the first thermocouple 430A is coated with a first candidate material and the second thermocouple 430B is coated with a second candidate material.
  • the vacuum vessel 410 is evacuated (e.g., to a pressure of 10 "6 Torr) and the temperature of the pair of thermocouple 430 is monitored until equilibrium is reached. For example, the temperature may be monitored until no variations greater than a threshold value (e.g., 0.1%) are observed for a set period of time (e.g., one minute). If the material-gas combination is being tested for a target temperature of operation other than room
  • thermocouples 430 are located within a black body cavity in a vacuum, any variations in temperature must be due to either heat conduction along the wires 435 or black body radiation, or both. Theory and experiment confirm that under these conditions, no difference in temperature between the pair of thermocouples 430 is observed.
  • an epicatalytically inert gas (meaning one that does not undergo a significant number of dissociation and recombination reactions when in equilibrium at the target temperature) is inserted into the vacuum vessel 410.
  • the inert gas is preferably one with similar properties to the candidate epicatalytic gas that is to be tested in order to minimize the possibility that non-epitcatalytic effects are responsible for any observed temperature difference.
  • the candidate epicatalytic gas being tested is Hydrogen, then Helium may be used during this stage of the method 500.
  • thermocouples 430 Assuming that the inert gas does not exhibit epicatalytic behavior in the presence of the candidate materials, any variations in the temperature of the thermocouples 430 that is observed as compared to step 520 will be due to heat convection by the inert gas (and any other trace gasses) present in the black body cylinder 420. Theory and experiment confirm that under these conditions, no difference in temperature between the pair of thermocouples 430 is observed.
  • the inert gas in the vacuum vessel 410 is replaced with the candidate epicatalytic gas. If the candidate epicatalytic gas preferably dissociates proximate to the first thermocouple 430A relative to the second thermocouple 430B (or vice versa), a steady-state temperature differential will result as described previously. Thus, a temperature differential will be observed between the thermocouples 430 that was previously not present (in steps 520 and 530). Theory and experiment have verified this behavior.
  • Tungsten and Rhenium thermocouples 430 are exposed to Hydrogen gas at high temperature and low pressure (e.g., at a temperature of 1900 Kelvin (K) and a pressure of 1 Torr), the Tungsten thermocouple 430A is observed to spontaneously heat relative to the Rhenium thermocouple 430B, and the observed temperature difference is thermodynamically stable.
  • high temperature and low pressure e.g., at a temperature of 1900 Kelvin (K) and a pressure of 1 Torr
  • the viability of using the candidate epicatalytic gas and the candidate materials to construct an ETD cell is determined based on the observed temperatures. Any combination that exhibits a large temperature differential in step 540 that was not present in in steps 520 and 530 can be used to construct a working ETD cell. In general, combinations with larger temperature differentials will result in more efficient ETD cells with greater power densities, within the other constraints imposed by the specific properties of the materials. For example, if the candidate materials have particularly low tensile strength, this may limit the size and possible geometries of the ETD cell. As another example, if a particular combination requires heating to an elevated temperature to operate, this will reduce the net efficiency of the ETD cell, as power must be expended heating the system. As a result, a combination that exhibits a lower temperature differential may result in an ETD cell that is more efficient or convenient overall.
  • FIG. 6 illustrates an alternate method 600 for determining the suitability of a given combination of gas, dissociating surface material, and recombining surface material, for use in an ETD cell 100, according to one embodiment.
  • some of the steps of the method 600 are performed in a different order and/or in parallel. Some embodiments of the method 600 include additional and/or different steps.
  • a stream of a candidate gas is directed onto a first candidate material. In one embodiment, this is done in an ultra-high vacuum chamber, with a pristine sample of the first candidate material being subjected to a stream of the candidate gas, the stream including dimer and monomeric species of the candidate gas.
  • a pristine sample is one that has been cleaned as much as possible. In other embodiments, non-pristine samples are used.
  • the gas stream impinges on the sample of the first candidate material, adsorbs onto the sample, chemically and/or physically reacts with the sample, and leaves (desorbs).
  • the monomer/dimer ratio of the desorbed flux leaving the first candidate material is measured.
  • the desorbed flux is analyzed by a mass spectrometer. In other embodiments, other diagnostic tools suitable for quantitatively identifying the desorbed species are used.
  • a stream of the candidate gas is impinged on a second candidate material.
  • this is done in an ultra-high vacuum chamber, with a pristine sample of the second candidate material being subjected to a stream of the candidate gas, the stream including dimer and monomeric species of the candidate gas.
  • non-pristine samples are used.
  • the gas stream impinges on the sample of the second candidate material, adsorbs onto the sample, chemically and/or physically reacts with the sample, and leaves (desorbs).
  • the monomer/dimer ratio of the desorbed flux leaving the second candidate material is measured.
  • the desorbed flux is analyzed by a mass spectrometer. In other embodiments, other diagnostic tools suitable for quantitatively identifying the desorbed species are used.
  • the measured monomer/dimer ratios are compared to determine whether the particular combination of gas and materials is suitable for use in construction of an ETD cell 100.
  • Desorbed fluxes that demonstrate monomer fractions in excess of gas phase equilibrium values make good dissociation surfaces 140, for the particular gas.
  • desorbed fluxes that demonstrate monomer fractions less than or equal to those of gas phase equilibrium values make good recombination surfaces 120, for the particular gas.
  • the combination of the particular gas and pair of candidate materials is considered to be suitable for use in construction of an ETD cell 100 if the difference between the monomer fraction measured for each surface is greater than a threshold amount.
  • the threshold used is selected based on the desired minimum temperature difference between the surfaces for the embodiment, with greater temperature differences requiring a greater difference, and hence a greater threshold.
  • an upper threshold is also used to place an upper limit on the difference in monomer fractions in order to filter out combinations that create temperature differences large enough to cause thermal damage to the ETD cell 100 and/or surrounding objects.
  • the above method 600 can be repeated for a plurality of combinations of gas and pairs of materials to determine those combinations which can be used in constructing an ETD cell 100 (other considerations, such as structural and economic feasibility aside).
  • Hydrogen bonds (-0.5 eV) are typically an order of magnitude weaker than covalent bonds ( ⁇ 5 eV), and van der Waals bonds are typically an order of magnitude weaker still (-0.05 eV).
  • covalent epicatalysis of H 2 operates well at -2000 K, it follows that epicatalytic dissociation of hydrogen-bonded and van der Waals-bonded dimers should occur at or below room temperature.
  • the ratio ⁇ (4.5 eV/2000 K), where 4.5 eV is the approximate bond strength of a Hydrogen dimer, is approximately equal to the ratio ⁇ (0.5 eV/220 K), where 220 K is well below room temperature, it can be inferred that a Hydrogen bonded dimer can easily exhibit epicatalytic behavior at room temperature in the presence of an appropriate pair of surfaces.
  • an ETD cell may also be constructed in which energy is transported across a cavity between an ionizing surface and a surface that is less active with respect to plasma ionization.
  • FIG. 2 is an isometric view of a system configuration 200 including multiple ETD cells 100 in parallel, according to one embodiment.
  • FIG. 2 shows a section of an ETD sheet that is three ETD cells 100 wide and two ETD cells 100 deep, for illustrative purposes only. In practice, ETD sheets will contain many more (e.g., hundreds, thousands, or even millions of) ETD cells 100.
  • ETD cells 100 When ETD cells 100 are arranged in parallel, the heat flux across the system 200 increases, but the temperature differential between the two sides of the cells remains unchanged. This is analogous to arranging cells in an electric circuit in parallel, where the currents add, but the voltage is unchanged.
  • the surfaces 120 & 140 as well as the heat transfer surfaces 100 expand across multiple ETD cells 100. This is beneficial for production, as the ETD sheet can be constructed layer by layer, using methods known in the art. In addition, adjacent cells share separators 160 (thus, each separator is logically part of four ETD cells 100). As described previously, with reference to FIG. IB, a single cavity 130 is shared by all (or at least some) of the ETD cells 100 in the sheet.
  • the heat transfer surfaces 1 10 are joined at the edges of the sheet with end walls 280 using gas-tight seals. Thus, the combination of the heat transfer surfaces 110 and end walls 280 make a sealed container that prevents the gas from escaping the cavity 130.
  • a valve (not shown) is provided between the cavity 130 and the exterior of the ETD device to enable insertion and/or replacement of the gas.
  • the separators 160 maintain a substantially constant separation 230 between the surfaces 120 & 140 throughout the sheet.
  • the separation 230 is selected from the range of about 0.01 microns to about 100 microns.
  • the separators 160 are equally spaced by a distance 260. Reducing the number of separators 160 increases the available surface area of the surfaces 120 & 140 at the expense of less regularity in the surface separation 260. Consequently, the distance 260 is selected based on the specific application's requirements and the rigidity of the materials used for the surfaces 120 & 140 and the heat transfer surfaces 1 10. In various embodiments, the distance 260 is selected from the range of about 0.1 microns to about 1,000 microns.
  • the distance 260 may be different in one direction than the other and/or non-rectilinear configurations (e.g., hexagonal cells) are used.
  • micro-particles e.g., spherical nano-beads
  • they are randomly or semi-randomly dispersed in the cavity 130. This has the benefit of requiring less fine control during the manufacturing process.
  • FIG. 3 is side-view representation of a system configuration 300 combining three layers of ETD cells 100 in series, according to one embodiment.
  • each layer is shown as being a single ETD cell 100, in practice, each layer can comprise many (e.g., hundreds, thousands, or even millions of) ETD cells arranged in parallel, as described above with reference to FIG. 2.
  • the choice to show three layers is purely for illustrative purposes.
  • the principles described herein can be used to stack any number of layers.
  • the individual layers are in good thermal contact with the adjoining layers.
  • ETD cells 100 are arranged in series, the temperature differentials of the cells are additive, but the heat flux across the system 200 is unchanged. This is analogous to arranging cells in an electric circuit in series, where the voltages add, but the current is unchanged.
  • adjacent layers share a heat transfer surface 110, such that the top heat transfer surface of one layer also serves as the bottom heat transfer surface of the layer above it, and vice versa.
  • the bottom layer 301 has two surfaces 350 & 360 and a cavity 355 containing a first gas.
  • the materials used for the surfaces 350 and 360 as well as the first gas are selected to optimize the system's operation when the input heat transfer surface 1 10A is at an expected operating temperature.
  • the middle layer 302 also has two surfaces 330 & 340 and a cavity 335 containing a second gas. Thus, the middle layer 302 results in a second temperature difference ⁇ 2 across it.
  • the materials used for the surfaces 330 & 340 as well as the second gas are selected to optimize the system's operation when the first internal heat transfer surface 1 1 OB is at an expected operating temperature, based on the expected operating temperature of the input heat transfer surface 1 10A and ⁇
  • the top layer 303 also has two surfaces 310 & 320 and a cavity 315 containing a third gas. Thus, the top layer 303 results in a third temperature difference ⁇ 3 across it.
  • the materials and gas used for the top layer 303 are the same as those used in the bottom layer 301 and/or middle layer 302.
  • the materials used for the surfaces 310 & 320 as well as the third gas are selected to optimize the system's operation when the second internal heat transfer surface 1 IOC is at an expected operating temperature, based on the expected operating temperature of the input heat transfer surface 1 10A as well as ⁇ and AT 2 .
  • the system configuration 300 as a whole provides a temperature differential between the input heat transfer surface 110A and an output heat transfer surface 1 10D of ⁇ + ⁇ 2 + ⁇ 3 , which can be significantly larger than the temperature differential obtained by any one of the layers 301-303.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
  • "or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

Abstract

L'invention concerne une diode thermique épicatalytique (DTE) qui comprend une ou plusieurs cellules de DTE. Chaque cellule comprend une première et une seconde surface comprenant une cavité entre elles, qui contient un gaz qui est actif au plan épicatalytique par rapport à la paire de surfaces. Les surfaces interagissent chimiquement avec le gaz de telle sorte que le gaz se dissocie à une vitesse plus élevée à proximité de la première surface qu'il ne le fait à proximité de la seconde surface. Ainsi, un différentiel de température stationnaire est créé et maintenu entre la première surface et la seconde surface. Dans diverses applications, de multiples cellules de DTE sont connectées en série ou en parallèle.
PCT/US2014/040089 2013-05-29 2014-05-29 Diode thermique épicatalytique WO2014194138A1 (fr)

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KR1020157036821A KR20160034856A (ko) 2013-05-29 2014-05-29 에피캐탈리틱 써멀 다이오드
AU2014274104A AU2014274104A1 (en) 2013-05-29 2014-05-29 Epicatalytic thermal diode
EP14803740.1A EP3003547A4 (fr) 2013-05-29 2014-05-29 Diode thermique épicatalytique
CN201480038411.8A CN105473218B (zh) 2013-05-29 2014-05-29 表面催化热二极管

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US201361828419P 2013-05-29 2013-05-29
US61/828,421 2013-05-29
US61/828,419 2013-05-29
US14/289,322 US9212828B2 (en) 2013-05-29 2014-05-28 Epicatalytic thermal diode
US14/289,322 2014-05-28

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US4425876A (en) * 1982-09-03 1984-01-17 Conoco Inc. Alcohol dissociation and waste heat recovery process for automobiles
US6924249B2 (en) * 2002-10-02 2005-08-02 Delphi Technologies, Inc. Direct application of catalysts to substrates via a thermal spray process for treatment of the atmosphere
US7070634B1 (en) * 2003-11-03 2006-07-04 Wang Chi S Plasma reformer for hydrogen production from water and fuel

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CN105473218A (zh) 2016-04-06
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EP3003547A1 (fr) 2016-04-13
AU2014274104A1 (en) 2015-12-17
EP3003547A4 (fr) 2016-12-28

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