EP1144920A2 - Procede et dispositif pour la realisation de thermobranches a structure en mousse - Google Patents

Procede et dispositif pour la realisation de thermobranches a structure en mousse

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Publication number
EP1144920A2
EP1144920A2 EP00945576A EP00945576A EP1144920A2 EP 1144920 A2 EP1144920 A2 EP 1144920A2 EP 00945576 A EP00945576 A EP 00945576A EP 00945576 A EP00945576 A EP 00945576A EP 1144920 A2 EP1144920 A2 EP 1144920A2
Authority
EP
European Patent Office
Prior art keywords
foam
thermal
conductive
thermoelectroactive
thermoelectric
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP00945576A
Other languages
German (de)
English (en)
Inventor
Hans BÖLLINGHAUS
Gunter Preiss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BOELLINGHAUS, HANS
Dettmann Birgit
VTV Verfahrenstechnik Verwaltung GmbH
Original Assignee
Bollinghaus Hans
Dettmann Birgit
VTV VERFAHRENSTECHNIK VERWALTU
VTV Verfahrenstechnik Verwaltung GmbH
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 DE19925960A external-priority patent/DE19925960A1/de
Application filed by Bollinghaus Hans, Dettmann Birgit, VTV VERFAHRENSTECHNIK VERWALTU, VTV Verfahrenstechnik Verwaltung GmbH filed Critical Bollinghaus Hans
Publication of EP1144920A2 publication Critical patent/EP1144920A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/13—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the heat-exchanging means at the junction
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/854—Thermoelectric active materials comprising inorganic compositions comprising only metals

Definitions

  • thermo-legs with foam structure parts area performance and efficiency of continuously dense thermo-legs (7) made of various thermoeletrics (3) according to the prior art
  • thermoelectric modules (1) and about 50 watts are supplied by a square meter of sunlit area on the potential rails of the electricity supplying overall system.
  • thermoelectric high specific area performances with efficiencies up to almost 7% are achieved with the latest thermocouples with non-focused solar radiation.
  • a module measuring 23 cm x 13 cm x 8 cm with a throughput of 75 ml / s throughput of a thermally delivering, fluid thermal exchange medium flowing in at 250 degrees Celsius and 38 ml of a thermally dissipating thermal exchange medium flowing in at 20 degrees Celsius generate a maximum of 175 watts Continuous power generated at 15.2 volts working voltage.
  • the efficiency is 5.5%. This would require 3182 watts of solar power, i.e. an approx. 2 x 2 m large solar irradiation surface, with which heat-trapping technology could be used to achieve over 250 degrees Celsius. Inlet temperatures of 200 degrees Celsius enable 125 watts of power with a lower required flow rate of the thermal exchange media. Despite the high energy density, the efficiency is only 3.7%.
  • thermoelectrics (3) with higher values of the figure of merit and corresponding effects. This was achieved by modifying the thermoelectrics (3) of the basic bismuth / antimontelluride / selenide variants, to which other metal and semimetal components were added in such proportions and changed doping, that thermoelectric multiphase alloys were formed, which are the result of disordered and disordered grain boundaries between many matrix crystallites with some electrically highly conductive transition phases in these grain boundary areas.
  • thermoelectric multiphase alloys were formed, which are the result of disordered and disordered grain boundaries between many matrix crystallites with some electrically highly conductive transition phases in these grain boundary areas.
  • thermo-electric arrangements with thermo-limbs (7) which are composed of a central, foamed passive leg part (4) with 2 terminal active leg parts (2).
  • the foamed passive leg parts (4) are specified foamed structures that, starting from natural carbon matrix (charcoal) or from cold-start coked, organic compounds, obtained through metal foaming up to electrically conductive plastic foam structures - with varied contact types described below terminal active leg parts (2).
  • foamed passive leg parts (4) allow the omission of a real technologically controllable foaming process and are therefore an enormous inexpensive, inventive basic element in itself, which can also be advantageously combined with functional elements of the thermoelectric arrangements.
  • Such carbon frameworks in stucco or as physical compression of the granulate / powder allow the varant-rich, final active leg contact to highly efficient vapor phase transport thin-layer technology on their surface.
  • the final applied, active thermal parts (2) are alternating from the p- and n- Conductivity type and form thermoelectromechanically active p / n and n / p transitions directly against one another or via intermediate contacts.
  • voltage-adding, electrically arranged in series and thermally parallel thermoelectric elements (6) to form flat modules that can be used as Seebeck or Peltier blocks made of suitable materials based on the powder-metallurgical model proposed.
  • passive leg parts primarily represent closed-cell, metallic and non-metallic foam structures. These are therefore referred to in the simplest form as foamed passive leg parts (4).
  • foamed passive leg parts (4) Various foam processes for non-metallic foams (31) allow a varied, adaptable palette for the design of thermal legs (7) and special conductive lacquers allow the formation of dense active leg parts (2) and passive leg parts with differentiated foam structures and, consequently, different names.
  • Foam-structured thermo-limbs (7) with a differentiated structure of the foam structure allow new types of thermoelectric arrangements which are described and described below in their structure.
  • thermo-limbs (7) Proposals for the design of thermo-limbs (7) with a foam structure component for efficiency-reducing heat loss.
  • Metallic foams (10) offer the possibility of producing thermo legs (7) with a foam structure component.
  • the laboratory-scale production of foamed aluminum was first achieved in a space staton and then also under normal gravity conditions.
  • the production of metallic foams (10) permits the processing of thermoelectroactive metals. Their thermo-octave degree of goodness (figure of merit) is decisively improved because the throughput of heat losses (8) actually fails.
  • thermoelectrics (3) have different suitabilities for the production of continuously foamed thermo-limbs (11) or composite thermo-limbs (12) or integrated active-passive thermo-limbs (14), which are defined below in terms of the method and the device (see claims 1 and 2).
  • Continuously foamed thermal leg (11) (claim 4. Figure 1)
  • thermo legs (7) with a foam structure component, from which the more demanding forms of the integrated active-passive thermal legs (14) with differentiated foam structures are derived (see claim 8) and to which they can be added in part or in full, depending on suitability and cost of the thermoelectric material (3) which has already been foamed in the same cell size.
  • the costs are reduced in the typical method for integrated active-passive thermo-limbs (14) with inductive and dielectric working components and a foamer (33) (see claim 8).
  • thermoelectroactive zones consist of metallic foams (10) or structures obtained by sintering pre-inflated, electrically conductive particles with surface-encrusted thermoelectrics (3) or sufficiently porous coal framework structures, with or without oxidized carbonized celluloses, sugar or proteins, with previously distributed, afterwards zonally fixed, inner, thermoelectroactive grain sizes (17) form thermoelectroactive zones (34).
  • thermoelectrics (3) When the surface of the cut foam surface is properly contacted with other thermoelectrics (3), the temperature differences between separate, thermally parallel contact points additively increase Thermo-EMK developed
  • the geometric shape comes from a suitable vertical cut, which in this type and composition is simply foamed - at most subsequently, superficially, density-modified foam structure surfaces (Ansintem metallic foams with flame arc or laser under protective gas)
  • open-pore modular toothing profiles on the surface (claim 14 , 4, FIG. 3b) are cut out mechanically or with a laser, which are then gently pore-smeared with indifferent conductive lacquer (18), and with the interposition of an indifferent metal foil ( 38) are pushed into one another.
  • the oxidant cold start coking (36) uses a propellant-like burn-off of organic substances, the admixed oxygen supplier of which leaves no salts and which, in reduced admixture, only allows partial oxidation of the batch mixture to the effect that a degassed carbon scaffold remains. Since this is possible out of the "cold phase", for example by glow wire or stoppinundundi ⁇ g, the inventive name oxidant cold start coking (36) is chosen.
  • the non-metallic foam (31) obtained by means of oxidative cold start carbonization (36) or thermal carbonization, because of its structure
  • the possibility of component-differentiated training is a kind of foam-structured carbon skeleton, with the possibility of forming conductivity-optimized intermediate areas (35) and electrothermally active end zones (34). It can also be added to thermoelectric arrangements of Seebeck or Peltier blocks by cementing profile contacting (39) or thermal guide profile contacting (40) (See claims 4 and 14, FIG.
  • thermoelectric modules (1) there is also the possibility of building up a mosaic of large carbon skeleton blocks by means of joint coaling (41), in which coal structure segments (42) are joined with suitable carbonizable glues and an in ductile resistance heating or other suitable thermal input in the joints of the assembled structural segments (42) converts the glue-filled joint into a connecting intermediate carbon structure layer (43).
  • suitable carbonizable glues and an in ductile resistance heating or other suitable thermal input in the joints of the assembled structural segments (42) converts the glue-filled joint into a connecting intermediate carbon structure layer (43).
  • current-carrying carbon fibers in the glue-pressed joints can gently effect thermal dissociation through localized resistance heating to form the intermediate carbon structure layer (43).
  • a partial or continuous cementing with indifferent conductive varnish (18) The strengths of the carbon skeleton dressings required for thermoelectric modules (1) can be adequately varied, depending on the starting materials and professional action, to cement hard and hard.
  • thermoelectric module (1) In the single rod version with metallic (10) and non-metallic foams (31), contacting bridge sink electrodes (13) convey the thermal current (5) through the entire series connection of the thermoelectric module (1). They can be seen in the end face-contacted, charge carrier-collecting, thermoelectrically indifferent collector hoods (15), which in this way implement the p / n and n / p transitions of the continuously foamed thermal legs (11) (see claims 4 and 5 in FIG. 1).
  • the indifferent collector hood (15) is primarily a suitably "comprehensively shaped” application hardened, non-positively cemented in the pores, indifferent conductive varnish (18), which is thermally and electrically highly conductive and electrically / thermally further contacting, connections for the preceding and subsequent ones End faces of continuously foamed thermo-legs (11) permitted.
  • indifferent conductive varnish (18) is thermally and electrically highly conductive and electrically / thermally further contacting, connections for the preceding and subsequent ones End faces of continuously foamed thermo-legs (11) permitted.
  • bridge electrodes (13) FIG.
  • collector hood can be internally armored in accordance with the design with outstanding thermally-inserting hot-cold conduction devices (21) (see claims 4 and 5 in FIG. 1).
  • thermo-legs They are the middle to predominant part of thermo-legs (7) with the function of a substantial improvement in the efficiency of the entire thermoelectric arrangement as a block of Seebeck or Pelter elements.
  • You contact the final active leg parts (2) They consist of thermoelectric, indifferent, primarily foamed, metallic and non-metallic material components with high electrical conductivity, in the form of metallic (10) or non-detailed foam (31), whereby a final density differentiation of the primarily closed foam structure is available
  • the optimized foam structure of the foamed passive leg parts (4) provides a heat resistance value that is several times higher, with significantly less loss of electrical permeability and thus the ability to drastically reduce the heat losses (8).
  • Assembled thermo-limbs (12) (see claim 7. FIG.
  • thermoelectrics (3) consist of so-called, two end active leg parts (2) which contact a central, foamed passive leg part (4).
  • the foamed, at the same time thermoelectrically, indifferent passive leg part (4) has the task of minimizing heat loss heat transfer, while maintaining the highest possible electrical conductivity. So it develops no or only very little of its own thermoelectric voltages.
  • existing active leg parts (2) form n / p and p / n transitions with one another with the task of developing thermal currents (5) when exposed to temperature gradients suitably applied to them. They are as intervals or thin slices of natural or synthesized thermoelectrics (3), e.g. B.
  • Integrated active-passive thermo-limbs (14) result in density (23) and component-differentiated foaming (27) (claim 8, FIGS. 3b and 4)
  • thermoelectric applications long recognized, because of their high thermal conductivity only partially suitable, therefore disregarded metals, can be used by the metal foam according to the inventive and procedural proposals as interesting and effective thermoelectrics (3) again. They are foamed in a suitably thick layer in such a way that in the end area in front of the two opposite surfaces of the formed layer of metallic foam (10) they pass into a substantially denser to foam-free state, which can be soldered, welded (also with ultrasound) or mechanical frictional contact. The denser structures close to the surface enable (see claim 14, claim feature contact anchor claw (22)).
  • the density-differentiated foaming (23) of metals and non-metals is the result of a regime for microwave and induction alternating fields, the proportionate dielectric heating of non-conductive or resistance heating components in conductive cause the still dense green runs.
  • a supplementary barometric and acoustic auxiliary regime may trigger the triggering and intermediate stabilization of the rising foam in the ready-to-blow, ready-to-hold phases.
  • the components of the control regimes and their mechanisms of action are named and explained. With the same or modified technical apparatus, a reformation that is still in the hot phase is carried out because the foam structure cell walls can still be polarized active phases (see claim 15).
  • integrated active-passive thermo-limbs (14) that can be obtained from metallic foams (10) are characterized by 100% material content of thermoelectric material (3) - apart from drinking water deposits in open-pore penetration areas of cut contacting surfaces - predominantly as metal, which with a densifying closed-cell structure of the metallic foam (10) into a fine-pored, near-surface, denser until ductile phase under the The final cover areas are transferred to this.
  • thermoelectrics (3) in the series production of thermoelectric modules (1).
  • thermo-limbs (11) The terminal top surfaces are contacted with the aforementioned electrical / mechanical cementing connection methods in a manner analogous to that of continuously foamed thermo-limbs (11) by means of indifferent collector hoods (15), conductive lacquer-bonded bridge electrodes (13) to p / n and n p transitions and with analog heat Cold guide devices (21) (see claim 5 derived from designs in Figures 1 and 3).
  • indifferent collector hoods 15
  • conductive lacquer-bonded bridge electrodes (13) to p / n and n p transitions and with analog heat Cold guide devices (21) (see claim 5 derived from designs in Figures 1 and 3).
  • analog heat Cold guide devices (21) see claim 5 derived from designs in Figures 1 and 3.
  • integrated active-passive thermo-limbs (14) straight or curved or angled shapes are claimed, as in the above-mentioned embodiments (see claim 7).
  • An advantageously applicable contact into which the dense foam upper structures penetrate, non-positive and solderable contacting is that with pre-tinned contact anchor claws (22) in the case of metal-foamed integrated active-passive thermal limbs (14) (see claim 14, FIG. 4).
  • the contact anchor claws (22) can also To be coated with a layer of titanium / silver / palladium that is indifferent in all respects.
  • non-metallic foams (31) capillary penetrating, later hardening inductive conductive lacquer (18) takes over the role of tin.
  • the foam structure surface with the contact anchor claw (22) is pre-pierced, wetted and then permanently clawed.
  • thermoelectric strands (28) (claims 13, 23, 27, FIG. 5)
  • thermoelectroactive metal pairings which can be realized within the framework of controllable, technical push-through methods.
  • thermoelectrics (3) a dimensionally stabilized, dense strand of previously primarily ultrasonically welded, cemented, glued or pressure-contacted, prismatic or suitable cross sections of intervals of successive, metallic - or other suitable for this process - thermoelectrics (3) is pushed through suitable medium to high-frequency induction fields, which are of a high intensity - and frequency-regulating regime for induction-melt-foam hood, dielectric heating, pressure surrounding protective gas atmospheres and frequency shaking by at For example, mechanically guided sound frequencies from alternating current-applied, vibrating plungers in annular gaps are subject to strong permanent magnets.
  • the strand to be pushed through composed of the intervals of the thermoelectrics to be paired (3), under reckoning and diameter increase, finally, a continuous, gradually adjustable, density-differentiated foaming in such a way that optimal p / n and n / p transitions and their simultaneous connection in series result.
  • the extruded green sheet intervals for extrusion-linkable thermocouples (7) are applied according to the three-layer method, the strand to be foamed has the advantage of component-differentiated foaming (27) with conductance-optimized intermediate area (35) and thermoelectroactive end zones (34) (claims 13, 11 , Figure 5).
  • the thermal entry for the p / n and n / p transitions of the strand-like arrangement is carried out by intermediate contacts tating, completely in the foam composite, fine-pored to dense, thermally electrically highly conductive, but indifferent zones, the strands laterally outwards - each offset by 180 degrees - in widening and extended warm-cold guiding devices (21) with Teflon coating (see claim 13, Figure 5).
  • a purely thermally transmitting ring contact is shown for the thermal contacting of the indifferent zone, which mutually continues outward into the outer thermally inputting surface areas of the warm-cold conduction device (21) constructed in this way.
  • thermoelectric strand 228
  • the alternating arrangement carried out in this way can offer temperatures tap, convert in the thermocouple transitions to electrical power and offer at the strand ends of the so-called thermoelectric strand (28) over already noteworthy working voltages down to the ten-volt range.
  • adaptable cuts and flat series connections of any working voltages can be realized, which are possible with Py ⁇ t / Chalkopy ⁇ t -Thermal pairs or galena-homojunctions with a few thermoelectric strands (28) reach the voltage values of car batteries.
  • thermoelectric strands (claim 13 derived from Figure 5) They are basically the same in structure, but allow the replacement of various thermal legs (7) with and without a foam structure portion. They present a veritable modular system that can always be repacked and then pressure-contacted within a tube without interference.
  • the indifferent, the p / n and n / p transitions between contacting, strangi ⁇ ner surfaces of the warm-cold guide devices (21) are provided on both sides with thin layers of conductive rubber (37) or suitably designed, elastic, indifferent metal foils (38) , which give the axial pressure contact a taut resilient permanent component. Surface contacting of large cells. metallic foam (10 ⁇ with impregnating alloy and contact anchor claws (claim 14 Figure 4)
  • thermoelectrically indifferent Zmnbleilot or other easily flowing, thermoelectrically indifferent soft solder can be introduced capillary into the flat-cut, open-pore cover surfaces of the finished cut blanks Blanks are accordingly already to be regarded as continuously foamed thermal legs (11), the ends of which only have to be made ductile and thus capable of contact by capillary tin solder receptacle.
  • the thermal current (5) is carried on in addition to the types of contacting already mentioned and claimed, on the underside, non-positively into the tin-offset, end-flat foam structure three-dimensional or multi-dimensional penetrating, suitably shaped, pre-tinned contact anchor claws (22) which pass into a further strong wire suitable conductor material (mostly copper), which in conductive varnish a indifferent (15) or thermoelectroactive collector hoods (19) to be molded.
  • a touch of silver, at least a gloss tinning is advantageous, since bare copper can develop all kinds of creeping signs of corrosion.
  • the wafer-thin silver coating is ideal - but must be protected from air containing hydrogen sulfide before the conductive varnish bedding.
  • thermo-limbs (11) made of metallic (10) and non-metallic foams (31).
  • the Gülcher thermo column consumed 170 liters of illuminating gas per hour with an - albeit very reliable - continuous output of the 66 compact elements made of nickel / antimony alloy thermocouples of 12 watts at 4 volt working voltage.
  • the connection in series resulted in a continuous short-circuit current of 6 amperes
  • the device was able to noticeably heat up rooms, while electrical power requires a much smaller cross-section in the same way in order to be able to pass without loss.
  • excellent framework conditions remain for the thermoelectric use of the metallic foams (10).
  • the following, long-proven metal pairings with the following thermal voltages (in millivolts) per 100 degrees Celsius temperature difference appear promising for the proposed embodiments of novel thermo-limbs (7) with a high percentage of foam structure:
  • thermoelectric modules (1) As a result of the thermoelectric modules (1) to be produced, the lengths of these continuously foamed thermal legs (11) can be selected to be significantly shorter (gain in electrical conductivity of the thermoelectric module) and thermal offers can be converted into electrical work with a high degree of efficiency.
  • the contacting of the ends of the integrated active-passive thermal limbs (1) or of the other proposed variants with a metal foam structure component to form p / n and n / p transitions that generate thermostream can be carried out using the above-mentioned and all well-developed, conventional methods.
  • thermoelectrics (3) Electrical properties of ore grown, hydrothermally crystallized.
  • natural compound semiconductors with regard to their use as thermo-electroactive grain sizes (171 as well as the intermetallic compounds and synthetic, semi-purifying elements and compounds These offer a huge selection of thermoelectrics (3) with far higher differential thermal forces.
  • Metals have the highest concentrations of free electrons 10 22 / cm 3 , but this is hardly temperature-dependent. There is little change in the amount of energy and speed of the electrons. Now, however, different energy, speed and concentration of the two charge carrier types - electrons and holes - are a strongly temperature-dependent characteristic of semiconducting compounds, which enable them far better than metals to form a potential between cold and hot contact points of the thermocouples made from them (see Figure 3a).
  • pyrite lumps with an effective charge carrier concentration of more than 10 ⁇ and a mobility of 200 cm 2 / Vs or lumps of chalcopyrite or those made of galena (higher values) differentiate a strong, semiconductor-typical increase in their conductivities when heated. This is evidenced by the simple attempt to connect the shiny ore lumps (compound semiconductors) in series with a 12 volt car battery, a headlight bulb and some wire.
  • the headlamp bulb suddenly burns brightly when the current conductivity zone of the ore-grown compound semiconductor has undergone a temperature rise of approx. 30 to 40 degrees Celsuis.
  • the different degrees of heating were used for the measurement of the thermal voltage.
  • the same experiment with a regular, cubic single crystal made of pyrite initially produces a bright beam of the tungsten filament, as is already possible with irregular chunks of chalcopyrite or arsenopyrite. It follows from this that disks made of this cubic single crystal are best suited for discrete active leg parts (2), since each direction in the crystal provides excellent conductivity and thus equally high thermal EMF. A warming of the through-grown octahedral chunks then results in significantly higher conductance values.
  • thermo-limbs (7) The simple test execution in summary clearly proves the long-known, semiconducting character of mineable orifices, glosses and gravel and thus their suitability for the extremely inexpensive manufacture of thermo-limbs (7), but better the foam structure part according to the invention.
  • the inexpensive pyrite - as well as many other electrically semiconducting crystal structures that can be mined - can be used at comparatively low cost (compared to expensive synthetic thermoelectrics, such as bismuth tellurides) for the production of thermoelectric current.
  • thermoelectrics such as bismuth tellurides
  • thermoelectric modules (1) "out of the mountain", whereby many thin disks from a crystal produce exactly half as many thermoelectric individual elements - with considerably lower internal resistance and significantly flatter size - than the use of whole crystals allows. Even razor-thin layers are equally effective for the development of thermal EMF.
  • the grains and dust of the ore-grown compound semiconductors which arise during the chipping of the ores can in turn be used in conductive lacquer embeddings for the production of thermoelectroactive collector hoods (19) or for the formation of thermoelectroactive end zones (34) (claims 4 and 6)
  • thermoelectro-active grain sizes (17) are given a field-like thermal effect by these fields in the resin-sensitive phases of paint base components Preferred direction in the later hardening composite (e.g. a thermoelectro-active conductive varnish (16)). Ion cleaning is also possible with Py ⁇ tk ⁇ stall structures (see claim 15) causes of thermal stress on pyrite and galena
  • thermo-voltage-forming components occur on the electron diffusion component or volume component, contact potential and phonon drag component.
  • the latter relates to an interaction between electrons and phonons, in which phonons move from the warmer to the colder end Taking electrons along. This component only plays a part in the low temperature range.
  • thermocouple (7) with a temperature gradient gets a much higher electron diffusion portion (electron pressure) at its hot end and the two differently tempered contact points of two such thermocouples (7) form a different, temperature-dependent contact potential at their differently tempered contact points sufficient thermal currents can flow, a sufficiently dimensioned, as thin as possible transition surface and a still sufficient charge carrier concentration in this thermoelectric element (3) formed into the layer is necessary.
  • conductive varnish-bonded pyrite and chalcopyrite disks on plane-cut metal foam surfaces give the best solution for high, loss-minimized, thermoelectric conversion
  • thermoelectric modules For the highest developable thermal EMF, the use of the combination of a hole semiconductor with an electron semiconductor is to be provided.
  • temperature resistance For permanent stress in thermoelectric modules (1) temperature resistance, a certain weathering resistance and anticorrosive behavior to contact materials are to be rated.
  • thermocouples made of pyrite and chalcopoly discs and layers For air-exposed thermocouples made of pyrite and chalcopoly discs and layers, a varnish coating is sufficient.
  • a self-conductive foam structure e.g. B. made of polyacetylene or in a conductive with conductivity (20) made conductive
  • a conductive with conductivity (20) made conductive is technically possible.
  • the entirety of the differently selectable conductivity mediators (20) results in the through-contact active phase (26) anchored in the cell walls of the foam structure, to which the latter can be added if this is electrically intrinsically conductive.
  • Doped polyacetylene shows metallic conductivity with a relative conductance as metals have.
  • a similarly slow-linkable one-dimensional conductor is polysulfurite with metallic conductivities from 1/10 ⁇ 6 to 1/10 ⁇ 7 x Ohmcm.
  • the pure form of the composition (SN) X obtains the highest conductance by bromine doping and has the composition (SNBr 0 4) x (see claim 17)
  • thermoelectroactive conductive lacquer (16) contains suitable grain sizes or / and additionally reinforcing (possibly nozzle-compatible) fiber components from conductivity mediators (20) in suitable proportions.
  • suitable grain sizes or / and additionally reinforcing (possibly nozzle-compatible) fiber components from conductivity mediators (20) in suitable proportions.
  • thermoelectroactive end zones (34) or collector hoods (9) always appears to be interesting. It forms itself out of pure tin metal through the so-called tin plague, but still has a high metallic conductivity in addition to self-developed thermal EMF.
  • the self-producing, thermoelectroactive grain size (17) (Ba ⁇ dlucke 0.1 eV) occurs simultaneously as an efficient conductivity mediator (20) with a specific electrical resistance of one ten thousandth of an ohm / cm in conductive varnishes or cell wall structures of non-metallic foams (31) (see claim 3).
  • the conductivity-imparting, medium-resistance sulfides of copper and silver occupy a middle position, of which Ag2S is a mixed electron conductor.
  • Lithium nitride L13N has a high ion conductivity at room temperature and is therefore, from an application point of view, a component of the through-contacting active phase and within a hermetic paint base compound. 26) of interest. Density or foam structures had to be completely sealed against water, otherwise the reaction to ammonia and alkali would be totally resistant. Titanium nitride or lithium-doped titanium disulfide (see claims 3 and 17). All of these compounds are suitable in a hardened / solidified, dense or foamed lacquer base component to impart conductivity to be.
  • the conductive lacquer base component which is also possible on a different chemical basis (up to hm too electrically self-conductive, for example based on polyacetylene, is offered for processing with compressed propellant in stock sprays according to the invention (see claim 16).
  • the lacquer base component which forms the self-adhesive composite after foaming, indifferent foam conductive lacquer (24 ) or thermoelectroactive conductive foam (25) can be non-conductive, but it should be better because of higher thermal current densities (polyacetylene), the non-conductive base component then having to be supplemented with conductivity mediators (20) to form a through-contacting active phase (26), while the self-conductive with these can be supplemented (see claim 17), thermoelectric potential transfer to the through-contact active phase (26) and their types of charge carrier transport (claims 3 to 9)
  • thermoelectroactive foam structure requires highly effective, thermoelectroactive grain sizes (17) and good "particle contacting" of all grain size components, including the through-contacting active phase (26), if it is to be cut, continuously foamed thermal legs (11) that give off higher electrical power densities.
  • thermoelectric end 34 the physical thermoelectroactive grain sizes (17) in turn take on a considerable part of the charge carrier transport. With their Thermo-EMF they accelerate this additionally. This increases the density of the thermal current (5).
  • conductivity mediators (20) are scattered in a surrounding, contacting manner. In the direction of the intermediate area (35) with optimized conductance, they take over the entire charge carrier transport, unless the material cell wall structure is involved in the transport.
  • thermoelectric modules (1) If this should become particularly solid, the active phases that hardly contribute to strength must not exceed a percentage share of the overall structure. Nonetheless, insulation panels, such as Styrodur, which are subject to greater use by users, can be replaced in shells of large-scale building shells by extensively thermoelectrically converting, but more strongly statically stressable surface units of thermoelectric modules (1). If foam structures that are to be heavily used only allow a reduced conductivity or so-called foam-stretching, through-contacting active phase (26), then extensive changes are made over the long night. As a result- a higher internal resistance of such thermoelectric modules (1) does not reduce their efficiency in the case of a longer conversion period.
  • Your "more extensive” line mechanisms are purely metallic and / or metallic ones with semiconducting or still involved ion lines with regard to directly touching particles of the conductivity mediators (20).
  • thermoelectric module (1) 0.1 micrometer are to be overcome between the metal particles present in chains and bushes.
  • the persistence, as well as the fat foam temperatures, can be adjusted by reducing borax-alkali-soda (sodium carbonate) in front of potash (potassium carbonate).
  • the silicons are the easiest to tunnel through sodium silicate layers. "The more" waterglass-like ", however, the supporting structure-forming component has to be, the more it has to be the load-bearing foam structure is hermetically sealed and surrounded by a sealing layer. The same should and can partially or completely make up the load-bearing shell structure of the entire thermoelectric module (1).
  • a general improvement in the active phases, even in glass bandages, allows methods of accompanying, sometimes also subsequent formation (see claim 15 ).
  • the following is a proportionally variable / supplementable, electrically highly conductive silicate composite structure which is suitable for the construction of the thermal legs (7) according to the invention with a high proportion of foam structure: conductive silver / conductive copper
  • Higher borosilicate components improve bismuth oxide 4.6 borosilicate strength, lower conductivity, Rosin 8.3 glass powder 2.7
  • Silver can be substituted by copper, nickel, aluminum turpentine 30.0 and non-metallic conductivity mediators (20).
  • a silver component of dusty copper dust or other suitable processes an extremely thin, anti-corrosive silver coating results on the copper metal particles, with the result of a permanent increase in the conductance value, which is based more on the exclusion of the formation of impairing CU2O or other transition layers.
  • thermoelectroactive grain sizes (17) from the intermediate transporting, through-contacting active phase (26) takes place via the same line mechanisms as within the through-contacting active phase (26) itself.
  • the common term for the entirety and effect of the thermoelectroactive grain sizes (17) located in the thermal legs (7) is the thermoelectroactive active phase (30) (see claim 3).
  • conductivity mediators (20) that also have thermoelectroactive potentials develop certain partners, but remain indifferent to others. In view of this, conductivity-imparting particles must be checked professionally so that no randomly occurring opposite potentials inhibit the development of the actual thermal EMF.
  • halving chalcogenide glasses with binary, temperature, quaternary thermoelectric systems made of S, Se, T ⁇ , As and Cd, Zn, Fe, Bi, Ti, Cu, Ag and such take an important position with regard to non-metallic, thermoelectroactive sealing and foam composites the base of some transition metal oxides - such as. B. CU2O and
  • thermo-electroactive active phase (30) in all thermal legs (7) proposed according to the invention, since only one material-specific voltage pulse of nx (5 to 50) volts is sufficient to immediately generate a low-resistance thermoelectric element (3) from the amorphous foam glass phase of a z. B to make continuously foamed thermo leg (7) (see claim 4).
  • This option allows the user to wait for high temperature gradients for thermoelectrical conversion after previous storage intervals and to deliver high power output to operator networks.
  • thermoelectro-active grain sizes For glass phase fixation contacting possibly sensitive thermoelectro-active grain sizes (17), these must survive the melt-phase embedding and contacting process without impairment. The lowest temperature ranges should therefore be selected.
  • a conductivity-improving formation of the through-contacting active phase (26), in which the thermoelectroactive grain sizes (26) are significantly involved is proposed (see claims 15, 18).
  • the glass- or fat-containing, indifferent conductive varnishes (18), thermoelectroactive conductive varnishes (16), indifferent foam conductive varnishes (24) and thermoelectroactive foam conductive varnishes (25) cool from the hot phase under the influence of electric fields and / or directly applied electrical potentials, may be exposed to the influence of certain sound frequencies.
  • temperature maintenance ranges may have to be completed, but the foam structures obtained must not be endangered. Sufficiently high conductivity values that can be achieved without formation are of course not necessary. Glassy, electrically conductive foam structures are made from.
  • Glass powder (glass fruit), mostly made of lead boron silicate
  • thermoelectric modules (1) exposed to solar temperature do not have to meet the strict tolerance ranges comparatively, such as electronic, filigree hybrid coatings on ceramic bases, the melt melting temperatures can be made selectively lower by graduated additions of alkali silicate, which reduces the choice of foaming agents, the controllability of the Foaming, as well as trap tunneling and beginning ion conduction of the through-contacting active phase (26) anchored in the glass phase up to their self-improvement when driving through higher working temperature ranges (see claim 18).
  • thermoelectroactive composites growth formation (46) of at least dense glass phase-fixed, large-sized, thermoelectroactive composites is possible if thin films to be drawn from the liquid retention phase with anisotropic thermoelectroactive grain sizes (17) seconds before their solidification on a low-temperature large volume, by a strong electric field penetrating the viscous glass film are polarized in the thermoelectrical preferred direction.
  • the foamer (33) can be a salt which gasses in the suitable temperature range without residues or organic matter - possibly with a defined carbon residue.
  • the remaining one, in the Carbon scaffold component integrating the foam structure can act as an additional conductivity mediator (20) and further reduce the internal resistance of the thermoelectric series connection (see claim 4).
  • thermoelectroactive grain sizes (17) must be selected in accordance with the foam foam temperatures.
  • the incipient tempering temperature ranges of natural or synthetic compound semiconductors that attack the lattice grid must be taken into account. Pyrite reorientates itself from 400 degrees Celsius, and up to 550 degrees Celsius there are fundamental changes in the temperature of the barn. It disproportionates in pyrrothin and sulfur above 550 degrees Celsius (see vapor phase transport in claim 15).
  • thermoelectrics (3) There are still hundreds of Pyntknstall structures of the same lattice constants that are suitable as thermoelectrics (3), with some of the elements involved, some of which have even higher temperature resistances, which are sufficiently anticorrosive when hot foaming of fats on boron-lead silicate base layer and do not blunt as regards their thermal forces true chemical binding partners for silicate binary, ternary and quatrenar complexes, the binding partners mentioned below also sometimes occur in bisecting glasses (claim 15). With FeS2 as
  • thermocouples thermocouples and with each other, with various suitability to be found for embedding in a glass phase.
  • thermoelectrics (3) that in all thermal and foam processes during the course of the process, the structure and surface contactability of the thermoelectric-active grain sizes (17) can only be impaired above the hot foam temperature level, so that they do not affect the development of the thermo-EMF To master the technological regime, however, there are overarching empirical values from the results of the baking technologies of the resistance paste systems for thick-film resistors, guideway thick-layer paste systems and conductive adhesives.
  • Temperatures can be stored in a compound, such as the cadmium selenide, which results in crimson cover enamel - at least 700 - 800 degrees Celsius ius baking temperature
  • thermoelectroactive foam conductive varnishes 25
  • conductivity mediators (20) and thermoelectroactive grain sizes (17) are only homogeneously localized and contacted in the pore walls of the closed foam structure at temperatures above 350 degrees Celsius (see claim 18) get cut.
  • epoxy resins can be foamed, which have been used for decades as a dense conductive adhesive in electronics with a through-contact active phase (26) made of nickel powder or silver powder.
  • Titanium nitride is an inexpensive to produce, golden-yellow to bronze-colored conductivity mediator (20) with considerable electrical conductivity and the highest chemical resistance (see claim 3). It can be used as a dominating, through-contacting active phase (26) in basic lacquer components, thermosets, thermoplastics, epoxies and feathers, in fact starting from normal temperature ranges up to hot temperature ranges (up to 800 degrees Celsius) are used equally.
  • the condition is the absence of long acting superheated steam or free caustic alkalis during hot setting or blowing processes.
  • the component-differentiated foam (27) (claim 11)
  • the most economical method for the consumption of Thermoelektnka (3), with a possible increase in electrical conductivity, is that of jointly foaming near-surface zones of predominant, thermoelectroactive grain sizes (17) with the exclusive participation of the conductivity mediators (18) in the rest, in particular the middle, of the layer thickness (see claim 11)
  • corresponding paste or dough-like consistencies with different active phase components are applied in layers and foamed together.
  • the result is a continuous, closed-cell composite with a thermoelectroactive active phase (30), which is primarily on the top and bottom sides.
  • Specially modified conductive adhesives, conductance-optimized resistance paste systems or conductive thick-film paste are suitable for this purpose.
  • Component-differentiated foaming (27) with density-differentiated foaming ( 23) to unite all claims features and applications see claims 4, 8, 11, 12, 13)
  • thermoactive transitions 13
  • dense p- or n-type thermoelectroactive conductive coatings (16) are used. applied to the transition surfaces in a suitable layer thickness and then pressed together until hardening.
  • intermetallic thermoelectroactive grain sizes 17.
  • the most striking property of intermetallic compounds is the brittleness, which conflicts with their other technical use.Therefore, in the cintical, especially Grimm - Sommerfeldian phases responsible for thermoelectrics (3), there are only a few cuts for discrete active leg parts without Risk of breakage (CNSb).
  • thermoelectroactive active phase (30)
  • the consistently metallic electrical conductance entitles the user to build up foam-stretched, thermoelectroactive active phases (30) that hardly need to be conductively used with through-contact active phases (26).
  • Suitable thermoelectroactive grain sizes (17) of available intermetallic compounds with a suitable number and mobility of charge carriers are - besides not mentioned here - cadmium antmonide CdSb (400 microvolts / degree Kelvin), magnesium stannide Mg Sn (270
  • Thermoelectro-active grain sizes (17) are mixed with indifferent conductive lacquer components in mixing drums, where wetting takes place to a paste-like consistency. Air-hardening pastes, thermoelectroactive pastes can be filled and stored. It corresponds to the past events and facts that the worldwide histonsch ⁇ and current lead extraction is largely from galena (lead gloss) (e), the automotive lead batteries are currently accumulating nationwide, but for an installed, thermoelectric power of 1 KW not even 10 kg of "lead ore" are required.
  • the chemically pure accumulator lead with sulfur is suitable for the large-scale, hydrothermal direct synthesis of galena (lead sulfide).
  • the brass-gold-shining pyrite was used for a certain time for the production of transistors and appears with sufficient properties interesting for optoelectronic applications. Uncleavable and hard, but can be cut into thin slices in its natural occurrence, it can be used immediately for thermoelectric pairing with the same-processable chalcopyrite or other natural or synthetic thermoelectrics (3).
  • the pyrite itself which is synthetically accessible, requires - like silicon - more complicated, more energy-intensive Crystal growing, which only delivers much smaller crystals.
  • the waste of natural pyrite S0 2 -environmentally polluting rust process for the production of FE2 ⁇ 3
  • the other highly efficient compound semiconductors is no longer justified.
  • the crystalline forms - and of which the cubically crystallizing, isotropic (without thermoelectrical preference) - are preferred for the compound semiconductors that can be selected from ore deposits.
  • Isotropic property means no preference for physical effects).
  • thermovoltage values for non-cubic systems specifying the values for a temperature gradient perpendicular or parallel to the stallographic axis.
  • Galena is also considerably anisotropic and becomes dense or reforming foam structures with suitable fields during the hardening or cooling process, in that the surface-localized dipoles of a galena particle make this a body-absorbing substance Mandatory notify movement component according to the field flooding. It is within the scope of professional action to determine the layer thicknesses of the tough paint or glass phases for sufficient penetration. It can be static high-voltage fields or those that are still superimposed with a low-frequency field component. In the case of ferromagnetic crystals, permanent magnetic fields also do this.
  • pyrite can be statistically aligned by means of a permanent magnetic field over pyrrothin which has arisen in the meantime (see claim 15, vapor phase transport).
  • a permanent magnetic field over pyrrothin which has arisen in the meantime (see claim 15, vapor phase transport).
  • vapor phase transport When crushing, tearing, ultra-fast and hard impact impact or impact mills usually introduce property-destroying lattice defects or triboeffects that have a performance-reducing effect, the finer the grain sizes.
  • lattice defects can in turn increase the electrical conductivity of semiconducting connections.
  • Galena and pyrite are still possible with themselves in homojunction as a highly efficient, thermoelectrical pairing.
  • the type and density of the charge carriers required for thermal currents to be generated can be set between approx. Plus 700 microvolts (defective conductor) and minus 500 microvolts (excess conductor) per degree Kelvin for lead-gloss PbS.
  • a thermal pairing of the two is ideally suited for solar temperature offers and provides a thermal voltage of 120 millivolts even at a temperature gradient of 100 degrees Celsius, which means that a series connection of 100 individual thermoelectric elements already produces open-circuit voltages of 12 volts.
  • the intrinsic conductance is high enough for strong thermal currents, although sufficient contact with the surface, for example with conductive rubber (37) or conductive varnish, is important.
  • the temperatures that can be applied are above the uppermost temperature limit of non-focussing thermal solar technology that does work with heat trap devices.
  • thermoelectrics (3) of the bismuth telluride series which can be permanently loaded up to 60 degrees Celsius, achieve far less (test measurement) than "naturally pure" lead-gloss crystals exposed to the same temperature gradient.
  • the advantage lies in solderability (after pretreatment) and great strength.
  • the cleavage and lower hardness of the lead gloss only allow discrete crystal wafers to be used from a certain size. Pyrite is hard enough. It can also be designed as an excess or defect semiconductor for homojunctions.
  • the natural forms have different, but always sufficient and much higher values of differential thermal power than the best metals used as a thermoelectric (3).
  • thermoelectrics (3) (Claim 9. 15) If the semi-metal selenium in foamed form after completion of temperature maintenance ranges above 72 degrees Celsius is brought into the black, metallic form, there is a highly active thermoelectric with differential thermal forces up to about 700 microvolts per degree Celsius in a range up to almost 200 degrees Celsius.
  • the temperature resistance can be derived from conventional selenium rectifiers.
  • Foamed metallic selenium subsequently brought into hexagonal recrystallized (black) form, has a strength similar to that of foam glass and similar thermal insulation values to rigid polyurethane foam or Styrudor, and in a denser form with a suitable dopant additive at 239 degrees Kelvin, a comparable electrical conductivity of 8 MS / m approximately like the metal chrome (7.8 MS / m).
  • a suitable dopant additive at 239 degrees Kelvin, a comparable electrical conductivity of 8 MS / m approximately like the metal chrome (7.8 MS / m).
  • thermoelectroactive collector hood (19) - beneficial application for active leg parts (2) with semiconducting waste from semiconductor manufacturing and processing industries (6)
  • thermoelectroactive collector hood offers significant opportunities to use different, semiconducting waste grain size classes of the same material in the semiconductor industry. Starting with wastes from the extraction of grown crystals, the production of wafers and their cutting, to wastes from solar cell production or chip production, fractions can be separated and used to produce this type of active leg parts (2) (see claim 6). What has been over-doped for the intermediate or end products of microelectronics, is outside of permissible measurement tolerances or is broken by contamination during further processing, such as the waste of polycrystalline or monocrystalline silicon in solar cell production - all of this is best suited for thermoelectroactive grain sizes (17).
  • the starting triple solar cell production also offers valuable waste rates of gallium indium arsenide, gallium indium arsenophoside, (GalnAs), GalnAsP, indium phosphide (InP), or other compound semiconductors suitable for monolithic tandem solar cell production. What meets or no longer meets photovoltaic requirements - all of this is still mostly suitable for generating thermoelectric potentials.
  • thermoelectroactive grain size (17) in an electrically conductive embedding are inexpensive thermoelectroactive Collector hoods (19) on foamed passive leg parts (4) in a form-fitting manner - can be applied for permanent contact over a wide area.
  • Indifferent conductive varnish (18) serves as an embedding compound for all thermoelectroactive grain sizes, an intrinsically conductive laughter base component being advantageous.
  • thermoelectroactive collector hoods (19) constructed in this way thus functionally become active leg parts (2) which can be cemented on in an electrically conductive manner.
  • active leg parts (2) which can be cemented on in an electrically conductive manner.
  • thermoelectroactive conductive lacquer (16) as previously described.
  • Suitable thermoelectroactive grain sizes (17) are all thermoelectrics (3) which are anticorrosive in the conductive lacquer composite.
  • Many thermoelectrics (3) are suitable for this, since there are hermetic, indifferent conductive varnishes (18) as a starting point. In this way, thermoelectric pairings with very high differential thermal forces can be achieved - from 400 to 200 microvolts per degree Kelvin.
  • thermoelectrics (3) for example between silicon and lead, tellurium, selenium, silicon carbide, platinum, carbon, boron carbide and constantan. Silicon carbide can be modified with doping over a range of 7 powers of ten in terms of its electrical conductivity up to relatively low-resistance values and thus be made suitable for thermoelectric arrangements.
  • Porous penetrating, anchoring, rubber-like forms of thermoelectroactive collector hoods (19) can also be applied in a contacting manner as an active leg part on foamed passive leg parts (4).
  • Active leg parts (2) designed in this way are dense, gradually composites, from softly clinging to hard consistency, of binding composites made from basic lacquer components of previously liquid, crosslinkable polyisocyanates and polyols or when setting trimerizing polyisocyanates.
  • the property of gradual elasticity that can be added to different degrees of foaming makes the PUR lacquer basic component, after being offset with active phase components, for each type of thermal leg (7) proposed according to the invention with a foam structure component as one of the most important.
  • thermoelectric converter units with expanded foam phases with non-intrinsically conductive phases Lacquer base component with consequently lower specific thermal current densities, can nevertheless deliver impressive electrical performance in the high efficiency range.
  • All the aforementioned semiconducting and intermetallic compounds with their approximate, high metallic conductivities, satisfactory to high differential thermal forces can be brought into an electrically conductive, soft-elastic to foam-like, jointing compound, which offers the best processing chances for large-area thermoelectric modules (1) in shells of building shells owns.
  • the thermoelectroactive conductive lacquers (16) which are necessary for the structural, functional design of each individual thermoelectric element (6), can advantageously be integrated by means of chemically docking normal PUR lacquers.
  • High temperature foaming of magnetite (claim 10)
  • thermoelectric (3) which becomes light in a foamed form and remains highly fireproof. Its use is inexpensive (see claim 10).
  • electrical conductivity 0.005 Ohmcm
  • Fe 3 0 4 is the resulting oxidation and waste product of every annealing treatment of steel and
  • Iron He developed 5.5 millivolts against copper thin layers and over 12 millivolts per 100 degrees Celsius temperature difference against other compound semiconductors. It can be p- and n-doped, with peak values of +12 millivolts and -12 millivolts at a temperature difference of 100 degrees Celsius, i.e. 24 millivolts in a homojunction. Its conductivity is excellent for thermoelectric applications, as is the granite-like fire resistance and weatherability. Thermoelectric pairing with sulfidic, selenidic, arsenidic other compound semiconductors that can be mined as ore is possible.
  • thermo-legs large-sized integrated active-passive thermo-legs (14) or continuously foamed thermo-legs (11).
  • high-strength carbon fibers see claim 10
  • Selenium can be foamed in the amorphous phase and thermally above 72 degrees Celsius at up to 200 degrees Celsius persistent, black, metallic form are permanently formed (see claim 15).
  • the strength of the thermoelectroactive foam structure is achieved with reinforcements made from selenium-offset, semiconducting glass fibers.
  • thermoelectrics heat-insulating, but current-conducting, porous grain sizes, such as hardwood charcoal or coke granules, which are coated with black selenium or other liquefiable thermoelectrics (3) and their previous, pore-penetrating surface incrustation by wetting with the liquid phase in Mixing drums took place and was subsequently converted into the crystallographic metallic form (see claim 4).
  • the incrustation of the thermoelectrics may have been polarized in the preferred thermoelectric direction prior to solidification on the still free particles before their contact sintering (45) - in parallel with the introduction of a ferromagnetic subparticle (44) at one point of the crust.
  • thermoelectric preferred direction and the ferromagnetic subparticle (44) are arranged with respect to one another with simultaneously acting magnetic and electrical field components in such a way that an orientation to be carried out later before contact sintering (45) is only possible with the easier to implement, mostly more penetrating magnetic field component (see claim 15).
  • at least the dense superstructures of thermoelectroactive collector hoods (19) and the like can be produced in such a way that the polarizing fields acting on them only have to penetrate the tough layer thicknesses of the basic sets from a narrow slot nozzle.
  • the emerging, monomeric bands with alternating 90 degree clipping can be layered endlessly to form a voluminous stack, which receives a complete directional characteristic through the piodic flooding of each newly applied layer, which photopolymerizes by immediately following doses of Ulf aviolet or blue light laser beams become.
  • the stack layering the winding of a glass band onto a cooling, elongated roll with periodic photopolymerization can also take place.
  • Metallic foams (10) occupy a large space in the production of the new thermal legs (7) according to the invention, since they have high electrical conductivities and the requirement for technological control of charge carrier transmission between thermoelectroactive (30) and through-contacting active phases ((26) as in Non-metallic foam structures are necessary - they can be made in a matter of seconds and then stored for any length of time. Modern metal foaming is contrasted by the long-established powder metallurgical sintering processes, which may have been considered for suitably structured thermal legs (7).
  • thermoelectroactive surface layer For electrically contacting caking - referred to as contact sintering (45) - of a thermoelectroactive surface layer, however, the pre-expanded particles in mixer drums can first be coated with a thinly viscous paste made of indifferent conductive lacquer (18) and, after drying / curing, again surrounded with a layer of thermoelectrically active conductive lacquer (16) become.
  • Pyrotechnics offers analog, sophisticated processes with processing the same consistencies, where instead of indifferent (18) and thermoelectroactive conductive lacquers (16) similar batch consistencies for black powder bark are built up on stem tablets and spheres. This would be a special form of sintering with thermoactive success and a high K value.
  • thermoelectric modules (1) powder metallurgical processes for pure metals do not lead to the expectation of a high level of thermal insulation in order to be able to build high-performance thermoelectric modules (1) with the relatively low thermal-EMF, and secondly, sintering, due to its grain boundary defects, impairs the high metallic conductivity, which is intended to compensate for the increased outlay in series connection . Since the causation of the latter is conducive to an understanding of the nature of thermoelectric mechanisms of action and the insight into the advantages of foam structures which can be introduced alternatively, it will be discussed below.
  • thermoelectrics (3) of the thermoelectric conversion taking place in low-temperature ranges detailed knowledge was obtained for the component milling, pressing and sintering with regard to the continuous design of thermal legs (7) of the bismuth-antimony-lead telluride series according to the prior art (see above), as well as for medium and high temperature Thermoelekt ⁇ ka (3), which are less suitable for non-focusing, thermal solar technology.
  • What are the comparative and positive aspects for foaming? Quite apart from minimal energy expenditure for the short-term foaming, compared to that for the sintering of metals lasting several hours, considerable qualitative differences regarding the achievable structures and their properties can be determined. Strongly porous sintered metals show noticeably increased thermal resistance values compared to homogeneous, dense metallic blocks.
  • the sintered composite still produces too dense, again "collapsed packing densities" of the sintered particles - with only limited thermal insulation, but with emerging disadvantages. They hang together with the cemented, merged boundary surfaces of the sintered particles. These transition zones have become impure - show a decrease in concentration or crystallization of internal metal particles or new substances taken in during the long sintering period. Transition zones can even become barrier layers.
  • Foamed metals on the other hand, have the highest achievable degree of inner surface, or the least use of compact metal for extractable foam volume, with the same purity as the compact metal. Energy and time are negligible compared to sintering.
  • the metallic foams that can be obtained have heat resistance values that are several times higher.
  • the metal walls of the closed structure remain in the short foaming phase of fine, pure metal with correspondingly high electrical conductivities.
  • the foaming which only lasts for up to ten seconds, does not permit any material-changing, unwanted installation processes, current-blocking shifts in concentration, contaminating metal attendants or the introduction of foreign matter (e.g. oxidants and the like). Therefore, metallic foams (10) are a novelty and the best starting point for heat loss reduction in thermal power generation in the Comparison to the heterogeneous structures of porous sintered metals or thermal electronics (3).
  • thermoelectrics (3) which leads to dense structures and is controlled by a complicated technical regime, reaches the highest, hitherto unmatched efficiency ranges thanks to interposed metal foam structures, and the entire regenerative thermoelectric generation of electricity reaches a completely new level.
  • FIG. 1 shows continuously foamed thermal legs (11) with a homogeneous active phase distribution in the form of a thermoelectric pairing of metallic foams made of tin-doped ⁇ -zinc antimonide and bismuth antimony alloy as the thermoelectrics used (3).
  • the thermal limb ends are contacted by indifferent collector hoods (15) and themselves represent a hardening of indifferent conductive lacquer (18) containing the bridge electrodes (13).
  • the most suitable arrangement of the alloys from cheap base metals develops in the solar temperature range approx. 30 millivolts per 100 degrees Celsius Temperature difference with high electrical conductivity.
  • the thermal insertion into the p / n and n / p transitions which form the black, indifferent collector hoods (15) is best carried out by means of incident, recombining solar radiation or otherwise.
  • FIG. 2 shows field-effective straightening processes that have already taken place for the pre-cut particles provided for contact sintering (45) with thermoelectroactive coating.
  • the ferromagnetic subparticles (44) can be seen, the white areas of which have been arranged under the influence of a magnetic field, while an simultaneously acting electrical field component detects the thermoelectroactive grain sizes 17) polarized in the resin-flow phase in the thermoelectrical preferred direction.
  • the upper part of the drawing shows three pre-bended, layered particles in this prepared phase, in mechanically induced positional disorder.
  • the middle part shows the re-alignment of a loosely poured total of these particles only under the influence of a magnetic field due to the directional effect of the ferromagnetic subparticles before the start of sintering.
  • the three upper, now exactly positioned, pre-biased particles and the total of the particles that have been arranged in this way are Thermoelectric preferred direction of the thermoelectroactive grain sizes (17) can be seen, which are then contact sintered (in the case of a field-effective regime below the Curie temperature of the material of the ferromagnetic subparticles (44)
  • FIG. 3a shows assembled thermal legs (12) using cut folding discs as thermoelectric (3) for corresponding active leg parts (2) - for example pyrite FeS2 and chalcopyrite CuFeS2-
  • FIG. 3b shows geometrical installation forms of bridge electrodes (13) and integrated active passive thermal limbs (14) which, according to the graphical representation of the cementing profile contacting (39) or the leading profile contacting (40), can be added as a result of the side-by-side arrangement of the shown series connections of the foamed thermocouples (7), which differ in density and component ) is a thermally absorbing, if necessary efficient thermal storage in the layer of the bridge electrodes (13), but overall warm insulating shell, for example a building shell, which allows gentle thermal compensation to the other side only by developing thermal currents (5).
  • thermoelectrically active end zones (34) are bonded with the indifferent metal foil (38), which is hatched in parallel hatching, and in this case are not directly contacted, but rather with intermediate contacting bridge electrodes (13). These can also be hardened with a conductive varnish or press-fit with an intermediate layer made of conductive rubber (37), which means a double screwing (not shown here) or anchoring of the possibly thermally storing, voluminous bridge electrodes into the rigid foam-structured connecting segments of the electrical insulation (48 ) was necessary.
  • the graphically illustrated geometric fitting profiles of the bridge electrodes (13) have, for example, copper or aluminum sheet cladding over their metallic or non-metallic foam structures - which are with or without a through-contacting active phase (26) - as mechanically solidifying hot-cold guiding devices (21) - and the whole can the cell volume is mixed with latent storage means,
  • FIG. 4 shows a thermo-electrically contacted, flexible, thermoelectric arrangement with integrated active-passive thermal limbs (14) by means of contact anchor claws (22).
  • the contact anchor claws (22) are, as shown, a type of pliers with claws, which are adjustable in their angular position to the warm-cold guiding devices (21) via the force effect that can be adjusted via the pivot point of the bedding wire (47) that emerges from them Allow variable positions and further arrangements of the thermal legs (7).
  • the bedding wire (47) transports thermal offers from the heat sinks and is therefore like this part of the warm-cold control device (21).
  • thermoelectroactive grain sizes (17) each contain py ⁇ t and chalcopyrite in the electrothermal active end zones (34), which, with good (ore) quality with a 100 degree temperature difference, approx. 60 millivolts per thermoelectric single element (6) provide.
  • bedding wire (47) and contact anchor claws (22) are made of copper, the pierced claw parts of which have a compensating covering made of Cu / Al or tin or titanium-palladium-silver, in order to avoid the copper's own thermal stresses against py ⁇ tk ⁇ stall-like compound semiconductors.
  • FIG. 5 shows a thermoelectric strand (28) made of non-metallic foam (31), which was produced using the push-through method and by means of the differentiated boundary layer foam (29).
  • the features of density-differentiated foaming (23) and component-differentiated foaming (27) are formed for each of the boundary layer-foamed thermal legs (7), which leads to the characteristics for integrated active-passive thermal legs (14) with regard to the individual strand-connected thermal legs (7).
  • Shown is a pressing, only thermal encirclement of the heat-cold guiding device (21) which widens outward into the cooling body or other suitable forms, the annular inner part of which is in a semicircular, peripheral, circumferential groove Boundary layer between the thermal legs (7).
  • the overall arrangement of the warm-cold guide device (21) is kept potential-free, but an intensive, thermal contact to the p / n and n / p transitions is established, which ultimately the central, thermally-electrically inter-contacting, indifferent zone mediated
  • the indifferent zone is formed by indifferent metal foils (38) and conductive rubber (37) of the same size as segments (claim 14).
  • the conductance-optimized, indifferent zone is therefore very dense, contains hardly any pores and is also functionally equivalent to the indifferent metal foils (38) in the cemented profile contacting (39), which optimizes the cross section in certain variants of the thermal guide profile contacting (40) (starting from FIG. 3) can also continue to the outside in suitably shaped warm-cold guiding devices (21).
  • thermoelectric strand (28) thermoelectric strand
  • thermoelectric string (32) pressure contacted thermoelectric string

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

L'invention concerne de nouvelles thermobranches (7) à structure en mousse, de nouveaux systèmes de thermobranches résultants dans des voies thermoélectriques (28) à couche limite expansée et des voies thermoélectriques (32) mises en contact par pression, ainsi que des types de composites courants à thermobranches expansées en continu (11), thermobranches composites (12) et thermobranches actives-passives intégrées (14). Les produits selon l'invention permettent une exploitation plus importante du potentiel thermoélectrique de matériaux semi-conducteurs déjà courants et une utilisation de matériaux semi-conducteurs inutilisables jusqu'à présent comme matériaux thermoélectriques (3) avec un degré d'efficacité thermoélectrique élevé. La proportion totale de structure mousse présente, de manière non homogène, des parties de phases actives homogènes ou différenciées et est généralement capable de minimiser les courants de chaleur de dissipation (8) qui réduisent le degré d'efficacité. L'invention concerne également des procédés connexes de reformage à effet de champ servant à optimiser les phases actives thermoélectriques (30) dans des structures à cellules fermées, en cours de formation ou de durcissement, de mousses non métalliques (31) ou d'assemblages frittés. Les procédés selon l'invention conviennent tout aussi bien à la génération de courant thermoélectrique qu'à la technique de Peltier.
EP00945576A 1999-06-01 2000-05-30 Procede et dispositif pour la realisation de thermobranches a structure en mousse Withdrawn EP1144920A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19925960 1999-06-01
DE19925960A DE19925960A1 (de) 1998-12-04 1999-06-01 Thermoschenkel mit Schaumstrukturanteil
PCT/DE2000/001728 WO2000073712A2 (fr) 1999-06-01 2000-05-30 Procede et dispositif pour la realisation de thermobranches a structure en mousse

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EP1144920A2 true EP1144920A2 (fr) 2001-10-17

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CN114386257B (zh) * 2021-12-28 2025-05-27 南京航空航天大学 强化被动散热型热电腿及其设计方法
CN114315353A (zh) * 2021-12-30 2022-04-12 吉林大学 一种P型(Bi,Sb)2Te3基多孔热电材料的可控制备方法
CN115188877B (zh) * 2022-07-27 2025-01-03 武汉理工大学 一种制备强织构和高热电性能柔性热电薄膜的方法
CN117574677B (zh) * 2023-12-18 2025-08-15 北京理工大学 一种提升粘接强度的结构骨架与胶混合接触胶接工艺方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL8801093A (nl) * 1988-04-27 1989-11-16 Theodorus Bijvoets Thermo-electrische inrichting.
JPH02106079A (ja) * 1988-10-14 1990-04-18 Ckd Corp 電熱変換素子
DE69132779T2 (de) * 1990-04-20 2002-07-11 Matsushita Electric Industrial Co., Ltd. Vakuumisolierter thermoelektrischer Halbleiter und thermoelektrisches Bauelement, das P- und N-Typ thermoelektrische Halbleiter benutzt
JP2862998B2 (ja) * 1990-11-29 1999-03-03 松下電器産業株式会社 電子冷却パネル
JP2936174B2 (ja) * 1990-04-20 1999-08-23 松下電器産業株式会社 電子部品
US5275001A (en) * 1991-10-07 1994-01-04 Matsushita Electric Industrial Co., Ltd. Thermoelectric cooling device
US5834828A (en) * 1993-09-20 1998-11-10 The United States Of America, As Represented By The Secretary Of The Army Nanoporous semiconductor material and fabrication technique for use as thermoelectric elements
JPH08335721A (ja) * 1995-06-08 1996-12-17 Isuzu Motors Ltd ポーラス状熱発電素子の製造方法
US5525162A (en) * 1995-06-26 1996-06-11 The United States Of America As Represented By The Secretary Of The Army Thermal conductivity enhancement technique
JPH0969653A (ja) * 1995-08-31 1997-03-11 Isuzu Motors Ltd 熱電材料及びその製造方法
JPH1041556A (ja) * 1996-07-25 1998-02-13 Mitsubishi Heavy Ind Ltd 多孔質熱電半導体及びその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0073712A3 *

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WO2000073712A2 (fr) 2000-12-07
AU5963000A (en) 2000-12-18

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