DE19925960A1 - Process for structuring thermo-branches with foam structural parts comprises placing layers of indifferent metallic foams or non-metallic foams of sufficient electrical conductivity above and below compact or thin layers of a thermoelectric - Google Patents

Abstract

Process for structuring thermo-branches with foam structural parts comprises placing layers of indifferent metallic foams or non-metallic foams of sufficient electrical conductivity above and below suitably compact or thin layers of a thermoelectric, forming metallic foams and optionally non-metallic foams of a suitable geometry and compactibility for the thermo-branch, and forming foamed or dense, electrically conducting or non-conducting organic compounds partially and completely with a thermoelectric uniform to the thermo-branches.

Description

Area performance and efficiency consistently of dense thermal legs (7) various thermoelectrics (3) according to the prior art

A solar primary supply of approx. 800 watts per square meter is still deprived of approx. 750 watts by the loss of heat flows ( 8 ) and radiating recombination heat of current, commercially available 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. In the meantime, thermoelectric, high specific area performances with efficiencies up to almost 7% are achieved with the latest thermal pairings with non-focused solar radiation. A module measuring 23 cm × 13 cm × 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 exchanging medium flowing in at 20 degrees Celsius, a maximum of 175 watts of continuous power 15.2 volts working voltage generated. The efficiency is 5.5%. This would require 3182 watts of solar energy, i.e. an approx. 2 × 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%.

State of the art in terms of heat loss reduction with continuously tight Thermos legs (7) with multi-phase alloys made from bismuth-antimony tellurides

Worldwide developments have brought new 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 further metal and semimetal components were added in such proportions and modified doping that thermoelectric multiphase alloys were formed, which were able to agree with disordered and disordered grain boundaries between many matrix crystallites distinguish highly conductive transition phases in these grain boundary areas.

These new, built structures of the alloy components bring with some determined, detailed proportions a significant reduction in heat conductivity, with little reduced, the same, in rare cases improved values of the electrical conductivity or / and differential thermal forces. The resulting, partly improved values of the can be adjusted to certain operating temperature ranges "figure of merit" (quality factor of thermoelectric conversion) are therefore a principal result of the "calibrated" disorder that Franz-Wiedemannsche- Law of the close correlation of electrical and thermal conductivity in its dominant effect limited.

However, these thermoelectrics ( 3 ) are heavier than average and very expensive. This affects the price of the finished modules accordingly.

The latest state of the art are thermoelectric arrangements with thermal legs ( 7 ), which are composed of a passive leg part and an active leg part ( 2 ). A claimed according to the invention, described below, foamed passive leg part ( 4 ) corresponds functionally to a passive leg part described in the invention "energy-regenerative surface element". This invention is registered at the German Patent and Trademark Office under file number 198 55 982.8, application number 101 16 559 and the priority date of December 4, 1998. The applicants are identical. The passive leg part is an inventive basic element of the invention already registered and consists primarily of charcoal-carbon frameworks, which as a whole or by compression of charcoal powder are formed into only electrically well-conductive, geometrically suitable volumes, which minimize the heat loss flow of the thermo-legs ( 7 ) and ultimately of two electrically and thermally well conductive active leg parts ( 2 ) can be contacted homogeneously over the entire surface.

The active leg parts ( 2 ) at the end are alternately of the p-line type and n-line type and form p / n and n / p transitions via intermediate contacts. In this way, thermoelectric individual elements ( 6 ) electrically connected in series and thermally in parallel are connected to form flat modules which can be used as Seebeck or Peltier elements.

In addition to the charcoal structures, the state of the art is the production of thermal legs ( 7 ) with a sintered structure portion from suitable materials based on the model of powder metallurgy in order to achieve a greater blockage of the heat losses ( 8 ). All structures that block heat loss can include enrichment of the near-surface lower layers and the coating of their surfaces for electrical conductivity optimization up to the ability to form thermal EMF. According to the state of the art, the active leg parts ( 2 ) can be anchored and inserted using technically professional application methods on these and partly in these structures of the passive leg parts.

As a result of the high thermal insulation of the central passive leg part with the above-mentioned structures, thermoelectrics ( 3 ) with high thermal conductivity can be used for the thermos ( 7 ) to be manufactured.

According to this new - and other - state of the art, the following invention now relates to the basic, central insertion of a passive leg part into a new generation of thermal legs ( 7 ) and adheres to the terminal contacting of active leg parts ( 2 ), the structures of Passive leg parts, as an extension, 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 ). Various foaming 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 permit novel thermoelectric arrangements which are described and described below in terms of their structure.

Proposals for the design of thermal legs ( 7 ) with a foam structure portion for efficiency-improving heat loss reduction, extensive cost minimization for thermoelectrics and weight reduction in thermoelectric arrangements Metallic Foams ( 10 )

offer the possibility of producing thermo legs (

7

) with foam structure. The Laboratory production of foamed aluminum was initially successful in a space station and then also under normal gravity conditions. The serially possible Production of metallic foams (

10th

) allows the processing of thermoelectroactive metals. Their thermoeoctric quality (figure of merit) is due to the throughput of heat loss stream (

8th

) actually fails, decisively improved.

The so-called spattering on the surface of a solidifying silver casting after the melting phase has long been an undesirable side effect of escaping, dissolved oxygen and is therefore one of the first indications of the possibility of producing metallic foam ( 10 ). The sparring can only be prevented by keeping air containing oxygen away during the melting phase.

With metal foaming it is necessary to have gas bubbles in a homogeneous distribution in one Metal liquid phase, at least briefly to keep it distributed until solidification one Foam structure stabilized. This challenge is currently being tackled. From today's perspective, the regime of the now comprehensively manageable metal foaming is a necessary basis for a new material generation, for example for crack-resistant, torsion-free lightweight car bodies, Support, wear and torsion stressed elements for static and dynamic bean spells is important.

An essential aspect of metallic foams ( 10 ) is, in addition to their strength and lightness, the optimization of a maintainable, high electrical conductivity, which is claimed for thermoelectric applications and which is claimed in accordance with the invention, with the development of thermal currents in now highly heat-insulating metallic structures (see claim 1).

In particular, highly closed-cell foamed metals, electrically conductive semimetals, semiconductors, intermetallic compounds or intermediate phases that already have high, differential thermal forces or even known thermoelectrics ( 3 ) must be observed for a significant increase in the efficiency of thermoelectric conversion that can be achieved by reducing heat loss. These 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, Fig. 1)

They are the simplest thermal legs ( 7 ) with a foam structure component, from which the more sophisticated 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, can be made. The costs are reduced in the typical process for integrated active-passive thermo-limbs ( 14 ) with inductive and dielectric working components and a foamer ( 33 ) (see claim 8).

The simple forms consist of metallic foams ( 10 ) or structures that are obtained by sintering pre-expanded, electrically conductive particles with surface-encrusted thermoelectrics ( 3 ) or structures that remain sufficiently porous, with or without an oxidized carbonized cellulose, sugar or protein, whereby previously distributed, subsequently form zoned, inner, thermoelectroactive grain sizes ( 17 ) thermoelectroactive zones ( 34 ). Continuously foamed thermo-limbs ( 11 ), however, mostly consist of a previously compact thermoelectric ( 3 ), which was foamed in closed cells with the same cell size throughout and in this thermal process there are difficulties ( 27 ) with regard to component-differentiated foaming due to the formation of poorly conductive or brittle, intermetallic intermediate layers or others property deteriorating processes would result. In addition, there are effective formulation recipes for non-metallic foams ( 31 ), which, however, only result in correctly structured conductance-optimized, possibly even density-differentiated foam structures in a homogeneous material composition via the dielectric heating - but with layer-differentiated addition of certain necessary active phase components for component-differentiated foaming ( 27 ) very much negative separation or internal corrosion zones would result. It is left to professional action to find out which formulation recipes are suitable for which type of foaming.

In order to obtain geometrical installation shapes of continuously foamed thermo legs ( 11 ) in thermoelectric modules ( 1 ), these are obtained by suitable cutting of the finished foamed thermoelectric material ( 3 ).

With suitable contact of its surface-cut foam surface with other thermoelectrics ( 3 ), an increasing thermal EMF is additionally developed by temperature differences between separate, thermally parallel contact points. The geometric shape comes from a suitable vertical cut, which in this type and composition is simply foamed - at most retrospectively, superficially density-modified foam structure surfaces (sintering of metallic foams with a flame arc or laser under protective gas). It can now be cut out mechanically or with a laser on the surface of open-pore modular toothing profiles (claims 14, 4, fgur 3 b), which are then gently pore-smeared with indifferent conductive varnish ( 18 ) and pushed into one another with the interposition of an indifferent metal foil ( 38 ). An external guide and cross-section reinforcement with optimized thermal conductivity and an optimized thermal trapping surface provide an advantageous, functional heat / cold control device ( 21 ). According to the features of claims 14 and 4, these two types of contacting are referred to and claimed as cementing profile contacting ( 39 ) and thermal guide profile contacting ( 40 ) with application possibility for all thermal legs ( 7 ) in thermoelectric power generation plants and alternative Peltier plants (see claim 14, 4, Fig . 3b).

There is another way, too electrically conductive, but hardly thermal Balancing structures come by using as ash-free organic as possible Substances can be coked freely or in limited volumes. The allocation measure volume within which the porosity or closed cell structure of the ver Having the permanent structure of the coal scaffolding graduate remains a matter of professionalism left. At least you can have dense glossy carbon surfaces and a more porous one Achieve an internal structure - even retrospectively through thermal surface coating tion in rich gases.

Possibilities of thermal or oxidative cold start coking ( 36 ) for the purpose of obtaining property-analogous carbon framework structures for continuously foamed thermal limbs ( 11 ) (claim 4)

The oxidant cold start coking ( 36 ) uses a propellant-like burn-off of organic substances, the mixed oxygen supplier of which leaves no salts behind and which, in reduced admixture, only allows partial oxidation of the mixture so that a degassed carbon structure remains.

Since this out of "cold phase" by z. B. glow wire or stoppin ignition is possible, the term "oxidant cold start coking ( 36 )" is chosen.

The non-metallic foam ( 31 ) obtained by means of oxidative cold-start carbonization ( 36 ) or thermal carbonization, which in its structure allows the possibility of component-differentiated formation, is a type of foam-structured carbon structure with the possibility of forming conductivity-optimized intermediate areas ( 35 ) and electrothermal active end zones ( 34 ). . It can also be added by ver cementing profile contacting ( 39 ) or thermal guide profile contacting ( 40 ) to thermoelectric arrangements of Seebeck or Peltier blocks (see he claims 4 and 14, Fig. 3b). There is also the possibility of creating a mosaic of large carbon scaffolding blocks by means of joint coaling ( 41 ), in which coal structure segments ( 42 ) are joined with suitable charrable glues and inductive resistance heating or other suitable thermal entry in the joints of the assembled structure segments ( 42 ) fills the glue Fuge converts into a connecting carbon structure intermediate layer ( 43 ).

Ultimately, current-carrying carbon fibers in the glue-pressed joints can gently effect thermal dissociation via localized resistance heating to form the intermediate carbon structure layer ( 43 ). Finally, a partial or continuous cementing with indifferent conductive varnish ( 18 ) is also possible. The strengths of the carbon scaffold dressings required for thermoelectric modules ( 1 ) can be varied sufficiently, depending on the raw materials and skilled work, to cement hard and hard.

In the single rod version with metallic ( 10 ) and non-metallic foams ( 31 ), contacting bridge 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-contacting, 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 suitably "comprehensively shaped" application hardened, non-positively sealing in the pores, indifferent conductive varnish ( 18 ), which is thermally and electrically highly conductive and electrically / thermally contacting, connections for previous ones and subsequent end faces of continuously foamed thermal legs ( 11 ) are permitted. In this respect, the connection of single rod shapes is possible via bridge electrodes ( 13 ) ( FIG. 1) designed with it, optionally provided with conductive reinforcements (wires) or which allows direct connections of bendy or angled shapes which can be achieved by means of conductive lacquer cementing (see claims 4 and 5) . The collector hood ( 15 ) can be internally armored in accordance with the device with protruding, thermally input heat-conducting devices ( 21 ) (see claims 4 and 5 in Fig. 1).

Active leg parts ( 2 ) (claims 6, 2, 7, Fig. 3a)

They consist of primarily dense, conductively cemented disks or layers of thermoelectrics ( 3 ), which can be metals, intrinsically conductive element semiconductors, compound semiconductors, intermetallic compounds or intermediate phases, multi-phase alloys or other suitable ones or their suitable, so-called thermoelectroactive grain sizes ( 17 ) in an electrically conductive embedding made of hardened, thermoelectrically indifferent conductive varnish ( 18 ), this physical bond of the active leg part ( 2 ) receiving thermoelectric potential on its surfaces of the internal thermoelectroactive grain sizes ( 17 ), added to the thermoelectric arrangement and further contacted and therefore as thermoelectroactive collector hood ( 19 ) from ther moelectroactive conductive varnish ( 16 ) is under-labeled.

Foamed passive leg parts ( 4 ) (claim 6, Fig. 3a)

They are the central to predominant part of thermal legs ( 7 ) with the function of a significant improvement in the efficiency of the entire thermoelectric arrangement as a Seebeck or Peltier element block. You contact the terminal active leg parts ( 2 ).

They consist of thermoelectric, indifferent, mainly foamed, metallic and non-metallic material components with high electrical conductivity, in the form of metallic ( 10 ) or non-metallic foam ( 31 ), whereby a final density differentiation of the mainly closed-cell, foam structure may be present.

The optimized foam structure of the foamed passive leg parts ( 4 ) provides a heat resistance value that is several times higher, with considerably less loss of electrical permeability and thus the ability to drastically reduce the heat losses ( 8 ).

Compound thermo-legs ( 12 ) (see claim 7, Fig. 3a)

consist of two terminal active leg parts ( 2 ), which contact a central, foamed passive leg part ( 4 ). The foamed, at the same time thermoelectric, indifferent passive leg part ( 4 ) has the task of minimizing thermal loss of heat transfer while maintaining the highest possible electrical conductivity. So it develops no or very little of its own thermoelectric voltages. The active leg parts ( 2 ) consisting of thermoelectrics ( 3 ) form n / p and p / n transitions with one another, with task development of thermal currents ( 5 ) when exposed to suitably applied temperature gradients. They are as intervals or thin slices of natural or synthesized thermoelectrics ( 3 ), e.g. B. cut pyrite and chalcopyrite discs with the end faces of the foamed passive leg parts ( 4 ) and others contacted with each other. The homogeneous surface contact takes over filling, curing, indifferent conductive varnish ( 18 ).

In order to achieve intensive heat input, the cut crystal wafers of natural and / or synthetic thermoelectrics ( 3 ) are connected to thermally concentrating end regions on the outer crystal wafer surface, which subsequently have a heat-transferring surface, which subsequently has a transition to bridge electrodes ( 13 ) (see FIG. 3a) . Accordingly, these are formed into surface-shaped heat / cold guide devices ( 21 ). The constructive solution to the thermal entry, which is made in the thermal guide profile contact ( 40 ) proposed according to the invention, can also be derived here in an exemplary manner (see claims 4, 14, FIG. 3b).

There are further analogue further contacting methods, such as for continuously foamed thermal legs ( 11 ), for. B. with thermoelectroactive collector hoods ( 19 ) as active leg parts ( 2 ) (see claim feature in claims 6 and 7).

Integrated active-passive thermo-limbs ( 14 ) resulting in density- ( 23 ) and component-differentiated foaming ( 27 ) (claim 8, Fig. 3b and 4)

Metals that have long been recognized for their high thermal conductivity and are therefore not considered suitable due to their high thermal conductivity can now be used again as interesting and effective thermoelectrics ( 3 ) as a result of metal foaming according to the inventive and procedural proposals.

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 layer of metallic foam ( 10 ) they transition into a substantially denser to foam-free state, which involves soldering, welding (also with ultrasound) or mechanical frictional contacts near-surface, denser structures enables (see claim 14, claim contact anchor claw ( 22 )).

The densely differentiated foaming ( 23 ) of metals and non-metals is the result of a regime for microwave and induction alternating fields, which cause proportionally dielectric heating of non-conductive or resistance heating of conductive batch components in the still dense green batches. A supplementary barometric and acoustic auxiliary regime may trigger and temporarily stabilize the rising foams in the ready-to-blow, ready-to-hold phases. In claim 10, the components of the tax regime and their mechanisms of action are named and explained. With the same or modified technical equipment, a reformation of the active phases which can still be polarized in the foam structure cell walls is carried out while the phase is still hot (see claim 15).

Thereafter, the total layer of metallic foam ( 10 ) obtained by density-differentiated foaming ( 23 ) - in this differentiated, closed-cell structure, so termed as a term - is cut lengthways and crosswise into so-called rod shapes in a tied active-passive thermo-leg ( 14 ) of suitable cross-section, as is normally the case is necessary for a favorable current-voltage ratio in thermoelectric arrangements. Accordingly, from active foaming ( 10 ), integrated active-passive thermo-limbs ( 14 ) can be characterized by 100% thermoelectric material ( 3 ) - apart from impregnated solder in open-pore penetration areas of cut contacting surfaces - predominantly as metal, which becomes denser with closed-cell cells Structure of the metallic foam ( 10 ) into a fine-pored, near-surface, denser until ductile phase passes under the terminal cover surfaces.

In addition to this, a step-by-step three-zone structure of integrated thermal limbs ( 14 ) is possible by attaching and foaming three-layer green body layers for non-metallic foam structures, which are characterized by a central, conductance-optimized intermediate area ( 35 ) with a responsible through-contacting active phase ( 26 ), which and underside electrothermoactive end zones ( 34 ) passes over. According to the invention, this method is referred to as component-differentiated foaming ( 27 ) (see claim 11). It saves large quantities of thermoelectrics ( 3 ) in the series production of thermoelectric modules ( 1 ).

The terminal top surfaces are contacted with the aforementioned electrical / mechanical cementing types of connection in a manner analogous to that of continuously foamed thermal muscles ( 11 ) by means of indifferent collector hoods ( 15 ), conductive lacquered bridge electrodes ( 13 ) to p / n and n / p transitions analog heat / cold control devices ( 21 ) provided (see claim 5 derived from designs in Fig. 1 and 3).

For integrated active-passive thermo-limbs ( 14 ) straight rod or curved or angled shapes are claimed as in the above-mentioned embodiments (see claim 7).

An advantageously applicable, in which the dense foam upper structures engaging, non-positive and solderable contacting is still with pre-tinned Kon contact anchor claws ( 22 ) in metal-foamed integrated active-passive thermal legs ( 14 ) (see claim 14, Fig. 4). The contact anchor claws ( 22 ) can also be coated with a layer of titanium / silver / palladium which is indifferent in every respect.

In the case of non-metallic foams ( 31 ), capillary penetrating, later hardening indifferent conductive lacquer ( 18 ) takes on the role of tin. For this purpose, the surface of the foam structure is pre-pierced with the contact anchor claw ( 22 ), wetted and then permanently clawed.

The differentiated boundary layer foaming ( 29 ) for the production of thermoelectric strands ( 28 ) (claim 13, 23, 27, Fig. 5)

According to the features of claim 13, a technically sophisticated, technically demanding method is proposed, which provides for an expansion of the dense differentiated foaming ( 23 ) to the differentiated boundary layer foaming ( 29 ) of thermoelectroactive metal pairs, which can be realized within the framework of controllable, technical push-through processes. According to the device, it is proposed that 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 method - thermoelectrics ( 3 ) pushed by suitable medium to higher frequency induction fields is subjected to an intensity and frequency-regulating regime for induction melting foam hood, dielectric heating, pressure surrounding protective gas atmospheres and frequency shaking through, for example, mechanically guided sound frequencies from alternating current-applied, vibrating plungers in annular gaps of strong permanent magnets.

As a result of regime control for selectable foam structures - regarding the proportions of dielectric and inductive energy inputs - the strand to be pushed through, composed of the intervals of the thermoelectrics to be paired ( 3 ), finally undergoes continuous, gradually adjustable, density-differentiated foaming to the extent that there are optimal p / n and n / p transitions and their simultaneous connection in series. If the strand-pressed green body intervals for strand-linkable thermal legs ( 7 ) are applied according to the three-layer method, the advantage of a component-differentiated foaming ( 27 ) with conductance-optimized intermediate region ( 35 ) and thermoelectroactive end zones ( 34 ) results for the strand to be foamed (claims 13, 11, Fig . 5). The thermal entry for the p / n and n / p transitions of the strand-like arrangement is carried out by inter-contacting, fully porous to dense, thermally electrically highly conductive, but indifferent zones, which lie completely in the foam composite, and which are offset from one another on the strand side - each by 180 degrees - In widening and lengthened heat-cold guide devices ( 21 ) with Teflon coating continue (see claim 13, Fig. 5). In Fig. 5 the indifferent zone is illustrated a purely thermal transferring Ringkontaktierung for thermal conduction and improve the overall so-structured heat-cold guide device (21) continues mutually outward in the outer thermally-entraining surface areas. The alternating arrangement made in this way can tap temperature offers, convert them to electrical power in the thermocouple transitions, and offer them at the strand ends of the so-called thermoelectric strand ( 28 ) via already noteworthy working voltages down to the ten-volt range. Adaptable cuts and flat series connections of any working voltages can be achieved with a simple method, which achieve the voltage values of car batteries with pyrite / chalcopyrite thermocouples or galenical homojunctions with a few thermoelectric strands ( 28 ).

Pressure-contacted thermoelectric strands ( 32 ) (claim 13, derived from Fig. 5)

They are basically the same in structure, but allow the replacement of various thermal legs ( 7 ) with and without a foam structure component. They present a real modular system that can always be repositioned and then pressure-contacted within a tube without interference. The indifferent, the p / n and n / p transitions between the inner, strand-contacting surfaces of the heat-cold guide devices ( 21 ) are covered on both sides with thin layers of conductive rubber ( 37 ) or suitable surface-formed, elastic-acting, indifferent metal foils ( 38 ) provided, which give the axial pressure contact a taut resilient permanent component.

Surface contacting of large-celled, metallic foam ( 10 ) with soaking alloy and contact anchor claws (claim 14 , Fig. 4)

If density-differentiated foaming ( 23 ) is not possible, but only homogeneously with the same cell size, then the thermoelectrically indifferent tin lead 84171 00070 552 001000280000000200012000285918406000040 0002019925960 00004 84052 or other easy-flowing, thermoelectrically indifferent soft surface in the open, porous silver plating, the open, porous surface Insert cut blanks capillary. The cut blanks are accordingly to be regarded as continuously foamed thermo-limbs ( 11 ), the ends of which only have to be made ductile and thus capable of contact by capillary tin solder. The continuation of the thermal current ( 5 ) takes place in addition to the already mentioned and claimed types of contacting with three-sided or more dimensionally piercing, suitably shaped, pre-tinned contact anchor claws ( 22 ) that forcefully penetrate into the tin-staggered, end-face foam structure and that fit into a further strong wire of suitable conductor material ( usually copper), which is embedded in conductive varnish to be indifferent ( 15 ) or thermoelectrically active collector hoods ( 19 ). A touch silver plating, 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 against air containing hydrogen sulfide before the conductive varnish bedding. In addition to simple, double-clawed contact anchor claws ( 22 ) and the curved, possibly spiral, flexible bridge shapes that extend from them, to central heat sink shapes in the extension, perform an important multiple function with regard to the formation of the p / n and n / p transitions, full thermal input Offers and extensive, three-dimensional adaptability (see claim 14, Fig. 4).

This type of tin-strengthening contact is therefore to be used for continuously foamed thermal legs ( 11 ) made of metallic ( 10 ) and non-metallic foams ( 31 ).

Metal selection for the production of thermoelectroactive, metallic, same-cell or density-differentiated foams ( 23 ) for continuously foamed thermal legs ( 11 ) with homogeneous active phase distribution and possible, dense embodiments of active leg parts ( 2 ) for composite thermal legs ( 12 )

In contrast to current, conventional, device-like types, comparatively only extremely weak heat losses ( 8 ) can flow along the thermos ( 7 ) according to the invention with a foam structure component, since the foam structures oppose an extremely high thermal resistance in comparison to dense metals. They are approaching the K values of foam concrete, since the cell walls can be made very thin - and based on this - very large inner surfaces. After all, the metallic foams ( 10 ) still have sufficiently high electrical conductivities.

That makes them attractive thermoelectric applications again. These have so far failed due to the high heat losses ( 8 ) and the - sometimes modest - thermoelectric single voltages.

At the beginning of this century, the Gülcher thermopile consumed 170 liters of luminous gas per hour with a - however very reliable - continuous output of the 66 compact elements made of nickel / antimony alloy thermocouples of 12 watts at 4 volts working voltage. The series connection resulted in a continuous short-circuit current of 6 amps. In addition, the device could noticeably heat rooms. Equivalent electrical power requires a much smaller cross-section in the same way in order to be able to pass without loss. By removing the high thermal conductivities of ductile metals, 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:

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 thermo-limbs ( 14 ) or of the other proposed variants with a metal foam structure component to the p-n and n / p transitions generating thermostyrene can be carried out using the aforementioned and all other sophisticated, conventional methods.

Electrical and material properties of ore grown, hydrothermally crystallized, natural compound semiconductors with regard to their use as thermo-electroactive grain sizes ( 17 ) as well as the intermetallic compounds and synthetic, semiconducting 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 , which, however, is hardly temperature-dependent. There is little change in the amount of energy and speed of the electrons. Now, however, the different energy, speed and concentration of the two charge carrier types - electrons and holes - are a highly temperature-dependent characteristic of semiconducting compounds, which enable them much better than metals to develop a potential between cold and hot contact points made from thermo-limbs ( 7 ) (see Fig. 3a).

For example, pyrite chunks with an effective charge carrier concentration of over 10 ¹⁵ and a mobility of 200 cm ² / Vs or chunks 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 differential thermal force of a randomly selected pyrite chunk in combination with nor copper wire was in the "actual" experiment described below Intrinsic conductivities of differently crystallized pyrites and other diverse crystals stall forms of gravel, screens and sheen - in the range between 20 and 80 degrees Celsius at about twice the subsequent table value of 130 microvolts / degrees Celsius.

The conductivity test with a small crystalline, irregular chunk of pyrite results in the following observation: When the circuit is closed, a start flows weak current, which only for the faint glow of a tungsten filament, but too simultaneous temperature rise of the surrounding, tip-contacted pyrite surface is sufficient. Finally there is a sudden blaze of light throwing light bulb if the current conductivity zone of the ore-grown verbin 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 yields  in the beginning, a bright ray of the tungsten filament, like that with irregular chunks of chalcopyrite or arsenopyrite is possible.

It follows from this that disks made of this single cubic crystal have the best suitability 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 significantly higher guide values. These are sufficient to operate two light bulbs via a wire tip contact out. A surface contact of the pyrite eliminates any Transition problems. Those included in the experiment, from a dolomite overgrowth Broken-out galena crystals (PbS) yielded further experiments Outstanding thermoelectric voltages and currents with a temperature that can be reached by solar energy offered and gradients, which due to their anisotropic property only with "correct oriented placement of the wire tips on certain surface parts of the crystal " were removable.

The simple experimental design in summary clearly proves the long-known, semiconducting character of mineable orifices, sheen and gravel and thus their suitability for the extremely inexpensive manufacture of thermo-limbs ( 7 ), but better the foam structure portion according to the invention. This means that the inexpensive pyrite and many other minable, electrically semiconducting crystal structures can be used to obtain thermoelectric current at comparatively low cost (compared to expensive synthetic thermoelectrics, such as bismuth tellurides).

According to the proposals according to the invention, divided fractions within thermoelectroactive collector hoods ( 19 ) or cut crystal wafers of larger, hydrothermally grown crystals of pyrite, chalcopyrite and others are similarly effective and suitable.

Pyrite often occurs in sufficiently dimensioned cubic single crystals and can be processed with copper to high-performance thermoelectric modules ( 1 ) "out of the mountain", whereby many thin disks made of one crystal produce exactly half as many thermoelectric individual elements - with considerably lower internal resistance and much 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 dusts of the ore grown compound semiconductors which arise during crystal cutting can in turn be used in conductive coating embeddings for the production of thermoelectroactive collector hoods ( 19 ) or for the formation of thermoelectroactive end zones ( 34 ) (claims 4 and 6).

Improvements to the thermoelectric properties

Growing thin layers that can be deposited on amorphous substrates also allow themselves to be transported or synthesized vapor phase transport. Likewise, tempering, ordering recrystallization is possible with or without polarization fields. The degrees of division - referred to as thermoelectroactive grain sizes ( 17 ) are given a thermoelectric preferred direction in the later hardening composite (e.g. a thermoelectroactive conductive lacquer ( 16 )) in the resin-tough phases of basic lacquer components under the influence of the field. Ion cleaning is also possible with pyrite crystal structures (see claim 15).

Causes of thermal stress on pyrite and galena

In the case of metals, element semiconductors, compound semiconductors, intermetallic compounds or intermediate phases, there are three thermoelectric components:
Electron diffusion component or volume component, contact potential and phonon drag component. The latter refers to an interaction between electrons and phonons, in which phonons carry electrons with them as they move from the warmer to the colder end. This component is only a determining factor in low-temperature ranges.

A semiconducting thermocouple ( 7 ) with a temperature gradient gets a much higher electron diffusion component (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.

So that sufficient thermostatic currents can flow, a sufficiently dimensioned, as thin as possible transition surface and a still sufficient charge carrier concentration in this thermoelectric ( 3 ) formed into the layer is necessary. The fact that there is a high level of thermal power in a thermoelectric element ( 3 ) that conducts electricity only moderately suggests that all non-electrothermal sections of the thermal current path ( 9 ) be made of other indifferent, but electrically highly conductive material - which should also be as heat-blocking as possible like metallic foam. Conductive varnish-bonded pyrite and chalcopyrite discs on plane-cut metal foam surfaces provide the best solution for high, loss-minimized, thermoelectric conversion.

For the highest developable thermal EMF, the combination of a hole semiconductor with an electron semiconductor must be provided. For permanent stress in thermoelectric modules ( 1 ), temperature resistance, certain weathering resistance and anticorrosive behavior to contact materials are required. A lacquer coating is sufficient for air-exposed thermocouples made of pyrite and chalcopyrite disks and layers.

Immediate and indirect foaming of non-metallic thermoelectrics ( 3 )

The process can only be called semiconducting connections in a limited selection Foaming can be done just as easily as metals. There is also a suitable one Selection that has to be post-treated to get the foam structure out of one non-conductive, glassy state in a permanently metallic semi-conductive convict. A considerable part cannot be treated with thermal aftertreatment a suitable, semiconducting state can be transferred without the foam structure reduce or destroy in its optimal structure. With sulfidic, seleni There are few meltable and arsenidic compound semiconductors and thus foamable - they previously suffer hopelessly over 800/900 degrees Celsius pyrolysis.

Indirect cold and warm foaming with organic paint base components (see claims 9, 10, 11, 16, 17)

For their placement in a self-conductive foam structure, e.g. B. made of polyacetylene or made conductive with conductivity mediators ( 20 ) is technically possible. The totality 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 it is electrically self-conducting. Doped polyacetylene shows metallic conductivity with a relative conductance as metals have. With electrodes made of polyacetylene, which are immersed in a paste-like electrolyte from a solution of tetra butylammonium perchlorate in propylene carbonate, considerable amounts of ampere hours can be stored in a new, metal-free battery type. Instead of the film state, a suitable, electrically conductive foam structure of polyacetylene can now be achieved, which considerably improves the conductance of the through-contact active phase ( 26 ) of the embodiments of the thermal legs ( 7 ) proposed according to the invention with a foam structure component.

The best metallic conductance is also promised by an active phase-improving foam structure made of poly-sulfur nitride S _(n) Cl ₂ (with n greater than 24 ). With increasing sulfur contents, the phases from liquid, plastic to solid can be realized and the electrical preferred direction of these one-dimensional conductors can be carried out with dipole-orienting post-forming processes by means of static, electrical fields (see claim 15 - post-forming). This is promising for certain chain lengths, since you can only wait until Resolzu stands before further chaining polymerization and can accompany the further chaining polymerisation with a postforming regime.

A similar one-dimensional conductor that can be chained lengthways is poly-sulfur nitride with metallic conductivities from 1/10 ^-6 to 1/10 ^-7 × 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).

Metallic and non-metallic conductivity mediators ( 20 ) for forming the through-contact active phase ( 26 ) in the dense or foamed structural composite (claims 4 and 6, 11, 17)

There are batch formulations for conductive lacquers which, according to the invention, can be spray-stored with an added propellant component and, after exiting, can be expanded to form a closed-cell foam structure (see claim 16). It is within the scope of professional action to determine the optimal compositions for certain relationships of electrical conductivity and achievable K values. Analogous degrees of hardness and stress in the order WD and WS can be achieved if partially substitutable polyurethane components are incorporated to form a composite. Accordingly, equivalent K values can be realized for the purpose of switching off power-reducing heat losses ( 8 ).

According to the features of claim 16, a joint is proposed as a result, the pure foam-like, thermoelectroactive conductive lacquer ( 16 ) which contains suitable grain sizes and / or additionally reinforcing (possibly nozzle-compatible) fiber components of conductivity mediators ( 20 ) in suitable proportions:
(Aluminum, copper, nickel, silver dust, glazed coal flakes, hard coal sand or powder, metal oxides, nitrides, borides, special ion and super ion conductors or other suitable - as indifferent through-contacting active phase ( 26 ), in addition to corresponding amounts of thermoelectroactive grain sizes ( 17 ) intrinsically and externally conductive semiconductors, compound semiconductors or intermetallic compounds The introduction of powdery, semiconducting, gray alfa tin into thermoelectroactive end zones ( 34 ) or collector hoods ( 19 ) always seems interesting. It is formed from pure tin metal by the so-called Tin plague, but still has a high metallic conductivity in addition to self-developed thermal EMF.The self-producing, thermo-electroactive grain size ( 17 ) (band gap 0.1 eV) also acts as an efficient conductivity mediator ( 20 ) with a specific electrical resistance of one ten thousandth of an ohm / cm in conductive lacquers or cell wall structures non-metallic foams ( 31 ) (see claim 3).

The conductivity-imparting, low-resistance sulfides of copper and silver occupy a middle position, of which Ag ₂ S is a mixed electron-ion conductor. Lithium nitride Li ₃ N has a high ionic conductivity at room temperature and is therefore of interest from an application point of view as part of the through-contact active phase and within hermetic varnish base dressings ( 26 ). Density or foam structures would have to be completely sealed against water, otherwise there would be a reaction to ammonia and alkali. Titanium nitride or lithium-doped titanium disulfide are totally resistant (see claims 3 and 17).

All of these compounds are suitable for imparting conductivity in a hardened / solidified, dense or even foamed base component. The conductive lacquer base component, which is also possible on a different chemical basis (up to electrically intrinsically conductive, for example based on polyacetylene, is offered according to the invention for processing with compressed propellant in stock sprays (see claim 16). The lacquer basic component which forms the closed-cell composite after foaming and is indifferent Foam conductive varnish ( 24 ) or thermoelectroactive foam conductive varnish ( 25 ) can be non-conductive, but should better be self-conductive due to higher thermal current densities (polyacetylene), the non-conductive paint base components then being supplemented with conductivity mediators ( 20 ) to form a through-contacting active phase ( 26 ) must, during which the intrinsic can be supplemented with these (see claim 17).

Thermoelectric potential transfer to the through-contact active phase ( 26 ) and its types of charge carrier transport (claims 3, 9)

The 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 continuous foamed thermal legs ( 11 ) to be cut should give off higher electrical power densities. In thermoelectroactive end zones ( 34 ), the physical thermo-electroactive grain sizes ( 17 ) in turn take on a considerable proportion of the charge carrier transport. With their thermal EMF, they accelerate this even further. This increases the density of the thermal current ( 5 ). In order to catch them, conductivity mediators ( 20 ) are sprinkled in tightly surrounding, making contact. In the direction of the intermediate area ( 35 ) optimized for conductance, these take over the entire charge carrier transport unless the material cell wall structure is involved in the transport. If this is to become particularly firm, the active phases, which hardly contribute to strength, must not exceed a percentage limit in the overall structure. Nonetheless, insulation panels that are subject to greater wear and tear - such as Styrodur - can be replaced in shells of large-scale building shells by extensively thermoelectrically converting the surface units of thermoelectric modules ( 1 ) that can be subjected to greater static loads. If foam structures that are subject to heavy loads only allow a reduced conductance or so-called foam-extended, 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 over a longer conversion period.

In the cell walls of the finished foam structures of thermoelectroactive foam conductive lacquers ( 25 ), mainly metal powder, but also metal oxides such as iron III oxide = hammer blow, nitrides and borides and possibly, as indifferent, only the charge carrier transport or the accepting conductivity mediator ( 20 ) of the through-contact active phase ( 26 ) organic one-dimensional conductors such as polyacetylene, poly-sulfur nitride, poly-sulfur chloride and special super-ion conductors in particle form (sizes from 1 to 10 micrometers) are added. Their "more extensive" conduction mechanisms are purely metallic and / or metallic with semiconducting or still involved ion conduction with regard to directly contacting particles of the conductivity mediators ( 20 ). In addition, there is a certain proportion of load carrier transport through the so-called trap tunneling (see claim 9). For electrons, this is the possibility of overcoming thin, but overall very poorly conductive to insulating zones, which slowly improve in "soft" or by using ion conduction to start the associations (self-formation).

The trap tunneling initially takes over part of the transport of the load carriers with organic lacquer bases, the already thermosetting epoxy resins, but especially with those containing fries. After a certain current flow time, "softer" structural associations show electromigration which increases the conductance, ie an optimizing migration effect of interconnect atoms, with a bridging, integrating effect for previously unrelated, locally located interconnect atoms. In glassy, hardened dressings, this automatic optimization of the conductance fails and can only be actively forced during the cooling, tough plastic composite in the treatment program of a reformation and defined for a long time (see claim 15). The trap tunnel accordingly has a different decrease in and / or remaining portion in
dense, indifferent conductive varnishes ( 18 )
thermoelectroactive conductive lacquers ( 16 )
and the
indifferent conductive foams ( 24 )
thermoelectroactive conductive foams ( 25 )
and can be of decisive importance if glass frits with a melting temperature of approx. 0.1 micron are to be overcome between the metal particles present in chains and tufts. The overcoming forces, as well as the frit foaming temperatures, can be adjusted by reducing borax alkali additive soda (sodium carbonate) before potash (potassium carbonate).

Sodium silicate layers are most easily "tunneled" by the electrons. However, the more "water glass-like" the frit component that forms the support structure becomes, the more the supporting foam structure has to be hermetically sealed and supported by a sealing layer. The same should and can make up the supporting envelope structure of the entire thermoelectric module ( 1 ) partially or entirely. A general improvement in the active phases, even in glass dressings, allows methods of accompanying, sometimes also subsequent formation (see claim 15).

The following is a proportionally variable / expandable, electrically highly conductive silicate composite structure which is suitable for building up the thermal legs ( 7 ) according to the invention with a high proportion of foam structure:

Conductive silver / conductive copper

Silver powder 54.4 / 46.2 Cu powder Higher levels of borosilicate improve that Bismuth oxide 4.6 borosilicate Strength, lower the conductance, Rosin 8.3 glass powder 2.7 Silver can be copper, nickel, aluminum Turpentine 30.0 and non-metallic conductivity mediators ( 20 ) be substituted.

Copper dust atomized with a silver component or other suitable processes result in a wafer-thin, anticorrosive silver coating 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 Cu ₂ O or other transition layers.

The transfer of the charge carriers charged with thermo-EMF from and to the thermoelectroactive grain sizes ( 17 ) from the intermediate transport, through-contacting active phase ( 26 ) takes place via the same line mechanisms as within the through-contacting active phase ( 26 ) itself. The generic term of the invention The entirety and effect of the thermoelectroactive grain sizes ( 17 ) located in the thermocouples ( 7 ), which are semiconducting and develop thermal currents, is the thermoelectroactive active phase ( 30 ) (see claim 3).

There are exploitable transitional forms of conductivity mediators ( 20 ) that develop therelectroactive potentials with certain partners, but remain different with others. With this in mind, conductivity-imparting particles must be checked professionally so that no accidental opposing potentials inhibit the development of the actual thermal EMF.

Semiconducting glasses (claims 3, 15)

The semiconducting chalcogenide glasses with binary, ternary, quaternary thermoelectroactive systems made of S, Se, Te, As and Cd, Zn, Fe, Bi, Ti, Cu, Ag and such take up an important position with regard to non-metallic, thermoelectroactive sealing and foam composites the base of some transition metal oxides - such as. B. Cu ₂ O and Fe ₂ O ₃ - a.

Their properties have already been detailed in terms of their suitability for storage tasks (Ovonics) checked. The main feature of the semiconducting glasses are the most controllable, rever sible, abruptly occurring high and low resistance states that they are for a certain time digital storage tasks made interesting.

The high-resistance amorphous and the crystalline, low-resistance semiconducting state are of exceptional interest for the use and mastery of an inventive, arbitrarily switchable, potential-forming thermo-electroactive active phase ( 30 ) in all thermal legs ( 7 ) proposed according to the invention, since only a material-specific voltage pulse of nx (5 to 50) volts is sufficient to immediately create a low-resistance thermoelectric ( 3 ) from the amorphous foam glass phase of a z. B. to make continuously foamed thermal leg ( 7 ) (see claim 4). This option allows the user to wait for high temperature gradients for thermo-electrical conversion after previous storage intervals and to deliver high power output to operator networks.

Examples of low-melting, glass-like composite basic components of indifferent ( 18 ) and thermoelectroactive conductive lacquers ( 16 ) and foam conductive lacquers ( 24 ), ( 25 ) (claims 18, 15)

Instead of the polyurethane composite basic component or other, up to the closed-cell structure of indifferent ( 24 ) or thermoelectroactive foam conductive lacquers ( 25 ), which cure tightly or closed-celled without thermal release, the results of previous versions become hot at 250 degrees Celsius in addition to those curing epoxy composite basic components according to the device further proposed glass frit-like basic components, which are known to have been developed for conductive pastes of baked-in conductive tracks for hybrid circuits on aluminum oxide or beryllium oxide ceramics. These have a glass composite which can be varied in terms of softening by the following and / or other addable melting components.

Lowest softening melting temperatures (340-400 degrees Celsius) show so-called glass solders with the following possible composition:
73.8% PbO with 11.2% B ₂ O ₃ 14.3% SiO ₂ , 0.2% Al ₂ O ₃
or 73.4% PbO with 20.0% B ₂ O ₃ , 6.6% SiO ₂ .

Optimization of conductance and formation of the through-contact active phase ( 26 ) (claim 15)

For glass phase fixation contacting possibly sensitive thermo-electroactive grain sizes ( 17 ), these must survive the melt-phase embedding and contacting process without impairment. The lowest temperature ranges should therefore be selected.

In this context, 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 same is achieved by the cold or hot frit-containing, indifferent conductive varnishes ( 18 ), thermoelectroactive conductive varnishes ( 16 ), indifferent foam conductive varnishes ( 24 ) and thermoelectroactive foam conductive varnishes ( 25 ), the influence of electrical fields and / or directly applied electrical potentials len, possibly exposed to the influence of certain sound frequencies. During the cooling process, temperature maintenance areas may have to be completed, but the foam structures obtained must not be endangered.

Sufficiently high conductivities that can be achieved without formation are of course superfluous. Glassy, electrically conductive foam structures are produced from:

• - Metal powder from single and multi-component systems as conductivity mediators ( 20 )
• - Thermoelectroactive grain sizes ( 17 )
• - Glass powder (glass frit), mostly made of lead boron silicate
• - Organic flux to adjust the viscosity
• - Plasticizers for wetting and cleaning where appropriate, metal reinforcements that can be introduced
• - organic solvents
• - propellant gasifying in the viscous glass state.

After the pre-cast or dough-rolled green layers have dried at 100 to 150 degrees, they are expanded to multiple layer thicknesses at temperatures between 350 and 500 degrees. Since the thermoelectric modules ( 1 ) exposed to solar temperatures do not have to meet the strict tolerance ranges comparatively, such as electronic, filigree hybrid circuits based on ceramics, the frit melting temperatures can be made selectively lower by graduated additions of alkali silicate, which reduces the choice of foaming agents and the controllability of foaming , as well as trap tunneling and the beginning of ion conduction of the through-contact active phase ( 26 ) anchored in the glass phase up to their self-improvement when driving through higher working temperature ranges (see claim 18). According to claims 15 and 18, 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 they solidify onto a lower-temperature large volume a strong electric field penetrating the viscous glass film can be polarized in the preferred thermoelectric direction.

The foamer ( 33 ) can be a salt or organic substance that gasifies in the suitable temperature range without residues - optionally with a defined carbon residue. The remaining carbon framework component integrating into the foam structure can act as an additional conductivity mediator ( 20 ) and further reduce the internal resistance of the thermoelectric series circuit (see claim 4).

Thermal stability of available, especially minable, semiconducting compounds for crystal wafers and thermoelectroactive grain sizes ( 17 ) (claims 3, 15); inexpensive easy to synthesize thermoelectrics ( 3 )

The selection of the thermoelectroactive grain sizes ( 17 ) must be made in accordance with the frit foaming temperatures. The incipient, lattice-attacking tempering temperature ranges of the natural or synthetic compound semiconductors must be taken into account. From 400 degrees Celsius, pyrite re-orientates itself in a crystalline way, and up to 550 degrees Celsius, there are fundamentally crystal-changing tempering processes. It disproportionates in pyrrothin and sulfur above 550 degrees Celsius (see vapor phase transport in claim 15). There are hundreds of pyrite crystal structures of the same lattice that are suitable as thermoelectrics ( 3 ) and have the same constituent constituents, some of which have even higher temperature resistances, which are sufficiently anticorrosive when briefly hot-foaming frits based on boron-lead silicate and do not relate to their thermal forces dull. As genuine chemical binding partners for silicate binary, ternary and quaternary complexes, the binding partners mentioned below also sometimes occur in semiconducting glasses (claim 15). With FeS ₂ as a thermocouple and among themselves, the following partners are possible, with various suitability to be found for embedding in a glass phase:

MA ₂ MAA "MAB MAM" BA ₂ MB ₂ MBB "

where M and M "occur as copper, iron, nickel, cobalt, cadmium, zinc, ruthenium, manganese, mercury, osmium,
where A and A "appear as sulfur, selenium, tellurium,
where B and B "occur as phosphorus, arsenic, antimony, bismuth,
whereby lead, tin and silver, by themselves and with other metallic partners, also lead to semiconducting but modified crystal lattices.

Examples of relative thermal voltages in different temperature ranges:

Overall, it is important to note for all thermoelectrics ( 3 ) that in all thermal and foaming processes during the process, crystal structure and surface contactability of the thermoelectroactive grain sizes ( 17 ) can only be impaired above the hot foaming temperature level, so that they do not affect the development of the thermo-EMF dull.

To master the technological regime, however, there is no such thing empirical values from the results of resistance branding technologies paste systems for thick film resistors, conductive thick film paste systems and Conductive adhesives.

With regard to the incipient risk of pyrolytic decomposition, there is comprehensive knowledge from the enamel industry, where at far higher temperatures coloring - actually more sensitive - compound semiconductors are stored in a frit composite at high temperatures, such as. B. the cadmium selenide, which results in crimson cover enamel - at least 700-800 degrees Celsius baking temperature. When hot-frying frit-containing, thermoelectroactive foam conductive lacquers ( 25 ), conductivity mediators ( 20 ) and thermoelectroactive grain sizes ( 17 ) are only homogeneously localized and contacted in the pore walls of the closed-cell foam structure at temperatures above 350 degrees Celsius (see claim 18). After the hot foams have cooled, they can be cut.

At temperatures that are 100 degrees Celsius lower, epoxy resins can be foamed, which with a through-contacting active phase ( 26 ) made of nickel powder or silver powder have been used for decades as a dense conductive adhesive in electronics. 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 the dominant, through contacting active phase ( 26 ) in paint base components, thermoset, thermoplastic, epoxy resin and frit dressings, in fact starting from normal temperature ranges up to hot temperature ranges (up to 800 degrees Celsius). The condition is the absence of prolonged exposure to superheated steam or free caustic alkalis during hot setting or blowing processes.

The component-differentiated foaming ( 27 ) (claim 11)

The most economical method for the consumption of thermoelectrics ( 3 ), in the case of 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 ) on the rest, especially in the middle, Layer thickness build-up (see claim 11). For this purpose, corresponding paste or dough-like consistencies with different active phase components are layered on top of one another and foamed together. The result is a continuous, closed-cell composite with a thermoelectroactive active phase that is primarily present on the top and bottom ( 30 ). Specially modified conductive adhesives, conductance-optimized resistance paste systems or conductive thick film paste are suitable for this. It makes sense to combine a component-differentiated foaming ( 27 ) with a dense differentiated foaming ( 23 ) (for all features and applications see claims 4, 8, 11, 12, 13).

The layers of paste or dough to be placed on top of each other of the green sheet to be expanded must be wetted cold beforehand in order to form common cell walls which merge into one another in the hot phase. As a result of such layer-by-layer differentiation, integrated active-passive thermo-limbs ( 14 ) are immediately available during cutting, which can be contacted with or with a thermally entering, indifferent collector hood ( 15 ) with an additional thermally well-contacting active phase ( 26 ) Contact anchor claws ( 22 ) (see figure 4 ). In addition to this rod-shaped embodiment, angled or curved design of the ends of the integrated active-passive thermocouple ends as well as thermally inserting cemented profile contact ( 39 ) and guide profile contact ( 40 ) are provided (see Fig. 3b). This ensures their direct, leading p / n and n / p contact for the realization of thermoactive transitions ( 13 ). When assembling thermoelectric modules ( 1 ), dense p- or n-type thermoelectroactive conductive lacquers ( 16 ) are applied to the transition surfaces in a suitable layer thickness and these are then pressed together until they have hardened.

Aspects of material selection of intermetallic thermoelectroactive grain sizes ( 17 )

The most striking property of intermetallic compounds is their brittleness, which prevents their other technical use. In this respect, the cintical, in particular Grimm - Sommerfeld phases, which are responsible for thermoelectrics ( 3 ), are only possible with a few cuts for discrete active leg parts without risk of breakage (CNSb). The brittleness could be reduced in a number of important thermoelectrics ( 3 ) and not in others. According to the invention, the latter can also be used to form a thermoelectroactive active phase ( 30 ). Processes that refine materials are completely eliminated. The consistently metallic electrical conductance entitles to the construction of foam-stretched, thermoelectroactive active phases ( 30 ), which hardly need to be conductance-supported 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 - in addition to those not mentioned here - cadmium antimonide CdSb (400 microvolts / degree Kelvin), magnesium stannide Mg ₂ Sn (270 microvolts / degree Kelvin), zinc antimonide SbZn (220... 300) micro volt / degree Kelvin). The data are relative thermal forces of the stoichiometrically producible basic substances, which can be increased significantly by suitable doping (embossing of p-type and n-type). Furthermore, there are zinc semblindable compound semiconductors that can be obtained by mining. For their use in thermoelectric arrangements, only rough, mechanical cleaning processes or selections of crystal types are required, since there are no calibrated microelectronic chips, but anyway only thermoelectric arrangements fluctuating in terms of power supply.

Procurement costs and technical outlay for natural thermoelectrics ( 3 ) in thermal legs ( 7 ) with a foam structure component

The cost of crystal cutting - especially for dicing - is low. Thermoelectroactive grain sizes ( 17 ), together with indifferent conductive lacquer components, arrive in mixing drums, where wetting takes place to a paste-like consistency. Air-curing, thermoelectroactive pastes can be filled and pre-rated.

It corresponds to the events and facts that have occurred that the worldwide historical and current lead extraction is largely from galena (galena), currently lead-acid automotive batteries are piling up nationwide, but for an installed thermoelectric one  Power of 1 KW not even 10 kg "lead ore" are required. The chemically pure Accumulator lead is suitable with sulfur for large-scale, hydrothermal direct synthesis of galena (lead sulfide).

The brass-gold shiny pyrite became a certain time for the production of transistors uses 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 equally processable chalcopyrite or other natural or synthetic thermoelectrics ( 3 ). However, the synthetically accessible pyrite, like silicon, requires more complex, energy-intensive crystal growing, which only yields much smaller crystals. The waste of natural pyrite (SO ₂ - environmentally harmful roasting process for the production of FE ₂ O ₃ ) and the other highly efficient compound semiconductors is no longer justified.

Aligning pronounced anisotropic thermoelectrics ( 3 ) in the thermoelectric preferred direction (claim 15)

In most cases, the crystalline forms - and of which preferably the cubically crystallizing, isotropic (without thermoelectric preferred direction) - are best used for the compound semiconductors that can be selected from ore deposits. Isotropic property means: no preferred direction for physical effects). For example, a specifically equally well-contacted transition with fine-grained, octahedral galena (PbS = galena) brings only part of the thermal current, like a correctly selected, equally large area on a single crystal that is in surface contact with a metal, compound semiconductor or other thermoelectric material ( 3 ) located. On the other hand, even large pyrite cubes (e.g. with a 5 cm edge length) show high conductance and the same differential thermal forces at every point on their surfaces - and even over the longest corner point connection. In this respect, grain sizes gently prepared from it always remain cubic crystallized pyrite granules or powder (even in a distributed state). Anisotropy is gradual. Thus, "disorderly" distributed weaker anisotropic thermoelectroactive grain sizes ( 17 ) produce higher thermal currents than "disordered" distributed more anisotropic.

In table books, one is satisfied with the specification of thermal voltage values for non-cubic systems with the specification of the values for a temperature gradient perpendicular or parallel to the crystallographic axis. A clear anisotrop The influence of antimony, cadmium and bismuth can be determined.

Galena is also significantly anisotropic and is found in dense or foam structures with suitable fields during the hardening or cooling process lubricated by the surface-localized dipoles of a galena particle as a whole physically an aligning motion component according to the field flow mandatory notification. It is within the framework of professional action, the shift thick of the tough lacquer or glass phases for sufficient field penetration average. It can be static high voltage fields or those that are still with are superimposed on a low-frequency field component. For ferromagnetic cri stable magnetic fields. So pyrite can be permanent Align the magnetic field statistically with pyrrothin that has arisen in the meantime (see claim 15, vapor phase transport).

When crushing, tearing, ultra-fast and hard impact impact or impact mills usually introduce property-destroying lattice defects or tribo-effects, which have a performance-reducing effect, the finer the grain sizes. However, lattice defects can in turn increase the electrical conductivity of semiconducting connections. As a result of the consideration of such processing-technical aspects, mostly mining-degradable, numerous, hydrothermally crystallized compound semiconductors for solar temperature ranges are suitable as thermoelectroactive grain sizes ( 17 ) in thermoelectroactive conductive lacquers ( 16 ) or thermoelectroactive foam conductive lacquers ( 25 ) in a simple way for regenerative, reactive energy generation Claim 15, formation).

Simple but efficient ways of increasing differential thermal forces through defect and excess treatment and impurity doping

Galena and pyrite are still highly effective with themselves in homojunction efficient thermoelectric pairing possible. The type and density of those to be generated The necessary charge carriers for thermal currents can be used for galena PbS between approx. plus 700 microvolts (defect conductor) and minus 500 microvolts (excess conductor) per Set degrees Kelvin. For this purpose, the galena = PbS after sulfur treatment as so-called defect semiconductor or by means of extracting vacuum treatment as Excess semiconductors are formed.  

A thermocouple of the two is ideally suited for solar temperature offers and provides 120 millivolts of thermal voltage 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. For strong thermal currents, the intrinsic conductance is high enough. B. with conductive rubber ( 37 ) or conductive varnish is important. The temperatures that can be applied are above the highest temperature limit of non-focussing thermal solar technology, but they do work with heat trapping devices.

The expensive, tin-lead-soldered thermoelectrics ( 3 ) of the bismuth telluride series, which can withstand normal loads of up to 60 degrees Celsius, achieve far less with 264 connections in series (test measurement) than an identical temperature gradient made from "naturally pure" lead-luster crystals. 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 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 ). It can be positively assumed that large quantities of compound semiconductors obtained at a site have relatively constant values. This is irrelevant for the series connection of thermoelectric individual elements supplying different thermal voltages with regard to a direct current output power, since the voltages and currents fluctuate depending on the temperature anyway.

Direct foaming of non-metallic thermoelectrics ( 3 ) (claims 9, 15)

If the semimetal selenium is in foamed form after completing Temperaturhal areas above 72 degrees Celsius are brought into the black, metallic form, the result is a highly active thermoelectric with differential thermal forces up to approx. 700 microvolts per degree Celsius in a range up to almost 200 degrees Celsius. The temperature resistance can be obtained from conventional selenium rectifiers deduce. Foamed, subsequently broken into hexagonal recrystallized (black) form tes, metallic selenium has foam-like strength and similar thermal insulation values such as rigid polyurethane foam or Styrudor on and in dense form at 239 degrees Kelvin comparable electrical  Conductivity of 8 MS / m about like the metal chrome (7.8 MS / m). With the peculiarity tional semiconductors Selenium are more easily traceable (because they are introduced into the melt barer) doping many effective thermoelectric pairings possible. Suitable Thurs The element semiconductors selenium provide additional external conductivity component and when exposed to light the thousandfold conductivity of the undoped Se lens.

The thermoelectroactive collector hood ( 19 ) - useful application for active leg parts ( 2 ) with semiconducting waste from semiconductor produce and processing industries ( 6 )

With the application of the thermoelectroactive collector hood ( 19 ) there are significant opportunities to use different, semiconducting waste grain size classes of the semiconductor industry with the same material. Starting with waste when extracting grown crystals, the production of wafers and their cutting, to waste from solar cell production or chip production, fractions can be separated and used to manufacture 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 during further processing, such as the waste of polycrystalline or monocrystalline silicon in solar cell production - all of these are 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 (GaInAs), GaInAsP, 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. With granulated, dense metallic selenium, edge losses in the manufacture of silicon wafers or primarily doped crystalline, optionally made from alumino thermally obtained silicon (see claim 19), the above-mentioned synthetic or mined compound semiconductors as contactable 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 lacquer ( 18 ) serves as an embedding compound for all thermoelectroactive grain sizes, an intrinsically conductive lacquer 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.

These are now a voluminous to thin-layer curing of a thermoelectrically active conductive varnish ( 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 1200 microvolts per degree Kelvin. Thermal forces that would soon dull in the case of weathered 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 with regard to its electrical conductivity to relatively low-resistance values and can thus be made suitable for thermoelectric arrangements.

On foamed passive leg parts ( 4 ), porous penetrating, anchoring, elastic, after setting, rubber-like shapes of thermoelectroactive collector hoods ( 19 ) can be applied as an active leg part. Active leg parts ( 2 ) designed in this way are dense, gra duell from softly fitting, to hard consistency possible, setting composites from basic lacquer components of previously liquid, crosslinkable polyisocyanates and polyols or in the setting of trimerizing polyisocyanates. The property of gradual elasticity, which can be added to various degrees of foaming, makes the PUR lacquer base component one of the most important, after being mixed with active phase components for each type of Ihermoskel ( 7 ) proposed according to the invention with a foam structure component. It is important to know here that large-area thermoelectric converter units with foam-stretched active phases with non-intrinsically conductive base component components can nevertheless deliver impressive electrical performance in the high efficiency range due to its lower specific thermal current densities. 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, grouting compound, which offers the best processing opportunities for large-area thermoelectric modules ( 1 ) in shells of building envelopes.

Namely, the thermoelectroactive conductive lacquers ( 16 ), which are necessary for the constructive, functional design of each individual thermoelectric element ( 6 ), can advantageously be bound by chemically docking normal PUR lacquers.

High temperature foaming of magnetite (claim 10)

The best suited for foaming (over 1500 degrees Celsius) is the compound semiconductor Fe ₃ O ₄ , which can be used as a thermoelectric ( 3 ), which becomes light in a foamed form and remains highly fire-resistant. Its use is inexpensive (see claim 10). Already as ore, it has considerable current conductivity (0.005 Ohmcm), is as hard as pyrite (hardness according to Mohs 5.5-6.5) and is also pure and concentrated, e.g. B. from the highly exothermic burn-up of iron turning chips. Fe ₃ O ₄ is the resulting oxidation and waste product of every annealing treatment of steel and iron.

It 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 one homo junction. Its conductivity is excellent for thermoelectric applications, as is the granite-like fire resistance and weatherability. The thermoelectric coupling with sulfidic, selenidic, arsenidic other than ore-degradable compound semiconductors is possible. The strength of continuously foamed thermo-leg ( 11 ) or integrated active-passive thermo-leg ( 14 ) is close to that of cinder blocks, which enables a load-bearing and sturdy use under sun-heated bitumen ceilings.

Reinforcing and conductance-optimizing reinforcements in load-bearing foam structure associations (claim 10)

In addition, thin, electrically conductivity-imparting, at the same time mechanically strengthening, fibrous reinforcements with a high functional proportion, but hardly any heat-reducing effect, can be introduced into the structural longitudinal structure of large-sized integrated active-passive thermal legs ( 14 ) or continuously foamed thermal legs ( 11 ). For example, high-strength carbon fibers (see claim 10).

Selenium can be foamed in the amorphous phase and thermally above 72 degrees Celsius permanently formed in a black, metallic shape that is resistant to up to 200 degrees Celsius be (see claim 15).

The strength of the thermoelectroactive foam structure is achieved with reinforcements made of selenium-offset, semiconducting glass fibers. A special form of a self-reinforcing, foam structure-like composite is formed by 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 then 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. The thermoelectric preferred direction and the ferromagnetic subparticle ( 44 ) are arranged in such a way that magnetic and electrical field components act simultaneously, so that orientation before contact sintering ( 45 ) can only be carried out later with the easier to implement, mostly more thorough magnetic field component (see claim 15). In the accompanying formation, at least the dense structures 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 viscous layer thicknesses of the green body approaches emerging from a narrow slot nozzle. In addition, the emerging monomeric strips can be layered endlessly with an alternating 90 degree tilt, which receives a complete directional characteristic through periodic flooding of each newly applied layer, which is photopolymerized by immediately subsequent doses of ultraviolet or blue light laser beams. Instead of the stack layering, the winding of a glass band onto a cooling, elongated roll with periodic photopolymerization can also take place.

Metal sintering or foaming

Metallic foams ( 10 ) take up a large amount of space in the production of the new thermoskeleton ( 7 ) according to the invention, since they have high electrical conductivities and the requirement for technological mastery of charge carrier transmission between the thermoelectroactive ( 30 ) and through-contacting active phase ( 26 ) as in non-metallic foam structures necessary - no longer required. They can be made in seconds and then stored for any length of time. The modern metal foaming is contrasted by the long-established powder-metallurgical sintering processes, which could possibly be considered for a correspondingly structured thermal muscle ( 7 ).

Certain regimes of controllable, beginning metal sintering or pre-sintered porous granules with applied metal skins / layers can lead to reasonably usable large-pore structures in the construction of thermo-limbs ( 7 ) which, with an insignificant reduction in electrical conductivity, show significantly increased thermal insulation and noticeable weight savings (see claim 4, surface-area crusted, pre-inflated particles). 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 varnish ( 18 ) and, after drying / curing, again surrounded with a layer of thermoelectroactive conductive varnish ( 16 ) will. Pyrotechnics offers analog, mature processes with processing the same consistencies, where instead of indifferent ( 18 ) and thermoelectroactive conductive varnishes ( 16 ) similar batch consistencies for black powder bark are built up on star tablets and spheres. This would be a special form of sintering with thermoactive success and a high K value.

Regarding the evaluation of results for the design of continuous thermo-limbs ( 7 ) from sintered qualities of never-before-processed metals / alloys / intermetallic phases / intrinsically conductive element semiconductors / compound semiconductors, a compelling level of knowledge derives from powder metallurgical processes in the production of thermoelectrics ( 3 ). The most differentiated manufacturing technologies for sintered composites for thermoelectric applications have been mastered here for some time. The results indicate that even the highest thermal emf has not yet been able to be used properly, because sintered composites of thermal legs always allow large amounts of heat loss to pass through ( 8 ).

Although there is the contributing phonon-drag component of the overall thermal EMF, according to which the phonon movement of the heat loss ( 8 ) carries electrons with it from the hot to the cold end, this addable component is calculated at room temperature: Thermonforce component is the phonon-drag component e = proportional 1 / T.

Powder metallurgical processes for pure metals therefore firstly do not expect high thermal insulation to be able to build high-performance thermoelectric modules ( 1 ) with the relatively low thermo-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.

In particular for the thermoelectrics ( 3 ) of the thermoelectric conversion taking place in low-temperature ranges, detailed knowledge of the prior art for bismuth-antimony-lead telluride series was obtained for component milling, pressing and sintering with regard to the continuous design of thermo-limbs ( 7 ) (see above) , as well as for medium and high-temperature thermoelectrics ( 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 brief foaming, in Compared to those for sintering metals lasting several hours considerable qualitative differences in the structures that can be achieved and whose properties can be determined.

Strongly porous sintered metals show noticeably higher thermal resistance values compared to homogeneous, dense metallic blocks. The sintered composite provides but still too dense, again "collapsed packing densities" of the sintered parts kel - with only limited thermal insulation, but with emerging disadvantages. they hang together with the cemented, merged interfaces of the Gesin ter particles. These transition zones have become impure - wise concentrates onslope or crystallization of inner metal companions on or during the long sintering period of newly absorbed substances. From transition zones can even Barrier layers will be.

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-cell structure remain fine crystalline, pure metal in the short foaming phase, with correspondingly high electrical conductivities. In this respect, there is an excellent suitability for the production of heat-insulating thermal legs ( 7 ) of thermoelectric converters.

The foaming, which only lasts up to ten seconds, leaves no material changing, unwanted crystallization processes, current blocking concentration ver metal contaminants or the entry of foreign matter (e.g. oxy danten and the like).

Metallic foams ( 10 ) are therefore a novelty and the best basis for reducing heat loss in thermal power generation compared to the heterogeneous structures of porous sintered metals or thermoelectrics ( 3 ).

The sintering of known, highly efficient thermoelectrics ( 3 ), which leads to dense structures and is controlled by a complicated technical regime, achieves the highest, previously unattained efficiency ranges through inter-layered metal foam structures and the entire regenerative thermoelectric power generation reaches a completely new position.

Description of the graphic representations

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 β-zinc antimonide and bismuth antimony alloy as the thermoelectrics used ( 3 ). The thermocouple ends are contacted by indifferent collector hoods ( 15 ) and are themselves a hardening of indifferent conductive lacquer ( 18 ) containing the bridge electrodes ( 13 ). The most suitable arrangement of the alloys from cheap basic metals develops in the solar temperature range approx. 30 millivolts per 100 degrees Cel sius temperature difference with high electrical conductivity.

The thermal entry into the indifferent collector hoods ( 15 ) which form black / n and p / n transitions and which form black is best carried out by means of striking, recombining solar radiation or otherwise.

Fig. 2 shows already performed, field-effective straightening processes of the pre-inflated particles provided for contact sintering ( 45 ) with thermoelectroactive layering.

In the same, the ferromagnetic subparticles ( 44 ) can be seen, the white areas of which were arranged under the influence of a magnetic field, during which a simultaneously acting electrical field component polarized the thermoelectroactive grain sizes ( 17 ) in the resinous phase in the thermoelectric preferred direction. The upper part of the drawing shows three pre-inflated, stratified particles in this prepared phase, in mechanically caused positional disorder. The middle part shows the regained alignment of a loosely poured total of these particles only under the influence of a magnetic field due to the directivity of the ferromagnetic subparticles before the start of sintering. In the lower part you can see in detail the three upper, now precisely positioned, pre-inflated particles and the overall thermoelectric preferred direction of the thermoelectrically active grain sizes ( 17 ) in their stratification, which subsequently operate in a field-effective regime below the Curie temperature of the ferromagnetic material Subparticles ( 44 ) are contact sintered.

Fig. 3a shows composite thermal legs ( 12 ) with the use of cut crystal wafers as thermoelectric ( 3 ) for the corresponding active leg parts ( 2 ) - for example pyrite FeS ₂ and chalcopyrite CuFeS _2nd These are applied with an indifferent conductive varnish ( 18 ) to plane-cut blocks of metallic ( 10 ) or non-metallic foam ( 31 ) in a homogeneous contact. In the same way, the bridge electrodes ( 13 ) are contacted with the tops of the crystal wafers, subtracting thermal stresses being avoided. A separate heat / cold control device ( 21 ) is indicated in the top left of the illustration - on the right is the direct radiation of a solar supply. In the case of assembled thermal legs ( 12 ), the largest volume fraction, as shown, is occupied by the foamed passive leg parts ( 4 ). These are generally only through-contacting and are not capable or provided for the formation of thermal voltages. Based on the graphic representation, he would bring a metallic foam ( 10 ) made of copper against pyrite, very significant, usable thermal stresses, which would make applications in this direction possible.

If non-metallic foam structures with non-intrinsically conductive lacquer base components are used, then conductivity mediators ( 20 ) must be provided in order to implement a through-contact active phase ( 26 ).

Fig. 3b shows geometric installation forms of bridge electrodes ( 13 ) and integrated active passive thermal limbs ( 14 ) which can be added according to the graphical representation of the cementing profile contact ( 39 ) or the guide profile contact ( 40 ). The result of the side-by-side arrangement of the shown series circuits of the density and component-differentiated foamed thermos legs ( 7 ) is a thermally absorbing, possibly in the layer of the bridge electrodes ( 13 ) efficient thermal storage, but overall thermally insulating shell, for example a building shell, which only about Development of thermal currents ( 5 ) enables gentle thermal compensation to the other side. The thermoelectroactive 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 conductive lacquer or press-fit with an intermediate layer made of conductive rubber ( 37 ), which in each case a double (not shown here) screwing or anchoring of the possibly thermally storing, voluminous bridge electrodes into the rigid foam-structured connecting segments of the electrical insulation ( 48 ) would be necessary.

The geometrical fitting profiles of the bridge electrodes ( 13 ) shown in the drawing have as mechanically solidifying heat / cold guide devices ( 21 ) with, for example, copper or aluminum sheet sheathing over their metallic or non-metallic foam structures - which are with or without through-contacting active phase ( 26 ) - and it can All of the cell volumes may be mixed with latent storage media.

Fig. 4 shows a by contact anchor claws ( 22 ) thermally electrically contacted, flexible in itself, thermoelectric arrangement with integrated Aktivpas sivthermoschenkeln ( 14 ). The contact anchor claws ( 22 ) are a type of pliers with claws as shown, which can also be adjusted in an angular position to the heat / cold conductors ( 21 ) via an adjustable force effect, if necessary, via the pivot point of the bed wire ( 47 ) that emerges from the rear ) and thus 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 part of the heat-cold control device ( 21 ). The cross-section and surface of the pierced claws communicate with the impregnated solder layer or a conductive lacquer layer with copper or silver powder components in the outermost region of the thermoelectroactive end zones ( 34 ) the external, thermal offer received by the heat sinks. Pyrite and chalcopyrite in the electrothermoactive end zones ( 34 ) are contained, for example, as thermoelectroactive grain sizes ( 17 ) in the integrated active passive thermocouples ( 14 ), which, with good (ore) quality with a temperature difference of 100 degrees, approx. 160 millivolts per individual thermoelectric element ( 6 ) provide. For the purpose of good heat-cold introduction, bed wire ( 47 ) and contact anchor claws ( 22 ) are made of copper, the pierced claw parts of which have a compensating coating made of Cu / Al or tin or titanium-palladium-silver in order to avoid the copper's own thermal stresses against pyrite-crystal-like compound semiconductors . In graphically and structurally similar arrangements, bare copper contact anchor claws ( 22 ) in pyrite can also be used to generate thermal current if corrosion problems are mastered (copper / pyrite = 66 millivolts per 100 degrees temperature difference).

In Fig. 4, a heat trap technology and prevention of Ver heat heat paths was not drawn in the drawing.

Fig. 5 shows a thermoelectric strand ( 28 ) made of non-metallic foam ( 31 ), which was produced in the push-through method and by means of the differentiated boundary layer foaming ( 29 ). Here, the characteristics of density-differentiated foaming ( 23 ) and component-differentiated foaming ( 27 ) are formed for each of the boundary layer-foamed thermal limbs ( 7 ), which leads to the characteristics for integrated active passive thermal limbs ( 14 ) with regard to the individual strand-connected thermal limbs ( 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 lies in a semicircular, peripheral, circumferential groove of the boundary layer between the thermo-limbs ( 7 ). Thanks to the groove-lining, foil-like layer of electrical insulation ( 48 ), the overall arrangement of the heat-cold control 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. In the pressure-contacted thermoelectric strands ( 32 ), which are not shown specifically here, the indifferent zone is formed by indifferent metal foils ( 38 ) and or guiding rubbers dimensioned with the same area ( 37 ) (claim 14). The conductivity-optimized, indifferent zone is consequently very dense, contains hardly any pores and is also functionally equivalent to the indifferent metal foils ( 38 ) in the cemented profile contacting ( 39 ), which in certain variants of the thermal guide profile contacting ( 40 ) (starting from FIG. 3) cross-section optimized to the outside can also continue in suitably shaped heating / cooling control devices ( 21 ).

Reference symbol list

1

thermoelectric module

2nd

Active leg part

3rd

Thermoelectric

4th

foamed passive leg part

5

Thermal current

6

single thermoelectric element

7

Thermal leg

8th

Heat losses

9

Thermal current path

10th

metallic foam

11

continuously foamed thermal leg

12

composite thermo leg

13

Bridge electrodes

14

Integrated active-passive thermal leg

15

indifferent collector hood

16

thermoelectroactive conductive varnish

17th

thermoelectroactive grain sizes

18th

indifferent conductive varnish

19th

thermoelectroactive collector hood

20th

Conductivity mediator

21st

Heat-cold control device

22

Contact anchor claws

23

density differentiated foaming

24th

indifferent conductive foam

25th

thermoelectroactive conductive foam

26

through-contact active phase

27th

component-differentiated foaming

28

thermoelectric strand

29

differentiated boundary layer foaming

30th

thermoelectroactive active phase

31

non-metallic foam

32

pressure-contacted thermoelectric strand

33

Foamer

34

thermoelectroactive end zone

35

Conductivity-optimized intermediate area

36

oxidative cold start coking

37

Conductive rubber

38

indifferent metal foil

39

cementing profile contact

40

thermal guide profile contacting

41

Conductivity charring

42

Coal structure segments

43

Coal structure intermediate layer

44

ferromagnetic subparticle

45

Contact sintering

46

Growth formation

47

Bedding wire

48

electrical insulation

Claims (20)

1. Methods and devices for the design of thermal legs with foam structure components,
characterized in that:
According to the inventive method, thermal legs ( 7 ) with a suitable dimensioned foam structure portion for the primary reduction of the heat losses ( 8 ) are manufactured in order to achieve a substantial increase in the thermoelectric efficiency of thermoelectric modules ( 1 ), which convert thermal offers into electrical work, by

• - Layers of indifferent, metallic foams ( 10 ) or non-metallic foams ( 31 ) of sufficient electrical conductance are electrically contacted on top and bottom by suitably compact or thin layers of suitable thermoelectrics ( 3 ),
  so that a suitable vertical cut of this areal overall composite results in geometric and functional components for Ihermoskel ( 7 ) with high electrical and low thermal conductivity,
• - metallic foams ( 10 ), if appropriate, non-metallic foams ( 31 ) with the ability to develop sufficiently own thermoelectric EMF (thermoelectromotive force),
  are designed with suitable geometric dimensions and contacting ability as geometrically adaptable and functional active components for thermo-legs ( 7 ),
• - Foamed to dense, non-metallic, electrically conductive to non-conductive organic compounds, partially or fully with Thermoelek trika ( 3 ) in suitable multiple composite structures equally to thermo legs ( 7 ) are formed.

2. The method and devices according to claim 1,
characterized in that:

• - Thermal limbs ( 7 ) with a foam structure portion are to be classified and assessed according to their proportions with regard to a thermoelectroactive active phase ( 30 ) and those of a through-contacting active phase responsible for charge carrier transport ( 26 ), the former forming the thermoelectrical EMF, which are in the the through-contacting active phase ( 26 ) moving charge carriers is impressed,
• - The entirety of special, partly different, particulate conductivity mediators ( 20 ) in dense or foam structures of the thermocouple ( 7 ) form the through-contact active phase ( 26 ) and primarily ensure charge carrier transport or electrical conductivity,
• - suitably particulate grain sizes of a p-type thermoelectric ( 3 ) within dense or foam structures of the thermal limbs ( 7 ) form the p-type and suitably particulate grain sizes of an n-type thermoelectric ( 3 ) form the n-type thermoelectric active phase ( 30 ),
• - The thermoelectroactive active phase ( 30 ) can partially take over the tasks of charge carrier transport, up to the complete replacement of special conductivity mediators ( 20 ),
• - from this a production-related classification with regard to geometric shapes and contacting joining techniques
• - continuously foamed thermo legs ( 11 )
  with homogeneous,
  with differentiated phase distribution,
• - thermoelectric strands ( 28 ),
• - composite thermo legs ( 12 ),
• - Pressure-contacted thermoelectric strands ( 32 ),
• - integrated active passive leg ( 14 )

results. 3. The method and devices according to claims 1 and 2,
characterized in that:

• - For the thermoelectroactive active phase ( 30 ) to be introduced into dense and foamed structures of thermal legs ( 7 ) in each case and primarily a unique, existing population of thermoelectroactive grain sizes of suitably divided intrinsically or externally conducting element semiconductors, compound semiconductors of naturally mineable occurrences of orifices, glosses and gravel or synthetically obtainable, likewise obtainable or representable, intermetallic compounds, intermediate phases or special, synthetically developed thermoelectrics ( 3 ) with optimized figure of merit, primarily also only with a high product of differential thermal power and electrical conductivity, which can also be obtained or represented by synthetic methods - can be considered,
• - For the, in dense and foamed structures of thermal legs ( 7 ) to be introduced through-contacting active phase ( 26 ) a multi-purpose, not mutually corrosive attacking population of particulate, corpuscularly dispersed conductive conductivity mediators ( 20 ) are used and that these gradually suitable divided metals , Metal oxides, metal nitrides, metal borides, non-metal borides and nitrides which are made externally conductive by suitable doping, metal sulfides, ion and super ion conductors, such as copper, copper sulfide, tin, silver, silver sulfide, aluminum, nickel, titanium, titanium nitride, lithium-doped titanium disulfide Magnetite are
• - Semiconducting chalcogenide glasses with binary, ternary, quaternary semiconducting silicate systems with sulfur, selenium, tellurium, arsenic and cadmium, zinc, iron, bismuth, titanium, copper, silver and those based on some transition metal oxides such as Cu ₂ O and Fe ₂ O ₃ and other, suddenly triggerable conductivity levels with one low-resistance, thermo-electroactive and on the other hand a high-resistance characteristic and the unlimited change between the two levels with regard to thermo-electroactive low resistance with voltage surges higher than 50 volts, with respect to high resistance with adjustable current surges can be achieved,
• - The degree of division of the through-contacting active phase ( 26 ) is mostly greater than that of the thermoelectroactive active phase ( 30 ),
• - Gray, always normal powdery, semiconducting, cubic microcrystalline lines alfa tin for the design of the thermoelectroactive active phase ( 30 ) thermoelectroactive end zones ( 34 ), mainly in intrinsically conductive, further made conductive structures of non-metallic foam ( 31 ), or in dense intrinsically conductive or conductive lacquer basic components for the manufacture of moldable thermoelectroactive collector hoods ( 19 ),
• - The cubic gray alfa tin is produced by cooling pure pulverized gamma tin at approx. -48 degrees Celsius with the greatest rate of formation and the formation of easily pulverizable, rhombic gamma tin by heating ductile, pure beta tin to over 162 degrees Celsius
• - to design the through-contact active phase ( 26 ) conductivity-optimized intermediate areas ( 35 ) with 0.5% bismuth or antimony tin alloy in powder form is used,
• - Elastic, conforming special forms for through-contacting ( 26 ) and thermoelectroactive active phases ( 30 ) can be generated by respective proportionate vulcanization of conductivity mediators ( 20 ) and thermoelectroactive particle sizes ( 17 ) in rubber, butadiene or diorganopolysiloxanes, or polymerizing in trimerizing polymers.

4. The method and devices according to claims 1, 2 and 3,
characterized in that:

• - The generic long-term foamed thermal legs ( 11 ) relate to those with homogeneous active phase distribution and those with differentiated active phase distribution,
• - Thoroughly homogeneously foamed thermo-limbs ( 11 ) with homogeneous active phase distribution, primarily from a previously compact portioning of a respective n-type or p-type thermoelectric ( 3 ), are closed-cell foamed and, in the simplest case, continuously foamed cells of the same size, in particular in the case of metallic ones Foam structures have, where appropriate, completed a differentiated density foaming ( 23 ) prior to final shaping or have been obtained by cutting them out of recoverable, density-differentiated foam structures of non-metallic foams ( 31 ) and also metallic foams ( 10 ).
• - To the continuously foamed Ihermoskeln ( 11 ) with a homogeneous and differentiated proportion of the active phase, depending on the design, those can be added, which are designed as a sintered composite pre-expanded, with thermoelectric ( 3 ) surface-incrusted particles and that the end face p / n and n / p transitions the continuously foamed thermal limbs ( 11 ) are intercontacted in this way with indifferent collector hoods ( 15 ) connected via bridge electrodes ( 13 ) or by means of cemented profile contacting ( 39 ) or thermal guide profile contacting ( 40 ),
• - The cementing profile contact ( 39 ) with an intermediate layer of indifferent metal foil ( 38 ) or the thermal guide profile contact ( 40 ) for the connection of p-type and n-type foam structures of all types of continuously foamed thermal legs ( 11 ) are used,
• - A consistent, sufficiently firm, by foaming pressure carbonization of organic substances adaptable to any internal hollow shape, homogeneous by contacting active phase ( 26 ) in the form of a carbon structure by oxi dante cold start carbonization ( 36 ) (with oxidant portion) or by hot carbonization, which can be electrically conductive leads to highly heat-insulating structures, the suitable cutting of which leads to continuously foamed thermo-limbs ( 11 ) with a homogeneous active phase distribution,
• a possible thermal aftertreatment of any degree of surface-adherent, densely differentiated foaming ( 23 ) of the carbon skeleton, reproduced by the cracking process of rich hydrocarbon gases with surface-compacting carbon deposits,
• Thermoelectrics are sputtered or evaporated onto the surface of the carbon structure,
• - In an analogous procedure, continuously foamed thermal legs ( 11 ) with carbon skeleton and differentiated active phase distribution contained therein can be produced by adding a previously differentiated wedged amount of thermoelectroactive in the suitably divided, compacted organic starting materials such as dense cellulose, starches, sugar and protein substances Grain sizes ( 17 ), subsequently leads to the formation of thermoelectroactive end zones ( 34 ) in the remaining carbon structure, which can be formed by plane or contour grinding and cementing conductive lacquer contacting to p / n and n / p transitions,
• - The conductance-connecting joint charring ( 41 ) of coal structure segments ( 42 ) represents the possibility of practicing a mosaic-like cubic joining technique, with which large carbon framework blocks for correspondingly large and diverse variants of thermal legs ( 7 ) are technically achievable by using the carbon structural segments ( 42 ) charred glues are joined and, via inductive eddy current, galvanic current-conducting or otherwise suitably caused internal heating in the joints of the composite coal structure segments ( 42 ), converts the glue-pressed joint into an electrically-interconnected coal structure intermediate layer ( 43 ),
• - In the glue-pressed joints of the prefabricated carbon structure segments ( 42 ), parallelized carbon fibers allow a gentle formation of the carbon structure intermediate layer ( 43 ) by means of resistance heating, which can be generated locally in the joints and is triggered by the flow of electrical currents,
• - Partial or continuous gluing or cementing of the carbon structure segments with themselves to large carbon framework blocks or subsequent functional contacting elements can be carried out by means of an indifferent conductive varnish ( 18 ) and this indifferent conductive varnish ( 18 ) is compositionally appropriate to the task, optimized conductance - with regard to thermal insulation that cannot be reduced thermal legs ( 7 ) to be finally manufactured,
• - In the case of continuously foamed Ihermoskeln ( 11 ) with differentiated active phase distribution, the feature of density-differentiated foaming ( 23 ) can be replaced or supplemented by that of a component-differentiated foaming ( 27 ), with regard to a zone-like distribution of the prevailing thermoelectroactive active phase ( 30 ) in terminal thermoelectroactive end zones ( 34 ), which go to a central, mass-predominant, indifferent, exclusive conductance-optimized intermediate area of the foam structure and that this more demanding zone structure leads to the so-called, integrated active passive thermal muscles ( 14 ) according to the invention,
• - Continuously foamed thermal leg ( 11 ) optionally with the inventive method of differentiated boundary layer foaming ( 29 ) in one go and with the formation of p / n and n / p transitions as a series circuit, in the form of so-called thermoelectric strands ( 28 ), are cash,
• - The feature of density differentiated foaming ( 23 ) in the strand-connecting differentiated boundary layer foaming ( 29 ) thermoelectric strands ( 28 ) for reasons of the constructive introduction of heat and cold control devices ( 21 ) primarily that the component-differentiated foaming ( 27 ) possible for reasons of savings for thermoelectrics ( 3 ) with regard to the thermoplastic legs ( 7 ) to be foamed.

5. The method and device according to claims 3 and 4,
characterized in that:

• - The indifferent collector hoods ( 15 ) have homogeneous end surface contacting, charge carrier collecting and exchanging, extensive applications which are hardenable, non-positively cementing, indifferent conductive varnish ( 18 ) in the surface-opened pores of the foam structure and are accordingly only capable of further electrical contact, but no own thermal EMF develop,
• - The p / n-intercontacting, series-connected arrangements indif ferent collector hoods ( 15 ) engaging in the same contacting the bridge electrodes ( 13 ) by using thermal-electrical, highly conductive, indifferent conductive lacquer ( 18 ) and shaping the bridge electrodes ( 13 ) to increase the surface area Heat and cold control devices ( 21 ) are designed to be thermally well-receiving and forwarding and thus result in the functional hot and cold contact points of the thermal legs ( 7 ), which are capable of forming a maximum thermal EMF in this embodiment of the device.

6. The method and device according to claim 2 and the preceding,
characterized in that:

• - For the conductance-optimized construction of thermo-limbs ( 7 ) with a foam structure portion, variants without technological application result in the intermediate step (pull-through method), but in particular also those with procedural steps of joining thermo-limb parts, the latter dividing their functional division into thermo-EMK-developing limb parts ( 2 ) and makes the thermal current ( 5 ) conductive, foamed passive leg parts ( 4 ) necessary,
• - especially activated leg portions (2) of availability, formability and effektivster usability of the original thermal elektrika (3) either discretely made of compact thermoelectric material (3), or their appropriate distribution ausformbaran depending on the material in advance adaptable thereafter ze ment hard springkittartigen or elastically soft, electrically-ther there are mixed contacting embedding compounds, which in turn require dividing types of trouble-free contact to the foamed passive leg parts ( 4 ) and to themselves,
• - Concentrated thermoelectroactive grain sizes ( 17 ) in natural rubber, synthetic or silicone rubber of different elasticity can be formed by permanent pressure components sufficient, homogeneous areal contacts to foamed passive leg parts ( 4 ) and with each other,
• - Active leg parts ( 2 ) are directly or indifferently intercontacted against one another, form the p / n and n / p transitions required for thermoelectric conversion and, in the case of their temperature differences, form the thermo-EMF and from primarily dense, electrically conductive soldered, welded, glued, cemented, optionally frictionally contacted disks or thinner layers of thermoelectrics ( 3 ), which can be metals, element semiconductors, naturally occurring or synthetic compound semiconductors, intermetallic compounds, intermediate phases and modern, synthetic multi-phase alloys with optimized figure of merit,
• - For the purpose of intensive, thermal entry, the cut crystal wafers ben natural or synthetic thermoelectrics ( 3 ) with thermally con-concentrating end regions are accordingly connected to thermally input surfaces on their outer crystal wafer surfaces and accordingly subsequently have a transition to bridge electrodes ( 13 ), which are accordingly surface-related to thermal entry are formed and thus fulfill the function of a heat / cold control device ( 21 ),
• - The constructive solution of the thermal guide profile contacting ( 40 ) is to be used before pictorial for thermal entry into the p / n and n / p transitions of discrete disc-like and layer-like thermoelectrics ( 3 ) in the case of active leg parts ( 2 ) designed in this way,
• - Such pre-designated thermoelectrics ( 3 ) as suitably particulate, so-called in this way, thermoelectroactive grain sizes ( 17 ) in a similarly shaped, contacted, hardened embedding in different conductive varnish ( 18 ) to the extent that equally discrete active leg parts ( 2 ) result that are functional as are further designated according to the device as thermoelectrically active collector hood ( 19 ),
• - The thermoelectroactive collector hood ( 19 ) accordingly a dense bond of the thermoelectroactive active phase ( 30 ) in the form of thermoelectroactive grain sizes ( 17 ) with the through-contacting active phase ( 26 ) in the form of surrounding curing of an indifferent conductive varnish ( 18 ), where the thermo- EMF can be tapped at the contactable surface contours of the thermoelectroactive collector hood ( 19 ),
• - Foamed passive leg parts ( 4 ) are the central to the predominant part of thermo-limbs ( 7 ) between two ends of the active leg parts ( 2 ) which are in contact with the surface in a homo gene manner, with the function of improving the efficiency of the thermoelectric conversion by substantially blocking the active leg parts ( 2 ) lend themselves to the loss of heat flows ( 8 ), which is why the foam structure is primarily a closed-cell, metallic foam ( 10 ) or non-metallic foam ( 31 ) with sufficient electrical conductivity and contactability without the need for a self-developable thermal EMF.
• - With regard to improved contactability of the end faces of foamed passive leg parts ( 4 ) are the same result of a previous density-differentiated foaming ( 23 ), which produces higher densities near the end face of the foam structure there.

7. Device according to the preceding claims,
characterized in that:

• - Composite thermo-legs ( 12 ) according to claim 4 each consist of two end active leg parts ( 2 ) and a central foamed passive leg part ( 4 ), the latter having a conductance-optimized foam structure in that it has a minimum of thermal conductivity with a maximum of electrical conductivity connects and this conductance optimization ensures that the adjacent, semiconducting transitions of the active leg parts ( 2 ) are left with a thermal offer for thermoelectric conversion that is hardly reduced by heat losses ( 8 ),
• - Composed thermal legs ( 12 ) in the form of single rods with indifferent collector hoods ( 15 ) contacted by bridge electrodes ( 13 ) with regard to their p / n and n / p transitions, provided that compact disks or layers of thermoelectrics ( 3 ) are processed,
• - the compact panes or layers of thermoelectrics ( 3 ) are cemented onto the end surfaces of the foamed passive leg parts ( 4 ) with gap-filling, indifferent conductive lacquer ( 18 ),
• - thermoelectroactive collector hoods ( 19 ) with bridge electrodes ( 13 ) as active leg parts ( 2 ) are applied in one go to the end cover surfaces of the foamed passive leg parts ( 4 ) and then cemented or afterwards as a finished form cemented with indifferent conductive varnish ( 18 ),
• - End forms and angled forms are kittet end with indifferent conductive varnish ( 18 ) for the purpose of contacting the p / n and n / p transitions,
• - These types of connections for single rod, arch or angle shapes for thermal trapping with recessed in them and protruding beyond their surfaces reinforcements of heating-cooling Leiteinrich devices ( 21 ) are optimized.

8. The method and device according to claim 6 and the preceding, characterized in that integrated active-passive thermo-limbs ( 14 ) have a continuous, obtained in one process, closed-cell structure made of metallic cal ( 10 ) or non-metallic foam ( 31 ), with respect Lich electrical conductivity, formation of a thermal EMF, thermal insulation and inherent strength is optimized, which is at least the result of a density-differentiated ( 23 ), but mainly brought in component-differentiated foaming ( 27 ) - with the characteristics of the sufficient presence of a purely through-contacting active phase ( 26 ) in the foam structure, which is partially substituted and or supplemented in the two terminal areas of the pair of legs to be contacted by a sufficient proportion of a potential-forming thermoelectroactive active phase ( 30 ). 9. The method and device according to claim 1,
characterized in that:

• - Metallic foams ( 10 ) and non-metallic foams ( 31 ) result of foaming from solid, defined liquid or with different consistencies and viscosities, multi-component, specially prepared phase, which when foamed in a density and component-defined - if necessary - differentiated, closed-cell foam structure is brought into place, if necessary with subsequent completion of formation processes in a still hot or tough phase and afterwards for cooling to normal temperature,
• - An incrusting one- or two-layer structure creates the conditions of an electrically conductive base with thermoelectroactive layer on pre-inflated particles of foam granulate or carbon structure - for the purpose of subsequent contact sintering ( 45 ) to foam structure-like volume-cutting and sawable or in the sintering process structure geometrically identical leads,
• - The incrustation-applied layers are produced by introducing the initially neutral, electrically intrinsically conductive or non-conductive particles into mixer drums, in which, in the first step, in the case of non-existent intrinsic conductivity, the addition of a suitably viscous paste of indifferent conductive lacquer ( 18 ) takes place and that after drying in a two-th mixer drum, a layer of thermoelectroactive conductive lacquer ( 16 ) is applied in the same way,
• the sintering takes place by suitable pressing, extrusion of the incrusted particles which are still wet in the outer layer or gradually predried, with the end result of multiple partial contact-making transition zones between the particles in the foam structure-like composite,
• metallic foams ( 10 ) are the result of a differentiated heating of metals, in which the closed-cell structure of the foam structure is the result of an impact-like, metallic vapor phase of these metals, the metals themselves being the foamer ( 33 ),
• - Metallic foams ( 10 ) are the result of a sudden energy input in their stored liquid phase, which contains a much lower boiling metal than the foamer ( 33 ) in a suitable proportion, which spontaneously evaporates due to the heating shock and thus the closed-cell structure of the metallic foam ( 10 ) builds up,
• - metallic foams (10) are a result of a sudden energy input into the dense liquid phase of metals, which contain a particulated or korpuskulardispers constantly swirling distributed held foamer (33) which vaporizes when heated shock,
• - Non-metallic foams ( 31 ) can be produced from electrically conductive, pure or composite, defined liquefiable elements or compounds using the same method,
• - Electrically conductive, non-metallic foams ( 31 ) optionally with a purely through-contacting active phase ( 26 ) and or with a thermo-active active phase ( 30 ) with a starting basis of paste-like consistencies of conductive thick-film pastes, electrically conductive-value-maximized resistance paste systems with thermally limited, organic lacquer base components and their auxiliaries The result of the thermally-induced, dissociative decay of a foamer ( 33 ), which takes place below the temperature level of impairment of the sensitive overall composite systems and their active components, such as conductivity mediators ( 20 ) and thermoelectroactive grain sizes ( 17 ), and provides indifferent cell gases that last for longer or permanent presence in the cells of the foam structure are anti-corrosive and indifferent and accordingly predominantly require sensitive, dielectric heating according to professional judgment to foam such composite systems make
• - Non-metallic foams ( 31 ) with a base of organic and inorganic, already electrically conductive basic lacquer components, such as polyacetylene, poly-sulfur nitride, or suitable organic chain compounds with polarizing side chains accordingly get a cell wall structure that is already conductive without an incorporated conductivity mediator ( 20 ),
• - Non-metallic foams ( 31 ) with frits made of low-melting glass components (at 320-480) degrees Celsius with the addition of conductivity mediators ( 20 ) and or thermoelectroactive grain sizes ( 17 ) to electrically conductively optimized and thermoactive dense, glass-like or foamed cell wall structures of a closed cell structure , whereby part of the load carrier transport takes place through trap tunneling.

10. The method according to claim 9,
characterized in that:

• - The production of density-differentiated foams ( 23 ) of metals and non-metals or suitable foamable, multi-component composite systems by acting low to medium-frequency induction fields with an intensity and frequency-regulating regime for induction currents to be generated and field-penetrating dielectric heating triggering microwaves, depending on the nature the components to be foamed, in particular with regard to their electrical conductivity, the energetic input component of the induction eddy currents acting via resistance heating in a melt-foam hood and the energetic input component of the high-frequency microwave fields acting via dielectric heating are varied with respect to one another and coordinated in a chronologically appropriate sequence or simultaneity,
• - An optimization of the necessary dilektri heating for melting and foaming is achieved only by means of a guideline-oriented setting of the microwave field intensity within a microwave broadband spectrum and then with a frequency-changing regime within the broadband,
• - An optimization of the induction currents for foamable conductive components with an intensity and frequency-influencing regime according to professional, metallurgical basic experience values as well as preliminary tests for the foaming of special metals and semiconductors as well as a dimensional or super ion conductor is carried out,
• - The technical apparatus for inductive foaming is a modified melting hood, with the basic concept of a single-layer cylinder coil and that a determinately pre-liquefied, dense phase with a constantly swirling foamer ( 33 ) by means of the introduction of a targeted energy surge with spontaneous purely physical evaporation of the foamer ( 33 ) is foamed up, the foamer ( 33 ) being a lower-boiling metallic or non-metallic component,
• - A distribution state of a previously particulate, afterwards mix-disintegrating, gaseously dissociating foamer ( 33 ) in the pre-maintained, determined liquid phase due to the temperature jump triggering the energy surge to spontaneous gasification and thus to the large volume-increasing homogeneous Foaming leads
• - For the production of metallic foams metal grit or powder or their ren sintered agglomerations soaked with a solvent with foamer ( 33 ) and after outgassing the solvent vapors the intimately mixed components metal and foamer ( 33 ) from the solid phase by energy shock to foaming to be brought,
• - Microwave fields, which suitably convert non-conductive components with a foamer ( 33 ) into a foam structure by means of dielectric heating, analogously only create a precisely and homogeneously tempered supply phase of the still dense, paste-like, viscous to viscous basic entirety of all components, which can then be entered via a analog energy surge such an amount of dielectric warming in the preheated holding phase cause its spontaneous foaming to occur through the thermally dissociative foamer ( 33 ),
• - If necessary, an expanding, controllable, pressurizing, barometric and acoustic auxiliary regime for the production of metallic ( 10 ) and non-metallic foams ( 31 ) is called, which is also enabled by broadband characteristics to trigger special physical, latent processes for components that build foam structure, to accelerate or it was enough to fix and stabilize conditions, such as frequent pressure - negative pressure states in the not yet fully foamed phase and fixation of the finished foam structure by means of permanently held negative pressure,
• - A sophisticated, gradually gradable, density-differentiating foaming ( 23 ) can be achieved by subsequent, longitudinal zone differentiated, inductive exposure or microwave exposure analogous to the crucible-free zone melting process with prefabricated, foam-structured coarse molds,
• - A near-surface, density-differentiated foaming ( 23 ) with infrared deep radiation takes place with regard to improved strength and contactability,
• - Surface reliefs and structuring for contacting by laser can be designed on the near-surface foam structure.
• Reinforcements in the form of carbon fibers and or metal fibers for optimizing the strength and conductance of non-metallic foams ( 31 ) stretched in the active phase are introduced,
• - A high temperature foaming of magnetite with and without the addition of a disper sen foamer ( 33 ) can be done.

11. The method according to claims 10 and 9,
characterized in that:

• - A component-differentiated foaming ( 27 ) for the layer grading of through-contact ( 26 ) and thermoelectroactive active phase ( 30 ) in the longitudinal course of thermal legs ( 7 ) is carried out within a continuous foam structure, by applying prepared, differentiated content of conductive thick-film pastes after triple-layer-wise preparation, Resistance pastes maximized in electrical conductivity with an organic lacquer base or on a frit base or the same modified modified conductive adhesive or conductive lacquer, a common foaming process is carried out,
• - The differentiation of the contents of the three batch layers is such that the middle phase only contains the through-contacting active phase ( 26 ), but the upper and lower ones primarily contain the thermoelectroactive active phase ( 30 ),
• - Accordingly, after the foaming, a swollen overall layer is formed in the form of a continuous, closed-cell foam structure, which can be designed in the near-surface areas for thermo-electroactive end zones ( 34 ) for p / n and n / p transitions and in intermediate areas ( 35 ) which are only further away from the surface and conductance having.

12. Device according to claims 9 and 10,
characterized in that:

• - Foamed passive leg parts ( 4 ), continuously foamed thermo leg ( 11 ), composite thermo leg ( 12 ), integrated active-passive thermo leg ( 14 ) thermoelectric strands ( 28 ) as well as the possible strand-assemble thermo leg ( 7 ) with foam structure portion for pressure-contacted thermoelectric strands ge ( 32 ) can be produced according to claim characteristics with regard to density-differentiated foaming ( 23 ),
• - With the exception of the simple forms of continuously foamed thermo leg ( 11 ) from the same cell, metallic foam ( 10 ) and in addition to those with a homogeneously distributed active phase in non-metallic foam structures, all of the aforementioned thermal legs ( 7 ) in their manufacturing process continuously or subsequently the process of one can complete component-differentiated foaming.

13. The method and device according to claims 9, 10 and 12,
characterized in that:

• - Thermoelectric strands ( 28 ) are the result of foaming of layers one behind the other, which can be produced as a preliminary thermoelectric series circuit of thermal legs ( 7 ) with a foam structure portion according to the invention and the method according to the continuous push-through method by a dimensionally stabilized, dense, even tougher or pre-dried, in the axial direction Defines pressure-contacted, glued, cemented or ultrasonically welded strand from intervals of prepared, portioned compositions of thermal legs ( 7 ) passes through technical apparatus for inductive and / or dielectric heating, the regime of which, according to the preceding claims of claim 10, for density-differentiated ( 23 ) and component-differentiated foaming ( 27 ) is adapted to the specific compositions of the portioned intervals of the strand,
• the process of gradually differentiating foaming to thermoelectric strands ( 28 ) leading to p / n and n / p transitions connected in series is referred to as differentiated boundary layer foaming ( 29 ),
• - The foamed, closed-cell merging intervals of the thermocouple ( 7 ) each with their p- and n-conducting electrothermal active end zone ( 34 ) in a narrow, fine-pored to dense, thermally, electrically highly conductive, but indifferent zone, which with thermal ring con Tacting strands laterally outwards, suitably extending and widening in a heat-cold guide device ( 21 ) receiving only thermal flow, the collector-like extensions are alternately offset by 180 degrees to the thermoelectric principle of thermal parallel connection for hot-side receivers and to realize cold-side receiving heat and cold control devices ( 21 ) with electrical series connection of the p / n and n / p transitions of the thermoelectric line ( 28 ),
• - Thermoelectric strands can be produced from metallic foams ( 10 ) and or non-metallic foams ( 31 ), can be meticulously anticorrosively and metamorphosed and can be foam-insulated in a highly heat-insulating manner and accordingly in the simplest, hand-crafted manner as any length of rod in any number of combinations of large voltages and powers gen, can be connected in series with excellent thermal insulation function at the same time, since a thermoelectric strand ( 28 ) can already supply working voltages in the tens of volt range if suitable thermoelectrics ( 3 ) are selected,
• - The strand-side, thermally entering surfaces of the heat-cold control devices ( 21 ) have electrically safe insulating, highly resistant coatings made of Teflon, Hostaflon or similar anticorrosive sealing, even unassailable and thermally stable polymers or other plastics,
• - Pressure-contacted thermoelectric strands ( 32 ) deviating from the total of permanently fixed thermoelectric strands ( 28 ) from Thermoschen keln ( 7 ) with foam structure proportions up to 100% and or dense Thermoschen keln ( 7 ) are otherwise manufactured in the same structure, with the difference that Axial pressure components acting from the ends of the pressure-contacted thermoelectric strand ( 32 ) adequately contact the p / n and n / p transitions and thin elastic layers made of thermally-electrically highly conductive conductive rubber ( 37 ) or indifferent metal foils ( 38 ) convert the pressure components into a homogeneous surface contact on the inner surfaces of the inter-segmented heat-cold conduction devices ( 21 ).

14. The method and devices according to claim 4 and preceding,
characterized in that:

• - In order to obtain geometrical installation forms of continuously foamed thermal legs ( 11 ) for thermoelectric modules ( 1 ), according to the method, the cemented profile contact ( 39 ) is used by:
• - These are foamed by suitable cutting, each p-type and n-type thermoelectric ( 3 ), given that surface-open-pore, modular-like, interlocking tooth profiles of both types are mechanically or laser-cut smoothly, with indifferent conductive lacquer ( 18 ) at the joining surfaces, plentifully smeared with poles and pushed into each other with the interposition of an indifferent metal foil ( 38 ) and in the sequence of this structure the series connection of the thermocouples ( 7 ) for tapped working voltages is realized,
• - In addition, the thermal guide profile contact ( 40 ) is used by:
• - An external guide and thermal-electrical conductor-optimized cross-sectional reinforcement of the indifferent metal foil ( 38 ) with likewise thermally optimized trapping surface advantageously provides the additional functional function of a functional heating / cooling device ( 21 ),
• - In addition, non-positive, solder or conductive lacquer-bonded end surface contacts of the cut structures of metallic ( 10 ) and non-metallic foams ( 31 ) by means of clawing, tin-plated contact anchor claws ( 22 ) in cells soaked with soaking solder or suitable conductive lacquer, near-surface cells are realized, with the outstanding, continuing Part that passes the bedding wire ( 47 ), possibly existing active leg parts ( 2 ), galvanically and / or solely purely thermally, heat and cold guide devices ( 21 ) with electrical insulation ( 48 ),
• - Suck in structures of non-metallic foams ( 31 ) instead of a soldered joint and soaking solder an initially thin, later hardening, electrically highly conductive component of an indifferent conductive varnish ( 18 ) on its upper surface from less than one to a few millimeters deep, and then a normal density close to the surface under normal temperatures, for the contact which is pierced at the same time, form anchored underlayer ( 22 ),
• - Double-clawed contact anchor claws ( 22 ) or such, double-sided, with spiral-arched intermediate extensions replace normal bridge electrodes ( 13 ) and thereby allow the construction of three-dimensionally archable thermoelectric modules ( 1 ),
• - The spiral arched intermediate extensions of the double contact anchors claw ( 22 ) have thermally contacting non-positive passage through heat sink profiles with suitable surface designs and according to the thermal entry for the electrothermal active end zones ( 34 ) of the thermal legs ( 7 ) and the end in the foam structures of the thermal legs ( 7 ) pierced claws the formation of p / n and n / p transitions.

15. The method according to claims 9 and 10,
characterized in that:

• - An active phase formation with regard to electrical conductivities and embossing for maximum development of thermal EMF in dense, in foam structures and the like, with regard to the initial thermoelectrics ( 3 ) - outside - and inside, with regard to the conductivity mediator ( 20 ) only after their localization in dense or foam-structured parts of Ihermoskeln ( 7 ) is carried out in order to form a high-performance thermoelectroactive ( 30 ) and / or through-contact active phase ( 26 ) and accordingly a previous, accompanying or subsequent formation takes place as required,
• - Accordingly, conductivity mediators ( 20 ) are formed with and / or in them to form an efficient through-contacting active phase ( 26 ) when fixation begins and takes place in dense and foam structures,
• - A reforming of the still hot / warm phase foam structures of non-metallic foams ( 31 ) is made by sending currents of a certain strength through the application of suitable voltages through the still hot foam structures, which work via mechanisms of electromigration and integration from before non-contacted, scattered localized lead atoms achieve an improvement in the through-contacting active phase ( 26 ),
• - Likewise, a reformation in still hot / warm phase by rich, so-called permanent polarization is achieved, the alignment of anisotropic thermoelectroactive grain sizes ( 17 ) can be carried out by appropriate static electric fields, possibly those that are overlaid with a frequency field component of suitable proportion is
• - In the hot / warm phase, such a re-formation of the thermoelectroactive active phase ( 30 ) in just-blown foam structures or the not yet set or hardened conductive lacquer compounds can be performed, and in particular with polarizing, electrical fields, an anisotropic, thermoelectroactive grain size ( 17 ) orientation in the thermoelectric preferred direction is possible,
• - Galena crystals, non-cubic crystallized pyrite and similar anisotropic crystal forms, in particular whirling systems, suffice the degree of division, within basic lacquer components are still sufficiently resin-like consistency, are subjected to an external polarization in the thermoelectric (crystal axis-oriented) preferred direction by means of electrical fields, with simultaneous current-imposing electrical conductivity through electromigration,
• - A thermo-EMF-improving, for various natural compound semiconductors, possible crystallographic tempering within hot glass phases can be applied by sufficient degrees of division of non-oriented, non-cubic-pyrite-like or exclusively isotropic, temperate compound semiconductors or intermetallic compounds in heat-resistant, glass-like embeddings before cooling Tightly hard or hot foaming to form foam-glass, thermo-electroactive structures that are viscous at temperatures, are subject to a crystal-transforming, field-applied tempering process with internal crystallographic and external preferential polarization, whereby in the case of a rapidly expanding blowing process, the field strength is removed and immediately afterwards the just finished, still hot foam structure is undiminished, if necessary intensified until complete cooling,
• - An unlimited number of suddenly triggered reversible formations between low-resistance semiconducting and high-resistance states of thermoelectroactive active phases ( 30 ) are possible, which consist of semiconducting chalcogenide glasses, which are binary, ternary and quaternary systems made of S, Se, Te, As and Cd, Zn , Fe, Bi, Ti, Cu, Ag and those based on some transition metal oxides such as. B. Cu ₂ O and Fe ₂ O ₃ and that, these switching states corresponding conductivity levels towards visibly achievable semiconducting low-impedance with voltage pulses higher than 50 volts and the reversal into the high-resistance state can be achieved with adapted current pulses,
• - ion cleaning and re-doping on crystal surfaces of natural compound semiconductors such as diaphragms, gloss and gravel are used to improve their thermoelectric and electrical properties,
• - A modification-converting, primarily thermal post-formation of meltable and foamable, non-metallic thermoelectrics ( 3 ) with a view to the formation of electrical conductivity and the ability to develop a thermo-EMF (against other thermoelectrics ( 3 )) is carried out and accordingly thermoelectrics with property characteristics 3 ) like the meltable and foamable selenium, which immediately after foaming in a glassy-amorphous state and after tempering in a suitable temperature-maintaining range is transformed into a semimetallic, electrically conductive, durable thermoplastic with strong thermoelectric properties - undergoes this thermal reforming,
• - Sulphidic compound semiconductors, such as galena, pyrite, chalcopyrite (gravel of sulfur) and other transition metal chalcogenides with suitable pyrite structures, are subjected to a thermo-chemical treatment which takes place under a thermal regime and which produces a crystallographic improvement in terms of purity, crystallinity and stoichiometry, with a doping which improves the thermoelectric properties thermoelectroactive grain sizes ( 17 ) of suitable degree of division can also be made from these compound semiconductors,
• - hydrothermally or otherwise formed, ore-like apertures, luster and gravel, if necessary, complete the process of ion cleaning and subsequent doping, if high differential thermal forces that can be achieved justify this,
• - On suitably density-differentiated, solidified surfaces of special metallic foams ( 10 ) or specially surface-pretreated, ver by means of transferring or synthesizing vapor phase transport with the addition of dopants via the intermediate stage of primary pyrrothine crystal synthesis, thermoelectrically preferred-oriented, doped polycrystalline pyrite layers are subsequently appropriately grown and anchored in a suitable manner Permanent magnetic fields grow as orienting pyrrhotin layers or crystals and, with lowering of the temperature, convert into preferred pyrite layers,
• - The transmitted vapor phase transport to suitable or so pretreated metal foam, magnetite, carbon or silicon carbide or titanium nitride growth surfaces with the addition of dopants and 5.2 g bromine / liter of a highly diluted protective gas atmosphere made of hydrogen / argon within a magnetically flowable autoclave for p-conducting or n-conducting pyrite - absorbs undoped pyrite at approx. 800 degrees Celsius in a closed autoclave that can be flooded with magnetic fields and pyrrothin in doped at approx. 550 degrees Celsius on the surface of the metallic foam ( 10 ) or the aforementioned growth surfaces , separates in a preferred direction-oriented form and finally forms pyrite with a high differential thermal power due to a suitable, reversing temperature regime and with the same sequence but more mild conditions with iodine,
• - the more aggressive vapor phase transport with chlorine different pretreatments of the surfaces of the still suitable metallic foams ( 10 ) is necessary or a chlorine-resistant thin titanium nitride intermediate layer obtained by laser sintering or waxing-up on the metal foam,
• the synthesizing vapor phase transport with iron pentacarbonyl or dieisen nonacarbonyl and hydrogen sulfide can take place under sensitive conditions in reactions below 200 degrees Celsius without simultaneous doping entry,
• - The synthesizing vapor phase transport under robust conditions at over 300 degrees Celsius with iron (II) chloride or iron (II) bromide or particularly gentle on the substrate with iron (II) iodide and hydrogen sulfide or from 450 degrees Celsius with sulfur and the aforementioned iron halides with doping input from the Vapor phase can take place
• - for p-type doping with elements of the 5th main group or VII. sub-group and for n-type doping with elements of the VII. main group or VIII. sub-group,
• - With regard to stoichiometry, in particular in the case of cheap pyrite and galena, in addition to other glosses, a sulfur treatment leads to the defect semiconductor and a vacuum treatment to the excess semiconductor and thus leads to the possibility of an immense increase in thermal EMF in an advantageous homojunction of these compound semiconductors with itself,
• - In the incrustation for contact sintering ( 45 ) provided, still freely movable pre-expanded particles in front of the same, the superficial insertion of a ferromagnetic subparticle ( 44 ) takes place at an arbitrary point of the still resin-tough crust, the thermoelectric preferred direction being coordinated with a magnetic orientation of the Weiss's districts of the ferromagnetic subparticle ( 44 ), which transfers the same to the entire particle and that the overall alignment of the thermoelectroactive active phase of the particle, which is forced by magnetic and electrical field components, is formed in a free floating phase,
• - After drying / hardening of the oriented particles, vibrate them under vibra tion and an easily producible penetrating magnetic Felkom component in a layering and aligning manner into ceramic hollow molds, after which they enter the contact sintering ( 45 ) under a flexible initial pressure,
• - A total volume, homogeneous, thermoelectrically preferred, continuous growth formation ( 46 ) at least of the dense structures of some variants of large-sized, thermoelectroactive collector hoods ( 19 ) or certain thermoelectroactive end zones ( 34 ) which transition into a compressed state at their outer end, and in particular Ther moactive surfaces for direct p / n and n / p transitions can be achieved with the process of photopolymerization by intensely flooding and orienting polarizing, electric fields only thin, viscous, monomeric green films of thermoelectroactive pastes emerging from a slot nozzle after a regime-penetrating, ultraviolet or blue laser beam has been emitted, photopolymerization is started, with the external solidification chaining and crosslinking of the molecules of the base lacquer component only ending after the process of layering or winding up the green body films.

16. The device according to claims 9 and 2,
characterized in that:

• - A pressurized, atomizable thermoelectroactive foam conductive varnish ( 25 ) is stored in sprays, with all nozzle-compatible components with regard to the thermoelectroactive grain sizes ( 17 ), conductivity mediator ( 20 ), up to fibrous reinforcements, which conductivity and strength-increasing values after the nozzle outlet give themselves immediately by the relaxing blowing agent self-building non-metallic foam ( 31 ), the blowing agent being the foamer ( 33 ).

17. The device according to claims 3, 2, 9, 10, 11 and 15,
characterized in that:

• - For indifferent conductive lacquers ( 18 ) and indifferent foam conductive lacquers ( 24 ), the following approach is used for a through-contact active phase ( 26 ) in addition to other suitable ones:
  optionally or in equivalent proportions
  Silver powder 54.4 / copper powder 46.2
  Bismuth oxide 4.6; Borosilicate 2.7
  Rosin 8.3 turpentine and blowing agent total 30.0,
• Copper or silver in the same component batches who can be replaced by nickel, aluminum and titanium and tin,
• are used as further conductivity mediators ( 20 ) in modifiable batches with epoxy resin or borosilicate titanium nitride, lithium-doped titanium disulfide, silver sulfide, copper sulfide, magnetite and hard coal powder,
• - One-dimensional conductors such as polyacetylene, doped and undoped poly-sulfur nitride, poly-sulfur chloride and other suitable, highly intrinsically conductive basic lacquer components for indifferent ( 18 ) and thermo-electroactive conductive lacquers ( 16 ) provide the basis for intrinsically conductive, dense structures and foam structures, which, if possible, are accompanied by a reforming regime oriented in the preferred electrical direction,
• - The remaining in the dense phase or closed-cell foam structures with basic lacquer components forming indifferent and thermoelectro-active conductive lacquers ( 18 ), ( 16 ), and the indifferent and thermoactive foam conductive lacquers ( 24 ), ( 25 ) themselves can be electrically non-conductive - but due to better development of the Active phases and a higher electrical conductivity, which affects the dense or foamed structures overall, are to be chosen primarily electrically self-conducting - although in the case of lack of self-conductivity, sufficient conductivity mediators ( 20 ) must be added, whereas an intrinsically conductive lacquer basic component can be supplemented with these.

18. The method and device according to claims 3, 9, 10, 11 and 15,
characterized in that:

• - For a glass phase fixation of the through-contacting active phases ( 26 ) or the thermoelectroactive active phases ( 30 ) in dense structures or foam structures, glass or frit components can be used as a gentle, low-melting borosilicate base of the following composition:
  73.8% PbO with 11.2% B ₂ O ₃ , 14.3% SiO ₂ , 0.2% Al ₂ O ₃
  or 73.4% PbO with 20.0% B ₂ O ₃ , 6.6% SiO ₂
• - After drying processes, pre-cast, viscous spread or pasty-rolled green sheets of the selected compositions of
• - Metal powder from single and multi-component systems as conductivity mediators ( 20 )
  • - thermoelectroactive grain sizes ( 17 )
  • - glass powder - lead / borosilicate
  • - Organic flux to adjust the viscosity
  • - Plasticizers for wetting and cleaning of insertable metallic heat and cold control devices ( 21 )
  or other reinforcements
  at 100 to 150 degrees Celsius, a homogeneously tempered liquid storage phase at 350 to 500 degrees is then generated and spontaneously inflated with inductive-dielectric energy to the closed-cell structure of a non-metallic foam ( 31 ) and, if necessary, flooded with re-forming fields and the like Influencing galvanic currents are reformed until they cool,
• - A wax-up formation according to claim 15 with the omission of laser light in an analogous manner with thin films from the liquid retention phase and thus the formation of unlimited large, preferably aligned, thermoelectroactive volumes which, at every conceivable perpendicularly executed interface, have qualities for n / p- and deliver p / n transitions,
• - The possibly reformed, dense, cooled phase device according to a highly heat-resistant indifferent or thermoelectroactive ( 18 ) conductive varnish ( 16 ) and the blown, cooled phase accordingly a highly heat-resistant, indifferent ( 24 ) or thermoelectroactive foam conductive varnish ( 25 ) on a glass or frit basis is
• - Alkaline - especially sodium silicate additive facilitates the formation of the trap tunnel at normal temperature with conduction at the beginning of ion conduction at temperatures of around 200 degrees Celsius - as well as a self-developing conductivity reforming if briefly such working temperature ranges were passed through under voltage,
• - Special forms of glass-like structures can be formed with semiconducting chalcogenide glasses according to claim 15, which can be switched on by voltage surges higher than 50 volts and by adapted current surges switchable thermoelectroactive active phase ( 30 ).

19. The method and device according to claims 3, 6 and preceding,
characterized in that:

• - Microcrystalline silicon from aluminothermic process with raw materials pure aluminum powder, potassium fluorosilicate or contamination-free quartz dust as an efficient thermoelectroactive grain size ( 17 ) for thermoelectroactive collector hoods ( 19 ), thermoelectroactive conductive lacquers ( 16 ), thermoelectroactive foam conductive lacquers ( 25 ) or as a powdered powder ( 3 ) is obtained
• - The aluminothermic reduction of a mixture of 125 parts of aluminum powder and 40 parts of pure potassium fluorosilicate leads to pure crystallized silicon which can be used in thermoelectric arrangements and by heating a mixture hermetically sealed against the outside atmosphere to 700 degrees Celsius, cooling the reaction material and washing with pure Hydrochloric acid and distilled water is available, the crystal fraction receiving improved thermoelectric properties by heating with dopants in the absence of air,
• for p-doping in aluminothermic batches, a small, well-distributed amount of boron trioxide, borosilicate or boric acid,
  for n-doping, a small, well-distributed amount of aluminum orthophosphate, aluminum diphosphate or aluminum metaphosphate must be taken into account according to professional judgment,
• - Borohydrides for subsequent p-doping, red phosphorus, yellow solid phosphorus hydrogen for subsequent n-doping of the microcrystalline silicon obtained by the reduction process are suitable, the requirements of sealing, a high degree of distribution before the thermal aftertreatment in the temperature range 900-1100 degrees Celsius, correct distribution quantity and then the stabilization of the protective gas atmosphere that is formed during the process during cooling of the finished doped batch must be ensured according to professional action,
• aluminothermic reduction of quartz dust and aluminum in compression and the same reduction of quartz dust with magnesium in compression leads to silicon, an excess of quartz dust which can be measured in a professional manner or the addition of magnesium oxide preventing the formation of silicon consumables from the magnesium silicide,
• - the reduction of quartz with coal in the electric furnace to technically pure, the reduction of silicon tetrachloride, bromide, iodide leads to very pure silicon,
• - The aluminothermic and quartz-carbon reduction silicon qualities in their thermoelectric properties can still be improved by dissolving in liquid aluminum with subsequent recrystallization, a distinctly larger crystal type of substantially greater purity being available.

20. The apparatus according to claim 14, characterized in that the cells containing the latent storage means of the foam structure of the bridge electrodes ( 13 ) in the cementing profile contacting ( 39 ) and the thermal guide profile contacting ( 40 ) to save thermal offers and to deliver them again for sustainable thermoelectric conversion are able.