SE9801798A0 - Thermoelectric device - Google Patents
Thermoelectric deviceInfo
- Publication number
- SE9801798A0 SE9801798A0 SE9801798A SE9801798A SE9801798A0 SE 9801798 A0 SE9801798 A0 SE 9801798A0 SE 9801798 A SE9801798 A SE 9801798A SE 9801798 A SE9801798 A SE 9801798A SE 9801798 A0 SE9801798 A0 SE 9801798A0
- Authority
- SE
- Sweden
- Prior art keywords
- thermocouples
- thermoelectric
- elements
- layer
- ceramic
- Prior art date
Links
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
- Measuring Temperature Or Quantity Of Heat (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
SOKANDE TermoGen AB Stugvagen 8 167 72 BROMMA UPPFINNARE LYCKE, HansHOLMGREN, LennartJONS SON, Bertil Stugvagen 9Backvagen 4TradgArdsgatan 3 167 72 BROMMA 177 60 JARFALLA185 32 VAXHOLM BENAMNING TERMOELEKTRISK ANORDNING PRIORITET AVDELAD/ UTBRUTEN Giltighetsdag Stamansokans nr BILAGOR AVGIFTER X Beskrivning, 3 ex Patentkrav, 3 ex Sammandrag 6 ritn, 3 ex Utlandsk text Anmalningsavgift Granskningsavgift utan ITS-granskning Granskningsavgift med ITS-granslming Extra kravavgift Bestallning av diariebevis Totalt X 3 St Overlatelser Fullmakt Prioritetsbevis Oversattning av priorbevis Forteckning SEK800 SEK3000 SEK1400 SEK X X X SEK52 Applicant thermogenic AB Stugvagen 8 167 72 STOCKHOLM INVENTOR LYCKE, Hans Holmgren, LennartJONS SON, Bertil Stugvagen 9Backvagen 4TradgArdsgatan 3 167 72 STOCKHOLM 177 60 JARFALLA185 32 VAXHOLM Name thermoelectric device PRIORITY SECONDMENT / broken away, Validity parent application No. APPENDICES FEES X Description, 3 ex claim 3 ex Summary 6 drawings, 3 copies Foreign text Application fee Review fee without ITS review Review fee with ITS review Extra requirement fee Ordering of diary certificates Total X 3 Permits Power of attorney Priority certificate Translation of prior certificate List SEK800 SEK3000 SEK1400 SEK XXX SEK52
Description
1 TERMOELEKTRISK ANORDNING Teknikomrade Foreliggande uppfinning avser en for hogtemperaturanvandning avsedd termoelektrisk anordning for omvandlande av varme till elektricitet genom Seebeck-effekten, 5 ett forfarande for tillverkning av anordningen samt ett forfarande for kontaktering av i anordningen ingaende termoelektriska element. TECHNICAL FIELD The present invention relates to a thermoelectric device for high temperature use for converting heat to electricity by the Seebeck effect, a method for manufacturing the device and a method for contacting thermoelectric elements included in the device.
Uppfinningsbakgrund Det finns i ett antal sammanhang ett behov av att kunna omvandla varme till elektricitet. Ett omrade med speciella behov är hogtemperaturtillampningar, det viii saga tillampningar i temperaturomrAden typiskt fran cirka 400° C och uppat. Sadana tillampningar kan vara att till- 15 varata overskottsvarme exempelvis i processindustrier, fran varmepumpar eller fran forbranningsmotorer och avgaskatalysatorer i fordon. Ytterligare exempel kan innefatta att tillvarata friktionsvarme fran exempelvis bromsar. Background of the invention In a number of contexts, there is a need to be able to convert heat into electricity. One area with special needs is high temperature applications, that is to say applications in temperature ranges typically from about 400 ° C and up. Such applications may be to utilize excess heat, for example in process industries, from heat pumps or from internal combustion engines and exhaust catalysts in vehicles. Additional examples may include utilizing frictional heat from, for example, brakes.
Detta kan astadkommas tack vare den sa kallade Seebeck-effekten, dvs en termoelektrisk effekt som innebar att spanning uppstar i en elektrisk krets sammansatt av tva olika metaller om de tva kontaktstallen dar metallerna mots har olika temperaturer; med andra ord har •25 anordningar som utnyttjar Seebeck-effekten en varm sida och en motstaende kall sida. Med halvledarmaterial kan en . • • • •relativt hog spanning uppnas pa detta satt, och genom • • ." seriekoppling av flera halvledarelement av omvaxlande p- . och n-typ kan man uppna spanningar av flera tiotals volt. This can be achieved thanks to the so-called Seebeck effect, ie a thermoelectric effect which means that voltage arises in an electrical circuit composed of two different metals if the two contact points where the metals have different temperatures; in other words, • 25 devices utilizing the Seebeck effect have a hot side and an opposite cold side. With semiconductor material one can. • • • • relatively high voltage is achieved in this way, and by • •. "Series connection of several semiconductor elements of alternating p- and n-type, voltages of several tens of volts can be achieved.
" En typisk termoelektrisk anordning for anvandning i ".namnda hogtemperaturintervall beskrivs i den amerikanska • .. • ".patentskriften US-A-4 459 428 (Chou). Denna skrift visar . . . . . . . .en termoelektrisk anordning for att alstra elektricitet ". . . . . . . innefattande parallellt anordnade, stavformiga, serie- ••• ••• •• • •• •••• •• •• • •••• •• •••••••• •••• •• ••• •• • •• •••• • ••• •••• 1:,• •• • : ••• ••••••• ••••••• •••• •• 2 kopplade, n- och p-dopade termoelektriska element, anordnade mellan tva Atskilda uppsattningar av kopparsegment och fastade vid dessa med utnyttjande av lodpasta som screentryckts till kopparsegmentuppsattningarnas inre 5 ytor. Utrymmet mellan elementen och kopparsegmenten är fyllt av en keramisk, gjuten massa, och anordningens yttre ytor är tackta av en keramisk tjockfilmsisolator. En anordning av detta slag har dock visat sig inte vara tillfredsstallande. A typical thermoelectric device for use in the said high temperature range is described in U.S. Pat. No. 4,459,428 (Chou). This document discloses a thermoelectric device for generate electricity ". . . . . . . comprising parallel, rod-shaped, series- ••• ••• •• • •• •••• •• •• • •••• •• •••••••••••• •• •• • •• • •• •••• • ••• •••• 1:, • •• •: ••• ••••••• ••••••• •••• •• 2 coupled, n- and p-doped thermoelectric elements, arranged between two separate sets of copper segments and attached thereto using solder paste which is screen printed to the inner surfaces of the copper segment sets. The space between the elements and the copper segments is filled with a ceramic, cast mass, and the outer surfaces of the device are covered by a ceramic thick film insulator. However, a device of this kind has proved to be unsatisfactory.
••• * • ••• • • • • • • Andamal med och sammanfattning av uppfinningen Ett andamal med foreliggande uppfinning är att tillhandahalla en ny och ferbattrad termoelektrisk anordning avsedd for hogtemperaturanvandning. Another object of the present invention is to provide a new and improved thermoelectric device for high temperature use.
Det är aven ett andamAl med foreliggande uppfinning att astadkomma en termoelektrisk anordning med minskad kanslighet for vdrmeutvidgning. It is also an object of the present invention to provide a thermoelectric device with reduced probability of thermal expansion.
Ett ytterligare andamAl med foreliggande uppfinning ar att Astadkomma ett enkelt forfarande for tillverkning 20 av en termoelektrisk anordning enligt ovan, vilket endast erfordrar ett fatal varmebehandlingar. A further object of the present invention is to provide a simple process for manufacturing a thermoelectric device as above, which requires only a fatal heat treatment.
Annu ett andamAl med fOreliggande uppfinning är att Astadkomma enklare kontaktering, dvs inbordes forbindning och yttre anslutning av termoelektriska element i en 25 termoelektrisk anordning enligt ovan. Another object of the present invention is to provide simpler contacting, i.e. inboard connection and external connection of thermoelectric elements in a thermoelectric device as above.
Ovan namnda och andra andamAl uppnAs med en anordning och forfaranden som uppvisar de sardrag som framgar av de bifogade patentkraven. The above and other objects are achieved by an apparatus and methods which exhibit the features set forth in the appended claims.
Enligt en forsta aspekt p foreliggande uppfinning 30 Astadkommes en termoelektrisk anordning avsedd for hogtemperaturanvandning innefattande termoelektriska element i en stomme av keramiskt material, varvid det keramiska materialet Atminstone partiellt bibringats en vasentligt forhojd porositet, foretradesvis overstigande cirka 30 %, 35 mera foredraget overstigande cirka 60%. According to a first aspect of the present invention there is provided a thermoelectric device for high temperature use comprising thermoelectric elements in a body of ceramic material, the ceramic material being at least partially imparted to a substantially increased porosity, preferably exceeding about 30%, more preferably exceeding about 60%. .
Enligt en andra aspekt pa foreliggande uppfinning Astadkommes en termoelektrisk anordning avsedd fOr htig- •• • • *0• • 000• • • 00 •• 000 • • • • •• •• • • 3 temperaturanvandning, innefattande termoelektriska element i en stomme av keramiskt material, varvid ledningsbanor for inbordes elektrisk anslutning och forberedelse for yttre elektrisk anslutning av de termoelektriska 5 elementen utgors av termiskt sprutat elektriskt ledande kontaktmaterial pa elementens andytor och pa ytor av stommen belagna mellan de termoelektriska element som skall forbindas. According to a second aspect of the present invention there is provided a thermoelectric device intended for high temperature use, comprising thermoelectric elements in a body. of ceramic material, wherein conduits for inboard electrical connection and preparation for external electrical connection of the thermoelectric elements consist of thermally sprayed electrically conductive contact material on the end faces of the elements and on surfaces of the body coated between the thermoelectric elements to be connected.
Enligt en tredje aspekt pa foreliggande uppfinning 10 Astadkommes ett forfarande for tillverkning av en for hogtemperaturanvandning avsedd termoelektrisk anordning, innefattand stegen att man bildar en gronkropp med en stomme av hardat, keramiskt material med dari inbaddade termoelektriska element; att man sintrar gronkroppen, 15 foretradesvis i skyddsgasatmosfar; samt att man elektriskt kontakterar de termoelektriska elementen for Astadkommande av ledningsbanor. According to a third aspect of the present invention there is provided a method of manufacturing a thermoelectric device for high temperature use, comprising the steps of forming a green body with a body of hardened ceramic material having thermoelectric elements embedded therein; sintering the green body, preferably in a shielding gas atmosphere; and electrically contacting the thermoelectric elements to provide conduit paths.
Enligt en fjarde aspekt pa foreliggande uppfinning astadkommes ett forfarande for att astadkomma lednings20 banor for inbordes elektrisk anslutning av andytorna hos termoelektriska element i en termoelektrisk anordning, som innefattar namnda element anbringade, foretradesvis ingjutna, i en stomme av keramiskt material, varvid ledningsbanorna Astadkommes genom termisk sprutning av elek- 25 triskt ledande material pa elementens andytor och pA ytor av stamen belagna mellan termoelektriska element som skall forbindas inbordes. According to a fourth aspect of the present invention there is provided a method of providing conduit paths for inboard electrical connection of the face surfaces of thermoelectric elements in a thermoelectric device comprising said elements mounted, preferably cast, in a ceramic material body, the conductor paths being provided by thermal spraying of electrically conductive material on the end faces of the elements and on surfaces of the stem coated between thermoelectric elements to be connected is boarded.
En femte aspekt pa foreliggande uppfinning innebar anvandning av mikroballonger, eller mikrosfarer, for att 30 i en termoelektrisk anordning, innefattande termoelektriska element i en stomme av keramiskt material, astadkomma varmeisoleringshojande porositet hos det keramiska materialet. A fifth aspect of the present invention involved the use of microballoons, or microspheres, to achieve in a thermoelectric device, comprising thermoelectric elements in a body of ceramic material, heat insulating porosity of the ceramic material.
En sjatte aspekt pa foreliggande uppfinning innebar 35 anvandning av mikroballonger eller mikrosfarer i kombination med ett bindemedel, foretradesvis en emalj, for att i en termoelektrisk anordning, innefattande termoelektri- •• • • 4• • .00• • • .0 •• 09,11 • • • ••• •• •• 4 ska element i en stomme av keramiskt material, anpassa det keramiska materialets varmeutvidgningskoefficient till de i stommen anbringade, fOretradesvis ingjutna, elementens varmeutvidgningskoefficient. A sixth aspect of the present invention involved the use of microballoons or microspheres in combination with a binder, preferably an enamel, in order to form a thermoelectric device comprising thermoelectric device. •• • • 4 • • .00 • • • .0 •• 09 , 11 • • • ••• •• •• 4 elements of a ceramic material frame shall adapt the coefficient of thermal expansion of the ceramic material to the coefficient of thermal expansion of the elements applied to the frame, preferably cast in.
Dessa aspekter pa uppfinningen kan som fackmannen inser kombineras pa godtyckligt satt, utan avvikelse fran uppfinningstanken. As is apparent to those skilled in the art, these aspects of the invention may be combined in any manner, without departing from the spirit of the invention.
Enligt en utforingsform avser uppfinningen en termoelektrisk anordning innefattande termoelektriska element, 10 foretradesvis p- och n-dopade halvledarelement, hadanefter benamnda termoelement, i en stomme av keramiskt material, varvid termoelementen är ingjutna i det keramiska materialet, sá att termoelementen tillsammans med stommen utgor en enhetligt sammanhallen kropp, pa vilken 15 erforderliga ledningsbanor kan astadkommas medelst applicerade ledande skikt. Detta medfor bland annat fordelen att anordningen bestar av fa delar, och att tillverkningen blir processtekniskt enkel. Anordningen innehaller inte nagra losa delar, vilket forbattrar hallbarheten och 20 underlattar handhavandet. Man kan vidare enkelt astadkomma onskad porositet has den keramiska stommen. According to one embodiment, the invention relates to a thermoelectric device comprising thermoelectric elements, preferably p- and n-doped semiconductor elements, hereinafter referred to as thermocouples, in a body of ceramic material, the thermocouples being cast into the ceramic material, so that the thermocouples together with the body form a uniformly cohesive body, on which the required conductor paths can be provided by means of applied conductive layers. This entails, among other things, the advantage that the device consists of a few parts, and that the manufacture becomes technically simple. The device does not contain any loose parts, which improves the durability and facilitates handling. Furthermore, the desired porosity of the ceramic frame can be easily achieved.
Det har befunnits vara fOrdelaktigt att utfora gjutningen av den keramiska stommen runt termoelementen sá att i den resulterande enhetligt sammanhallna kroppen 25 respektive termoelements bada andytor är frilagda pa motstaende sidor av namnda kropp. Harvid kan kontaktering, dvs inbordes forbindning och forberedelse for yttre elektrisk anslutning av termoelementen, enkelt utforas efter gjutningen. Detta fOrenklar och effektiviserar 30 framstallningsforfarandet. It has been found to be advantageous to carry out the casting of the ceramic body around the thermocouples so that in the resulting uniformly held body 25 the respective surfaces of the thermocouples are exposed on opposite sides of said body. In this case, contacting, ie inboard connection and preparation for external electrical connection of the thermocouples, can easily be carried out after casting. This simplifies and streamlines the manufacturing process.
FramstallningsfOrfarandet effektiviseras enligt uppfinningen ytterligare genom att termoelementen infor ingjutningen i stommen inte är slutligt varmebehandlade utan utgors av raamnen, sa kallade gronelement. Detta 35 medfor att den slutliga varmebehandlingen av termoelementen utfors efter det att dessa är ingjutna i ovan namnda enhetligt sammanhallna kropp, dvs i samband med varme- •• • •• • behandlingen av stommen. Med andra ord slutvarmebehandlas stommen och termoelementen samtidigt, vilket minskar antalet erforderliga varmebehandlingar. Samtidig varmebehandling av termoelementen och stommen underlattas am 5 termoelementen och det valda keramiska materialet har Atminstone i det narmaste samma varmeutvidgningskoefficient, med beaktande av det keramiska materialets porositet. According to the invention, the manufacturing process is further made more efficient in that the thermocouples before the casting in the body are not finally heat-treated but consist of the frame, so-called green elements. This means that the final heat treatment of the thermocouples is carried out after these have been cast into the above-mentioned uniformly cohesive body, i.e. in connection with the heat treatment of the body. In other words, the body and thermocouples are heat-treated at the same time, which reduces the number of heat treatments required. Simultaneous heat treatment of the thermocouples and the body is omitted on the thermocouples and the selected ceramic material has at least almost the same coefficient of thermal expansion, taking into account the porosity of the ceramic material.
SAsom ovan angivits har det enligt uppfinningen 10 overraskande visat sig att man kan pA ett fordelaktigt satt pAverka varmeutvidgningskoefficienten has det keramiska stommaterialet genom att man fore gjutningen av stommen iblandar mikroballonger (eller mikrosfarer) tillsammans med ett bindemedel, foretradesvis en emalj, i den 15 keramiska slamma som anvands for gjutning av stommen. Detta ger en mojlighet att anpassa det keramiska materialets varmeutvidgningskoefficient till termoelementens varmeutvidgningskoefficient, foretradesvis genom valet av vilket bindemedel som iblandas det keramiska materialet. 20 Darmed undviker man att spanningar uppstAr mellan det keramiska materialet och termoelementen dA anordningen utsatts for hoga temperaturer, vilka spanningar skulle kunna leda till sprickbildning och, i vArsta fall, att anordningen blir obrukbar. As stated above, according to the invention it has surprisingly been found that in a advantageous manner the coefficient of thermal expansion of the ceramic body material can be influenced by mixing microballoons (or microspheres) together with a binder, preferably an enamel, in the ceramic before casting the body. sludge used for casting the frame. This makes it possible to adapt the coefficient of thermal expansion of the ceramic material to the coefficient of thermal expansion of the thermocouples, preferably by choosing which binder is mixed with the ceramic material. This avoids stresses arising between the ceramic material and the thermocouples when the device is exposed to high temperatures, which stresses could lead to cracking and, in the worst case, the device becoming unusable.
Sasom ovan angivits kan man enligt uppfinningen vidare pAverka varmeledningsfOrmAgan i den termoelektriska anordningen genom att man Astadkommer en porositet has det keramiska materialet. Enligt en fOredragen utforingsform av uppfinningen kan namnda porositet Astadkommas ge- 30 nom att man i det keramiska stommaterialet iblandar mikrosfarer eller -ballonger. Mikroballongerna har en sluten yttre yta men ett ihAligt inre, sá att sma valdefinierade och val fordelade hAlrum eller parer bildas i det keramiska materialet. Genom iblandning av mikrobal- 35 longer Okar stommens, 0ch darmed hela anordningens, varmeisolerande fOrmAga. Detta bidrar positivt till den termoelektriska effekten, eftersom en storre temperatur- 6 skillnad over anordningen kan bibehAllas, vilket i sin tur resulterar i att en hogre utspanning och en storre stromstyrka kan erhAllas. Dessutom tillAter en hogre porositet en snabbare uppvarmning och avkylning under 5 tillverkningens varmebehandling. As stated above, according to the invention it is further possible to influence the thermal conductivity of the thermoelectric device by achieving a porosity of the ceramic material. According to a preferred embodiment of the invention, said porosity can be achieved by mixing microspheres or balloons in the ceramic body material. The microballoons have a closed outer surface but a hollow interior, so that small defined and electrically distributed cavities or pairs are formed in the ceramic material. By mixing in microballoons, the heat-insulating capacity of the body, and thus of the entire device, increases. This contributes positively to the thermoelectric effect, since a larger temperature difference across the device can be maintained, which in turn results in a higher output voltage and a greater current strength being obtained. In addition, a higher porosity allows for faster heating and cooling during the heat treatment of the manufacture.
Det har befunnits fordelaktigt att vid kontaktering av anordningen ha en hogre varmeledningsfOrmAga i det parti av stommen som ligger narmast den yta som ska kontakteras. Detta ger fordelen av battre varmebortledning 10 vid kontaktering genom termisk sprutning (sAsom beskrivs nedan) av ledningsbanor. Enligt en utforingsform av uppfinningen ges darfor ett ytlager av stommen vasentligt lagre porositet an ovriga stommen, foretradesvis genom att detta ytlager Astadkommes Atminstone vasentligen utan 15 inblandning av mikroballonger. Detta ger dessutom en hogre styrka has detta ytlager, vilket medger att halten av mikroballonger i ett av ytlagret omslutet inre lager kan okas, vilket ytterligare akar den termoelektriska effekten. It has been found advantageous to have a higher thermal conductivity in the part of the body closest to the surface to be contacted when contacting the device. This provides the advantage of better heat dissipation 10 when contacting by thermal spraying (as described below) of conduit paths. According to an embodiment of the invention, therefore, a surface layer of the body is given substantially lower porosity than the rest of the body, preferably by providing this surface layer at least substantially without the interference of microballoons. This also gives a higher strength to this surface layer, which allows the content of microballoons in an inner layer enclosed by the surface layer to be increased, which further increases the thermoelectric effect.
Ovan namnda mikroballonger kan exempelvis utgoras av ballonger av glas, skummad aluminiumoxid eller annat skummat keramiskt material, exempelvis kiseldioxid (Si02) eller zirkoniumdioxid (Zr02). Mikroballongernas diameter kan typiskt vara mellan 10 och 250 pm, foretradesvis am- 25 kring 150 pm. The above-mentioned microballoons can, for example, consist of balloons made of glass, foamed alumina or other foamed ceramic material, for example silica (SiO2) or zirconia (ZrO2). The diameter of the microballoons can typically be between 10 and 250 μm, preferably around 150 μm.
Sam ovan angivits är det fordelaktigt att stommen av keramiskt material samt de dari ingjutna termoelementen inte an slutligt varmebehandlade utan utgor en sA kallad gronkropp. For att Astadkomma en for gronkroppen till- 30 racklig styrka infor slutvarmebehandlingen, dvs sintringen, kan flera metoder anvandas. En sAdan metod innefattar att cement tillsatts till den keramiska slamman, varav stommen skall gjutas, sA att gronkroppen hardar hydrauliskt till tillracklig hArdhet. Denna metod ger en mycket 35 stark keramisk kropp. En annan metod innefattar att tillsammans med, alternativt istallet for, namnda cement, tillsatta starkelse eller liknande organiskt material i • • •• • • SO• • 000• • • • • • • •• • • • • • • • •• •• In • to..•...0 • • • • • ego *Ike *ego 4.4o 7 den keramiska slamman. Efter det att denna slamma fyllts i en form for gjutning av den keramiska kroppen sker uppvdrmning, exempelvis till ca 80° C, varvid starkelsen tar upp vatten och fungerar som ett lim i gronkroppen. Vid en 5 efterfoljande sintring forgasas starkelsen och bildar sma porer i keramen. En fordel med att anvanda starkelse är att porerna som bildas ytterligare Okar stommens porositet med dartill fOljande positiva effekter, sasom redovisats tidigare. Dock ger anvandningen av cement en nagot 10 starkare gronkropp. As stated above, it is advantageous that the body of ceramic material and the thermocouples cast therein are not finally heat-treated but form a so-called green body. In order to achieve a sufficient strength for the green body before the final heat treatment, ie the sintering, several methods can be used. Such a method involves adding cement to the ceramic sludge, of which the body is to be cast, so that the green body hardens hydraulically to sufficient hardness. This method gives a very strong ceramic body. Another method involves, together with, alternatively instead of, said cement, added starch or similar organic material in • • •• • • SO • • 000 • • • • • • • • • • • • • • • • ••• •• In • to .. • ... 0 • • • • • ego * Ike * ego 4.4o 7 the ceramic sludge. After this sludge has been filled in a form of casting of the ceramic body, heating takes place, for example to about 80 ° C, whereby the starch absorbs water and acts as an adhesive in the green body. During a subsequent sintering, the starch is gasified and forms small pores in the ceramic. An advantage of using starch is that the pores that form further increase the porosity of the frame with the accompanying positive effects, as previously reported. However, the use of cement gives a slightly stronger green body.
Kontaktering av en anordning enligt uppfinningen kan i och for sig ske pa olika satt, exempelvis genom screentryckning av ledande monster, elektrolytisk fdllning, lodforbindning mm. Enligt uppfinningen har det dock visat 15 sig fordelaktigt att for kontaktering applicera ledande material genom termisk sprutning eller s& kallad sputtring, varvid det ledande materialet deponeras direkt pa den termoelementen innehallande kroppen, dvs i det foredragna fallet pa det keramiska stommaterialet och termo- 20 elementens andytor, och bildar ledningsbanor i form av skikt. Darigenom uppnas, forutom en enkel och billig kontaktering, att anbringade ledningsskikt kan goras mycket tunna. Det har aven visat sig att termisk sprutade skikt har fordelen att besitta en inneboende viss mojlighet 25 till rorlighet. Darigenom minskar riskerna for sprickbildning och liknande vid rorelser pa grund av spanningar som uppstar genom varmefOrandringar. Contact of a device according to the invention can in itself take place in various ways, for example by screen printing of conductive samples, electrolytic filling, solder connection etc. According to the invention, however, it has proved advantageous to apply conductive material for contacting by thermal spraying or so-called sputtering, wherein the conductive material is deposited directly on the thermocouple-containing body, i.e. in the preferred case on the ceramic body material and the thermal surfaces of the thermocouples. , and forms conduits in the form of layers. In this way, in addition to a simple and inexpensive contacting, it is achieved that applied conductor layers can be made very thin. It has also been found that thermally sprayed layers have the advantage of possessing an inherent certain possibility of mobility. This reduces the risks of cracking and the like during movements due to stresses that arise due to heat changes.
Flera metaller ger mycket god ledningsformaga och ldmpar sig val for namnda kontaktering, t ex koppar, guld 30 m fl. En fOrdel med att anvanda koppar är att kontaktbleck av koppar for yttre anslutning av anordningen latt kan fastas, exempelvis genom punktsvetsning. Ett problem med manga av dessa metaller, inklusive koppar, är dock att de kan reagera med termoelement som är halvledarele- 35 ment och forsamra eller forstora dessa. Dessutom erhalles en kraftig overgangsresistans mellan termoelement av namnda typ och metallen, vilket minskar anordningens termoelektriska effekt. Dessa problem loses enligt uppfinningen genom att man atminstone pa termoelementens andytor forst anbringar, foretradesvis genom sputtring eller termisk sprutning, ett tunt sparr- eller overgangsskikt, av ett med halvledarmaterialet kompatibelt ledande material, foretradesvis tenn-tellurid (Sn-Te) pa den varma sidan och nickel-antimon (Ni-Sb) eller tenntellurid pa den kalla sidan. Ett sadant skikt astadkommer aven en lag overgangsresistens mot bade termoelementen 10 och metallen. Andra exempel pa lampliga material for detta skikt kan vara molybden (Mo), nickel (Ni), jamn (Fe) eller en blandning av nickel och aluminium (Ni-A1).. Several metals provide very good conductivity and are suitable for the said contacting, eg copper, gold 30 etc. An advantage of using copper is that contact plates of copper for external connection of the device can be easily fixed, for example by spot welding. However, a problem with many of these metals, including copper, is that they can react with thermocouples which are semiconductor elements and assemble or enlarge them. In addition, a strong transition resistance is obtained between thermocouples of the said type and the metal, which reduces the thermoelectric effect of the device. These problems are solved according to the invention by first applying, at least on the face surfaces of the thermocouples, preferably by sputtering or thermal spraying, a thin barrier or transition layer, of a conductive material compatible with the semiconductor material, preferably tin-telluride (Sn-Te) on the hot side. and nickel-antimony (Ni-Sb) or tin telluride on the cold side. Such a layer also provides a layer of transition resistance to both the thermocouples 10 and the metal. Other examples of suitable materials for this layer may be molybdenum (Mo), nickel (Ni), iron (Fe) or a mixture of nickel and aluminum (Ni-A1).
Det har enligt uppfinningen visat sig fOrdelaktigt att anbringa namnda forsta skikt endast pa termoelemen- 15 tens andytor, det vill saga inte pa det keramiska stommaterialet vilket gOr det mojligt att anbringa det forsta, tunna sparr- och overgangsskiktet redan fore ingjutningen av termoelementen i stommen. Detta medger i sig att ett stort antal termoelement, i forekommande fall 20 till och med overstigande det antal termoelement som innefattas i en termoelektrisk anordning, samtidigt kan forses med namnda sparrskikt, vilket effektiviserar tillverkningen. I det fall anbringandet av sparrskiktet sker fore gjutningen utfors detsamma foretradesvis genom 25 sputtring. According to the invention it has proved advantageous to apply said first layer only to the face surfaces of the thermocouple, i.e. not to the ceramic body material which makes it possible to apply the first, thin ridge and transition layer already before the thermocouples are cast into the body. This in itself allows a large number of thermocouples, if any, even in excess of the number of thermocouples included in a thermoelectric device, to be simultaneously provided with said ratchet layer, which streamlines production. In case the application of the ridge layer takes place before the casting is carried out, the same is preferably carried out by sputtering.
Efter bildandet av namnda enhetligt sammanhallna kropp, som pa termoelementens andytor fOrsetts med det anbringade forsta skiktet, pasprutas metallen, vilken foretradesvis utgors av koppar, for astadkommande av 30 onskade ledningsbanor. Trots att det med halvledarmaterialet kompatibla ledande materialet har en samre ledningsformaga an exempelvis koppar paverkas den totala ledningsformagan mycket lite, genom att det forst anbringade sparrskiktet kan goras mycket tunt. Sjalva 35 kontakteringsmonstret kan exempelvis skapas genom direkt skiktmonsterstyrd sprutning eller genom sprutning genom ••• • • • • •• • • • •• • • • •• • • • •• • • • • • • • •• •• • • :•••••••••••••••••••:•••••• 9 en over den enhetligt sammanhallna kroppen palagd schablon eller mask. After the formation of said uniformly cohesive body, which is provided on the face surfaces of the thermocouples with the applied first layer, the metal, which is preferably made of copper, is sprayed to provide the desired conductor paths. Despite the fact that the conductive material compatible with the semiconductor material has a more common conductor shape than, for example, copper, the overall conductor shape is affected very little, in that the first applied ridge layer can be made very thin. The contact sample itself can be created, for example, by direct layer sample controlled spraying or by spraying by ••• • • • • • • • • •• • • • • • • • • • • • • • • • •• •• •• •: •••••••••••••••••••••• • •••••• 9 a stencil or mask applied over the uniformly held body.
Den termiska kontakteringssprutningen kan utgoras av exempelvis plasmasprutning, ljusbagssprutning, tradsprut- 5 fling eller pulversprutning. Enligt en foredragen utforingsform av uppfinningen utgors den termiska sprutningen av en hoghastighetsflamsprutning (VHOF), som Astadkommer en storre tathet hos de pasprutade kontakteringsskikten och darmed battre elektriska egenskaper. The thermal contact spraying can be, for example, plasma spraying, light bag spraying, wire spraying or powder spraying. According to a preferred embodiment of the invention, the thermal spraying consists of a high-speed flame spraying (VHOF), which provides a greater tightness of the injection-molded contact layers and thus better electrical properties.
Enligt en alternativ utforingsform av uppfinningen kan det ledande skiktet utgoras av jam, varvid inget separat sparrskikt kravs. Jana lampar sig dessutom mycket val for termisk sprutning. Eftersom jam n dr en samre ledare an exempelvis koppar kravs emellertid att ett kon- 15 takteringsskikt av jam n anbringas mycket tjockare an vad som kravs med koppar, vilket okar bade vikten och omfanget hos anordningen. According to an alternative embodiment of the invention, the conductive layer can be constituted by jam, no separate ridge layer being required. Jana also makes a lot of choices for thermal spraying. However, since a coil conductor of, for example, copper is required, a contact layer of iron is required to be applied much thicker than that required with copper, which increases both the weight and the scope of the device.
Halvledarmaterialets kanslighet for reaktion med anliggande kontakteringsmetaller är varmeberoende, dvs 20 halvledarmaterialet är kansligare vid hogre temperatur. Vid tillrackligt lag temperatur har det visat sig att denna kanslighet är forsumbar. Enligt uppfinningen kan detta utnyttjas genom att sparrskikt med fordel inte anbringas pa de av halvledarelementens andytor som befinner 25 sig pa den kalla sidan. Denna utforingsform av uppfinningen kan sasom inses.dock endast anvandas i de fall man kan sakerstalla att temperaturen pa anordningens kalla sida kontinuerligt kan hallas tillrackligt lag, typiskt under 100° C. The probability of the semiconductor material for reaction with adjacent contact metals is heat-dependent, ie the semiconductor material is more sensitive at higher temperatures. At sufficiently low temperatures, it has been shown that this probability is negligible. According to the invention, this can be utilized in that chimney layers are advantageously not applied to those of the face surfaces of the semiconductor elements which are located on the cold side. This embodiment of the invention can be understood, however, to be used only in cases where it can be ensured that the temperature on the cold side of the device can be kept sufficiently low continuously, typically below 100 ° C.
Elementens storlek, utseende och antal kan varieras efter aktuell tillampning. Det har enligt uppfinningen. visat sig fordelaktigt att de termoelektriska elementen har en typisk langd av mellan 5 och 15 mm, foretradesvis ca. 8 mm, och en typisk area av mellan 10 och 25 mm.2, 35 foretradesvis ca. 20 mm2. Elementen ar inte bundna till en viss form. Det har dock visat sig fordelaktigt med en •••••• • •• •• •• •••• •• •• • • • • • • • • •• • • • • • ••• • • • • • 4:,••• ••• : ••• • ••• • ••• •••• • • •••• • • ••• .• •••• • 10 S • * * • • • • • • •• • • • • • Olt • •• parallellepiped- eller cylinderform, vilket ger elementen fyrkantiga eller cirkulara andytor. The size, appearance and number of elements can be varied according to the current application. It has according to the invention. proved to be advantageous that the thermoelectric elements have a typical length of between 5 and 15 mm, preferably approx. 8 mm, and a typical area of between 10 and 25 mm.2, preferably approx. 20 mm2. The elements are not bound to a particular shape. However, it has proved advantageous to have a •••••• • •• •• •• •••• •• •• • • • • • • • •• • • • • • ••• • • • • • 4:, ••• •••: ••• • ••• • ••• •••• • • •••• • • •••. • •••• • 10 S • * * • • • • • • •• • • • • • Olt • •• parallelepiped or cylinder shape, giving the elements square or circular end faces.
Antalet element anpassas efter vilken utspanning som onskas. Den utspanning som kan erhallas frdn vane ele- 5 ment är typiskt 0,3 volt, vilket multipliceras med antalet seriekopplade element for erhallande av onskad utspanning. Enligt en foredragen utforingsform onskas en utspanning av ca 14 volt, vilket erfordrar 48 stycken seriekopplade termoelektriska element. Bade hogre och 10 lagre utspanningar kan givetvis erhallas. Uppfinningen är som fackmannen inser inte heller begransad till seriekoppiing av elementen, utan aven andra kopplingar kan forekomma, exempelvis parallellkoppling eller kombinationer av parallell- och seriekoppling. Detta anpassas givetvis 15 efter vald tillampning. The number of elements is adapted to the desired output voltage. The output voltage that can be obtained from the usual element is typically 0.3 volts, which is multiplied by the number of elements connected in series to obtain the desired output voltage. According to a preferred embodiment, an output voltage of about 14 volts is desired, which requires 48 pieces of thermoelectric elements connected in series. Both higher and lower bearings can of course be obtained. As the person skilled in the art is also not limited to, the series connection of the elements is limited, but other connections can also occur, for example parallel connection or combinations of parallel and series connection. This is of course adapted to the selected application.
Den fardiga anordningen kan ses som en modul som i sig kan serie- och parallellkopplas med liknade moduler. The finished device can be seen as a module which in itself can be connected in series and in parallel with similar modules.
For att skydda anordningen mot yttre paverkan samt for att astadkomma elektrisk isolering av anordningen an- 20 bringas foretradesvis ett yttre, skyddande holje som omger stommen med de dari anordnade termoelementen och darpa anordnade kontakteringsledningsbanor. Detta holje kan foretradesvis utgoras av ett skikt av keramiskt material, foretradesvis en emalj. Enligt uppfinningen har det 25 visat sig fordelaktigt att detta skikt anbringas genom termisk sprutning, foretradesvis genom plasmasprutning. Darmed underlattas tillverkningsprocessen ytterligare. Detta skikt kan aven anbringas genom exempelvis vatsprutning. In order to protect the device against external influences and to provide electrical insulation of the device, an outer, protective cover is preferably provided which surrounds the body with the thermocouples arranged therein and contacting conductor tracks arranged thereon. This casing can preferably consist of a layer of ceramic material, preferably an enamel. According to the invention it has been found advantageous that this layer is applied by thermal spraying, preferably by plasma spraying. This further facilitates the manufacturing process. This layer can also be applied by, for example, water spraying.
Det har enligt en foredragen utfOringsform av upp- finningen dessutom visat sig fordelaktigt att utanpa ovan namnda skyddande skikt anbringa ett ytterligare skyddande skikt av en blandning av yttrium (Y) och zirkoniumdioxid (Zr02), exempelvis genom termisk sprutning. Detta ger 35 dels en okning av anordningens hallfasthet, dels en jamnare temperaturfordelning Over anordningens varma respektive kalla sida. ••• ••.: :••••••••••••:••• •••••••• •• ••••• •••• ••• ••• ••••••• •• •• : ••• ••••••• •••••••• :•••••• 11 Uppfinningen kommer nu att beskrivas ytterligare med hjalp av exemplifierande utforingsformer med hanvisning till bifogade ritningar. According to a preferred embodiment of the invention, it has also proved advantageous to apply an additional protective layer of a mixture of yttrium (Y) and zirconia (ZrO 2) to the above-mentioned protective layer, for example by thermal spraying. This gives partly an increase in the half-strength of the device, and partly a more even temperature distribution across the hot and cold side of the device. ••• •• .:: •••••••••••••: ••• •••••••• •• ••••• •••• ••• ••• • •••••• •• ••: ••• ••••••• •••••••• • •••••• 11 The invention will now be further described with the aid of exemplary embodiments with male reference. to the accompanying drawings.
Kortfattad beskrivning av ritningarna Figur 1 är en schematisk perspektivvy av en anordning enligt en foredragen utforingsform av uppfinningen; figur 2-7 illustrerar schematiskt de i ett forfarande for astadkommande av anordningen enligt figur 1 in-10 gaende stegen enligt en foredragen utfOringsform av uppfinningen; figur 8 visar schematiskt en delsektionsvy samt en forstorad del darav av anordningen enligt figur 1; figur 9 visar schematiskt en delsektionsvy och en 15 forstorad del darav av en anordning enligt en alternativ utforingsform av uppfinningen; och figur 10 visar schematiskt en delsektionsvy av ytterligare en alternativ utforingsform av uppfinningen. Brief Description of the Drawings Figure 1 is a schematic perspective view of a device according to a preferred embodiment of the invention; Figures 2-7 schematically illustrate the steps according to a preferred embodiment of the invention included in a method for effecting the device according to Figure 1; figure 8 schematically shows a partial sectional view and an enlarged part thereof of the device according to figure 1; Figure 9 schematically shows a partial sectional view and an enlarged part thereof of a device according to an alternative embodiment of the invention; and Figure 10 schematically shows a partial sectional view of a further alternative embodiment of the invention.
Detaljerad beskrivning av foredragna utforingsformer Narmast beskrivs en foredragen utforingsform av en anordning enligt uppfinningen med sarskild hanvisning till figur 1 och figur 8. Detailed Description of Preferred Embodiments Next, a preferred embodiment of a device according to the invention is described with particular reference to Figure 1 and Figure 8.
Den termoelektrisk anordningen 1 är avsedd for om- 25 vandlande vid hogtemperatur av varme till elektricitet genom den sa kallade Seebeck-effekten. Anordningen 1 utgOrs av en langstrackt, plattformad, enhetligt sammanhallen kropp eller modul med tva fran kroppen utskjutande kontaktbleck 18. Anordningens 1 tva motstaende sidor med 30 storst area utgOr anordningens 1 sa kallade varma respektive kalla sida. Ytan pa den varma sidan är avsedd att ligga an mot en varmekalla, exempelvis en katalysator eller bilmotor, och ytan pa den kalla sidan är avsedd att ligga an mot ett kylande element, som exempelvis ä.r 35 anslutet till en bils kylsystem. Anordningen 1 innefattar ett antal n- och p-dopade termoelektriska halvledarelement 10, nedan benamnda termoelement, parallellt an- :.'•..". .".:"• .".•••• ••• • • ••• ••••••, • •• • • •••• •••:• : ••• ••••••• ••• ••• •••• •• 12 ordnade i rader. De n- och p-dopade elementen 10 är vaxelvis kopplade i serie, dvs varje p-dopat element är kopplat i serie till tva intilliggande n-dopade element och vice versa, varvid den ena kopplingen till ett 5 intilliggande element är anordnad p& elementets kalla sida och den andra pA elementets varma sida. Undantaget är det forsta 10a och det sista 10b termoelementet i serien. Dessa bAda element är kopplade till kontaktbleck 18 for yttre kontaktering av anordningen 1. Termoelemen- 10 ten 10 är utformade som lAngstrackta, parallellepipeder med rektangulara andytor. The thermoelectric device 1 is intended for converting at high temperature from heat to electricity by the so-called Seebeck effect. The device 1 consists of an elongate, platform-shaped, uniformly cohesive body or module with two contact plates projecting from the body 18. The two opposite sides of the device 1 with the largest area constitute the so-called hot and cold side of the device 1, respectively. The surface on the hot side is intended to abut against a heating cold, for example a catalyst or car engine, and the surface on the cold side is intended to abut against a cooling element, which for example is connected to a car's cooling system. The device 1 comprises a number of n- and p-doped thermoelectric semiconductor elements 10, hereinafter referred to as thermocouples, in parallel with:. '• .. ".." .: "•.". •••• ••• • • •• • ••••••, • •• • • •••• •••: •: ••• ••••••• ••• ••• •••• •• 12 arranged in rows. The n- and p-doped elements 10 are alternately connected in series, i.e. each p-doped element is connected in series to two adjacent n-doped elements and vice versa, one connection to an adjacent element being arranged p & the cold of the element side and the other on the hot side of the element. The exception is the first 10a and the last 10b thermocouple in the series. These two elements are connected to contact plates 18 for external contacting of the device 1. The thermocouples 10 are designed as elongated, parallelepipeds with rectangular end faces.
Termoelementen 10 dr ingjutna i en stomme 12 som utgors av ett keramiskt material, en emalj, ett bindemedel samt i stommen 12 inbaddade och fOrdelade mikrobal- 15 longer eller mikrosfarer 13. Termoelementen 10 stracker sig mellan motstAende sidor av stommen 12 sA att elementens 10 andytor är frilagda frAn stommen 12 och bildar tillsammans med stommens 12 motstAende sidor tva motstAende jamna ytor. The thermocouples 10 are molded into a body 12 which is made of a ceramic material, an enamel, an adhesive and in the body 12 embedded and distributed microbalances or microspheres 13. The thermocouples 10 extend between opposite sides of the body 12 so that the end surfaces of the elements 10 are exposed from the body 12 and together with the opposite sides of the body 12 form two opposite smooth surfaces.
PA anordningens varma respektive kalla sida är pA termoelementens 10 andytor anbringat ett forsta, sputtrat, mycket tunt, elektriskt ledande, inre skikt 14, sasom ovan beskrivits. Materialet i detta inre skikt 14 är kompatibelt med det material som termoelementen 25 utgors av och utgor darfor ett sA kallat sparrskikt eller overgangsskikt mellan termoelementen 10 och ytterligare kontakteringsskikt. Tack vare sputtringen kan detta forsta skikt 14 anbringas mycket tunt. On the hot and cold sides of the device, respectively, a first, sputtered, very thin, electrically conductive, inner layer 14 is applied to the end faces of the thermocouples 10, as described above. The material in this inner layer 14 is compatible with the material of which the thermocouples 25 are formed and therefore constitutes a so-called ridge layer or transition layer between the thermocouples 10 and further contacting layers. Thanks to the sputtering, this first layer 14 can be applied very thinly.
. . PA sparrskiktet 14, samt pa den yta av stommen 12 30 som är belagen mellan de termoelement 10 som skall sam- • • • • • •mankopplas, är anbringat ett andra, hoghastighetsflam- ••• • •sprutat, yttre kontakteringsskikt 16 av ett material som •• • —ger en mycket god elektrisk ledning mellan termoelementen . .10. Detta yttre kontakteringsskikt 16 är nagot tjockare •35 an sparrskiktet 14 och svarar for den elektriska ledning- ••• • •en mellan termoelementen 10. Detta kontakteringsskikt 16 • • • ••• • • • • • •• • • 00• • Go.• • • 0 •• 000 0 • • • •• •• : 13 bildar de langstrackta ledningsbanor som seriekopplar termoelementen 10 med varandra. . . On the ridge layer 14, as well as on the surface of the body 12 which is coated between the thermocouples 10 to be connected, a second, high-speed flame-sprayed outer contact layer 16 of a material that •• • —provides a very good electrical conductivity between the thermocouples. .10. This outer contact layer 16 is slightly thicker than the ridge layer 14 and is responsible for the electrical conduction between the thermocouples 10. This contact layer 16 • • • ••• • • • • • • • • 00 • • Go. • • • 0 •• 000 0 • • • •• ••: 13 form the elongated conductor paths which connect the thermocouples 10 in series with each other.
I anordningens 1 ena ande, pa dess kalla sida, är tva inledningsvis namnda, langstrackta, rektangulara kon- 5 taktbleck 18 av anordnade. Dessa kontaktbleck 18 är i sin ena ande 18a anbringade mot det forsta respektive det sista seriekopplade termoelementet 10a, 10b och skjuter ut fran dessa parallellt med termoelementens 10 andytor i anordningens 1 langdriktning pa ett sadant satt att 10 kontaktbleckens 18 respektive andra ande 18b skjuter ut utanfor sjalva anordningen. Kontaktblecken 18 är i sin namnda ena ande 18a punktsvetsade till respektive termoelement 10a, 10b och är avsedda for yttre elektrisk anslutning av anordningen 1. In one end of the device 1, on its cold side, two initially mentioned, elongate, rectangular contact plates 18 are arranged. These contact plates 18 are mounted in their one end 18a against the first and the last series-connected thermocouple 10a, 10b and project from them parallel to the end faces of the thermocouple 10 in the longitudinal direction of the device 1 in such a way that the contact plate 18 and the second end 18b project outside the device itself. The contact plates 18 are in their so-called one end 18a spot welded to the respective thermocouples 10a, 10b and are intended for external electrical connection of the device 1.
Anordningen 1 är vidare innesluten av ett vatspru- tat, sintrat, elektriskt isolerande, skyddande skikt 20. Undantagna är de fran anordningens stomme utskjutande delarna 18b av kontaktblecken 18 som inte är forsedda med nagon ytterligare belaggning. The device 1 is further enclosed by a water-sprayed, sintered, electrically insulating, protective layer 20. Excluded are the parts 18b projecting from the body of the device from the contact plates 18 which are not provided with any further coating.
Slutligen och som ett alternativ kan anordningen 1 vara fOrsedd med ytterligare ett pulversprutat skyddande skikt 22. Detta skikt 22 är anordnat att ge dels en forstarkning av anordningen 1, dels en jamnare temperaturfordelning Over anordningens 1 varma respektive kalla 25 side. Denna utforingsform illustreras i figur 9. Finally and as an alternative, the device 1 can be provided with a further powder-sprayed protective layer 22. This layer 22 is arranged to give both a reinforcement of the device 1 and a more even temperature distribution over the hot and cold side of the device 1, respectively. This embodiment is illustrated in Figure 9.
Harnast beskrivs ett typiskt exempel pa dimensionering och materialval for anordningen enligt den ovan beskrivna foredragna utforingsformen. Anordningen 1 antar formen av ett ratblock med de ungefarliga matten 30 120 X 40 X 10 mm, undantaget de fran kroppen utskjutande kontaktblecken 18. De termoelektriska elementen 10 har en langd av 8 mm och de rektangulara andytorna har matten 4 x 5 mm. Materialet i termoelementen 10 ä.r bly-tellurid med iblandade dopamnen. De rektangulara kontaktbleck 18 35 som är anordnade for yttre anslutning av anordningen är av koppar. ••• ••• • • • •• • •• • • •• • •••• • •• • • •• • • ••• • ••• • • • •••• •• • • • • • ••• • • .•: : : ••• ••••••• •••••••• •••• ••. 14 Stommen 12 utgors av ett keramiskt material, alumina eller aluminiumoxid (A1203); ett cement, kalciumaluminat (3Ca0-A1203); en emalj, 94C1001 Flux frAn Cookson Matthew Ceramics; samt mikroballonger 13, Fillite 150 fran 5 Astmoor Industrial Estate eller Sil-cell 140 frAn Stauss Gesellschaft. Materialet i sparrskiktet 14 är pA den varma sidan tenn-tellurid (Sn-Te) och pA den kalla sidan nickel-antimon (Ni-Sb), vilka material är kompatibla med den bly-tellurid som termoelementen 10 utgors ay. 10 Materialet i det yttre kontakteringsskiktet 16 är koppar. Sparrskiktet 14 har en tjocklek av omkring 5 pm och det yttre kontakteringsskiktet 16 har en tjocklek av omkring 100 pm. Most recently, a typical example of sizing and material selection for the device according to the preferred embodiment described above is described. The device 1 takes the form of a steering wheel block with the harmless mat 30 120 X 40 X 10 mm, with the exception of the contact plates 18 projecting from the body. The thermoelectric elements 10 have a length of 8 mm and the rectangular end faces have the mat 4 x 5 mm. The material in the thermocouples 10 is lead telluride with the dopants involved. The rectangular contact plates 18 provided for external connection of the device are made of copper. ••• ••• • • • •• • •• • • •• • •••• • •• • • •• • • ••• • ••• • • • •••• •• • • • • • ••• • •. •::: ••• ••••••• •••••••• •••• ••. The body 12 is made of a ceramic material, alumina or alumina (Al2O3); a cement, calcium aluminate (3CaO-Al 2 O 3); an enamel, 94C1001 Flux from Cookson Matthew Ceramics; and microballoons 13, Fillite 150 from 5 Astmoor Industrial Estate or Sil-cell 140 from Stauss Gesellschaft. The material in the ridge layer 14 is on the hot side tin-telluride (Sn-Te) and on the cold side nickel-antimony (Ni-Sb), which materials are compatible with the lead-telluride on which the thermocouples 10 are formed. The material of the outer contact layer 16 is copper. The spar layer 14 has a thickness of about 5 μm and the outer contact layer 16 has a thickness of about 100 μm.
Materialet i det skyddande, isolerande, vAtsprutade 15 skiktet 20 är en emalj, narmare bestamt 94C1001 Flux frAn Cookson Matthew Ceramics. Det eventuellt ytterligare anbringade skyddande skiktet 22 är av zirkoniumdioxid (Zr02), vilket ger de egenskaper som ovan beskrivits. The material of the protective, insulating, water spray 15 layer 20 is an enamel, more specifically 94C1001 Flux from Cookson Matthew Ceramics. The optionally further applied protective layer 22 is of zirconia (ZrO 2), which gives the properties described above.
Figur 10 illustrerar en alternativ utforingsform av 20 uppfinningen. Enligt denna utforingsform är stommen 12 utford i lager med olika porositet, ett inre lager 12a mellan tvA ytlager 12b. Tillsammans bildar ytlagren 12b och det inre lagret 12a en stomme som forhAller sig till ovriga komponenter sAsom den enhetligt sammansatta stom- 25 men 12 pA det satt som beskrivs ovan. Ytlagren 12b har typiskt en tjocklek av 0,5 mm och saknar helt inblandade mikroballonger. Det inre lagret 12a kan innefatta en storre andel mikroballonger 13 an vad som är fallet med stommen 12 enligt den ovan namnda foredragna utforings- 30 formen. Figure 10 illustrates an alternative embodiment of the invention. According to this embodiment, the body 12 is challenged in layers with different porosity, an inner layer 12a between two surface layers 12b. Together, the surface layers 12b and the inner layer 12a form a body that relates to other components such as the uniformly assembled body 12 on the set described above. The surface layers 12b typically have a thickness of 0.5 mm and lack completely involved microballoons. The inner layer 12a may comprise a larger proportion of microballoons 13 than is the case with the body 12 according to the above-mentioned preferred embodiment.
Nedan beskrivs en foredragen utfOringsform av ett forfarande enligt uppfinningen med sarskild hanvisning till figurerna 2-9. A preferred embodiment of a method according to the invention is described below with particular reference to Figures 2-9.
En forsta gjutformsdel 31 fOrses med en sjalvhaf- 35 tande yta 34 som Astadkommes med en sjalvhaftande tejp. PA denna yta placeras i parallella rader ett antal n- och p-dopade termoelement 10 enligt ovan, som faster mot "•14 •• ": : : • :: • ." : .0. 00 00oo. 646 04166 60 tejpen, varvid termoelementen 10 placeras efter varandra sá att vartannat termoelement är ett n-dopat och vartannat ett p-dopat termoelement. Termoelementen 10 utgors av varmpressade halvledarelement med en blandning av bly (Pb), tellur (Te) och dopamnen, som Astadkommits pa ett i och for sig }cant satt, vilket dArfor inte kommer att beskrivas mer ingaende. Termoelementen 10 är emellertid inte slutligt varmebehandlade nar de placeras i den forsta gjutformsdelen 31, utan utgor sa kallade granele- 10 ment. A first mold part 31 is provided with a self-adhesive surface 34 which is provided with a self-adhesive tape. On this surface, a number of n- and p-doped thermocouples 10 as above are placed in parallel rows, which adhere to the tape, the tape, 646 04166 60 tape, wherein the thermocouples 10 are placed one after the other so that every other thermocouple is an n-doped and every other a p-doped thermocouple.The thermocouples 10 consist of hot-pressed semiconductor elements with a mixture of lead (Pb), tellurium (Te) and the dopants, which are provided on a However, the thermocouples 10 are not finally heat-treated when placed in the first mold part 31, but form so-called granular elements.
Termoelementen 10 är vid placeringen i gjutformen redan pa sina andytor forsedd med ett genom sputtring anbringat forsta sparrskikt 14, som pa den varma sidan ar av tenn-tellurid och pa den kalla sidan av nickel- 15 antimon. When placed in the mold, the thermocouples 10 are already provided on their face surfaces with a first spar layer 14 applied by sputtering, which on the hot side is made of tin-telluride and on the cold side by nickel-antimony.
En andra gjutformsdel 32, som utgor gjutformens lock, anbringas i vatsketat forbindning mot den forsta gjutformsdelen 31, som i sin ena Ande är forsedd med ett hal for ifyllnad av gjutmassa 11. Gjutformsdelarna bildar 20 tillsammans en gjutform 30. Dimensionerna hos de respektive gjutformsdelarna 31, 32 är sadana att termoelementens 10 Andytor anligger vAtsketatt mot gjutformsdelarnas 31, 32 mat riktade ytor. Gjutformen 30 placeras darefter pa hogkant, varefter en gjutmassa 11 fylls i formen 25 under vibrering. A second mold part 32, which forms the lid of the mold, is applied in liquid connection to the first mold part 31, which in one end is provided with a hall for filling molding compound 11. The mold parts together form a mold 30. The dimensions of the respective mold parts 31 32 are such that the end surfaces of the thermocouples 10 abut liquid against the mating surfaces of the mold parts 31, 32. The mold 30 is then placed on a vertical edge, after which a molding compound 11 is filled in the mold 25 during vibration.
Gjutmassan 11 astadkommes genom blandning av 55 % C96 fran HoganAs, 20 % kalciumaluminat, 5 % 94C1001 Plux fran Cookson Matthew Ceramics, samtliga i pulverform, samt 20 % Fillite 150 fran Astmoor Industrial Estate. 30 Efter noggrann blandning av pulvren och ballongerna tillsAtts vatten sa att en slamma med tjock konsistens erhalles. Denna slamma utgor namnda gjutmassa 11 och hAlles i den med termoelement 10 forsedda gjutformen 30. Gjutmassan 11 far dArefter harda i rumstemperatur till en 35 keramisk stomme 12 innefattande de i stommen 12 ingjutna termoelementen 10. The molding compound 11 is obtained by mixing 55% C96 from HoganAs, 20% calcium aluminate, 5% 94C1001 Plux from Cookson Matthew Ceramics, all in powder form, and 20% Fillite 150 from Astmoor Industrial Estate. After thoroughly mixing the powders and balloons, water was added so that a sludge with a thick consistency was obtained. This sludge constitutes said casting mass 11 and is kept in the mold 30 provided with thermocouple 10. The casting mass 11 is then allowed to harden at room temperature to a ceramic body 12 comprising the thermocouples 10 molded into the body 12.
SO 0OO • • 110 00 OO 00.41 • .00 • 0* • • 0 • • • • • • 0 0 • • 00 • • • • • 0410 • • • • 041, IPSO • • 00.0 • • • • • • 16 Efter denna hardning far anordningen lufttorka under minst ett dygn. Anordningen är nu som sa kallad gronkropp klar for varmebehandling, vilket sker i en vakuumugn under 30 minuter, varvid trycket i ugnskammaren pumpas 5 ner till 5 x -6 atmosfarer. Darefter fylls kammaren till atmosfarstryck med nitrogen (N2) eller argon (Ar) och uppvarms darefter till cirka 700° C, varvid uppvarmningstiden bor vara minst 1 timme. Denna temperatur halles sedan i minst 30 minuter, varefter avsvalning sker i 10 ugnen med densamma avslagen. SO 0OO • • 110 00 OO 00.41 • .00 • 0 * • • 0 • • • • • 0 0 • • 00 • • • • • 0410 • • • • 041, IPSO • • 00.0 • • • • • • After this curing, the device is allowed to air dry for at least 24 hours. The device is now, as so-called green body, ready for heat treatment, which takes place in a vacuum oven for 30 minutes, whereby the pressure in the oven chamber is pumped down to 5 x -6 atmospheres. The chamber is then filled to atmospheric pressure with nitrogen (N2) or argon (Ar) and then heated to about 700 ° C, the heating time being at least 1 hour. This temperature is then kept for at least 30 minutes, after which cooling takes place in the oven with the same switch-off.
Nasta steg är att forse anordningen 1 med ledningsbanor 16 for inbordes elektrisk seriekoppling av termoelementen 10 samt for yttre anslutning av anordningen 1 via det i seriekopplingen ingaende forsta respektive det 15 sista termoelement 10a, 10b. Detta utfors genom att masker eller schabloner 36 anbringas mot anordningens 1 kalla respektive varma sida. Maskerna 36 är forsedda med rektangulara hal som efter anbringandet mot anordningen 1 i respektive hal inramar Andytor av tva varandra mar- 20 liggande termoelement 10, varvid det ena är p- och det andra är n-dopat, samt den mellanliggande ytan av stommen 12, sá att seriekoppling av termoelementen kan astadkommas. For de tva termoelement 10a, 10b vars andytor är avsedda att utgOra den fOrsta respektive den sista and- 25 ytan hos namnda seriekoppling, är de motsvarande hal i den mask 36 som ska anbringas mot denna sida sa utformade att genom vartdera halet endast namnda forsta respektive sista andyta inramas. The next step is to provide the device 1 with cable paths 16 for inboard electrical series connection of the thermocouples 10 and for external connection of the device 1 via the first and the last thermocouple 10a, 10b, which enter the series connection. This is done by applying masks or stencils 36 to the cold and hot side of the device 1, respectively. The masks 36 are provided with rectangular slides which, after application to the device 1 in the respective slides, frame face surfaces of two adjacent thermocouples 10, one being p- and the other being n-doped, and the intermediate surface of the body 12, so that series connection of the thermocouples can be achieved. For the two thermocouples 10a, 10b whose end faces are intended to constitute the first and the last end face, respectively, of said series connection, the corresponding slides in the mask 36 to be applied to this side are designed so that through each tail only the first and last andyta framed.
Ett yttre kontakteringsskikt 16 av koppar anbringas 30 sedan pa de inramade ytorna, d v s pa respektive sparrskikt 14 och pa den yta av stommen som är belagen mellan de termoelektriska element som skall forbindas inbordes. Detta skikt 16 anbringas genom hoghastighetsflamsprutning (HVOF) och genom maskerna 36. Det inre skiktet 14 utgOr 35 salunda ett sparr- eller Overgangsskikt som dels skyddar termoelementens 10 andytor fran toxisk paverkan fran det yttre skiktet 16, dels sanker overgangsresistansen mellan ••• 0O. • • • • 00 • 00 • • 0O • 0600 • 00 • 0 GO • • ••• • .0 • • • • • 800 • 041 • • • • • 000 • • • • : .0. 00. .00. .041. O410. OLDO 17 termoelementen 10 och kopparskiktet 16. Efter anbringande av kopparskiktet 16 och efter avlagsnande av maskerna 36, utgor detta skikt 16 ledningsbanor for inbordes elektrisk anslutning av termoelementens 10 andytor. Dessa lednings- 5 banor 16 kan tydligast ses i figur 7. De i anordningen 1 innefattade termoelementen 10 är nu seriekopplade med det forsta respektive det sista termoelementets 10a, 10b kopparskiktbelagda andytor, som är anordnade pa den kalla sidan av anordningens ena ande. An outer contact layer 16 of copper is then applied to the framed surfaces, i.e. to the respective ridge layer 14 and to the surface of the body which is coated between the thermoelectric elements to be connected inboard. This layer 16 is applied by high speed flame spraying (HVOF) and through the masks 36. The inner layer 14 thus forms a ridge or transition layer which partly protects the end faces of the thermocouples 10 from toxic impact from the outer layer 16 and partly reduces the transition resistance between ••• 0O. • • • • 00 • 00 • • 0O • 0600 • 00 • 0 GO • • ••• • .0 • • • • • 800 • 041 • • • • 000 • • • • •: .0. 00. .00. .041. O410. The OLDO 17 thermocouples 10 and the copper layer 16. After applying the copper layer 16 and after removing the masks 36, this layer 16 forms conduits for inboard electrical connection of the end faces of the thermocouples 10. These conduit paths 16 can most clearly be seen in Figure 7. The thermocouples 10 included in the device 1 are now connected in series with the copper-coated end faces of the first and the last thermocouple 10a, 10b, respectively, which are arranged on the cold side of one end of the device.
Sprutningen illustreras schematiskt i figur 6 och anbringande av skikt genom ytbelaggning genom HVOF astadkommes genom foljande steg: Ett pulver av det material som skall anbringas till-fors en HVOF-spruta; pulvret blandas med en sprutan till- 15 fOrd bargas och forslas av bargasen till ett munstycke; vid munstyckets utlopp astadkommes en flamma genom en tillsammans med syre till sprutan tillfOrd branngas; pulvret lamnar munstyckets utlopp med hog hastighet, cirka 500 m/s, varvid pulvret smalter nar det passerar 20 genom flamman och sprutas i form av smalta droppar pa det foremal som skall belaggas och astadkommer en ytbelaggning pa detsamma. The spraying is schematically illustrated in Figure 6 and application of layers by surface coating by HVOF is accomplished by the following steps: A powder of the material to be applied to a HVOF syringe; the powder is mixed with a syringe fed to bar gas and transported by the bar gas to a nozzle; at the outlet of the nozzle a flame is produced by a flue gas supplied to the syringe together with oxygen; the powder leaves the outlet of the nozzle at a high speed, about 500 m / s, whereby the powder melts as it passes through the flame and is sprayed in the form of narrow drops on the object to be coated and provides a surface coating thereon.
Yttre elektrisk anslutning av anordningen 1 mojliggors darefter genom att man pa namnda respektive forsta 25 och sista termoelements 10a, 10b andyta anbringar ett langstrackt, tunt, rektangulart kontaktbleck 18 av koppar. Dessa bada kontaktbleck 18 svetsas i sin respektive ena ande 18a till namnda andytor genom punktsvetsning. Kontaktblecken 18 skjuter ut fran respektive termo- 30 element 10a, 10b vinkelratt mot dessa i anordningens 1 langdriktning parallellt med termoelementens 10 andytor sa att kontaktbleckens 18 respektive andra ande 18b skjuter ut utanfor sjalva anordningen, vilket bast kan ses i figur 7. External electrical connection of the device 1 is then made possible by applying an elongate, thin, rectangular contact plate 18 of copper to said face surface of the respective first and last thermocouples 10a, 10b. These two contact plates 18 are welded in their respective one end 18a to said end faces by spot welding. The contact plates 18 project from the respective thermocouples 10a, 10b perpendicular to them in the longitudinal direction of the device 1 parallel to the end faces of the thermocouple 10 so that the contact plates 18 and the other second 18b, respectively, project outside the device itself, as can be seen in Figure 7.
Harnast anbringas ett skyddande, elektriskt isole- rande skikt av emalj 20. Detta skikt 20 anbringas genom vatsprutning. Emaljskiktet 20 anbringas pa ett sadant :••• :••• • ••.: • • :.•••••••••••:••• ••••• ••:::•: •••••• •••• : ••• •••••••• • : •••• • •• L8 satt att hela anordningen, innefattande stommen 12 och termoelementen 10, tillsammans med kontakteringsskikten 14, 16 innesluts av detta emaljskikt 20. Undantaget är de utanfor stommen 12 utskjutande delarna av kontaktblecken 5 18 som inte emaljbelaggs. A protective, electrically insulating layer of enamel 20 is applied immediately. This layer 20 is applied by water spraying. The enamel layer 20 is applied to one such: •••: ••• • •• .: • •:. ••••••••••••: ••• ••••• •• ::: •: •••••• ••••: ••• ••••••••• •: •••• • •• L8 sat that the whole device, including the body 12 and the thermocouples 10, together with the contact layers 14, 16 enclosed by this enamel layer 20. The exception is the parts of the contact plates 5 projecting outside the body 12 which are not enamelled.
Slutligen astadkommes en slutlig varmebehandling av anordningen genom sintring i ugn i cirka 700° C till dess att anordningen uppnatt samma temperatur som ugnen och darefter i ytterligare cirka 10 minuter. Avsvalning sker 10 darefter i ugnen med densamma avslagen. Vid denna slutliga varmebehandling astadkommes emaljering av emaljskiktet 20. Finally, a final heat treatment of the device is achieved by sintering in an oven at about 700 ° C until the device has reached the same temperature as the oven and then for another about 10 minutes. Cooling takes place 10 then in the oven with the same rejection. In this final heat treatment, enamelling of the enamel layer 20 is accomplished.
Claims (14)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE9801798A SE9801798A0 (en) | 1998-05-20 | 1998-05-20 | Thermoelectric device |
| PCT/SE1999/000861 WO1999063791A2 (en) | 1998-05-20 | 1999-05-20 | Thermoelectric device and method for manufacturing of said device |
| AU46619/99A AU4661999A (en) | 1998-05-20 | 1999-05-20 | Thermoelectric device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE9801798A SE9801798A0 (en) | 1998-05-20 | 1998-05-20 | Thermoelectric device |
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| Publication Number | Publication Date |
|---|---|
| SE9801798L SE9801798L (en) | |
| SE9801798D0 SE9801798D0 (en) | 1998-05-20 |
| SE9801798A0 true SE9801798A0 (en) | 1999-11-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SE9801798A SE9801798A0 (en) | 1998-05-20 | 1998-05-20 | Thermoelectric device |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU4661999A (en) |
| SE (1) | SE9801798A0 (en) |
| WO (1) | WO1999063791A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010035724A1 (en) | 2010-08-28 | 2012-03-01 | Daimler Ag | Manufacturing method of motor vehicle component e.g. heat exchanger with thermoelectric generator, involves contacting semiconductor element of thermoelectric generator in series with overlying conductive material layer |
| DE102012205098B4 (en) * | 2012-03-29 | 2020-04-02 | Evonik Operations Gmbh | Thermoelectric components based on dry pressed powder precursors |
| DE102013219541B4 (en) | 2013-09-27 | 2019-05-09 | Evonik Degussa Gmbh | Improved process for the powder metallurgical production of thermoelectric components |
| DK3196951T3 (en) | 2016-01-21 | 2019-01-21 | Evonik Degussa Gmbh | RATIONAL PROCEDURE FOR POWDER METAL SURGICAL MANUFACTURING THERMOELECTRIC COMPONENTS |
| US20190181320A1 (en) * | 2017-12-13 | 2019-06-13 | Purdue Research Foundation | Electric generator and method of making the same |
| JP2020150215A (en) * | 2019-03-15 | 2020-09-17 | 三菱マテリアル株式会社 | Thermoelectric conversion module |
| GB2585045A (en) * | 2019-06-25 | 2020-12-30 | Sumitomo Chemical Co | Thermoelectric device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5364495A (en) * | 1976-11-22 | 1978-06-08 | Matsushita Electric Ind Co Ltd | Ceramic case for thermoelectric transducer |
| US4459428A (en) * | 1982-04-28 | 1984-07-10 | Energy Conversion Devices, Inc. | Thermoelectric device and method of making same |
| US4687879A (en) * | 1985-04-25 | 1987-08-18 | Varo, Inc. | Tiered thermoelectric unit and method of fabricating same |
| US4907060A (en) * | 1987-06-02 | 1990-03-06 | Nelson John L | Encapsulated thermoelectric heat pump and method of manufacture |
| DE69130654T2 (en) * | 1990-04-20 | 1999-08-12 | Matsushita Electric Industrial Co., Ltd., Kadoma, Osaka | Vacuum-insulated thermoelectric semiconductor consisting of a porous structure and thermoelectric component |
| CH680541A5 (en) * | 1990-07-12 | 1992-09-15 | Landis & Gyr Betriebs Ag | |
| JPH09153647A (en) * | 1995-11-29 | 1997-06-10 | Chichibu Onoda Cement Corp | Heat conductive substrate for thermoelectric conversion module |
-
1998
- 1998-05-20 SE SE9801798A patent/SE9801798A0/en not_active Application Discontinuation
-
1999
- 1999-05-20 AU AU46619/99A patent/AU4661999A/en not_active Abandoned
- 1999-05-20 WO PCT/SE1999/000861 patent/WO1999063791A2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| SE9801798D0 (en) | 1998-05-20 |
| WO1999063791A3 (en) | 2000-03-16 |
| WO1999063791A2 (en) | 1999-12-09 |
| SE9801798L (en) | |
| AU4661999A (en) | 1999-12-20 |
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