US2397756A - Thermoelectric device - Google Patents
Thermoelectric device Download PDFInfo
- Publication number
- US2397756A US2397756A US470032A US47003242A US2397756A US 2397756 A US2397756 A US 2397756A US 470032 A US470032 A US 470032A US 47003242 A US47003242 A US 47003242A US 2397756 A US2397756 A US 2397756A
- Authority
- US
- United States
- Prior art keywords
- thermo
- electric
- sulphur
- tellurium
- selenium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229910052714 tellurium Inorganic materials 0.000 description 12
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 229910052711 selenium Inorganic materials 0.000 description 11
- 239000011669 selenium Substances 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 125000004354 sulfur functional group Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- 230000005676 thermoelectric effect Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
Definitions
- thermo-electric devices consist of improvements in or relating to thermo-electric devices.
- Many different proposals have been made for producing suitable elements for thermocouples and in particular for'obtaining a high degree of sensitivity in thermopiles. It is known that to obtain a high sensitivity it is necessary that the substances used must possess a high thermo-electric power and that the loss of heat from the irradiated surface must be kept as small as possible.
- To minimize heat loss it has been customary to use the thermo-electric elements in the form of fine wires or strips sometimes joined end to end but these arrangements are delicate and are apt to be injured by shockor vibration.
- One object of this invention is to provide compositions suitable for thermo-electric elements of high and variable thermo-electric power and low heat conductivity which shall be strong and tough and readily worked.
- compositions should have the following properties:
- composition is made from a metal or from two or more metals combined with two or more elements of the sulphur group.
- composition consists of one, two or three metals with elements of the sulphur group.
- the convenient metals are silver, copper, lead and thallium and the elements of the sulphur group are sulphur, selenium and tellurium.
- thermoelectric elements contain two or more metals combined with two or more elements of the sulphur group the thermo-electric effect is secured by arranging that in one thermo-el-ctric composition the proportion of a certain metal or compound (or of certain metals 'or compounds), is comparatively high whereas in the other thermo-electric composition the proportion of the constituent metals and elements is substantially difierent.
- a metal such as silver may be melted with sulphur and selenium to form a composition for use as one element in a thermo-electric device.
- This composition may contain minor proportions of other metals such as copper or lead and/or tellurium.
- one element herein referred to as the positive element may have a composition as follows:
- thermo-electric power against platinum can be varied within a range of about 130 to 1200 microvolts per degree centigrade.
- An increase of sulphur and reduction in selenium increases the thermo-power.
- Increase in tellurium decreases the specific resistance and the rate of change of resistance with temperature.
- the amount of copper is preferably less than 2%
- the amount of silver may range between 70 and 80%
- the amount of selenium may range between 10 and 15%
- the amount of sulphur may range between 5 and 10%
- the amount of tellurium is preferably less than Copper and silver and tellurium with selenium and sulphur are melted together to form a composition for use as another element of a thermoelectric device (say the negative element) and the following is one example of an appropriate composition, the figures being given as percentages by weight:
- thermopiles for detecting and measuring 7 radiation V 1. In thermopiles for detecting and measuring 7 radiation:
- compositions are not brittle but quite tough and they can be made into suitable forms for securing, say'by welding, toconducting supports and to irradiation surfaces.
- the present invention can be used in conjunction with that described in my United States patent application Serial No. 470,031 filed December 24, 1942, that is to say, the two compositions may be used in the form of little sturdy bodies (say conical or cylindrical bodies) secured to the outer ends of supporting pillars of conducting material and the tips of these bodies may be secured to the back of a metallic foil the outer sur-' face of which is the irradiation surface.
- little sturdy bodies say conical or cylindrical bodies
- thermo-electric powers of the two bodies may be of opposite sign so that their thermo-electric effects are added when the deviceis in operation in a completed circuit.
- thermo-electric couples the conditions or requirements may vary and, as has been pointed out, the thermoular use of this invention-a simple test. may be necessary to determine the optimum composition it is a subsidiary feature of this invention that in- 2.
- thermo-converters for converting alternating to direct current In,thermo-converters for converting alternating to direct current;
- thermopile selection of the resistance and sensitivity of the thermopile. It is one of the practical advantages of the present invention that the resistance and the sensitivity of the thermopile can be independently varied to an outstanding extent.
- thermo-electric couple having a positive thermo-electric element-comprising a fused material'containing between 70 and 80% silver, less than 2% copper,'10 to 15% selenium, 5 to 10% suliur, and less than 2% tellurium, and a negative thermo-electric element comprising a fused material containing 25 -to copper, 25 to silver, 30 to 35% tellurium, 5 to 10% selenium, and less than2% sulphur.
- thermo-electric element comprising a fused material containing between to silver, less than 2% copper, 10 to 15% selenium.
- thermo-electric element comprising a fused material containing 25 to 30% copper, 25 to;35% silver, 30 to tellurium, 5 to 10% selenium. and less than 2% sulphur-r ERNST SCHWARZ.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Photometry And Measurement Of Optical Pulse Characteristics (AREA)
Description
Patented Apr. 2, 1946 No Drawing. Application December 24, 1942, se i'ilal No. 470,032. In Great Britain July 2,
3 Claims.
This invention consists of improvements in or relating to thermo-electric devices. Many different proposals have been made for producing suitable elements for thermocouples and in particular for'obtaining a high degree of sensitivity in thermopiles. It is known that to obtain a high sensitivity it is necessary that the substances used must possess a high thermo-electric power and that the loss of heat from the irradiated surface must be kept as small as possible. To minimize heat loss it has been customary to use the thermo-electric elements in the form of fine wires or strips sometimes joined end to end but these arrangements are delicate and are apt to be injured by shockor vibration. When attempts have been made to construct these fine or thin elements from metals or compounds of high thermo-electric power like metallic tellurium or bismuth or antimony or their alloys they are found to be very brittle so that they are diflicult to handle and do not effectively resist shock and vibration.
One object of this invention is to provide compositions suitable for thermo-electric elements of high and variable thermo-electric power and low heat conductivity which shall be strong and tough and readily worked.
The conditions which these compositions should fulfil are that they should have the following properties:
(1) High and reliable thermo-electric power capable of variation.
(2) Low specific resistance. (3) Low heat conductivity. (4) Good mechanical properties. (5) Appropriate melting point neither too low nor too high (e. g. between 500 C. and 800 C.). 6) Resistance to oxidation (on heating in air). (7) Weldability to metals such as silver or gold. (8) Stability either in air or vacuum. (9) In certain cases, as in pyrometers, a low rate of change of resistance with temperature.
According to this invention a composition is made from a metal or from two or more metals combined with two or more elements of the sulphur group.
All the conditions mentioned above are fulfilled if the composition consists of one, two or three metals with elements of the sulphur group. The convenient metals are silver, copper, lead and thallium and the elements of the sulphur group are sulphur, selenium and tellurium.
It is to be understood that if both thermoelectric elements contain two or more metals combined with two or more elements of the sulphur group the thermo-electric effect is secured by arranging that in one thermo-el-ctric composition the proportion of a certain metal or compound (or of certain metals 'or compounds), is comparatively high whereas in the other thermo-electric composition the proportion of the constituent metals and elements is substantially difierent. By alteration of the proportions it is possible to fulfil all the nine conditions set out above.
A metal such as silver may be melted with sulphur and selenium to form a composition for use as one element in a thermo-electric device. This composition may contain minor proportions of other metals such as copper or lead and/or tellurium. For example, one element herein referred to as the positive element may have a composition as follows:
Per cent Copper 1 Silver 78 Tellurium 0.6 Selenium 1.3 Sulphur It is found that by varying the proportions of the elements in the above composition, the thermo-electric power against platinum can be varied within a range of about 130 to 1200 microvolts per degree centigrade. An increase of sulphur and reduction in selenium increases the thermo-power. Increase in tellurium decreases the specific resistance and the rate of change of resistance with temperature. Thus in producing a positive element the amount of copper is preferably less than 2%, the amount of silver may range between 70 and 80%, the amount of selenium may range between 10 and 15%, the amount of sulphur may range between 5 and 10%, and the amount of tellurium is preferably less than Copper and silver and tellurium with selenium and sulphur are melted together to form a composition for use as another element of a thermoelectric device (say the negative element) and the following is one example of an appropriate composition, the figures being given as percentages by weight:
Copper 27 Silver 32 Tellurium 33 Selenium v 7 Sulphur 1 proportions may increase the thermo-power of' thepreferred arrangement the bodies above referred to are conductively connected, say by electric welding. to the supporting pillars and to the foil orreceiver.
This invention can be applied to the following uses:
V 1. In thermopiles for detecting and measuring 7 radiation:
said compositions and may also improve the'mechanical properties by making the bodies tougher, more ductile or harder. Thallium may also be added. A, simple test may be necessary to determine the appropriate proportion of such additions because their effect varies with the composition of the remainder. V 7
These compositions are not brittle but quite tough and they can be made into suitable forms for securing, say'by welding, toconducting supports and to irradiation surfaces. V
The present invention can be used in conjunction with that described in my United States patent application Serial No. 470,031 filed December 24, 1942, that is to say, the two compositions may be used in the form of little sturdy bodies (say conical or cylindrical bodies) secured to the outer ends of supporting pillars of conducting material and the tips of these bodies may be secured to the back of a metallic foil the outer sur-' face of which is the irradiation surface.
These bodies are semiconductors.of electricity and have a low heat conductivity. 7 V
The thermo-electric powers of the two bodies (in relation to gold or platinum) may be of opposite sign so that their thermo-electric effects are added when the deviceis in operation in a completed circuit. r
It will be understood'that for differenttypes of instruments involving the use of thermo-electric couples the conditions or requirements may vary and, as has been pointed out, the thermoular use of this invention-a simple test. may be necessary to determine the optimum composition it is a subsidiary feature of this invention that in- 2. In,thermo-converters for converting alternating to direct current;
3. In the transformation of radiation energy (say from the sun) into electric current;
4. For measuring degree of vacuum (as the sensitivity of the thermo-electric device increases as the gaseous pressure diminishes);
5. In electrical relays aflected by radiation as a in burglar alarms;
selection of the resistance and sensitivity of the thermopile. It is one of the practical advantages of the present invention that the resistance and the sensitivity of the thermopile can be independently varied to an outstanding extent.
I claim: r a
1. A thermo-electric couple having a positive thermo-electric element-comprising a fused material'containing between 70 and 80% silver, less than 2% copper,'10 to 15% selenium, 5 to 10% suliur, and less than 2% tellurium, and a negative thermo-electric element comprising a fused material containing 25 -to copper, 25 to silver, 30 to 35% tellurium, 5 to 10% selenium, and less than2% sulphur. 1
2. Apositive thermo-electric element comprising a fused material containing between to silver, less than 2% copper, 10 to 15% selenium.
' 5 to 10% sulphur, and less than 2% tellurium.
'3. A negative thermo-electric element comprising a fused material containing 25 to 30% copper, 25 to;35% silver, 30 to tellurium, 5 to 10% selenium. and less than 2% sulphur-r ERNST SCHWARZ.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB2397756X | 1941-07-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
US2397756A true US2397756A (en) | 1946-04-02 |
Family
ID=10905759
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US470032A Expired - Lifetime US2397756A (en) | 1941-07-02 | 1942-12-24 | Thermoelectric device |
Country Status (2)
Country | Link |
---|---|
US (1) | US2397756A (en) |
NL (1) | NL65724C (en) |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2602095A (en) * | 1950-06-03 | 1952-07-01 | Gen Electric | Thermoelectric device |
US2762857A (en) * | 1954-11-01 | 1956-09-11 | Rca Corp | Thermoelectric materials and elements utilizing them |
US2790021A (en) * | 1953-11-24 | 1957-04-23 | Milwaukee Gas Specialty Co | Thermoelectric generator |
US2811569A (en) * | 1954-12-15 | 1957-10-29 | Milwaukee Gas Specialty Co | Contacting semi-metallic electrical conductors |
US2811570A (en) * | 1954-12-15 | 1957-10-29 | Baso Inc | Thermoelectric elements and method of making such elements |
US2811571A (en) * | 1954-12-15 | 1957-10-29 | Baso Inc | Thermoelectric generators |
DE1043435B (en) * | 1954-07-12 | 1958-11-13 | Baso Inc | Process for the manufacture of a thermocouple |
US2902221A (en) * | 1956-06-22 | 1959-09-01 | Minnesota Mining & Mfg | Burner control system |
US2921973A (en) * | 1957-04-16 | 1960-01-19 | Westinghouse Electric Corp | Thermoelements and devices embodying them |
US2952409A (en) * | 1955-11-21 | 1960-09-13 | Minnesota Mining & Mfg | Temperature sensitive control apparatus |
US2953617A (en) * | 1957-04-16 | 1960-09-20 | Westinghouse Electric Corp | Thermoelements and devices embodying them |
US2972653A (en) * | 1953-11-24 | 1961-02-21 | Minnesota Mining & Mfg | Thermoelectric generator |
US2972654A (en) * | 1953-11-24 | 1961-02-21 | Minnesota Mining & Mfg | Thermoelectric generator |
US3095330A (en) * | 1959-12-07 | 1963-06-25 | Monsanto Chemicals | Thermoelectricity |
US3132488A (en) * | 1959-12-07 | 1964-05-12 | Monsanto Chemicals | Thermoelectricity |
US3852118A (en) * | 1970-05-11 | 1974-12-03 | Minnesota Mining & Mfg | Thermoelectric composition |
US3853632A (en) * | 1967-04-20 | 1974-12-10 | Minnesota Mining & Mfg | Thermoelectric composition |
US3873370A (en) * | 1972-09-25 | 1975-03-25 | Atomic Energy Commission | Thermoelectric generators having partitioned self-segmenting thermoelectric legs |
US4029520A (en) * | 1972-10-02 | 1977-06-14 | Minnesota Mining And Manufacturing Company | Thermoelectric generators that incorporate self-segmenting thermoelectric legs |
US4061505A (en) * | 1971-10-08 | 1977-12-06 | Minnesota Mining And Manufacturing Company | Rare-earth-metal-based thermoelectric compositions |
-
0
- NL NL65724D patent/NL65724C/xx active
-
1942
- 1942-12-24 US US470032A patent/US2397756A/en not_active Expired - Lifetime
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2602095A (en) * | 1950-06-03 | 1952-07-01 | Gen Electric | Thermoelectric device |
US2972653A (en) * | 1953-11-24 | 1961-02-21 | Minnesota Mining & Mfg | Thermoelectric generator |
US2790021A (en) * | 1953-11-24 | 1957-04-23 | Milwaukee Gas Specialty Co | Thermoelectric generator |
US2972654A (en) * | 1953-11-24 | 1961-02-21 | Minnesota Mining & Mfg | Thermoelectric generator |
DE1043435B (en) * | 1954-07-12 | 1958-11-13 | Baso Inc | Process for the manufacture of a thermocouple |
US2762857A (en) * | 1954-11-01 | 1956-09-11 | Rca Corp | Thermoelectric materials and elements utilizing them |
US2811569A (en) * | 1954-12-15 | 1957-10-29 | Milwaukee Gas Specialty Co | Contacting semi-metallic electrical conductors |
US2811570A (en) * | 1954-12-15 | 1957-10-29 | Baso Inc | Thermoelectric elements and method of making such elements |
US2811571A (en) * | 1954-12-15 | 1957-10-29 | Baso Inc | Thermoelectric generators |
US2952409A (en) * | 1955-11-21 | 1960-09-13 | Minnesota Mining & Mfg | Temperature sensitive control apparatus |
US2902221A (en) * | 1956-06-22 | 1959-09-01 | Minnesota Mining & Mfg | Burner control system |
US2953617A (en) * | 1957-04-16 | 1960-09-20 | Westinghouse Electric Corp | Thermoelements and devices embodying them |
US2921973A (en) * | 1957-04-16 | 1960-01-19 | Westinghouse Electric Corp | Thermoelements and devices embodying them |
US3095330A (en) * | 1959-12-07 | 1963-06-25 | Monsanto Chemicals | Thermoelectricity |
US3132488A (en) * | 1959-12-07 | 1964-05-12 | Monsanto Chemicals | Thermoelectricity |
US3853632A (en) * | 1967-04-20 | 1974-12-10 | Minnesota Mining & Mfg | Thermoelectric composition |
US3852118A (en) * | 1970-05-11 | 1974-12-03 | Minnesota Mining & Mfg | Thermoelectric composition |
US4061505A (en) * | 1971-10-08 | 1977-12-06 | Minnesota Mining And Manufacturing Company | Rare-earth-metal-based thermoelectric compositions |
US3873370A (en) * | 1972-09-25 | 1975-03-25 | Atomic Energy Commission | Thermoelectric generators having partitioned self-segmenting thermoelectric legs |
US4029520A (en) * | 1972-10-02 | 1977-06-14 | Minnesota Mining And Manufacturing Company | Thermoelectric generators that incorporate self-segmenting thermoelectric legs |
Also Published As
Publication number | Publication date |
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NL65724C (en) |
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