Patent US4764212A successfully refreshed from Google Patents.
US4764212A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Thermoelectric material for low temperature use and method of manufacturing the same
Assignee: Komatsu Ltd
•
Filing: 1987-02-19
•
Granted: 1988-08-16
•
Expires: 2007-02-19
Abstract
Abstract This invention relates to a method of manufacturing thermoelectric material which has the steps of quenching a thermoelectric alloy in a molten state at a quenching rate higher than 10 3 ° C./sec into a membrane or powdery form and subjecting the membrane or powder to cold-forming or sintering. The thermoelectric alloy is a Bi--Sb series alloy having a composition represented by {(Bi.sub.100-x ·Sb.sub.x).sub.100-y ·E.sup.II.sub.y } 100-z ·E I z where E I represents a group III or group IV element, E II represents a group IV or group VI element, x represents a number of 5-20, y represents an integer of 0-20 and z represents a number of 0.05-10, respectively.
Inventors
- 👤 Takuji Okumura
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 13:47
CPC Classifications
C; C22; C22C; C22C12/00; C22C1/00; H; H10; H10N; H10N10/00; H10N10/80; H10N10/85; H10N10/851; H10N10/852; Y; Y10; Y10S; Y10S420/00; Y10S420/903
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
52 words
A method of manufacturing thermoelectric material, comprising the steps of: quenching a thermoelectric alloy in a molten state at a quenching rate higher than 10 3 ° C./sec into a membrane or powdery form and subjecting the membrane or powder to cold-forming or sintering while maintaining the alloy in a metastable state.
Claim 2
Independent Claim
52 words
A method of manufacturing thermoelectric material, comprising the steps of: quenching a thermoelectric alloy in a molten state at a quenching rate higher than 10 3 ° C./sec into a membrane or powdery form and subjecting the membrane or powder to cold-forming or sintering while maintaining the alloy in a metastable state.
Claim 3
Dependent Claim
71 words
A method of manufacturing thermoelectric material as defined in claim 1, wherein the thermoelectric alloy is a Bi--Sb series alloy having a composition represented by {(Bi.sub.100-x ·Sb.sub.x).sub.100-y ·E.sup.II.sub.y }.sub.100-z ·E.sup.I.sub.z where E I represents a group III or group IV element, E II represents a group IV or group VI element, x represents a number of 5-20, y represents an integer of 0-20 and z represents a number of 0.05-10, respectively.
Claim 4
Dependent Claim
37 words
A method of manufacturing thermoelectric material as defined in claim 2, wherein the Bi--Sb series alloy of the above-mentioned composition put to the molten state is quenched at a quenching rate capable of forming the nonequilibrium phase.
Claim 5
Dependent Claim
21 words
A method of manufacturing thermoelectric material as defined in claim 2, wherein E I represents a group IV element and y=0.
Claim 6
Dependent Claim
58 words
A method of manufacturing thermoelectric material as defined in claim 2, wherein the Bi--Sb series alloy in the molten state is quenched to solidify by jetting out the molten alloy onto a metal roll of 200 mm diameter and 20 mm width rotating at 500-4000 rpm under a jetting pressure of from 0.5 to 4 kb/cm 2 .
Claim 7
Dependent Claim
49 words
The method as set forth in claim 1, wherein the step of quenching produces a membrane or powdery thermoelectric material having a crystal grain size of a sub-micron order of magnitude and the step of cold-forming or sintering occurs at a temperature below the crystal grain size coarsing temperature.
Claim 8
Dependent Claim
63 words
The method as set forth in claim 2, wherein said Bi--Sb series alloy is prepared by using Bl 100-x · Sb x (where x=5-20) forming an intrinsic semiconductor as the Bi--Sb series matrix alloy, adding the group II or group IV element as the p-type dopant within the stated range; and adding the group IV, VI elements as required for group III dopant.
Claim 9
Dependent Claim
32 words
The method as set forth in claim 2, wherein said Bi--Sb alloy when subjected to the quenching and forming steps shows a p-type conduction at about 77° K. to about room temperature.
Claim 10
Dependent Claim
30 words
The method as set forth in claim 7, wherein the step of adding a group III or group IV element is in an amount greater than the equilibrium solidification amount.
Claim 11
Dependent Claim
55 words
A metastable thermoelectric Bi--Sb series alloy having a composition comprising: {(Bi.sub.100-x· Sb.sub.x).sub.100-y· E.sup.II y}.sub.100-z· E.sup.I.sub.z where Ei represents a group III or group IV element, E II represents a group IV or group VI element, x represents a number of 5-20, y represents an integer of 0-20 and z represents a number of 0.05-10, respectively.
Claim 12
Dependent Claim
55 words
A metastable thermoelectric Bi--Sb series alloy having a composition comprising: {(Bi.sub.100-x· Sb.sub.x).sub.100-y· E.sup.II y}.sub.100-z· E.sup.I.sub.z where Ei represents a group III or group IV element, E II represents a group IV or group VI element, x represents a number of 5-20, y represents an integer of 0-20 and z represents a number of 0.05-10, respectively.
Claim 13
Dependent Claim
15 words
The alloy of claim 10, wherein E I represent a group IV element and y=0.
Claim 14
Independent Claim
102 words
A method of preparing a massive solid thermoelectric semiconductor alloy having a dopant concentration greater than the equilibrium solubility of the dopant comprising the steps of: (a) forming a solid alloy in powder or thin laminar form by chiling a molten semiconductor alloy composition containing a dopant in a concentration greater than the equilibrium solubility of the dopant in the solid semiconductor alloy at a cooling rate greater than 10 3 ° C. per second, and (b) compacting said powder or thin laminar alloy by heat and pressure under conditions of temperature and time chosen to prevent substantial precipitation of the dopant.
Claim 15
Independent Claim
102 words
A method of preparing a massive solid thermoelectric semiconductor alloy having a dopant concentration greater than the equilibrium solubility of the dopant comprising the steps of: (a) forming a solid alloy in powder or thin laminar form by chiling a molten semiconductor alloy composition containing a dopant in a concentration greater than the equilibrium solubility of the dopant in the solid semiconductor alloy at a cooling rate greater than 10 3 ° C. per second, and (b) compacting said powder or thin laminar alloy by heat and pressure under conditions of temperature and time chosen to prevent substantial precipitation of the dopant.
Claim 16
Dependent Claim
13 words
The method of claim 1 wherein said alloy is a Bi--Sb series alloy.
Claim 17
Dependent Claim
71 words
A method of manufacturing thermoelectric material as defined in claim 13, wherein the thermoelectric alloy is a Bi--Sb series alloy having a composition represented by {(Bi.sub.100-x· Sb.sub.x).sub.100-y· E.sup.II y}.sub.100-z· E.sup.I.sub.z where E I represents a group III or group IV element, E II represents a group IV or group VI element, x represents a number of 5-20, y represents an integer of 0-20 and z represents a number of 0.05-10, respectively.
Claim 18
Dependent Claim
37 words
A method of manufacturing thermoelectric material as defined in claim 14, wherein the Bi--Sb series alloy of the above-mentioned composition put to the molten state is quenched at a quenching rate capable of forming the non-equilibrium phase.
Claim 19
Dependent Claim
21 words
A method of manufacturing thermoelectric material as defined in claim 14, wherein E I represents a group IV element and y=0.
Claim 20
Dependent Claim
58 words
A method of manufacturing thermoelectric material as defined in claim 14, wherein the Bi--Sb series alloy in the molten state is quenched to solidify by jetting out the molten alloy onto a metal roll of 200 mm diameter and 20 mm width rotating at 500-4000 rpm under a jetting pressure of from 0.5 to 4 kg/cm 2 .
Claim 21
Dependent Claim
49 words
The method as set forth in claim 13, wherein the step of quenching produces a membrane or powdery thermoelectric material having a crystal grain size of a sub-micron order of magnitude and the step of cold-forming or sintering occurs at a temperature below the crystal grain size coarsing temperature.
Claim 22
Dependent Claim
63 words
The method as set forth in claim 14, wherein said Bi--Sb series alloy is prepared by using Bl 100-x · Sb x (where x=5-20) forming an intrinsic semiconductor as the Bi--Sb series matrix alloy, adding the group III or group IV element as the p-type dopant within the stated range; and adding the group IV, VI elements as required for group III dopant.
Claim 23
Dependent Claim
32 words
The method as set forth in claim 19, wherein said Bi--Sb alloy when subjected to the quenching and forming steps shows a p-type conduction at about 77° K. to about room temperature.
Claim 24
Dependent Claim
30 words
The method as set forth in claim 19, wherein the step of adding a group III or group IV element is in an amount greater than the equilibrium solidification amount.
References Cited (Backward Citations)
US4347076A
Cited
US4395464A
Cited
US4404028A
Cited
US4473402A
Cited
US4410490A
Cited
US4592781A
Cited
US4613371A
Cited
US4589918A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1991-08-16 | 1992-02-15 | 1992-08-16 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1995-08-16 | 1996-02-15 | 1996-08-16 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1999-08-16 | 2000-02-15 | 2000-08-16 | $7700.00 | Window Closed / Lapsed |