WO2006068325A2 - Production method of thermoelectric semiconductor alloy, thermoelectric conversion module and thermoelectric power generating device - Google Patents

Production method of thermoelectric semiconductor alloy, thermoelectric conversion module and thermoelectric power generating device Download PDF

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WO2006068325A2
WO2006068325A2 PCT/JP2005/024186 JP2005024186W WO2006068325A2 WO 2006068325 A2 WO2006068325 A2 WO 2006068325A2 JP 2005024186 W JP2005024186 W JP 2005024186W WO 2006068325 A2 WO2006068325 A2 WO 2006068325A2
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alloy
heuslar
thermoelectric
member selected
formula
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WO2006068325A3 (en
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Kenichiro Nakajima
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Resonac Holdings Corp
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Showa Denko KK
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Priority to US11/793,439 priority Critical patent/US7849909B2/en
Priority to CN2005800426075A priority patent/CN101080506B/en
Priority to EP05822572A priority patent/EP1831418A2/en
Publication of WO2006068325A2 publication Critical patent/WO2006068325A2/en
Anticipated expiration legal-status Critical
Publication of WO2006068325A3 publication Critical patent/WO2006068325A3/en
Priority to US12/941,790 priority patent/US7997325B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/10—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying using centrifugal force
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/068—Flake-like particles
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/854—Thermoelectric active materials comprising inorganic compositions comprising only metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • the present invention relates to a production method of a thermoelectric semiconductor alloy, and a high-performance thermoelectric power generating device using a thermoelectric semiconductor alloy produced by the production method.
  • This application claims the benefit pursuant to 35 U.S. C. ⁇ 119 (e) of U.S.
  • thermoelectric power generation utilizing thermoelectric conversion of converting waste heat directly into electricity is attracting attention.
  • This thermoelectric conversion is effected by such a mechanism that when temperature difference is generated by assigning one end of n-type and p-type semiconductors to a high temperature and another end to a low temperature, potential difference is caused and electricity is obtained.
  • the principle thereof has long been known.
  • thermoelectric power generation had been used only for limited uses such as application to space probe, because the semiconductor used for the power generation is very expensive, but in the late 1990s, a high-performance semiconductor was newly discovered and since then, aggressive development such as study on materials for practical use, production of modules and packaging test has been made.
  • thermoelectric semiconductor examples include filled skutterudite type, cobalt oxide, suicide and Heuslar type. It is recognized that with these materials, high electric conductivity, high Seebeck coefficient and low thermal conductivity can be achieved at the same time. For enhancing the performance of each material, a great deal of effort is being made. Along with elucidation of properties as a semiconductor, alloys having a Heuslar or half Heuslar structure have come to draw attention as an excellent thermoelectric semiconductor.
  • the Half Heuslar alloy is represented by the formula: A 3 . ⁇ B ⁇ C, wherein A and B are each a transition metal, C is a Group III or IV metal, and a space group is Fm3m.
  • the half Heuslar alloy is represented by the formula: ABC, wherein A and B are each a transition metal, C is a Group III or IV metal, and the space group is F43m.
  • thermoelectric semiconductor having a Heuslar structure for example, Nishino et al. have reported an Fe 2 VAl system of giving an output factor comparable to that of Bi-Te system in the vicinity of room temperature.
  • the Fe 2 VAl system is expected in view of the theoretical value to exhibit thermoelectric performance higher than the Bi-Te system and noteworthy as a practical material.
  • a heat treatment for a long time of about 10 days is performed. Considering mass production, the heat treatment for such a long time is not preferred because this causes increase in the cost.
  • Patent Document 1 JP-A-2001 -189495 (the term "JP-A” as used herein means an "unexamined published Japanese patent application")
  • Patent Document 2 WO03/019681 Al
  • Patent Document 3 JP-A-2004-253618
  • Patent Document 4 JP-A-2004-119647
  • Non-Patent Document 1 Yamanaka et al., Kinzoku (Metals), Vol. 74
  • Non-Patent Document 2 Matsuura et al., Journal of Japan Institute of
  • Non-Patent Document 3 S. Shuto et al., Proc. 22nd International
  • thermoelectric semiconductor In most of conventional methods for producing a thermoelectric semiconductor, the alloy raw material is melted by arc melting, and annealing of the molten alloy for a long time is performed multiple times or a shaped body is produced at high temperature under high pressure by using a special heat shaping apparatus. Thus, the productivity is not taken account of at all.
  • an object of the present invention is to provide a high-performance thermoelectric conversion module, a high-performance thermoelectric power generating device, and a thermoelectric semiconductor alloy for constituting such a module or device.
  • thermoelectric semiconductor alloy comprising nearly a single phase can be produced.
  • the present invention has been accomplished based on this finding and includes the following inventions.
  • a method for producing a Heuslar alloy comprising quench-solidifying a molten alloy at a cooling rate of 1 x 10 2 to 1x10 3o C/sec to produce a Heuslar alloy represented by the formula: A 3 . ⁇ B ⁇ C (wherein A and B each is at least one member selected from transition metals such as Fe, Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W, and C is at least one member selected from Group 13 or 14 elements such as Al, Ga, In, Si, Ge and Sn).
  • a method for producing a Heuslar alloy comprising quench-solidifying a molten alloy at a cooling rate of 1 x 10 2 to 1 x10 3 °C/sec to produce a Heuslar alloy represented by the formula: ABC (wherein A and B each is at least one member selected from transition metals such as Fe, Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W, and C is at least one member selected from Group 13 or 14 elements such as Al, Ga, In, Si, Ge and Sn).
  • a and B each is at least one member selected from transition metals such as Fe, Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W
  • C is at least one member selected from Group 13 or 14 elements such as Al, Ga, In, Si, Ge and Sn).
  • thermoelectric conversion element using the alloy described in any one of (3) to (5).
  • thermoelectric conversion module using the thermoelectric conversion element described in (6).
  • thermoelectric power generating device using the thermoelectric conversion module described in (7).
  • thermoelectric power generating device described in (8) A waste heat recovery system using the thermoelectric power generating device described in (8).
  • thermoelectric power generating device described in (8) A waste heat recovery system using the thermoelectric power generating device described in (8).
  • solar heat utilizing system using the thermoelectric power generating device described in (8) A solar heat utilizing system using the thermoelectric power generating device described in (8).
  • A is at least one member selected from transition metals such as Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W
  • B is at least one member selected from Group 13 or 14 elements such as Al, Ga, In, Si, Ge and Sn, 0 ⁇ x ⁇ 0.8, 0 ⁇ y ⁇ 0.3)
  • transition metals such as Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W
  • Cis at least one member selected from Groups 13 to 15 elements such as Al, Ga, In, Si, Ge and Sn, 0 ⁇ x ⁇ 0.8, 0 ⁇ y ⁇ 0.9, 0 ⁇
  • thermoelectric conversion module and a thermoelectric power generating device each exhibiting high performance over a wide temperature range from a low temperature near room temperature to a high temperature region of 700 0 C or more can be provided at a low cost.
  • a production method of a Heuslar alloy or half Heuslar alloy for the production of such a module or device can be provided.
  • a trace element can be uniformly doped in the entire alloy or can be made to replace a specific site in the crystal structure, whereby replacement of a specific site is facilitated, for example, the V or Al site OfFe 2 VAl may be partially replaced by Ti or Si, respectively, or Ti or Sn of TiNiSn may be partially replaced by Zr or Sb, respectively.
  • Fig .l is a schematic view showing a strip casting apparatus used for the production of alloy by quench-solidif ⁇ cation.
  • Fig. 2 is a back scattered electron imageback scattered electron image of quench-solidified TiNiSn alloy.
  • Fig. 3 is an X-ray diffraction pattern of quench-solidified TiNiSn alloy.
  • Fig. 4 is a back scattered electron image of normally cooled TiNiSn alloy.
  • Fig. 5 is a back scattered electron image of quench-solidified Fe 2 VAl alloy.
  • Fig. 6 is an X-ray diffraction pattern X-ray diffraction pattern of quench-solidified Fe2VAl alloy.
  • Fig. 7 is a plan view showing one example of the thermoelectric conversion module.
  • the Heuslar alloy according to the present invention is represented by the formula: A 3 . ⁇ B ⁇ C, wherein A and B each is a transition metal, C is a Group III or IV element, and the space group is Fm3m.
  • the half Heuslar alloy is represented by the formula: ABC, wherein A and B each is similarly a transition metal, C is a Group III or IV metal, and the space group is F43m.
  • thermoelectric performance can be further improved by substituting a part of V of a p-type element with Ti, or substituting a part of Al of a n-type element with Si.
  • thermoelectric performance As for a p-type element, in the formula Fe 2 Vi -x Ti x Al, it is preferable to set 0 ⁇ x ⁇ 0.8, and it is more preferable to set 0.1 ⁇ x ⁇ 0.35, thereby improving further thermoelectric performance.
  • thermoelectric performance As for an n-type element, in the formula Fe 2 VAl j.ySi y , it is preferable to set 0 ⁇ y ⁇ 0.3, and it is more preferable to set 0.1 ⁇ y ⁇ 0.2, thereby improving further thermoelectric performance.
  • thermoelectric performance can be further improved by substituting a part of Ti thereof with Zr, and substituting a part of Sn thereof with Sb.
  • a part of Ti thereof with Zr
  • Sn thereof substituting a part of Sn thereof with Sb.
  • setting to be 0 ⁇ y ⁇ 0.3 is preferable, setting to be 0 ⁇ y ⁇ 0.1 is further preferable, and it is possible to improve thermoelectric performance mostly by setting to be both 0.3 ⁇ x ⁇ 0.6 and 0 ⁇ y ⁇ 0.1.
  • the electrical properties and thermal properties of the Heuslar alloy according to the present invention can be adjusted by adding, as an additive, B, C, Mg, Cu, Zn or a rare earth metal such as Y, La, Ce, Nd, Pr, Dy, Tb, Ga and Yb.
  • the ratio of strongest peak of the Heuslar phase or half Heuslar phase is preferably 85% or more, more preferably 90% or more.
  • This peak ratio is defined by IHS/(IHS+IA+IB)xlOO (%) from a strongest peak (IHS) of the measured Heuslar phase or half Heuslar phase, a strongest peak intensity (IA) of an impurity phase A and a strongest peak intensity (IB) of an impurity phase B in the powder X-ray diffraction measurement.
  • thermoelectric semiconductors comprising the Heuslar alloy of the present invention
  • these semiconductors may be electrically connected through an electrode or may be directly connected through an antidiffusion layer.
  • the crystal grain diameter of the thermoelectric semiconductor produced from the Heuslar alloy is preferably smaller in view of reducing the thermal conductivity by the effect of lattice scattering, specifically, 100 ⁇ m or less, and from the standpoint of preventing abnormal grain growth due to excessive sintering, inhibiting dust explosion or enhancing powder-filling property, more preferably from 10 to 50 ⁇ m.
  • the grinding method is not limited and known methods all can be employed but, for example, a ball mill, a pot mill, an attritor, a pin mill or a jet mill can be used.
  • the jet mill is preferred despite its relatively high grinding cost, because a continuous operation can be performed, a necessary measure for the prevention of oxidation or dust explosion can be easily taken, and even a fine powder of about 20 ⁇ m can be processed in a relatively short time.
  • the quench-solidified alloy obtained in the present invention has good grindability and therefore, a fine powder of 20 ⁇ m or less can be obtained in a shorter time at a high yield.
  • the shaping method of the alloy is not particularly limited, but when a powder of several ⁇ m obtained by pulverizing the alloy is shaped under a pressure of 0.5 to 5.0 t/cm 2 and the obtained green compact is sintered in an inert atmosphere at 1,100 to l,400°C, a thermoelectric semiconductor element comprising fine crystal grains having a crystal grain diameter of 100 ⁇ m or less can be produced.
  • the powder produced from the alloy obtained as above already comprises only a Heuslar or half Heuslar phase and therefore, when shaped into a green compact by uniaxial shaping and sintered in an inert gas such as argon or in vacuum, a sintered body comprising a Heuslar structure or a half Heuslar phase can be easily produced.
  • a thermoelectric conversion module By processing such a sintered body into a predetermined shape and connecting p-type and n-type, a thermoelectric conversion module can be produced.
  • thermoelectric conversion module A and thermoelectric power generating system which are preferred embodiments of the present invention, are not particularly limited in their construction, but examples thereof include a thermoelectric conversion system B shown in Fig. 7. As shown in Fig. 7, a heat exchanger 13 such as heat sink is provided on both sides of a thermoelectric conversion module A to construct the system.
  • a plurality of fin materials is erected on one surface side of a substrate.
  • an insulating material insulating layer
  • the temperature becomes low at one part and becomes high at another part and therefore, this can be used as a cooling/heating source or a thermoelectric power generating system.
  • thermoelectric conversion module A The high-temperature contact side of the fabricated thermoelectric device is closely contacted with the heat exchanger 13 A on the waste heat side through an insulator, and the low-temperature contact side of the thermoelectric device is closely contacted with the heat exchanger 13B on the cooling water side through an insulator.
  • thermoelectric conversion system B a temperature difference is generated in each of the p-type semiconductor thermoelectric element 9A and n-type semiconductor thermoelectric element 9B connected to the high-temperature contact side and low-temperature contact side, as a result, electricity according to the temperature difference based on the Seebeck effect is generated by thermoelectric conversion.
  • thermoelectric conversion system B produced by the present invention not only waste heat on a large scale including those in various industrial furnaces and incinerators but also waste heat such as exhaust gas from various cogenerations, water heaters and automobiles, and natural energy (e.g., ground heat, solar heat) can be utilized with high efficiency.
  • the thermoelectric conversion module A of the present invention is suitable for waste heat recovery system, solar heat utilizing system and Peltier cooling/heating system, atomic power thermoelectric generating system, and biomass system.
  • Example 1 Sponge Ti (purity: 99% or more), sponge Zr (purity: 99% or more), electrolytic Ni (purity: 99% or more) and Sn metal (purity: 99.9% or more) were weighed to give a half Heuslar-type (Ti x Zr 1-x )NiSn composition after casting, and high-frequency melted at a temperature up to 1 ,700 0 C under 0.1 MPa in an Ar atmosphere. Thereafter, by using a strip casting apparatus shown in Fig.
  • Fig. 2 is a back scattered electron image showing the cross section of the alloy obtained as above. As seen from this, the alloy flake has a uniform structure in the entire region. Also, it is known from the X-ray diffraction pattern of Fig. 3 that the structure is a half Heuslar structure. The ratio of strongest peak of the TiNiSn half Heuslar phase was 100%. This alloy was ground to 200 ⁇ m or less by a disc mill and then pulverized at
  • the average particle size d50 of the obtained powder was 3.0 ⁇ m.
  • the yield of the powder was 80% based on the amount charged.
  • the obtained powder was shaped into a size of 15 mm x 15 mm x 30 mm under a shaping pressure of 1.0 t/cm 2 by a shaping machine in a glove box controlled to an oxygen concentration of 300 ppm or less, and then kept at l,200°C for 3 hours in vacuum, thereby obtaining a sintered body.
  • Sponge Ti (purity: 99% or more), sponge Zr (purity: 99% or more), electrolytic Ni (purity: 99% or more) and Sn metal (purity: 99.9% or more) were weighed to give a half Heuslar-type (Ti x Zri -x )NiSn composition after casting, and high-frequency melted at a temperature up to 1,700 0 C under 0.1 MPa in an Ar atmosphere. Thereafter, the alloy was solidified by using a cast iron mold in a width of 20 mm. The cooling rate at this time was estimated to be about lxlO 2 °C/sec.
  • Fig. 4 is a back scattered electron image showing the cross section of the alloy obtained as above. As seen from this, a plurality of phases non-uniformly is present in the alloy. The ratio of strongest peak of the half Heuslar phase was 80%.
  • Electrolytic iron purity: 99% or more
  • ferrovanadium Fe-V, JIS FVl, V purity: 87%)
  • Al metal were weighed to give a Heuslar-type Fe 2 (V x Tii -x )(Al y Sii -y ) (0 ⁇ x ⁇ l, 0 ⁇ y ⁇ l) composition after casting, and high-frequency melted at a temperature up to 1 ,700 0 C under 0.1 MPa in an Ar atmosphere.
  • a strip casting apparatus 20 shown in Fig.
  • the molten metal was poured from the crucible 1 through the tundish 2 on the water-cooled copper roll 3 rotating at a spherical velocity of 0.9 m/sec to produce an alloy flake 5, and the alloy flake was collected in the container 4.
  • the average thickness of the alloy flake 5 was 0.28 mm.
  • the cooling rate was estimated to be about 7xlO 2 °C/sec.
  • Fig. 5 is a back scattered electron image showing the cross section of the alloy obtained
  • Fig. 6 is a powder X-ray diffraction pattern of the alloy. As seen from these, a Heuslar alloy comprising a single phase can be obtained by the quench-solidification method. The ratio of strongest peak of the Fe 2 VAl was 100%.
  • This alloy was ground to 200 ⁇ m or less by a stamp mill and then pulverized at 0.5 MPa in a nitrogen steam by a jet mill, NPK-100NP manufactured by Nippon Pneumatic Mfg. Co., Ltd.
  • the average particle size d50 of the obtained powder was 13 ⁇ m.
  • the yield of the powder was 60% based on the amount charged.
  • the obtained powder was shaped into a size of 15 mm x 15 mm x 30 mm under a shaping pressure of 3.0 t/cm 2 by a shaping machine in a glove box controlled to an oxygen concentration of 300 ppm or less, and then kept at 1,380 0 C for 3 hours in vacuum, thereby obtaining a sintered body.
  • the Heuslar alloy of the present invention can be used as a thermoelectric semiconductor for thermoelectric conversion systems.

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Abstract

The present invention provides a method for producing a half Heuslar alloy including quench-solidifying a molten alloy at a cooling rate of 1 x 102 to 1 x 103°C/sec to produce a Heuslar alloy represented by the formula: ABC (wherein A and B each is at least one member selected from transition metals such as Fe, Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W, and C is at least one member selected from Group 13 or 14 element such as Al, Ga, In, Si, Ge and Sn), and a high-performance thermoelectric power generating device using the thermoelectric semiconductor alloy.

Description

DESCRIPTION
PRODUCTION METHOD OF THERMOELECTRIC SEMICONDUCTOR ALLOY, THERMOELECTRIC CONVERSION MODULE AND THERMOELECTRIC
POWER GENERATING DEVICE
TECHNICAL FIELD
The present invention relates to a production method of a thermoelectric semiconductor alloy, and a high-performance thermoelectric power generating device using a thermoelectric semiconductor alloy produced by the production method. This application claims the benefit pursuant to 35 U.S. C. § 119 (e) of U.S.
Provisional Application No. 60/640,242 filed on January 3, 2005, and priority is claimed on Japanese Patent Application No. 2004-374218, filed December 24, 2004, the contents of which are incorporated herein by reference.
BACKGROUND ART
To cope with the regulation for emission of carbonic acid gas and energy conservation, thermoelectric power generation utilizing thermoelectric conversion of converting waste heat directly into electricity is attracting attention. This thermoelectric conversion is effected by such a mechanism that when temperature difference is generated by assigning one end of n-type and p-type semiconductors to a high temperature and another end to a low temperature, potential difference is caused and electricity is obtained. The principle thereof has long been known.
Conventional thermoelectric power generation had been used only for limited uses such as application to space probe, because the semiconductor used for the power generation is very expensive, but in the late 1990s, a high-performance semiconductor was newly discovered and since then, aggressive development such as study on materials for practical use, production of modules and packaging test has been made.
Examples of the substance taken notice of as a next-generation thermoelectric semiconductor include filled skutterudite type, cobalt oxide, suicide and Heuslar type. It is recognized that with these materials, high electric conductivity, high Seebeck coefficient and low thermal conductivity can be achieved at the same time. For enhancing the performance of each material, a great deal of effort is being made. Along with elucidation of properties as a semiconductor, alloys having a Heuslar or half Heuslar structure have come to draw attention as an excellent thermoelectric semiconductor.
The Half Heuslar alloy is represented by the formula: A3.χBχC, wherein A and B are each a transition metal, C is a Group III or IV metal, and a space group is Fm3m. The half Heuslar alloy is represented by the formula: ABC, wherein A and B are each a transition metal, C is a Group III or IV metal, and the space group is F43m. In the case of using a Heuslar alloy as a thermoelectric semiconductor, the design is difficult due to numerous combinations of elements, and one proposed guideline therefor is a method of using an electronic number as a rough standard.
With respect to the thermoelectric semiconductor having a Heuslar structure, for example, Nishino et al. have reported an Fe2VAl system of giving an output factor comparable to that of Bi-Te system in the vicinity of room temperature. The Fe2VAl system is expected in view of the theoretical value to exhibit thermoelectric performance higher than the Bi-Te system and noteworthy as a practical material. At present, for the production of a half Heuslar alloy as a thermoelectric conductor for use in middle and high temperature regions, a heat treatment for a long time of about 10 days is performed. Considering mass production, the heat treatment for such a long time is not preferred because this causes increase in the cost.
Also, it is known that in the TiNiSn system having a half Heuslar structure, when Ti is replaced by Zr or Hr, both high output factor and low thermal conductivity can be achieved in a high temperature region of 3000C or more and the dimensionless figure of merit ZT as a rough standard for the performance of a practical material exceeds 1.0 at 693K. The performance of this system is expected to be enhanced in future.
When a Heuslar alloy is produced by casting, high melting point metals such as Ti, V and Zr are contained therein in many cases and a skilled technique is required for the quench-solidification of high-temperature molten metal. Also, a casting technique in vacuum induction furnace and inert atmosphere is necessary because of handling of a readily oxidizable metal as represented by Ti.
[Patent Document 1] JP-A-2001 -189495 (the term "JP-A" as used herein means an "unexamined published Japanese patent application") [Patent Document 2] WO03/019681 Al
[Patent Document 3] JP-A-2004-253618 [Patent Document 4] JP-A-2004-119647
[Non-Patent Document 1] Yamanaka et al., Kinzoku (Metals), Vol. 74
(8), page 54 (2004) [Non-Patent Document 2] Matsuura et al., Journal of Japan Institute of
Metals, Vol. 66 (7), page 767 (2002)
[Non-Patent Document 3] S. Shuto et al., Proc. 22nd International
Conference on Thermoelectrics, 312 (2003)
In most of conventional methods for producing a thermoelectric semiconductor, the alloy raw material is melted by arc melting, and annealing of the molten alloy for a long time is performed multiple times or a shaped body is produced at high temperature under high pressure by using a special heat shaping apparatus. Thus, the productivity is not taken account of at all.
In the light of these problems, an object of the present invention is to provide a high-performance thermoelectric conversion module, a high-performance thermoelectric power generating device, and a thermoelectric semiconductor alloy for constituting such a module or device.
The present inventors have found that when a raw material alloy is melted and the molten alloy is quench-solidified at an appropriate cooling rate, a thermoelectric semiconductor alloy comprising nearly a single phase can be produced.
DISCLOSURE OF INVENTION
The present invention has been accomplished based on this finding and includes the following inventions.
(1) A method for producing a Heuslar alloy, comprising quench-solidifying a molten alloy at a cooling rate of 1 x 102 to 1x103oC/sec to produce a Heuslar alloy represented by the formula: A3.χBχC (wherein A and B each is at least one member selected from transition metals such as Fe, Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W, and C is at least one member selected from Group 13 or 14 elements such as Al, Ga, In, Si, Ge and Sn). (2) A method for producing a Heuslar alloy, comprising quench-solidifying a molten alloy at a cooling rate of 1 x 102 to 1 x103°C/sec to produce a Heuslar alloy represented by the formula: ABC (wherein A and B each is at least one member selected from transition metals such as Fe, Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W, and C is at least one member selected from Group 13 or 14 elements such as Al, Ga, In, Si, Ge and Sn).
(3) An alloy produced by the production method described in (1) or (2).
(4) The alloy as described in (3), wherein the ratio of strongest peak of the Heuslar phase or half Heuslar phase is 85% or more. (5) The alloy as described in (3) or (4), wherein the average particle diameter is from 1 to 100 μm.
(6) A thermoelectric conversion element using the alloy described in any one of (3) to (5).
(7) A thermoelectric conversion module using the thermoelectric conversion element described in (6).
(8) A thermoelectric power generating device using the thermoelectric conversion module described in (7).
(9) A waste heat recovery system using the thermoelectric power generating device described in (8). (10) A solar heat utilizing system using the thermoelectric power generating device described in (8).
(11) A Heuslar alloy represented by the formula: Fe2V1-X Ax Al 1-yBy (wherein A is at least one member selected from transition metals such as Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W, B is at least one member selected from Group 13 or 14 elements such as Al, Ga, In, Si, Ge and Sn, 0<x<0.8, 0< y <0.3).
(12) A half Heuslar alloy represented by the formula: Tii-xAxNii-yBy Sni-zCz (wherein each of A and B is at least one member selected from transition metals such as Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W, Cis at least one member selected from Groups 13 to 15 elements such as Al, Ga, In, Si, Ge and Sn, 0<x<0.8, 0< y <0.9, 0< z <0.3). (13) A method for producing the Heuslar alloy represented by the formula: Fe2Vi-xAxAli.yBy (wherein A is at least one member selected from transition metals such as Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W, B is at least one member selected from Group 13 or 14 elements such as Al, Ga, In, Si, Ge and Sn, 0<x<0.8, 0< y <0.3), comprising quench-solidifying a molten alloy at a cooling rate of 1 x 102 to
Figure imgf000007_0001
(14) A method for producing the half Heuslar alloy represented by the formula: Tii.xAxNii-yBy Sn1-2C2 (wherein each of A and B is at least one member selected from transition metals such as Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W, Cis at least one member selected from Groups 13 to 15 elements such as Al, Ga, In, Si, Ge and Sn, 0<x<0.8, 0< y <0.9, 0< z <0.3), comprising quench-solidifying a molten alloy at a cooling rate of IxIO2 to lχlO3°C/sec.
According to the present invention, a thermoelectric conversion module and a thermoelectric power generating device each exhibiting high performance over a wide temperature range from a low temperature near room temperature to a high temperature region of 7000C or more can be provided at a low cost. Also, a production method of a Heuslar alloy or half Heuslar alloy for the production of such a module or device can be provided.
When the method of the present invention is employed, a trace element can be uniformly doped in the entire alloy or can be made to replace a specific site in the crystal structure, whereby replacement of a specific site is facilitated, for example, the V or Al site OfFe2VAl may be partially replaced by Ti or Si, respectively, or Ti or Sn of TiNiSn may be partially replaced by Zr or Sb, respectively. BRIEF DESCRIPTION OF THE DRAWINGS
Fig .l isa schematic view showing a strip casting apparatus used for the production of alloy by quench-solidifϊcation.
Fig. 2 is a back scattered electron imageback scattered electron image of quench-solidified TiNiSn alloy.
Fig. 3 is an X-ray diffraction pattern of quench-solidified TiNiSn alloy.
Fig. 4 is a back scattered electron image of normally cooled TiNiSn alloy.
Fig. 5 is a back scattered electron image of quench-solidified Fe2VAl alloy.
Fig. 6 is an X-ray diffraction pattern X-ray diffraction pattern of quench-solidified Fe2VAl alloy.
Fig. 7 is a plan view showing one example of the thermoelectric conversion module.
BEST MODE FOR CARRYING OUT THE INVENTION
The Heuslar alloy according to the present invention is represented by the formula: A3.χBχC, wherein A and B each is a transition metal, C is a Group III or IV element, and the space group is Fm3m. The half Heuslar alloy is represented by the formula: ABC, wherein A and B each is similarly a transition metal, C is a Group III or IV metal, and the space group is F43m.
As an example of Heuslar alloy of the present invention, Fe2VAl type can be exemplified, and thermoelectric performance can be further improved by substituting a part of V of a p-type element with Ti, or substituting a part of Al of a n-type element with Si.
For example, as for a p-type element, in the formula Fe2Vi-xTixAl, it is preferable to set 0<x<0.8, and it is more preferable to set 0.1<x<0.35, thereby improving further thermoelectric performance.
For example, as for an n-type element, in the formula Fe2VAl j.ySiy, it is preferable to set 0<y<0.3, and it is more preferable to set 0.1<y<0.2, thereby improving further thermoelectric performance.
Moreover, as an example of half Heuslar alloy of the present invention, TiNSn type can be exemplified, and thermoelectric performance can be further improved by substituting a part of Ti thereof with Zr, and substituting a part of Sn thereof with Sb. For example, in the formula Tii-xZrxNiSni-ySby, it is preferable to set 0<x<0.8, and it is more preferable to set 0.3<x<0.6. Moreover, setting to be 0<y<0.3 is preferable, setting to be 0<y<0.1 is further preferable, and it is possible to improve thermoelectric performance mostly by setting to be both 0.3<x<0.6 and 0<y<0.1.
The electrical properties and thermal properties of the Heuslar alloy according to the present invention can be adjusted by adding, as an additive, B, C, Mg, Cu, Zn or a rare earth metal such as Y, La, Ce, Nd, Pr, Dy, Tb, Ga and Yb. In a preferred embodiment of the present invention, the ratio of strongest peak of the Heuslar phase or half Heuslar phase is preferably 85% or more, more preferably 90% or more. This peak ratio is defined by IHS/(IHS+IA+IB)xlOO (%) from a strongest peak (IHS) of the measured Heuslar phase or half Heuslar phase, a strongest peak intensity (IA) of an impurity phase A and a strongest peak intensity (IB) of an impurity phase B in the powder X-ray diffraction measurement.
When combining p-type and n-type thermoelectric semiconductors comprising the Heuslar alloy of the present invention, these semiconductors may be electrically connected through an electrode or may be directly connected through an antidiffusion layer. The crystal grain diameter of the thermoelectric semiconductor produced from the Heuslar alloy is preferably smaller in view of reducing the thermal conductivity by the effect of lattice scattering, specifically, 100 μm or less, and from the standpoint of preventing abnormal grain growth due to excessive sintering, inhibiting dust explosion or enhancing powder-filling property, more preferably from 10 to 50 μm.
In grinding the Heuslar alloy, the grinding method is not limited and known methods all can be employed but, for example, a ball mill, a pot mill, an attritor, a pin mill or a jet mill can be used.
The jet mill is preferred despite its relatively high grinding cost, because a continuous operation can be performed, a necessary measure for the prevention of oxidation or dust explosion can be easily taken, and even a fine powder of about 20 μm can be processed in a relatively short time.
The quench-solidified alloy obtained in the present invention has good grindability and therefore, a fine powder of 20 μm or less can be obtained in a shorter time at a high yield.
The shaping method of the alloy is not particularly limited, but when a powder of several μm obtained by pulverizing the alloy is shaped under a pressure of 0.5 to 5.0 t/cm2 and the obtained green compact is sintered in an inert atmosphere at 1,100 to l,400°C, a thermoelectric semiconductor element comprising fine crystal grains having a crystal grain diameter of 100 μm or less can be produced.
The powder produced from the alloy obtained as above already comprises only a Heuslar or half Heuslar phase and therefore, when shaped into a green compact by uniaxial shaping and sintered in an inert gas such as argon or in vacuum, a sintered body comprising a Heuslar structure or a half Heuslar phase can be easily produced. By processing such a sintered body into a predetermined shape and connecting p-type and n-type, a thermoelectric conversion module can be produced.
The thermoelectric conversion module A and thermoelectric power generating system, which are preferred embodiments of the present invention, are not particularly limited in their construction, but examples thereof include a thermoelectric conversion system B shown in Fig. 7. As shown in Fig. 7, a heat exchanger 13 such as heat sink is provided on both sides of a thermoelectric conversion module A to construct the system.
In the heat exchangers 13A and 13B, a plurality of fin materials is erected on one surface side of a substrate. In the case where the substrate is a metal plate, an insulating material (insulating layer) is preferably disposed on the outer side surface of each electrode 10 or on the entire surface of the substrate so as to prevent a plurality of electrodes 10 from shorting. When a DC current is passed to the thermoelectric conversion module group B in this mode, the temperature becomes low at one part and becomes high at another part and therefore, this can be used as a cooling/heating source or a thermoelectric power generating system.
The p-type semiconductor thermoelectric element 9A and n-type semiconductor thermoelectric element 9B constituting the thermoelectric device are electrically connected, for example, in series or in parallel to fabricate a thermoelectric conversion module A. The high-temperature contact side of the fabricated thermoelectric device is closely contacted with the heat exchanger 13 A on the waste heat side through an insulator, and the low-temperature contact side of the thermoelectric device is closely contacted with the heat exchanger 13B on the cooling water side through an insulator. In the thus-fabricated thermoelectric conversion system B, a temperature difference is generated in each of the p-type semiconductor thermoelectric element 9A and n-type semiconductor thermoelectric element 9B connected to the high-temperature contact side and low-temperature contact side, as a result, electricity according to the temperature difference based on the Seebeck effect is generated by thermoelectric conversion.
When the thermoelectric conversion system B produced by the present invention is employed, not only waste heat on a large scale including those in various industrial furnaces and incinerators but also waste heat such as exhaust gas from various cogenerations, water heaters and automobiles, and natural energy (e.g., ground heat, solar heat) can be utilized with high efficiency. Accordingly, the thermoelectric conversion module A of the present invention is suitable for waste heat recovery system, solar heat utilizing system and Peltier cooling/heating system, atomic power thermoelectric generating system, and biomass system.
The present invention is described in greater detail below by referring to Examples, but the present invention is not limited to these Examples. (Example 1) Sponge Ti (purity: 99% or more), sponge Zr (purity: 99% or more), electrolytic Ni (purity: 99% or more) and Sn metal (purity: 99.9% or more) were weighed to give a half Heuslar-type (TixZr1-x)NiSn composition after casting, and high-frequency melted at a temperature up to 1 ,7000C under 0.1 MPa in an Ar atmosphere. Thereafter, by using a strip casting apparatus shown in Fig. 1, the molten metal was poured from the crucible 1 through the tundish 2 on the water-cooled copper roll 3 rotating at a spherical velocity of 0.9 m/sec to produce an alloy flake 5, and the alloy flake was collected in the container 4. The average thickness of the alloy flake 5 was 0.25 mm. In this casting, the cooling rate was estimated to be about 7χlO2°C/sec. Fig. 2 is a back scattered electron image showing the cross section of the alloy obtained as above. As seen from this, the alloy flake has a uniform structure in the entire region. Also, it is known from the X-ray diffraction pattern of Fig. 3 that the structure is a half Heuslar structure. The ratio of strongest peak of the TiNiSn half Heuslar phase was 100%. This alloy was ground to 200 μm or less by a disc mill and then pulverized at
0.5 MPa in a nitrogen steam by a jet mill, NPK-100NP manufactured by Nippon Pneumatic Mfg. Co., Ltd. The average particle size d50 of the obtained powder was 3.0 μm. The yield of the powder was 80% based on the amount charged.
The obtained powder was shaped into a size of 15 mm x 15 mm x 30 mm under a shaping pressure of 1.0 t/cm2 by a shaping machine in a glove box controlled to an oxygen concentration of 300 ppm or less, and then kept at l,200°C for 3 hours in vacuum, thereby obtaining a sintered body.
A block of 4 mm x 4 mm x 15 mm was cut out from the sintered body and measured for the Seebeck coefficient α, electric conductivity p and power factor Pf=α2/p at 200 to 5000C by using a thermoelectric property evaluating apparatus,
ZEM-2 manufactured by ULVAC-RIKO, Inc. These measurement results are shown in Table 1.
(Comparative Example 1)
Sponge Ti (purity: 99% or more), sponge Zr (purity: 99% or more), electrolytic Ni (purity: 99% or more) and Sn metal (purity: 99.9% or more) were weighed to give a half Heuslar-type (TixZri-x)NiSn composition after casting, and high-frequency melted at a temperature up to 1,7000C under 0.1 MPa in an Ar atmosphere. Thereafter, the alloy was solidified by using a cast iron mold in a width of 20 mm. The cooling rate at this time was estimated to be about lxlO2°C/sec. Fig. 4 is a back scattered electron image showing the cross section of the alloy obtained as above. As seen from this, a plurality of phases non-uniformly is present in the alloy. The ratio of strongest peak of the half Heuslar phase was 80%.
A block of 4 mm x 4 mm x 15 mm was cut out from the alloy flake after casting and measured for the Seebeck coefficient α, electric conductivity p and power factor Pf=α2/p at 200 to 5000C by using a thermoelectric property evaluating apparatus, ZEM-2 manufactured by ULVAC-RIKO, Inc. These measurement results of Example 1 and Comparative Example 1 are shown in Table 1. As seen from these results, the performance was apparently decreased as compared with Example 1.
[Table 1]
Figure imgf000015_0001
(Example 2)
Electrolytic iron (purity: 99% or more), ferrovanadium (Fe-V, JIS FVl, V purity: 87%) and Al metal were weighed to give a Heuslar-type Fe2(VxTii-x)(AlySii-y) (0<x<l, 0<y<l) composition after casting, and high-frequency melted at a temperature up to 1 ,7000C under 0.1 MPa in an Ar atmosphere. Thereafter, by using a strip casting apparatus 20 shown in Fig. 1 , the molten metal was poured from the crucible 1 through the tundish 2 on the water-cooled copper roll 3 rotating at a spherical velocity of 0.9 m/sec to produce an alloy flake 5, and the alloy flake was collected in the container 4. The average thickness of the alloy flake 5 was 0.28 mm. In this casting, the cooling rate was estimated to be about 7xlO2°C/sec.Fig. 5 is a back scattered electron image showing the cross section of the alloy obtained, and Fig. 6 is a powder X-ray diffraction pattern of the alloy. As seen from these, a Heuslar alloy comprising a single phase can be obtained by the quench-solidification method. The ratio of strongest peak of the Fe2VAl was 100%.
This alloy was ground to 200 μm or less by a stamp mill and then pulverized at 0.5 MPa in a nitrogen steam by a jet mill, NPK-100NP manufactured by Nippon Pneumatic Mfg. Co., Ltd. The average particle size d50 of the obtained powder was 13 μm. The yield of the powder was 60% based on the amount charged. The obtained powder was shaped into a size of 15 mm x 15 mm x 30 mm under a shaping pressure of 3.0 t/cm2 by a shaping machine in a glove box controlled to an oxygen concentration of 300 ppm or less, and then kept at 1,3800C for 3 hours in vacuum, thereby obtaining a sintered body. A block of 4 mm x 4 mm x 15 mm was cut out from the sintered body and measured for the Seebeck coefficient α, specific resistance σand power factor Pf=α2/σat 200 to 5000C by using a thermoelectric property evaluating apparatus, ZEM-2 manufactured by ULVAC-RIKO, Inc.
These measurement results of Example 2 and Comparative Example 2 are shown in Tables 2 and 3. [Table 2]
Figure imgf000017_0001
[Table 3] Thermoelectric Properties of Heuslar Element Fe-V-Al
Figure imgf000018_0001
It should be noted that the data of n-type thermoelectric semiconductor are shown in Table 2, and the data of p-type thermoelectric semiconductor are shown in Table 3.
INDUSTRIAL APPLICABILITY
The Heuslar alloy of the present invention can be used as a thermoelectric semiconductor for thermoelectric conversion systems.

Claims

1. A method for producing a Heuslar alloy, comprising quench-solidifying a molten alloy at a cooling rate of I x 102 to lxl03oC/sec to produce a Heuslar alloy represented by the formula: A3.χBχC (wherein A and B each is at least one member selected from transition metals such as Fe, Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W, and C is at least one member selected from Group 13 or 14 elements such as Al, Ga, In, Si, Ge and Sn).
2. A method for producing a half Heuslar alloy, comprising quench-solidifying a molten alloy at a cooling rate of IxIO2 to lxlO3°C/sec to produce a Heuslar alloy represented by the formula: ABC (wherein A and B each is at least one member selected from transition metals such as Fe, Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W, and C is at least one member selected from Group 13 or 14 elements such as Al, Ga, In, Si, Ge and Sn).
3. An alloy produced by the production method as set forth in claim 1 or 2.
4. The alloy as set forth in claim 3, wherein the ratio of strongest peak of the Heuslar phase or half Heuslar phase is 85% or more.
5. The alloy as set forth in claim 3 or 4, wherein the average particle diameter is from 1 to 100 μm.
6. A thermoelectric conversion element using the alloy as set forth in any one of claims 3 to 5.
7. A thermoelectric conversion module using the thermoelectric conversion element as set forth in claim 6.
8. A thermoelectric power generating device using the thermoelectric conversion module as set forth in claim 7.
9. A waste heat recovery system using the thermoelectric power generating device as set forth in claim 8.
10. A solar heat utilizing system using the thermoelectric power generating device as set forth in claim 8.
11. A Heuslar alloy represented by the formula: Fe2Vi-xAxAl1-yBy (wherein A is at least one member selected from transition metals such as Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W, B is at least one member selected from Group 13 or 14 elements such as Al, Ga, In, Si, Ge and Sn, 0<x<0.8, 0< y <0.3).
12. A half Heuslar alloy represented by the formula: Ti1-xAxNii-yBy Sni.zCz
(wherein each of A and B is at least one member selected from transition metals such as Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W, Cis at least one member selected from Groups 13 to 15 elements such as Al, Ga, In, Si, Ge and Sn, 0<x<0.8, 0< y <0.9, 0< z <0.3).
13. A method for producing the Heuslar alloy represented by the formula: Fe2Vi.xAxAli-yBy (wherein A is at least one member selected from transition metals such as Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W, B is at least one member selected from Group 13 or 14 elements such as Al, Ga, In, Si, Ge and Sn, O≤x≤O.8, 0< y <0.3), comprising quench-solidifying a molten alloy at a cooling rate of 1 x 102 to lxl03oC/sec.
14. A method for producing the half Heuslar alloy represented by the formula:
Figure imgf000022_0001
Sni-zCz (wherein each of A and B is at least one member selected from transition metals such as Co, Ni, Ti, V, Cr, Zr, Hf, Nb, Mo, Ta and W, Cis at least one member selected from Groups 13 to 15 elements such as Al, Ga, In, Si, Ge and Sn, 0<x<0.8, 0< y <0.9, 0< z <0.3), comprising quench-solidifying a molten alloy at a cooling rate of IxIO2 to lχlO3°C/sec.
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