JP4645575B2 - Thermoelectric material manufacturing method, thermoelectric material, and thermoelectric conversion module - Google Patents

Description

  The present invention relates to a thermoelectric material.

Thermoelectric conversion modules using thermoelectric materials are expected to be used in various applications, and in order to improve their performance index Z = α ² / (ρ × κ) and power factor Pf = α ² / ρ. A technique for preventing the occurrence of element cracking in the manufacturing process of thermoelectric materials and thermoelectric materials has been proposed (for example, Patent Document 1). Here, α is the Seebeck coefficient, ρ is the electrical resistivity, and κ is the thermal conductivity.
JP 2004-143560 A

In the prior art, it has not been possible to obtain a thermoelectric material that simultaneously achieves a high figure of merit and high mechanical strength or mechanical properties.
That is, in general, when the crystal grains in the material are refined by pulverization or the like, the mechanical strength increases (Hall-Petch law), but the electrical resistivity ρ increases when the orientation of the crystal axis becomes disordered due to the refinement of the crystal grains. It has been known. Therefore, in the conventional technique, the powder material is extruded to improve the crystal orientation and make it finer. Moreover, since the figure of merit becomes small at an extrusion speed lower than 12 mm / min, and the thermoelectric material is easily cracked at an extrusion speed higher than 300 mm / min, processing is performed at an extrusion speed of 12 mm / min to 300 mm / min. Furthermore, in order to prevent the coarsening of crystal grains, the extrusion temperature is set to 525 ° C. or lower.

However, since the above-mentioned grain refinement and disorder of the crystal axis orientation occur at the same time, even when the orientation control by extrusion processing and the control of the extrusion conditions are combined, a higher performance index and higher mechanical strength or machine It has been difficult to provide a thermoelectric material that simultaneously realizes the characteristics. In particular, the applications of thermoelectric conversion modules using thermoelectric materials are extremely diverse, and various sizes from 1 mm square to 40 mm square can be assumed as the size of thermoelectric conversion modules. Accordingly, assuming that a thermoelectric element used for a small thermoelectric conversion module is cut out from the thermoelectric material, improvement in mechanical strength or mechanical characteristics is extremely important as a characteristic of the thermoelectric material. Furthermore, when the characteristics of the thermoelectric material are improved by detailed control of the extrusion conditions, it is extremely important to reliably take out the material having the desired characteristics when the material having the desired characteristics is obtained.
The present invention has been made in view of the above problems, and an object of the present invention is to reliably produce a thermoelectric material that simultaneously realizes a high figure of merit and high mechanical strength or mechanical characteristics.

  In order to solve at least one of the above objects, in a BiTe-based thermoelectric material, an alloy is used as a starting material, and when an extrusion process is performed using a mold in which a pressure shaft and an extrusion shaft are not on one axis, a processing temperature of the alloy is reduced. The thermoelectric material is manufactured at a temperature range of 100 ° C. lower than the melting point to 20 ° C. lower than the melting point of the alloy and an extrusion rate of 1 mm / min to 12 mm / min. In other words, in BiTe-based thermoelectric materials, the orientation of crystal axes that have a large effect on the figure of merit and the refinement of crystal grains that have a large effect on mechanical strength or mechanical properties are in a trade-off relationship. It is difficult to set a preferable value. Therefore, there is a limit to the improvement in performance in the technical idea of simultaneously realizing a high performance index and high mechanical strength or mechanical characteristics in consideration of both the orientation of crystal axes and the refinement of crystal grains.

  Therefore, in the present invention, as described above, the processing temperature is set in a temperature range from 100 ° C. lower than the melting point of the alloy to 20 ° C. lower than the melting point of the alloy. This temperature range is a temperature that cannot be adopted to prevent the crystal grains of the alloy from becoming coarse, and is a considerably high processing temperature in the extrusion process. That is, in the present invention, by adopting this temperature range, it is possible to allow the thermoelectric material to be constituted by large crystal grains as compared with the conventional technique, and to make the direction of the crystal axis easily aligned. Yes.

  Therefore, the crystal axes can be aligned by performing an extrusion process in which the pressure axis and the extrusion axis are not on one axis with a mold having a different pressure axis and extrusion axis. That is, it can be controlled so that most of the specific crystal axis is oriented within a certain angle with respect to the specific direction. Moreover, it can control so that a crystal grain turns into a flat crystal grain long to one side, and the longitudinal direction faces a specific direction.

  Furthermore, in the present invention, the extrusion speed is set to 1 mm / min to 12 mm / min. This extrusion speed is a speed that is set so that crystals do not grow uniformly in the extrusion process of the BiTe-based thermoelectric material using a mold having a different pressure axis and extrusion axis. That is, according to this processing speed, crystal grains in which distortion remains can be generated. Therefore, a non-uniform fine structure (subcrystal) appears in one crystal grain, and from the viewpoint of mechanical strength or mechanical properties, this subcrystal functions in the same way as fine crystal grains, and has high mechanical strength or mechanical properties. The thermoelectric material can be provided. In the present invention, since the characteristics of the thermoelectric material are improved by aligning the crystal orientation, the evaluation may be performed using a figure of merit or a power factor.

  In addition, the processing temperature suppresses excessive coarsening of crystal grains, but allows a certain degree of coarsening, aligns the crystal axes by extrusion with a mold in which the pressure axis and the extrusion axis are not on one axis, and crystal grains Any temperature may be used as long as the subcrystal can be introduced into the inside. Therefore, for example, in an alloy having a melting point of 575 ° C., an arbitrary temperature (475, 520, 555 ° C., etc.) can be set within a range of 475 ° C. to 555 ° C. In an alloy having a melting point of 595 ° C., an arbitrary temperature (495, 535, 575 ° C., etc.) can be set within the range of 495 ° C. to 575 ° C.

  Furthermore, the extrusion rate may be a rate at which processing can be performed so that subcrystals are introduced into the crystal grains in a temperature range of 100 ° C. lower than the melting point of the alloy to 20 ° C. lower than the melting point of the alloy. When the extrusion speed is low, the processing itself can be performed, but the sub-crystal is hardly introduced into the crystal grains, and the crystal grains are likely to grow. Therefore, in the present invention, the extrusion speed is set to 1 mm / min or more. Further, it has been found that when the extrusion speed is high, it becomes impossible to process due to a broken mold or the like in the above temperature range, and the processed material is easily cracked. Therefore, in the present invention, the extrusion speed is set to 12 mm / min or less. Therefore, the extrusion speed can be arbitrarily set within this range, and can be set to 1, 1.2, 1.5, 2, 3, 5, 7, 10, 12 mm / min, for example. A range in which any two values within the range of the extrusion speed are set to the minimum value and the maximum value may be set.

Here, the thermoelectric material may be a BiTe-based thermoelectric material. That is, when at least one element selected from the group consisting of Bi and Sb is expressed as (Bi, Sb), and at least one element selected from the group consisting of Te and Se is expressed as (Te, Se), It is known that a material having a composition of (Bi, Sb) ₂ (Te, Se) ₃ becomes a thermoelectric material having a rhombohedral crystal structure (space group R3-m (-is usually expressed above 3)). It has been. In this crystal, the electrical resistivity in the direction parallel to the c-plane is smaller than the electrical resistivity in the direction parallel to the a-plane. Therefore, the figure of merit of the thermoelectric material can be improved by controlling the orientation of the c-plane. Note that in this specification, crystal axes such as c-axis and a-axis, and crystal planes such as c-plane are crystal axes and crystal planes when the crystal of space group R3-m is expressed in hexagonal crystal form. The thermoelectric material may be a BiTe-based thermoelectric material. In this sense, the composition is different from (Bi, Sb) ₂ (Te, Se) ₃ as long as the space group R3-m has a crystal structure. May be.

  In order to obtain a high-performance thermoelectric material, it is preferable that the starting alloy is a powder containing fine crystal grains and the crystal grain size is 1 μm or more and 50 μm or less. Such powder may be obtained by roll-type liquid quenching or gas atomization of the molten alloy, or may be powdered by scattering the molten alloy using the rotation of a rotating disk, or obtained by melting after weighing. The obtained alloy may be obtained by pulverization.

  In the sense that a thin film having a crystal axis oriented in a certain direction can be easily prepared, a thin film obtained by roll-type liquid quenching (alloy containing crystals with a fine grain size, and a crystal structure is a powder Can be equated). That is, in this thin film, since the c-plane tends to be parallel to the film thickness direction, when this thin film is set while being laminated in the mold, the extrusion process is performed at a low processing pressure. Can do.

  In this specification, when the crystal axes are defined for the atomic structure of the thermoelectric material, the same crystal grains are used if the inclinations of specific crystal axes (for example, a-axis facing different directions) are within 15 °. In addition, the structure in which the inclination exceeds 15 ° is assumed to be different crystal grains. The inclination of the crystal axis can be obtained, for example, by measuring an arbitrary cross section of a thermoelectric material with an EBSD (Electron Back Scatter Diffraction) apparatus manufactured by TSL, and analyzing the measurement result with analysis software. . Further, in this specification, the size of a crystal grain (crystal grain size) is defined by the radius of a circle having the same area as the crystal grain area in a certain cross section. The area of the crystal grains can also be measured with the above-described EBSD apparatus.

  Further, in the present specification, the orientation of crystal axes fluctuates across a boundary in the same crystal grain, and the angle difference between the c-planes on both sides of the boundary is within 5 °. When the angle difference is 5 ° or more, the crystals on both sides are called sub-crystals. That is, since such sub-crystals substantially share the c-plane, the electrical resistivity in the a-axis direction substantially parallel to the c-plane is small, and the figure of merit can be easily increased. On the other hand, since the a-axis is inclined in adjacent subcrystals, the mechanical strength or the mechanical characteristics are improved against the above-mentioned Hall Petch rule.

  Further, in the mold, the direction of the alloy is changed when the alloy is extruded, so that a shearing force is applied to the material in the extrusion process. Therefore, the direction of the extrusion shaft only needs to be different from that of the pressure shaft, but preferably, the extrusion shaft is set to intersect within a range of 30 ° to 150 °.

  In addition, the above extrusion process should just be performed at least once, and an extrusion process can be repeated as needed until a thermoelectric material becomes a desired characteristic. Furthermore, in the present invention, since the processing is performed in a relatively high temperature range, if the thermoelectric material is left in the mold in a state where extrusion is not performed by applying a shearing force, the crystal grains may be coarsened. . In addition, the starting alloy must be set in the mold in a temperature range in which structural changes such as crystal grain coarsening do not occur.

  Therefore, after the extrusion process, it is preferable to cool the mold in a state where the thermoelectric material exists inside the mold. That is, the thermoelectric material is present in the mold in the continuous manufacturing process of the thermoelectric material in order not to cause a change in the orientation structure or texture in the alloy of the starting material before the extrusion process by the mold. In this state, the mold is cooled to a temperature range that does not cause a change in the oriented structure or texture of the thermoelectric material or the starting material after the extrusion process.

  That is, in a continuous thermoelectric material manufacturing process, after the mold is cooled, the starting material is set in the mold, the extrusion process is performed in the above temperature range and processing speed, and the cooling process is repeated. According to this structure, it can prevent that a crystal grain coarsens in a starting material before the extrusion process by a metal mold | die. Moreover, it can prevent that a crystal grain coarsens with the thermoelectric material which remains on the extrusion shaft side of a metal mold | die after an extrusion process. As a result, it is possible to reliably manufacture a thermoelectric material having desired characteristics.

  In addition, when the mold is cooled, the orientation structure or texture is changed to a temperature at which the orientation structure or texture cannot change before the change of the orientation structure or texture occurs in the thermoelectric material remaining in the mold. What is necessary is just to employ | adopt the structure etc. which cool after the extrusion process so that the time when a metal mold | die is hold | maintained at 380 degreeC or more may be 40 minutes or less. According to this configuration, in the manufacturing process of the thermoelectric material, it is possible to prevent the crystal grains from becoming coarse and to reliably manufacture the thermoelectric material having desired characteristics.

  In addition, in the thermoelectric material in this invention, it is preferable that the average of the aspect ratio of a crystal grain is 0.6 or less. That is, in the BiTe-based thermoelectric material, cleavage is likely to occur at a Te-Te joint portion parallel to the c-plane, and by performing extrusion with a mold in which the pressure shaft and the extrusion shaft are not on one axis as described above, Crystal grains long in the a-axis direction parallel to the c-plane can be generated. Therefore, the smaller the aspect ratio indicating the length of the crystal grains, the more the crystal grains have c-planes. In the present invention, a thermoelectric material having an average aspect ratio of 0.6 or less can be manufactured. Of course, the crystal grains having such an aspect ratio may contain the sub-crystal.

  The aspect ratio can be defined by measuring a cross section in a specific direction in the thermoelectric material with the EBSD device and analyzing the measurement result with analysis software. In this specification, the distance between two points that are farthest apart at the grain boundary of the same crystal grain is defined as the major axis, and an ellipse having the same area as that of the crystal grain is considered. The short axis / long axis is the aspect ratio. Therefore, the aspect ratio is calculated for all the crystal grains in a certain cross section, and the average value may be 0.6 or less.

  Furthermore, it is preferable that the subcrystal is contained in crystal grains of 5% or more of the previous crystal grains. In other words, the mechanical strength or mechanical properties of the thermoelectric material can be improved when the abundance ratio of the subcrystal is 5% or more.

  Furthermore, the average crystal grain size of the crystal grains is preferably 10 μm or more and 15 μm or less. That is, in the present invention, the coarsening of the crystal grains is allowed to some extent, but if it is allowed without limitation, the mechanical strength or the mechanical properties may be reduced according to the Hall Petch rule. However, if the average crystal grain size of the crystal grains is 10 μm or more and 15 μm or less, high mechanical strength or mechanical characteristics can be ensured.

  Further, the c-plane is preferably aligned in a specific direction, and in a crystal occupying an area of 80% of a cross section obtained by cutting the thermoelectric material in a direction parallel to the specific direction, the specific direction and the c-plane The angle is preferably less than 27 °. That is, since the figure of merit becomes higher as the c-plane is aligned in the crystal grains, it is preferable that the abundance ratio of the crystal grains having a small angle between the specific direction and the c-plane is higher. According to the manufacturing process of the present invention, In a crystal occupying an area of 80%, the angle between the specific direction and the c-plane can be less than 27 °, and a thermoelectric material having a high figure of merit can be manufactured. Note that the angle between the c-plane and a specific direction can also be defined by measurement using the EBSD apparatus and analysis by analysis software. In this specification, the specific direction in a crystal occupying 80% of a certain cross section When the angle with the c-plane is within x °, the x is called the degree of orientation.

  Further, since the thermoelectric material manufactured as described above has a high figure of merit in a specific direction, the thermoelectric material is set so that the specific direction (the specific direction in which the longitudinal directions of the crystal grains are aligned) is the energization direction. The thermoelectric element is manufactured by cutting the material. And if the thermoelectric element obtained is combined and it is set as a thermoelectric conversion module, a high-performance thermoelectric conversion module can be manufactured.

Here, embodiments of the present invention will be described in the following order.
(1) Thermoelectric material manufacturing method:
(2) Extrusion conditions and thermoelectric material characteristics:
(3) Examples and comparative examples:
(3-1) N-type thermoelectric material:
(3-2) P-type thermoelectric material:
(4) Other embodiments:

(1) Thermoelectric material manufacturing method:
FIG. 1 is a flowchart showing an embodiment of a method for producing a thermoelectric material. In the present embodiment, first, an element that is a raw material of the BiTe thermoelectric material is weighed and melted to create an ingot (step S100). That is, an ingot of at least one element selected from the group consisting of Bi and Sb and at least one element selected from the group consisting of Te and Se is weighed, and (Bi, Sb) ₂ (Te, Se) The composition is ₃ .

  After weighing, these elements are once melted and cooled by various means, thereby producing an alloy ingot having a desired composition. Next, the ingot of the alloy is rapidly cooled by a roll type liquid quenching method to produce a thin film powder (step S110). That is, an alloy ingot is melted and sprayed onto a rotating roll to form a thin film powder. Of course, the liquid quenching method may be a single roll method or a twin roll method. Further, after melting each weighed element, the step of cooling to ingot may be omitted, and the molten alloy may be liquid quenched. Here, in order to perform the continuous extrusion process using a mold, it is preferable to prepare a sufficient amount of powder to perform a plurality of extrusion processes.

  When the alloy powder material is prepared, the powder is set in a mold in a chamber (not shown) (step S120). FIG. 2 is a schematic diagram illustrating an example of a mold for performing the extrusion process. In this embodiment, the mold 10 is a rectangular parallelepiped, and a rectangular hole 11 a is formed in the surface 11, and a rectangular hole 12 a is formed in the surface 12 adjacent to the surface 11. The hole 11 a is formed from the opening in the surface 11 in a direction perpendicular to the surface 11 and extends to a predetermined position inside the mold 10. The hole 12 a is formed in a direction perpendicular to the surface 12 from the opening in the surface 12, and is connected to the hole 11 a inside the mold 10.

  In the present embodiment, the direction in which the hole 11a extends and the direction in which the hole 12a extends are orthogonal to each other, the hole 11a being a pressure shaft in the extrusion process, and the hole 12a being an extrusion shaft in the extrusion process. That is, in this embodiment, the extrusion process is performed by setting the alloy powder into the mold 10 from the hole 11a and pushing the material from the hole 11a with the plunger. In the present embodiment, the thermoelectric material 20 remains in the mold 10 after the extrusion process, and the mold 10 is configured so as to be able to assemble the mold 10 (not shown) for taking out the thermoelectric material. Etc.).

  In this embodiment, when the thin film-like powder used for extrusion is produced by a roll quenching method such as a twin roll method or a single roll method, a thin film having c-planes aligned in a direction parallel to the film thickness direction is produced. be able to. Therefore, when the thin film is set in the mold 10, the processing pressure in the extrusion process can be reduced by stacking the thin film so as to be aligned in the thickness direction of the thin film. This is because the c-plane is aligned in the thickness direction of the thin film, and deformation resistance is reduced.

  When the powder is set in the mold 10, the inside of the chamber is evacuated, and after the evacuation is completed, argon gas is introduced into the chamber (step S130). That is, the atmosphere of the mold 10 is replaced with argon gas. Thereafter, the mold 10 is heated by a heater (not shown) (step S140), and the mold 10 is set to a predetermined set temperature. In this embodiment, this preset temperature is set in the range of a temperature that is 100 ° C. lower than the melting point of the powder material to a temperature that is 20 ° C. lower than the melting point.

  When the mold 10 reaches the set temperature, an unillustrated plunger is set in the hole 11a, and an extrusion process is performed at a predetermined extrusion speed while applying a shearing force to the powder material (step S150). In this embodiment, this extrusion speed is set in the range of 1 mm / min to 12 mm / min. In this embodiment, the end position of the extrusion process by the plunger is set to a point (E shown in FIG. 2) where the hole 11a and the hole 12a intersect, and the extrusion process by the plunger is ended when the plunger reaches the end position. To do.

  At this time, a shearing force corresponding to the extrusion speed is applied to the material to be extruded by the set temperature. As a result, a thermoelectric material having a high performance index and high mechanical strength or mechanical properties can be obtained. That is, according to the above extrusion treatment, the average aspect ratio of the crystal grains can be 0.6 or less, the degree of orientation in a specific direction can be 27 ° or less, and a high figure of merit can be realized. Further, the average size of the crystal grains is 10 μm to 15 μm, and 5% or more of the total crystal grains include two or more subcrystals therein. Therefore, high mechanical strength can be realized.

  In the present specification, a coordinate system as shown in FIG. 2 is set for the thermoelectric material 20 for explanation. That is, in the thermoelectric material 20, the X axis is set in the direction in which the hole 12a of the mold 10 extends, the Z axis in the direction in which the hole 11a extends, and the Y axis in the direction perpendicular to both axes. According to this definition, the c-plane tends to be oriented parallel to the XY plane in the crystals in the thermoelectric material 20 by the extrusion process, and the specific direction related to the degree of orientation is the X-axis direction.

  As described above, the thermoelectric material after the extrusion process simultaneously achieves a high figure of merit and high mechanical strength or mechanical properties. However, if this thermoelectric material is held at the above-mentioned set temperature, the crystal grains become coarse. There is a possibility that the characteristics may be lowered due to a decrease in the degree of orientation. Therefore, in the present embodiment, the mold 10 is cooled by a cooling mechanism (not shown) in order to obtain a thermoelectric material having good characteristics obtained after the extrusion process (step S160).

  It should be noted that various configurations can be adopted as long as the mold 10 can be heated in the above-described heater and the mold 10 can be cooled in the above-described cooling mechanism. For example, it is possible to employ a configuration in which a heat source is disposed around the mold 10 and the periphery thereof, and energy is supplied to the heat source at a desired timing to heat the mold 10. Moreover, the structure etc. which flow the cooling medium for cooling a metal mold | die 10 and the metal mold | die around it are employable.

  When the mold 10 is cooled to a temperature at which the thermoelectric material 20 can be taken out by the cooling as described above, the thermoelectric material 20 is taken out from the mold 10 (step S170). A material processing step of cutting out the thermoelectric element is performed on the manufactured thermoelectric material. Moreover, when manufacturing a thermoelectric material continuously, the process after step S120 is further repeated.

FIG. 3 is a diagram showing a profile of temperature and plunger pushing amount in the continuous manufacturing process as described above. FIG. 3A is a graph showing a change in the mold temperature over time, with the horizontal axis representing time and the vertical axis representing the mold temperature. FIG. 3B is a graph showing the pushing amount when the plunger is pushed into the pressing shaft, with the horizontal axis representing time and the vertical axis representing the pushing amount. When the powder is set in the mold 10 and the evacuation and the argon gas replacement in the atmosphere are completed, the heating of the mold 10 is started at time t ₀ in FIG. 3A.

In the present embodiment performs heating towards the set temperature Ts, When the die 10 at time t ₂ reaches the set temperature Ts, perform extrusion process by the plunger at a preset extrusion rate. Pressing amount in the material of the mold 10 by the extrusion process gradually increases, when at time t ₃ the plunger reaches the end position E of the extrusion process shown in FIG. 2, the mold exit the extrusion process 10 Start cooling. As a result, the temperature of the mold 10 rapidly decreases and reaches a temperature Tt at which the thermoelectric material can be taken out from the mold 10 in the chamber in a very short time.

Therefore, when the temperature Tt is reached at time t ₅ , the thermoelectric material 20 after the extrusion process is taken out, and further, setting, evacuation, argon gas replacement, etc. of the powder mold 10 are performed again, and again at time t ₆ . Perform heating. In the present embodiment, the mold 10 is set so that the time t ₄ -t ₁ when the temperature is equal to or higher than the specific temperature Tf is equal to or shorter than the specific time interval. That is, as shown by the alternate long and short dash line in FIG. 3A, when the mold is not cooled, the time that the temperature is maintained above the temperature Tt becomes extremely long, and the thermoelectric material remains in spite of the end of the extrusion process. There is a possibility of coarsening of crystal grains.

Therefore, in the present embodiment, the cooling mechanism capable of cooling the mold 10 is configured so that the characteristics of the thermoelectric material do not change excessively with temperature. It has been found that when the specific temperature Tf is 380 ° C. and the time t ₄ -t ₁ is 40 minutes, the characteristics of the thermoelectric material controlled by the extrusion process are not deteriorated. As described above, it is possible to reliably obtain a thermoelectric material with good characteristics by heating and cooling the mold, and it is possible to mass-produce thermoelectric materials in a short time by repeating this process. is there.

(2) Extrusion conditions and thermoelectric material characteristics:
Next, the relationship between the extrusion conditions for the extrusion process and the characteristics of the thermoelectric material will be described. FIG. 4 is a graph showing a temperature range that can be selected as the set temperature Ts and a range that can be selected as the extrusion speed in the extrusion process. The horizontal axis represents the processing temperature, and the vertical axis represents the extrusion speed. In the present invention, when the melting point of the alloy as the starting material is Tm, the processing temperature can be selected in the range of Tm-100 ° C. to Tm-20 ° C. Moreover, the extrusion speed by a plunger can be selected in the range of 1 mm / min-12 mm / min. Therefore, the extrusion conditions can be set in the range of the region R ₀ indicated by hatching in FIG.

  In general, the longer the time for holding at a high temperature, the easier the atoms in the structure move and the crystal grains grow. In a polycrystalline structure, the smaller the crystal grains, the higher the mechanical strength or mechanical properties. Therefore, conventionally, when a powder material is used as a starting material, processing at a low temperature has been preferred. However, in the present invention, the temperature is set relatively high and a certain degree of crystal grain coarsening is allowed. Furthermore, the extrusion speed is set so that crystals do not grow uniformly even in this temperature range.

Therefore, according to the present invention, relatively large crystal grains can be obtained, but the degree of orientation of the c-plane becomes extremely high due to the extrusion treatment at a relatively high temperature. On the other hand, a subcrystal is introduced into the crystal grain by the stress applied to the crystal grain. As a result, it is possible to produce a thermoelectric material that simultaneously achieves a high figure of merit and high mechanical strength or mechanical properties. Region R ₀ shown in FIG. 4 shows the extrusion conditions that can produce such a thermoelectric material.

In the region R ₁ where the processing temperature is lower than Tm-100 ° C. and the extrusion speed is slower than 12 mm / min, the thermoelectric material has a high deformation resistance and a poor degree of orientation. In addition, the processing temperature is Tm-100 ° C. to Tm-20 ° C., but in the region R ₂ where the extrusion rate is slower than 1 mm / min, crystal grains grow and become a thermoelectric material with low mechanical strength or mechanical properties. End up.

Furthermore, in the region R ₃ where the processing temperature is higher than Tm−20 ° C., the degree of freedom of crystal grain movement is too high, and crystal grains grow excessively, resulting in a thermoelectric material with low mechanical strength or mechanical properties. Further, in the region R ₄ where the processing temperature is lower than Tm-100 ° C. and the extrusion speed is higher than 12 mm / min, the mold 10 is broken or clogged, and the processing temperature is Tm-100 ° C. to Tm-20. In the region R ₅ where the extrusion speed is faster than 12 mm / min, the thermoelectric material cracks, and the extrusion process was impossible.

(3) Examples and comparative examples:
(3-1) N-type thermoelectric material:
Next, a thermoelectric material (Example) manufactured under the above-described extrusion conditions and a thermoelectric material (Comparative Example) manufactured under other extrusion conditions will be described. Table 1 below shows the characteristics of the thermoelectric material obtained when the powder of an alloy having a composition of Bi _1.9 Sb _0.1 Te _2.7 Se _0.3 (melting point is 575 ° C.) is extruded under the conditions in the table. Yes.

  In the above table, the predetermined temperature holding time indicates a time during which the mold 10 is equal to or higher than a predetermined temperature Tf (380 ° C. in the present embodiment) determined in advance. Further, the degree of orientation P is determined by measuring a cross section obtained by cutting the thermoelectric material 20 in a direction parallel to the XZ plane shown in FIG. 2 with the EBSD apparatus manufactured by TSL, and analyzing software (name: OIM, version 3. This is a value obtained by analyzing in 5). FIG. 5 is a graph for explaining the degree of orientation P, showing the ratio (%) to the total cross-sectional area by accumulating the frequencies of crystals whose angle at the measurement point is θ or less. The horizontal axis represents the angle θ between the specific direction and the c-axis, and the vertical axis represents the integrated frequency (%).

  In the EBSD device, it is possible to acquire crystal orientation information appearing on a specific cross section of the thermoelectric material 20. Therefore, in this embodiment, a 250 × 250 μm region in the cross section of the thermoelectric material was measured in 0.5 μm increments, and 250,000 pieces of orientation information were acquired. This orientation information indicates the orientation of the crystal axis at each point, and the orientation of the c-plane can be specified based on this orientation. That is, as shown in the upper left of the graph of FIG. 5, the c-axis direction θ (X in the XZ plane shown in FIG. 2) with respect to a specific direction (for example, a direction parallel to the X axis shown in FIG. 2 on the cross section). If the angle with respect to the axis is specified, the direction of the c-plane (90 ° −θ) with respect to the specific direction can be specified.

  In order to macroscopically evaluate the crystal orientation of the thermoelectric material 20, it is only necessary that the orientation of the c-plane at each point can be defined for the entire cross section. The degree of orientation P shown in FIG. 5 is an index for performing such macroscopic evaluation, and the solid line shown in the graph is a value obtained by integrating the angle θ between the specific direction and the c axis from 0 ° to 90 °. Show.

For example, when the cumulative frequency at a certain angle θ ₁ is H ₁ , the crystal whose angle between the specific direction and the c-axis is equal to or less than θ ₁ in the entire cross-sectional area is H ₁ % of the whole. This is equivalent to the presence of 100-H ₁ % of crystals in which the angle between the specific direction and the c-plane is 90 ° -θ ₁ . Therefore, in the present embodiment, the angle θ _{2 at} which the integrated frequency is 20% is acquired, and 90 ° −θ ₂ is defined as the orientation degree P. That is, the orientation degree P indicates that the angle between the specific direction and the c-plane is less than 90 ° −θ ₂ in a crystal occupying 80% of the total cross-sectional area.

  Furthermore, the average particle diameter, aspect ratio, and subcrystal abundance ratio in Table 1 can also be measured by the EBSD apparatus. That is, in the present embodiment, a structure having a crystal axis different by 15 ° or more is defined as a different crystal, and the grain size is a radius of a circle having the same area as the structure of one structure in a certain cross section. It is defined as Therefore, the crystal axis is measured by the above-mentioned EBSD apparatus, and it can be defined whether the crystal axes of adjacent measurement points are the same crystal axis or not depending on whether the crystal axes differ by 15 ° or more. Based on this, grains can be defined.

  Further, the aspect ratio is a value corresponding to the length of one crystal grain, and in this embodiment, the short axis / long axis of the ellipse having the same area as the crystal grain is used as the aspect ratio. That is, the grain boundary of the crystal grain is specified by the measurement by the above-described EBSD apparatus, and the two most distant points in the grain boundary are extracted, and these distances are set as the major axis. An ellipse having this major axis and having the same area as the area of the crystal grains surrounded by the grain boundary is defined. Since this ellipse has a shape corresponding to the length of the crystal grains, in this embodiment, the minor axis / major axis of the ellipse is used as the aspect ratio.

  Furthermore, in this embodiment, the orientation of the crystal axis fluctuates across a boundary in the same crystal grain, and the angle difference between the c planes on both sides of the boundary is within 5 °, When the angle difference is 5 ° or more, the crystals on both sides are defined as subcrystals, and the ratio of the number of crystal grains including subcrystals to the total number of crystal grains is the subcrystal abundance ratio. In addition, since the BiTe type thermoelectric material in this embodiment is space group R3-m, there is arbitrary in the direction which should be the direction of an a axis within a crystal. Therefore, the a-axis angle may be a minimum value of the crystal axis angle that can be defined on both sides of the boundary.

Furthermore, the power factor in Table 1 is a value indicating the performance mainly due to electrical characteristics among the performance of the thermoelectric material 20, and is a value measured in a specific direction. Therefore, it can be evaluated whether or not the performance of the thermoelectric material 20 is enhanced by orientation or the like. Of course, the thermoelectric material 20 may be evaluated based on the figure of merit. Further, the maximum shear stress is F, which is the load when the thermoelectric material 20 after extrusion is broken by applying a shear force in the Z direction shown in FIG. When the length in the h and Y directions is b, it can be calculated by the following equation τ. Therefore, the mechanical strength or mechanical characteristics of the thermoelectric material 20 can be evaluated by this value τ.
τ = 3/2 · F / bh

As shown in Examples 1 to 6 of Table 1 above, extrusion was performed at a temperature range of Tm-100 ° C to Tm-20 ° C (Tm is the melting point of the alloy) and an extrusion rate range of 1 mm / min to 12 mm / min. When the time for carrying out the treatment and maintaining the temperature above the predetermined temperature is 40 minutes or less, the thermoelectric material 20 having a large power factor and high mechanical strength or mechanical properties can be produced. That is, the degree of orientation is less than 27 °, the average particle size is 10 μm to 15 μm, the average aspect ratio is 0.6 or less, the subcrystal abundance ratio is 5% or more, and the power factor is 4.1 × 10 ⁻³ W / A thermoelectric material 20 having mK ² or more and a maximum shear stress of 49 MPa or more can be produced.

  As shown in Table 1, when the degree of orientation is less than 27 °, the c-plane is aligned in a specific direction, so that the thermoelectric material 20 having a large power factor can be obtained. The aspect ratio is the same, and in the BiTe thermoelectric material cleaved on the c-plane, the longitudinal direction of the crystal grains is directed to the specific direction. The smaller the value of the aspect ratio is, the longer the crystal grains are in the direction parallel to the c-plane. The average aspect ratio is 0.6 or less, and the thermoelectric material 20 having a large power factor is obtained. Can do.

  FIG. 6 is a schematic diagram for explaining the crystal structure, and schematically shows crystal grains in the cross section Sc when the thermoelectric material 20 is cut along a plane parallel to the XZ plane. 6A is a crystal structure when the extrusion process is performed within the range of the processing temperature and the extrusion speed in the present invention, FIG. 6B is a crystal structure when the extrusion process is performed at a temperature lower than the range of the processing temperature in the present invention, FIG. 6C shows a cross section of the crystal structure when the extrusion process is performed at a temperature higher than the processing temperature range in the present invention. The grain boundaries of the crystal grains are indicated by solid lines and the grain boundaries of the sub-crystal grains are indicated by broken lines. .

  As shown in FIGS. 6A to 6C, if the processing temperature and the extrusion speed in the present invention are used, the crystal grains become flat and the aspect ratio can be set to a small value of 0.6 or less. On the other hand, as shown in the figure, if the temperature is lower than the processing temperature in the present invention, the growth of crystal grains is not promoted, so that the characteristics of the crystal grains in the powder as the starting material remain and the aspect ratio is It will not get smaller. Furthermore, if the temperature is higher than the processing temperature in the present invention, the growth of crystal grains is promoted, and the effect of eliminating the orientation due to the coarsening of the crystal grains appears rather than the effect of keeping the aspect ratio small. Therefore, with the processing temperature and extrusion speed in the present invention, the thermoelectric material 20 having a large power factor can be produced while keeping the aspect ratio small.

  Furthermore, as shown in Example 1 to Example 6, when the average particle size is 10 μm to 15 μm, it is possible to increase the degree of orientation without excessively coarsening the crystal grains, and at least of these crystal grains. By introducing subcrystals in 5%, it is possible to simultaneously realize a large power factor and high mechanical strength or mechanical properties. That is, as shown in FIGS. 6A to 6C, if the temperature is lower than the processing temperature in the present invention, the growth of the crystal grains is not promoted, and the grain size of the crystal grains in the thermoelectric material 20 after the extrusion treatment is determined in the present invention. Smaller than the particle size of the manufactured material (FIG. 6A). Moreover, if it is temperature higher than the processing temperature in this invention, the growth of a crystal grain will be accelerated | stimulated and the particle size of a crystal grain will become larger than the particle size of the material manufactured in this invention in the thermoelectric material 20 after an extrusion process.

  Therefore, when the crystal grains do not contain subcrystals, the mechanical strength or mechanical properties are 6B> 6A> 6C. However, the crystal grain shown in FIG. 6A includes a plurality of subcrystals Cs. For this reason, even if the crystal grains themselves are larger than FIG. 6B, the presence of subcrystals contributes to elements that affect the mechanical strength or mechanical properties such as the ease of cracking in one direction, and the case where the crystal grains are small. Similar mechanical strength or mechanical properties can be ensured.

  On the other hand, when the thermoelectric material 20 is manufactured with extrusion conditions different from the above temperature range and extrusion speed range, and with a holding time longer than the above-mentioned predetermined temperature holding time, a large power factor and high mechanical strength or mechanical characteristics are realized simultaneously. I can't. For example, in Comparative Example 1 (processing temperature 460 ° C., extrusion speed 15 mm / min), the mold 10 was damaged and could not be processed. Therefore, at a processing temperature of 460 ° C., the extrusion speed of 15 mm / min can be said to be excessively fast. Similarly, in Comparative Example 2 (processing temperature 520 ° C., extrusion speed 15 mm / min), the thermoelectric material 20 after completion of extrusion was cracked, and the production could not be completed. Therefore, even if the processing temperature is increased to 520 ° C., the extrusion speed of 15 mm / min is not a speed suitable for processing the thermoelectric material 20.

  Furthermore, in Comparative Example 3 (processing temperature 565 ° C., extrusion rate 5 mm / min), the average particle size is coarsened to 16 μm, and the aspect ratio is also a large value of 0.8. Accordingly, the processing temperature of 565 ° C. is excessively high, and as shown in Table 1, the thermoelectric material 20 has a small power factor and shear stress under these extrusion conditions.

  Furthermore, in Comparative Example 4 (processing temperature: 460 ° C., extrusion speed: 5 mm / min), the average particle size is as small as 8.3 μm, but the subcrystal abundance ratio is as small as 3.51. Further, the aspect ratio becomes a large value of 0.65 due to the small average particle diameter. Therefore, the processing temperature of 460 ° C. is excessively low, and as shown in Table 1, the thermoelectric material 20 has a small power factor and shear stress under these extrusion conditions. Furthermore, in Comparative Example 5 (processing temperature 380 ° C., extrusion rate 0.8 mm / min), the average particle size can be set to a very small value of 4.7 μm, and the maximum shear stress can be increased, An orientation degree of 36 and an aspect ratio of 0.72 become excessively large, resulting in a small power factor.

  Furthermore, in Comparative Example 6 (processing temperature 520 ° C., extrusion rate 0.9 mm / min), the subcrystal abundance ratio is a large value of 7.2%, but the average particle diameter is also a large value of 16 μm. For this reason, the maximum shear stress is as small as 45 MPa. Further, Comparative Example 7 (processing temperature 555 ° C., extrusion speed 1.2 mm / min, predetermined temperature holding time 45 minutes) is within the mold even at the processing temperature and extrusion speed at which a thermoelectric material with good characteristics can be produced. It is shown that the characteristics deteriorate when the holding time is long. That is, the processing temperature and the extrusion speed are the same conditions as in the above-described Example 3 and Example 4, but the predetermined temperature holding time is as long as 45 minutes, so that the crystal grain size becomes coarser to 18 μm. The ratio was 0.73, the degree of orientation was 30 °, and the subcrystal abundance ratio was 4.9%. Therefore, the characteristics are degraded as compared with the third and fourth embodiments.

以上の表２の実施例７〜実施例１１に示すように、Ｔｍ−１００℃〜Ｔｍ−２０℃の温度範囲（Ｔｍは合金の融点）かつ１ｍｍ／分〜１２ｍｍ／分の押出速度範囲で押出処理を行い、既定温度以上に保持する時間が４０分以下であったときには、大きなパワーファクタと高い機械強度または機械特性とを有する熱電材料２０を製造することができる。すなわち、配向度が２７°未満、平均粒径が１０μｍ〜１５μｍ、平均のアスペクト比が０．６以下、亜結晶存在比が５％以上であり、パワーファクタが４．２×１０^-3Ｗ／ｍＫ²以上、最大せん断応力が４９ＭＰａ以上の熱電材料２０を製造することができる。 (3-2) P-type thermoelectric material:
Further, Table 2 below shows the characteristics of the thermoelectric material obtained when the powder of the alloy having the composition of Bi _0.4 Sb _1.6 Te ₃ (melting point is 595 ° C.) is subjected to extrusion treatment under each condition in the table. Yes.

As shown in Examples 7 to 11 of Table 2 above, extrusion was performed at a temperature range of Tm-100 ° C to Tm-20 ° C (Tm is the melting point of the alloy) and an extrusion rate range of 1 mm / min to 12 mm / min. When the time for carrying out the treatment and maintaining the temperature above the predetermined temperature is 40 minutes or less, the thermoelectric material 20 having a large power factor and high mechanical strength or mechanical properties can be produced. That is, the degree of orientation is less than 27 °, the average particle size is 10 μm to 15 μm, the average aspect ratio is 0.6 or less, the subcrystal abundance ratio is 5% or more, and the power factor is 4.2 × 10 ⁻³ W / A thermoelectric material 20 having mK ² or more and a maximum shear stress of 49 MPa or more can be produced.

  On the other hand, when the thermoelectric material 20 is manufactured with extrusion conditions different from the above temperature range and extrusion speed range, and with a holding time longer than the above-mentioned predetermined temperature holding time, a large power factor and high mechanical strength or mechanical characteristics are realized simultaneously. I can't. For example, in Comparative Example 8 (processing temperature 485 ° C., extrusion speed 15 mm / min), the mold 10 is broken, and in Comparative Example 9 (processing temperature 550 ° C., extrusion speed 15 mm / min), the thermoelectric material 20 is cracked. The manufacture could not be completed. Also in this composition, it can be seen that the extrusion speed of 15 mm / min is not a speed suitable for processing the thermoelectric material 20.

  Furthermore, in Comparative Example 10 (processing temperature 585 ° C., extrusion rate 5 mm / min), the thermoelectric material 20 has a small shear stress due to the coarsening of the average particle diameter and the increase in the aspect ratio. Furthermore, in Comparative Example 11 (processing temperature 485 ° C., extrusion speed 5 mm / min), the average particle size is small and the degree of orientation is poor, so the thermoelectric material 20 has a small power factor.

  Furthermore, in Comparative Example 12 (processing temperature 380 ° C., extrusion rate 0.5 mm / min), the average particle size can be made extremely small and the maximum shear stress can be increased, but the degree of orientation and aspect The ratio becomes excessively large and the power factor becomes a small value.

  Furthermore, in Comparative Example 13 (processing temperature 550 ° C., extrusion rate 0.5 mm / min), the subcrystal abundance ratio is a large value of 8.5%, but the average particle diameter is also a large value of 16 μm. For this reason, the maximum shear stress is as small as 42 MPa. Further, Comparative Example 14 (processing temperature 575 ° C., extrusion speed 12 mm / min, predetermined temperature holding time 60 minutes) and Comparative Example 15 (processing temperature 575 ° C., extrusion speed 12 mm / min, predetermined temperature holding time 120 minutes) are good. Even when the processing temperature and the extrusion speed at which the thermoelectric material having the characteristics can be manufactured, the characteristics are deteriorated when the holding time in the mold is long. That is, when the predetermined temperature holding time is as long as 60 minutes and 120 minutes, the crystal grain size becomes coarse, the aspect ratio and the degree of orientation increase, and the subcrystal abundance ratio decreases.

(4) Other embodiments:
In the present invention, the pressure axis and the extrusion axis are on one axis at a temperature range of 100 ° C. below the melting point of the alloy to 20 ° C. below the melting point of the alloy and at an extrusion speed of 1 mm / min to 12 mm / min. It is only necessary to produce a thermoelectric material that simultaneously achieves a high figure of merit and high mechanical strength or mechanical properties by extruding with a non-mold, and various configurations other than the above-described embodiments can be adopted. . For example, the mold 10 is an example, and as long as the pressure shaft and the extrusion shaft are different, the angles of the two shafts are not limited, and the present invention is not limited to the embodiment in which the two are orthogonal to each other. Moreover, the diameters of the holes may be different between the pressure shaft and the extrusion shaft. In other words, the hole along the extrusion axis may be smaller than the hole along the pressure axis. Furthermore, when holding the mold 10 at a predetermined temperature, the temperature and holding time can be adjusted so as not to change the orientation structure or texture of the thermoelectric material 20.

  Furthermore, the powder of the alloy to be extruded is not limited to a thin film prepared by roll-type liquid quenching, and a material obtained by pulverizing the alloy using gas atomization or a rotating disk may be used, or the alloy ingot is pulverized. You may use it. Of course, the material may be reduced with hydrogen or the like. However, in the present invention, since the particle size of the material after extrusion is controlled by the above-described extrusion conditions, it is preferable to make the particle size of the starting material equal to a predetermined particle size, and more specifically, 1 μm to 50 μm. It is preferable that

以上の表３において、実施例１２〜１５および比較例１６，１７は合金のインゴットを粉砕した場合の例、実施例１６，１７および比較例１８，１９は単ロール液体急冷によって出発材料を製造した場合の例、実施例１８および比較例２０，２１は双ロール液体急冷によって出発材料を製造した場合の例、比較例２２，２３はガスアトマイズによって出発材料を製造した場合の例である。 Table 3 below shows the relationship between the average value of the crystal grains contained in the powder of the starting material, the subcrystal abundance ratio after extrusion, the aspect ratio, and the maximum shear stress. The alloy composition in this table is Bi _1.9 Sb _0.1 Te _2.5 Se _0.5 (melting point is 593 ° C.), processing temperature is 530 ° C., and extrusion speed is 3 mm / min.

In Table 3 above, Examples 12 to 15 and Comparative Examples 16 and 17 are examples in which alloy ingots are pulverized, and Examples 16 and 17 and Comparative Examples 18 and 19 are starting materials manufactured by single-roll liquid quenching. Example, Example 18 and Comparative Examples 20 and 21 are examples in which the starting material is produced by twin roll liquid quenching, and Comparative Examples 22 and 23 are examples in which the starting material is produced by gas atomization.

  As shown in this table, in any example, when the crystal grain size is 1 μm to 50 μm, the subcrystal abundance ratio is 5% or more, the aspect ratio is 0.6 or less, and the maximum shear stress is 49 MPa or more. . Therefore, when the crystal grain size is 1 μm to 50 μm, the thermoelectric material having the above-described characteristics can be obtained depending on the processing temperature and the extrusion rate in the present invention.

It is a flowchart which shows the manufacturing method of a thermoelectric material. It is a schematic diagram which shows an example of a metal mold | die. It is a figure which shows the profile of the temperature in a manufacturing process, and plunger pushing amount. It is a figure which shows the range of processing temperature and extrusion speed. 5 is a graph for explaining an orientation degree P. It is a schematic diagram for demonstrating a crystal structure.

Explanation of symbols

10 ... mold 11a ... hole 12a ... hole 20 ... thermoelectric material

Claims (3)

An alloy of at least one element selected from the group consisting of Bi and Sb and at least one element selected from the group consisting of Te and Se is formed by a mold having different pressing and extrusion axes. Extrusion process in which the pressure shaft and the extrusion shaft are not on one axis at a temperature range of 100 ° C. lower than the melting point of the alloy to 20 ° C. lower than the melting point of the alloy and an extrusion speed of 1 mm / min to 12 mm / min. there at least once rows, after the extrusion process, the mold thermoelectric material time is 380 ° C. or higher in the presence in the interior of the mold is cooled to be less than 40 minutes,
Thermoelectric material manufacturing method.   A thermoelectric material comprising at least one element selected from the group consisting of Bi and Sb and at least one element selected from the group consisting of Te and Se,
  The angle difference between the crystal axes is within 15 °, the average crystal grain size is 10 μm or more and 15 μm or less, and the average aspect ratio of the crystal grains is 0.6 or less. In a crystal in which a sub-crystal having an angle difference of 5 ° or more within 5 ° or more is included in 5% or more of the crystal grains and occupies an area of 80% of a cross section parallel to a specific direction, The angle between the specific direction and the c-plane is less than 27 °,
  Thermoelectric material.   A thermoelectric element cut out from the thermoelectric material according to claim 2, comprising a thermoelectric element having a direction in which the longitudinal directions of the crystal grains are aligned as an energization direction,
  Thermoelectric conversion module.

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