WO2015030238A1 - セラミックス材料、および熱スイッチ - Google Patents
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- WO2015030238A1 WO2015030238A1 PCT/JP2014/072936 JP2014072936W WO2015030238A1 WO 2015030238 A1 WO2015030238 A1 WO 2015030238A1 JP 2014072936 W JP2014072936 W JP 2014072936W WO 2015030238 A1 WO2015030238 A1 WO 2015030238A1
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Definitions
- the present invention relates to a ceramic material whose heat transfer performance varies with temperature, and a thermal switch using the ceramic material.
- Patent Document 1 an element that switches thermal conductivity by applying energy (magnetic field, electric field, light, etc.) to a transition body sandwiched between electrodes, a substrate 1 and a carbon nanotube layer
- the switch which switches the connection state which the base material 2 which it has contacts, and the non-connection state which does not contact is disclosed.
- VO 2 that causes an insulator-metal transition
- the thermal conductivity is increased by 60% around a transition temperature of 70 ° C.
- Patent Document 1 an electrode, wiring, and the like are necessary to switch by applying energy. Moreover, in patent document 2, components other than what itself changes in thermal conductivity are required, and an actuator is provided to change the contact state. Therefore, the switch becomes large and the mounting location is limited from the viewpoint of heat resistance. Moreover, it is difficult to manufacture a complicated shape.
- the change in thermal conductivity is small (3.5 W / (m ⁇ K) to 5.5 W / (m ⁇ K) in VO 2 (Non-Patent Document 1)), and the heat dissipation and heat insulation can be switched. The characteristics are not obtained.
- An object of the present invention is to provide a ceramic material capable of changing the heat transfer performance depending on the temperature, and a thermal switch using the ceramic material.
- the present inventors have found that the above problem can be solved by controlling the representative length of the microstructure of the ceramic material. That is, according to the present invention, the following ceramic material and thermal switch are provided.
- any of the intervals GI heterogeneous material particles and heterogeneous material particle is the representative length L a of the microstructure [1] to [3] A ceramic material according to any one of the above.
- the distance GI is 0.1GI ave more 10GI ave following the dissimilar material particles and the different material particles [ 4].
- the base material is SiC
- the dissimilar material particles include at least one selected from the group consisting of O, B, C, N, Al, Si, and Y.
- polycrystalline constituted by ceramic material according to any of the grain size d of crystal grains is the representative length L a of the microstructure [1] to [3].
- a thermal switch that uses the ceramic material according to any one of [1] to [13] and whose thermal conductivity changes with temperature.
- the ceramic material of the present invention has a heat insulation effect with low heat transfer performance at low temperatures, and has a heat dissipation effect with high heat transfer performance at high temperatures.
- the heat transfer performance of the ceramic material of the present invention changes due to changes in ambient temperature, self-sustained heat in which the heat transfer performance is switched on (high heat transfer performance) or OFF (low heat transfer performance). It becomes a switch. This eliminates the need for components such as a drive unit, and can reduce the size. In addition, the mountability is high and the degree of freedom in shape is high.
- Embodiments 1 to 3 of the ceramic material of the present invention are schematic views showing Embodiments 1 to 3 of the ceramic material of the present invention.
- Embodiment 1 in FIG. 1A is a ceramic material configured by a composite material in which different types of materials are dispersed in a base material.
- Embodiment 2 of FIG. 1B is a ceramic material comprised by the porous body.
- Embodiment 3 in FIG. 1C is a ceramic material composed of polycrystals.
- the ceramic material of the present invention has an apparent mean free path of phonons at room temperature (L AMFP ; Appliant Mean Free Path) (Equation 1)
- L AMFP (3 ⁇ thermal conductivity) / (heat capacity ⁇ sonic velocity)
- representative length L a of the fine structure is 0.1L AMFP ⁇ L a ⁇ 100L AMFP , thermal conductivity increases monotonically between 100 ° C. from room temperature.
- the apparent mean free path (L AMFP ) of the phonon is calculated from Equation 2 to Equation 1.
- the thermal conductivity, heat capacity, and speed of sound in Equation 1 above for calculating the apparent mean free path of phonons are values at room temperature of the single crystal of the base material constituting the ceramic material.
- the speed of sound is the speed of sound transmitted through a single crystal of the base material. That is, the ceramic material is configured to include a certain material A as a base material. However, when the certain material A is a single crystal, the apparent mean free path of the phonon according to the thermal conductivity at room temperature, the heat capacity, and the speed of sound ( L AMFP ) is calculated.
- SiC thermal conductivity 410 W / mK (Source: Japan Society for the Promotion of Science, High Temperature Ceramic Materials 124th Committee, “SiC New Ceramic Material” (hereinafter, only the title))
- density of 3.21 g / cm 3 Source: “ SiC-based ceramic new material "), specific heat 690 J / gK (source:” SiC-based ceramic new material "), heat capacity 2215 kJ / m 3 K (source: calculated from density and specific heat described in" SiC-based ceramic new material "), Speed of sound: 10360 m / s (Source: Japanese Patent Laid-Open No. 8-149591).
- AlN thermal conductivity 170 W / mK (Source: International Publication No. 2013/061926), Density 3.26 g / cm 3 (Source: “Ceramics Dictionary 2nd Edition” Maruzen Publishing), Specific Heat 734 J / gK ( Source: The Chemical Society of Japan “Chemical Handbook II Revised Edition 5” Maruzen Publishing), heat capacity 2393 kJ / m 3 K (calculated from the above density and specific heat), sound velocity 6016 m / s (Source: International Publication No. 2013/061926) ).
- Thermal conductivity of Si 3 N 4 180 W / mK (Source: Japan Society for the Promotion of Science Advanced Ceramics 124th Committee “Silicon Nitride Ceramic New Material” (hereinafter, only the title is shown)), density 3.19 g / cm 3 (Source) : “New silicon nitride ceramic material”), specific heat 710 J / gK (source: “silicon nitride ceramic new material”), heat capacity 2265 kJ / m 3 K (calculated from the above density and specific heat), sound speed 11780 m / s (source) : JP-A-8-149591).
- phonons and conduction electrons are responsible for heat conduction, phonons are dominant in ceramic materials.
- the heat conduction by phonons is affected by the structure having a length close to the free path of phonons.
- a phonon having a longer free path than the length of the structure is scattered by the structure and hardly transfers heat, and a short phonon can transfer heat without scattering.
- the length of the structure as referred to herein, is a representative length L a of the microstructure of the.
- the representative length L a of the microstructure a typical length for representing the microstructure of the ceramic material.
- a composite material in which a different material is dispersed in a base material is a particle spacing between different material particles
- a porous material is a pore-to-pore spacing
- a polycrystal is a crystal grain size (a grain boundary-to-grain boundary spacing).
- Representative length L a of the microstructure is more shorter material than L AMFP, since the phonon representative length L a of the microstructure is scattered by the fine structure than longer material than L AMFP increases, the absolute thermal conductivity The value becomes smaller. Further, it representative length L a of the microstructure of the shorter material than L AMFP is largely changed thermal conduction by phonons depending on temperature than long material representative length L a is from L AMFP microstructure, temperature The difference between the thermal conductivity when the temperature is low and the thermal conductivity when the temperature is high is increased. On the other hand, when a representative length L a of the microstructure resulting in less than 0.1 L AMFP, because excessively increasing phonons are scattered by the microstructure, the thermal conductivity does not change even by changing the temperature .
- L AMFP ⁇ L a ⁇ 100L AMFP may be more preferable.
- the particles of the material B are present at a certain distance in the material A which is the base material.
- the representative length L a of the microstructure, the spacing of the material B particles are present at a certain distance in the material A which is the base material.
- pores C are present at intervals of a length in the material A as the base material.
- the representative length L a of the microstructure the spacing of the pores C.
- the material A as a base material is a polycrystalline body having a certain grain size and has a grain boundary phase D.
- the representative length L a of the microstructure is the particle size.
- the free path of phonons has a distribution in the range of about 0.1 nm to 1 mm.
- the above structure is nano-order (in the case of nanostructures)
- the thermal conductivity is a value (for example, 0.8 ⁇ High ) that is close to the thermal conductivity ( ⁇ High ) that the material originally has at that temperature.
- the ceramic material preferably has a thermal conductivity at 100 ° C. of 1.5 times or more of the thermal conductivity at room temperature for use as a thermal switch. Furthermore, the ceramic material preferably has a thermal conductivity at 200 ° C. that is at least twice that of room temperature.
- the material may be any material as long as the heat conduction due to phonon conduction is dominant, and is applicable to all ceramics.
- Preferred examples of such ceramics include silicon carbide, aluminum nitride, silicon nitride, alumina, yttria, magnesia, mullite, spinel, zirconia, cordierite, and aluminum titanate.
- a material having high thermal conductivity such as silicon carbide, aluminum nitride, or silicon nitride is preferable because a difference in thermal conductivity between a heat radiation state and a heat insulation state is increased.
- Representative length L a fine structure, it varies depending on the material, in the range of 1 nm ⁇ 1 [mu] m, preferably 1 nm ⁇ 500 nm, more preferably 10 ⁇ 100 nm. Although it differs depending on the material, there is roughly the following relationship. (1) 1 nm to 10 ⁇ m corresponds to 0.1 L AMFP ⁇ L a ⁇ 100 L AMFP . Further, (2) 1 to 500 nm corresponds to 0.1L AMFP ⁇ L a ⁇ 20L AMFP . Further, (3) 10 to 100 nm corresponds to 0.3L AMFP ⁇ L a ⁇ 3L AMFP .
- (3) 10 to 100 nm can also prevent the absolute value of thermal conductivity from becoming too small by limiting the lower limit.
- a material A in the (base material) is sintered in a dispersed state a material different from the base material at intervals of a representative length L a microstructure ( Figure 1A: Embodiment 1).
- a material A in the (base material) is sintered in a dispersed state a material different from the base material at intervals of a representative length L a microstructure ( Figure 1A: Embodiment 1).
- a material A in the (base material), the base material to precipitate particles of different materials at intervals of the representative length L a microstructure Figure 1A: Embodiment 1).
- a material A (base material) to form pores at intervals of the representative length L a microstructure (Figure 1B: Embodiment 2).
- FIG. 1A shows a first embodiment configured by a composite material in which a different material (material B) is dispersed in a base material (material A).
- the particles of the material B exist in the material A at intervals of a certain length.
- Representative length L a of the microstructure is the distance between the particles of the material B particles and material B.
- the particle B 2 at the shortest position among the particles B i around it is selected, and the distance between B 1 and B 2 is defined as GI.
- GI is the representative length L a of the microstructure. Therefore, it is preferable that 0.1L AMFP ⁇ GI ⁇ 100L AMFP . That is, even if there is a distribution in the distance between the different material particles and the different material particles (even if the distance is not constant), the GI is preferably within the above range, and 80% or more of the GI is within this range. It is preferable to be within. By forming the ceramic material so that the gap GI between the different material particles and the different material particles falls within such a range, a ceramic material whose thermal conductivity varies greatly depending on the temperature can be obtained.
- interval GI heterogeneous material particles and heterogeneous material particles is preferably not more than 0.1GI ave more 10GI ave.
- a base material (material A) of the ceramic material as in the first embodiment SiC is cited.
- the different material particles (material B) include those containing at least one selected from the group consisting of O, B, C, N, Al, Si, and Y. More specifically, SiO 2 , Al 2 O 3 etc. are mentioned.
- the ceramic material is formed such that the volume ratio of the material B is smaller than that of the material A.
- GI ave is preferably 10 to 500 nm.
- the ceramic material of Embodiment 1 in which the gap GI between the different material particles and the different material particles is controlled can be obtained by firing the raw material powder having a predetermined particle diameter under predetermined firing conditions.
- a dispersing agent crushing to primary particles, press-molding and firing, the variation in the gap GI between the different material particles and the different material particles when sintered. Less.
- FIG. 1B shows an embodiment of a ceramic material constituted by a porous body. This embodiment has a structure in which pores C exist in material A at intervals of a certain length. Representative length L a of the microstructure is the overall length is the distance of the pores C.
- PI is the representative length L a of the microstructure.
- the pore C 2 at the shortest position among the pores C i around it is selected, and the distance between C 1 and C 2 is defined as PI.
- 0.1L AMFP ⁇ PI ⁇ 100L AMFP Even if there is a distribution in the interval between the pores C and C (even if the interval is not constant), it is preferable that the PI is within the above range, and that 80% or more of the PI is within this range. Is preferred.
- Examples of the ceramic material as in the second embodiment include a SiC porous body.
- PI ave is preferably 10 to 500 nm. When PI ave is within this range, the porous body can function as a thermal switch near room temperature.
- the ceramic material according to the second embodiment in which the pore interval PI is controlled can be obtained by firing the raw material powder having a predetermined particle diameter under predetermined firing conditions. Moreover, the dispersion
- FIG. 1C shows an embodiment of a ceramic material composed of polycrystals.
- This embodiment is constituted by polycrystalline particle size d of crystal grains are representative length L a of the microstructure. Therefore, it is preferable that 0.1L AMFP ⁇ d ⁇ 100L AMFP . Even if there is a distribution in the particle size d (even if the interval is not constant), d is preferably within the above range, and 80% or more of the total is preferably within this range.
- the ceramic material such that the grain size d of the crystal particles is within such a range, a ceramic material whose thermal conductivity greatly varies depending on the temperature can be obtained.
- 0.1L AMFP ⁇ d ⁇ L AMFP In the case of greatly changing the thermal conductivity, it is preferable that 0.1L AMFP ⁇ d ⁇ L AMFP . However, in this case, the absolute value of the thermal conductivity may be too low. Therefore, in order to greatly change the thermal conductivity, 0.1L AMFP ⁇ d ⁇ 100L AMFP is more preferable. However, when it is desired to keep the absolute value of the thermal conductivity high, L AMFP ⁇ d ⁇ 100L AMFP In some cases, it is more preferable.
- the particle diameter d is preferably 0.1 d ave or more and 10 d ave or less.
- Examples of the ceramic material as in the third embodiment include SiC polycrystals.
- d ave is preferably 10 to 500 nm. When d ave is within this range, the polycrystal can function as a thermal switch near room temperature.
- the ceramic material of Embodiment 3 in which the particle diameter d of the crystal particles is controlled can be obtained by firing under a predetermined firing condition using a raw material powder having a predetermined particle diameter.
- the ceramic material as described above can be used as a thermal switch because its thermal conductivity greatly varies depending on the temperature. For example, as shown in FIG. 2, the thermal conductivity of a ceramic material increases abruptly at a certain temperature above room temperature.
- a thermal switch is a material that can switch between a low thermal conductivity state (adiabatic state) and a high state (heat transfer state).
- a thermal switch whose thermal conductivity increases when the temperature rises can be said to be in an OFF state because the thermal conductivity is low below a certain temperature (first temperature).
- first temperature a certain temperature
- the thermal conductivity becomes high, and it can be said that the thermal switch is in the ON state.
- a temperature control structure can be produced by providing the thermal switch of the present invention around a heat generation source that generates heat.
- the temperature adjustment structure refers to a structure having a function of adjusting temperature while effectively using heat from a heat generation source.
- the heat generation source that generates heat refers to the one that generates heat, and is not particularly limited.
- the temperature adjustment structure changes the heat dissipation state between the first temperature and the second temperature that is higher or lower than the first temperature, thereby adjusting the temperature due to the heat of the heat generation source and improving the performance of the one equipped with the temperature adjustment structure.
- the heat generation source include a battery pack, a motor, a CPU, a control circuit, an engine, a brake, and a gear box.
- a structure provided with a thermal switch around these is a temperature adjustment structure.
- an indoor temperature control structure can be provided by providing a heat switch in the building material, window, and sash.
- the following configurations (1) and (2) are also preferable modes.
- Example 1 In order to reduce the variation in pore spacing even when sintered, a silicon carbide powder having an average particle size of 100 nm was dispersed using ethanol containing a dispersant. This silicon carbide powder was press-molded to prepare a disk-shaped molded body having a diameter of 30 mm and a thickness of 6 mm. This molded body was fired at 2050 ° C. in an Ar atmosphere to obtain a porous silicon carbide sintered body.
- This sintered body was observed with an electron microscope, and values of the silicon carbide particles and pores constituting the sintered body were measured from the image.
- the average value of the particle diameter of 10 arbitrarily selected silicon carbide particles was 100 nm. Further, for 10 arbitrarily selected pores, the distance between the pores and the nearest pores among the pores around the pores was measured, and the average value was 100 nm.
- Example 2 A silicon carbide powder having an average particle diameter of 20 nm was press-molded to prepare a disk-shaped molded body having a diameter of 30 mm and a thickness of 6 mm. This molded body was fired by a spark plasma sintering method (SPS) (1400 ° C., 10 minutes) to obtain a porous silicon carbide sintered body.
- SPS spark plasma sintering method
- the sintered body was observed with an electron microscope, and the values of the silicon carbide particles and pores constituting the sintered body were measured from the image.
- the average value of the particle diameters of 10 silicon carbide particles arbitrarily selected was 30 nm. Further, for 10 arbitrarily selected pores, the distance between the pores and the nearest pores among the pores around the pores was measured, and the average value was 30 nm. Since the mean free path of SiC phonons was 54 nm, it was confirmed that the pore spacing was 0.1 to 100 times the mean free path of phonons.
- Example 3 A molded body was prepared in the same manner as in Example 2, and the molded body was fired by a spark plasma sintering method (SPS) (1400 ° C., 30 minutes) to obtain a porous silicon carbide sintered body.
- SPS spark plasma sintering method
- the sintered body was observed with an electron microscope, and the values of the silicon carbide particles and pores constituting the sintered body were measured from the image.
- the average value of the particle diameter of 10 arbitrarily selected silicon carbide particles was 52 nm. Further, for 10 arbitrarily selected pores, the distance between the pores and the nearest pores among the pores around the pores was measured, and the average value was 55 nm. Since the mean free path of SiC phonons was 54 nm, it was confirmed that the pore spacing was 0.1 to 100 times the mean free path of phonons.
- the thermal conductivity of the sintered body was 7.8 W / (m ⁇ K) at room temperature (25 ° C.), 12 W / (m ⁇ K) at 100 ° C., and 16 W / (m ⁇ K) at 200 ° C. It was confirmed that the thermal conductivity increased from room temperature (25 ° C.) to 100 ° C.
- the results are shown in Table 1.
- the thermal conductivity at 100 ° C. was 1.5 times or more of the thermal conductivity at room temperature, and the thermal conductivity at 200 ° C. was twice or more than the thermal conductivity at room temperature.
- Example 4 A molded body was prepared in the same manner as in Example 2, and the molded body was fired by a spark plasma sintering method (SPS) (1500 ° C., 10 minutes) to obtain a porous silicon carbide sintered body.
- SPS spark plasma sintering method
- the sintered body was observed with an electron microscope, and the values of the silicon carbide particles and pores constituting the sintered body were measured from the image.
- the average value of the particle diameter of 10 arbitrarily selected silicon carbide particles was 95 nm. Further, for 10 arbitrarily selected pores, the distance between the pores and the nearest pores among the pores around the pores was measured, and the average value was 98 nm. Since the mean free path of SiC phonons was 54 nm, it was confirmed that the pore spacing was 0.1 to 100 times the mean free path of phonons.
- Example 5 A molded body was prepared in the same manner as in Example 2, and the molded body was fired in an Ar atmosphere (1400 ° C., 2 h) to obtain a porous silicon carbide sintered body.
- the sintered body was observed with an electron microscope, and the values of the silicon carbide particles and pores constituting the sintered body were measured from the image.
- the average particle diameter of 10 silicon carbide particles selected arbitrarily was 23 nm. Further, for 10 arbitrarily selected pores, the distance between the pores and the nearest pores among the pores around the pores was measured, and the average value was 25 nm. Since the mean free path of SiC phonons was 54 nm, it was confirmed that the pore spacing was 0.1 to 100 times the mean free path of phonons.
- Example 6 A molded body was prepared in the same manner as in Example 2, and the molded body was fired in vacuum (1400 ° C., 2 hours) to obtain a porous silicon carbide sintered body.
- the sintered body was observed with an electron microscope, and the values of the silicon carbide particles and pores constituting the sintered body were measured from the image.
- the average particle diameter of 10 silicon carbide particles selected arbitrarily was 22 nm. Further, for 10 arbitrarily selected pores, the distance between the pores and the nearest pores among the pores in the vicinity thereof was measured, and the average value was 26 nm. Since the mean free path of SiC phonons was 54 nm, it was confirmed that the pore spacing was 0.1 to 100 times the mean free path of phonons.
- Example 7 A molded body was prepared in the same manner as in Example 2, and the molded body was fired with a hot press (1400 ° C., 1 h) to obtain a porous silicon carbide sintered body.
- the sintered body was observed with an electron microscope, and the values of the silicon carbide particles and pores constituting the sintered body were measured from the image.
- the average value of the particle diameter of 10 arbitrarily selected silicon carbide particles was 57 nm. Further, for 10 arbitrarily selected pores, the distance between the pores and the nearest pores among the pores around the pores was measured, and the average value was 63 nm. Since the mean free path of SiC phonons was 54 nm, it was confirmed that the pore spacing was 0.1 to 100 times the mean free path of phonons.
- Example 8 A mixed powder obtained by adding 5% by mass of Y 2 O 3 and Al 2 O 3 as sintering aids to silicon carbide powder having an average particle diameter of 20 nm is press-molded to form a disk shape having a diameter of 30 mm and a thickness of 6 mm. Prepared the body. This molded body was fired at 2000 degrees in an Ar atmosphere to obtain a dense silicon carbide sintered body.
- the thermal conductivity of this sintered body was 18 W / (m ⁇ K) at room temperature (25 ° C), 28 W / (m ⁇ K) at 100 ° C, and 38 W / (m ⁇ K) at 200 ° C. It was confirmed that the thermal conductivity increased from room temperature (25 ° C.) to 100 ° C.
- the thermal conductivity at 100 ° C. was 1.5 times or more of the thermal conductivity at room temperature, and the thermal conductivity at 200 ° C. was twice or more than the thermal conductivity at room temperature.
- Example 9 A mixed powder obtained by adding 5% by mass of SrCO 3 and Al 2 O 3 to silicon carbide powder having an average particle diameter of 20 nm was press-molded to prepare a disk-shaped molded body having a diameter of 30 mm and a thickness of 6 mm. This molded body was fired at 1500 ° C. in an Ar atmosphere to obtain a dense silicon carbide sintered body.
- the sintered body was a polycrystalline body composed of SiC and a grain boundary phase containing Sr, Al, Si, and O around it.
- the value about this SiC particle was measured from the electron microscope image.
- the particle size of 10 arbitrarily selected SiC particles was measured, the average value was 35 nm. Since the mean free path of SiC phonons was 54 nm, it was confirmed that the particle size was 0.1 to 100 times the mean free path of phonons.
- the thermal conductivity of the sintered body was 2.5 W / (m ⁇ K) at room temperature (25 ° C.), 4.2 W / (m ⁇ K) at 100 ° C., and 5.8 W / (at 200 ° C. m ⁇ K), and it was confirmed that the thermal conductivity increased from room temperature (25 ° C.) to 100 ° C.
- the thermal conductivity at 100 ° C. was 1.5 times or more of the thermal conductivity at room temperature, and the thermal conductivity at 200 ° C. was twice or more than the thermal conductivity at room temperature.
- Example 10 A silicon carbide powder having an average particle diameter of 20 nm was press-molded to prepare a disk-shaped molded body having a diameter of 30 mm and a thickness of 6 mm. This molded body was fired at 1500 degrees in the air atmosphere to obtain a dense silicon carbide sintered body.
- this sintered body was observed with an electron microscope, it was observed that it was a polycrystalline body composed of SiC and a grain boundary phase containing Si and O around it.
- the value about this SiC particle was measured from the electron microscope image.
- the particle size of 10 arbitrarily selected SiC particles was measured, the average value was 30 nm. Since the mean free path of SiC phonons was 54 nm, it was confirmed that the particle size was 0.1 to 100 times the mean free path of phonons.
- Example 11 An aluminum nitride powder having an average particle diameter of 40 nm was press-molded to prepare a disk-shaped molded body having a diameter of 30 mm and a thickness of 6 mm. This molded body was fired at 1400 degrees in a nitrogen atmosphere to obtain a porous aluminum nitride sintered body.
- Example 12 A silicon nitride powder having an average particle size of 25 nm was press-molded to prepare a disk-shaped molded body having a diameter of 30 mm and a thickness of 6 mm. This molded body was fired at 1400 degrees in a nitrogen atmosphere to obtain a porous silicon nitride sintered body.
- This sintered body was observed with an electron microscope, and values of the silicon nitride particles and pores constituting the sintered body were measured from the image.
- the average value of the particle size of 10 arbitrarily selected silicon nitride particles was 30 nm. Further, for 10 arbitrarily selected pores, the distance between the pores and the nearest pores among the pores around the pores was measured, and the average value was 30 nm.
- This sintered body was composed of silicon carbide particles of about 10 ⁇ m, and pores were arranged at intervals of about 10 ⁇ m.
- the measured thermal conductivity of the sintered body was 45 W / (m ⁇ K) at room temperature and 40 W / (m ⁇ K) at 200 ° C. Therefore, it did not function as a heat switch that switches between a heat insulation state and a heat radiation state.
- the thermal switch of the present invention can be used as a switch whose heat transferability varies depending on the temperature.
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Abstract
Description
(式1) LAMFP=(3×熱伝導率)/(熱容量×音速)
で定義したとき、微構造の代表長さLaが0.1LAMFP≦La≦100LAMFPであり、熱伝導率が室温から100℃の間で単調に増加する。
(1)ある材料A(母材)の中に、微構造の代表長さLaの間隔で母材とは異なる材料を分散させた状態で焼結する(図1A:実施形態1)。
(2)ある材料A(母材)の中に、微構造の代表長さLaの間隔で母材とは異なる材料の粒子を析出させる(図1A:実施形態1)。
(3)ある材料A(母材)の中に、微構造の代表長さLaの間隔で気孔を形成する(図1B:実施形態2)。
(4)粒径が微構造の代表長さLaのある材料Aの粒子から構成させる多結晶体(微構造の代表長さLaの間隔で粒界相が存在)(図1C:実施形態3)。
実施形態1~3について、さらに説明する。
図1Aに、母材(材料A)中に異種材料(材料B)が分散した複合材料によって構成された実施形態1を示す。本実施形態は、材料A中に材料Bの粒子がある長さの間隔で存在している。微構造の代表長さLaは、材料Bの粒子と材料Bの粒子との間隔である。ある粒子B1に対し、その周りにある粒子Biの内、最短の位置にある粒子B2を選択し、B1とB2との距離をGIとする。
図1Bに、多孔体によって構成されたセラミックス材料の実施形態を示す。本実施形態は、材料A中に気孔Cがある長さの間隔で存在している構造を有する。微構造の代表長さLaは、気孔Cの間隔である構造長さである。
図1Cは、多結晶によって構成されたセラミックス材料の実施形態を示す。本実施形態は、多結晶によって構成され、結晶粒子の粒径dが微構造の代表長さLaである。したがって、0.1LAMFP≦d≦100LAMFPであることが好ましい。粒径dに分布があったとしても(間隔が一定でない場合でも)、dが上記の範囲内であることが好ましく、全体の80%以上のdがこの範囲内にあることが好ましい。結晶粒子の粒径dがこのような範囲内となるようにセラミックス材料を形成することにより、温度によって熱伝導率が大きく変化するセラミックス材料を得ることができる。
上記のようなセラミックス材料は、温度によって熱伝導率が大きく変化するため熱スイッチとして用いることができる。例えば、図2に示すように、セラミックス材料は室温以上のある温度を境に急激に熱伝導率が増加する。熱スイッチとは、熱伝導率が低い状態(断熱状態)と高い状態(伝熱状態)とを切り替えられる材料である。温度が上昇した場合に熱伝導率が高くなる熱スイッチは、ある温度(第1温度)以下では、熱伝導率が低いため、熱スイッチはOFFの状態と言える。一方、第1温度より高い第2温度以上では、熱伝導率が高くなり、熱スイッチはONの状態と言える。
気孔の間隔のばらつきが少ない成形体とし、焼結した際にも気孔の間隔のばらつきを少なくするため、平均粒径100nmの炭化ケイ素粉末を、分散剤の入ったエタノールを用いて分散させた。この炭化ケイ素粉末をプレス成形して、直径30mm、厚さ6mmの円盤状の成形体を準備した。この成形体をAr雰囲気中で2050℃で焼成し、多孔質な炭化ケイ素焼結体を得た。
平均粒径20nmの炭化ケイ素粉末をプレス成形して、直径30mm、厚さ6mmの円盤状の成形体を準備した。この成形体を放電プラズマ焼結法(SPS)(1400℃、10分)で焼成し、多孔質な炭化ケイ素焼結体を得た。
実施例2と同様に成形体を準備し、その成形体を放電プラズマ焼結法(SPS)(1400℃、30分)で焼成し、多孔質な炭化ケイ素焼結体を得た。
実施例2と同様に成形体を準備し、その成形体を放電プラズマ焼結法(SPS)(1500℃、10分)で焼成し、多孔質な炭化ケイ素焼結体を得た。
実施例2と同様に成形体を準備し、その成形体をAr雰囲気中(1400℃、2h)で焼成し、多孔質な炭化ケイ素焼結体を得た。
実施例2と同様に成形体を準備し、その成形体を真空中(1400℃、2h)で焼成し、多孔質な炭化ケイ素焼結体を得た。
実施例2と同様に成形体を準備し、その成形体をホットプレス(1400℃、1h)で焼成し、多孔質な炭化ケイ素焼結体を得た。
平均粒径20nmの炭化ケイ素粉末に、焼結助剤としてY2O3、Al2O3をそれぞれ5質量%添加した混合粉末をプレス成形して、直径30mm、厚さ6mmの円盤状の成形体を準備した。この成形体をAr雰囲気中で2000度で焼成し、緻密質な炭化ケイ素焼結体を得た。
平均粒径20nmの炭化ケイ素粉末にSrCO3、Al2O3をそれぞれ5質量%添加した混合粉末をプレス成形して、直径30mm、厚さ6mmの円盤状の成形体を準備した。この成形体をAr雰囲気中で1500度で焼成し、緻密質な炭化ケイ素焼結体を得た。
平均粒径20nmの炭化ケイ素粉末をプレス成形して、直径30mm、厚さ6mmの円盤状の成形体を準備した。この成形体を大気雰囲気中で1500度で焼成し、緻密質な炭化ケイ素焼結体を得た。
平均粒径40nmの窒化アルミニウム粉末をプレス成形して、直径30mm、厚さ6mmの円盤状の成形体を準備した。この成形体を窒素雰囲気中で1400度で焼成し、多孔質な窒化アルミニウム焼結体を得た。
平均粒径25nmの窒化珪素粉末をプレス成形して、直径30mm、厚さ6mmの円盤状の成形体を準備した。この成形体を窒素雰囲気中で1400度で焼成し、多孔質な窒化珪素焼結体を得た。
平均粒径10μmの炭化ケイ素粉末をプレス成形して、直径30mm、厚さ6mmの円盤状の成形体を準備した。この成形体をAr雰囲気中で2200℃で焼成し、多孔質な炭化ケイ素焼結体を得た。
Claims (14)
- 室温におけるフォノンの見かけの平均自由行程LAMFPを
LAMFP=(3×熱伝導率)/(熱容量×音速)
で定義したとき、
微構造の代表長さLaが0.1LAMFP≦La≦100LAMFPであり、熱伝導率が室温から100℃の間で単調に増加するセラミックス材料。 - 100℃における熱伝導率が室温の熱伝導率の1.5倍以上である請求項1に記載のセラミックス材料。
- 200℃での熱伝導率が室温の熱伝導率の2倍以上である請求項1または2に記載のセラミックス材料。
- 母材に異種材料が分散した複合材料によって構成され、異種材料粒子と異種材料粒子の間隔GIが前記微構造の前記代表長さLaである請求項1~3のいずれか1項に記載のセラミックス材料。
- 前記異種材料粒子と前記異種材料粒子の間隔GIの平均値をGIaveとするとき、前記異種材料粒子と前記異種材料粒子の間隔GIが0.1GIave以上10GIave以下である請求項4に記載のセラミックス材料。
- 前記母材がSiCであり、前記異種材料粒子が、O、B、C、N、Al、Si、およびYからなる群から選ばれる少なくとも一種が含まれるものである請求項5に記載のセラミックス材料。
- 前記母材がSiCあり、GIaveが10~500nmである請求項5または6に記載のセラミックス材料。
- 多孔体によって構成され、前記多孔体中の気孔と気孔の間隔PIが前記微構造の前記代表長さLaである請求項1~3のいずれか1項に記載のセラミックス材料。
- 前記気孔と前記気孔の間隔PIの平均値をPIaveとするとき、前記気孔と前記気孔の間隔PIが0.1PIave以上10PIave以下である請求項8に記載のセラミックス材料。
- 前記セラミックス材料がSiCの多孔体であって、PIaveが10~500nmである請求項9に記載のセラミックス材料。
- 多結晶によって構成され、結晶粒子の粒径dが前記微構造の前記代表長さLaである請求項1~3のいずれか1項に記載のセラミックス材料。
- 前記結晶粒子の前記粒径dの平均値をdaveとするとき、前記粒径dが0.1dave以上10dave以下である請求項11に記載のセラミックス材料。
- 前記セラミックス材料がSiCの多結晶体であり、daveが10~500nmである請求項12に記載のセラミックス材料。
- 請求項1~13のいずれか1項に記載のセラミックス材料を用いた、温度により熱伝導率が変化する熱スイッチ。
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WO2016152687A1 (ja) * | 2015-03-23 | 2016-09-29 | 日本碍子株式会社 | セラミックス材料、及びその製造方法 |
JP2016216688A (ja) * | 2015-05-26 | 2016-12-22 | 国立大学法人名古屋大学 | 熱伝導率可変デバイス |
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JP6492210B1 (ja) * | 2018-05-18 | 2019-03-27 | 株式会社フジクラ | 熱整流性基板および熱電発電装置 |
JP2019201181A (ja) * | 2018-05-18 | 2019-11-21 | 株式会社フジクラ | 熱整流性基板および熱電発電装置 |
JP2019200030A (ja) * | 2018-05-18 | 2019-11-21 | 株式会社フジクラ | 熱ダイオードおよび熱ダイオードの製造方法 |
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JP6632885B2 (ja) | 2020-01-22 |
JPWO2015030238A1 (ja) | 2017-03-02 |
EP3042885A1 (en) | 2016-07-13 |
EP3042885B1 (en) | 2022-06-01 |
EP3042885A4 (en) | 2017-04-26 |
US20160137555A1 (en) | 2016-05-19 |
US9656920B2 (en) | 2017-05-23 |
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