JPWO2017135030A1 - Magnetic composition - Google Patents

Abstract

In the present invention, 100 {(Pb (1-x) yBax) ZrO3} · αM1 [wherein M1 is at least one selected from La, Bi, V, Nb, Ta, Sb, Mo and W. , X is 0.15 or more and 0.34 or less, y is 0.94 or more and 1.02 or less, and α is 0.1 or more and 1.9 or less. ] The magnetic composition which has as a main component the complex oxide represented by this is provided.

Description

  The present invention relates to a magnetic composition, specifically a magnetic composition exhibiting an electrocaloric effect, and a heat transfer device using the same.

  In recent years, in small portable devices (smartphones, tablet PCs) and electronic devices such as data servers, the performance of electronic devices is reduced due to the heat generated by a central processing unit (CPU) and hard disk (HDD). Problems such as shortening of life and failure are becoming apparent. For such problems, thermal management in electronic equipment is important. However, a small electronic device such as a smartphone has a small power supply capacity and does not have a space for installing a large cooling device. Therefore, in such a small electronic device, the temperature is currently controlled only by means of heat radiation through the housing, and the heat source and the housing are thermally coupled by a thermal sheet or the like to release heat. On the other hand, large electronic devices such as servers have sufficient power capacity and space, and therefore air conditioning equipment such as air conditioners, Peltier cooling devices, and the like are used.

On the other hand, Non-Patent Document 1 reports Pb _0.8 Ba _0.2 ZrO ₃ as a material having an electrocaloric effect (hereinafter also referred to as “EC effect”). In Non-Patent Document 1, this Pb _0.8 Ba _0.2 ZrO ₃ is formed into a thin film by a sol-gel method, and the EC effect is measured. As a result, it is described that the Pb _0.8 Ba _0.2 ZrO ₃ thin film described in Non-Patent Document 1 exhibits a large EC effect at 290 K near room temperature. The electrocaloric effect is an endothermic phenomenon caused by a change in entropy when the electric dipole moment in a substance is aligned or disturbed by a change in electric field.

A Giant Electrocaloric Effect in Nanoscale Antiferroelectric and Ferroelectric Phases Coexisting in a Relaxor Pb0.8Ba0.2ZrO3 Thin Film at Room Temperature, Biaolin Peng, Huiqing Fan, and Qi Zhang, Advanced Functional Materials, Volume 23, Issue 23, pages 2987-2992, June 20, 2013

  In a small electronic device, heat dissipation through the casing as described above is limited because the surface area of the casing is limited. Therefore, the temperature of each heat source is measured, and when the temperature exceeds a predetermined temperature, the performance of the CPU or the like is limited (suppressing heat generation itself). That is, the temperature rise of the housing may hinder the performance of the CPU or the like.

  Moreover, in a large electronic device, a sufficient cooling effect can be obtained by the air conditioning equipment as described above. However, since the power consumption is very large, there is a problem that a power cost is required for heat management.

  Accordingly, the present inventor has paid attention to the above-mentioned electrocaloric effect and has come to consider using a magnetic composition such as a Pb—Ba—Zr composite oxide exhibiting this electrocaloric effect for a heat transport device. In this phenomenon, a control voltage is required. However, since the above complex oxide is a highly insulating ferroelectric material, power consumption is very low, power cost is low, and even small portable devices with limited power capacity are used. It can be used.

  On the other hand, when the magnetic composition as described in Non-Patent Document 1 is used for thermal management of a large-sized electronic device such as a server that needs to handle a larger amount of heat, a higher electric field is applied to the magnetic composition, which is higher. It is necessary to obtain an EC effect. However, the magnetic composition as described in Non-Patent Document 1 has a problem that leakage current may occur when a high voltage is applied. This problem is particularly noticeable in a high-temperature environment because the magnetic composition generally decreases in insulation properties as the temperature rises.

  An object of the present invention is to provide a magnetic composition exhibiting a large electrocaloric effect and having a high insulating property, and a heat transfer device using the magnetic composition.

  As a result of intensive studies to solve the above problems, the present inventor prepared a specific amount of Pb in the Pb—Ba—Zr composite oxide, and further trivalent, pentavalent, or hexavalent. The present inventors have found that a magnetic composition exhibiting a large electrocaloric effect and having a high insulating property can be obtained by doping the above metal.

According to the first aspect of the present invention, the following formula:
_{100 {(Pb (1-x} ) y Ba x) ZrO 3} · αM1
[Wherein M1 is at least one element selected from La, Bi, V, Nb, Ta, Sb, Mo and W;
x is 0.15 or more and 0.30 or less,
y is 0.94 or more and 1.01 or less,
α is 0.1 or more and 1.0 or less. ]
The magnetic composition which has as a main component the complex oxide represented by these is provided.

According to a second aspect of the present invention, a composite oxide containing Pb, Ba, Zr and M2,
M2 is at least one element selected from La, Bi, V, Nb, Ta, Sb, Mo and W;
The content mole part of Ba with respect to Zr100 mole part is p mole part,
The molar content of Pb with respect to 100 mol of Zr is q mol,
p is 15 or more and 30 or less,
q is (100−p) × r (wherein r is 0.94 or more and 1.01 or less),
Provided is a magnetic composition comprising a composite oxide as a main component, wherein the content mole part of M2 with respect to 100 mole parts of Zr is 0.1 mole part or more and 1.0 mole part or less.

  According to a third aspect of the present invention, there is provided a heat transfer device comprising at least two electrodes and a dielectric portion made of the above magnetic composition located between the electrodes.

  According to the 4th summary of this invention, the electronic component which has said heat transfer device is provided.

  According to a fifth aspect of the present invention, there is provided an electronic apparatus comprising the above heat transfer device or the above electronic component.

According to the present invention, the magnetic composition having a specific composition, e.g., _{100 {(Pb (1-x} ) y Ba x) ZrO 3} · αM1
[Wherein, M1 is at least one selected from La, Bi, V, Nb, Ta, Sb, Mo and W;
x is 0.15 or more and 0.30 or less,
y is 0.94 or more and 1.01 or less,
α is 0.1 or more and 1.0 or less. ]
By using the material represented by the above, it is possible to provide a magnetic composition having a large electrocaloric effect and high insulating properties.

FIG. 1 is a schematic cross-sectional view of a heat transfer device according to the first embodiment of the present invention. FIG. 2 is a schematic cross-sectional view of a heat transfer device according to the second embodiment of the present invention. FIG. 3 is a temperature-ΔT diagram (10 MV / m) for samples 95 and 101 in the example.

  Hereinafter, the magnetic composition of the present invention will be described.

In one embodiment, the magnetic composition of the present invention contains a composite oxide represented by the following formula as a main component.
_{100 {(Pb (1-x} ) y Ba x) ZrO 3} · αM1

  The “main component” means a component that is contained most in the magnetic composition, for example, a component that is contained in an amount of 50% by mass or more. In particular, the main component is 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, for example, a component contained in 98.0 to 99.8% by mass, or It means a component that is substantially 100% contained.

  In the above formula, x is 0.15 or more and 0.30 or less, preferably 0.20 or more and 0.30 or less, and more preferably 0.20 or more and 0.25 or less. By setting the x value in such a range, greater insulation and EC effect can be obtained. Further, by changing the value of x, it is possible to adjust the temperature at which the temperature change (hereinafter also referred to as “ΔT”) due to the change in the electric field exhibits a peak value.

  In the above formula, y is 0.94 or more and 1.01 or less.

  In one embodiment, y is 0.94 or more and less than 1.00, for example 0.94 or more and 0.999 or less, 0.95 or more and 0.999 or less, 0.965 or more and 0.999 or less, or It can be 98 or more and 0.99 or less. When y is less than 1.00, grain growth is unlikely to occur, a dense magnetic composition is obtained, insulation is improved, and a larger electric field can be applied.

  In another embodiment, y is greater than 1.00 and 1.01 or less, preferably 1.001 or more and 1.010 or less, for example 1.005 or more and 1.010 or less. By making y larger than 1.00, the value of ΔT can be made larger.

In the above formula, M1 is at least one doping element, and is selected from La, Bi, V, Nb, Ta, Sb, Mo and W. Of these doping elements, La and Bi are trivalent (ie, La ³⁺ and Bi ³⁺ ), and V, Nb, Ta and Sb are pentavalent (ie, V ⁵⁺ , Nb ⁵⁺ , Ta ⁵⁺ and Sb ⁵⁺ ). And Mo and W are hexavalent (ie, Mo ⁶⁺ and W ⁶⁺ ).

  In said formula, (alpha) is 0.1 or more and 1.0 or less, Preferably it is 0.5 or more and 1.0 or less. By setting α in the range of 0.1 to 1.0, the insulating properties of the composite oxide are improved.

In one embodiment, the magnetic composition of the present invention is a composite oxide containing Pb, Ba, Zr and M2,
M2 is at least one selected from La, Bi, V, Nb, Ta, Sb, Mo and W;
The content mole part of Ba with respect to Zr100 mole part is p mole part,
The molar content of Pb with respect to 100 mol of Zr is q mol,
p is 15 or more and 30 or less,
q is (100−p) × r (wherein r is 0.94 or more and 1.01 or less),
The main component is a magnetic composition containing as a main component a composite oxide, wherein the M2 molar content relative to 100 mol of Zr is 0.1 mol part or more and 1.0 mol part or less. The composite oxide may correspond to the formula _{100 {(Pb (1-x} ) y Ba x) ZrO 3} composite oxide represented by · Arufaemu1 described above.

  In the above formula, p is 15 or more and 30 or less, preferably 20 or more and 30 or less, more preferably 20 or more and 25 or less. By setting p in such a range, greater insulation and EC effect can be obtained. Moreover, the temperature at which ΔT exhibits a peak value can be adjusted by changing the value of p.

  In one embodiment, r is 0.94 or more and less than 1.00, for example 0.94 or more and 0.999 or less, 0.95 or more and 0.999 or less, 0.965 or more and 0.999 or less, or It can be 98 or more and 0.99 or less. When r is less than 1.00, grain growth is unlikely to occur, a dense magnetic composition is obtained, insulation is improved, and a larger electric field can be applied.

  In another embodiment, r is greater than 1.00 and 1.01 or less, preferably from 1.001 to 1.010, for example from 1.005 to 1.010. By making r larger than 1.00, the value of ΔT can be made larger.

In the above formula, M2 is at least one doping element, and is selected from La, Bi, V, Nb, Ta, Sb, Mo and W. Of these doping elements, La and Bi are trivalent (ie, La ³⁺ and Bi ³⁺ ), pentavalent (ie, V ⁵⁺ , Nb ⁵⁺ , Ta ⁵⁺ and Sb ⁵⁺ ), and Mo and W are hexavalent. (Ie, Mo ⁶⁺ and W ⁶⁺ ).

  The content mole part of M2 with respect to 100 mole parts of Zr is 0.1 or more and 1.0 or less, preferably 0.5 or more and 1.0 or less. By setting the content molar part of M2 with respect to Zr100 molar part in the range of 0.1 or more and 1.0 or less, the insulating properties of the composite oxide are improved.

  The composite oxide of the present invention exhibits an EC effect that generates heat when an electric field is applied and absorbs heat when removed.

  The complex oxide may be a perovskite type.

  By having M1 or M2, the magnetic composition of the present invention exhibits a large EC effect in a relatively wide lead composition region (ie, a relatively wide range of y or r). The present invention is not bound by any theory, but the reason is considered as follows. In a ferroelectric ceramic having a perovskite structure containing Pb, it is considered that Pb deficiency occurs in the final composition after firing because Pb of the ceramic volatilizes due to the high vapor pressure of PbO during firing. The EC characteristics at high temperature are likely to be affected by the Pb deficiency, and the lead composition region where an effective EC effect can be obtained is considered to be very narrow. In the present invention, since the donor ion (M1 or M2) is added, it is considered that the influence of the Pb deficiency on the EC effect is reduced.

  In one embodiment, the average particle size of the magnetic composition of the present invention may be preferably 0.5 μm or more, more preferably 0.5 μm or more and 10 μm or less, and further preferably 1 μm or more and 5 μm or less. By having such a particle size, it is possible to further increase the withstand voltage and electrocaloric effect of the dielectric portion. The average particle diameter can be measured using an electron scanning microscope.

  The magnetic composition of the present invention exhibits a large EC effect particularly at 323K to 453K (50 ° C to 180 ° C). Moreover, the magnetic composition of the present invention exhibits a very high insulating property. That is, a high voltage can be applied. Therefore, a high electrocaloric effect can be obtained by using the magnetic composition of the present invention.

  The temperature range showing a large EC effect can be adjusted by changing the content of Pb and Ba, particularly the content of Ba, in the Pb—Ba—Zr composite oxide.

The magnetic composition of the present invention exhibits high insulation properties, for example, 1 × 10 ⁸ Ω · cm or more, 1 × 10 ¹⁴ Ω · cm or less, preferably 1 × 10 ⁹ Ω · cm or more, 1 × 10 ¹² Ω or more. It has a specific resistance of not more than cm, more preferably not less than 1 × 10 ⁹ Ω · cm and not more than 1 × 10 ¹¹ Ω · cm.

  The magnetic composition of the present invention exhibits a ΔT of 0.7 K or more, preferably 1.0 K or more when an electric field of 20 MV / m is applied.

  The magnetic composition of the present invention exhibits a ΔT of 1.0 K or more, preferably 1.5 K or more, more preferably 2.0 K or more when an electric field of 30 MV / m is applied.

  The magnetic composition of the present invention exhibits a withstand voltage of 20 MV / m or more, preferably 30 MV / m or more.

  The magnetic composition of the present invention can be obtained, for example, by mixing Pb, Ba, Zr and M1 or M2 oxides or salts and firing them. It is possible to adjust the Pb content in the obtained composite oxide by mixing Pb, Ba, Zr and M1 or M2 so as to have a predetermined ratio and adjusting the Pb concentration in the atmosphere during firing. it can.

  Next, the heat transfer device of the present invention will be described with reference to the drawings. However, the shape, arrangement, and the like of the heat transfer device and each component according to the embodiment described below are not limited to the illustrated examples.

  As shown in FIG. 1, the heat transfer device 1a according to the first embodiment of the present invention includes a pair of electrodes 2 and 4 and a dielectric composed of the magnetic composition of the present invention located between the pair of electrodes. And a body portion 6. When a voltage is applied between the electrodes 2 and 4, an electric field is applied to the dielectric portion 6. As a result, the dielectric portion 6 generates heat. When the voltage between the electrodes 2 and 4 is removed, the electric field applied to the dielectric portion 6 disappears. As a result, the dielectric portion 6 absorbs heat.

  The shape of the dielectric portion 6 is not particularly limited, and can be formed into, for example, a sheet shape, a block shape, and other various shapes. The molding method is not particularly limited, and compression, sintering, or the like can be used. Moreover, you may mix and shape | mold with binders, such as resin or glass.

  Although it does not specifically limit as a material which comprises the electrodes 2 and 4, Ag, Cu, Pt, Ni, Al, Pd, Au, or these alloys (for example, Ag-Pd etc.) are mentioned. Among these, Pt, Ag, Pd, or Ag—Pd is preferable.

  The electrodes 2 and 4 may have a function of transporting the amount of heat of the dielectric part in addition to the function of applying an electric field to the dielectric part. Therefore, from the viewpoint of heat transfer, the material constituting the electrode is preferably a material having high thermal conductivity, such as Ag.

  The shape of the electrodes 2 and 4 is not particularly limited, but a shape that covers the entire surface of the dielectric portion 6 is preferable from the viewpoint of heat transfer.

  The heat transfer device of the present invention uses a dielectric portion made of a material exhibiting a large EC effect, particularly at 323K to 453K (50 ° C. to 180 ° C.). Therefore, the heat transfer device of the present invention is preferably used as a heat transfer device, typically a cooling device, in electronic devices such as smartphones, tablet PCs, and data servers whose temperature during heat generation is 323K to 453K. it can.

  As described above, the magnetic composition of the present invention exhibits a very high insulating property. Therefore, the dielectric layer of the heat transfer device of the present invention has a high withstand voltage, and a high voltage can be applied between the electrodes, so that the change in electric field can be increased. As a result, it becomes possible to increase the temperature change (ΔT) due to the change of the electric field.

  The heat transfer device according to the first embodiment of the present invention has been described above. However, the present invention is not limited to the above embodiment, and various modifications can be made.

  For example, it can be set as the heat transfer device 1b as shown in FIG. In the heat transfer device 1b according to the second embodiment of the present invention, the plurality of internal electrodes 12a and 12b and the plurality of dielectric portions 14 are alternately stacked. The internal electrodes 12a and 12b are electrically connected to external electrodes 16a and 16b disposed on the end face of the heat transfer device 1b, respectively. When a voltage is applied from the external electrodes 16a and 16b, an electric field is formed between the internal electrodes 14a and 14b. Due to this electric field, the dielectric portion 14 generates heat. When the voltage is removed, the electric field disappears, and as a result, the dielectric portion 14 absorbs heat.

  In one embodiment, the laminated dielectric parts 14 may all have the same composition, or one or more dielectric parts having different compositions may be laminated.

  By adopting such a structure, it becomes possible to apply a stronger electric field to the dielectric portion 14, and a larger ΔT can be obtained. Further, since the internal electrode also functions as a heat propagation path to the inside of the dielectric portion, efficient heat management is enabled.

  In the heat transfer devices 1a and 1b described above, the electrode and the dielectric portion are substantially in contact with each other, but the present invention is not limited to such a structure, and an electric field can be applied to the dielectric portion. Any structure can be used. The heat transfer devices 1a and 1b have a rectangular parallelepiped block shape, but the shape of the heat transfer device of the present invention is not limited thereto, and may be, for example, a cylindrical shape or a sheet shape. Etc. may be included.

  The heat transfer device of the present invention absorbs heat generated by the heat source mainly when the electric field is released and absorbs heat, or when the temperature of the heat transfer device decreases due to this heat absorption. The heat transfer device of the present invention releases absorbed heat to the outside mainly when an electric field is applied to dissipate heat. Therefore, the heat transfer device of the present invention can be used as a cooling device.

  The present invention also provides an electronic component having the heat transfer device of the present invention, and an electronic apparatus having the heat transfer device or electronic component of the present invention.

  Although it does not specifically limit as an electronic component, For example, a central processing unit (CPU), a hard disk (HDD), a power management IC (PMIC), a power amplifier (PA), a transceiver IC, a voltage regulator (VR), etc. Light emitting elements such as integrated circuits (ICs), light emitting diodes (LEDs), incandescent bulbs, semiconductor lasers, parts that can be heat sources such as field effect transistors (FETs), and other parts such as lithium ion batteries, substrates, heat sinks And parts commonly used in electronic devices such as housings.

  Although it does not specifically limit as an electronic device, For example, a mobile telephone, a smart phone, a personal computer (PC), a tablet-type terminal, a hard disk drive, a data server etc. are mentioned.

- In the preparation of the thermal preparation of the conveying device _{100 {(Pb (1-x} ) y Ba x) ZrO 3} composite oxide represented by _{· αM1, Pb 3 O 4,} BaCO 3, ZrO 2 and _Nb 2 _{O 5} Alternatively, the Ta ₂ O ₅ raw material was weighed so as to have the composition shown in the following table, and pulverized and mixed with partially stabilized zirconia (PSZ) balls. After drying, it was calcined at 1000 ° C. for 4 hours, and an organic solvent and a binder were added to the calcined powder and pulverized and mixed to form a slurry. A green sheet (thickness: 40 μm) was formed from the obtained slurry by a doctor blade method. A Pt paste was screen printed on the green sheet. The green sheet on which the Pt paste was printed was pressure-bonded so as to have a layer structure as shown in FIG. 2, stacked, and then cut to produce a green chip (5 mm × 7 mm × 0.5 mm).

The green chip (2 g) was degreased at 450 ° C. to 550 ° C., and then enclosed in an alumina sealed sheath together with 10 g of PbZrO ₃ powder, and baked at 1300 ° C. for 4 hours to produce a laminate chip. An Ag paste was applied to both ends of the obtained laminate chip, baked to form external electrodes, and a sample (heat transfer device) having the structure shown in FIG. 2 was manufactured. The composition of the sample was confirmed using ICP (inductively coupled plasma emission spectroscopy) and XRF (fluorescence X-ray measurement) in combination.

(Evaluation)
・ Evaluation of electrical calorific effect (ΔT evaluation)
An ultrafine thermocouple was directly attached to the sample, and the temperature change (ΔT) at the time of applying and removing the electric field was measured. The results are shown in the table below.

-Operating temperature The temperature at which the value of ΔT measured above was maximized was determined as the operating temperature. The results are shown in the table below.

The judgment criteria are as follows.
When satisfying the following (a) to (c), it was determined as “G”, and when none was satisfied, it was determined as “NG”.
(A) The temperature at which ΔT is maximum is in the range of 50 ° C to 180 ° C.
(B) An electric field of 20 MV / m can be applied, and ΔT is greater than 0.7K.
(C) An electric field of 30 MV / m can be applied.
“X” indicates that Joule heat is generated, and “−” indicates that measurement is not performed.

  Typically, sample number 101 where x is 0.3, y is 0.97, M1 is Nb, α is 0.1, and sample number 95 not including M1 is an electric field of 10 MV / m. FIG. 3 shows a temperature-ΔT diagram when measured by.

  From the above results, samples within the scope of the present invention have high insulation and large ΔT at operating temperatures suitable for use in electronic equipment, and can maintain insulation even in an electric field of 30 MV / m. confirmed. In particular, when x is 0.25 or less, ΔT when an electric field of 20 MV / m is applied is 1.0 K or more, and it has been confirmed that the characteristics are further improved. Further, as shown in FIG. 3, it was confirmed that the sample 101 of the present invention doped with M1 has an overall ΔT higher than that of the sample 95 not doped with M1, and has a wide usable area.

  The heat transfer device of the present invention can be used as a cooling device for various electronic devices, for example, small electronic devices such as mobile phones in which the problem of heat countermeasures has become prominent.

DESCRIPTION OF SYMBOLS 1a, 1b ... Heat transfer device 2, 4 ... Electrode 6 ... Dielectric part 12a, 12b ... Internal electrode 14 ... Dielectric part 16a, 16b ... External electrode

Claims (11)

Following formula:
_{100 {(Pb (1-x} ) y Ba x) ZrO 3} · αM1
[Wherein, M1 is at least one selected from La, Bi, V, Nb, Ta, Sb, Mo and W;
x is 0.15 or more and 0.30 or less,
y is 0.94 or more and 1.01 or less,
α is 0.1 or more and 1.0 or less. ]
The magnetic composition which has as a main component the complex oxide represented by these.   The magnetic composition according to claim 1, wherein M1 is at least one selected from Nb and Ta.   The magnetic composition according to claim 1, wherein y is 0.965 or more and 0.999 or less. A composite oxide containing Pb, Ba, Zr and M2,
M2 is at least one selected from La, Bi, V, Nb, Ta, Sb, Mo and W;
The content mole part of Ba with respect to Zr100 mole part is p mole part,
The molar content of Pb with respect to 100 mol of Zr is q mol,
p is 15 or more and 30 or less,
q is (100−p) × r (wherein r is 0.94 or more and 1.01 or less),
A magnetic composition comprising a composite oxide as a main component, wherein the molar content of M2 with respect to 100 mol parts of Zr is 0.1 mol parts or more and 1.0 mol parts or less.   The magnetic composition according to claim 4, wherein M2 is at least one selected from Nb and Ta.   The magnetic composition according to claim 4 or 5, wherein r is 0.965 or more and 0.999 or less.   A heat transfer device comprising at least two electrodes and a dielectric portion made of the magnetic composition according to claim 1 located between the electrodes.   The heat transfer device according to claim 7, wherein a plurality of electrodes and a plurality of dielectric portions are alternately stacked.   The heat transfer device according to claim 7 or 8, which is a cooling device.   An electronic component comprising the heat transfer device according to any one of claims 7 to 9.   An electronic apparatus comprising the heat transfer device according to any one of claims 7 to 9 or the electronic component according to claim 10.

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